SON(rcHEMICAI, SYNIIIISIS AIID CIIARACTERIZATION OF PR.ECT ...

SON(rcHEMICAI, SYNIIIISIS AIID 

CIIARACTERIZATION OF PR.ECT'RSORS FOR 

DEP1OSITION OF THIN FILMS OT CERAMIC 

MAISRIALS TOR GAS SENSORS 

A Dissenation Submitted lo the Deparrnent of Ch€mistry, 

Quaid-i-Azam Un iversity, Islamabad, in panial tulfillmenr ofthe 

rcquirehenr for the deAree of 

Doctor ofPhilosophy 

Inorgsnic/Analytical Chemistry 

by 

Sy[ .uzannitl{'assain 

Deparhnent of Chemistry 

Quaid-i-Azam University 

lslamabad 45320, Pakistan 

(November 2009)

DECLARATION 

lhis is ro certiry lh.t lnis disertation.nfiled .Son@h.otc.l Sy,rt.rir ad 

chttuctqization of Precr6oa lot Deposition ot Thir Ftth of Cenhlc Matalntt tol 

Cdr.tezr,rs" subniltcd by Syed M@Dnil Uu$!i! is Mepled in its pEs.! fom by 

thc Dcpannenl ol Clenistry, QEid,iAe Udv€siry, IsloDabad, paliscon, 6 

saGrying the pdnial Equi@.nr for rh. deCE of Do.rot oJ Phitotoptt i 

/1, a lttie I /h o I e or ic C I e n it I t!, 

-21-'--z-- 

Dr Ri0 Aio.d, 

C.S.O., NuclearChehisrryDivision 

PINSTECqNiIoR, 

CPS Dielorrte, NESCOM, 

P O. Bo\ 2216, 

Prct Di &i! B.drn.h

DECI,/\NATION 

I i! crd6d |h.[ li..nFiurrl elit xrr DqfaD.d a let.d..L rly 

t hotuLr, D.larn dof tuirry, etd&i-Aa Untrqdry,ICet dar32& 

od bailr. Ofl'd!.ril Codd S]l!t o oICS) hldlb. 

To d! td of ry l@wlcdsc |h. ao* i! qliEt |!d hr rtltt t .a F.ed t, ey 

otdlru. @yddm ft.tt cvr|ldd of pt"D h* 

iil 

sr.d Mrr.Dr|l llt|.i. 

D.DdG Of.L-dt 

qd&i:Azm, IrlnElit 

I!&rb.d 45320, P.lritu

DEDICANON 

'Ir.Ub rytt*t tu 6td 

nD4 oqaL.t -a * 

.a@vqmt ,4t tu rt b h&l N 

,,{r!'l.tqNtfide.

ACKNOWLEDGEMENTS 

It b my piivilcge ro b. v€ry thd}in b 6y Esearch supeNi$r Prot Dr. MuttnE.d 

M.rlr, Ilp.rtnoi of Ch@tr.y, Quaid-i-Azd Uaiv6iry, Ista@h6d for his 

invduble guiddce dtl imas. co-op€r.lio.. Duing this .nd.avou in spit€ of his 

p!!.@Wdion !. pFvided all h.lp, pEciou sugg.stioN & m@uagcn€n! which 

.oued n io conpl€r. tnis task in dn . No mand how in onctuiE I thoudr ny d!l.i 

!!!, I alw.rr feh benq a0a di$Nbn with hin. I cmor imosine oyonc lhsl wolld 

b. m@ @miftd ro htu snddtr or 0!eir r$eh rhd Dr Mr!.i 

I wbh to crprcs my gEtitu&., to Dr. Iht.z Q.Err. Menb€r Def€r@, Di Sy.d 

Wlll.y.t Hrs.i!, Mcmbd Sci.G, Rshl.l Atud Atri Dir.tor cen ht of hstitut. 

Of Ind!$rial Conlrol sysr@ (Ircs) pa&ilt n foi providins rcquiEd f&ihi€s dd 

potdtial vd&s, etich played a vibl Dt. in @nducling ed @mpl.tion of lhis wo*. 

Appuiotion gG !o Dr. Sr.d T.iDot Hun., pFfsor Dr. Jmil AtE.d, Dr 

lbtihddh dd Prcf. Dr, Sy.d Abn.d ri@izt for th€ valuabtc discussions, 

Suid&e 6d ledioB poofMdins ofoy rh6is. 

I rculd lik io lh.nt alt my leehcn .sFcistly pmt Dr Ani! B.d!t. ed pof. Dr, 

s.qlb A[ fo' providing ho6] suppon. 

I wtdd .lso lik ro rlEnk my Col.gu€ b.ft l. UCS, L.b 4l {.1 42 of the 

D.trrnueltoflnory. c/An.btlc.t Cbeoktry for th€ir limely co.opmiion. 

Fitully I edd.l€fljtclt lite 10 pay bantu glritutcs' ro my b.toted p@nls md by 

fmily wh6. inv.lublc nodl suprbit &d .DcoMgmcnrs hav€ tao a b.eon oI ligh 

ihrcugh out ny edwddonal &hi€v.Ddtt 

At tn. lan bft ml lcse, th. rct. of rhoe pdeDjirid *toe tM6 @utd nor b. 

d'splayed in wods bul will r€nain in ny o.mo.ies, Tbrtrk yuu. 

Sy.d Muodl I|us.i.

PREFACE 

'Ihb th6b @Nisls ofthe cha$q!: 

Ct ptr r Fdna iftld@lid ro llt. bctic @@pl! of tle smndisy, c.mic 

natdialt, p$uerq thin filn t cbniques aid s bd.f d.sipiion of aah of the 

*FriE !t l &.tniqu.r Fg{dilg p@tue6 ald thi! fle cbtic&rblioll s6ing 

Eeb&is, @rc€tt of b.rd g.p @giMin8 boctgoutrd t tcv@l ro rlc $bjet. 

Cbrpt r 2 .xplairts th. axpdin€ntal dcraib of €@ch w* ircludinc aynrhcss of 

p|eeB, cbdr&t rirrtioog tL.rE l dMposirid latrcG of !@ulsB .tong wirh 

cv.lutio! of sod. of tbe kindic Ddd.L6, thin n|o f.bricarion 6d physicat 

cb@tqiz.tion of Aiaxi.l C\ ZnO lrd &O, .long wirh Z.O tuing pbp€njca 

€Fi.[y for dblml {d lydocdtor d! dlo Flgtld. 

Ch.pt6 3 desls Bilh rBolt! ed dikwion Egddirg ou 6!diDgs. 

R.&Mc.! ae gilcn .l ta .!d ofad chrpt r. Firrly roEc g.e6l mclulioF for all 

of tlc sod( e dnwn md Mu.. fd poctibb nli@ dirstioG of srdia e Fojer.d. 

SFcin .xpait@irl d€bils e givo in .pp.ndioier for eady rcf.ence.

LIST OF CONTENTS 

CHAPTER-I: INTRODUCTTON 

Ll.l Honogc!@B roD@h.nirtyofliquid sy'cm 2 

I.1.2 g.r.reA@u. smtmilry of liquid-tiqoid lnd tiquidslid 3ystcrs l 

1,2 So@hmjcd 3tnth€ei! 6 

1.3 SoMbdisry GquipEdt3 E 

r.3.1 th. ulir@nio cl@ing bath 9 

t,4 Cc!@icMt ri.ls rU 

1.4,1 C.rdic @arile d a 8$ s6sr v 

1,4.2 U3iig dopalts lo aldc rMlclcctviry t3 

1.4,3 S.Mrqchir.chr@ L 

1,4,4 S@ing|@hdi@ t5 

L5. Sel*don of e.6t pdi||@od.5 psueB for ulMic !@$l | ? 

Nilr.d cl@ical vlpou d@sittd rabDjq@ 

iii

1,5.1 

't.5.2 

t.5.2.1 

t.5.2,2 

1,5.3 

1.5.4 

1.5.5 

1.6 

r.6.1 

t.7 

l_7.1 

t.1.2 

1.t.1 

t_7.4 

I.8 

1.8.1 

1.8.2 

1.8,3 

1.8.4 

1.8,5 

19 

Bsic fanG of Fdiictoqt6 oopldG 

An ovdiew of rh. .heni'lly of mcr.l Fdik tonares conpl€x€g 

o(ygcn b@dd 9{il(don& @bpla6 

Chdicd ections of n bl Fdi&.tomrc 

Ctdiltry of .lloxid6 MoR)hl ard @iio.l@holn.3 

t(M.lN(cHrlo14 

Ctdft Ey ol4tal.!to,(tlrr6 

Comp6ntiv. !tudy of de peclNn synlhcsir.d 

Tbi! Filo codingJtt'cDaai.t3 

Ultenic A.rolol A$bnd Chcmicrt Vlmu D.@!itim 

clAAc!'D) 

PFunoB ctuetedzatior i€chdqrc! 

Foudc! irasfonn inlied rFcirosopy (FTIR) 

MuXilEl@ ('H, rt ) NMR sp€cnor@py 

Singlc clystal X.ny dab an lFis 

ltin filh ch.-t6izalio!, 3rerw, chdicd coElDsitio4 and 

s.eiD8 elcoor di66copy (sEMyEFst disp6iE x-ny @FE 

Optic.l lb€orltion rtudica 

El@rical rcsist nc. tt@u&Ddt 

l9 

20 

24 

77 

l0 

l5 

49 

4l 

43 

45 

4E 

4E 

50 

52 

5l 

54 

56

1.9,1 Themognvimereric ealysis (TcAi/D.rivative rhemog.vimerf 56 

(DTO) 

T.9.2 TGA-FNR 

1.9.3 Kitutic pardaeS sntdi.s 

REFERENCES 

CqAPTER-2: EXPERIMENTAL DETAILS 

2.1 Matftiols md Methods 

2.2 c6sd ll€.drc for synrhes of nEl.t F-dikerourcs &d addrcr 

2-3 Sin8l. qtsialx-a! oalysh 

2.4 Pancm plarirg on cermic subsrab 

2.5 Thin filrn detosilion by Utlrenic Amet Asisled Ch.mi.al 

2.5.1 Ilin film groq1h nechejsn dd conditioG 

2.5.2 Eldtri€ 6isr&ce nesuenenr 

2.5.3 ca s6bsm.su@enr 

&EFERENCES 

CHAPTER-3: RESULTS & DISCUSSTON 

3.I ConpMdve study of synthesis Dures 

3.2 'HNMR&rrc 

NtvIR sludies 

3-3. Cryst l srructur. &alysis 

3.3.1 Stetul ddysis ofdi [(N,N-dimct\yletheotmine) aquo coppd (I) 

Gt .l Jcu(dhrexoA.)0lo)h 0{) 

I3.2 stur@l sllye. of bis raeDt&eronak, bB relheotmmer zinc (ltJ 

tzr (.(rc)r (..): t(t5) 

I l,l S@duml mnrJi\ot kh lN.NnimedJ ethonotmin. , z bc ( ) iodide 

l( dD..)zr ll. (2U 

l-3.4 SrdctuRl a,ulysis orbis (Gerytac.romre) bis (N.N- 

51 

58 

10 

E6 

92 

96 

98 

99 

l0l 

t02 

t04 

108 

III 

lll 

lt4 

ll7 

t2l

didcrhldetujGP N,o) Izr (.oc)! (d!..lDl (16) 

3.3.5 Stru.nld d.tyris of dcc!. F-@lliodimbidN,Ndimci[y@i'ndde)- 123 

h.dldoc (ID l(h" o'(do),(o .)rl €{) 

3.3.6 Srucru.l e.lr3b of rir(@rylaeiosle) b'! (squ) zi@liM (rv) 127 

ctldidc tz(..r)b OI'oh lcl (r9) 

3.4 ftcml studi.g 

130 

3.4.1 'ft.@rl lrdiliry of M (!@)ll atd M (rldli @d$.x6 

3.4,2 Kilctic p€ftn.t 6 

3'43 TCA-FnRslrdiG 

3,5 Thin filn chFctdialiot 

1.5.1 S@in8 .LctM nicio6olt 

3.5,2 )(RD rMi.s 

3,5,3.1 ZnO thin filn oprical d!i! 

3.5.3.2 ZOr tbir flD oFicd d.h 

3,6 Th. detric.l rcsbrivily D6UJtlMt 

3.6,1 El*lricd ch{-r.izado ofd. &i! ZnO ftm 

3.7 Gd s$ins sMiei 

3.7.1 ZnO @ti!g a .rb&ol ss@ 

3,7.2 ZrO codiog s oxlr@ 3cd!o. 

3.7.3 znoC@ting!l n n 6t Sr5 (M€rbr$.) !.!M 

CONCLUSIONS 

REFERE}ICES 

AXPENDICES 

CURRTCIULM ITIAE 

130 

t12 

t37 

l4E 

t4E 

t52 

t5? 

t5? 

ltE 

160 

r60 

t62 

162 

165 

166 

l6E 

t70 

t16 

t9l

Fi8u! ll: 

Iigurc 13: 

ligw 18: 

LIST OF FIGURES 

Conterts Pag. 

Soud pbpagado! i, a liquid showils €liialion bubble 2 

fomatior & @llap* Edd ulteDic nEqrcncy (2040 kflz) 

Caviblion in homogdous liqui.ls 

caviltjo! i! hdcrcse@w (t*0 pha*) 

Cavitation in h.r.rcs.@u Crc ph3e) 

Clssification of the chcmicd ed 

Cavit2lion i! a priticula& mnG nedim 

Tlc ulEedc bath for sorochcnical synlh€sis 

liquid-liquidmcdiu 3 

liquid+olid m.diM 4 

pbysicrl cffccts or 5 

Illrshtjon of dcpLLd g6jn boddriB d th. .ffccF of s 

Ert@ing gb or thc coDducrion F!e$ 

Horiend appe&h Lhin nh gov'lh mechmicm duine 

v.nrcrl appMh for lhin filh gm*ll heh&is dqing 

Flow shcl for elving ndeuls snudlE by Crys&tlognph.r 

Moleulr sltutw or [Pd(crH,qD] 

Ih.mDl eUipsid rprcsst tion of ihe stm.tric uii of Zn, 

{14-o:XOrC:Hrro (3-{CH,oH} cjrlrl\D, with llle orhq half 

ofllE moleul. shoM s a d8hcd b6ll dd stick dmwile 

BaU &d stick rcprcs.nradoo or th€ zn4 (l+O) skclen 

3howitrg rh. vcrtq shar.d double tetnhldrcn of zinc Ghaded 

do@) wih inr.Eritial ond6 (op6 circl.t 

Schcmalic diagm of SEM 

R.action trcdu.r wten elaroN @ bonbdded on rhe 

xRD paftm of lhD 6ln ob6in d &om .onDtex 

( u-oH h ( dma.r, (drEHJ:l 

Encrry band *hcm€ for a *hi@odtrdo. 

Two point prob. t6r $lup 

3 

l6 

42 

45 

48 

49 

53 

55

ise2o: Fou ptube le$ enp. Pbh. I & 4 ca..y cuMr (D 2 ed I s5 

ncs6 voltrsc (!) 

Fi8@ 21: Sch.matic vi.w &d bl@k di.gm of a TGA-FTIR syscD 57 

Figw 22: Thc fig@ illuFarg [ow rh. coppd/gold p.n.fu lNw fonncd 94 

Figuc23: SometrAical coppo/goldpauem plared @rmic sub$rate 95 

Figr24: UAACVD S.t-Up fortni! nlndAosition 96 

FigN 25: Sch4Etic di.g@ of T{o Prcbe r.!rin8 €hmbd fo. 98 

Fsis&ne n swDdr 

FiSw 26: Pi.iorial yiev of .sfubty us.d ro snrdy gs ssing prop.fiy lO0 

ofthin fird 

Fis@ 27r The srmcrdc uir oI tcu(dmaexoAc)(Hro)l: shoMnS tnc I 12 

ld€lin8 ehmc used in ihe tqi ed ta!l€$ .romic 

dirpla@i. @ at tb. l0% Iaet 

figw28: Th. Istrice srere of tcu(dm&xoAcxHror, sbowing ll! 

dinenc uil! linLing rtrougn bridging acdsL goups dd a 

nelwort of H- bon b io fom polymqic Elrcrk 

Figw 29: Crysl'l ss.r@ of tzn(&&)r(eE. Thmd .ltipeids @ I 14 

dtah sr l[. 5070 Ip€I, hydrogd aron sphds e.r dbitnry 

iadii. Only th. najor dierd.Ed Doidid e shom 

Fige3o: Moleulu structe of [dt@)Zdl llE 

Fi8@31: Th. @-plae Mrc of rh€ Z!4Ot rirg with iodirc llons ll8 

dispoed i! a ,rar-l|r.@r ,mss rhe nng 

FiglE 32: Th. aroD nhbcrine sLd. of c@pLx,lz(!@)r(dn&H)1. l2l 

dirpl@md( cllipeid. e drah at ln. 5el. probalitity l*l 

Fisel3i Th. cry$al-p&kins dia€m of[zn(a.acL(dh&H)]. Hydrcg.n 122 

bonds @ snoM d doied lid6 

FiguF 34: Motcculr slncruF of (zr,O{d@)r(OAc)rd sho*ils Oc 124 

atom nmber sh.me 

Fisft 35: Thc .sFsadc ujr of tz(&&)r(H1o)zlct showin8 the t27 

lab.li.e shd. Lred in th. t xr .!d r.bt6; .lomic 

displgm@l' e d llc 3d,i ld.t 

trsue36: Ilr lsie srucni€ of lzie(rrrHpDlcl showins wirs D8 

Iinlirg rhrcugh lrinucded chlorim arom ed a nen@* ofH-

Fige 3E: 

Fi$e 4l: 

FiSuc 50: 

FiSuF 52: 

TOA cwa showirg d*oDposirion of Cu (.@) 111 

TGA cwes at difremt flow r.t of Cu (a.!c)D 137 

TOA cwes !r diflffit hating B1e oICu (@), 117 

3D lvatcr F6ll plot of mR 3p.chm of Cu(s@L l3E 

Gm schnidi (cs) cw. orcu (acac), l3E 

FTIR sFcirun ofp@ @nplq A evolvcd g6 ptufiI. ofcu 139 

TOA/DTG cw. of [C(tl,na.)(oAo(H:o)], ar a healine ia& t41 

of ls'C/nin sdq nitrogo aftospb@ st a ftow 6i. of 40 

TCTSDTA link d mR sp€cFa showing sysrdatic 142 

dc@mposirion of tc(dr@XoAc)(H,o)l' 

TGA/DTG cw6 slo*itrg lhe dMpositon of 143 

tzn(.@),(@)'l 

Litrkcd raA-InR spetra of tzn(&e),(ca),1 

TCA/DTG crc dDwirg d@npositid of 145 

FTIR spqrun of (a) [zn(@D.dneag] @nplq E@'ded ar 146 

@Et nDerarur, (b) &d (c) aei.un of Biduat|]',5s affd 

h6titr8 at 160'C sd 360'C 

TCA,TDTG cws showing th.m.l dccomFsirion of t46 

t(ztr? o,(dm)2(oAc),ol 

IGA/DTG/DSC cw* showing 0!. ddohpoiirion of t47 

tZ{a@)3(H1O}lcl 

SEM ilutltiDg lbe l[in nln oI Cu in 4yo H, i! N, on sd. 148 

SEM mimgsph 3howilg coppd ne&l n6o particl.s 148 

Slsing dc.ton nicbgFph of Z.O deposicd f.o6 149 

SEM imses of Sn doFd /udop€d z.o tln 

showing zno SEM ib!s. &riv.d ftm 

(zn? q(do.),(oAc)rol 

r4l 

150 

rt0

Fige 63: 

showirs SEM imagc of aor 6 depGncd (a) dd d€st€d (b) l5l 

XRD profiles of copFr filn 152 

X-ny dill@tioo p.n o of C! film deposired or eda glss 153 

XRD p.itce of ZnO filn on cfuic srbsdlr6 

XRD paft.m of thin 6lrn ofzno 

)(RD pan@ ofdop.d/udop.d ZnO rlin filn 

xRD patt*n of lilm deposir.d win tz(@)r(n1o)lcl s ! 

e'@ ndaial a) at 200 qC. b) ar 500 t 

Optical rtuoitnnce ofzno liln on tused sitica qudrz 

Ab6orydos @flici.nt ( d1 ) !s ploron 66s, Gv) @. or 

Iw-vBibl. s!@irM of Zrq lhin 6lD delosii.d oD @mic lS9 

Absoryiion c@nici.D1( dr ) !s ptoroo odgy (hv) cw. of t59 

Tdp.ratur€ q R$ist'!@ n*ll@€nr. of th. nnc oxide 160 

filo un&r d oxyao aftolph@ (A), veuu (.) &d air (.) 

Semnivily ofzno rhin filrn ar vdioB r.DFarw 164 

S6itiviiy Esposc s ietion of €$6ot @ocftllion for 164 

thiD ZnO filn d op.Rcd at 60 t 

SeNnivity 6pone 6 a tunciion of elh&ol concc.lratio! for l6t 

llin 6lt! of hO $ opai.d !r 60 oC 

El.ctrical rcspoBc of dopp.d /udoppcd sosr at 

S.Nrcspo@tin of filn in oxyg@ ovibm.nl 

s1&r e!o@ rim. of lilD in etud ss 

t54 

154 

156 

t57 

151 

t5E 

166

Table 2l 

Tablc I l: 

Table l2: 

Tdble I9: 

Tdle 22: 

LIST OF TABLES 

Sone g@ine rulaids for thr indNtrially iqp.lrli 14 

Powd.r x{ay crylt l dria oft. d.oompo*d maLrid Ircn conpl.x 52 

Strlh.g ofMcbl Orgtuic Conpl.x* aj 

Grc*rh condiriod for the depdirion ofn.ral onde lhin filD lion 97 

Rei.livitr or zro Oin 6ln (0.8 FD) dcposir.d on diffcmr sold 

pan€h pl.Gd cmic subsrtat , 

co4p{ison of ch!!.Eris1i.s IR ab$rprion f.equ@i.s (cni) of 

M(a@)i edM (lhd\ od &si8.lmBof inporrdl IRaberplion 

teqencie of nw conpouds h.ving gd.Et foduta, 

M(a.ac)r (Lt, M(acft)r (L!. 

'E& rrcNMRrht of cmplcxe. 

crrdll data for tcu(dma€XoAcxH,or: (la) 

&lci.d 8oD.$ic dal! for (11) 

Crysrrl D.t! orz! (&e)? (€), 0t 

soE. impondt bold ldstb tAl dd arclcs tdesl &r (15) 

tlydrcso bonds fo! (lt [A ed d.c]. 

crysid dlla 6d sirocr@ rcfDcncnr for tdtw)znrl. (21) 

Bo.d lcnsthr tAl for (11) 

Bod &gles [d€8] foi (21) 

Cq6lrt dll! rd (Z& oddm)r(OAobl e0) 

Bond l.ns[N IA] dd egles [d.sl for l(zn, o(dma!(oAc)r0l (20) 

ciystal dll! fd lz(@tGloDcl 09) 

s€r€cLd bond lelgrhs iAl ed e8l€s ld€sl for (19) r2e 

'Ih. inrhd*uld hydegtu boD& ror (t9) t29 

Dab obrlin d fro6 TCA a&tys s, lll 

P@xpomtial f*ior (A) ed ArLdiors @Brant vslE uilg lj5 

104, 

105 

t09ll0 

|lt 

lll 

ll5 

lt6 

t\1 

119 

t20 

t20 

t21 

125 

128

As,r'r |!d Xiret.d3 ndodr 

T.U.3: .Lrigdioo Eery dlb obt tEdtuTOAdtFir!ftgrtift!,loi 135 

ndlodolodc& 

Sd.o.l: 

8.t s. u: 

f.i.d. III| 

I 

tr 

Itr 

ry 

LIAT Or SCAEMTS 

C!ryih ot.dvrdiql E hL.L T$. d So.t6i..l 

Ltulqa. 

sctddc ryl!..en ft. d..oqairicr of KUfr..> 

(o&Xto)l1to cof'Eqe..l 

P),tolyrl, of zn(!4..Xe4 

Deory.id@D.crDio d?r(cXdD..H) 

I,I8jr OF AI'ET{|,ICTS 

Prinr dlting or-icrr hdt fornutdoo, 

EorF tod €qudh d.tido. 

mX &nIis Of Tih Fildi 

IE{ Cutls Sblirg Adivdo h.{g M.srG4 

tc2 

t42 

145 

P*eJ 

t76 

t7t 

ln 

lE0

LIST OF ABBREVIATIONS 

2.4-p. &di@L 

d6l{ 2,4-pdiedioE 

OAc ,{c.tat 

-OR Altoid. 

o Ethaolmine 

TEA Tne0&oldin€ 

ild 2,2,5,5-Teruethyl-l,thcpt@edio@tc 

tbdH 2J,6.GT.hoethyl-3,tb.ptsn€nione 

dn&H \ N-dimctbylaDi@thml 

ddE N, N-dihelhyl&eldid. 

PPh Tiphcnylphosphinc 

CHNS-O Clrho4 hydseen, diE g€n, sulphu ed oxygm analysd 

MOCVD M.i.l{rgdic c!@icd Epou dcposilion 

UAACVD Uliruonic &r@l rlsin d crpmi.d v.pou depositioi 

EDX E .r$/ dbp€Bivc X-ny 

NMR Nucl.s trsgndic rcsm.e spe.ieeopy 

TCA,SDTA ft.mognvin€ityîhuliitroudifcrcntielrh@ataortrsis 

DTG FiBr ddivatire rbcdog6vio.r.y 

FIIR Foqid a@sfo@ i.fnFd sFcrrc$py 

ECA Evolvcd g6 dalFis 

SEM S.ernine cl@tror micDs@py 

IRD X-6y dilt!.tion 

AAA! Alonic stslFio &rtta 

USP ulr@nic spEy ptbty3is 

ro CC) Omr Tdp@lw 

Tr0 CC) loel. de@nposilion idp€rane 

Tr CC) 20lc dMeposirio! i.hF6he 

T- eO M.ximu decoDpo3iri@ &npe..re 

JCPDS ,oifi Comine for povdd difr&rion n&rd.rds 

ICDD Inr.Earionat cryslat difftrction data 

CRT Cdhod.6y tube 

MIK Modcln@kinclis 

A PRxpotr dial f&!or 

E Acrihtion ffigy 

K Arh.nious co$ra 

Pl,Zf Lsd ZiMniu Tiilst! 

)))) UltEsbd

ABSTRACT 

A sinlle &!d & efici€ sonochenical D.thod ha b€ln usd for ihc ay.rh6es of 

Eiety of rcDon€d m.&l 9dildoMLs lil. M{@), (l-r), Mltld)" (tG[), bis 

riph.nylpbGphin zinc (II) cblo.i.le zn (PPhr ) cL O7), N,N-dineliiyleamjd€ z. 

(dma, (r8) sd new hct€rcI€plic adduci liLe [Cu(dre)(oAc)(H:o)lz (14). 

ICuttErOH)' N- (oAc)l:l (23), Izn(!E\(au (t5) (wkE s = ctheolmmq 

&3c = edyr@rooatc) IztrG@),(dmeH)l 06) (wh@ dlreH = NN- 

dinethyldido.th6ol), t(znp,(dDa),(oAoel @0) (wher dna= N.N 

dincthylaet$ide), [dr@)zdl. (21) tzd!@cxH,o]lcl (19), tNilGEA)rt,(oAc),1 

(22), (qh* TEA= LidheddiE' &d OAc = &er.t ),. All th* @mpl*€s hav. 

ben chdabnz.d by n,p,, CHNS-O, AAAS. FTI& NMR ud Singlc Cry$als Xdy 

aralysis techniqu.s. 'ftmal behavioa ldn€ics, dd €volved gs padem of th€ 

ptFte6 und.r onaollcd 6vim@1 Bfr sndied by Tca/sDTA .nd TGA,FIIR 

lehriqu€s. Bed on thmal dd €volvcd gs srudiB d a, m€cheism of rhemal 

d€@nposition he ba wo*ed out. IFs ndly synthelied coDpt€x€s havc been usd 

lor th€ falicllion of !u zio, Zlo troped witb s , Ztq &d mcr.Iic @ppq rhi! 

fiLtrs @Dprilin8 of @oprnict* of si* tu8q Aon 20 to too M bt indiS@uty 

d.v.loped ultasoDic a.resol aslisl.d ch€nical vapou d€penion CJAACVD) r€chnjqe. 

Thc moryhology ad conposilion of thj! fitm w@ .mined by SEM. EDx ed 

pow

Chapter I

.O INTRODUCTION 

l.l Sonochemistry 

Chcnical t@tio! equiB cn6$, i! onc fom d dotha to prcc.€d. TEdirion l sol@ of 

cersis e het, lidt, d ioniziDg Ediarion. Anor[d modh $u@ of oqey di'I.6 from 

itditionol ecrgy so@es in duation, pcaw, md s.r8y pcr molcclle is uhsohic 

iradiatiol High iat nsi9 ulft$u4 i! liquids, pod@s &oulic €avit rioi, which mts $ a 

$|@ of cers/ ed m b. u*d to .nlrae ! widc tug. of cbmicd pt@s.r. Srch 

.pplicltio$ of uldqoud hav. ben sroupcd udd th. godd Im€ csttcd $n@hcmisny. 

Onc of the Dost imporbnt cwnt applicatioD of sorcchmistry hs ben lo lhe synihesis 

ed modifi€tion of imrseic mt.dals.''" 

The chdical .ffcds Esulting from lhe iradi.rion ofaqucous sotution with ulr.dobd wcre 

t61 rcponed in 192?'r'r but rhe prd€ss w6 essriatly urouc[ed uirilthe nid 1980s. 

Sin@ late 1980'! qFrirenid s:rudi6 \N@ @ied out h utt!@lic &iiviii6. intrcdue

IltoduriN Stuxhatittry 

a 

ot€ c./ct! 

FE@ l: Soud FoFgatior in a liquid showing @viratioo bubbl. fomdion & ollap6. 

u.d.r u]l|@lic |!!q!dct (m-4O rIL) 

,A1 tbL point b[bbLs @UaIe a!.1 !rDd@ int e loc.l heling (rcudly abour 5000 t) dd 

high prcsues (.bout lmo ar@pt rcs), fd . duFriotr of l€ss d'6 50ps (pico - sonds) 'r ii 

su@diog comprssion cycLs. This O@ss llrimlely generalcs suflicidl mout of lh. 

endgy for ch.nicrl .rd @heical eff.!ts, which is rcspodibL to s.l@te aclivity of 

chdicil r&lion rhDuch rhe @nic c.virlios- 

Tbe cn nic.l .ffaE of !h.a$ud a.I itrto thE .6'' homg.Bls FMlmi$.y of 

liqui&, hetebg.@us sehenisEy of liquid-liquid or liquid-slid sysr.s, dd 

encaralyris (which ovclap rhe 161 rwo). Beue crvitltion c& |lt ple only in liquids, 

chenic.l rcations do not genehlly @ur during th. lltEsonic Fadi.tion of so,i.li or slid- 

l.l.l Honoaetroo|a SoDo.hcDirtIt ol Uquid SysLm6 

In a h

dd.rq.&..d 

La.BlLa. 

Fbst 2, C.vit ti@ in hob€!@3lhuidr. 

Fof rndr@ 6. hrdrclysis of liioDDlEnylc.rc. prod6 ..uot . of diph.tic orborylic 

&ids.t 3fC r?Es.nt' ililuccd r.r. @h.!ffini rt rb@r l+15 f wilh *t! altyl (R) 

sut6rituar (slFF Ritr ibll, c[tl bo?ropyl &d rd{utyl). Thb @uK bc dE ro Eb&i.d 

cfi..6 od mt asin d eitt ey ovitrtionrl h.ldng .fre|. 

r.r2 Hclcrogcr.o.rs roroch.Dirtry of liquiHhuid & Iqull.€olid ryst os 

ro t.tcregcd@G liquid-liqlid .).L!b, .pid cnt lsiftdlid is po$iblc dE lo inl.e niing 

by dico.tr.ni.g / i.nin8 / sboct-w.6 rlrl inr.rdion of dE s.d 6.ld eitb liqli& 

liquid booid&t. R dilioi foncs rd oi@ stl.lnirg of lh. phe boui&ry d.L.ar6 

resFflrlid ol r.5ets !!d Fodxa rb.1 iFFrs.s dnilg of botbL eith [quils &d 

tru6porrrlioi of b6l eith d.r5 inEosiftclliod. FiE .mbi6.tri@ i! ! liquid-liqlid 

bd.ogdds syst d by siclliod gsrlr |!dlc.d tb. tiob|ls of i@i$ibb liquids (G.& 

,4u.o!! / orglnic nirtuEs) by cnir.tiold co[.pi. tDn cle dispti@s 3!d fm 

Ito|! 3: Crvitltid in b.NdogcM (trc phe) li,quiGliquid !'.diuE 

3

HolmFvadleont-Witiig @ctio! bcilrr!.lr tm imieibl. liqui& icld! hjgh p.lMn8. of 

d€irld product unde! s@ietion il).dpariron b 

)))Trfi2!oC 

"'gEJ 

O,C"*. 

70 -aO < 109/. 

Vl. Sonieno winom Soicarion 

In B bGtdosa.ou liquid-slid 3y3ld! acoulticBly iDdu.rl c.vftaion €nLnc.d phylical 

cfic.r, *bich aE direrly .$&iltcd with ds|o'l rnlny dg@-oeialic ra.iioE, In thi3 

ryd.n tb. i e.ft.! prodw.Frndlaid in u.3onic fcld whi.h irdlB e aymn tic 

@lLpc ofrh. oritaiiolal rci& d qr&dd irrqa.e slicn @ *vesl dtG lugd lld 

lh. te@ dity sir.i dF Gll i! ! di@jd of liquid Foenry dmusb th. @iy *hich 

i6pi!g!. q ! ri. slid su6@ !t !.leiti6 ldiDrrld fr@d loo oi' s illurEncd ir 

nsuc a. 

Flgm 4: Csvi@im i, b.t N8@su (rwo pt@) liquid-slid m.di6.

'I!t phaotMotr is thc origin of *ell k&M Nsion, pining ed sutf4 cl@ilg efi€d. or 

utE$ud, Resmce c.lity sie d.p.ndr on fr.qumy, but ai 20 Ulz s@h qtedd€d 

interfM efrets @ no1 obsdcd wirh solid Donicler shsller rhaD -200Fo. 

H.i€rcgdos sondh.hisrt of liquid+lid sylr.m e paniculdly ed b produ€e 

o,emm€iallic conpoud! with hid % yicld in which m..hdi.al effed.e likes a€ouslic 

cavitatiG, brbbl* iiplodins c{ b€ applicd to Enovc pasiv.tidg ldy€$ aon Eetals in 

onls 1o bEak dou briltlc soli& swh s b&s sd cstalysrs lo ilct€s. surf&e aM, nss 

trdtsfd dd @liotr .!tcs in m6t or8&om.ldlic r.&tions. 

*\t )))))), 

Iis !.tisr.d MagBiM b etul for pFlling c'igndd\ Elgdt 

ft@ is r vid. chdic3l .rd physicd i.qu.B thal bigh ilccity ult!&u!d @ b. in([lc.d, 

i! hoooemE &d bci.rogmu sioch.bilft of liquidliquid ed liguid&lid sysrm 6 

d.ooEtlt d $imariolly i! Fige 5. 

FiguF 5: Cla$ifidion of rhc chcm'..I sd phy6ic.l .traB of drlMud.

1.2 SonochemicalSynth€sis 

To exploir the tul po&ntirl of CvD, ncd of suiralL pEcleb for deposning $in filh of 

oclll/or nctal oxidc @mDries of ntumdcrial e eva-incEains demonds of tedher. 

