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Imprint Template Advances and Surface Modification, and Defect Analysis for Step and Flash Imprint Lithography Publication No._____________ Todd Christopher Bailey, Ph.D. The University of Texas at Austin, 2003 Supervisors: John G. Ekerdt and C. Grant Willson Step and flash imprint lithography (SFIL) is a relatively new technique for patterning high-resolution polymer features on planar substrates. This technique has been used to produce features smaller than 30 nm in size through many imprints, pattern a substrate with existing topography, and also to produce functional optical and electric devices. The ultimate manufacturability of SFIL for high-resolution applications depends on the ability to manufacture high-resolution imprint templates, and also to produce imprint fields that are relatively free of defects caused during the imprint process. The primary goal of this work was to investigate the generation and propagation of defects produced during the imprint process, and this involved various material and process development efforts. A process analogous to that used in the photomask manufacturing process has been created for manufacturing imprint templates with features smaller than 30 nm. Using a thin layer of electron beam resist and a thin Cr film resulted in the vii
mitigation of the shift in feature sizes during the etching steps. Additionally, by substituting ITO and deposited SiO2 for the Cr allows similar feature resolution, and the final template possesses charge dissipation capabilities needed for end-of-line inspection. The quality of the surface treatments deposited on the template using a fluoroalkyltrichlorosilane is dependent on the substrate used, and also on the degree of hydration of the substrate. Several materials were tested for compatibility with the current surface treatment, and it was found that deposition of the surface treatment on Si3N4 and SiOxNy resulted in films that possessed coverage and durability similar to that of SiO2, but that films deposited on ITO lacked mechanical wear durability. It was found that exposing a dehydrated SiO2 substrate to water vapor for various times followed by the surface treatment precursor resulted in greater deposition of film species on the surface with increasing water exposure. A defect analysis was performed for SFIL, and it was discovered that the defect trends over time are strongly dependent on photopolymer material properties. Early results indicated that the dominant failure mode during template/substrate separation was that of cohesive polymer failure. By redesigning the etch barrier material blend, the elongation-to-break of the photopolymer was increased by more than one order of magnitude. This material change resulted in the elimination of the cohesive failure mode, and allowed faithful replication of features through more than 400 imprints. It was discovered that imprint film thickness variations can have a dramatic effect on the pattern contrast. This pattern contrast was modeled for various film thickness combinations, and this effect is believed to impact defect detection in optical inspection equipment. viii
Page 1 and 2: Copyright by Todd Christopher Baile
Page 3 and 4: Imprint Template Advances and Surfa
Page 5 and 6: Dedication This is dedicated to my
Page 7: I want to thank those who aided in
Page 11 and 12: Chapter 4: Review of the Reaction o
Page 13 and 14: Appendix D: Conversion of KLA Data
Page 15 and 16: List of Figures Figure 1.1. Schemat
Page 17 and 18: Figure 5.3: Water contact angle and
Page 19 and 20: Figure 7.25: Images captured during
Page 21 and 22: Figure B.8: Program diagram for Swi
Page 23 and 24: “source” and “drain” region
Page 25 and 26: computing power is required. Microp
Page 27 and 28: Photoresist Substrate Mask hυ hυ
Page 29 and 30: Tool Price ($) $100,000,000 $10,000
Page 31 and 32: material. This material takes the s
Page 33 and 34: planarizing/transfer layer was coat
Page 35 and 36: patterned relief structures is alig
Page 37 and 38: Contact lithography predates the pr
Page 39 and 40: 8. Chou, S.Y., P.R. Krauss, and P.J
Page 41 and 42: SFIL IMPRINT PROCESS DEVELOPMENT Ch
Page 43 and 44: substrate that changes in chemical
Page 45 and 46: In modern photomask production, imp
Page 47 and 48: and CD-SEM inspection, and also all
Page 49 and 50: Requirements for Transparent Conduc
Page 51 and 52: quartz substrates. Percent transmis
Page 53 and 54: a) b) Figure 2.5: (a) 30 nm trenche
Page 55 and 56: nm, so the normalization to film th
Page 57 and 58: with increasing anneal time, up to
Page 59 and 60:
2.12 shows line/space features poss
Page 61 and 62:
a) b) Figure 2.14: SEM micrographs
Page 63 and 64:
a) c) e) Index Index Index 2.7 2.5
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function of ITO thickness is much g
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esidual layer only. The right plot
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it is mentioned here for context. T
Page 71 and 72:
Some results are shown in Figure 2.