'fte outc for lh. synlhois ofa sFcinc prausor is flolhci challenging asFci in lailorinS 

th. objenvc. PeFquisiles for thc d6is.i.g ofpr€cwr for thc nalaial $icn@ .pplicarions 

e lEi|y; sinpl. od higl| yi.ld sy h.ric Dute! 6y h.ndlio& facile trons. snd notr. 

loxicity. Cndcnlly in bbodtory S.tne* iehlique is b.ing wed fot lh. sy.lh6is of 

pr.clMs. Tlft !@ds lp€cisl anediod lr..lneni like el€clion of hishly Puc chenical, 

moistrft fi* solv.o! pH @lttol ed ircd .rnoslhe. fo! the stnth*is of pFcle6 

Howd, $reh.dical n lho

u&E taxltclE3 arlPrmttt! 

in ! p.rticdate .n@ hdiu 

Thu!, cavilation sfles as ! n.8 of @MDl[tils lle difta. *rsy of soud irto a uiqE 

s.t ofoiditi@ to ptodu.. unaul m!&ri.h toD diselv.d (&d gcmnlly voldil.) $lurion 

oerso.t ltic p|qrsor'. B06, @LLpo. of d@ bub6Ls &d @stic wit lioE Focss 

duirg dtrmic .n!&cc ttc cL@iclt pr.€s i! vti.ty of chmicd licl& i €. 

inorlllic,r*' orsdic sy hesir,z'5 polFaeriatiorLta ald clcci.och€bisi.l'Jr .t ldge 

*dc &d dbo plays 6 iEponut reI. in prcpdilg th. *id. iang€ of dgsoD€tallic 

c@!ol|!d! invobirg @{rdiD.& @npldir8 p.niculdly th* of Mg, c'! Ni. &d !.i@l 

t6Biti@ rrds ar l4 rdrpd.nN ulda ubre .n with his! Pd@n tteld od in shon 

rinc thd @nvdtioMl m.tbo

Lilc wir !Fta! lelyla@ioe| @nplq6 lwtr wilb .ltali n rds sdochcni.dly dd 

sivc @tivc m.bl sp@is (M) ..g., Ro.tivc ri.!.| pDducld ton ulrMic dcrio! of 

niclcl ectyl&aonare ud sodjb, tuE in situ wiih 1,5 cycloFnradi.nc (COD) |o yicld 

NdcoD),.rr 

r(adc) + f& -\ 

Ni 

JF(Q" 

ln @nvdlioml synlhesis pN€dw rcLl sbonyl 6mplex6 e @$ibl. by this 

p$.de tom tosilion belal hdidca, edju .rd clrbon nonoxid., bul rht r.actio. 

Gquird t mp@turc of 10G300"C u&r high pelsue. den who uing frcshly pepded 

tuckds mciab, 'Ihe e of sn@h.misrry f&ilirab the ductior st€ps to yGld the €quir€d 

prod@t udq mitd .onditioB.s 

*,^, Ni.co.(l be). ))). THf. lOC .,, .^w(r. 

-.-" 

; i*".-i j j:r-: j--:' w,(cutl 

.,^.__. Na. CO. (4.4 bdl. l,). THr. tOC 

vc|Jfiftr) _ j:==lidtYt6H:: j-r:-:+ v(.o)6 

MocL -4-4919+ Mo,(co),o' 

Anothd linph orSrdotuelallic @lioa dhibiling hdl@d ihpDv€nent undd snicaiion i.e. 

B&bicr Ea.iioq ihc couplins of b€trzdd.hy& dd l-brcmoh@tan in thc pescncc of Li 

givs 90% prcd@t by enication.t 50 lllz in 25 milut€ ed ody 8vc prcdud .n r ? hoN 

!r Mn t.hpcr.lw Mrhorn sicai@.'' 

1.3 SotrochembtryEquipocois 

A vsicty of rldi6 bavc bea u!.d for ultenic ilEdiatior of $luriod. Th.E @ lne 

gdcal d6igB in N pres y: tbe ultlloijc ddine ba ! the tErducqn ad ultsodc 

pbb., Th. ulirenic dtuins bath is cl.dly thc nost essible s@ of labo8tory 

ult@ud ed h4 ber ued su@$iirlly in prsent ludies for ue stnthess of neialorsdic 

complqcs, So w. willdieB iri worLing in dclailheF.

13.1 Th€ Ultr$onic Cleoning Baah 

Th€ sinpL Ultre c cLiring harh i20-{O XW) is by f{ tbc msr sid.ly.vanabL md 

ch@pesr $up of trltarcnic imdialion for lne chdical labotatory md f@nd lo b. hst 

€liable sd cffelive sre for laboratory{crl. $noh.nbtty 4d als p.mit.sy conlol 

ovcr mbi.nr t npcratur ard ormsphm.IrE utlmnic bltt 6 nevd b€ led di@dy 4 a 

E-tion vcss.l befls of pmbl.m Mialed li*e @Nsion betws thc valls dd 

coflaninltion ildued by enveloping laFur ed Cass, The nonnal $ag€ dEFforc involv6 

U. imeBid of $antL.d Slss rcacdon v.ssels inlo lhe bath ihat plovnles a fairly even 

disffiburio. of .n€rgJ irto d. @tion mdilm. Th. R4tion vcsl doca @r nad ey sp€ial 

adalidion, it cd b€ ple.d into the both. r.d ltus d in.a almpIEE or Pt$@ ce bc 

aadny maintoiftd thrcugholt a en@h€mical @tion 4 shown in Figur T Thc @ounl or 

endgy tnat @ches lh€ r&don lhsucn th. vessl walh is lo*, notuallv tEtwan I fld 5 

wm?. Additional tbmos|aric @arDl h Fquired in ult a$ni. clding barhs beauF thcir 

t.nFratlc @8ml is genddly pd. 

r\ 

ngue t: Th. ulrMnic ba$ for $trch.mical stdhesis. 

Thc p@ums should bc Elativcly voldil.lo -biere bi8! e@henicd vicldt b.@s fi. 

primrry erochcdcal @diion sire is lhe lapour i$id. th. cavibdon bubbld.rt In addidon, 

however, lbe solve vapout p6sM snouu bc low al lnc $nic.tion tnperaturc' b€au$ 

sigoifi@t slv. valolr insi& the bubbl. Edll6 the blbblc olapc€ effici4v .nd lnus 

I. conclusion $.6heni.al i4hrique did a lol in €.ndcemfl ol or8{onelallic Mcrions lo 

pEpN pollM md ontiDes to erped in|o the ada of noomar.rials.

1.4 Cerrmic Msterirl$ 

Cmic hatcials re inorSrnic @mpouds @aisiine of Del.llic dd mn-ncl,.llic 

elmoh nainly cslesoriad 4 ond€s, nili&s dd cdbid6, which @ h.ld bge$er 

with ioni. dd / or ovd€nr bodds. Oxid.s @ c@sidcrcd lo b€ onginal dd l&gesl 

gmup of availade eluic rM&dals dE lo Ucn ch.nical inerrnes, sood theoar 

prcFrtid ed 6i$dce Io oxid.iioo. As thc oxygo is lh€ non cl@iroEstlive divalot 

.l.m.n! mos! oxi.les h.vc sigdificd deg@ of ionic bo.ding. As a !€sull, they 

gcn 6lly havc the €hqrct rislics of ionic drslals, i.e., hi8! €lectrical sislivily, oplical 

ualsF ocy, dismgEeGb, lo* then l @odwtivity ond chcmical stbilily Thde * 

$be exeDtioro i! $tnch oxid6 of indiM ed lin e el*rically @ndwtiv. qhile 

oth.s such.5 beryllid oxid. have hid thetdal conductivily Cdmic natcrials m 

b.ing lt rliliondlly €trcou!8.d in ndy lcy tehnologid including @muicatioB, 

.l@t @i€ Dd etonrtion 4d bele oflhci! nehdical dd rheEEl sLbilirv ucd i! 

detricrl, oplicd &d Mencdc devic. Such batdiak 3c now cl6sin.d udd 

electoereica ed dntoguishcd from olher foctional cerdics swh as advmced 

sttunDl c.ranics. E* e eru of ihe eroninent ctuic matdi.ls with thcir po$ible 

Tin Oxid., (S r), is ! sood .latnca! conductoi, bisliv tastoFni ro th€ vbiblc dd 

hiehly En.crive h infilcd t gion of sFcl$n. It is wd in .tcigv saving coatings lor 

plare gls (E-slN), tish bulbs,r' dtupdd htating .lcFmts, dti$anc coarings. 

tusp€dt cl.ctqle b pholovolt ic els, @di!8s fd eld *llt ud oxvgd e@R for 

a fiEl .onaol in conbNlion .dgin€s €lc. 

TitaniM oxide, (TiO, como'ly knoh s Titlda" fld is rsis:ral b oxid.tio! md 

pasivc roBlrds rhe chdicd !n&k ai Mn l.mpe6ne od ha vi

oic@leltonic dais. Zi@ a b de otcd in @iing t clnology dw ro its hid 

sa.n8rh, fr&ire touslnc$, dEtul slabiliiy, hiei rcfladiv. irdex ed los oPdcal 

zirc odd. (ZnO) is ! !*tu! pi.@ldEic @t rial wirh tr nadoB a!pli@!oB. Likc: 

pi.4lertic dBiq (Fo$dl|6) codilgs for phol@nductive devies, nd-lind 

Bistos (vdistos), ov.r volbg. pFiectoB sd hy&o€bon sc@t.sp{'.lly .th.@I. 

Eowrcr, it has m .h€nic5l rcsislae€ to comon eid ed baca so ils w is edrict d. 

sili@n dioxid. (SiOJ .le trou a silio t a tujor indle.ial c.mic mLri.l qirh 

@y .pplicltions, espeidly in eldEonic itrdNtry in dE fom of *ni@nducror 

coatiDgr, Sili€ is rcsis16i to no$ of th. @@on ch.nical eagents at pom 

rmpqatw dd 6 a.ts 6 e exelteft .lccrricd iGuldtor wirh v.ry lo* $emal 

qFlsio! .!d g@d esttt!re !o tldtd 3hocls. Ilis tuldi.l is .l$ ur.d a 

pasivliion lay6 ir .!.rsy-t tDg Nhit cnnl dN (E-sl6t, sutfae diclccrric ed 

dopins baiicB in *ni@nducto. d.vices, int€meidlic di.latrics diffusion so'@s,'' 

flch bMi.c, osdltiotr po@t'on ot srainl4! sl*l in oucle& F aot*l_ PRPrat'o. ot 

opdcd fbcr ed beid t.yq for stror fibs for gls @ti4sit 

Adv&ed cq.dc mor.dlls @ u!.d h bdy fo6 lif,e poqds, thiD filbs, libcB dd 

nomlilhr Convolional synfi€sis ofn thod likc elid sllte rcadior! vhich involves 

nixins, r.p.ded cycle of niltirg folloved by calcinatio$ !t hi8lt€t t mpsatw e nor 

pa.ticulsly iurtd for @idg!.n

1.4.1 Ccr|nic Cortiry As A Grs S.Nor 

A grs $mr is a d.vi@, *nich is bascd on th. 6isrd@ chdgc induc.d by lhe s6 

chdierptior/twriotr! wirh adub.d nolaul.s on the surface g?ically exploited in 

thc sroing nedemotg," cs $NoB halc found widespread applietioN both in the 

honc md indstry, D4pit itr valE, how.r, ndy ch.I@84 .xist in fabricatinB d 

aliable tur b.foa it cd be dploy.d. ltLdly, gs se@a dFuld exlibil a higlt 

s4ilivity lo vapo$ for $ticb lhey N &si8!€d lo d€l€t, Ga s.@B h.vitg 

si@ld@tirg oxi&3 e call.d @mic 96 tu$. qhjch s. onc of tne Dosl 

suc@sstul ssiiiv. maiqiils wd util now,( a HiEI snsitiviiy, conpalibility wilb 

Dicro.l€ctrodc, low cost. dd for indu$rigl lpplicaliou, k a sreat chtll.nsine job in the 

ti.ld of nor lahtulogy. S.lc.rivity ed strbility issB b.!om. dd morc chrlldging 

in bqsh indEiisl dvirolwdl *irt [ig[ lcnp.6turE, bigb pd@, @nramimts 4d 

dr@ic ss flow. Tnc be naldials dost wid.ly ued for ccmic grs s€ME ffi 

t@irion nEtal oxid.s, such s ZnO, TiOr, sd SnO, re the n6i widely invesli$led. 

O$ srtuoB berl on ZnOa6 e smsitive to infl.imble ges 6d in lnis cotrExt,ltt€y 

noi only hav. bc.n adop€d as nodel sy$.G for frudaE€rtsl sMiB, b ale a bae 

hdaials for lhe dcvcloplMt of wiou s.Ns for the d.telion of la*t seh 4 Hr 

CO, NO', co,, cH. ed olhd hydr@.bos. ft€ oxi.le sits l.yd h6 beo flbti€red 

in dif@nt phtsical foms such 6 ihin lilm,lhick film, butk psll.n etc, Howev€r,lh€ 

Oin nh fon is expetcd to be mosr .fldive sin@ eGing i. baically a surf&. 

phdontun dd is sbl. io undqgo rvcaibl. sqf&c eacii@s wilh gei For empl., 

hy

ctuic mat.rials like zno, ZtOu, erc., acr a! a sdi@ndrcting ud have b€en pt paEd 

by tM.rcw ttr!@ likc spurcri4,q ' CvD ed tbmri spou!|i6,r $tapri!1i!&ro 

so!8cl oulEsr5 Dd othd mcihods. Anong emic m5&nah, zno w6 the 

first studied fo. sNing, b€caue tbe @nducliod prce$ in th.& maEnah can depend 

hsvily on glin bou&ri*. Th€ gs sming .hatad€nnict of the ZnO lhjn IilG wd 

$duaGd rhrcugb rhe 8s F6iriviry (sJ, d.fined by: i 

s! = R'/R! 

wh@ P! is th. iilm 6i$anc. in at dd P{ i5 the filn rcsist{c. in th. PEence of tbe 

gd, ThB S. b noE thu sjty for EdEins rr*s, siE llc !.Mr sislone dcc66 

in a FducinS.llosphre. Thc s4ilivity i5 tlso defned 6 R.Ait { in lhis csc ss is 

Iess thd uiiy for educing 8q!. 

1.4.2 Usitrg Dopants to f,trhrrce Sctrsor Sel4tivi.y 

DEing css sdsing n*Gh@t, dqe!* in Fsista'e t!*cs pl@ shd coarqi 

srbstate is €xposd io sqsing 8s d@ ro idduction of €l€cirons inlo @nduclion buds of 

odalond. Gigw 8). Bease olthis lack of elalivity, a nMber of tchnjqu.s Mre 

adopted to hinihjt lhc sigt l obt iFl ftoi uddirEd ge. On otmon foi@ ro 

inirod@ $letivity i o a n.Ll oxid. $uor k additioD of $itablc melallic dopet hto 

O. @t rial. Foi exmple. doping s.o wnh paltadiu lhat hs ben used as a cat l/sl 

duing lh. oxidation of m.thd. uu.lly incrcs.s lhe s6itivitv towdds lhis gss in the 

I. me cs6 il is rcl n@. Fd tupl., BirLcf€ld et ,1.," noted soDc ibporlanl 

chde* in Tio:-bsed *nsos for CO .nd hy.ltos.n det€clion, whe. th6e dcvices weE 

tuodified wilh AlrO3 or Y:Or dmugh a b.ch&i.at mixin8 pto4s vh.n Ahos wa 

idrcduc.d ro thc sysr.m, rhc EsroN B only dependsl on the @n@nFadon of 

hy{tro8d prcsot ed ws itudsitiv€ toqsds CO, whet d d additi@ of Y:Or 

ir@d the s.lecliity lowdds CO. ntis cnld.enent ws thought io occu eithd 

threugb oodiftelioB of rh. spae ch{gc cgton ol tii.r4 or bv .Ienna the gain 

boun&y @ acrl or nek fotuatiotr tet@n th. cry$rllit s Dopdll hNe .le be€n 

ued iD order to inhbn erarn Stosah duing hstins ln s srudv bv Bonrnr er al '0 

niobiu dd lst lu wrc introd@d into TiO, beou. of th. sinild ionic aia or the 

.alioB. Nol only did thc doped frlms h!v. a moE p.sittcnl eEre phe in tbe 

Pr*ne of high c6FnnFs, bul th€ av.dg. gEin siu d*c.s.d &on 200 m i. pw 

tl

TiO! hdt d al l000ec to 150 M or 50 M for liobiw dd r&talM doD.d film 

elp.divelt. Som of th. rt?icrl ctuic @rials us€d s *Bor for veei, of ge, e 

T.bL lr Sme ssinS md.ri.ls fd6E ildtsEi.ly iDpon nt hy&@rtos, 

CH, 420-550 

s.q tBil 430-480 

sDo! IBilql 48G520 

S!O! tso:l 180-420 

F.!or IPq 39o4t0 

ZiO 250J00 

ZÔ 610-?00 

ZrO tll 

52F700 

I.Dpcnrure Rrtrsc ('c) 

5E0{E0 

750-850 

400 

stro!lsorl 390410 

c_H. SnOl 380420 

crl 150-250 

t4

1.4.3 Setrlor Architectur€rg 

se$inLYPq@itL 

B6i&s scls E rdi,l optinizlioa BoE iEpondt is to tailo..l@trical FoFni6 of 

inc s.IM by fsbdcaljlg wicty of ponm pt.Ed tutrdductiog subsrrdo dd thu to 

selecl suilable delign for ga losing device (Figw l8). E&h tlesign c& b.hav. v.r, 

ditr@tly whcn exFsd to g!.. ft. adv.dn8.s Nciat d with cistancc tailoting @ 

pdiculdly inporlrnt for &rcloping afford.blc eldEo.ics for pt!)c*iDs eNr olQur 

M&y c€@ic ndeials crhbn vcry hig! $ist!n6, rcquirinS complical.d cituiEv to 

pr€ciely h.6uc in fi€ MQ rrg€, Medwhile ollter materials h.ve higl conductivity, 

d.liry it difficull to d.rd &cl!e in GidlM aftd ga .xPos@ Typically dopdt 

b'r.rid is .ddcd ro alrs Bistdrc.s, wtich dierr.ly itl{,te th. s@ilivity Esloe 

tim., FetoB like, tdtide si&, addition of suitabte dopmt, tubsrrate patt n plsting 

d6ig4 thjckss &d uifodiiy of 6ln nNl b€ 1aken i o@oulwhdon wels to 

d.velo! rnd d.@trsllle ! ** s@r d.vi4. 

1.4.4 s.ruiry Mechlnitm 

Alrhoueh md.l oxide sosts hiv. bcd sludicd for ov.r 30 yc4, th.tc e siSnificdt 

dimcuu€s in m.tils a devie that fspoddt el.cdrely b a 8a 

of inte!*t whil€ mdv 

d@n6 dirt o! thc b6r ncrhod 1o cretc ! *l@tiv. ddie. e uddtardinS of baeic 

gs $sitivity pnncipls @ b. uetul i! cxpbjniog the problcn 

Nu€oc Mt riats hlv€ b..o Fpoded to bc @blc d d.r'l oxide *sof in luding 

boln sitrsL (c,g", Z!O, SBO!, WO! TiO1, ard F€rO, ltd multiaFpoftnt oxi

httro.lutiN Stuize Metwiw 

E"in 5o/o 

02 

Grain Boundary 

R.ddos Cd 

Depktioa fry.' 

E, with 

E!@tdg G"s 

n€u E. Uustliaon of d.plcLd 8r"in boundri6 &d 0F .frars of a Educing gd on 

rh. @ddid p!'s.@ e 

ln 6is sddio, th.E b a ldg. dducr.E sirhir r gI!D, hd rh. FM of i.ric4 

orygo ml@la on tlc s!rf@ of tlF gFin lcds to . &pbnon of .letros in tiis a@ 

As ! esul! lh. surfr. of ! gBio is v.ry MktiE @op.Ed to tbe buL, An, p|rEs llar 

alres tle type or nMber of oryga rF.i6 .dsort d will @s a $hG@ cbaee (e ,e 

os o o, - o' o zol. nr" rrgoitu& of shich ve6 win l!. mounl of adelt€d 

oxygen. For exmple, n cd be nor.d ih|l a chag. in tcnFrarr wil rrr rhe 

Bi$ee be se both th€ charg. of rhc aurl@ sFcis s well s th€ir cov@ee @ be 

al|rsl in 1his prGss. No* coNid.rirg rh6e t ?6 of.ff6h, tlE Esisrafte ol ! gd 

sensr in the p@ne of lir is .xFct d ro b. hidr b@Nse ihere h a largp nunber of 

oxye.n ion sp€i.s o llE slrfM th.l hav. dnwD .l*trDns frDm l[c urdqlyine mtal 

on&. r.r llis ti@, a ga coms in con€.lsith th. ftral oide vhicn n abb to @t 

wi[ iLal oxyge4 rh€ onb$tio! prdrcr5 (3uch s Cq ed wa|. ) &pon dd rhe 

cle[o6, f(fudy tzlFd o. 0!. surfrc., e clur.cd ro rhc mtal otd., rhdrby 

d€.EirA lhc sist .a. nE cqu.dm bd* deibc tbis pl\'Bs for a nodel ndd 

oxid. ssr Eering *itt dton |tbdi&, 

l6

402+e-O 

co+oG)rcor+i 

seledon of Ltsdidt lot UAACt/D 

'Ihc oxygo ionosorpiion aues elecEon t dlfcr from th€ surf&c of th. gnin rowdds 

lh. adsorb.d sFcid thw ldding lo th. fomtio! ofm eletron deplekd surfa.e. Tnis 

vdi6 thc el6lrical @nd!.rivig oI tb. smi@nd@loi Unfonu,ut€ly, ey ga rhal m 

rta.t on the n rd oxid. in lhis vay vill qu* r sinilrd 6i$ae .hegc. Hae, a 8a 

s.Mr dBigned io d.r.ct CO dE to lhc mchuis slDM abov., d .xFri6e r 

sigral wh6 hydiocdboN e prcsot dd vicc v.s. 

1.5 S€lection of Metsl B-diketonates as Prccursors for 

Ultr|sonic A€rosol Assiiled Chemicd Vrpour D€position 

TechDique 

Duing ite past dcod., sith th. ralid da.lopn nl of lLe mosi.nc6, lhe litdt@ 

dcMibe ! tuge of appbehs for 3y hcsizjlg rhin filo @mpdsilg of nelal oxidc 

mopaniclq aing 6 vdidy of inmgeic or m.lal orgdic precusors PEEquisites foi 

th. s.l6tioD of prcusr for the n[teiial ei.ne dpplicatiotu e puity, simpl€ dd 

hid yicld Elihdrc rott s, @y handlb& feib slobee and rcD-toxicirv TlTe of th. 

liged is ale impoi.lt h lhe 5.M of Providirg $lubiliry or volalilily for 

lrdlforurion to ebtion or eN phse. Ligud should b. abL lo @ouol the nydrolylis 

rat s of p*clN6, polyndzlio4 surf@ Prop.rtics tud lexte of th. Dalenal &d 10 

fod thin filn or nsoparticls. The nost ponbing prEuss for flbic.lion ofn€t l 

oxidd filDs d tLfinit.ly lhc molsul4 hsviry alrcady nclal-oxy8.n bo.ds, nm.ly 

m.r.! t{ird@l.s'5 Mon

Setechon of Lisand. Jot UAACVD 

noE @moily ued liged!, such 4 dnclH, ea" PPh, &eiat , if a$ached wilh acac 

I'e&ds, have prcvided a d8ir€d sutface chcnhlry, nmliodlity sd enlde lbiliiy io 

tue a.Gol foDalion dnd prcv. 10 be Sood p@UME for UAACVD. By tltcriog 

sufc cb@ist y of thc a@ p@les w e able to gd thin filt nd.l oxidc 

moplnicld loverds iehnological rppliclliou. Sinndb Phtsical and ch.nictl 

prep.nis cs b. lailorcd by .lt ring 0F strlctw of 0{ilcionai. lieand.' u Tbe 

voldility of ttee precusoB c& be iturs.d by inc€6in8 the 3t .ic hinde.&c. i.e., 

(a@ > rlhd > thd) de to inctwnrs shieldbg of hidly positiv. ch&s€d ncrd c.nte 

dd r.dslio! of ilt moleul& GM inr@.don in lhc $lid si.rc. S.vcal of th. oxidc 

@!6nicl6 pFpdcd FoD M(@l pFclm6 ald oxyg.n-@ntaining elt.nls E 

Tioz, t'F.roferoa. t"Garor, zno, In or, vroi, Mror, Taror, Hfor . ad snoll{' 

onc .xelLnl m€dod, piod*red by Niedqb..Ser dd @work G,31 s using oolv 

M(@L pFcl@B and b.nz/die elvdt h3 Fldu.€d tuy of rhe afomdtioNd 

nct l oxi&s. Ss.ad @wo*66 t baE stni!6iz.d re3o. by h@tirg F{mc)t vith 

oLylmioc, ol.ic rcid, ud 1,2-hqadea&diol. It @mp.n$r Pith oild 

m.tylacctoiales or eclal. p@UMr5! Fe{&rc)3 is le$ costly sd the moPanidc 

plodwt! are of conp@bl. uifodity md mono disFDity. M.ial &.tvl&.1otates also 

posg low noisnlc s@itivity, nodslr.ly rcLlile, md€ring rh.n ls sl|gplibl. io 

nydotysis, *hjch is a @mon disadv&itgc of melat altoxide sd b,lid6 tr Ths 

p@lets for CvD poa$* mut bei 

Shble doug}t 6l rooD lempdate. 

Su{fi.i€nt rclatility al low t np.Btre dd Uw it e be .$ilv 

ldsDon d to th. r.r.tion an v/o @udeBirg in tc li!Ec.Fbility 

of b.i!s p.oducld in . hig! degc of Puily- 

A suffici.nl lsg€ t€mp windolt'' b€tw€d cvapouation &d lhm.l 

86r F?4v.! P-Dttztovto conptdn 

U* of&etate, ell|doldind. N.N-diocihyl.lbeoluine ed N,N dimethylacelamid€ 6 

h€t ol.ptic ligmds impan dtra volaliliiy lowrd! deonposition duine UAACVD 

1.5.1 Basic Festor€3 of pJlketon.tes Complex€i 

Th€ cheninry of Detal p-dik toMl6 in a 3cN. r.fl4t3 the difreEnt €r$ in the 

doelopnenl of inorg&ic ch.ni$ty s s whole. Th€ c@rdimlilg ability of 

Fdik tonales is now reU esLblhh.d. A ldge Duob.r of dik lomt€s &€ knoM to fom 

neial cmpld€s. The p€domirmr chclaiing cheet r of p-dik€to@t s leads to a 

detrc of the nucl@ily of thc prs!fus A3 a Gsult sall panicl€s de geodally 

oblai'.d ane. hydrolysis of M(oR)* (p-dik.lonar*), sin€ rhese li8eds d. surf.c. 

capping G.genb ed polln iiatiod loctds. For.xdple, Ac.ryld€elon ce slabilire 

l)m{iEd colloi& d.dv.d from rhc Sn(OBu).EtOH systeE shich mrc ued to 

eklonte trsrspenl ed .ondrcliv. oiid. nlm,s R*tios wiih @tylrcelooe hale 

be! €oNid.r.d ro b. simpl.. Howd, dd apons h!rc indi€rcd ihar ac.tylac.tone 

d be 6ily modili.dF elo. d.gnd. to oxc arsrlgrret i! oild @ldilio4, d.Fndine 

otr tbe $lv.nr. 9-di&€tonat s and cbt d ligods m iabiliz. polytEl@ oxorselleal* 

g@cDLd by hydrclysis a obscd in c{* of iraniM. A gowilg inic..st in lhe nelal 

(dd o4!!G rclll) ddiEtiv.s or pnikto.6, &d a nhb.r or novcl ligdds mployed 

fq i!. !u.poe, 6 wll a nc* @npouds of F.viosly troM lied.!., halc huhjplied 

Fd ^do6 sho$ of l.lFnol butomdism,0F htdrcgcn em of th€ CHR'soup a 

rctiEred by the sdjssl C=O goupsr ad a @nju8sL syslem @ &i$ by a prclonic 

shift. Th6e taltone6 cxist in.quilibriM wilh.eh olhd, ed sElcrwlly th€y posess 

a cis @.fig@rion ud syn Gi$id) @nfomstior udd dpprcpnate @rdiriom the 

enolic hydmg€n srom of th. liSed ce b. Fpleed by a detal cation to prcdet a sixnenbercd 

chelsted rirg, lh.cby shifting kctFnol cquilibnu in fdvor of lhe €nol fon. 

'\>(- 

JJ 

l9

R3 

L-2 

-l .L ,K 

* \i!\c' 

J: d 

Mh 

chel.ting Rilg 

ULACm T..hnigy! 

Th. k to

Eo*E 

U4!e!P!.thriqu.s 

The hbloiical b6ckgrcud of nelal p{ikdrons nay b€ n&e bek by lhe work of 

ftnb€s tt-re di$us th€ sy.th6es of acetyl@tonates of alkai, alk tinc .eth md 

iDsilion m.rak, In nirel€€nlh conry Urbain'ormr lrepartd a@tyleebnalB of 

thdiua! 6im. l&lbtuuq iilrim ed gldoliniu. h lhc se p€riod otner 

!!gr.hd suc.ed.d in peF.ing 9nir.ion.r* of F. (Itr), co(IID, cr (lll), s(tD, 

Mn CID ald Cu (u). wmd'q srnrh.si!.d @dpls porasim nondnobm bis 

(&etylaceton.t.) plltinu (ll) {d discEs.d lhd one ofth€ u€tyl a€aonc srcups is 

bonded h th. nomal nmd dmugh a six.n.mb.rd .helated rine dd orhd is aft!€hed 

lhroud ihc @tivc n€lhyl@e gou! dd M co.fmed in 1962 by X-ny 

Dilth.t'e'o !Mi.d lh. @cijon of h.d ndid6 vilh @tyleelo@ ed mad. sne 

intqBring ob*tuii@- ,t@rding ro hiD boor ricbbnd€ giv.s ionic sp6i66 

B(@)r cl wh€a Fet€d with erylaton , wh.@ boo! t iflloddc sivcs a '€!rzt 

@ndd B(@c) F, wdq sinjld @ndnioro. 

Ros)hein el sl,,rr0 inv€stigdted lh€ Eaciion of Ticli wilh @H in ethcreat medim 

drd rponed $e fomtion of dddud fomulaicd s Ti (a@).c13 Ebo. In 1904 Di.th€y 

EFaad ih. above synthsis in solvoc litc .rhs, chlorcfom, &d gl&ial acaic aid 

aod bola&4 in @h elvoi, alroducr *ldch @ueaonded lo Ti{a@}rclr. ft. Pllduct 

@ siva dtc fofrul. ITi(@ljr.TicL *nich is a rriba of Ti(.*>Ch br aDlosy 

'ith ih. p@dwt! si(ac&Icl .Hcl ed z(e&)fl obt isl i! rh. .oGpondins 

@iioos wiur sili@D md zironiu r.r@hlorid.. nF inreFsring formulEtion made 

@inly on thc b!si! of malogj, dd quot d in icxr b@kr ed rreari*srrr was foud to 

have no Eql bsb who Mebrorra dd corcrkcs'r'?showd by nol.culd w.isht 

m€l|@cnl. in bazn ed by chcnic.l ed cmducrivity melhod ttDi ilE hc prcdrct 

is a non@6ic rctr{letrolyr. which @ bc Fpllgred simply N sir o{r

UlUCYD f.chniaws 

d*tib.d th. prtp.ndon of!.ctyberom of calcin, boriun, b.rylliM, ed zinc tln 

b.sic a5lt! of th.s cl.ro.ore drl altyl@ior. Sig'inc.lt conEibutionr in rhis field 

vw nttL by Mor8r! .nd @w*6r'! wno plblisH $our rwo dozn p+..s on nel.t 

Fditcton t€ dring | 9l4l92E, d@g eirl rhc chc6i5try of acctyl..aones of. nMbe' 

of clcDat3 v@ lmM up ro 1914. 'Ilw ls cl3 .ugg6rcd lhll Fditciom ligdd! 

dd 'rrqr "to thc nd.l .ton, rrd 0Ey rko 8a!. r F.liniMry ide cerrding 0E 

ilbility .nd 3li[le of 6.irl t ctyl*rioDt! conplad. It B $98.!rcd thlt lhc 

3r.bility of ecryl.ccromr. of .l!|mt wir! ditr r'nr v.lcnci6 follo* rlc odcr: 

uivded

,=o, 

H-q( )4 

I=o 

R 

Aroturic cbre|r of ch.l.L ring 

CollnD cr al.,'! Mtrm.d rh. eidc@ for $turicity or rhe hAis of elsr.ophjlic 

substiMo! ra.lic ocMirg at th. 3{r$on .ton of six-bmb€cd a..tyl!..todr. 

ring, I! a erid of anicb ir iMgoic synlh6is, Young ci al,'a d*nb€d ! d.r!il.d 

p@.de for th€ pEp@ton of Snik roDc d.ivaiv€ of s f€. .toears. Mmhrtr 

chim.d thc i$ladon of tri! (a@tylacotondi.s) of ldurdd, neodFim, sadoliniw 

sd 'ltcrbiw, 

which l^@ leponed b b. t . liod wter of cryst llialion, Matsh 

D6u.d ihe nole votm. of aI th€s. @dpl€x$, Calvh ed Bailsr':6 inv.sti$tcd thc 

Fl@g.phic GductioD of! few Fdikcrofrca for th! tu$ time ald $e nexr Gpon on 

thi! 5rF.t .ppoEd i! l95O by Lsntc,r" Solmr quactlon ls nploy.d for rh. 

islarioo of P-dit tonal6 zii@niM &d hdiri@. 

Tlr 1950s @y bc @Nided a lhc ruing ,c6 in lhc fi€ld of netd Sjfictomtas 

chchi!try; duiig this dne noE rhs 100 pspa! alpejld ddriry mi.ly sith physic.l 

F.pcrtics ud udttical applic*ions, Lrontc cr a1,1" ncaured IR sFct! of mctd 0dik 

to..les &d bads obsotd m6d 1600 md 1525 @r ww sign€d io C:-O 

atrd C:C slr.tchine nodes 6p..riv.ly. Repl&m€nt of nethyl eroup by a 

rifluoroncthyl group sircngih€c fi6e bond! ed thw shifl.d to high€r wavc nwb.r 

bul *t!k@ D.i.l oxy8.n bond ed shin d to low wvc nub6. 

B.U.dy .t .l.rtr3o lrd f.* orh6, al$ liudi€d i!&!r.d 3p*to of pnik !omr6 of a 

nMbcr of clddts od $!'pon d rhc BigMdr Ea& by l@m& a at.r' Howrcr, 

Nrl,lEoto rld M&t.ll'rr Ercrs€d lhc abov. sigrm.nB dd attribdcd b4d. euDd 

1600 ed 1525 cmt lo C:-C ed C:-O ltet hing notles 6Fcriv.ly. Lltci, 

.tt hple wE Dadc by *vedl tu*d 10 cxpllin the disrcpdcy. 

Fmdis dd @wort€B"2 publbh.d a si6 of pap.B on fomation .onstants of9' 

dikctonii.s of lege nmba of elem.nrs in aqu@us mediu. m€ds of solva! 

Lmpml@ ald ine natE of n t l ion on th. sr.bility of lhes onpl.x.s wG ako

UtaCYDTahnl 

sMicd- In additioo th.y r.vide! $c mcihod of prcpdarioi of a 'ub.r of m.rd 

Urb6ilr0': synthsizEd hydnrcd tir &ciylMioMtcs of l&rheM, &ttotiniM, ttrerbim 

ed t ttati! of qiM. Th* @dpl.xc3 6 .xp.d irs c@din.lioD rDhd {ilh 

bridsi.s p {ikcto@ra lisu& by olisoma fonDion. Mon of th6e coEDtq6 hs 

b!.n synthcsiad by thc ncldhc'i! @tion bctEn sodim or umodm slls of 

I nikcid,.s $d a marrh cbloridc d F.&r h sLr m.rhsol s sorv6rs. Us. of 

chlotidc sdls *!s Flfdcd ovd silri.s betuc of gral.r @diration powr of nir{. 

io8 wnicL n€ulB @npl.x co ainirg nitr.rc s cooidinflirg grlup. 

In r*@t th qnuy br of @rk hB bq doe tow.rd! the syathcsb of hhotepiic p- 

dil.to@t6 @Dplcx.' Horl.y c. e, ctft.lrt Epon d hohoteflic 6timon' (rrD p- 

dilcroMlg tsb(thd)bl, (iM = 2,2,6,6-ict'd.rhyl,3,5-h.p&&dioMlc) &d sh(fodL (fod 

= 2,2{in r[yt{,6,?,7,8,8,8-hc .neG3,5_lEpr6.di@r!) fiDm sb(oE0r.rd thc 

.quirdcnb of fi. .Dprlprid. lig.ad. 'nE* Mt6 ds studiql r[. u]ltlviotd sDer! 

of r fev D.t l @iyl.ceroEr6 rnd oi rhc bsis of rhe m.lsehdrs th.y doubrcd th. 

posibilfty of Nmtic ch&.!.r is six-mhb.Ed &.iyl.elonA. chcl.t d dns. 

M.rrl 9-d&dom h.y bG @vdi.ndy divid.d inro th. foltowina ftu desoriG 

d.p6dirg upo. tbc hodc of boding of lig&d noi.ri6 to h.Lt .roh: 

o oxygo bold.d p{ik loBro @npl.xs 

o cabon botrd.d 9-

ldtudrctiq UAACVD Techniaue, 

In the pr$e sndy we d€al with "a.{c" sd 'td" s t- l€to+nolar, a bi{enrar. 

lighdr, !o the chmisty of s@h ligdds will b€ discusd in d.6il her. 

A m.Ll 6tioo replaces rhe enolic hydrcg.n of ligdd 6d a six-memberd chelaied ri.g 

is prcdued. B-rlik€rorar6 eior RrCOc (R) = C G1 o mly n$ction s a lised in 

srcEt w's. Wlln. a.ti4 a uidcnlaG tigord. n M fom siDple salb with highly 

cl6loposiriE ncials es. If o c(cHt{BcocHr, but ir is very @ rbd 0diLroEls 

ooi.ty is ljrk d ro @td oGGl aroh rhrcu8h on c.rbonyl Srcup o.ly. Sili@n alon hs 

ben &pictcd 6 r.t?hedDl with 9iit lotu doi.tt bchwing s uidat c liged. 

Usud no& of p{ik tone bonding is ro acl6. bidc ai.lisdd. Meral €to. Gpl&6 

th. .nolic hydrc8d of d€ ligand add foms ! sir ncnbd ch€lde ring. Deld.lisglion of 

th. .l€tlon cloud in ch€lar€ rile hs b.en 3ulis€sted or rhe basis of smc 

physioch.hicd cheelaistic to €ndow it wilh . @nain noul ofdonaric chd@ler. 

.[\ 

R\ \,c-o. 

*/ 

\.t C-O 

Si!c. th. €nol.t ior @ies a singl. @gativ. chsge, neral alon 6 rc&t wnh on or 

mor cnobte ions to gie eiihd n€ut.l moleulca or chdg€d nol@ules, depending upon 

utc @o'di@lioD nMbq (tu) &d v.lcncy (n) of cenbal neial alom. This typ€ of bondins 

givca ris b thG difl@nt tlT.s ofdqivaiivB. 

{t) 

(2) 

(3) 

(l) rvl.r d < 2! : 

A.oDplq ior Day &sult if @odi8tion nMbd of mebl ioD t Ls &a double rh. 

plimdy val6cy. Comon exmpl.s e si(&aclcl:, Ni(gmlL, Br: and Sn(&e): M.: 

25 

M

x-my e.bstu of Ni(acac)r B! irdicar.s o oct h.dt l srucrw in qhicl the rcurzl 

rceiyl@io!. (le1o fom) G bon l€d through oxyecn 6roh, 

Whd @ordin tion nubq (m) of th. 6eul ior is doublc rhe primaly valocy (n). th€ 

nelat Fdikeide e foned b.h.v* s e ider @hpl* or neutnl conpl.x. 

f ,"r, 

t/ 

to---( 

,N \H 

t-__\ 

Slluchc of M(.@)i 

comon exMpld of lhis cla of @npound e B{&eL Al(@c)b, Th(@c)q 

Fe(a@)r, eb. In wbich n€tal arons q. c@ldimriv.ly etud€d. In viee of imr sslr 

fotudtio4 th.e d.rivaiives siow prdonir&tly colalot behsvior, i.e. $lubilit io 

comon orgei€ solv.nt ed volaliliry. 

{3) wie! n>2n : 

Ifdt tudimtion n@bd is Dore tha doubl. ih. Fimary v.l€ncy, the nolaul€ so 

fomed bebrvG a trwis eid &d @hid6 ihc d$i&d @rdina,tion €ither by 

pobndiztion o. by adducr fo@tiotr. c.s. Ni(rcrc),.2n1o, tN(&&)L, tc(a@),lr. 

tM{4@),bipyl, Izn(&&),(NE)t cic. 

26

-. 

\ -/ 

"\-i---.-.' \ 

I ddq 

-rl 

-L-c-*, "-J.--.- -, 

"r_=,".-._',-" J' 

srtrnE or Nd@),.2H,o 

The @nplcx* 6le bebave a @valmt dDpou*Ls &d Ihe mrdiDrion nwbq of 

rcrd iowards oxygd is gaenlly 6. 

r.!.21 Ch.bL.l R€.crio4 of n irl FdtLior.id 

'nE prepd.tion, physical pbp€rtiB md slrlclu€ of l&g€ rMbd of p{ikdomtc 

@npl€x$ have @eiv.d @middbl. atlotion; lhe study of their ch€Dical crite s for 

elving studual probl€E and .lso io explos od pFpetive n€thods for a vei.ty of 

nclrl d€rivltiv$ of Fdit€1ona&s $ oc not..sily fomed by tund @ion lout s. 

EleEoptilic $bsrilulion @tion 

In son@h.mical @tion Fdiketomt4 ligdd gcn r.lly ud€rgo redistribulion r€edon, 

r.pleenor @rior dd addnct lomaiion, & the chenistry of sh r€dction qill bc 

Fdil@todt s of c(D, AIGD, l(lID, c(lv), r(Iv), z(lv). H(Iv),vov), rc0ll). 

Cdlll) od NioD und€Bo Edjst ibution *tion with a nubd of oelll chclard !o 

fom mix.d lieard @npld6 If th. .@b.E of crchdgsble ligandr e s. thc 

@tion b.r@n r*o rclal cbeldg m bc win n a followine. 

M-4'{4&.r+MArrB*q + 2tvld.xBr 

wlErcM = neidatoD.n - nMberof ligDd!(equltohalf 0E@ordinationnmbo) 

md x = 1,2,--------. (n-l). 

27

ltuodurion UMcvDTechmqres 

I!'fr!r.d, UltdioLg NM& X-Ey po$ds p.{d .rd PolNgnthic sftrdi.s hÊ mrdi.d 

ilt ligrd Edisuibrtid E!.tioN. Ir!. lgrnd &{iltribltior l*rionr hlvc bm divid.d 

. E*chdgc of uiddIlt€ ligard 

. ExchbSc of bil6ta& lie.nd 

Io c* of qch.ns. of ui{@l'& lis&d wnich inwl6 dchasc ot F dikebnatc 

6dicd with ui{dl!r. ligrld @i.ty e I'nicd. Iris t}?c of r.dist ibutio! wa fist 

!@r!iz€d for zirconiun 0v) F{ikeioratc .nd Zt 0V) chlodde. Reacriod @ied oul i. 

THF &d wielid of mix.d haloe€rc Onikelomto) zt (lv) conplexB wt 

z4@\+32'at --!f- a2(s&Pl3 

zt@)1+zrc\ m, 2z(!4),c1, 

3zdrce)r+z€\ --Iq+ aa(ace)rcl 

ThG r..ti@ of z(sc..). .nd (r1cJH')rzrle rclultr in *cbdsc of botb halosd ard 

cyclGpe aiidyl lisrDd. 

zr(&&)a + (rLcrHJ),Z& --I9!4+ 2(Ir-c,Htz(r.&) 

Th. qchese orn.uryl dd phdyl soup! in (CHt, sn(M): ed (C6Ht, S.(ac&)? is 

Rali@ betwn F(ac&[ ed $cl. qults in chlor daivdivd 

2F{s@}r + 3sncl. --EQ&e 315a1!g1,g1,1 + 2pccti 

F€(@)j +Mcl. Hoa", Iu(*),ctl * r"cl, 

Th. id.@ol6d{ bi+ntare lrg&d exchrasp E&iio6 @u upon nixins the $hn@s 

of r$o @rat ch.lal6 h.vilg lh. s@ nuba of crchdg.au. ligrrd. i.c., tte dchdg. 

2a

of g,Ine t{ik€lonc and p.t to€sid ligmd b.lw@n two @ppcr coFplex€s in b.l1hc 

ct (@)', + cu(.de), + 2 c\(a@)(adc) 

othd dmplcs &j b2rd@, abzE a@. eac/ad. (ac.ion di-cdboxylic e$er dion), 

baqdac rerhyl eb-(ersledon) erc. f olllm &d 516r! synrhB'zed $e frixcd 

lg&d cheldes of 9!€ Al (Ar(B) &d AI(AXB)E, qhft A dd B e slmrricd b! 

d.lrltc lig&ds noi.ri6, G.g. .etyl-.tonc, hqaflere &ctyl*.rorc ed dipi$lotl- 

d.th@ i! chl@b.nz@ elution. 

Plrt and mn€d oxygo bonded 0-diL.tomtc @6plexes ud.rso a Eiety of 

rpL.dcnl re&tion, Ihc poduct depo

lnto.lutiu U.IACVD Tatuioues 

'ft. conplq Ni(ac&), r..cB with prindy dLyl hdid6 in di-b.ltlyl fommide (DMF) 

ro 8iv. tuinly Eono C-dkyl.lion pr.d@l!, 

Ni(@) + nx -J!4+ clircocg(R)coclll 

Th. cotal metd dton id l:ny oxygd bond.d p-dikelooate .omplcxls h4 a Endcocy 

10 iFru. ils coordimtion nmber by adducl fomation wilh lcwis bas like mDonia, 

pyridilc, Gttdmlmift, N,NiinethyLth6oluiE, 22-pyridin. &d cpha&rhrcli . 

Whd @rdilalion nmbd of lB th& doubL fic oxidarion nMbcr otthc mnal mi'l 

.i{n! c.donic @mplexcs of tbe typ. tsi('4}l ' Cl @ fodcd trlich Gdd Io rdd on 

Lwis eid Dol4ul6 likc F.Clj or Aucl, to {om th€ d.dvati* iwe or [si(d$]l 

lFGClrl , i! ebich eion &t! 3 . doM to l.wis acid. IrE shbility of the adduc6 vdi.s 

wid.ly ed i! en c.s.s ..s. i! ldrhaoB 9dl.rotr 

crnlol be IlIN.d unda nild otrditioB wirhoul dccompcirion. 

tcs, thc .ddud uler mol*ul6 

ZrOClr.HrO + J8aH I : l(acdoni'rilo 2 - rcLboxy.thuol) (z(uc)].H,olcl 

I l(&ctodtnle:2 - mc mxydh@l) 

zI{!@)4 + dtrt*H Td* r Zn(*-)"-a*u 

Iclcu(dne)]. + 2M(@c, + cqM:(@){!oH),(dde)4cl + 2ac&H 

1.5.3 Ch€ntutry of Alkorids IM(OR)" I rld AmiDorlcoholrt s 

t(Mc),N(cH'),oHl 

M.lsl o[on{ks IM(ORL] e @mNidly .vlilable for nmbq of mdds likc 

{Ti(OR).), Al(oR}, z(OR} wh.rc, oR goup is butdidc, pFPoxid€ ud ethoridc 

Mdr ofthe mebl alkoxidd N on€n $lid in @nrat to ilBt of silicod sd titoim .1c., 

hid dorcr activity of oxys6 ato@ ot aUoxid. pmits bitdiDr of nonon€tic alkoxid. 

i o oligo d polrh.dc attuctuB tM(OR)iln druslt doubly bndgjng G, or Itiply 

bidsins (pr) Fsitiod. for iurecq nict.l tlkoxide [Ni(oR]|. dd @ppq altorid.s 

tC(OR)d.. nr6. polymsic @r4irls e.c 8cMally i@lublc in at@hols a1 @n 

30

tntrcdtcrion Ut 4CvD Tecluiq,et 

I 

M.'l) 

t 

I 

"-1t" 

Bddging,It Bridging,Fl 

I! sh tt?. oftddgi!& bond ldglhs vary i! thc oda M4R l.minsl < M+roR < M- 

ll!.OR. IlEe stlucts @ So.nlly r.t incd in non-pold oredic nedi6, In this way ii 

hs lhe prcbability of lirking two or th@ n rlb in th. fod of oligonaic uirs$nr 

rnd lLB hclp€ in &sigirs of hmo or hcr.o nulti@mopoiot shsre $ue p@lN6. 

Mctal alkoxid6 M(OR)" @l .$ily wiih th. poroB of 6 lsse vdi.ty or holrculcs 

.r!.cially with doior tunctionNliad al@hol &d l!3 6y ch.@cal nodification e 

Drd. pcsibl. to &him lurlblc pbFni"s ofotg&ic hydmty ddivativa $itabL for 

cvD. 

In e atr€mF to obtain solublc nick l dkoxidc conPl*es. do@r nmdoDiiad olkoxid. 

gmup6, sEh s diD.lhyl@ilo-isopropoxid. [OCH{M.)CH:NMo] h.v. b*n uriliFd. 

but th. Grhiig producl b e iElpaobl. nix$s of tNi(OCH(Me)CHrNM.rhl sd 

tL(PdOrDN(OCH(Me)cs?NMo)Cll:.rrs 9-diketonatoalkoxidB of Ni(ll), such as 

tNia(OMeXP{iL).(Mcor0d h!rc al$ ben synth.sisd,'" but thee 4 iruolublc jn 

Simibdy polldoric Cu(ll) .lkoxid6 ICu(OR)rl" 

(R = Mq Pr, Bu), show such hehav,or 

in which alohot dcbesc @ns giv. iMluble @pp.(lD 2'naloxvdhond. 

tcq(rctloMcL} wt.6 mimal*orftL of @prq lik tc(ocr&NMe?rl is a 

nononr, volatle ed $lublc. Coppq (U) dkoxides a.c nad€ sohbl. bv sing 

.ll@xlrl@hols wilh E add,lion! O{onor sic (ltoc?HaOCTH.OM€) or siih a lonsa 

.r.bonchlinfo.lhcctt .6lchi?vcd*ilh'BuOC2ILOH- 

Aninoal@hol r!!€*nts &othq clss ofdlcohoh us.d to . ld€e qi41 in Fent cvD 

.rd sl-get prce$ilg- Vriou elheoldiB hNe als b@n u.d $ a meds lo 

inDoE bicdEEtue of co.ri!gs.'{ Mdd minodl@hol.ta h.w b.cn inre$iElt 

studi.d ed h.v. @i!ed incsing andto! d@ to thcir role for th. srnthBis of 

hore dd h.r.o'mebllic mimal@holat DFusoB rlhs for chdical vapou 

3l

dcposilion to fm .cmic oxides, md 6 3uch e of i er€st in thc ccr4ics ed 

Prinaiy ed econdaty minoalkoxid. ofiyF OECHRCIITN(Mt), havc provei to b€ 

mE .fficid lLd 2-n lhoxycthoxid. fo b@rjlg doM .ggrcgdion and lhN. 

prcviding volatility.'4 dloxyalohol, ed mi&al@hols have bc.n ued fo. 

inlcmolcute slabiliz.don of otgdoduidm dd otaeogrlli@ with the lim to 

rrq rrl 

obt in dolcl orseoFelsllic @npou& lor iDdurial u6 

The Ea.iio of ?r'./v{incihyldineth@l (druH), (Mc)tN(cHrloH with "BuU ud 

"BuLi/BuK tspetively 6ults in th. fodlion of fie hono- md hcterc'nc!.llic 

akond*u:tMe,N(qr?)'olil. tud t{M.,N(cH,),o)trLi'&lo, nlh.r thd nixed 

SiEilodt nulti@mpoMt sllodilllHiobid h.tNodal @nPlqe lSNh(oEt).{4' 

OErhLurO- dtu.),1 and [s rbloEt brFr OEtr:rFro drrueutroHh] rr have bem 

pr.pard by lhe Eetion of IsrNb'lOEr),21 dd th. d'n'r'rucrion'lis'd alcohols 

(dMH) ud found 1o be siiablc pdusor fot CVD. Slrorrim dobde @ pron*rog 

mldi.ls for MOCVD, Thc d..omposnion prcd(t.on|3'ling thc SrNb, sioichion'rv' 

cd be u!.d s fdoel*tdc m@ory aPplic.tions. d@ to ihet lo* poldizrdon tuisu€ 

d

UAic YD T.chntq4! 

(2) dt ios t*o mnodolatc @Ltc grcl4. ir a cis @ntrgustrotr srd tm chclating 

drtuH ligdds, Bolh @mplqes disslv. rudily in drn&Il to lom stable slutrons, md 

e good prdus6 for th. d.positior ofNio thn lil$ by el-r.l tc.bniqrcs 

t*b* ,.po,r.'tt "t huu. d.--$tat€d th6t rcetylac.tone cd b. sily dodified i.. , 

a.e,"d. , oro "ggr.e"ro"t '" undd dild @ndilioN, d.Dending on rh. slv61 u$d 

Meial p-dikdomtcs conpounds c.n €Nily Eact wilh donortunclionalilcd alcohols 

(dn&ro at @h tdtrpente ald fo@ addsG swh s zn(eb (dn&H),r@ Ca(e&D 

(dmdH).'6r simildy artd@t of isst ucrual co:(ee)r(p_oH):cq(&n&).c14 bd 

Nir(@X}-oH)rcu.(dba)qcl. wE synt sizc{t bv ltabjd .1.1,'d bv Fa'tidg 

opFoFiate douls of r.dddic N, N_dindhvlaoinoalr@lo @Ppe4l) chbnde with 

pnikctolar€s ofco0l) ud Ni0D. In ce of.l@holvsis @ction, h€ating b equiEd for 

obpLL moval of 9{ilctoDar6 or duoxi& *iih cl8sical alohols ID3@hclsrhc 

tunctioral llloxide lis&d! i.e, O(Csr)hX fX = OR (.lkoxvalohols). N& 

(alonolmiF)l 6 a.t s ch.L ins edor bndsins listnd 

wilh intdolouls O- or N. do@r sit s As & exmpl€ in conpound 

cut(OCH(CHr)cHrNM.J, dE chelario! rrk* pb.. bv liorins thc altoxid' oxveen sd 

the dono! site N of @bo Mhol 10 fom fivc Dmeb.rcd nner @EPlex 

l'.ldu sohajl ct.al.,rd rcrDi..l, stdheis of tl'li(.@XdDa€tltlcl widr lh' 

subcrinrtid of @e && sreup of Ni(@) *i$ dtn&H in p€srce or [clsnocH]l 

rld ths able !o inft6. ils slubililv 6 wll d lh. volatlig of lh' complq This 

suhtioi@ mad€ ttrc pcuNr ejt bl. fd lhin filb dcPositio' tn th' crvsr'l shrt@ 

molsul* e linked via G-H--CI hvdmgcn bonds lo fom centosvmmetic dinen 

hwtvilg lh. O-H erolF oft[c ducH liS.nds md dE Cl dios ft s bud thtt

elubiliry of $-dit€lomles or altorid€s of Ni, Cu, Sn, €rc. io@d ai.r odduct peduct 

or ligand rcplacencni by fiDction l olcohoh deFndins on their ability to act 6 a 

chelatjrg ligdd Fthq ihu ! bridging @e. Anitual@hob e oio norc cffcient lhu 

alkorydcohols in thb rcsp.ci, 

lelublc poltbqic o.i.l d*oxid6 of Ni, Cu, 54 ctc, @ be elubilied an€t 

subslitlnion of alkoxid. wiib tn no.dlizld .l@hols depoding on lh.t obiliry to 4t a a 

chelating ligald ralh.r thd a bndgiry one. 

_4. 

Sular .r..I.,'d sy hBiad bist2

Thes€ p@ursors w€E choea fq .a. of mmufactuq $lubility ,rd st bility in solution 

&d dcposilion FrfoM, paniculely for hrg.salc d$uf&nE. 

1.5.4 Ch.nbtry of M€tll Crrborylrte3 

Anons th. cirborrsta! a..tat lig$d B prcf@d du. to its .biliry b lDld clNly 

$vcnl n.lrl iom foming ldse suptuolcculd sfuctN. The &.lales acl hosltv 6 

bddgitrg-chclalinS ligsnds idead of limpl€ ch.bting or bddgiig 

.-r+ /9-M 

R-.(. _o-M 

Ih. difrdc. in thc IR .b$rption fi.q@des of th€ cdboxvlai. strmctrjcal md 

s'@ctrical strc&hilg bonds previdd inf@.tio6 about th€n @ordination DF, for 

insrsne, ! dir!r4@ of Ao = (D!O: - u' Cq) < 200 @r i.dica&s a bddgrng 

bctr"uio-,'t' tl* lig$& favor th€ forution of .xtqsirc n two*s sd gels' 

PolFlcl@ @nplqcs of tilolim aton&s wirh .c.1!L like Ti6O(F-oR)a(OR)a(p' 

OAc)i!6 x4 oblain d s1 oon t Fpemtue, wh€6 al hi8h temFr.tu€ oxo sFcies 

116 Tko6(OR). (!4rcR)6'4? 9w obtaircd. The pd Lbilitv of crnoxvlar' lisods 

cm 6uh in poou mtcrials s poo$iry i5 b.ing gdmcd by th€ siB of lhe R_8mup 'd 

h hs b.€! foud lhal thc @.rivig of m.tat tl|

ROH + R'COjH + RCO^'+ HO 

n!. rc&tion chmisLa of @boxylales deFnds on lhe expaimenul conditions lik€ 

stoichion.try, frcidM

M .l5o rcDoned s Sood prusor for th. d.posiiion of rux€d melal oxide thjt ilft in 

alpDpria& rloicbioD.dic drio by AAcIr'D. 

ArologoB 10 thG, Hollinesronl €ral..lra hs ds synlh.sisd hono dd 

hd.Dbioclallic .Ldvdils oftin minoalkoxid. Iitc sn6or (d4&)., sn6 04 (oEr). and 

lsn(d@), cd(@),1, ror nix€d nctd dirlc. 

A si6 of silG cartbxylatd .long *ilh lh.n hiph.nylPhG?bin. lddwl 6niairi.3 

unlatMled goups within $e li8lrd have bd strth€siscd by Ed*lrds et al.,trtlt likc 

lAsqCRl and [AsorCR(PPbh, whm R = CH2CN, H1C=CH, H?C{HCH:CH1' 

M.GIXE(MC), Ph(tDc{rfl. Triphetrrlphosphine adducts or lil!.r B-dikdomr€srt6 

lAgL(PPh)l (! - eac, dpm, tfe, hf&, fod) nave ale bee. svnfi*ised ed elaluaied 6 

!r!.iNs for lh. dcF3iriotr of silvd 6lnt aing a@$l 4br.d chdic.l vaFu 

It is beliqed rhd @rgr. !d piikdomre dcrivativ€s of 3d divsl.ol lBEidon meuls, 

such N Niol)r1t and Cu(lI) h!v. a nat*cd i4docv to polvh*ik. Fot inslle 

tNi(a@)2h which is e 6cac-bddg.d linuclcs sp€cis,'B re duins alcohol dchase 

twdc, slvc imlublc .ick l (u) 2-methqy.thoxi& tNi(octt|.oMeHr, sd.6 

rc&lior of tNi(acacrli with mircol@hol, saw uinoal@holares of nickel 

tNi(octl.OM.)'11, qdich b momh€ric, vol.rile dd eluble it host ol {h' org&'ic 

s.lvcnis sd. ths, 6 b. usd 6 pot4l ptccsot for CVD 

1,5,5 Conp.rrtive Study of the P.ecursors Svuihatu'd 

Mcbl Hikctomtes IM(RCOCHCoR')"1. e mos{v u*d in the rabri@tion ofnetal 

oxi1) is on€n obsPed foi divalal, 

ldgc.lclMts, sEh s .lkdim €adh melals {Ci, St Ba) ft€ vol.tilirv is sovcmed bv 

thc bult of thc R dd R -srDups 6 wll d th. ctE of lhc Detal shich wiu ddmine 

thc &sree of Nei ion (n) Ot p-dikeiond€s csilv fom addutr wi$ ncurral 

moldulG 'L' M Gnirdonnl\ Lil mosr lik lv havine Dtrcsd or oxvs€n d6or sr€s 

swh s Mtcr, .l6hol5. eihe$ eines, minoalcohols €!c Fomadon ofddducis reduces 

socialion but sklility prcbl.N in &€ v.poq Ph@ nusl ,le be coNide!€d LU

UAACvDI!.httS!3! 

McLl .&on&! i! d!. $lid fotrrl @utd 6r m6r $e elubility st'd volatility 

requircme s ofcvD. Ho{cv6. 0E hid Eactivily oabili9 ofth. n t l-alkoxide bond 

i&l* th@ efi! $anhg Eardial for sFlh€is of v{i.ty of hd@lepli. pEclNts 

M(oR)". . & whcF, xn k Hikcro'.tcs or OCR which al$ cnh'e th.t sLbilirv 

itftud cosslinl in p€dce of mist@ strd thdforc n*d ro srot undet in n 

Md.l miN.lcrhola&s @ hidly ai! s@iiiv., but O.y c& fom srablc homol@lic. 

h!&relc?tic norcn i.llic edor bct@ bim.bllic ddlirwle @tdi@lion 6nplcx6 

by tc&ting *ith dlkoxide ard &eiatc drcug)l o, N chcl iot sd' thu' b..ome nor€ 

Gr€.dvc tbe sinplc tlqrdrondB itr ddaing bvdrelvsis l.le' htrsliIg 4ercelljon 

dd, thus, indwing volatility, Th.e FoFrti$ n.k€ lhen a 8@d dnSlc $@e pEclMr 

fd delosilins mulriorPon !$ boold or hetenrut l dide threud MOCVD- 

Met l ceborltalcs 6tecisUy 4.t!ics of, Zn, Cu, Cd, Co. a fieir hvdtar€s' @ 

@m@irlly !v!ibbl. 6d @ b. eidc ltlvdmB cithlr bv hcarug in oven at a 

tanFrare of 80-90 oC for 3-4 lDs follo$td bv dc$icsto' 6r rca'r lhc m'i'r ac'itte 

wiih.c.tic dhydlid€ ot wilh 2-m.thoxy€$aol (in situ) Cdboxvlates d' g€n"ally 

iNlubl. in dsrdc $lrcnt3 de ro tLe Eqd of thcn Ugand! 10 act a bridgjng o! 

Th. dcgF of &!6eialion (Foleuld @mpt.ritv o. lucl*itv) d"id6 th' olisondic or 

polrd€nc dute of th€ rctulring rp€cics tM(o, CR)h1., wh€& n stald! for iI€ dege 

of .ssiatior Mctnl dboxyLriB mighr b. dislv.d in lh. p@M of mdd alloid's 

or solubiliry my inc@ wilh the inc@ in catbon atons Th. cdboxvl4es with $e 

sndlen lubd of 6bon .toc, qhicb @ elubL itr o4eic d.dit for h6t el@'ntl, 

@ 24lhylh€H@ls. C{boxylrcs @ 8.Ma!lv non'rclaf le howver liqrid 

csboxylG _ sw .l$ PRpaFd lor s ombd of n Els lAl M& B& C5. Y) bv 

Mdns 2{2-bcinoxyethoxyl) eiloxye.tic 4id (MEEA) *ith @tar€s' hv'ltoxid'e or 

6bonal.e to €nld.e il! vohlility 

M.B! orgdic @hplq€s. o! Lhe b4b of phtsi@_cheniclt prcpcniea @ b' oDPaFd 

w h rcfcrc!@ to their $lubility in orgdic aolvd! in ordd on M G{ik€bn'&sx 

.ddlcll > M(oAc)r(&@E)r > M(ORI > M(p- djt rotut6)" > M(q CR)i , voLtilig: 

M (9.dik€rodco" .do&H > M(oAc!(d@Hh > M(F- dik todtcs),'> M(oRt > M(o: 

38

CRl, opponuiry b fom srabl. hcGDn tdlic sFcid: M(OR)h > M(O? CRlh > M 

(dbe)" >M(P-iikt, ed cs. ofhydDlysis: M(oR)" >> M(q CR)" >> M(Hik)". 

1,6 Tbitr Filo Coraings/Nrno-Mrtedols 

Neo crysiallirc cerunic oiide @atings *ilh 6 prcp.i moaholoSy e atlr&li4 m 

incRising ini.nt in diillFt applicd fi.lds now a day. Sydlcsis ouG play a cruci.l 

Dle in prcpod!8 cmic dai€riaL, Nomally nulti4ompor€nl emic narnals hN. 

b€€n prepded by solid $aL hedodotogy which involv.s phvsical niring ofmct llic 

hydsxid., ondc, cnboaat , tr!l. or sulphltc doleial follo*.d bv he.r Mh'd at 

high lcmp€rstde aPpoximslely ol llo0'C to ploduce rsFclivc oxides This melhod 

cutrs in potdcs vilh oN erain d, agglob@ted structrc wilh lov 3u.f@ aM 

&d hcnce ils opplicaiion rcslncled lo vcry Mow indstnal 6el& 

h ordci ro obiartr lltitr film of .6@dc @dic m!&ials !r low tcDFBt@, following 

chebical synth.sis l*hniq@s wilh s proFr norPhologv have b*n @d dd dddoFd 

ovr rhe rast few d.qdd. CvD,lrr sDir oarb& slny Pvrctvsis rto trt eLcr@horai€ 

deposiiion, vacuun coatins, @ar nix ptu@$ ( sol scl d.l painting).'s clecno$dic 

Nisted vapou d€position (powdd @ating), plasm sp6ving ed ulusonic spttv 

pymlysis (USP)'&'ere ermples of5uch l4hrqEs 

Ch.dicd vtlou .lcposition {cvD) b a v€stil. proc€$, whi€h is suirable for Flducing 

hiehly coffonnal ihin film and pold6, @mFies of nenpalticl6 ChcEical vapou 

.tepGilion my b. deined 6 th€ Seneric Im. for a reg€ olpto@sses th3t Esuh in th€ 

deFsition of rhin filns of mr€riols vi6 lhe d@onposidon of ch.nical pFufuB al or 

ned !o a subsiral€ surface. Unlik traditional chemical ractions, in which F&dons 

uuauy ('ru in homgmu $lution or g6, CvD lwlio$ tate pl4 otr a two- 

dimosio.d $lid surfs. i,., the substdc. Genelallv th€r€ e two tt!6 of cvD 

pro6e' Oie is lhysicd v.pou Depositio! (PVD) $lich iNlld's vacuM 

dapo@liol! sPutterins, noLc e b@n @iLxv ed ion Pl,ning S6ond is Chenical 

Va!o( D.position (CVD) houing veiety of depositioo cchniques like. atnosth€lic 

06@ ch.Bicd lapou deposirion (APCVD), lo{ pastuc ch'nical lapou 

d.losition (LPCVD), plsna Ni$.d Gtldcld) chmical vapou deposilio' (PACVD' 

?ECVD), photuhcnical vapou dcposition (PCVD), tM ch'dic'l vapour deposilion 

(LcvD), n t l-orssic ch.mical vaPou depositioh (MOCVD), chcnical b@ epitaxv 

(cBE), ulrNnic &t@l 4is1€d cvD (UAAcvD) 

l9

C\'D b nom.lly pqfom.d in a low prssw v&um rcacro., which @n!i31s or lhe 

follo*ing psns: a t@tor chdb€r; grs 6icr; ewe nDt{ials; dd the suiabl€ en€rgv 

slE i.c., .iu.r lh.md hdting or plau. dd$r, for the d@nPosition of pElNt 

ro mcial /or nclst oxid.. The ceid gs nows tbnu$ tl)e soN. r€ad5ts thd arc 

usulty $lid!, ud picrr up ere q@tity of lh. b!rai.l. SonElie tbe ceid gar sill 

at$ b. a E&t rt. Thsc m.t€nab e hix€d in E mixhg .hmbq sd tho injccied inlo 

ih. E .tiotr chmbd. wh.rc tb. E&t !ts, undd th. irll@e of 8&i flo* rcGs thc 

Larcd $b€ta€(s) on *hich chemi.d tadion(s) lake pl!.e to dcPosir a b.idor nd.l 

ond. filn, In dsce, CVD system r.lies on thd convffion of prccsor in v.Pou fom 

dd drlu o o t h€.t d 3ub$!r. Dl!.€d ir $irlble @tor, *h@ th€ pFuer is f6l 

diffuled ed th.n adaft.d to subsitlr. surfac. @adng a micrc lavd of d.posidon 

CVD h6 sv.dl inpondt adldtlges thd m.ke n thc ptcferFd dcPosidon lahnologv 

in IMy apdi€no6.1$ TtEs d b.; CvD hs I|ieh drowing pow.i thar t suit'ble ro 

co.r conpLx !urf!c.s h.ving @nptcx ontos ll k Nr Glliclld to s lin@fai€})t 

.lepoitio!, edich k a b?icdl f.ate of sPun€rirs, cvapoMtion md othd PvD 

Ddhod.. CVD ha tbriv.ly his! &po6itio 6G. For thi.k codingr, in tom cag 

mrinct4 thick, CVD ptoes i3 S4eDlly cmpeliivc 

dn@ical rhd PvD prces. CVD na rhc pot€ndal to p.rfon el€ctiv' dcposinon 

i.c.. d.losirion of a film on on€ surf@ in rhc PFse 

ofeoth.r. For exdplc' coPp" 

oft.n morc .asily deposils oD conduciive sutf&4 lha o! di€l€citic or's Howoer' 

CvD is not ! uiEsal @lring patll@ 

onc rojor disadvebge is ihat CvD ned hid Eedon l€nP€ratu€s of 600oC or mot' 

and ir w tu6d that mdy sub6lratd e @t lh.@tly stable udd rh* ldFBtG 

Fofiunably, with lhe induction of plasm CvD and MOCVD paniallv ofset this 

pmbl.n, Amlhd disadvehge k fta1 PW flm @ bc difficutl lo obr4d bv CVD 

bcse Imy 3i& t@tios ()cs, .sFciallv in delat{rydic CVD l1jis pobl€b d 

b€ conhou€d by d@citing filn 6d.t opti6i4d @ndrtioro' I1Fs. CvD ptoces*s e 

neid ald @y lpprc&h direl ftbticdion of ond. thin nln nom elid dd liquid 

pdusoB. R6eeb4 h5re nDdc lot of ddvd@.nt in CVD Ecbliqu' egddinS 

@tio! chdinty @d proes @nlrol Th. Eponed CVD oelho& on@ Fqdc a hiSn 

d.gt c of ephisticaton . @nEol. to ohain t dcsitd thin filn Remdv, 

son@h.eicat itr dialion Lcbniq@ i.., UAACVD ha b4o d.signcd @d d'lcloped to 

40

lnttuduction U/l,4Cl/D ?echniqwt 

p€FE sFcific clmic filbs, @mpri*s of @o padicle which qlibil @v.l 

poFriid rbat ditrGr nom rhoe of @ldids with nicc siad f€rm. Tnb ltrhniquc is 

npid dd rbo suitablc for norue€loc mixr@ ofrhe iDvol.rile prcccors solulionj as 

t'ey q€ lrruponcd to h.aled subslrare by mtu of gaMiquid serosol, sheE they 

d.compo* to the find neLl or nelal oxide 6nfom.l rhin liln. The suce$ ol 

sFlhdir of t!i! film 6 b. judgc

I 

{a. 

bbl&.€b,H 

-fL-) 

l- 

Flg@ 9 Hodzo.t l lppoeh r[i! litm grcrvtb @heis d'mg UAACVD. 

c-ta v:L. ..\ 

trt-r t-r lr- 

t 

Fgw l0! Verticd apprc&h for din fitm gb{1[ MhsisD durile UAAClr'D. 

Vqtidl ap!rce! ws foutd ro bc mG $ir6tc ro gddr. *!@t rhat spny.d diEdy 

ol|o h€rr.d sub6rr.E pl4d ar rt horlom of ctdhd to g.t hiShly cdfofrol filD loder 

@ ol ervibnnMl ed rhus esrag. of &mst€ @ he rcsiicted ro a hirinum v.tE 

stich is mt posi6L i! bditulal eproch. 

1.7 hccorsors Ctroctedzatior TechDiques 

ovd th€ pal de.ad€s, the d.vetopMt ed ch@terizlrion of marldats havc be@ft 

ie6itrSly stEhliz€d dE to rt .vq-il|.6bg i.n,nd! plaed or qudity. Thc sEal 

itrdn 'r n|l|qi.l *i.@ ha .rEt d r i6d for sleifc .ldrdcd rsts lo d@r.riz. 

rhe ino.ldic tud or8ei. tuedab rirh Ftiabiliry, To rrcvid. tull info@{ion ahou lh.

Pre.6or Chrodtzano, 

pcues, ditrddt avaihbl. analttic.l t chnique likc ilAuld sp@tom.&r, nucld 

mgnetic 6o@ce sF.t omdd, cHNs-o &aly*r, .lonic abcolpdon spe.Eotu€r€r, 

singl. crysld x-6y qBlFh, d.l theml snslysis have beer urili-d. 

1.7.1 Elenentrl Anrlysis 

Clasictl tEg.l tcchniquF br*d on oxygen trjn @Dbustior nethodolry wrc N€d for 

th. 6:rin iio. of clrbotr ed lydoea @nrcnc,rs whc@ for niEos@ t]"ical 

Kj.ldahal mcthod ws s.d.'e Now a d.ys @mp!ri*d equipncn e sEilable for rhe 

Blimalion of C,H,N,S ed O which wort oi thc principal of orid.rive degmd.tion &d 

cvolv€d @nbstion gdlo md wft holatld b/ cltrotutographic r.clDiqc b€fole 

di@cd io delc.tor for qMtiqtioo. 

1.72 Fouricr Trer3foE hfnred (FTIR) Sp€crrodcopy 

lrtn rcd sFctlospy is a v.ry Fwtul t .hiiqu. for the ch@r.nztion of ch@icals. 

'Iltoe nqu€nci* of IR ndiadon, which mlch thc raual vibr.tional frco@ci€s of rhe 

mol@ul€ in q@$ion, arc 6bso6€d, ed th. aoey absorb.d sw€s to incEse lhe 

mplirude ofihc vibdtion l notion ofthc bonds in tn€ nolccde. Only 0ro* bonds lhat 

h.vc a dipole non@r od cbdges 4 a turcti@ of tim. e 6psbL of llsorbinS 

Baae of hiSI sp€!d, gratd reluiion, sd inprov€d sig!.lro-noise ftio, FTIR 

spdhoscopy is now .mployed foi ltr applic.lior oI IR sp€cto$opy. In the fouier 

td$omation of lh. int rf€rogm lidl cov.dne rh. *hol. tcqucncy mge, rylically 

SOOO-400 cn_' ed ! @mputer blilt i. o&hine, @vetu n ilb a plot of alsorprion 

against *N.-!Mb.r mnbl* ln. !su.t slerim obiained by thc tnditiord m€thod. 

Th. piciodal vi€v of s infrared intdfeom€t r is snom i! Figrc 2l. 

1.7.3 Multinucl.gr ('H, r3C ) NMR Spectrosopy. 

NuclF naslaic rc$me o,{MR) sr..Eospy is s hiCy $Eitivc iechnique widety 

!*d for rhc afudy of sln&nlal inlom.lion ond inta/ind noleuld int€rotion. 

Eld.Dte havilg at l.rsl on mrndly ecunirS ieroDes *ilh a rstd Ain 0+ O) is 

Mdble ro NMR studi$, 

All NMR rctive rucl.i hay .or rcsonaie ai thc see positiotr ed r€don behind rhis &cl 

is ilal .hmically diffcMt lwl€i @ diff.E ly shi€lded fiom ih. s!,plied magne c 

6cld bs@ efat lhc tusndic field. Hln r'rrhc tructei my E€xpc5s 6;

Il.tr=H.(l-d) 

Prctusor CtuKl.tization 

W!@ a i5 3hieldilg osta ed is ind.Fnd@r of atpli.d mrgnelic ficld bn hisbty 

depeddt or rh. cheDicrl sEucnm of $c mol@u]. dd rheir valEs d. el€ly 

d€t€mined by magnetic dd €hctonic €nvirome ofthe nuclei b€ingobsrycd.Ihft 

is m rcfc@e or raFal 4rc *ith espat 10 which positio! of lin6 @ bc d6uEd, 

tbeEfoE &is dilliculry is €novrd by rabnS itrto @sid@rion fi.ld i.dcp.nddr psrrs 

pd million (!pn) shitu rclative to d eliirary rcf.Fne suhsiance. Nomally 

letluelhylsilde (IMs) is lalcn d intemal rcf.mce for mdy rcsoro. 

ln ce of rH NM& chmicd rltns inregdtio' rElB, sblF ofpe*r d@ ro spin-spin 

couing e very ecitiv. lo lh. Dol(uld genetric dif€rcnces. Direcr i.fomation 

aboul th. Etft ad nub.i of pmlon pGent in a .hehic.l @mpomd wei€ obtain€d 

non chenical shili \€1u6. Thc !€16 of coupline @6&nt rcflar l!€ miu. of bonding 

or ovibm.it b.rv@ rh. D6ir ofrElei_ 

'rC N'1,4R ir ddogus lo bui lcs pBilive ro rH NMR. Ilis proves to b€ d impoltari 

lool in stuctual turlrsjs of or8mic @npodd thrcugh iderrificarion of envnomoally 

dineml @bon atom, This tebniqrc bs $he cmpti€riotr th.t is loi hc.d iD rH 

NMR.'C foad to be NMR &tive Mlh. spin Z 6 prcton &d prcsr mruralty in Lt% 

abude€. Tlis low abuddce ofrrc Evesls rlur olly &w NMR elirc nwl.i pesdt 

vbich rcsFtc ir the mag!.iic fi€ld. 

'rC Ni {R !pea! s[ow a singlc pesk fo. @h ch.ni.atly non{quivztar csbon aron in 

cotrlzsl lorH NlvR $nict 3hok moiipl.l foi €&h Foron position. IF rrc chenical 

shifl adoptcd th. s@. principl.s 6 rhos of rH, althoud ihc lrlical resc of cheDical 

shins is mwh lo4{ than for rH (by a febr of.bout 2o). 

r.7.4 Siqle Cryst l X-rly D.ta Atrllysis 

Sructw of compoud w be det€din d with the help of @nput ! controlled 

Nronatic difh.cton€br, *hich ne3s@s ihc Bngs,s eSle (o) @d irietuir, 0) ror 

dh b*l Efletion. A *cll dcfiled c.ys6l sEucnrt irdjetes thar in $lid star. thc 

ligotls, n Ll ion ed mion fill rhe space in a rcguld pa.kin8, his packinS is sually 

held by co-ordimL, .l€cbosr.ric or by H-bondihg. w.tl dcfin€d singl€ crysrat havins a 

size of a fcw idth of. m i! RguiEd for sruct@ dd.miFdon. wljle pr€sjns th€ 

d,t , a si.s of diftlction pltcN h.E be. @.d.d frcm rhe €ryslr, *h Fanm 

corcspoid, to o ditr &!t crrsr.l didLtion, 1n. cryst ltosraptrer conv.ns $.se Bo,

PMrCi,..En ation 

diftsional inqges i.to a rhrEiiftnsionat nod.l of r[c d.nsnt of .ter.ons 

thrcu8lour rh. cr$ral lsing rh. mrbemdcd t chdq& of Founq T@sfom. h briel 

.ah sFt ffiponds to r difldem it!. of v{i.lio! in lh etdoon d.rsity: rtE 

crys|.XoendE. Ns dct mi@ rr,i.tr vdilrior oclonds ro whi.h 3@r \indsi"s), 

the Flativc arfigths oI tl!. spot6 in difl@nr images (tur8i,8 arl r.4titrS) ed how th€ 

vdiari@ sbould be @mbiicd to yicld rhe ro&t el€crio! &siry @n rj,r8). In&i4 js 

Scmlly romplist d iitnE s Moi^d.th9 Nnc.n Th6€ difi.cnr scD6 

undenakd by cry$allogeplEr us.d for srnctuE itlwidnrion e glphicaly Gprce.r.d 

-t ^.^ 

:r 

tD t 

FLre ll: Flw shet for solving 6d@!ld sEu.luF by crysrallogbpter. 

Mol@|I stluctuB of lag. runb€r of mrrl o.gei. qnFulds *w d.i.@i!.d 

lnng lhis rchniqu.. R@ndy tn. crysrar sreftE of rhc @6prei tp(Cir?qht hs 

b.en Ed.rcDniedzor (Figurc t2) at lmK rsing @rcnr sphisricsrd equipmenr, 

aulting i! iEprcv€d Feisid cmp€rd ro dE pBids stlldr.4 

45

Figurc 12: Mol.cul& strmr@ of tpd(CjH,Or)2]. 

P r. tu| e I C hra r I e r i et io n 

M.zll{ ct at..d in thcir p6p.r onpaEd ibcir sFwro&l d.la Mth Kny@€va dai. ,o: for 

lhe s. c@poud [Pd(crH'Q)rj on lhr bsis of Fsnts obr.incd duins sinsle.rysbl 

X.Fy &Elysis, Both agrc.llt.l i[e conpl.x crysr,lliz.s in lh. sp&c grcup p2tn wid 

1wo nol6rd6 in lI€ qi1c.ll, Kryu€v{ srat.d rhat rhe Pd codpl.x is plae, Mdhd cr 

al., on &c bdis of llt€n siaiislical sEltsis disgrc wirh rhh ed sid dar tn two 2j, 

p€nLe{tionate ligturls sc nor l@!ed d&tly in rhe Mc ple but m tilcd with 

qFd to th. PdO. plec b, 1.4" 0 ). 

Rodn.y P. f@eU .1.61.,?@ cponcd nol€cut& srructur€ (rigu. lt) of zinc clurrs 

tzn,oio:Cfir1l3-{CH'oH)CJlliN}:l h5ving 161 €Mple o{ thc rely seen double 

t tEl|.totr (Figw l4). Thc @mplex sr.enr G foud ro b. sliStrdy dhortcd clpFd 

Eigo!.l piisati. alq8mcni Esch of ih. t*! |lralcdlois of zilc @araitu d 

intestiiirl l4-o dd e 3ym€r1-Elal.d throud d in6bn c! .. to@r.d zn{4), 

whhh ale sFes s a shs€d venex linldng lhe rwo halv.s. Ite edges of rhe 

teudEdFns e aI bnd8.d by 12, l2-@6rcs cxc€pr for lhe edgc UnrinS Zn(t ) io Zn(4) 

ad zn(3) lo a(4). It Zr(l) ro zn(2) cd8. is bridsed rl, l2 by rwo oxyscB of c 

e.lar6 that mdd olh.dis be typical !2, 12 li'ksg6 b€rwn Zn{2lzn(4) dr! h(3> 

Zn(4). ft.s. si4l. aroh bndg6 effecdv.ly rcsrrid tne Zn(tF(l2Fzn(4) mgl. lo 

99.0ra9,

p.-. 

..^ 

'{c 

r! 

*\\ 

ft.i.+ 

ft.jd I 

P rccwsor C htoct.r r2utoi 

Figu..l} Thmd ellipsoid rcprepnratioo ofthe Figurc t4t Ball ed siick 

NrlMciric uil of zn,(h-qxorc:Htrc (3- reFaolirion of lhc zo4(14-o) 

{CH1OH}CJEN)r, with thc othu half of lh€ skeleroD showins the ven x shaed 

nolcltc shoM a a dahed batl and srick doublc aadedrcn of anc rsn ded 

,t"*ios aromsr vid inrsurdl oxid; (opei 

Thjs r€sul$ in distorlion of th€ zirc ter.alcdred givine a sbon edge qith a Zn-Zn 

*p€ntion of ody 2.9887(7) A. All fou ujque Zn @cF havc difee elviFmco|.9 

thd@b. gbuFd,i o dinoicd et hcd6l {zn(4)l or dinoned t!l!"nedr, lzi(t-j)l 

ln bdef thb rshrjq@ rc1 only gires ih. md6!l@ sructwr of compoud bul .lso 

giv6 g.on tric€l pafud.B.totrg wirh rh. bonding paned of mehl-ioq tiSed! dd 

don pEeor in the nol.clld sFrctuE.

1.8 Tbin Film Chracteriation, Structure, Chemictl 

Compositlon, and Morphologi 

The strrctunl and morpnobgical popenics of rhin film e of prime inpone@ 

beu.e th.y prcli.lc nucn infomado. about the natur of rhe mi@nductor Midial. 

S@ing €leIrcn nicmsopy (SEM). eturgy disF6ive xdy dalyrh {EDX), Fwdd 

i 6t dim'a.bnEld (XRD). W-visible !D

As 1h. bem inlencts wirh mple it creates vuios sigoals Gecondary electon, intcnal 

cuMl photon mision clc,i) all of whjch 6 bc apFopriar.ly dcrcded. Appopriale 

d.t.cloa 6 @ll*r . tuDabl€ 8lcdon of thc etetroB dift.d, ed ln. ourDur d b. 

ed to nodulatc lhc bridltl.s ora dhodc 6y tube (cRT) whoe x- ad y-irpuls d. 

drivcn in slncbtudso with the x-y volls.s ra8 rile rhe el.clron bm. In this {ay & 

irnage h prcduced on th€ CRT; dery loint $at the b€m sriik s on lhe sde h 

mPPd di@dy onto a @tuponding point on lhe s{ftn. 

Thi! im8. is hiehly M8nifi.d dd uutty hs lhe "l@P'of . rlldirion l simspic 

inag. bur *i1h a mu.h b.n6 rcelurion. Th. inaB.s produc.d in th€ SEM e of thF 

iyp.s: 8{ondary electron imae6. ba.tsqtl.Fd cl.clron inages, dd elem€ntal X{ay 

baps, Mosdy so.rLly deFo6 d€ used in SEM for inage fomarion. Sccondary dd 

h@*$dLed dem6 @ @nvoriomlly ep.Eled @rdi.g to rhcn d€rsi.s. A 

d.lelor suc[ 6 rh. Ev.drhan Thomlcy dd*ror @ be wd b @Ue.l *cond.ry 

.l.ctrons ed conv.rt then ro a signal rhar ir mplified 10 prcdrce d imge of rhe 

Ar lddiliooal eldEor ini@tion of @jor imponde in ihc SEM oa6 wh.n rhc 

Dr'h&y eletrDc @llid. wilh ed ejer . .oE clecron lion d lron in th $tid, 'Drc 

ercn d .ion will dMy lo ik grcud slrr. by enirliog eithci a chm€l€rislic X{ay 

pholon or e Aug€r el€ciron along wirh s@onduy electons ed bacl scalt red clecrons 

(Fi8e 16). A modcm tEnd in el4tron nicroeopy is ro fil X{.y ealysis equipmc 6 

a bolkn awry. Bonbcdins ! sFcibo virh elerroG €ug X-6ys of 

cieddistic lml.ngths dd ddgi4 1o b. enin€d ftoD th€ rrot *h@ lhe h.m 

sttilca the sp€cim.n. CoDPlnq dalysis of rh€ wlyel€4th (Wavelogrh DispeBile 

sp.clros@py) or dqsy sp.crn (ErErsy Disp.sive speclro$opy) mak€s it po$ible to 

m4w &cu"r€ly th. nai@ &d qwiity of diII€ml elflent! in ihe mar6iat. 

FlSur€ 16: R@tion Fod@1 when €l€clrons de bonbddcd on th. sD{ifteo, 

49

O@ of th. gMtcsr str.qlhs of th. SEM is iB ability lo suow exmiurio! of wples 

*ithoul ri@@6mine sp€imcn pEp@*ior. 

1.8: X-Rsys DitrnctioD 

Sobe of 0r. nat .ial 9rcp€nie! IiL ihemal, m@hdicll. opricat, m8&tic, elerric, 

cl@ical, opricd amwl! &d Ediatio! cspoBe @ of gdte* inleEt in @rerial 

$iae 6*h. Ite X-6y3 e elet o@gnelic mv6 of v.ry shod wvddgtn 

@upyinS th. rcgior b.tw.en 8,lrm ad ulraviol€r oys i! the €tecrromasn€tic 

A*tm. LoE jr l9l2 discoveEd the phdondotr ofx-ny diftaction by crysrats. 

lor thi! filtn sturlx i!-plec dift!.tio. r..hriqrc ha ben used b€3ue who rb€ 

smple layq k r@ thiA O. X"ays @ compLrely tresirt d by the subsratc ed no 

diftelion 3igndl sppas due lo thir film narerirls. In cse of in-plrle diffrddion, a 

@Uin cd b.d ofx-a$, wirh waveldgth r -0.5 -2 Ao 0.540590 ed 0.?091l7 tor 

Cu &d Mo $Uru BFctiv.ty) is ieid.n| otr a speim.a ar a g@ing 6gh, rhe 

IF!.tnlion d.p1i of the bd i6 linited 10 within about I OO h of tns suf.c. ed onlv 

n@rcs diffi&t d bemq wl ch e setEEd reely pdallcl ro rh€ s$ptc surfu md 

hde b*&s la,ttie pld6 rhar re (n@ly) perFndiculd ro rhe sde surfac.. Ilr.e 

ple.s e i@ible by olhq tc.hniqq. Kswing rh. &rste of difEcrion dtt 

Mv.l4gih oflh€ incide X,6ys, d srBcing b.tsBn the plmB c& be delemined. 

In powd.r n.fiod Nignilg @net bll ind.x to e&h rcn€dion is nol & 6y job. h is 

ond posiblc for l[€ sinpl. @npoud! ofhid srlmcEy nlhd t@ ta.sq srnm of 

low strac|fy. For a cubic aynd, with uir ccll diD4ion &, ln. sp&og ofieo.cdng 

,F*rt;E 

CmbininS *ith BEgg\ equrion giBi 

I = 2 & si. oey' h'? +l?+r2 

sio r oe= (t:q?+P)rtl4ad, 

'ft*foE, for prioitivc cubic srnm a1l incgnl vrtB of bdic.s h, k &xr I @ rosibte. 

Pow.tul @nput ri&d soffw@s e Bed fo. irdqine powdd diftrctio! parcms for 

hiehly symD.tric dr51.l lyst ms sEh s cubh, tetragonat, onlorhohbic dd hcx.gonat 

whilc for olh.r sy$eos rhe pltlco oft.! @ruins of.ldge trwbq ofovc lppjne lilcs 

.nd irddog @ be mch mrc dimcdl or 4n rmposrbt.. 

t0

JcPDs (Joint Comiite fo' Poed6 Diflieriod sbrdltds) dd rcDD (hLnarional 

Crysfil Dim_&ton DaIa) fi16 @ n6dy Bcd 6 finger prid Dellodr lor dle 

idatiication of crysr.d strrctw. When rhc XRD panm of the smpl. h6 ben 

m€du.d dd bolh the dM sp&ings $d inr.osities of the linca @ E@ded, rh.se @ bc 

nt hd .g.iBr tbe palrero of t oM ampob& in tnc JCPDS ed ICDD dda n14 

dd ths cb t idmdfi.d 6ity. A ce is b.ing srrdi€d for cady GfeMc., Howdd, 

lhis app@ch .!oes nor wolk for doryhous smpl€s or if the inpuiry ircMes noe 

Mehe .r,.1,,1d studicd F*dd X-Ey cry$.I dda of th. d@mpc€d utcnd tun 

€onplq [Zn6 (oAc)s (tr-OH)r (dne)r (dn*H)r] which appded 6 zno ed marhed 

th. dara with ICDD otZiO [0]-089-051l] e &6 sucdstully. (Fisue l7&dTable2) 

FiglE l7: XRD paBem of lhin frln oblaincd di.r dMDpcins tzn6 (oAc)! (,1_OHh 

(dne)r (dnelot conplcx 

5l

Tlbh! 2 Po*ddx-E cry3hl dah of $c dMmF6cd m,l.ri!tfioh onpt*. 

I 11.7969 2.814.1 100 

2 34.45t1 2.@33 002 

J 16.2E99 2.41554 r0l 

47,5884 1.9185 lu, 

5 56_6376 t.6252 lt0 

62.9151 |.4168 103 

The Scbmr cqution ws cxltuiv.ly us.d in Gstiblting ih. !rcEge crysr.tulc sias of 

rhc rcr.l h.ral oxid. cr),srdtirc film. Ih. Flariolship of.ryst jtne size ro X-6y lin€ 

brcad€dng is given by th. Schftr €quaiion: 

L = 0.9 ! PCos €B 

fte !d@ of I is 6ualy h6E d in Ediu $rr@ thc inrasiry cquats th. tult widrb at 

hdJddimM (FWITM) ofth. p.ot bord.ning i e6iry, L b.ing rhe pdniclc airc, L is 

Mv€length of incident x-ny bed. The factor of 0,9 di*s frod the swed lioe shape 

oftb€ dilE&tion FaI ed rhc smed cryst ltire slD!., which is only .pprcxjmic. :d 

The Eehdis of XRD a.su€s to b. id..i i.c., a perf€d crynal md e ilcidon bem 

rhat i5 @hpoed of Frf@tly prall€l ed sriicrly nonochrcngdc radiation. In a.tual foct 

lhese conditioN nev€r cxir &d lhis eiv* ris lo two liniritr8 egl6 wher€ diflrelion 

@u. b tbc Esid tEt€n 2er al|d 2q, rhe s!r&r Eiutc in a @ii,ucliv€ 

interf€Er@ *tD* Idinu is al BEgg &gl€ 2 OB *tril€ in otha Fgiotu dcsrrucriv. 

interferc@ llkes pla* reulting h no difliacio._ rf lheF d. (m + l) pld$ in the 

crtsral dd L beilg lhc peticl. si&, wh€n rhe ditrraci.d iniasity is plott€d s a fibcrion 

of 20, rh. widrh of tbe rlittacrd cwc incrt9g 6 rhe thicts$ of rhe crysrat dcB6, 

siM th. ssule tuse (20r - 2er) ilrllt.g s h derc'a 

1,83 Optical Absorytion Studie, 

Opticd qb$rption neN@ne s likc .b$iption €cficior ad oeryy b.!d gap 

Frfomed or a dual bean UV-VrS-NIR abmdon 

52

l,trodu.tion Opttal Studi.t 

spetopholon t r. Oplical akorpdor/tresmirtde n crlculatcd a I tunctioo of 

sav.l.ngh s rhe mi@hmmt d light is $Dn€d ll$ugh thc sple md conpaEd t) 

thc lieht in lhe dcr@ b.d. Fom rlE val!. of .b$rpdon cafficiert s@ u*tut 

pdmt 6 lit .qgy bed gap @ bc calculd.d lo 6e mi@.duclitrg b.havior of 

ljr4 Energ Brnd Gsp 

Matcri.l. *h@ elclric potEnies fdl in-b.twen @lduc|on dd insutaroE @ 

chrmt rized 6 smicmdrcloi To unde6rDd snimducro. ct.dmdic popeni.s, on. 

cd slan with th. photocl..tri. .trecr 6 a wen knosn ph.no@non, *h.E 

photGlccrbns e €nitl.d frcn tbe mar.r rhoueh rhe absoryrion of sufficicnl coergy 

fon .Lalrcnagncric hdiation (i.e. pho!on9. IrE nidoun crcrgy rhar is rqliEd fot 

lh. .mission of d cletu from a nEd by liShl irrdidim (p/Dr&re.rDtr) is &fiEd 6 

,@.trerjoi . O.ly thoF photos @ ablc lo ktrat dr $. phor@l@notu whoe 

e!.tgynv(h is the Plocks co6t ) n iound ro b€ noF |h{ nal.rial\ wor* fun rion. 

In f&i tn. compl of woil tunclion ir r[e phdcteric p@ss is simild ro lbe @n@pl 

of Ih. 4rgl bard ga! of ! mi@dducling narqial. In slid"$ab phrsicr rh. bed eat 

Ei 6 th. eftrgy difi.Ene b.red rhc roD ol rhe valc@ bdd .d lh. bonoo of rhc 

@n

El ecnical resbtate ne8neke its 

Desir.d bsrd gap ofa msr.ii.l @ b€ &hi.vcd by @rblling thc @nposirid ofedain 

mi@nd@tor alloys. R.endy, it ha b.a shoM thd by ch&ging de MGtret@ of 

a eniconductor it is po$iblc to mipular. i6 band gap, Th. fin l fom ofde band gap 

eqution is 8ih b€lou (Dcbil.d denvdion is siv@ in App.ndix-ttD 

E1.9"o?'t'?=G 4.0'? (.vl 

Tltc opricd bdd 8ap ofrhc liln t calcular.d by plonine graph, 

E=h!(eD 

St"jdt lirc dlrM eud cw. *iU gi* brrd 8!' Ele di&ctly in €v. 

r.8.5 El.ctrical Resbtinc€ Mssrr€nent 

ft is a t!B@ of th€ Mt*id'r su.fae iildnr Esislna to.mn1flow Mde.iat.s 

sldic Bisdvity @moily oasud by qiry €itha rh. t*c or fou-poi pobe 

netho&.:@ no n!€* n€thod., ue ptub€e sli9ed lin@ly or in s squ. p.nch thnl 

6nt .i th. surface of1h. r€st mt rial. W€tud,10 neos€d thc eanlt surf@ eshdvny 

ir 1916 by fou prcb6 mcrhod. b ce or rwo-pobe n ihod {Fisw r9), cumr is *nr 

through o.. pbbe add enB $rcWh s@.d pFbc. A q?icd volrn t r or po&mior€rer 

is ued lo ncMe th€ volhgc b.tw@ thcs rwo prcbe.laFrom U. voltag. dd clm 

t!@umcnt lh. surfacc rcsistiviry @ be ncswd by uing thc following equadon. 

Rd -V4 =2&+ 2Pe+ & 

R. @nlact r*isl&ce bciwn lh. @reridt surface dd lhe pDb. touchine sufsc., &! is 

lhe spElding rsislaDe a6.

oprtnnp ropcorun ,o(|'r5o t 

.l.r!ii'lrf.'..*r n$n 19: Two poini prcbe resr etup, 

ngu 20: Four p@b. 

Eh.ui@l tutktuewn nts 

Th. fN prob. turhod (rigoa 20) II@uB rhc volrage pordri.l of r[. ma&riat surf@ 

by $ir8 two 6F. preb6. Tbe pio66 do @|.a.ry @y cufrdr .rd dus alimirarina 

lhc n dd Ra csurd in lseprcbe turhod. h lnis le sde BLdvny is .xpc*!.d 

by the follosing equarion if all prob* aE .qurl si&si 

p+ 2 d (vt) 

Wt E -p" n surf& Esidivny. Id ce of fN Fob. bidt qu.tiry fN-poili t rd is 

*.€*srry !o get Fp€.l.bb rd Fliabl€ Firriviry valn.. 

* 

t sr *tup. PFb. l & 4 cdy dMt 0) 2 tud 3 I|Mfts 

55

1.9 Thermal Studies 

T1| sreup oftechniqu€s ir which ene physical ed ch@icsl prcpeni.s ofa subsidce, 

a mixtw ddor rca.rion 6i,rnE @ &ilmincd B a tunction ofrcmFt rw or iime. 

*ni|sr rhc sple ji ebj6r.d to a orrlolt.d cmFFne ch!U.. Tte ptus@ roy 

involvc hcding or mliis (dymic} o. holdirs rh. r.op.6tN consdr (ierhedrl), 

or sy combietion of th.s., Ttu€e bsic t clDiques of rhmd&alysis r€ wd for rlF 

rh@.l chldlerianion of dy @t ri.t, i.e, th.moSnvinetric Mlysis 

(rcAyddi$live thdnognvinct y (DTc), ditr r.rriat ih.ml a&lysis (DTA).d 

difr@ntid s.ming cdorimt y (DSC). Aeth.r ibFrtaot.hypb@led l4hniqE is 

TCA-FTIR that deeib€s th. drdiysis of g&e o. volatiL components rhar ee .volved 

frod . smpl€ udelgoing ihmai ealysk, 

t.9.1 Thermogrevinet ricArclyrir(IcAylhrivrdvc 

Thcrnogrrvln.try (DTG) 

Thmognvim€ty is a q@rirative l€ bniqk in which the lN in wiehl h li@ued s 

5 fiuction of tdp@rw (dymicrlly) or rih€ (iethem.Uy) hdd a o,llothd 

avitoMcnl. TG hs ew ben @€iry $ pow.rtuX &.t!iq{c for hpidly s63ing 

r[ td8l stsbility of vrioB suldale' DTC is a Detbod of .xpBing dE Esulrs of 

TG by giving the fiIlr ddihtiE Nc s . fincrion of r€hD.rsru€, d limc! ene 

ov..lappirg qctiod nay be hoE cl.aly cvident aom the DTc cw. onq app.a'! to 

llsblc lhe @rcslondinS ditrmndal th.m.l enlysis or dif€Enrial lc@ing 

calodn tdc (DSC) c@a lhis tlshobe my sin i! ilcrFcrils th.mrt &ir. ed 

!1miigtul c@paism b.teq wplG. Th. DTG cw. al$ Fpr.sis rh. mdimm 

1,9,2 TGA-trTtR 

ftc TGA-FTIR muplilS wd dqigod ro pdvide . lruly oprimized iDt€rfe b.rGn 

$c two IEmm€ s, i.., nEnobdac. (Tc ) dd Foqiq rrasfom inrred 

spectobeGr (F[IR). TL htlhdsl€d ToA.FflR Ehnique nat€s i Ddsible to 

.ktedi!. thc cdpositios dd .listribdioB ofdmosr atl rh. gs@6 producti.volled 

frtb @t rids dui.g TO,4r !trd th@ d.lu!r. lnc d@mpGirion ecbdisG ot rhc 

oalcii.b. Tl| sh.malic qd pictonal vi{ ofTGA-FTtR i! shoM i! Fig@ 2 t , 

56

TGA-PTIR EquipDol 

IbN 2l: Scbeuti. view rld Bldr Di.gan of I TGA-FTIR !$EE. 

51

I! wpl6 @ heLd st a givd Latirg hrc fiDm @m r.mFEtft lo ih. dsiEd 

cop.6lu& in €itha e ien g6 such B ultr.-pwity nii.ogcn or oxidi2ing g6 such 4 

an oi oxy8.n. Th. all h pla!.d in the lR *ming t th Ior del4rion of lhe 

d@npolnion prcducrs and atso kept ar t50.C ro prcvent lossibl€ ond.Barion. IR 

deL.tion tug. us€d is bctw6 450 a.d 4500 cd'. I! rhe m& slelh e reded 

dril@Bly ir the fom of wrer fall (FisG 2l ) .t . Epid nr. of 16 s6r Fi sFcrru 

al a &$lution of 4 cm r ( 1hc bi.l rin€ for 16 $s is abour 16 scondt ad sn.sards 

spetal M8. clEfuteri$ics for a Fniculd turdion l 8!oup ce be setel€d sd |he IR 

alaorptioi bandr i, rhc tu8. inleed.d &d disllay.d s a liocdotr of tiDe / d 

14Fnr@ uiag en.we. Th. Bultirg cwe (Cn€ni8m or cm-Schhidr cwe 

Figw2l) is a v.ry u.tul wEy to conp@ $. r.sulls of rh. sp.ctrcs@pic ealysis witn 

TGA wighr lo$ ed by @nplring theF spera with E[Du phse libtu]. TCA-FTIR 

is a $irabl. hrIh@red ldhriq@ for sinullsew i.lcdjfidion dd q@iifidion of 

aolv.! vol.riL prcducls,':r r:D Tlte TcA-FtR dara ce sugg.n pcsibl. Eeheisas 

for ihe degradation of pre.uso6, howv.r, intoletltion tuy b4on compli.aled od 

ft. @upling yiekb a powrtul altlricat rehniqu. ihat codbing r[. qudratire 

€splbililica of TC and thc quatir.riv. c.pabiliri6 of FTIR sperospy. Such coupled 

stst m cov€rs wid. mas of .pplicaiioG luch d outgsins of malerials, dct ction of 

6idurb, rtdysis oI additive, aging and ttcomposition po@s$s, @oD€iilivc eatysis, 

chlEcldiatiotr ofmtual and E* harerjats, d6ory1ion b.havior, dalysis of synrhesis 

puses, thmal ed oxiddirc .Lc@posidon of pElMr salt h of curinS poceses 

md €vapoualio. and sublim.rion p@eses. 

1.93 Ki&iic Parrnet r3 Strdies 

Kinetics srudia hav. h

a ditr@nrid sming c.lodn &r (DsC). Two diews wircn by Flym,'r ort Rcich 

ard lditra disus*d att impoidr tecbriqud so fa. avaitablc !t ih.t ritue for dvatuarine 

llte kirctic pamd€B with the help of TcA dara. 

Mdy lin.ds trthod! .xin b chaEcldi4 rhc d.gErt rion ot v&iou miai.ls. Thqe 

e a nMb.r of metho& e3il!!le fo. rhc dalution of ldncic t,lmct r. fbn TG 

cw.3 such d the F@he &d C@ll n.thod."r Fuo$ dd Reich n€lhod:E nt Ve 

Kftvclcn\ m.thod,:r' Hoowitz.!d Metzgd he6od,:'tDo F edmd,s meitod,tL 1t 

Doylc\ n rho4a s Rcich, Le dd L.vfs method,zr. a Ftyn4zE, w.I md 

ozw's malod'Mr Coars ad R.dfd m.rho4a TaeL oa oiu meihod,,s e 

chaft.i4,u Brcido.rr 'e Kissinger e .rc Addirionalty sonvN b*d n.1ho& lite 

nth od.r kin rics, nodclfe! kinetio (MFK) sd ad@c.d modelfree kin€ris d. als 

avail.bL fo. the di@t nc$wodr of &irdie panm.&B lioh ln. dala avlilabL by 

It is gomlly ac*pted thlt nareiials d€gad4ion obetr rbe basic.qualion. 

dd /dt=k(T) (l-d) " Ec. Ll 

Bn@ k is ite Mctio! FL sDsta.! n is rhe ordq of thc @ai@, dd q is 0r 

@maliz.d Eidt los, d.fincd 6 follows : 

E4 1.2 

In Eq. 1.2, wl h rhe si8hr !r tine t md Wr is tlt iniridt dd W,de inal w.ighl of rhe 

smplc. Tlc tmpqatu. dep.ndace io Equdon 1.1 dl.B rhrolsl the rc4tion 6re 

tm k *hich is aued b b. of th€ arhcnis fotu: 

E4,ll 

Vhe. A i! th€ pre€xporcnlial facror, Er is som€ activaiion encrgy, ed R h rh. gas 

PdtaF th. sinpldt *ay !o 6dtz ierh.@d (q slaljc) lhmogBvibenic dala is lo 6r 

it to Eq. Ll 't!is would 'caulr in adjustils $. valu€s for k dd n. R.p.alilg ar sd€El 

t€mpmih leads to a spectum for k(T) which. via Eq. 1.3, ce b. used to calcllate 

ralEs for A ed Et for rhc @tion. 

59

Chaltqja':3t prcpose d iethemal nerhod for ihe nedwmor of kineiics pm.ter. 

He dlso begi6 with lhc b6ic kjnedc €qu.tion! (Eq. LI ed Eq, Ll), bui fims lhem in 

teds of wighl EMi.ing d dne q rcp@rt d by w: 

S-^*'*'* 

H€ thm ht?othdias thll om nn€ of gaftciiog kincdc

ln enc n@ l€qt wrlq Rozy.*i a rl.,ar a trtc a mc gacral apFoeh by nol 

sisDilg {a) = (l {)". 'ftey us.d sbnd!'d rietc .qutioa, but i! i,r.sd f{m: 

[g = rot [a E. r.8 

Thc lcft-hd&ide is DMcd (o). lrd k(I) is, in th. usual tuhioa rrt@ d @ Arndiu 

s(c)=(r)=A.+.^r 

fte aulho$ rcxl d€ahed a rcdwd rim. (nd, as 

L 

to5 k thc time wh€c a = 0.5. OD. q thctr plot o 

cbdging th. tin $al. of.qu.lio. L9 l.a& to; 

*,="(*) 

Ec Lc 

Eq. Ll0 

v6B td. Rozycki at$ &t€d lhrt 

Eq. L I1 

*lt@ B is a @!ea!t d.F.d.rl @ tbc vdE of g(o). vdB of g(a), ,lons wirh B, bre 

ben tsbdaled- Using a gnphicd mtlro4 oft @ plol thc qF.ircltal drra and 

onp@ ir *irh tbe d6r.ri.rl plot of a !.M tr6d for vdiou e(a) n@tio6. Wlich 

evd N mosr clo*ly oarch.s thc dFdn@td d!l! is rh6 &}c! a g{d). 

Ro?cki et al.,"L a1 @ntinrc by d.sdbins . @hpurcr prcsu fot lss subjelive 

d€ledination of g(d). Bsd upotr thc @npbxity, howvct, it dod @1app€{ b ofier 

&y dislircl advatages ovet lbc other meUodq ed ths will not be .ove€d heF Ir 

e€n€d, i$ihmal oethods suiler in elation 10 dlMic m.thod! in lhlt @mpedvely 

larg€ mouts of d.r! re required, FurtlEnorc, . ncw wple is utili4d for each ies1, 

*tlich i!tt!d@s addirioaal etror into th. m.s!m.nl. If lle @don pceds 

claliv.ly qui.kly, em. of th. msr.rial mly h.v. ract d duilg rh. span of rin€ lhe 

spl€ w being h€ted ro |hc isoth.nn l t mpcFtur. Finally, this &chriq@ do.s nol 

ptovid. in&malio! about lh. kircnca of dcgBdlrion ov.r a @nti!@B t@pdalw 

rgiotr" but ooly ar dkEtc sLg6-?rr To di$B sD. of lb€* isB in d€Lil. 

!!$e!.8 reDlly tm ro dyndic (mni$tr.dl) TCA t chliqes. An dmPL of 

such a r€hniqE is lhar of F|Etm !trd cs.mnilt *ho alplicd a @Fietb@,1 

th.@ereie.t ic re.hniq@ to th. dcgndltior of calcim oxala& !t@byd!!rq Th.y 

6l

su.d a !@tsBi!s r*lio! *l@ ! @tad, P, s6 to ! elid pbder (s) dd t 

P(elid) --------+ s(solo +qga!) 

Thcy mle ! g€ne6l 6tc .xp6sion for $b Ea.tiorj 

dT 

p 

Eq.l.l2 

WI.F, W is th. wight of solid l€minils dd F is th. heatilg nr.. Using a sinele TGA 

tnoc, Eq. 1.12 6 b. appli.d at two poinls on the cw€, Th4 lhe esults @ b. 

/ iw\ 

arocl--J = rarosw - 

-Ai 

If cqual Miped &mp@tw irt€nals ae .hos 

plot of A log [.d w/dr] ad A losw will b. litud. 

Thir dellod involrc3 only a single lhmogm md ale p.6il3 lo snrdy over a 

cd imN tenFri@ E!sc. Horwq sh t chniqE suff4 ir rht ir Equi!6 sloF in 

sLct .M of th. thcmog@. Illjl intrldEs alp@iallc .rc. it lhe &alr5n of 

kimtic pcmaerq {hich my Dake d.t mimion of th. onttdl vagu.. 

' ""0,"(i) =" [^',*,^(i)]-,.,* 

Eq. 1 l3 

(i.e., A x (l/T) b h.ld @Etanr), a 

Aroihd rcchuqu. in dynmic thmogravinctry i! thal ol veidbl€ hcatilg nle R€ich 

dd @w*631tt d.EloDcd this mrcl m.thod for cabdsting n {d Er' Thev bcgt! 

h.rrilg r sqlc rl r s.t sc od th.n, rnd a sp@fi€d @nvdi@ wa @he{ {F 

h.ri!8 nte rc ch.ngcd. 'n$ s@ld h.ding 6tc @uld be Lidd ll!& th. initial 6tc' 

bur th€ E*NheB fou

h r.L to b. lowr rhd lhe fi6t 0', ELcs ro Ihe vdE ofn- olre @ chet @sindcy 

of th. v.l@ by @.$tudng & i$dFm &d sut6lituting valB in ih. foUowilg 

"=[^,*(SJ,r^'*"r] 

Eq. Ll5 

wilL ihis choic. of PPh come lllc n..sity lh,l the 61nrin8 t EmoSm b. 

uymelrical ed dinilc{y cw€d !t boln .rd!. Thc adv6lag6 of this m.thod itrclude 

lbc n cd for o y r 3ingl€ thaboslm, ls r.dlcl in lte da&" a!4 @ordins io ihc 

autho6, lc$ labor rhd the oth.r mctio&, Klowing d wht @nw6ion io chaq. lh. 

h.jlilg nl6 could prcFnl son difrculd$ sd consdt'ttB a disadveiasc, s doa ihe 

n*essity for th. utm.trical th€mogrm, 

ve Kic!.I.n ei.a.l 1'3 Mied th€ ptrclyli! of {@d ba!€d on lhe smplioi th.t 

@ton od.r to b. I ad @d s .ppreximltior for .xpon€ntial lem in st nded 

ArhqioB @u.tio! 1.3 and @u.li6 cm6 ro b. 6 follows, 

,fl1 rf"1 e -,11-1 e.,1,, 

lP (er" I t Rr. ll \ Rr" ./ 

Eq.l,l6 

\vhoc, Tm is lhe tchD€ratN at I)HiDm convc$ion dle. wlh this appoiih.don is 

subnitut d in cqurror l I fld lhd idegdi.d th. Gslldng equiion com$ 10 be ar 

,"Jv.= Eq.I l7 

ftc nrh h.nd tid. c+Elim m b€ bta s otuia l. 6'nrina ir eqution 

Eq. I 18 

A plor of ln I vs ln T yi€ldr a sraidt lin whose sloF will gile d. vale of rclivaiion 

.Mgy E , ed int@p is A. The nain diedvsllgB in lhis neihod e lhtl v.luc of n 

nu$ b. krou pdon. By lhb m.lhod cxtn ly low vale of.ctiEtior 6dgy i3 

63

obtai&d.'rr Irl ldvet g6 i5 itat it nc€d. only on the@gru for th. cvrluiion of 

L.rd, Horewitz &d M€tzgs'.1q'o deiin.d lems dif€ently in o.ir m.thod. For ey 

ptblysis wbw all prodwl5 e ed6, ih.y lppli€d peudGffi ordd kj.c1ics. This is 

de ro lhe facr th.r dFi. @tion o&r 'tr', .tpli6 1o Mqtlri@ rrd rct wighls of 

pd&rr for sh a cs, cl)!r@!!rid tlmitu cdaldt a$d i[e .qulrion @ne to be 

Eql19 

'I!e auibo$ dcfm.d en ler$ in ordd lo i egiale Eq l.l9: w/vo= l/e ar the 

lcmD@$rc 1, ard 0 = T T" ft. dt sllp is 4plying eh. bllhmarical 

I l, olr 

i"l'-Tlt I 

Iflhii b $bsdtuad into Equatio! l.19 alosg*ilh thc ory i€ds' onc fn& 

Eq 1.20 

bhllll=I4 uq. r.zr 

Iq, RT,' 

hl '_'! l = -:L E4 t 22 

lE0 l Rt 

FrcE Eq. 1.19, plonirg ln ln (w,ryo) v.6B e should sive a ttlidt li@ with slop. 

proponional to E.. Thb valE, along wiih .q!.tion | 22, yi€lds ! sull fot A Nole thal 

this 6ulr appli€s only lo . singte&etion pyrolysis tEt results in onlv cA@us 

podwls. I! $nc othq cer Ei@ only ! filclion of the toial w.i8ht is volalilied md 

em Gidual elid m.i!i d tbe 6d of thcmrl ddDpositi@ Fetion Thcv nad. 

s@ oodificanos in ihc dislirg kimlic c$ltioD For tbd plrPos tb.v defn€d & 

Eq L2l

whd'\/' is rh. i.$ tuining at a livo t np@tE, wi ed {r e the ionial dd 

final llrses r.speively. R is 8s consrd! T! is lhe rfernce tempcratw showiog 

tuinM reigh los,ard0=T-T,. Wl6lnln [w, -wr /w qd is plotlcd agaiisl0, 

a straight linc is ohained tbe sloD. of which by expFsion of €qulio. 

(E = sloF RTj ) gie6 |he val@ of acivsnon eMs/ &d i mpr A (Fte 

'ftis meilDd is aplic.blc lo Imy d.8rodltion @ndilions, y.t n sufl6 ene 

disadvatages, A shonS one is th€ ne.d for $e @1ion ord€r, n, lo bc knoM b.lbr 

hdd. Als, lMy NMptioB e iileMt in Ois nethod so it should only b€ EPplied lo 

! mw r.Dp.dre tulge. To its dedn, thouSL ir d6 no1 rcquilc mAemqt of 

slop6 in slEp !16 of fie themoerlrr B do me of 6e pcvioEly nddded 

Friednd.lr D siancd with eolh€! melhod thai involves nor€ rh& onc thcmoslus al 

dilTft h€ating rai.s, By dif€r€rtialirg the equatior do/dtB=A( E/Rr)d dr€ elalion 

tor the del€mirahotr of kinetic pMneters N gi.ven by followirS €q 

--dc .-^. E 

rrp dr - 'inu, - RT 

(c) = 0-{)" 

E4 |.24 

'IrE .&dta!e of thh Delhod is thal, since evcdl values of Er @ cal.ulard, ev 

chege in th€ Kn tica of the degadation qoul

o la@ wU Mth orha licBnre !du6. Howvd, this D.thod do6 EquiE noE the 

on. h..ti!g ntc, &d tbu FoF thm onc 3mpl., which ould €N uellai y in $e 

Elrcid.tion of Er is quitc sinple by oawa's mcthod'roar tMed s "isonveîonal 

m.thod" which t e dl.sion ofDoyle's t.chniquc sd preFnrs th€ added advdtag. 

rhat my ch6g. of n chaim is obviou! by chdgcs in tlD slop.s of ln. lind al 

djff.mt .otrv.BoN. Hovwd, bdljpl. hc.lir8 dLs icquie ev.ral @dq ln€Efoa 

D6sibly intodwing mB. Sidplified cqution !n r appuimtioa appli.d fot thc 

cdculdion of kiftlic pamel.a, is giM bclow. 

dlogP/d.l/I =0.at7 E:/R 

E4 |.26 

PIol of lo8 p vr l/T for ! sivo yalue ofo giv. . stni8ltt lite, sloF will siv. valu€ 

ofE. 

Iunlrmorc, caLutdting r y!.lu€ for A k 6thd compl€x dd lndine "n" Equies. son 

of rrial-dd{tur pMedw, 

Anoth.r p@.dw, thlr of coots snd R.dfd, rD b.8in in a sinild tl]sa as $al of 

Boido.a !t Hovqq, in this insta@, .quriou e 6ied out in t@s of ! e. 

st njng with the sllldard nre equlioB (l.l ed l 3) ald irt SIdnA 

pda 

I (l-oJ' 2 6 

leads 10; 

For \ alus of a : O l. one cd nesled o) md hiSlt cm in Lhe *nes to yield 

d_ ARr:lr _ 2Rr le-.. -, 

pE. \ E. l 

Conbining lcm lads lo 

. " . r,m)(. tnr) e. 

'F-l.o..ll'Tl-- 

Using &. 1.29 il b evdid€ th.t plotring ln q/Tr vesus l/T should give a lin.e Fsult. 

lh. slopc N rmply t'R baause. at snalld or tor n=4. 

should b€ c$dtially conskrt. 

66 

Eg. |.27 

E4 |.2E 

Eq.1.29 

- ARI- 2RTI 

ue Gm h;:-tr-=pE. 

\ r, ,r

nt Coars &d R.d@,8 .pplicd thh n iiod io th! d€Sradalior of PIIE wilh 

ettufa.tory Bults. Th. dara plot.d 3hoe ! liod Fspo4 but th. L volus re Dwh 

low s @mFred wiih the Hobwitz/Mctzga h.thod. Thi! nay be due lo lhe difr€En 

mathardical terhe s irwlv.d in bolh m.thods. 

O!. adsltag. of tbis hal'od ir its sinplicty ed 4y !ppm!.h for dlra udlizstion. 

Howd, caulion should be llld wlrcn us,is this pl@dm siM @!t i! limit lioro, 

s@h a fldl a od m cb,n8. of mchaim, appli€d. Ove$ll, ihis technique wodd 

probdrly be stul for obhining pr.limiEry v.lEs foi ldnctic pm.i€rs! paniculaly in 

0E 6ly sLgq ofth€ degradalion. 

Ki$irga !0 ssmcd thai msimM uciion Bt coftspon.ls to DTG ndim of TGA 

cw. dd equally applies io both I' ed ns odd scdoN. Ilie equiion Bed fot $e 

€siitultion ofr.inedcs p€imeleB h giv.i b.low. 

"1;;='[;-o-"r:']-[T) 

.f Bl . fRAl E 

[r;./ LEI Rr. 

,_"fra"rar)l=6a!. 

L (l -dif I RT 

Eq. l.l0 

wh6 P = b€dbg 6te (X/mir), ,{ = p|lqpoMli.l h.tor (t), E = actiEtion ade/ of 

0r @rion (U/ool), x = univ.Fal Gd CoNant (8.314 J,t!ol-K), r- = t opsale at 

wnich rbe ditr.mrid wighr los cnc b al a luihm (K), t = ordd of r@rioa q = 

@w.6iotr or dicred taction. 

Ti is wiglt los at DTG tMiDd of TC-cw.. For ! sitrgl€ fir.1 orda @1ion whetr 

n=l, the Xleilsdt €qBlion cd be Mitt n a 3uch; 

Eq l.3l 

Actiwt o! mr8y, E, w b€ esdmt€d fion th. slop of plot of ln(p/T.r)vs uT. &d 

.xpoMlial fa.tor A &06 th. irt rc.pl. 

T!€lc &d Da?t a twit€ th. tsic Arhcso6 .qutio! in rens of &np6dt@ sd 

rin.. Then. th.y t€aruge &d ralc th. logdilhn l4ding !o, 

E9|t2 

Asdn, plofting F v6s l/T yields . saaighl linc wilh slopc PFFrtiod to q dd 

iitcrlpi Flal.n to A. T!. aurloB h.v. applicd this Delhod 10 degradt'tion of vdioN 

61

polycdbonales eith s@ succes. IlE ea!. of applyine ihis t@hnjq@ €ncoulg.s rhe 

Fs.Nh.r to m€dre r€l@ of Er 

Now mod.m lhdal ismn€nL e cquipp.d eilh $n!e dd hclp a lot in calcuhnng 

thc tinctics pameteR Srch $n*N3 @; 

. n'oddLireris 

. Model netjrdi€ 

. Adwed Mo&l &e kinctiB 

tro odd kinedcs in rhe stanLrd soft-\'@ opton bes.d o! or. dtnMic cwe, u.s 

sinplc nathcnati.s to delivd a s.t of kinctic p{eele6 for fimher elculation of 

sctivnioD er€t8y &d ord{ of @tiotr by $e method of lcast squ6. ftis te.hdqu€ is 

valid only for simple raction but wng foi complcx re5.lion. 

vy@vkin tlesig€d Mod€l Ee ldn€dca (MFK)2'r for the d€t€nination of kinetica 

pam.G6 Ging TGA,/DSC .lre3 ed qa bed on de fouowi.g two alsmprios: 

l. Th. a.livalion .n.$/ is not dwF @nsl@t, but @Nlant oily for a 

po.iicul& @nBi@. (a) 

2. 'IlE Arn@iou cxpE$ion for lhc r.Dp.Etrc deFddde letaid ia 

Eq. l.3l 

dc/dt i! nle of @tion in i', ko is Pr.4por€ntial f&lor or rat€ coNlanl al innnie 

t.hp.ntw, Er is &tivalion 4ergy in J molr s tundion of onvesion d, R is gD 

@Btor = 8,31 J ml'' K', T is splc t opdatlc i! K c is otrvdion of Faction, 

f(c)or s(a) @riotr 6odel ard N is ordd of eaction. 

Th. i .gEl€d fom ofthe 6tc eq@rion ha lhc foUoeing appame: 

I.e(d) = ko.Rli/qd)€s' rmr Eq.l-34 

Thj! .qudon cd be sed ro calculal. thc .ecialed lcivaiio! .nerg:/ Ea for .lcry 

@nv.rsioD if or 1413 dyruic n su.mtt with diffmt heating ni6 @ availabl.. 

To ue applied kiretics Ginulaiion. @nvcsion plol, iecoovsion plol). dris .eq 

68

fomulalioD cquircs no knowledge of the Eaciion mod.l (f (c) d e (dD. 'ftc 

infomation le.ded for lhe applied tin€tics is inplicity inclu

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E4

Chapter 2

Etp.ritudol 

2.0 EXPERIMENTALDETAILS 

2.1 M.terials and M€thods 

Aral9ical s8d. reaedns pNhed fNn SigmdAldrich wre N.d ror tlrc syn0.sis of 

th. p@us$ wiilbul frnlhu puificllios {d dl €xperim@ts w€r€ p!.fomed in air 

ltrcshph.a. All otbtr slvoa s@ p@h!s.d ftom E-M@L BDH ed kb Sa ed 

rw u.d a sulpli.d. All srnth* wc Frfomcd uder ultlenic iradiadon ains a 

20 lHz ulF.sdic gdcnto. M.lting poinE 9e d6uEd vilh a Gallc.(mp 3A-3790 

.ppEtB. El@@tal a!,lys (CHNO & Zn) r@ pc.fod€d Bing a CHNS-O Fhrn 

EA I I 12 $olr%r of Thmclelror &d e Alohic Ab$rpIid A$llzr (GBC). FTIR 

rp.cEMr we @rded with rhe FTIR Nqu 470 of Thmo Ni@1.1 uing sfi 

M6sry ddisn.d for ue wilh nEfro Ni@Ll\ AvardR dd NquR Fouicr 

t difom infrared (FTIR) spetrcm€le'!. H NMR .trd rrc NMR sFcrra w.E mordcd 

on a Brulcr 300Mgz NMR slecFon t r ii M.OD, C6D6, CDCIr sol iotu at Mm 

tcmp@lw; th. MeOD, C6D6, CDCIr 3ig!.h w@ @d to lock the field dd all 

ch.mical shins bp6) @ giv6 rchliv. to Gll!futhylsilrlc (IMSI Snd. crFt l xdy 

Ardysis lc hniqE v6 uscd for bol6ul.d *lenE &alys uing a @mpurd 

conlollcd $tomlic dift'&lonetd st 100{2) K wilh tutrcbrcoatic Mo Kd ndi.don 

&d fic orcgs s@ ta!!iqe, $,nich h4@ th. Bdeg's egL, 0 &d hrcNity, l. for 

@ch h$ Fo.clion. SEuctw EEMdI pbc.dw 10 $lve n 6 a@@dy 6 posible 

s don by EfriDg llle position of don 0eugh altomiic eftEe b€sed on l*t' 

sq@ h.thods. Ili@al studis srd d.conP4iiio. Patletus \^@ sM'.d w

2.2 Genelsl prcc€dure forsynth€scs of metsl 0-diketonsa$ end 

adduct complercs. 

Synth@ of o.ld 0niketo!a16 ww @i.d out by tbe @tion of marl !.lL sucb 6 

chloddca, niiraca, iulphat s, dichrcmtG etc,, with q!tupri.r€ douls of cpetivc Pdikelorcs 

or monical $lutiG of P-dit too6 in a 250 trrl dLmcycr ilal. 

Amonicd solution wd pepa&d, by nixing 3.0 g (0.03 nol) acelylac.lotr€, 12 nL 

disrilled sat.r dd 2,4 nL of 3? 7o amonis elution. Ilt @ntenls w€F .xpoed lo high 

incGiry ullso c wav€s of A€qdcy 2040 tHz itr & ultrdsonic bath for sboul half d 

tou ro *v.61 how, deFrdins upos rh. lde of m.lrl ed piikctoB Solid mN 

vs $D6dt d oui nlrce4 @b.d *rchi ti@s wnh ory@ic elvat ldd dticd i! oM 

at 50 'C. Thc dricd prcdu.l m puifed by dislvitS in $itall€ orsdic solv.lt ud 

pLc.d in t!@r or .t oom temFntw for crFllliation. Using this 8.n Bl Foedw 

wdal of i.\c knoM as Ell s n w netll orgeic ompla* ww pFpd.d 4d 

chd&leri4d lo' their sructue ed applicslion. Chd@t@slic pam.t ts fo! 1he 

synih$s of.ll compld6 @ d.pict d in Tabl. 3. 

86

t 

x^ 

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;t 

x* 

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liI 

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6 

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6 

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3 

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I 

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4

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t 

! 

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SE 

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eq ;3 =9 

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TI 

EEi i EEi .F. 

:-e ii: 

3 

:! *E 

n Et 

ae 

*E€ 

d 6 

$ :- E r g ;:? EE F:i 

3 I I f, 

! 

E 6

? 

a 

E 

E 

I 

t 

$ 

FA 

ie 

lir x 

I 

s 

d, 

I 

,9 

r

(J 

p 

E 

t 

d9 

!!; 

ctE 

g 

E 

6 

I F9 sa 

Fg 

53 

\9 FO 

€9 

R 

EE 

!ai 

j 

f, I FI 

:.! 

>5 l{ i3e ii l! 

li9 ;e 

:r. 

a 

I^: .: 

=t! II + E.i !iE 

,!! 

! 

I 

! 

.: 

:6 ! 

+i 

:--a 

q 

3 

a 

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J9 

6

x 

o 

9. 

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6 

5!F 

F3 

3U 

:s 

efi' 

f 3 I Ea 

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.s.s 

-; =.E R ;3A 

! F 

a-i 

fEE 

.j.9 

i 

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EEI=; 66: 

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g3 IÊ ;l 

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vl

2.3 Single Crystol X.Roy Anrlysis 

siagl. crylol t+ay atulysR 

Int Biiy data of M fr.r., (r{, and M (thd).lr0-r2t Cmpte\6 we€ ollecred on a 

Sids Snan CCD l-K a6.d€t6tor dilnldoncl.r.' Daia rdedo$ ME Derfoned 

NiDS SAINT- 'If!. sEenE 6 $lved by dircl mdhodsr ed Efincd by tult-marrix 

l€an sq@s d Ir lsing lhe SHELXTL-PC pek ec.r The irttuity d a *irhid de e 

drge 2.63-24.99 wG collsted at 291 (2) K. A total of 2601 Eflstiotu w.ft Borded 

of which 974 reo.crion! w.rc obsred on fic bdis of I>2 s (l) Tbe final I md ,R, 

s@ 0.0322 ad 0.0%3. resp€clively. 

X-ny silelc crFrrtlognphic dara rN [Cu(dN4(OCOCH)(Hro)4 0l) ws @llet d 

or ! K.ppa CCD diftlctone&r al 150(2)K sins Mct" ddiation (0,71073 A) in thc 

tn i! ma. of 4.1| to 30.090 otr a cryshl of aptoxinale dindioN 0.3 x 0.1 x 0.2 .n. 

Dala w€r€ @ddr.d for Inr€dz, poleialion md lbsorplio4 refin€D.nl ws by i!l- 

nahix leei'sq@es on rg. The ldeest r$idu.l pektble ws 0.s42 dd 4.903 eAr, 

The Dofeur& rtn&t$ of lr(eac),(OHcfia\H)h Gt rc d€rmin.d Ni.s a 

Botq AXS SMART APEX CCD diffo.tonEtq at 100(2) K sith nondhsmric Mo 

Kd Ediadon ard th. o6.ea sce &.hriq@. Th. eir .ell wa dermircd lsiry SAINT+ 

1 od the data rcre coreled lor absorption using SADABS in SAINT+ I .The srruciue 

M elved by dircct D.thods md eiincd by full Mnix lesr squ@s agaiisl ts wii\ all 

Efle€1io6 uilg SHELXTL 6. Re6lcdent of& .xtincrion mfffciot ws fobd ro be 

i6isDficaDt. All rcn-hydrogd a,rotu B@ Ffi&d eisotropicdly. fte wcidrcd R- 

f@1o. wR ed soodn* offit e bad on l, convorioral R-faclo6 R @ b.s.d on F. 

*id aser b *rc fo. n e.rivc ts. The tjtl€shold dprssion of ts > 2d(d) n uyd only 

sinsre crFrar difli&tion daia for $e tzn(aca4,UnmH, 

(16) ws collecred on a 

Brukd AXS SMART APEX CCD difticloield al 100(2) K sing honGbrcmaric Mo 

Ko EdiarioD wilb om.g. s@ te.bniqE. Thc uil @ll vs derEmiD.d Bing SAINI+ 

add d€ d.r. *.8 e@tc

sinale .rtstal tat mdltsls 

Efr€d uisoiropically. AU hydrcg€n atotu w.e placed in calcdal.d positioN &d were 

Efn€d wirh e istopi€ displaene pdMeld 1,5 tim.s (nelhyl) or 1.2 dmcs (all 

oth6) thll ofde djaent srbon !toh. 

TlE nol.culd sr.lcie of lflrde)zn llt \19, vu detdfti,Nd by Single crysr.l x-ny 

odrsis uinB NoniE rapp! CCD diit_.cloncLr ar 150(2)K with gBphite 

rulchrcmdkd MGKa Edilrion, (0.71073 A) in rhe rh.u mge of5.68 lo 3O.O3o. on a 

crystal of EppbxiDql dinensions 0.35 x 03 x 0.25 hm. Dau were corcct.d lo! 

Lomq poleiziion ard aberyrion; Efit@.ni @ by tuU-mabix l6t-sq@s on ts. 

All non.hydrog.n.lm3 $e r.fircs ebouopically! hydegd alom w.E included al 

calculatcd posirioN. The hgest rcsidual pcalctole ws 0.521 ad -0.844 .. "Ar 

Moleulq slnrtu& of 2,7 o, ,V, fi$c?&/ (20), ws der.mined oo APEX2 Kappa CCD 

dift..loneter sing a er.phiic nonehrcmtcr wirh Mo-Ka-radidion (t = 0.?10?3 A) 

ar @n |cnFEturc. The sEucrrE w6 elvd by rtiEd mer[ods dd rc6n€d by 6rl. 

d5trix l€Nt sq@$ h€lho& {SHELXL 97), , On qll F, dau. Nor-hydogen aroms wre 

Gf!.d 4istropicdly h.ving & disordd, whd6 dis.d.rcd aroms wE inctud.d in d 

i$tr.pic. TIF Hdohs v@ posirioned gomctri€lly on alt m€thyt csboo arons uing 

tbe techniqua D giv€n in SHELXL 9?. 

Ihe horeule stu. r of1@ @q), (Hro)rlctl (2r')w detmincd 6ina. Risa*u 

AFCTR MNury CCD diff:a.ron r€r wirh gr.pnile mo!@hrctured MoKc adialion O= 

0.?1069A).. Irr strrctue M solved by sing dir€cr d.thod., Sirg? L0 ed r€fincd by 

Sh€H97. e Alt dE non-hydegd atons wF re6n d sieiropic.It. IX. H dons 

atlachcd lo oxyg..s wrc Elincd horopic.lly, Othq hydDsen aloms were l@i€d ar lne 

colculatcd positioG sd refined a dding abms. 

Th€ molccdd sfstuE of ICul(DOH)rN-(OtCrzl 123) rc dcrcdir.d using a 

tugatu AFC?R M.rcury CCD dift{ctonaq with gaphite non@bro@led MoKa 

Edhtio! (I= 0.? 10694),. Ile iructw ws stved by uing dnel helhods, Si!97 i0 ed 

93

Flptiwhbl Pan n Pbt4e O, C.tuni.s 

2.4 Pattern Plating On Ceramic Substrate 

C-tmi. substrates s.E us.d fo. padm plari.g 10 rDle il suir.ble for gs ssing 

dcvie, Two |eh@logi6 w@ usd for Sold p.nd pladngl om is Itlical rcB hybnd 

te.hmloSy iBluding Sold i.* 6 a p6{.. Th. sond oe, in which fi6dy se 6ad. $. 

.chmh slbstlare condlctor by oari.g !.ry tbin filn of copFr usinS indigenous 

ftthodology and ch.dic.l fomnlatio! (Se apFndir-l). The idea b€hind using two 

Ddnodologid w6 ro f*ilicr. dE EFdhcr ro eler in avlihble nelnod. Hybrid 

t. n.obgy is qune.fficicnt but €rFisiv.. @ rhc coaary l!. ch.mic.l barh &posidon 

mthodology n simplc, cncalEr and pbve to b. b.nefi.e.t for th. rcseher workinS in 

tbe gas sen$r field, The followirS flow chari (FiguE 22) shows how d. €onductor gold 

patten ed fsbncatrl on th. etmic aubltnte by oaling v.ll-adhercd lhin la)€r of 

opFr on mrondulor emic sub6[ar.. 

rt 

h.*. 

- 

c*id,-r.b- 

J. 

E _l 

c'['f.t 

cr-.-- 

Fl3rrc 22: Th. figu€ illustrales now $. copper/sold palt ms weE foltrd

Eq{nM a! Patu^ PIdn$ On Cc@nat 

Usioe abovc nalodoloS,, vdiety of gold patt n plabd c.mic subBtrat r (Fig@ 23) 

*@ faD.icar.d fc t* dlpo6iti@ of rbjn 6l![ .!d dpl@ dE 3!ir.bb Fnd rlich @ 

b. !$d a ga 36ing &eic. .rrcc6$rlly. 

!---= 

a 

l-l 

tf 

ET 

E I 

Fho|! 23: Sod Tt?icd Orcold Prn tu Plsrcd C.fuic Sub.lr.rs, 

= 

2J Thir Filn DeDoritioo (UAACVI') 

In th. pcsnt hrk w us e t'|rr@ni. Aionid (Colc PrlF), fnild rirn slfd€sip€d 

dllivdy systco (Fite 24) io t@lal. &orol. ed spny.d on r.rLd 

3ut6r..r. .| $inble &co-I$itid reEpq.llE. Quarir.liE el'ni@ of pre|llw 

F.p&d by dilelring in a suitlbL slEor s @nri!@Bly injc.red Oed . dEd 

vdve ed iroifeftd fmt lrcn pbton pump to tu ultrenic aronia lpny nozle. Tbe 

tr@le proded d ffil i! e .v&ut d qu{r .trDbd. D. nigh Friry aiuoeEn / d 

oryS€o a ceid g6 drs th &twl b . *lFr'e pl"""a "t rt" to,to. ot " "n,"*. 

b.ded al suiuu. renpeduE. A5 rb€y !s ovd or coru ilro @trta.t witb ! lelrcd 

subsr.te, th.y Ea.t or d..ot!p@ fomirg r @tid phe ed @ d.posit d olro rlF 

shd.t . Tt! $b6r€i. rGqGItrlE is oiri.d ..d @ intb.oc. shal r.stirs wil t& 

ple TtE we!.c gB g@ 4eed rrd mpp.! ir liqrit rirrogo rrq, 

I- 

! 

a 

a

nguF 24: UAACVD Ser-Up for ihin nln .tepGirion 

I\i,t Fibn It positk, IUAAC'I'D) 

TIE clj@dy uscd UAACVD el-up doca noi EquiE ey sleitlir€d .rd cxpc6iv. 

.quip@nt, allows for contiruous prlducrionlire meuf&rwiog, dd elininare lhe ue 

of cxFsivc. cnvibnEd.ly lDntut d lo:ic pl4so6. UAACVD t chricue off6 

enai! r&dr.g6 for d.positirg thir tiln of €@ic mt riats conpnsine of 

Mopaniclc!, srch 4 ue of inerFnsile pEumn, provi&s bigh d.gF of 

6bpcii@ @Ebl, ruit uc for co i.uolr produrion, deF6n on a wi& chok of 

subst ar.s, p@i&.onrrol ol @vd8e e., @rsl.r

lhin Filn D.pos|ld (uAAcvD) 

gs dd @grtirc Fssw wh@ it d.cobpos ro dclal or tutd ond€. The 

d@nposition rcldil. product w @llcctcd in liqqid rirrogd cold trrp b avoid 

T.bl.r .l Crewlh @ndiliod for th. d€Dosiion ofn€lll oxidc lbj! filn by UAACVD. 

x 

91

251 Ele.trlc R€sltt.nc. D€{suremcnt 

Elciktl fttilr@ n BuMl 

The .lericd cisrivly trEerctut of ri. efuic oxi

Elecri.al rcskt@e @at 

T.bl.F 5 Rautvity of ZnO lhin filn (0.8 Fn) d€posiled on diffftni eold pattcn 

plat d crmic subsit r.!, 

aFolFn nsLd*it!6btL 

wrl - Crs..do..l AB 

2.5.3 Grs SensiDg Meliurem€nt 

oro) 

I L05 15.37 0.3 l.]6.1 

T 

13.4 t3.? 0.8 t.26X 

3 I Ll4 0,3 1.910 23.79 

0.789 0.3 1.18., 

20 24 0.E 

25_6 5.54 2.0 14.62,5 

s t8.85 t7.36 0,3 33.2KO 6.106 

The d.pditd thh film ws pl&e

c6 Stui^gMdMl 

Ilg.E 2a: Picrdial vi.w of eDDly ur.d b finy G.. siog Fqaty of tli! Eto 

tu)

REFERENCES 

L Sicms, SMART ud SAINT- Situ6 Aratlrical X-ny i.srnu.nrs Inc.. 

Madisa Wiscin, USA, 196. 

2. A. Alro'J@, M. C's.3m, C. Gi@!@, A- Cu.€lilrdi. J Appl Cryst.1993, 

26,343. 

L c. M. ShcldticL, SHELXTL-PC (v6io! 5.1), Si@d Ardjr{.jt bsrumdc, 

Inc., M8dien,wl.l97. 

4. BNI@ Adveed X-ny solutios &t/r'a (v6io. 6.45), Btut€r AxS rnc., 

M.di!o4 Wi*oBir USA, 199?-2003, 

5. Bn*d Adr"n@d x,ny Soluriou SMART for \yNT120oo (v6ion 5.628), 

Bdkd AXS Inc., Madis., Wieotuin: USA, 1997-2002. 

6. Bnrka Adhc€d X-6y Solurios SHELXTL (V6ion 6.10), Bruld AXS Inc.. 

Mdbo4 Wistuini USA, 2000. 

7, Btuk{ Advdced X-by SotulioG, SAINT (V6ion 6.45), Brukq AXS Inc., 

M.rtiet! WisNi!: USA, 1997.2003. 

8. (.) Bn*€! Adveed X-ny solulioB, sMARa for r,ltT2o0o (vdsion 5.62s), 

Blukd AxS lrc., Modisoa WislNi,! USA 19?-2002. (b) BruId Advd.cd 

X{y solutioG SHEIXTL (veuion 6.10), Bruka AxS rnc., Madi$n, 

Wis6ir: USA, 2000. 

9. G. M. sheldri.k, sHEtx91, Ptusak fu th. Refa.ment ofctr alstuctuer, 

Unjvdity of coninS.!, c.!fuy t99?. 

10, Alrom€, A,; Bul!, M. C,i Camatli, M.; Clsamq c. L.; ci&oveo, C.i 

GuSlieli, A.; Moliimi, A. G C.r polidori, c,; Srfgla, R. J Appl. Crr,t. 

r99,32, 115n19. 

ll. Cl.Ee W, !4cta Crys| t{''t,C43,1E9-j9t. 

l0t

Chapter 3

3.0 RESULTS & DISCUSSION 

3.1 CoDptrrtive Study of Syothsis Rout. 

TLe $nochenical L.hniquc involve mixilg of $. E&ianl5 in th€ poFr Dold ratios &d 

hs s cdSe in tcms of simplicity, lih. ed hid yicld oYer sLtrddd schLnk lahoique ibr 

lbe syntheis of honolcFic, hct@l.plic ed honobin tdlic onPl.x.s Schlenl tub€ 

r@hnicw als n.cds sonc sEinsqr @ndilions swh s drnPe chdicols' in n g6 pH 

@ntol ed EcoM i.chdqqe to get th. d.sired Produt Fot conpdisn berseo lhe lm 

Eerhodolosi6, v.i€ty or @oplex6 likc O),' (9),r O1),': 06)'r@l)'6 (22f pEPsed 

son@h.mic5lly dd conv.nliotdl $hl6k tub. t.chnique e Presni.d in subsqu€nl 

cDcL + 2ciH,o,H + 2CH:COoN! --Tll*6P 2NaCl + cu(cH,cocHcocHr, + 

c(cH,coo)r.aH:o + 2dmrcH -Mmi tc(dtuHxcH,coo)Il:ol' 

c!(cHrcoo).4HrO + 2dMH 

din..H = (cHrlN,CHr'cH1 OH ) 

zi(crH'oir + N(cHj)r.cH:.cHr oH -ffi 

bYsdum 

zn(crH,oi) + NrCHrr.CHr CH}OH 

2CI{TCOOH Yield = 6OY' 

2HCl + Cu{CHTCOCECOCHT' 

,0}) I h6, aq! 

t02 

+ 2Hro 

Yi.ld = 30oZ 

Ic(dDtHXCHrcoO)n'o}+ 2H:O 

z(crsiq>.N(cH,l.cHlcllloH 

Yield= 75 % 

zo(c,H,o:! N(cH:r.cH, cH: oH

N(cHrcoo!.rH:o+2N(clr,.cH:.oH)i rc**#Er+NltN(cH:cH:oH)J:(cHrcoo)'4H:o 

tdio'i'l dini[!iol 

NirCH,COOr.lHio+ 2N(CH, cHr'oH! NitN(cH1cH:oHlD(cHrcoo):3Hro 

sncr:+ 2crHroJ 

Slirsd ov@idt 

42.r, + 2(cHJ)'s(dm&D -&!q!Hffipll!' Iznr(cH,)2N.H:.cH: oH)I + 4Hr 

!7d. , 7.r{.LN cH, cH, oH ---4)ll.l4F:5j_' tznrcH.r2N cHr cH: oH - 4HI 

'.. 

hLh&ol:mtdvtua0 

cwlat *c*rqgdl 

S.bd.! I CdpeiM oronMtioml S.hlenl T!b' tnd sseh'Fidl Tcl[iqu' 

Thc.bovc s.hcDttic @bPdien shos cldlv lhlt the e of en@h'nic'l lelltiqe M 

foEd lo b. b.ncfici.t for dF strnh66 of wictv of neltl oreonic @6Plex6 Wc hav' 

cxteNiv.ly €xplorcd &e e of @ino.Loxid€s, o'dikeloml4 dd cdborvlates a lisqds ror 

th. pEplttlion of such q?. of @bPlde ttnt Fov.t to bc g@d P@lmr for UAACVD I' 

cde of N,N-dn thvla.ebnidc @d triPhqvlphosphin€ liSEnds Fsulting coDphx€s' ie 

D.tsl @F is wdpp.d iD. bl.nlci of o4eic tigtlds thu hating thc coBpl€r eluble in 

Bosl coMon ore&ic slvdts ed incFdins ils utiliv s CVD pEdsr' Ie sFth6i4d 

@opl€x.s sw ch@teriz.d bv vdioB phytico-lult'trcrl t€chniqws' such 6 np' IR' 

thmogrlvimeEic sdysis, hultinelry NMR 8d sinrle cry36l x'6v &tlv$s 

103

3.1 lR Studies 

So@ iblolldr R .tcorption t!qu@i6 of M{a@)i .nd M{IML @oplq6 e 

rDr.scDt d in Table 6. ln meol &aylaeiotut [M{&&)i], (r'9) ih. abslPrion bfld 

d@ to C{ d.l c=o bo!d! fall.t 1608-1566cm I anrl1552'1500 cortsp€liv.lv on 

dptcxador ofs wilh oelal Gw b€rds !t ??2{64 .rd .t 459 _650 d r.pF! dE 

lo ring tlefotution and M4 absorPtion rcsFctivelv. Other bd& c g 

' 

Cltr dcg.!'rat 

dcfo@rim n l4l5-13E5 @_', cHr srlmelric dcfomrrion !r ll?0-1356 dn, cll in 

pl& b.ndbg !i I 195 - I | 90 d r, CHr MkinS at 10221004 cn" C-cHr sttltchitrg dt 

937-91 di ed CH out of plae tF!!di!g st 800-??0 cm ' Edis u!.ff€d'd bv lh€ 

TrbLr 6 Conp&ien of ch,trt risti€ IR aberltion fi.qMci* (.mr) of vdioB 

M(*&)i snd M (tbd\ @nPldc. 

r5l7 

t52t 

104

Ih. absorltion b&d du. to C{ 

ln@tal.Enmethyl lpplh.diordr. [M-(rhd)"](1F13), 

ed C=O borrs @ E@rded !t 1575-1550 c6 ' .nd 1525n500 m r F3p@tiwty Tlc 

bonds in tbe ms. El3-788 dr ltd helow 600 cn'@ dE to dng.Lfodstion md 

MO shctch Fspstively. Other bard e.8., CI|l degwntc .Lfomation .t i4l5'1385 

@'r, CHr syrDeEic dcfomarion .l 137G1356 c6', CH in plae boding al ll95 

ll90 chr, cHr tuking ai ll44l0l9 mi, c-CHr stElchiog ai 937_921 cn' dd CH 

ou1 of plam bedhg at 971-91 I co r tui$ uatral€d bv a ch@ge in mctal 

Sme inpod.d IR t!q@ci6 of naly sy h6iz.d oDPos& @ 8is 

in TabL 6r 

TibLts 6r Asigrm. s ofinpor'dt lR-absoQtion iilqu.nci€s of new@npowds 

having sen ral fomul., M(sd), (LD, M(&..! (Lt 

qe4[!4!-L 

t4 l5 l6 t7 IE 20 

The evid.nce ofih. fomaiion of tc(doaexoA.Xn o)h 0a) cs b' cxpLin€d on th€ 

hosis of IR absrption frtqu@cy datt ln IR snrdv oxvgo ofdm&H i! lrlo 

bonded |0 a 

$!t€t nol4ule drclgn !t-bond, lo cdnon dd &d l*o @pp'r !1oms, aberb !035 

't 

@i whcFs 6e -OH ir Mcr and ol@hol abcorb at l24o cm ' This decEas' in 

ahsrpd@ nq@cy i.c" &oB 3240 lo 3Ol5 cd I Eflel! brideing oxvgo aron Th' 

als.rDiio! of tfllining inPortant b€Dds $ch s C'N sl'ttchilg Acqumv ofdncsH i3 

obFd.d .t 1l?91135 cdr, svmeEic alt t h of C& !&rch€d to @p!er in thc 

'ive 

105

D@bcad rinB of dm&H app.s at 2953-2877 cdr (For conpaien, rh. srm.tri€ 

Cth strlrch spFirs .r 2970 d r for cycloFni.rc.t ), CH, sEttching ab$rytjo. bdd of 

eeLlc wd oben.d 6t 2825-2?83 cn', C=O lrdching frquency ofacelatc Itoup was 

obePed at |791-1771 cm , rbsorDtion b@d! du to M.O bond! oPp4d al oo7 Lm 

lrd a vcry brad aberprior band at 1700-1500 cD ' is d@ ro P!!s€M of non hvdogo 

bondcd ft@ OH grcup of wter in the complcx, All ih.e ch&&terbtic vibnliondl 

6Eq@ncis e in lin. vith the struciue dalyed by single crysld x-dv Mltsis 

In IZr(@)r (o)rl (lt, rhe N-H, fiE oH sts.hine; N-H our.f-9ldc b.ndins c'N 

frqu.nci€s w€R foMd ar l4OO cm , 32o8 cn r' 84q_770 chr ed I lo?_lllo ch 

EsFctivcly, indicaL pltsfte of @imdntol C{borvl sltdchins dbeQlion buds 

for rh. &.tylacaorttc lieand sd nqly fomcd M-N &d M-O boDtL, lbtqb ar 1580' 

917 cm r&d 650 cmr Esp.ctively, indicatine Oc stNctrc of m.tal conpl.x 3 analvsed 

by sidBlc crystll x-ray &alysi3. 

cL@t .isnc vibanond nEqudcid i.e., C-c, C-N dd cO of odpt.x l(dtu)znll! 

l2ll w@ obkned lbsorb at 883 cmn,1064crrDd 1466 cntrcsp€ctivclv Th€ trc 

ns bands lom.d du to Zn-N ed ln_O .pP€ed d 63t ed 458 cm r' sho$ rh' 

Som. imporra lR vibmlioMl llequencies o'H dd c'N for [zn(@O: dnaeH] (16) 

.pF4d al 326S'1240, 1252- l 194 cdr indi6t. fie !@c' 6f ethdolsune Als $' 

syn|mic and etl3yreeEic CHr vibBtioN obs.

.low 590 cdr. c{ strrrctitrg frqency of eelate eloup m ob.dcd al lTlt @r 

indicaiB th.pFsnce ofboth eeunirl€ dd ac.iat grout in lhe @oPl.x 

Thc no6r 3islifi@r lR .b$rparion bards in onpld tz(@b (HrO) , lcl (r9) b ltE 

pcence of beds ar 1528 dd l57l cn r for nchl bondcd C-O ad 1410 ed l!84 cn l 

for c-c ofe.tyl&.tonar€ goup.8 In.onpdien wih nlc.cetyt..eto@ wh.rc lhe lwo 

CO bohds give ahodd ptl&m at 1600 rld ltoo @j dd tw C{ botds giv. ! bod 

D6neF ar l450.rn 1260 mr This dec&& in @sp41iv€ sbsorltior n'eqEocies 

indica&s ch.tation of Ztsslon by &.lylaetodt gtolp. A very blosd b.nd at 3'100- 

l06E m_r B dE to *!rer noleul. pFhl in thc @Dpld A stre.8 b6td at 53E ch-' is 

du. to Yibration of M-O bonds. 

In ihc IR sp..uu of [Zn (Phr)q CL] OD 

lhc @@tic stdchirs vibtalios app4'td 

sr l48O cmr, $hile th. C-H oul ofplhe d.lomem .Pp.!red 5( 741 cm r' Anode' 

inpon&t b&d ws at 1433 cdl which is due to Ph-P srcup 

lR $srflion bsrdr in cs or tZ. (dm)d OE) e: wlk ab$plion b8nds at 294' 

2866 cri is dE lo c-H scelchios in cEi cdbonvl Sioup of acel.nidc shos 

3lr.iching d ltSl-15l? m N-o ffib d a.l@id. s al 14l?_138a o ft' c_N 

boldssr€.bandFnm.t lo2ocn' AbcorPlio!b!d3ductoM-N tPFd!'low600 

AU lh6. ch@t ristic IR vibdnoDd n!q!@i6 h.v. ben Nigncd lo svnth6iztd 

@mpl.x.s d. in agre.n.ni witb thc nol{dd sitlct!€s s detmincd bv single crvslal 

t07

3,2 rH NMR rd '3c NMR srudie! 

The rH NMR sle.tm of &clyleione b .onpliqt€d beaus of l€to_ool 

rautobqth.v Fmn rhc flative int 6ti6 oflhc sienal n b.oD$ cl@ iha! enol fom 

pt domiturcs in ile.quilibnm nixtw al rcom rcop@l@. Integaiion shos th.l the 

ni(w @ntqils 86 % mol &d 14 % kdon . The st ong .leshi.ldin8 of $e .nol 

hy&oxtl proto! is a cons€qwG of inu.Foleuld hydbgd bond fomtion The 

nugldic equival4@ of th€ n€thyl lrouF of the ool fom indi€l€s s Bpid €rchege 

of tb€ hydrogen alom b€twan two oxyg.os Thu &.tyl@tone gives five si8lal 

@n6londing to 6vc difcF DT.s otProbtu owine ro bolh k to dd 4ol fotu. 

wlEn uiylac€tone b chelated wiih the n€tal aiom the €quilibriu tunhd shins to*dd 

lhc @olic fom. Th. hydrogd atom ofrLe .@lic fom is rcpl&€d bv th. ne&l ion TtN 

ody two typ.s oI Proto6 de tt6.n1 in nei.l conpl€xes (Table 7) The 6ul1s d 'n 

lst€ene eponed dli.r lor sn(acac}.'" 

I! the 'll 

N]'& s!€Euo of t!. @tylelomro @EPlqcs 9'ltl6l9' ln' sisal oi the 

nethyl goup moicli.s appd in the exp4!'rd Fgion wilh tvpical multiplicnv ed 

'J aH, 'H) coqting cosbnr' Th. chenicd shin for thc mehvl Pmlon or vdo6 

&.tyl@totulo @mpld6 exhibil$ singlet it !rc @ge of 1 844'1 94 pPm, ohil' CH 

protos gavs singlet in lhe rdee ol52-5l2ppn Simildlv olhet li8.'qnds atrachcd lo 

etyhdon lo odpl.x.s $ch s 2-mindth6ol dd N,N dimelhvluin@Unol gave 

sig'ldl in lhc.xpeEd rcgiob tn rrc NMR lh. drgMd6 ol $e 'rC signal fdls in 

dp@t d regi@ Ite CHr ercuP of 4.tvl&donales (9'15J9) gav' signal at 2? 52' 

Tnis Mv 

2?.99. 25.0E ppo .x@F fd cmd.x 15 whct sigEal ryp'ls ar 19 l8 Ppn 

b..ttribut d to lhe two.thfloldin g@uPs.na.hed .t dos posidons The dbonvl 

grcup of &etyla€.todi. gav€ sigral at 191.19 19612 ppn Sinil&lv olher 

ch.E r.dstic NMR shitu Elar.d to .th.hed liS.ds Oabl. ?' 't!) fdl i! 'xPet€d Fgm 

affl a[ lhb dala dc.lc.l tlEl fic chcmical 3hiis 6sign'd to svnrh$iz'd conplexes N 

in arl€dclt wirh thc mol€cular strctu. .let mined bv singlc civstal x-mv analvs's 

108

t * 

* 

d 

E 

1 

e I $ 

-a 

;6 : !l; :1is 

r5 

'{'}*.1 

s, 

| 

T 

.*l 

.E 

g 

\Af 

+"tr 

lrr. 

.s.3 r. 

:i{I 

;i, 

:; 

o 

d 

.$ 

-6 I 

a 

,$ 

"$ 

r$ 

o 

'1r

e 

E 

i9 

F 

I 

I 90 

90 

-t 

v 

3 

I66 

t60 

N 2 

g E 

o 

I 

3 

? 

t 

69 IE€ 

2E 

!t tll 

: 

:.9 gg9g^ 

E I38 3E

3.3 Crystrl Structure Anslysir 

Crysral gruaw. Atultsis 

33.r structure Amlysi! of lC!(dnaeXOAcXH'o)1, (14) 

I}c c.ysrrl dd!, Efiftnot pdmctcs, sel.ct d geom.trical tutdcd snd mol€culd 

sEu.tw of(14) e shoM in T.!l.s 8,9 &d Figw 2? $pelively 

I.blq{ Crysr.l

o(5>c(7) |.23T2) o(r){d2)'N( D 85.34{t 

c(4!cu(2)-o(6) 

qa)-cu(2)-N( I ) 

o{6)-cu(2}N(l ) 

Cryeal Snu.twe Arylysts 

98.67(5) 

95_48(5) 

158.6E(5) 

Sym.rry rdsfomaiion ed to go@le €quivaleoi alom: -t, /_ 1,2.'t+l /2 

Flg{rc 2?: Ir€ stl@€lric uir of tCu(dia.XOAcXHrO)1, 

$h@ u..d in rh. lcxr ed tabl.s; atomic displ@64ts d al th. 30el. bvcl 

showins lhe lab'lins 

Alihough the latlico m b€ visualikd s bei.g conslruct d lion linking dimd ol 

fmlla tcu(dn&)(OAcxHzo)h lhis beli$ lh. compLxiiv of this noiclv, 6 the two 

nd.l sr.B @ auiL distinct C(t) ba ! foqt@dimlcd CuoN @rdi don sphd 

conprisilg one O, N-chelating dne, one O_bridgine dma' md a mono'tenhte ac'tllc 

srclp. Ite geom.try is a diirortetl s!!.t pl4M t

Crynat stuctu. Analt,t 

ftc bile aglc of t!. dm&H ligttd, o(6tsu(lFN(2) . [85.05 (5)" ], is cloelv 

onpdblc ro rhe e8l. h ompoud Epon.d'r [cu(ocHMecHrN El,t] o (l)_ 

Cu(llN(l) = 80.?0 (8)o. ed also i6 .obdr courePsnr: lcorcHlco:r,rdmmHhl 

81.67 (5f. 

ftc bond l.nstt cu(lFN(z) t2 0348 04) Al is comp@bl€ with tlte elosous 

dkra!€ b othd.opFt onpl.xes @ntrilirg dino.lcohol ligods.r3l5 seh c 

Cu(oCHM.CHTNM€,' [Cu-N - 2.052 (3) A; tcu(OCM.rcH]NM.r)rl tcu N = 

2 052 (t Al. dd ircuLOcH{CH,NMe,hh[Cu-N-206014rAl 

Wlil. ihe two d!@ liseds bebls siDildty, th. wboxttaa srcuPs 

do !or' Tn' &aaie 

@nleE.l on C(1) is bidcnlate add btidges th. two net l ccrtre; fie C_O ad C=O bond 

l6gds & disrircr [c(l !O(l ) 1.2922( l9), c( I !o(2) I 2391( l9) Al dd n is ln' shond 

CO eroup which is involved in $c loned, wcakq bndSine ini€etion {o(l)'cu{l) 

1.9a40(ll), o(2 )-cu(2) 2.1?s102) Al The s@nd soup hs'd oo c(?) is 

monoddL| *ith tsp@r 10 @ppd to(alcu(2) 

1 996(12) Al bur @8agcs in hv&og'n 

bondins with lhe one ofthe lani@ waleB to(5) H(7A) l97l A, o(5) O(?) 2844 Ai 

Clrstal St tct0e,1tubB 

FiS!rc 2E. The lani@ sEwte of {Cu(db&XOAcXHtOr, sLo*i!8 diGric uis 

linldng dtough bndginS n4tat goups dd a retwotk of H' bon& to fm polvmqic 

3.3,2 Structure Anrlysis otzD (scrc)h (er) (15) 

IF singlc.crysral x-hy struct@ coDfirms the sp€ct o$opic data Th' hol@urd 

3rEtE of (13) G shoM ir risc 29 

Flsut 29; Crys&l 3iructN of tzr 

$e 504/0 14.1, hyd&lpn .lon sphc d al ebltlry 

(a@), (.a)tl (1s) IlFnal ellitsoidi @ dram al 

6dii. only dE mjo. dield.Fd 

l14

Crtttal gmnr. AMIlta 

Th. sirutur. show tm type of dilordd: Thc .l6hol oxyso aron dd the 

'N lieand 

eh or€ h disrderd old rwo pcitios. Th. occr4dcy 6ti6 & 0 526(4) to 0.474(4) 

forthcOHsrcuptud l:I (lmfn€d) forlleee@ions IltG'@c4bonalomor€&h 

noi.ty {@ Fsri!.d ro b. nat eithin a sl4d.rd deyi.liotr of0-1, cdboo .roB C2 and 

C4 wE Estnined to bc ieitopic wirhin ! 3taffl"rd d.viatioo of 0001. sd tll 

disrdecd 6bon atoN B@ qlraired to h.ve th. s,fu mbotoPic displ&helt 

!€t@.t r s lhcn di$rds€d @ulctDdl5 TlE zift io hs a dinofi.d eralcdttl 

Seonetry 

swouded by lwo .4 mions ding s biddtlt€ Gdonor liSuds sd tso 

monoddtat eincltsol ligands c@rdi$ring vb rhe N tio@ in Eas pGition !o @h 

ot!d. A smsry of dt c4st ltosnPhic data sd e8rcodr pam.l.s fu (15) m 

Siv.n in T!bl. l0 ed *l4i.d bond ldgth dd egl6 e rcco'd€d i' Table I I 

I.bbr r0 crFtal D|l,r of lz! (@)D (*01 Gt 

ChHnNrOJn 

185.?5 

t00 K 

PN 

5.3009(7) A 

9.3?24(r2) A 

9.5074(12)A 

?3.149(2)' 

p 83.479(2)' 

76.56r(2)" 

z: 

I(000): 

I1>2{Dll 

5 

439.1500)Ar 

202 

0,50i0.05x0.02 

2.24" lo 2E.28' 

2159 (Rd = 0.02) 

4554 

Rl = 0.015?, eA2 = 

0.0866 

Rl = 0.035?, wR2 = 

0.0856

Cryttal Stuaue ,tmlts\ 

All hydregd alo6 q4 plac.d i! calculatqd pcitio6 .td w@ Efned wilh d 

isoFopic di3pl@ndl pd@e1er 1,5 (mcthyl, hyt!$xyl) or 1.2 tin s (all orhes) that or 

th€ adjedt 6bon or oxyg@ alom. 

Trblc- u SoDe impotu Bond l.igils tAl.nd uslcs tdcgl for(15) 

c0Alc(2A) 

c0AlHoA) 

c(2Alo(r) 

c(2Alc(3A) 

c(3Alc(4A) 

q4Alo(2) 

c(lB)-c(28) 

c(2Blo0) 

q2BlcoB) 

c(38)-c(48) 

c(3BlEOB) 

c(4Blo(2) 

c(4Btc(5c) 

c(6!c{7A) 

N0lzno) 

N0!H0G) 

o(llzn0) 

o(2!zn(D 

c(?Alo(3,4) 

q3^Hr(3C) 

q3B)-H(4) 

zno|o(2)#l 

zn(llo(lPl 

zn(llN(l)rl 

1.50r(9) 

0,9800 

1.2t5(4 

l.4l6(8) 

L352(9) 

1.321(o 

1.537(9) 

r.263(6) 

1.398(8) 

1.464(9) 

0.9500 

1.155(o 

1.5r9(10) 

l.5l2G) 

2.1210(t9) 

0.9200 

2. 99(15) 

2.109704) 

t.314(4) 

0.E400 

0.8400 

2_109704) 

2.1199(15) 

2.t27q19\ 

o0)-c(2Alc(3A) 

o0)-c(2Alco A) 

q3A>C{2A).C0A) 

c(4A)-c(3A)-C(2A) 

o(2)-c(4A)-C(54) 

c(3Alq4A).C64) 

c(28)€08)-H0D) 

H0D)-c(l BIH0E) 

r{ lE)-coB)-H0 F) 

N( r ).c(6){(7A) 

N0!c(6)-H(5A) 

c(6)'NO)'zn( ) 

c(6)-N( D-H( 

zn( !N(llH( lc) 

I o) 

H0 a)-No)-H( l H) 

c(2A)-o0 !zn( I ) 

o(3AlC(?alc(6) 

o(rA)-c(7AlH(?A) 

o(2)#rzno).o(2) 

o(2)*l-zno >oO)#l 

q2Fl -zn0).N( D 

o( D.ztr(llNo ) 

o(2Xl-znolN(l)+l 

o(2>a0INoxl 

N0)-zn(llN( I )tl 

125.4(6) 

r7.2

.bh! 12 Hydb$n bondr for (15) IA mddesl. 

Crylal Srtudue lMllsts 

DII...{ d(D.fl) d(rL..{) d@-.^)

Fisrn 30: MolRuld sEuc@ of CroHiLNaOZtu 

Crystdl Snrcturc A@ltvs 

ngre 3t The nd-plle ndN ofth. Z|1Or nng wit! iodirc ttos dispos'd in a 

,r4d-M.r @mss Bc nng 

Con.lric FIuetcB of (21) @ d@icr.d in Ttble 13'l5 

ll8

T|bha l3 cBsr.i data &d 3i.!c1N Ff!@61 for t( dD&)zr Il. (21) 

Crystal syslan, sprcc greuP 

F(000) 

Thaa d8p fd dlt elddon 

R.fl*tiw@[4t d/Eiqe 

Dlla/Gsitdnls/Pa@d€a 

FiDd R indi6 [F2sisd(l)] 

ccDc, 

Cx Hs Ir Ni 04 Zr'. 

ll03.E5 

150(2)K 

a= 13.3?770(10)A 

b= 13.377?0(10)A 

c - 25.5059(3) A 

4564.6rA N 

2504 

0.35x0.1x0.25m 

5.68 ro 30.03 d.8. 

CD4talStretv. ANIlsit 

-18+h

T.bler- t4 Bond lcnglhs [A] 

I-Zb 

h4 

ZFN 

oq4) 

O-Zrg2 

N-C(2) 

N-C0) 

N-COA) 

Nq3A) 

2.s28112) 

l,93t303i 

1.9606(r4) 

2.0917(r7) 

t.423Q) 

1,931303) 

1.456(7) 

t.46eNq3A) 

c(1>N-C(34) 

coAlN-c(3A) 

q2),N-C(2A) 

c(D-N-C(2A) 

c0A)-N-C(2A) 

c(3AlNa(24) 

c(2>Nq3) 

103.78(?) 

106.38(7) 

86.E8(6) 

l18.6(4) 

t23.54(4) 

I12.r5{s) 

r20.6802) 

0.4602) 

t28.75(7) 

l l r.7(6) 

t14.4(4t 

39.4{4) 

61.0(4) 

r41.2(4) 

I I t.9(3) 

a.El4) 

13.2(4) 

108.7(3) 

108.50) 

r09.2(5) 

N-C(2A) 

N-C(3) 

q3>c(4) 

c(3Alc(4) 

c0olco D 

c0o).co2)+3 

c0 r>c02) 

c02>c03) 

c02!co0x3 

c0).N-c(r) 

c0A).N-c(3) 

c(3A)-N-C(3) 

c(2AlN-C(3) 

c(2!N'zn 

c0lN-zn 

C(lA)-N-zn 

c(3A)-N-zn 

c(2A)-N-zn 

c(3)-N-2tr 

c(4)-c(3),N 

N-C(3AlC(4) 

oq4!c(3) 

o-c(4!c(3A) 

c(3){(4)-C(34) 

c(l l)-c00)-c02)#l 

c(10>c0D-c02) 

c( l3!c0 2)-c0 D 

c0 3!co2!c0 0)*3 

c0 rlc{12}c(10x3 

SyI|@E nerfomdioa ued to €F!@l. .quivalol alom: 

ll y-114,-x+514,-z+ | 14 42 -y+sl4,t+l 14,-z+l 14 

i3 -x+3D,-y+12'-z+112 

120 

Crysbl St4ttn Analttis 

1.502(4) 

l_510(6) 

1.46(6) 

r.53r(4) 

r.295(E) 

|.19217) 

l.!86{?) 

l.3ls(r D 

t.19217) 

109.5(5) 

7r.l(3) 

45.3(3) 

142.(3) 

r4.6(3) 

l l r.9(3) 

ll0.180?) 

102.2E06) 

r5.2Q) 

9.2(2) 

l12.5(4) 

0.2(2) 

ll3.(3) 

l10.7(2) 

45.1(3) 

120.?(5) 

li9.E(s) 

9.(6) 

r20.9(6) 

u9.5(5)

3,3.4 Slrucrur. Amlystu ofZD (ecrc): (dnrclD (lO 

CryttolSlrrctue AMIlss 

Th. cryltslline stucrurc of (16) hss al&ady b.en rcponed' ud shoM in FigN 12 dd 

33. Ar a quict rcfcFn@ the mi! .rysirllin si.lctE fdrlE e ooe again disus€d 

h*. Th. hydrcxy H aton in zn(a.ac} dmeH ea l@at.d in a direr..t loui.r mp 

dd w6 rcfin€d ieropicaly. Thc o-H bond disiar@ ws r.slrain d ro be 0.90(2)4. 

AI olhd H dom wE plaed in c,lcularcd positios (C-H = 0.98 dd 0.9A) dd 

wq€ E incd sid Uib (H) val@s or l.s(m.thyl) or 1.2 tim€s (n thylenc) U4 of rhc 

Metbyl H atom w€ allowed to ot4re b b€st fir the cxpdimmtal .l.clron dcnsiry, Thc 

higlest peat ed d.cpest hole d. lost d a1 0.86 md 0.864, rclpectiv€ly from aton 

Znl. 

Fls{r. 32: The atoo dubqiig $h€De ot @nplq, zn(acac)"(dnaeH). Displ&emenl 

clliFoids @ diaM al lhe 50elo lDb6bility lev.t. [R.t 3l 

rhe nolccul& srruci@ of zn(eac), &reH is i$srrucrual wi$ Ni(aEc),(dnrcH) orl 

cdmc)r(dncr0. Th. goneric dvircm.'r mud 

dislorted @ialedron wilh O-Zn-O .birc, e8l$ €loF 

(O'l fo. ihc @c grcups, On @.rry, |be dn&tl lig.d, 

t2l 

0E 6tnl n€lal .tom is a 

b 90e [89.48 (6I ed 87.?5 

which foms ! fiv€'D.nbed

Cryttal Snudwe Atulysis 

ch.lat€ ring and h3 n salld G-Zn-N bire dch 177.51(6)" l. ftE zn-A bood 

l€nglh for O. && lis&ds rus. ftom 2.0429(15) to 2.0719(15)A. fteF d. slshly 

lo.8d the th. coreaondins disranc.s (2.0t 2-o5A) foud for zn(dd) HrO, a.d 

zn(e@r2Hro.'zr sd de snaller than cof,cspodding disidc6 (2.109? 2.119)foud 

fo. Zr(.@)r (d). rh. ZFN bord ls$n ob€d.d h@ is 2.2195(t7)4, $til€ rho* 

for the ocial.dEl compl.xes like zn(a€e), (.!)r, Ipyds.Hl (Zn(pydcxlydc.H)l3H:o 

Qyd, s a6.prridinedimide dd pydcH N ptridiMliqboxyl'c &d.)rd 2.1270, 

2.01t dd 2.0124 EsDerivelv. 

iY-ll 

ll 

ll 

ll 

ll 

ll 

ll 

rl 

ll 

ll 

rl 

rl 

3..... 

Flgurc 33: I1tc crystal-p&king diag@ of Zn(acao)d@. Hydogd bonds de shoM 

t22 

I 

ll 

tt 

li 

II 

rl 

ll 

ll 

ll 

I 

tl

3.3.5 Structure Anlfy3b of lZn|O, (OAc)n , Unorl (20, 

C,tstal gtuw,lultsis 

Deuib ofc.yst l dab, d.r! olccftn dd sEEte Efncndt @ s fotto*s: 

rrbkr 16 c4sr.l DEla of [zn'o' (oAc)10 . (dna> ] (20) 

Enpi!icrl tcrH4N,olznt, 

t254.27, 

lo0K 

Zl 

r{000r, 202 

4651.6(3) Aj 

CA. 0.50 ^ 0.05 x 0.02 

18.5951(6), A 

10.6718(4),A 2.24'ro28.2E 

24.0520{8) A 62?0 (Rd= 0.0107) 

$ 102948(2). 4554 

It>2401: 

Rl = 0.04?2, 

eR2 = 0.0719, 

ccDc # 6%289. 

crysrd 3rMrG of tzn,q(qc,Htr(3-{cH,oH}c5H,N,l:r lzn(r4ot(OAc)r0@z!, 

oAc = @t r.i !z = prrein€l,x dd lzn q(o.CMoo(l-Meim), 

t-M.in = Idedylimidaalcl," h"d ba publish€d. TIe cry$lr s[teluc hale 

siDild gonetry s of th€ ritl. c@pobd bur in ou c& rh. remind tisd& hav€ 

oo.diEtion rbrough N,atoms imlad of O.aion. Ihe crysrd strudw of ihe ct$ter 

mFuad tzqor (OAc)o . (dmD I i, @rsr1Mciic in $:hich cetud Z!-a1oh ztr 

(l) b lilked to six zn-stom thrcugh rw O-!roE3. Th6e o.aloms fom (u.-O) 

@rdimtion silh Zn-abms. Th. bond dirla@, of z(D-Oo) tl.%9(3) ,1.] dd zn(4)o(l) 

0.964(3) Al c n@ly.qual wii|tin cxFrimrd @B- siDitdly, zn(2!o(l) 

t1.91(2) Al ed zn(3>o(D n.915(3) Al e at$ !.dly.q!.1.Ir tonsd tusc k for 

@niral ed t€minsl Zn-atoms. In ihis Z.{lusla, lh@ N i6 &.iate lisdds which 

t2l

Cryttal Snudu. Awlrsx 

b.id8! th. Z!-alom ia pai6 s shoM in th. FiSe l4 alog wilh {!. stom rubdirg 

$hdc. Tsble U eiva ch@teiislic bo.d l.ngt[ &d bond del$, Ihe gomeEy 

eud lhc entral Zn-qlon is slighdy disroflcd @abcdnl wih basal plde .otuinins of 

o-atom3 Io(2), o(2'), o(10), o0o)l tsrDs.rry cod. 

'- $V2, t+1D, z)ote.t. 

lised! lad th. apicd posi(@ c covqed by rF o.aroN (Ol, Ol') of (r.-O) the 

smcty dodd h(2) is slidtly distorkn Eftn€dral with thrce O-aloms (Ol, 04, dd 

09) i! thc b6sal pltue whjch b.loogs ro thE eelale ligard. &d ln. eic.l rbsnior is 

occ'.pied by o(l ). A sinil& s€onery mud zn (t) €xists eirh bsal ple. @nsisiing ol 

tqi), q6) a.d O (ll)l &d rI€.pical posirion is mdidr.d br ql). Th. bond 

gconetry mud Zn {4) b diltortld rigonal biprMidsl wilh th€ basal plde conshring 

or tqD, o(8), &d o(10) I .d lh. qiat po6irio6 @ ocdpi.d by ql ) ed q | 2). rhe 

zn(4) is oui ofpLe [o(?), O(8), &d O (10)] by a dish'ce of o.o48o(2t A and rh. shin 

is bw.d. O(1)In this hcpl&El€ zift ctqE rh. Zn,..A! dkrlss in 0!. sr1McEic 

uite 3.0169(7), 3.1888(5) ed 3.213E(5) A, wh* the shone$ is belwen $c canrr.l 

dd rhc cdiol Zn-alom. The C-O bod dist !c rcdiztd in ln€ acciyt ligads of lhe 

artM€tric uii which brids€ zn-otohs hav. res. of L231(5)_ 1.2s3(5) A. nE tong*r 

q9}-o(l I) bond h4 a vale of 1.268(5) a, ll!. oxygcn o(!) jojls itc tm synmery 

rcl.Ld motifs itrto heptduclee zinc clustci. Ir ihis clut r rhe r€ninal moiety N, N_ 

diEerbyla.et nid. is disord.ed ovcr rwo ciics bdirg @updcy taio ot 66.5133.5 yo. 

The bciiyl sroup of aceLmide presmt in Dqjot ponion of $e .li$d.Gd noiery ma&.s 

iDtqnoleular B-boding of C-H.. __O t,?e. 

t24

Cryealgrctue lnotrs$ 

Fig!rc 14: Mol@urd SiructuF ot lz"1ot (OAc) n . (dnah l showins ihc atoD nmb.r 

$hcnc dd bo!di!g, Ite H.alod! e obirlcd for cldiiy, 

SyrM.ty code. (t -'r 14. -)41,2, -:. 

Trbl.r u seleded bond kngn! tA) md e 

Zrl -41 

Zal 42 

Znl--Ol0 

7^2-41 

Zn2-43 

ka-44 

tua-49 

zla--€l 

zu--{5 

za3-46 

z!3--Ol I 

Zn4-41 

2n4 47 

ha-48 

7tA 4l0 

l.%9(3) 

2.t1t(t) 

2.119 (3J 

1.916(2) 

|.951(l) 

|.976(4) 

r-956(4) 

1.915(l) 

t.974 (4) 

r.951(3) 

1.949(3) 

r_964 (l) 

2.0r4 (4) 

2.020 \4) 

2A1s (J) 

\25 

les \") tot Iznlot toL4c) to . tddahl 

o4-{3 

oH3 

o6-c5 

07 {5 

o8--

ZtA-412 

7,nr.421 

02 {l 

o3-{t 

Ol--2nl-42 

Ol-Znl--Ol0 

Ol-Zal--{l' 

Ol-Zil--

02'-7tt4-41 

O8-Zn4--410 

o2'-Ja4-4a 

O10-Zn4-412 

o2' Lr4-410 

o2'--?,a4-4r2 

Znl-A1-tu4 

Znl-4l Za3 

Zil-4l Zn4 

Znz-41-Zn3 

z^2,4t-LA 

Zn3-41-264 

92.77 (t4) 

95.070r) 

168.4104) 

83.0004) 

1).49 (t0' 

84.13 (r4) 

r_61 02) 

110.37 02) 

100_1603) 

112.13 04) 

1ll.03 02) 

110.9 02) 

Symctry cod€s: (i) -r+ lD, -)412, -t 

Ct stal StNtue Atulrsh 

07 {5-{6 

o8,-{?-49 

o9-{7--{8 

ot t--{9-{r0 

olG{9--411 

olM9_cl0 

o l2--{ I I A-N lA 

o l2--41 I A--{ l24 

NIA--{| lA- -ct24 

o12 {llB NlB 

o l2--{ I I B-{ l2B 

NIB--,Cl lB-{t28 

3.3.6 Struclur. Arglysi! of Z(!c.cb 0r'o)rcl (19) 

7.9(5) 

r26.4(5) 

115.76) 

l1?.1(4) 

t2).6(4) 

lr9.l (4) 

126.t (7) 

r r6.0 (7) 

1r7.8 (7) 

112.6 03) 

1r2.3 06) 

r34.4(18) 

The molccurd siNctu€ of(19) is shoM io Figure 15. Tlc cmrdination .nvircme of 

Zr doh in ZrOt moiety osisr of oue biddille OO th.bting @lyl@roMt &d 

ttu noDod@t.rc stcr nolculs. The Ztor exbbir! a disroi.n iqle{ripris 

g@melry, Th€ av.rage Zr-Odislsce2.l8l9 A mdlhebitc mgl€sOl,Z!l-O2, Ol-Zrl- 

04 &d 05-211-06 @ 75.75(5)', 76.32(5) dd 75.5?(5) Esleciively se in sood 

ssl!46r wjth rho$ rporred for z(@)r.?t P.i6 of nol€.d6 c tirLd by O-H o 

hydregcn bonds in cyclic dim.rs. which a. furlher p&ked irto . thre{indsiotul 

fiuMrk by chaiB of GH Cl trifNaled hydrogm bods. 'fte ZFOI bond lcn$b is 

lorya lhd ttc rcsr ofZ-O bods! d@ ro th. .longltion .fl€.r oflydrcgcn bondine. 

Figlc 35: Th€ ayneeuic uir of IZ(@)r(IIzO)r1Cl dbwitrs th€ llb.liDg sh.m€ 

ued h the & md iabl€s: aronic displ@ndis s€ a1 th. l0% level, 

127

Cry$al 9rctw. lwDtit 

Thc ov@ll lattie rtructw g.n oted by th. O-H' O and O-H Cl hydrogd bood! is 

ri$n 3{: I1ic llnie sEucre of tz{@)b@,o)dcl shoeing Mns UntdDs rlftusl 

binucated chbnrc abn sd a n€rmrk of H-bo s. 

I.u.ts r8 crystd .td! rd [a(@](H1o)dcl (19) 

ZTOsCBHlCl. z 

460_02 

PI F(000) 415 

9.1990) J.4 to21.5() 

r0.408 o) 

7816tJ6t7 

. (A) 1.478 (t) 44t5t0n49 

oc) 70 r82 (rD 1.061 

po 70.64?(10) 

(41 0.0618 

rc) ?2.?55 00) 0.41,r,451 

9?5.0(4) ccDc # 614643 

128

T.bLr 19 s.lected boDd lagrhs (A) nd esl6 O 

z(llq6) 

z(1)-q3) 

z(1>o{2) 

k(tlo(4) 

zr(l).o(5) 

z(!!o0) 

z(t>o(l) 

z(l)-o(E) 

0(6)-2( I )Eo(3) 

0(6)-2( r )"o(2) 

o(4!z(t )-o(D 

o(5!z{r }o(r) 

q6).2(l !o(?) 

q3),zdl |o(?) 

o(2!z( l )-o(7) 

o(4tzd l)-o(7) 

o(5>z( llo(7) 

o(1!z(t |o(7) 

0(6)"2(l )"o(8) 

o(3)-z(l |o(8) 

2.t370{t3) 

2.t424(tX) 

2.1506(13) 

2.15971t3J 

2.180801) 

2.233qt2) 

2.2756(t4) 

2.2156(t4) 

l r5.60(s) 

75.79(5) 

17.69(5) 

140.96(5) 

t44.22(5) 

75.24(5) 

l.2r(5) 

r39.93(t 

1545(5) 

?0.r (5) 

80.98(5) 

138.2r(5) 

fo! (19) 

q2lzdllo(8) 

q4)-z(rlo(E) 

o(5)'zr(1).o(8) 

o0Iz(D-o(8) 

qlz(rlqE) 

c(D.o(D-z(D 

c(3>o(2)-z( r ) 

c(6}o(llzi(l ) 

c(8|o(4|z{l ) 

c0 D-o(5)-z(r ) 

c0llo(6!a(r ) 

o(3)-z( r).q2) 

q6),2(r)-o(4) 

o(rlz(r !o(4) 

o(2)-z{r !o(4) 

q6lzdllo(J) 

o(llzr( D-o(5) 

o(2)-z( D-o(r) 

o(4lz(D-o(5) 

q6lzdrlqD 

q3).2{r ).o( D 

q2>z(rtqD 

T.bL! 20 The intmd@ula hydesa bords ror (19) 

Crystol tvtw. Avltsh 

69.52(5) 

144.67(5) 

14.21(5) 

1r0.24(5) 

7t.2E(5) 

133.86{1D 

ll8,l?o2) 

r36.390D 

134.35(12) 

133.0902) 

133.0802) 

149,176) 

14.46(5) 

16.321s) 

79.98(5) 

75.51(5t 

71.74(5\ 

l16.5l(5) 

121.98(5) 

142.99(5) 

80.l(5) 

75.7Sls) 

Sl,lm.ay oasfom.tios ued ro B€neEF .qujvalftt don!: x. y. z & .^. .) . .z 

D E DII(A) n^(a) D^(A) DflA(.) 

o7 H71{ ol 0.87(3) I 90(l) 2_1618(t9l 174(' 

o7 H78 cll 0 790) 2.29{1) 3.069s(r t t?10) 

o8 H8A cll 0.86(1) 2.25(3) 3.0%?(16) r68(2) 

o8 H8B cI 0.90(l) 2.r?(3) r.05t6(rt l61l) 

129

3.4 Tbermal Studies 

3.4.1 Th€rnrl Strbtlity ofM(!cac). rnd M (thd)" conplcrog 

IEmd studid of (r{) M(@)h obplexB \N@ cdi.d o at. hotilc 6t of ldc 

minj to obw. rh. thcmal .tcconposilioD b.haviou ed to d€r€qirc th. degradad@ 

De.bdism. The ihmoEd obtlined udq dyndic TcA ees wcE r&lysed to give 

pc'@aagc wigLt loss a a nDc$d of ledpc6t@. In ordd b dcamift $€ th.dEl 

sllbility lr.nds rle lemp@t@ chanct€rislic v.lu€s wft evdlu.ted. The chdacEnstics 

enpdrtue 3eh a To (lenpdll@ oet of d@nporirion), Tro (anFdtN for l0% 

*igh lds), T! (r@pqile for 20y. wishr los), ord Ts (t mFBtuE of bsim@ 

€te oI degodalio!) w@ calculaied dd are pBentcd in Tablc 2l dd codpl€te 

rh.@oam lr@ D@r €d s ApFndi,\-lll 

To, 10, T!, and T.- @ rhe main.ritetu iddh.ting rhc rhm8t sr.bilily ofadplcxes 

&d dey @ ale thc ele f@r@s of Tc cw6. IlE hisrE lle valE of T0, Tb, T&, ud 

Tm rh. higbd wilt be lh€ tb.mrl silbiliry ., 

B6ed on lcsl vrl@ iemp@l@, Cr (M)3 [ T0 (179 "C) od T.(28a 9] w foud 

io be nct ,!d Zn(@)r I To ($ oq &d Te(193 oC)] rc tlE la$ slblc. -Ilis 

rlability rcf6 to th. m.laltigand bond srrclgth and fouowine ordfi h8 ben poposed 

for vdiow mclal &.iyla€ero@l! daivadvs for lh€n s:r.biljty. 

Icr (&&}l > Icu (a@)rl > IAI (&ac)rl >Ni (!@)r lco (@rl > 0r' (&ac)d > 

T!. L@iMl $lid @id@ in ce of .@..ddq6 wc meLt oxid. in @r of rbe 

cds.xcF in Cu, Al ed Cr @lyl@romt conplex.s, wh8 sublidalion rak6 plrce 

iNled of dMnposilion which i! i! @ofomity wirh UE pfl€nrage tosss of tu 

obrri!.d fiod TC cwe dd TCA-FTiR strdy, 

130

I.bL 2L Dda oblrin d fton TGA tualwb. 

cc) 

t-, 

l9l 291 

3 33.72 

220 

242 

12 120 

It 

l6t 

t3l

SiDjl&lr, b!..d on 16r \ulrc r.mperarw d.r. orM (l|)d)i @npl€r€s (1G12), hish.r 

th.nDi stabihy wls found in Cu (i!dh I T0 (173'c) dd T*(288'c)] ud lowr 

d.rbility @ ob$Ncd in Al($d)3 I To (?a oC) ed Tnreo3 oC)]. TC cunes of all M. 

!@ @nplqe show oe to fou siifi@t t.DFdru. r.Eilios of rcigh lo$ wi$ 

comon &d sp..ilic arag6, rcm.d s singl. slage, rwo $ae.s, thft sr.ges and fou 

sta8.s of themal degradatioo Fspectively. The themal deconposition of thee 

@nplq6 tak plrcc @rdin8 !o nehais involvilg thc d@mposilid pMss of 

org&ic ligdd lit!.hed ro ndd aron or ud€rgo sublim.riotr or pln of it ud.r8o 

sublinatioo sd have some co$id@lion oo the themal dceraddion ncch&ins. 

3.{2 Kirctic P.rrneters 

Kiocric p!fu.r.6 ssh a activation .n ray ( EJ , Ad.nious coBlanl (L) &d 

exponlndal f41oB (A) of rhe conplq.s (l-22) weF calculaled frcn t\mogm 

l@d.d iom @h |.mperltw to 500'C in niirog@ alrnoQh@ .i diffcMt h€ling 

61ca, viz. 5, lO, 15, K min I. The TGA sd DTC cutrs.xhibit d on. ro fou disdncl 

degradation zorcs dcp€nding upon the m1@ ofmeral orgdic conplex, Homver, al rhc 

low hanils Ftc of 5 Kmin r, in $m€ ces le$ lMbq of deendation bnes Erc 

foud. Arh.niou @israt (k) @d €xpon€ndd fados {A) vdtu€s w€E cslcdar€d from 

d.mogr@ by applying Ki$inger od Oaw. n€$ods (Tlble 22), wherru tbe 

&iivltion €r€rgy w.re deamitud by applyilg Mod.l Fe Kiftiics, nih ordd, C@Ls & 

R.df.o, Ki$ilgcr &d ozdw. n thodr aming singi. &d nutti sLp6 d€@mpGnion 

E@tion for a panicule &ne sing TGA/DTG dal!. 

1!. Elalile snnplicity of nd od.r ud hod.l fta kberi$ eiv6 iis lDlcrnat for th. 

enimation ol a.tilador dr$, of Delgt orgaic @hpl.x6 baving single srep dd 

multi$ep degEdalion 4ne @sp€ctiv.ly. In addition to this. hodel frce kinelics also 

tak6 coNi.lexdio! of ddiblc tudo!, s enain @mpLx @tion e Evesibl. ed 

hdiecs typical &dktion d.rgy d€Ftr&dcy otr 6rv6ion by s rclati@shi! 'Er = f 

(a)" vherc d is co.vcsio! of chdical @lion. 

Adiwlior ffi$/ v.lues w€E c.lculared Ning ydioB do

nultisLp pr@s thar b cotrolled by the rat ofslovstslcp dd rhu.pF s 3 singh 

srcp. Ilis is d€ fton the rhetual ltudy of Cu (&&) (Table 22) which is singt€ srep 

d.composnion &d edvatio. €n rgy valu€s i6uEd by nth onLr, R€dfm, Kisingd 

.rd Ozw. oedod N dnost s€. Ho@vcr, nodcl t . tir€rics o{ rhm@alysis 

eelion orcu (ace> siv.s v&idblc erivadon eoes/ valu€ (1084? KJ/molc), nosr 

pobably dE to irs @ndcx dr@ of dc.omposilion i..., ( sbtimrion plls 

dtumpqition @rion g06 side by side speistly ot hid.r ienrEdtw s anfim by 

rcaidual nas ed TCA-FrIR d.ra). In such ces rh@l ouicome G conroll€d by rhc 

fi. of th. slow6r sLp. &d rhB .pp.&s d ! sinSte slep duing TCA snrdy, Cdlical 

exminaiion ol data aho N€dles rha! in ce of simple d@onposilion rcrcdo., 

etivario. cMgy dda st s|an-up rdF€rw nswd by Dodel ft4 kiftriq match 

with dll other merhodologiB sppticd. Ilis is bc@e rh€ sysrcb is not fe Aon 

€quiUbiih at rhc $an of tenFEtuq th€ scrivation mdgy is r.nFrarw d.pendenl 

bc.!B of the lemlerw d.!rde@ of cquitibrim J)ttssw. The daIa ats rcvatcs 

lbal at high{ t np.rarw rheG is d @Bid€oble chege in acdvation encrgy s 

n4rcd by MFK. ftc lt&n behind is, at hiS! t mpdtG s'stem bccom. fd fron 

equilibrih dE to rhe panid p6src of ga$N la(otr poducr \hicl in rutr 

in rcN or d€cce $. 4tvarion cnergy appr.ciably. Th$. obsFalions were not 

rob4 ${ile omF.i'g rhmdnat'licat d.ra of z,(thdh , Al (s@} wirh Cu(a@h 

whcR all gives sinel€ sr.p decomposirio! pa$etu but h€r. the value ofacrivation €nd8y 

for Zn(thd)r d At (@.)r €alcular€d by MFK foud ro b. albosr con$st lhrolsh our 

ixe d.g.ad.tim hehoiso &d i1s vatue is dN lo |be !€lu6 calcutar.d by .I ot[cr 

.oNation.l D.lhods. On the conr"ry Cu(&a€t shosed continous d4rcM in 

&lirltio. oer&| witb ns in r.npedrc. tn ce of nulrinep deonposition psrt.m, 

le @mponnd Ni (ea.):, zo(@)r(*)x, zn epht: clr, a los vztuc of &rivarion 

6d8y al sllrr up remp.isrw indicat s rhdl tn€ proess is dittusio. conrrou€.I mrh.r 

thd *ineticdty @ntrotl.d. Sotid phe @tbc of the ir?. (elid r etid + Cs) onq 

besin udd kn ric contrcl, s in c@ of conpoud cu{dce}. Fc (ac.c)r sd 

Iz(ec)bcl,ollcll, lnft ar $rn-up renpqlrE, &rivlrim cncrs/ js much hishd 

8rd s lh. reDFrarue g@s hjSher ib valu. d€cres.s duc b thc €don ihat now $c 

r€&uon beore n@ dd mor. ditruion coitroll€d i..., rhickn€$ ofdr€ slrf&c lay€r of 

@npolnd .Ledy r.a.r.d ircqs\ ebicn 6ft in lh. diftusion of thc glgE pFdrcl 

becomilg hle dctemining . Duing thc rrdsnio! fron a tin.r. to a d libioronrrolled 

@liot! om tlEFfoF * . decr* in &1iEtiotr @qg}. pFiou treh€r ro

obsw€d rhis tT€ of d€Fndercy in e@d plmltsis. Sinildly on thc basis of csidual 

!)1,s of thmal cwes for the @DDouds 14-20 involving nultist.p d{onposition 

panm, rc sfcly say thrr h.e dMhposition @don G predonimt ovd sublindtion 

cx@pt for tI€ conpoud Zn(PPhjhclr (whcE sublimtion is doninaal). 'Itis cm be 

jlirided on l[. baie ofhigl &dvation adgy !r $.n up rcnp.6rw. 

Arh.nios p@reld $ch a pr{xporotial fa.lor dd sp€cific r!1e co$lorl (Tabl€ 

22) fo! a nMb€r ofconpound havins sinsle ed multtur.p d€@mFsirion or $blimton 

@tio! e calculaled by qpical Kissirgcr dd Oaw model eqDtioB.rrThc vals 

@lcuLt d by @h m€Ood 0Fu8h @t in eood agrcm. wirh .eh odBr yet 

indep€ndlnt ofthc h€atilg r.ie, 

It is th.rcforc conchding thal rh. acrivolion dergy nor only d.Fds on rh. equiUbnM 

Pltss@ (P0) of thc @hpoud but ale on parrial prcssw of tbe Brj@u @ibn 

ptodut. In addilion to this a.tivarjon cne$/ calculsLd tlrcugh nodet Ii.. kiEdca giv6 

valubl. infotmtion EgddinS d.@mposirion Fathisn duing thmal ,odysis 6 

coDpaFd ro orhd Dodcls. Howvq, dlla d@ not yi.ld dy d.llil€d hfmadon sbout 

the raction mshdis .sp.cialy for nor rh6 singtc si@ de@oposilion pattem b6€d 

l14

9 

b 

I 

€ 

3 

e 

5 

3 

d 

t 

i 

Y 

: I I 

e 

I 

J 

d 

H 

i E d 

s 

a 

3 = 

! 

: 

I 

5 ! ! E 

,l a 

: 

E 

l 

? 

a 

t 

g 

a 

F s 

; z d z 6 

a 

? 

i 

s 

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i 

E 

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q 

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,t

f 

n 

s 

I 

z 

d 

,E 

I 

,5 

.! 

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a 

8 

n 

5 

t 

3 

I 

a 

: 

.E 

E8. 

3 

l& 

Fd 

* 

F 

3 

3 

! 

I E 

I 

{ 

a 

! 

s 

3 I J 3 ,5 

F H 

i 

f 

a s r 

! 

d 

a 

3 

€ Ii g 6 ! d I d 

ti 

I 

B 

g 

t 

€ 

! a s 

ig 

s€ 

d 

I 

s 

a

3.43 TGA-rTIR Studics 

Ddohposilion behavior of Cu (ac&): {l) dwing TcA &alrsis de shoh in risw. 

l7a, 37b ed l7c. On gindual irclle h t mD.dr@, ih. TGA dd DTc cw6 

exlibn sin8l. step degmdadon pM6s in t\thpdanrc rege 210 - 268 oC. The 

bs(2J-pataGdiodt ) @ppq (tt) bcsin to sublin e ar 2lo t ed il w6 obeded 

lhal lublimaiioi/de@nposidon t€mpcnrws is ind€p.ndeot of rh€ nalure of cdid 

s6 (Fig@ 3A) ed floy mre (Fig@ j7b). Thc b€baviour of or bis (2.4, 

p€nbn diomt ) @!ps (D io 4% H1 dilukd wilh nirogen atrnospherc is io conrlsr 

with rh. sludy madc by v.Combos rr 9n@ pb ('@D dd C! (thdh rr sho*s 

de@nposnion !t lenpoalw 3I4l oC. 

I 

.!l 

FkuE J?r: ICA Cw.s showine dccoDposjlor 

Figu. 37b: TGA-Cws .r diflftnl DTC C66 .t dilt e.l 

l.l7 

I

Howvd hic}lc! h€arins hle.tin the oNt of dmnPosiijon sd T- t(l hiehd 

i.bF6tu. d &picled in Figft 3?c, 

Iigd 38, Epr*nls a thcdin 6io."l plol ol IR aberbsre spcdta vs tne A 

3D wd€falt plol is usetul for prcs.nling tnc chdges thol oer io ihe inf@ed 

sFcti oE rlE @tE of {he TC &tlysis. Eah a!6orb.@ bdd.lory lh. *avc 

nMb.r *ale eprcsnts fu.tional goup of th. €rolved gs.s, 

Fl$ElE. 3D w.t r lall plot ol mR Sperjun 

IE waierfall plol displ.ys a sri€s of sp€clrun toE 35 lo 50 ninut4, duing the 

olldion no lR absDtion bands ob*ned up ro 35 ninuca. The infomation 

gain.d iion rlc water fall plol show.d lhal ihilial wight loss wa mainlv due to 1he 

los or bis (2,4p.n1anediorare) opper (ll) s sublinc ptoduct The @d.la!on 

berw.n th€ fst derivaliv. plol of w€ighl los, qle fall plot md Gm-Schnidl 

r@Bltuction (Figft 39) is exGll.nl. Th. evolv€d S4 pofile palt m studied 

thmrSi TGA-mR in 210 ed 270'C ale @lfmed lhb appD&h ed shov€{t d 

ab€otpion bdds rcsmble wjlh (1) dl th€se t€mp@t@. 

schnidr (cs) c'e- 

138

Thd evoFed g6 pF le studi.d al Ddinal of Cm Sclmidr cwc ws cohDrEd 

wilh FnR ofpw @DpoDd (r) Gise a0) ed foud io be frgcr pinrs ro mh 

oilEr. A Iinl. bir diffcrence i.lh€ position of absorpiion beds d€ d!.10 lhe l€@n 

tbat aberpti@ ba.& in dr 8.su $ar. tlo mt @incid€ *irh tb@ in lhc liquid 

ll*fl 

.4 ( 

,,rr"',^,rr-r.-",.'-'] l:::f h' 

IL r/ 1!,el I 

;;i;L * 

" """t -___;;t" -"i;;-----=;a^--=a; 

*'-J* lrl\(,'il,L, 

Figurc40 FTIR SD.clrM of pR comptq & e\ otv.d gs pro6te. 

On the bab of TGA-mR study ir h temi that thc conpl.x ed€,go $bliMtio. 

iakld ofpyrolysis G Fr fotloeins schtu . 

c! (@c), dd - cu (&&, 4 

Th.mosBvimetric aralysG (rcA) ed denvdive thcdosnvim€riic (DTG) cuNes 

for d@npojriotr of [C(dr@XO,{cXH,ot: (rO @ shoh in Fise 4l. A |h6 

slep pathway for decomposition is obsred wi1h 8ladud loss ofwater (foud 7 94% 

.alc. 7.91 %) ar a t.mFErw tuC! of lO, t j4.C. In tbe s@nd and thid ncps o 

tor.l weight los of 61.4s % is &cord.d dre b eljminaiion of &.rar€. dim€rhyl 

ethml @itr. sDd N,N din rhyl €theal goura. This obsdlrd $ ,n lilc wiln dr. 

FIIR of€volvcd 96 prodet tzko at @iou time ioieNats s shoM in IiCre 42. 

'IA. @Elalior bei$cn dr DTG cNc a.t li*ed FT|R sD.clM sho*s th in rh. 

initial 5 dilut* (up io l34o c), H2o is losi, showing ab$Drion ol 3?oo, &d 3500 

€Dr, The H-o'E b.nding atso sivd ris ro tG abco,prion ar 171? m r, Abov. tj4 

oC, linle

addition to CHr stretching, dcforuij@ absorytion p€L lirt€d epetrun 't" also 

shoM C{ sEdchirg at 1793- l7?0 m'r of&eiste Ab$Dtion '@ l?50 cm r is 

checldisica of vapou phe aldehytle c&bonyl snetch 3how.d the prcen c of 

diEelhyl elhaml, The p.al at 1232 cmr@ bc teembly signcd to a C-N strdbh 

of a ienia.y N,NiiDetbyldirc-r I! C-O slmer.ic sr.tching at tO?4- 1040 cn l 

isderopF*neof R- CHIOH 3Dup of dn& aDdth6shosa tujor lo$ in 

wish al DTG ndina. LinLd sp6tlm "d" @rtrtu thc lo$ of cidual producr 

a indiqt d by th€ absnce of CHj stciching absorption bud, al]mdric 

dcfodltion vibEtion od ltmet ic vib6tio[ laving qidrc of 30-62 % .gainsi 

26.12 % of 9@ 6pFr plu littL impuily of copp.r oxi&. Bas€d o. th.* 

obseNdrion!, . plmbsis m*hanim suppoded b pGviou workrr for rhe 

d@oblosidon of [cu(db&XOAC)(HrO)], io @ppd o€ial ha b€en elabonicd in 

Scb€me IL It is @nalle to b.lieve thal !ft.i ihc los of Mid &d ctatc moleule 

in th. iritial dcconposition st.ps N-cu bord is opered at hi8!d t€mp.raEe to 

libdate 3pccics [A] r'trich ud..8o FH abshetion io poduc. sp@i* tBl md N,N 

{iim€thyl uino .orn 1. Sp..ies [B] rsdily udqsoB rcdrctiv€ elimin.lio. to 

libqd€ db&H .!d crystauic @ppd mo p6nicl.s. 

'fte thmal stabiliry od vol.tility of tCuidne)(OA0(HrO)1, @y vary wirh 

solvdt. ld tolu.r. solutior! thc conplex hs sulficiot srabiliry dd volatility to 

sft a a pfeuer for th. dcposition of opp.r @o paniclcs, wll adhdn &d 

Mdour @bon @nLEiEdon, The d@mpositiotr behvior of c.pp.r (U) 

dineilyldino .thoxide, tcu(dme}lr6 *hich h sublinabl. dd wreFqsitivc 

@mpl€x b lcmp.hrre depddent. Solid thin film gtoM from Ois @nplex at 200 

oC @isc of @ppd detd frE from ey @ntamilEtion bui ai 300 "C, ih. @mplq 

yields thh filn @nainiog. niftE of Cu(o), Cu (I) od Cu {lD ond6 p.odlced 

evd b.l6 nitroa€n €Niromcnt, 

140

w 

I 

i 

I 

Fisuru 4l: TCA,/DTO cwc of ICu{dna.XOAcXrrrO)1, at ! herine &t€ ot 

ls'C/min. udr nilroSo ahosp[erc 

100 

50 

l@ 

50 

-tm 

350 

Hlm 

,iso 

tm 

J() 

't 

a floe at of4o ml_/bin. 

4000 3J00 3000 2500 2000 

Wde!unb6m, 

1500 1000 

Fkln 42: TCA,/SDTA Lintcd FIR sFct! showing sysraarc dtonposnion 

of [cu(dd&XoAcxHzo)1,. 

IG Ob 1c!(&-)(0 cIHpD 

Lurd4tua?l9r,ir c 

d 

500

cru+-ctt,CU 

{ c!+ HocHrcllr,l{ct!, 

.- IB] 

'lq:,,5 

It 

*l 

HiNT 

H'L '02 

s.h.E. Il sch€@ric Epr.hrarioi ror d.mmpGirjon or [Cu(

Th€ TG cW. of th€ conplcx shos ! rhEe skp wielt los at temp.ratrcs tuges 

dud 100 - 210, 210 - 260 ed 260 - 400 'C h eive a rcsidual value closc to thar 

erTet d for a c@plcr. @ov.hion ro zic oxid. sd volatile by-pmducts. I!. DTG 

cwc shos the prcmineni .xolhffiic p.rb. Th€ p.il dowd 200 'C is Nigned 

ro th. Elee of @inoc&dol rnich yieldcd a weight loss of 12 %, This is in 8@d 

rgIt4.nt vith the th.@tic.l stoichiodet ic valu. of 3l .6 % for dioo erheol. The 

s@nd ud lhird exothemic p.slc ar 240 ed 3?0 qC d€ 6si8n€d ro rhe wcieh los 

d@ to elyhc.rm. ligddr bplilg up ad bcing tosl6 votsrile @i6ial io l6yc 

2l%of AO 6 the nml rcsidu., 

In ce of TCA-FTIR sudi€s ofcomplq (t5) tn O.nnal dcconposnion palem is 

itr lir. with il| innNd dal. of the aolld geoE peducrs Lten .t ftiou rine 

inleNal&tmpdtes $ shoM in Fig@ 44, 

Absorpuor tqrc|cy cn_' 

lisur. 14. Lint d sp*rla of TGA-FTrR: r) FTrR specllm or Zn{a6c)r(ca}l ar 

@n lmFEtuF, b) an* harirg to 2OO oC, .) evotvcd gs sperrM below 2OO aC 

(naiDly mino.thsol) d) evolved ss sp4irm ar 250 'C, (Dainty ecH) e) 

@lvcd 86 sFcEm above 3oo "c (mai, y.c.ro@), 0 €votved crs speroD ar > 

350.C. 

t! 

a 

t 

l4l

It is tunabl€ 10 believe rhd rh. minel|reol liead t lost 6F1- Tlljs is support d 

by ihe €volvc gs lR sp4trm below a tnpdture of 200 'C whicb shows 

pbmindt p@lc for Ate OH, NH, 6d C-H grcups !l 3650-3600 cn 1, 340G3268 

cn and 300G2E50 cD ' rcae.tiv.ly (sp€ctrun c), ed also by th. FrlR sp€cau 

of ihc sidE of Ihe TCA studi€s .r 200'C whrch clely lhos the abs€e of 

prodiMl @hcth4ol F*s (Sperjum b). ln tlc sond sra3. !hov.200'C th. 

widrt los B due to on of the @c miois llaling a ogH, a colfimcd by rhe 

erolv.d 96 GF.rnn d), The a*H is pob.bly fm.d by abslFdiotr of . pDlon 

fron Ure Maining liged, which ulriMtely al bidEr temp€ratute in the arrnosphec 

ofoxygd shs to be rcerilg wirh oxyg@ io fo@ vollril. @Dpoudr acdone &d 

CO, wirh distincl bands al 1220. I 160, ed l74O cn r (3p6tu c) l€aving p@ ZnO 

T!.e frdings arc supponcd by FlvioB wok.r? Bas.d otr tr FIIR sFctta ofrh. 

aolv.d ge wc suggesr rhe fouowing pt@lysis nc.htuis for the deompositiot 

ofzn(&&Xqtl ro zinc oxide (sch€@ D. 

zr(@D(a) -+!+ zn(@h+ 2(@) 

(€) = (HrNCrH.oH), ee = crH'O, 

z(a@), S!+ a@H+2co,+cHrcocHr +zno 

3@cH -+!+ 4cHrcocqr + 3co: 

s.b6. In: PyrclFis of Zn(a@Xq] 

Th.se fadings e contfiy io a prcviou srudy ra $ in which rhe mine group 

fa.ililaG dn€Itl (rO ( ris@ at shos r\.1 

th€ deconposition ofrhc conpl.x ys complctcd a14tO oC with . Esidul @$ ot 

r9.2 %, e val!. @6istent ro ZnO b€ing lhe frn l ploduct, Th€ complex lhors ihE 

wi8h1 los. Ite 6!st wighl toss 24.48 9o is d!. lo los of dneaH. TXis ws 

ontimed Aom the FTIR s!.crm of rcsidu.l nsrs oblain d !fter healing fie

complq d 160 0C r'fiich shos dbenc. of ch!@rristics tlnEd{ perl6 dd l@ving 

b.hhd Zn(@), s a sidud nds. (Fisw 43. sp.crum b) 

Thc *cond od third w€ighr 10$6 e 26,79 rd l2,l % (calc. 56.? 0/o in lot l foi 

.@) od @ dsigDed to l6s of two a@. A lid. incJts iD wighl noo ih. 

.alculat d v.le ir cviddt d& to sublim.tio. ch@tdisrica ofzinc rc.gl@tonare 

to $be .xEnl &d for lhis Gen thi! 9F of prccusoG &€ ed with sdve1r8.s in 

CvD r€chniqus. llE mor€l of e&H laving zoo 6 6iduc *ould t &6 pl@ 

via hydDg.n lbshacdotr. Thi! obwadon h onnmcd by *eing the residnal FTIR 

sF.rrun drar slDws .linination of t licd e& F.ts. Cige 43.sFu@ O on 

the bais of ihe above obs.Faliotu $d rhdFol deomposition studi€s of mehl 

ut',la..1oB1a by psioq etuhcr:'a d@npGinon mdh&is (s.hd. Iv) 

ofzn(d60ldn&aH) is suggqred d h€low. 

zn(ac&)z.dneaH --!!49r z(*> t* a-""ut 

zaatrl, -=6- - a4H l+2cor l+cH.cocH, I I aror 

ja*H -jiij:) 4cHrcocHr l+.lco: I 

scbd. Iy. DecoDposition n.ahdism of zn(@):(dh€aH) 

t. 

I 

I', 

I ra rao ito zta lra :rtr 350 -__--c. 

Flgur 45: TGtDTc cw6 showins daoDposiiion of Zn(@), .dfrcaH. 

145

I 

I 

E 

Flgurc {6: ITIR srBrrum of a) Zn(@c),.dnaH complex @orded rLr @n 

l.nFEtrc, b and c sF.tu ofrsid!.d m.s anq h€rjng al 160 qC dd 360 oC. 

TcA 6!d DTc €wcs fo. the d@ftposirion oflzi,o, (oAc)b. (dna),1 (20) w.E 

r..orded in d dl.oSe enviommr &d dc ahom in Fisrc 47. 

rlgurcl?t TCA/DTC cw.s showinS thmdl desnposirion of 

tzd'or (oAc)m (dmajrl 

t46

Th. TG cue ofrhc .onpl* sho*rd a sndual wi8h lN (5470) up ro 500 "c due 

ro bmins of NN dimethylacehfridc fonowd by @tat€ Gxothdic) decobposd 

to @toE, Cq aod H,O lo sivc. Esidual v.l@ 46 y' cl@ !o th.r qpel€d fo a 

complctc @nvdsion ro ZoO foded dE to oxid.tion wirh th€ oxye.n conr€nr of the 

cdpld. Tlq! I e or8rnic EsidE loft afrq 500'C d @nfm.d by rbc F R 

TGA ed DTG cllrc for the deonFsirion of bb aqrc uis aeiyt@lonaro 

z,toDiu (lv) chbnde ta(ace[Gixot]Cl (21) w@ @orded in u oxysen 

dvilrEat e'

3.5 Thin Film Chractedzation 

3.5.1 Scrlrtry Electron Microlcopy 

FigrE 49, shos a SEM inag. of d.posn d @ppc. p.nicl6 on sd. efen 3ubsrFie 

duing UAAcvD of Cu(6cac)r. Il'c ndem€nt ftom the SEM imae. indicales 

tbl th* e Mo plrticle mging tDn 100-200 m. EDX lr.lysis al$ @nfid 

thd lhc 6ln is cmpriss of pu. @pps ' 

S€e Appmdixnll . 

Fig!rc 49r SEM ilus$rins lhe $in filn of Cu in 470 H, in N, on soda gats. 

Fieui! 50, shoM a s.iMing .l..r!tr nicDopy inage of rh. deposircd coppq 

pdnicld ddircd fton tcu (dnc).(oAc) Hrolz duine UAACVD on ermic 

sulstll . Thc pdiclc sia D6w &oD rh. SEM ie.g. ildiete rhd dle @ 

Mo particulEoc wil! sias rdeinS frem 40 m to 80 M. I!€s p6nicl€s nse. up a 

filrn Iblt q'!Es io b. wifom qd s@ilL EDX Fsdll Drcle ds1 1he filh 

cobpri!* ofpuc @pper nmo prnicb (S@ App€ndixlrr). 

Ft!rc 50: SEM niwgnph showing opFr mc|al Mo ponicl.s. 

148

Fielw 51, ddqibB ! sdhg cletror nicoscopy inas€ of rh. d.positcd zno 

p6nicla ddivd 8oD zr (.@X6) duils UAACVD @ cfuic substra&. Th. 

n@uffit &on the itug. itrdicat r uif@ &positid of ZnO n.ro panicles 

wilh 3iks tuginS from 30 m ro 60 @. EDX eaty3b confins rhlr thc filn 

qEFis ofp@ zie oxid. p.nicb (S6 Lppddix-[} 

FirlE 5r: S@ning EldDn bicbgnpt of ZnO &Fsit.d Aob bis{2Jp€nL!.dioute).bis(.thetuinOzinc{rr). 

The SEM in!8a of dE tin dopcd ed udop.d ZrO firh! daiv€d aom zn (@), 

(d@IO dring UAACVD on tuic sbe.rr. indiclr6 irs gr'Iurd ch!@cr Mrh 

3! avds. snin sir! rE{tu€d fr@ th.e ieg6 w itr lle Erse of30 *tO m. 

'nE nicr litwtutal iEag6 Gisw 52) i*.n ror .tt dopcd dd udoFd sdpt.s 

Erql.d thrt tbe Snin si4 id ga.6l *s s,Is fo. Sn dop.d ihd fc udop€d 

m!l*. Th@ inDs.s rle Bel.d lhal doped fitG r* d@a wiu boE 

spbdicrl er.ia rh& urdoD.d fln. 

IrE moryholog/, su.hc. 3rtucr@ rnd composirion of lho tilm d.dv.d froh 

t(zl' o{dm),(oAc)01 dEi.8 uAAc\aD s i!v61i9r.d by sEM. Figa 53, 

show a e!mi!8 el*hon oim@py i@g. of the dcposired ZnO panicl* iD 

Nilrogcn 4 450 .C, Th. SEM tni@8nph cxtibils th€ uifodity of Ue nlin ed 

plrticuhte wiil siz6 tuging tsD 20 m io 40 M ard .iso indiclrs m d.fet 

f@1ion. EDX $udy sho*ed thal flh @mpris of pm ZnO !)m,srtictcs (S@ 

149

Flsurc52: SEM images oiSn doped /sdopcd ZnO fitn. 

Figur. 53: showiis zno sEM imee denvcd fom t(zn,q(dm),(OAc)r0l 

The morphologx surface srtuctu ad conposnion oI ZO: filn tabricar.d froe 

@mplex [z(acac)r(H:o)cll duihg uaAcvD ss invesrigar.d by sEM. tige 54, 

snow a s@ing e!.cron mic.oscopy inage of $e deposjl.d ZO, paniclG s 

delosit d (a) ed anei mealins in Nirros€n ar 5oo .c (b). The sEM microelapn (a) 

t50

SEM- Studiet 

o'nd oily qlibit ihc uifomiry of th. film bdicatiq no .lefecr fomlion, 

Hollq, . crEtul qditution of SEM nicres.ph (b) *ould Bulr i! lh. 

obw8tion of ih. €neryin8 of doF delircd erai$. Duilg m.5lir8 traledt 

Pll)ls, ZrO: g.n 6lly undcrg6 *v.El p@siry strg6 of tuov.l of pmsiry, 

fomaior of !.w ghins, md erain Eo${h ed rcsnnng in the charSing of nsr€risl 

FDFrti.i{ It! @Fpcition ofdlEil€.l6ln d delhin

3.5.1 XRD Studie! 

)

Evelogth of incide.t light wa 55,4 m dd h cmpahblc ro 40-80 m s 

I 

t" 

I 

ngurc 56, Xaly difltutior plrcm ofcu filb dcposir€d on soda glas subsraic. 

lh. )(RD palcrn of . ZDo 6tm fahieled fiDn tzj('@), (aE prEuer wirhin 

e &gle @ee of l5 b 80! is shom in Fiew 57. Ih. ZnO tu foud in irs heugonal 

WEEiL forD GIee goup P6rdc, . = 3.186, c = 5,206, JCPDS 3Lndlrd rtara pDF 

# 050644). IlE prcloMed (002) psk locsr.d ar 2€ = ]4.4t indiola a Dcfeenriol 

on@ration dong the c-dis p.rpodicutr io thc suhrde surfae. This obsdalion 

is very clo* ro thc prcvios srudy..l 

PMat t chniqs uludonic ero$l ejlt d chetuic.l vapou deposjtion h6 e edge 

ovq dE ultr&nic itradiaiion 6in.d $tutio! rcure,.! $iic.h @ bed oh 

tadidolal peipiiarion lh@ry &d involvB nul(ptc d€Fsiijon cycle. Typically 20 

d@osition cyclcs w€rc p€rfomcd b.forc utbeenic iradiarion of subsrar.s. Th€ 

ti8[ El@ity hicrejcc goduc.d duirs uir.$aic iftdiarion Move rh. krc€ ud 

l@ely hond€d particl$ od signjfi@t Edu€lion in rh. qwriry of aderbed 

Fnict s My eour for rh! cnl&cd crrsralidty &d !rcf.turi.l ori.nradoa atong 

(002) pldc, wh.r s io ou cs.. ultn fft drcpl€i of pEler EvDa llmw s,a 

di.ltibution i! tu8. of a f€w mi€roDcid @mes in conla.lwirh hot subsfi*e ed 

d@btxg to hiel y sifom spol ta tiln with e.tec.d dlstdtiniry ard 

prefeential(002)pldeof p@zincoxideinoxys.ncnvituMe . 

l5J

* 

I 

n * i J ,i l z-I-l-;' 

_ Pan rt.,rrdi _ 

FtrE 57: XRD p.nd of ZoO Fih on C@ic Sub61,ar.s. 

'Ir'. panicl. siz. B qtculard Nilg ih. S.hec cqu.1i@{ [t = r\ ,. / p @sO], 

with r b.ing fte .venged din*ion of rbe.ryslauites, K the Schftr @6lan1 (a 

em.st'al.rbihry coffiel h rhe dngc 0.8A); l, is the wvelogth of X_Bysi dd 

F is {F int sEi brsdrh ol a dfl*ton (i! 6di@ 20) l@cd ar 20. p for dc (002) 

Fal foud h€r. is 0.2362! d (0 = l?.205',,!=1.5405 A) A$uins K io bc 0.9, 

6ulls '! I ldue for thc !vm8.d cltsrat sia of 35 ns! which is in g@d lg@mdl 

wilh tbe vrlB of3G.60 M n4ued by SEM. 

f-;-l 

figln 58 : )(RD Pan@ of rtrin fitm ofzno. 

154

th. sEir 3ia of dop.d /udoFd zno thin 6ln fab.icated filn t Zn (a@Xdn&H)l 

*6s deicmined 6ing D€by€-Sch@i Eqution."'P€d( i etuitics, dapa€ins, 20 

valu* .nd inlcA.l b€adlh of th€ cfledions w€& det min d with X'Pen Dd! 

'I!c avdg. gBjn si& B calcula&d E foud i! the torge of 25 + tO m. The 

calculat d sain sit a8@s with lhe 6ultl ohained by sEM. The X-ny difi@don 

dlb @ofirb€

Figrrc 59: XRD patreo of.lopc

Tb.rvdagcCsncntsof rhirfilDfoudiobe@wdTarom%wiichdDpro 1.8 

u I 

06 % by m.aling a Atitut d duing EDX study.'' 

t0i 

62 

..",*.**"r'L,nl" b 

zo 30 .kt 5

m is cb!tu|ristic fo. thc$ lhn filn! sd h |glt@6r wi0! valE Eponcd 

edlid!'. Tle iDc@cd usmirlalce in rhe lisible md n€a IR rcgion is due to rhe 

wid.! bald glp of zIO. Thc opticd lberprio! @fnciar v.lE (d,) wh'cb *s 

d€temi&d from rrsnirtale m€Numor M ued b pmd$e Snph ot tr (.V) 

w (a. i hv)': (cvt , whe@ r is thictngs , hr is rhc cnds/ of itrcjdmr lishr whi.h 

gave , oplical bdd gap encrgy of ZnO ihin liltn prped by ulrrGodc a@sol 

siird chdicd vatDlr depqilion, cqual ro 1.02 .V Fig@ 62. This valrc is clos 

lo th. reponed value 3.2? eV rl 

L 

Figurc 62r Abearion coemcienr (d?) vs phobn .ndey Ov) cude of zno $io 

Thc optj.al ilorFr.rcy otlhin 6tD depGircd on quliz or gt6s @inly dep.nds on 

i|mtmi@, dcposiiion @!ditio6 dd oxi&iio. pt14es @uiDe duinS thc 

gm*'ll of thitr filo. A moderac ab$rplion b€rreei jjo od 400 m ndy po$ibly 

d's fron d. dep d@or ard aeeplor lev.ls origiErine foD &c dlrglilg bo(h. 

The F.mi-lcv.l, a@ording ro Mott dd Davis lie! berwccn the deep donor ad 

.@ptor sral6. 11q. fihs e opaquc i! rhG dravjot.t Fgion of sFctim. 

!.5.1.2 Z.Or thtn fdD Optic.t D.rr 

IIe &€orprion chdcbislics ofthe Z,O, tiln deposncd on qu.tz M inv.stisaLd 

Ng . tw-Visible specroneler. Figue 63 show.d ab6orb&e vs waveldSlh 

Elarionsbip in rhe wav€lengh region of 2OO-700M, IlE filn M r@p@nt &d 

giv6 abeDrion .dg. nry 235 m. Tni dl|! is jn .gtudt with rhc Drlviou 

158

5 

0.4 

o7 

0.6 

0.5 

o.4 

0.3 

o.2 

0.1 

WM|s Abo.banco SDectE Of ZrO2 Thin Flm 

Oepodbd Oh Qurz Substs te- 

o 

m 3{X) 400 5|I) €00 

W.vd.ngt||(n|||l 

700 800 

t[C!n 63: W-visiblc sFclrum of aor rhin filn d.Dosilcd on.@dic sub6dd€. 

$ 

l 

FiglE 6r: Ab$rFion oemdenr id: ) v! photon enersy (h!), cw€ of zO, din 

IrE odcal absrptior cefrFicd .o. Nu rhc aberptior .dg. ws calcu.r.d lion 

the t tujssion sp€cr&n uling equdon o = lo(l/t) ,Jr wheE .T, is thc 

t59

ft|eilrle ald f is lhc lhickns of |h€ filn. Thc bad gap ceiry of Zq thitr 

filn *s.sri@lcd by plotdng (q.r.hu)' Gvf st! (.v) for ! fitE thickK 500 m 

gw. a cW. 4 shou i! Figr 64, It cd b. sn thlr th. plor is lin@ in thc egion 

of sfug ab$rPtio!.de.. !"\tapolaliog th. lilE ponion nd the ocet aberptiot 

edge to X*k eive the bdd gap €nergy vsl@ .qul ro 5.01 .v. Tlc Esdts e 

@Dt@bL wilh droe of 1i. Taub4: - 5.l2cV, 

3.6 The Electrical Rcsistivitv M€asurement 

3.6.1 Elechicil ch.rscterizotior of the thiD ZnO fflms 

El6iricat cha&ledation ol the thin zno lilns 8roM throueh UAACVD w6 

ceied out by th€ two-probc nclhod a shoM in Figu.c 25. R6islivity ve6u 

hperaru€ b dill€rfrt €nvibmmB iB shoM in FiSw 65. 

ii raao 

E 

9ro 

5ro 

TdDcrrF Y. Bsi.Elg ir diEdoa 

\ 

H-= 

3,l * | 

lqt 2m lato :l{tt 

Figue 65: T€np€Etur€ vs R€sist&c. Msu@ents of th€ zinc oxide film udr e 

oxysen atmospheE (^), vacuu (r) ed .ir (r). 

In tE c6e of d atnospher of air or vauui, & ircFe in €lcctical ffiislivily is 

obw.d abov€ 200 'C. A likcly rqsoo for th. inclca* of elarical Esislivity is rhe 

Mvailability of oxyg€n requir.d for oaupdtiotr at th. int€alitial zinc sii* or a1 lhe 

oryg€n v&ei siies. In pdios sludi.s it h3 b.cn obsN.d tl$u8} th€ 8lo*4h of 

ZnO frlDs udd didercnl oxy*n pdtial plwus (por) thlt fic* filrB beore 

clo* io sioichionei.ic wi$ fMr sirknid dcfak belo* lor toE po,.'7lhe 

d6t!4 of pO: d..@s th. populaiioo of d8dbg bondr @nra, lnich .mding 

ro Mon dd Davis 'r 6 &1 6 dep donor rnd dep rc.cptor d.f@rs, *tdcb @ 

160

xtD g,A.t 

ctrd.dry re[' c.nlar ft( th. rro4o.t T]. i8ulc of lt ldvtt .m'bd 200oC 

in & ad vEe .uLd rqln b rodtty d|& b mrbg d ot 6.sc 

tuglilg toda ritd Dry:L (|!. i! tu ddqt d.ltity oa qa ddLbtc 

duilg H!ftddb. !r tL fll's rydhdr.d '!d.( e o:(yts e.|ph.!., l!. 

Dqd.lioo of rb ddcl ..G! ir oldDirld lrt lt..!ei!, '! s .dimo! 

lbqte of .L.rrlc.l lldrtui0 tdh tt ir..r of |-T.riG 

t6l

3.7 Gas Sensiog Studies 

3.7.1 zro Cortirya! Ethanol SeNor 

S.vcol oxid. Ealdials comor y ed 6 .theol giB s.@E ircluding p@ and 

mciddoF.l snor,r'a In,or,6t"' Tior,6"r 2!0?,6 wo.,tt Moo:.?r od cu:o?a. 

Mdy lls.Nh4 Fponed ftdt pN Znotqr &d n t liop.d ZtrO@ !* wid.ly 

ued to tletc€l lhe slcohol vapou. 

In O. pemt study 96 sser wnln eipo$d lo eilel vapo$ @Es ! cbdg. in 

rcsi3irle dep€nding or lemp@te ed 8ar cordddior Thc .frcr of op.raring 

l@p€..1w B foud to play e ihponel rele ir der@ilirg rt sosniviiy of 

ZnO film e6or io cthqol vapo6, The msiDm eGilivig of 1.95 w6 Deeud 

ar 60 "C, howr ar rcoh lenp€Fr@ (25 .C) irs sponF md Fcovery dne 

itrMe! t@y fold. conpsred ro 60 qC. A plol of o!€r.ring lenp.ratm ed 

etuirivity for 500 ppm elheol valow is pllst d in Fig@ 66. h 8.ncDl d.E 

cxrst & opr'mu opmring lopdtE at which rh. n*hadim ofdsorplion ed 

dissiltion of a 8s on ihc panicular surf@ ce &hi.ve the tuinu g@itiviiy. 

Th. Figes 67 indi€ied $at th€ Etarid bctwd sal'itvity ed eftdol 

corc4ttitiotr is lincd. which help in adj!$ing the @ncentralion oI clhdol v.!om 

loweds ir! sitiviry. Ibe g6in siz (25 + 5 m) of lh. ZaO film deposiG! by 

u|raonic AACVD t6hniqw exnibndd ex..Ucd *Bniyiry ed &prcdEibitity .ven 

The Fie@ 68 shows thsl.tt6 inniatBhrlr@ M srabitiz.d, rh€ inj.cl.d eteol 

ancr !ain8 theugh rh€@onaric.tly @Eoll€d rubc maintaincd .t a empdru. of 

150 t lo avoi.l sy condesalion rlm inro valou ph4 dr! srrit s wirh lhe 

s!rf@ of ZrO rhin 6lo in the iet clEnb.r. the Esislsne of rhe *er daGa$d 

ed soon aid ii bdom€s $twar€d. Aftd few s(od when th. crhqol valDs kR 

EDoled due io cvlpoMiiotr, the Fsislora ofrhe *cor jncFaed. ,nE Eelion 

b.1qd €rh@l eld ioni. oxysen spei€s (O) lat6 place in lrc ditr r€ft ways s 

CrHJOHiSas) +O- s CHTCHO + HrO + e 

crHOH (ea) - H + czHJO (3ufa..) 

ctlro - H+CHfHO 

162

cH3cHo + o (bulk) + cHfOoH + O (v&eci4) 

ft. EsaoM ed E@vcry tine (1imc for lrpexinarcly 90 '/o rcsisLc chrnse) for 

eihdol vapou /an nixlue for 500 ppm co@@Fation 5l tqnpmtw of 60 'C is 

aloul l0l5 e@ndr with g@d epbdu€ibilily. A lubs of es.@her, worted on 

s@i!r pop.ni6 ol ZnO din film prcduccd by qptsy p)roly$s' rowald, eLhtrol 

valoB sd Epoded th.t filrn layd of 20 |!! in thickn€$ showed *Bilivity in 

tctua of Fthe high elhdol onccnr.ation (100G 5000 ppm) al l50J50eC ard 

beli€ve tnol al thh much hid oFraring tcnp@lw! th€y did nol tlepcid on th€ 

@r@tr,rion of .rh,nol.tt An erhel s.@r brs.d o. ZnO MoDds prcpered by 

hydrotheml ndhod,Tt showed hiSI $nsitiviry 10 cthmol concenEarion mginS 

n@ l0 to 2000 ppm at 310'C, ailh good BpoN and t@!dy rin€. Funlmoai 

ZnO ieowiE .lhdol g.s $Dor shos€d high sosilivity ed f6l rcsponse lo 

elbeol s6 !t @nenndon up io 200 ppn with oFBrine rcmp.ratN of 3O()oC,E 

Ou rdulb ha & .d8c over rhe stldi€s in tems of top.nr@ ed @ing 

16!0 .. Sihil&ly ou 6ul!s e foud ro be m@h b€ft€r thm rhc pEviosly 

EFt&d mrko $ in wiich EspoEc ud Fcovcry tidc is aboul 24 ninur.i, 

S*ing fflos pr.pEed rylier sinS a vdicty of l*hriq@s i.c, pl6Da.nltrc.d 

.hmic.l Epou deposnioo (pEcvD).q spdy pr@tysis,* &d slEn Fiiins,tr 

r&hed to @rclusiotr lhar rhe sDor chda&nsdcs of sdsing filfts d€ sflecied by 

lbe morpholo$/, film sftar@, dd filr! rhickl:s, whi.h e dcrcniDed by lh. tith 

pre.p@lion Focedu€. In addilion, the wo.king s.nsing r.hpenrw md filh 

thichs e othd impondl fa.roB rh.t alfd |he gs $6ir8 pop.rri.s in terEs of 

scilivity, r$poroe, md @ov€ry ljne. 

lor . pdticuLr @n@F6rion of cth!@t $po$, $y 500 plBL rhc sditivily 

d€cEs.d dnost 100 7o ds the r.nD.raru. ws raiscd lhn 60 to 2OO oC. Itrcs. 

6nlc e in @ntrdy b peviou worlq in whjch th. sirivity i.clt5s wih 

imEsing op@ring !enF!ah{e,% (Fige 66) nr incoryomrion of I yo Sn in ZrO 

rhin tiltu sbos d inprovenenl of el€ciricst odudivity of bulk ZnO, which 

de@.d wilh the inc@ of SnO doparr coMnuldon (Fige 69) . bmc. 

incras. $e qsitivity of ZnO thir filD appeiably for €lhmt v.Dom. 

l6.l

asr.ttlvlty ol ztto thln FIlm v. fq$.ute 

fi8uF 66: S.nyn\ rrt of aO Lhin filn d veio6 remp€ralrfts 

{. 

Pt 

SensitiYity Responsa OIZnO fhin 

Filn 

FtlE 67: S@itviy rcspoN s tuncrion of €rbool @@ltrarion fo. $h ZnO 

filn a op€tatcd ar 60'C.

E 

!to 

a 

25 

20 

o 

Ethnot co.c.ntrcttoh v. s@t 

o 50 100 150 200 250 

Fi$re 68: Seuitivily Espons 6 a fhdion of €lhmol con@trarion for rhin fln 

ofzno a opdar.d at 60'C. 

E" 

E 

!'" 

rn|dh.h!oo.l.G-,dhhFh 

FiSun 69r Electric€l Esponse otdopped /undopFd sener al op@ring rempeiar@ 

ot60 t. 

3.7.2 zro Co..itrs.s OrygeD S.osor 

Thek thio filns cd b€ sed as .ffici€nl oxygen !e@s; lbe drc! in .lahical 

Eitiivity could wihess dk wher rhcs. fitG qed.xpoed to the flow ofoxysen 

Ior ?0 ninut6 ai 50" C- {Fisw ?O) 

165

I 

a 

T 

lt 

!2 

l0 

8 

6 

2 

Efdotoryad d R€irt E 

io 6|) 

Fig@69r Seer Rcspo4 Tine of Film in Oxygm avirc@ot. 

The t!tup in clcclical rcsistiviry cd posibly be ir!.ed ro nF ir€o.Doralion of 

oxygo al sn dcf6l sites. A mininu Bisriviry is &hj€v.d wna lhc oxysen 

@h3tion @ches the opdmw l€vel r.quircd lor rh€ desjRd d&gling bonds 

Fpurldon b ZnO ehch is achicvcd in 20 mitutcs, Th. filnha inc@ in oxyg.n 

concenlrado! ovcFdoFs the ddgling boods population in th. uir ccll ed as a 

6ut dr 6i$iviry is dgain inc@ed b highd vsl@s !n r 45 min$6. 

3.7.3 ZrO Cortiug rs Nstural cs3 (Methrnc) Srnso, 

ZnO $in f,ln ga sNr (d6isn.) whq cxFed lo olrltal gs eug ! chegc in 

6i5eM ar. i€nFratud of20o "C. 'ne es F6ing h.chaism nomdly acc@t€d 

for eni@nderor s@. supposins rhd rh..nviomdrd oxyscs (q) ad$rbcd on 

th€ surfee a Or'or O- by renoving rh€ el@lron deosity fioD dr. @oducrion bed. 

developing a d.pl.rion r.8ior o. the surfae_ 1L @tion ljn@ncs will b€ s 

o! (s6) € or (ab6o.H) 

o, (absorb€d) +e +o, 

oi+t '2o 

Wh@ meftae 8s mol&ule con€ in o.t .l with dlis aderb€rt oxy8.q leoding !o 

& illle cbqgc lasfer upon lh. lah of.lcLo! ro rle 6rdudio! b.dds.o Th. 

d@let,on rcgion crcaied by lh€ chehhorylion of Oj on tbe suface nov fi ed by 

166

cletrons &d lhs rcsi$de chd8. M obsded ad thE i!).i!e in h.ishr of 

@nd@tion be& or conducrivity obsded. nE tosibility of a G&tion of neftee 

sa *ill! zro thin nltn ca be explajned B follos; 

CtL + 4[o1 +CO1+2HrO+4e 

Thc cffer of oFntinr cnpentuF s found 10 play & inFrt d ole in 

deLnnining tll. s@ililiiy ol ZnO filn seNor to naruEl gas. nrc nqiE@ 

BpoE a obsved !l a rmFEtw ol ar 200 oC, howd.r at lo{ rempdde nor 

or{y iii respoN. tim. incEes bur ole md it5 @irivity d@rcses @ifolds. A 

ploi of opeFting temFrarues ard emidvny for 500 dd 1000 ppm mtual ga is 

pGat d in FiSw ?0. In geocBt ficrc €xist d optihm ops inS renpoln!. ar 

shi.h t!€ nccheiss ol de$Ation ed d@nFsition of a ga on th. pfiiculd 

sud@ @ ahide th. fuinM s@itjvity. 

E 

e 

I 

-FaecrE 

(Iil) 

ri8orc 70: S.Mr R€spols Tine of Filft in Nar@l 8e (Melhe) eNircmenl. 

Th. sditivily rcssdirg response lime in ou c& is Dwh lowo (lO min,) rhd th. 

ldioa sludy (40 njn.),'r \h* atimoDy oxirt (sho, b u*d for rh. d.lecrion 

t67

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t72

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173

Conclusions 

Son6hmical t€chnique can be efatv.ly u$d for th. synilFs$ of ! vdiery of 

volalile hetal oreeic pEcusoB for the grcslh of thin filn of mcravrehl oxide 

Bing dtr.enic &rcsol. ssisred chmicat vatou d.pcilion rehniquc (UAACVD). 

U3ing thh tehnique &!e!al netilconplcxa such s mek! Fdilcromrs lik M- 

(&&L 0-9), M1i!d). (10-13), bis triphdylphospbioc zidc 0D chlodd. zn (rPhj ), 

cl, (14, zn (dm, (18) sd n.w herdol.pric add@t lik [z.(mc)?Gaf] (15), 

(h(e&),(dh&H)l (16), tNitGEA)1,(oAc)tl eD, (zr{d@),(oAc)rd (20) 

(dn&)z!rla @l), tcu(dnae)(oAcxtlo)l: (r4), t brt(EroH),-N- (oAc)l? cul 

(r3) md ta(&&)rG:o)lcl (r9) kE prcp@d b hi8h yields 6d chreteize by 

wioN physi@ddrlical tcchliq!€s lilc, D.p, CHNS-O, .romic alerprion 

ddlzer, FTIR, nultinucled NMR md singl. crt5el xaay anrlFis. Srith.ric 

rcsulls cl.aly indi@t rhal applicaiion of p{it tonat€s od minoal@hol ddivadves 

ofn t l lads ro low nuclediry @hptex6 wirh simple sroichion.uic rario, whit. 

involv@nt of Fboxylate goup yi.ld oligonric poducr wilh omplex 

ltmogr.vinetric atudies indic.tca that coopl€x€s de@mpoed .le&rly b 8iv. 

mehl in cs. of @pper p!€cwr tc(dD&XOAcXHTO)1, (lO &d netd oxid. in 

ce of 2irc FeuMr lik tzn(@),G.!l Os), tzj(a@),(d@rDl (16), 

t(znidm),(oAc),01 foi zioc oxide ed [z4edr(H,o),]cl (19) for zi@niw 

Bed o! lcast vdlue lenpenlucs i.e,. To tud T.- d.riv€d fton rhemal dau 

followinS ordr hs ben popoed for vsios neial @tylac€ionar. d{i!a1iv6 fot 

tcr (&dc!l > tcu (eac),] > tAl (.*0t >Ni (acac, tco Gc(nt > IMn (a@)rl > 

Enerey ofacti!€lio. was deremin d by applying Mod.l Fe Kj.elics, orh oid.r, 

coa,ls & Rcdf.ra Kbsinser ed oawa m.thodr Nsuins singl€ 6d mutri stcps 

dbonpcirion mcdon for a paniculr zorc uing TGA,/DTG d.i!. Dsla cvdtcs 

lhal for singlc $ep d.@hposilion par€m, sclivation eicrSy tlab foud to b. very 

clos h *h @. Howver in nulristep demposirior parhwatr the sff we

s.d MFK rcsults d€ noe aulh.ntic 6 @npar.d to mu.lly calculit d by 

spllyilg olbd n dtodologi€s. M@hdis of lbmd

PPEIIDD(.I. 

APPENDICES 

P.tt m Phti4 or C.dbic Sublrnts. 

RcDove rh. d!s! oils, sre*s, h&d 6rtk erc., n@F the sudse of @mic 

subsra& by ntuing fi*t by acelon. followed by 1,1,1 richlorcelhe. od thei dry in 

IMMERSION SILITR" 

Solt'tion t. AgNO3= 15 s/l (dissolved in dhrill€d wa&4 

NH4OH= Add amonia sluliotr (37%) to silvd nira. elurion r,ill 

rhe precipirate fom.d Ediselvcd, 

Solution 2. KoH = 15 9l (diselvcd indisriucd rd,u, 

Soluiioo 3. Clu6s = l5ell {disllcd i! dislill.d wat€r) 

Mix de th@ elution in I : ! i I lado ed dippcd itr€ cl6cd cemic subsrdc jo lhe 

mixtE lill a v.ry i@ llycr of silvcr fo@ed on cemic slbstFre. ( t -2 r ihickrcs) 

ELECTROLESS COPPER 

C!SO{5E!O = 200 -250g/l (dislvcd indisrill.d waIq) 

HlsO. = 5-7 El 

N. K(C.O.&) = 0.2 to l.0sl 

Teop.r.iurc = 35-40 !C 

Tib.ollod.Eior - dcp.ndng ulon lh. rhictoc$. 

Disslv€d th. ingredieol in applopriate weights $pesr.ly in disrilcd *arcr, nix 

fid ed Dr&. the vol@e lo one jilre. ttiplrd rhe silva @ated etujc $h6t. ir 

th. nixrE rill a very fine llter of @p!E fomed on ctuic subsrzr., (2-l F 

I. PHOTO RESIST PRINTING Trv EXPOSER 

. Pboro@isl ltln .ppli.d ov€r copper pht d ro rce 

176

. A Eut i! pL..d ov.r pnoto@bt lilo to dcvelop Ddem. 

. Plotocilt illD i! erpo.d, 

. Ptorodnt iD.C. i! ddeloFd. 

. P.nd b rnlrf€r.eil ro @pp.r nh by.t itn& 

A@oliud p.n!lpb.t. = 20% (Sh! ofl@ppa flom udesirod 

Plaa) 

!. Sqlphodc A.trl Dip = r|y. 

a. Ptoao 6art i. tiripp.d ott 

Gold Pl.li!& 

. DE - Photor€dst (ftis wil @ovc phobqi6i fion @pF 

pslar) 

K ,{! (Cr9r - llocn (d'slved ir diditl.d wrcr) 

l

A'PPENDIX-II M btmric.t ddiv.rtoD otB..d crp E rar. 

8m. iDport Mth@tiql egu4ions u$d for dcdvation of oprical bed gap d€ 

{l Eql 

wlft "4" is absltio. cocfiicien!'.f'b tr&imi(6nc.,..1 i! rhickn sof tiln. 

Accodirg to |]s GnerF/ cq@lion; 

E(J) =lv or E= E I 

E 

E(.u= -L t.&2 

tiJ 

E.2 

By multiplying E9. I with Eq. 2 and puftiDs rhc vatuc of c, x C = (ln l/T), on nsht 

sid., l!! cqDario @@ ro be; 

By siDpliftilg, 

ElEvlxd:xP 

(E.art(cvf 

Plor of hv (cD w (a.r.h vt (.9;, wil sivc {!. cwg D6ma $.ish rie nom 

|n. ce! o! X-6xis Mll giv. lhe valuc of.nd$, baod 8dp. 

tlE

APPENDX-[I EDX s!ftr ot aL ahi! 0lD! 

EDX ofcu thi! frln 

EDX ofzlo ddn 6tm 

EDXofSndotEd ZnO fiin fitm 

t79

EDX ofzor ihi! fh 

tE0

APPENDD(-ry TGA/DTG Crn€ u.d for tt. dsrr.Ddr of 

T 

MFK 

MTK 

Actv.rio! Ener$/ urlog Mod.l Fu Ktbetig (MIK) .nd 

!d Ord6 Kbdi4 

Activ.tlor E!.Ia/ Cun6 

lr 

rlrr:l:l:fi" 

..,:;.-... -,-,- * s-E-': 

lEt

.i$*n-*."i3:-.+-qi._*i-*Tr.Es_* 

182

a 

MFK 

MFX 

a 

l': 

l: 

l8l 

I 

iS.HF--

6 

Nth Ord.r 

MTK 

Nth Ord.r 

184 

App6dicies

8 

MFK 

MTK 

t85

9 

MTK 

'l 

'i 

I 

t86 

:;:l 

*1

la Cx(fr)t 

u Zn(tld), 

MTK 

t81

l5 

zn(6d), 

MIK 

l8E

t6 

Mrt( 

It zn(PPhlc! 

MTK 

189

zr(PPh),cL 

z(@)3 (H2o), . cl 

MTK 

a(ael (H1o>. cl 

190

20 tzn' A (de) 

(oAc)d 

Mrx 

(oAc)'d 

NitGEA)3]' (OAc)' 

Mrx 

l9l

NdGE {DL @ac} 

Ntlr Od.r 

- f,'!-=rso 3169"- 

tt2 

Alradici6

Datc OfBinh 

CURRICULUM VITAE 

E-mit. hu-.nnir_469@yalel.@n. 

Fnuonon.l O!.li6etiol 

Sy.d MlElmil Husin 

12619 Off@re Colony, Qader Road, N.d 

0l-01.1957 

L M.Phil. (AMl,lical 4norgeic Chemisrry) 

Iirn Quidl-Am Univdsiry,Isl@abad in Oct,l98l 

2. M.sc.(Alalrlical/tnorymicchenhiry) 

IionQuid-l-Am Unive6iq,,Islmbad in 

Jo,l9?9. 

Bd4&[I9rlq @.Phil) 

. nuiotrd sMies of Fi6r TEn$irior Sqi6 Bt NMR. 

Elp.rt nc.. 

!!!E!!& 

AE of Shdv. 

l Trc Year T.aching Exp€deG i! eluc CoU.8.. 

2. Twoty Six y.$ cxpcri.n4 in rcpuie ReseKh 

o.emiarion. (ICS) 

3. Assisone b Ngtionat luthonry @OIA) pdrist!! in 

Llr field of OPCW dppro\.n .4upddB. 

l. Sn ct ulinin8 Ggarding Sufs@ Tqibol !t 

Chi@ (1994) 

2, One lvak Tning Ar Menld Toll€do (Swirzdled) 

rcgardins 'ftmd Anatlttsis Equipnen. (2004) 

3. One Weet Tninin8 Al Agitdr Techotogi.3 

(singapo&) rcrddiis cc-Mds. (2005) 

4. Two WeLTraining R.eaiding Disposst of Industrial 

Emuenl ar china. ( 2006) 

5. Trcv€k CC-Mss Tnining h Analysb of 

Hyde6bo! ar Chjna (2007) 

r . Analyrical Ch@isny. ( InsEuer al Alrlrsjs ) 

2. Comsion Slu

2 

2. 

.t. 

tluis$ess 

5, 

PAPERS SUSMITITD 

synth*is / ApplicdlioE ofAdltoiv.. 

Oryaonellllic SyDlh.sis 6d thcir Checrcnados 

sir'g CC-Ma, GC, FlI& TCA,/DTae DSC, CHNS, 

O, Alonic Ab6orption tudyei W-Vi' 

SFcnophorom.ld. ttPLC, 

Somcb.bicd lytrihBtu,tterod d@rpoliaion rbd iingL crylt.l 

slNcture of lz(rsc)t(Brollcl coEpound.,{ pruuBor for 

lbi! filE d.po.ilio! by lrite.ic .enrel srltt d cb.biqr 

v+our d.!@ldor. Muz.mil, H.; MaA.r; M.; l(na*s, &; 

Mo$lire, E,; &d Taj@al H. r,// KoeM Ch.n S@,20n/8, 

291lL),92-96. 

Pro.loctior ofllydEg@ url C.rbo! N.notubd nor Crr.Mc 

Daodpdirio! of M.th.!G ovd Nicq..lrDbr Modifk 

S{pt i.d Crt.lFt!. Taj.lmul, H.; Mazhr, M..; SaMr, l.t Shc@. 

G.; Mljrmhil, H.r Fai,cd,L. Bul!.r@eak Chen.Soc 20{?. Vol,28, 

Sy!O6ir, Them.l Deoupottio! ?.tt n .!d Sirgle C.yrr.t X- 

R.t Sttix* o(diE..i. ICu ilE.. (OCOCgtsrOh: r Precono. 

lor.tc Aerorol Adlred Cn.dkrl v.pou? D.poltrioo orCopFr 

M.trl Tli. Filn!. M&nd, M. Husaii S. M.,raizpubbloi, 

Oabneie K@iok-Kdhn; Ki€m C . MolW - R Il. KM Chen.Soc 

2@6, V o1,2, N o.9,.W | 572 - | 57 6. 

Coturio. B.b.dor ofTi|n|lo ir.or.rd rtah L€rd tr 

Sulphuric .(ld uodiribg brrh, 70 Inremarionar'onat Synp6im on 

Advdced MaL.rials ( l7- S.p .21! SerJoor ) Pakist&. 

Hig[ Efeci.lcy ZoO Nuo 5.!ror, f.briqrjon Ard 

M@bbil Huss.in, MuldmAd M,zjd, Tajmut Hlei!, 

Nzwdsh A Klr6, Jowatl oJ hutu Chenicat Soc P.p.r 

Ac..pt.d (MeuscnF # @-08-39!24). 

SF.h.rs rd Cryrhl sbutM of NJ{-.ri6crhvLruelhdoLb 

Z.GD tiodxG, NN.d6.syr--t-c.h.@hb CdoD Uodd., 

Ed N,rl-(di6.rhrt ri!o).rh&ol .ddEr of CdgD riodid.. 

Naved Ahe, Muhdinad M.zh&. Atiti_ T. Kea, Kiem. C. 

Morroy tud Mu,!@il HBein. Jouaol Of Moleculv StMt*4 

(Mahwctjpt 4 atsisned: a8.S-J26). 

t94

PAXER.S TO EA SUBMITTED 

l s.loct oL.l S}!O.|lt, Tl|! nb D.po.tdolj I t.rD.t.!d X- 

Rry Stul@ Ol Hlg! Nldortty Zhc Clu..r Z||l Ora N, 

2. OEai.rt ud O|| Sul4 rtnd.l of tnDD.Mr ZlO tll! ttlD 

d.po.lt d rroE . !d pir..nor Dy dr.eltc rrlaotc &tt d 

.t.Drc.l v.po! d.F.tdoL 

3- Irq'o.ldo! .bdh. of opDo uo p.dLt . froo @pp.r F 

d0..ro!.tr rd .Ebo.lcoloLa. by .lan|o!h r.MoL sL!.d 

ct Dh.l v{ou dqotito!. 

195

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