Page 73 and 74:
5. Widden, T.K., et al., Nanotechno
Page 75 and 76:
45. Lewis, B.G. and D.C. Paine, MRS
Page 77 and 78:
3.1 BACKGROUND Chapter 3: SFIL Etch
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3.2 EXPERIMENTAL For the imprinting
Page 81 and 82:
The fluorinated additive experiment
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Formulation M2 did not polymerize.
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adhesive forces at the two interfac
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Chapter 4: Review of the Reaction o
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such as annealing. Each of these ex
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on colloidal silica particles. 9 He
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Figure 4.2: From Chuang, et al. 16
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was achieved by exposing the surfac
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Cras, et al. 37 compared various we
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where X is either an alkoxy group o
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with increasing temperature. They a
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from liquid and supercritical CO2.
Page 105 and 106:
hydrolyzed intermediates. These res
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limiting film thickness. This is in
Page 109 and 110:
authors observed a decrease in the
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to form SAM films of at least moder
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was able to predict the networking
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39. Ruzyllo, J., et al., Proc. Elec
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77. Allara, D., A.N. Parikh, and F.
Page 119 and 120:
Chapter 5: SFIL Imprint Template Re
Page 121 and 122:
5.1.3 Self-Assembled Monolayer Rele
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ITO, followed by plasma-enhanced ch
Page 125 and 126:
5.3 RESULTS AND DISCUSSION 5.3.1 Fu
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a) b) Water Contact Angle F:Si Area
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Imprinting Durability of FOTS on Fu
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At the time of this writing, no oth
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Methanol adsorption below 130 K fol
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of the SiO2 layer to define the tem
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treatment films of at least modest
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imprinting durability. Due to the r
Page 141 and 142:
Chapter 6: Effect of Substrate Hydr
Page 143 and 144:
The Ag 3d5/2 XPS peak at 368.3 eV f
Page 145 and 146:
dθ Equation 6.8 ( ) 2 OH , 3 3 −
Page 147 and 148:
Concentration (nm -2 ) 5 4.5 4 3.5
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Mass (mg) 14 13.9 13.8 13.7 13.6 13
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silanol coverage for temperatures b
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increasing film density with increa
Page 155 and 156:
7.1 INTRODUCTION DEFECT ANALYSIS FO
Page 157 and 158:
The fundamental question to be answ
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placement in the die array must be
Page 161 and 162:
an exposure source that is used to
Page 163 and 164:
the transfer layer. The BARC was sp
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Figure 7.5: UT MER South cleanroom
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English rating denotes the number o
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wall of the cleanroom was a large c
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The results of the particles genera
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the wafer chuck, and we have attemp
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7.4 RESULTS & DISCUSSION 7.4.1 Temp
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a) that protects the master from co
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determines the absolute value of co
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a) b) c) Figure 7.16: Resist images
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Figure 7.18: Evolution of slope (so
Page 185 and 186:
Figure 7.19: SSE for the data in Fi
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and 92 in the denominator is 3.95;
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a) b) Figure 7.22: (a) Obvious patt
Page 191 and 192:
Table 7.1: Percent standard error i
Page 193 and 194:
a) c) e) Defect Density (cm -2 ) De
Page 195 and 196:
defect bins reveal an increase in d
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detected defects in one particular
Page 199 and 200:
imprints show little or no increase
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a) b) Defect Density (cm -2 ) Defec
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Figure 7.35 shows a defect composed
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a) b) c) d) e) f) g) h) i) j) k) Fi
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a) b) c) Figure 7.34: Example defec
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a) b) c) Figure 7.36: Example defec
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Figure 7.37: Stress-strain comparis
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7.6 CONCLUSIONS The SFIL cleanroom
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Chapter 8: Effect of Film thickness
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8.2 EXPERIMENTAL A Woollam M-2000 s
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a) b) Figure 8.4. (a) Irradiance sp
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intensity of the Xe lamp, and RspCC
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a) b) Contrast Contrast 10 9 8 7 6
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a) b) Figure 8.7. Contrast response
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a) b) c) Transfer Layer Thickness (
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contrast prior to subsequent etchin
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The etch barrier imprinting fidelit
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evaluation needs to be undertaken t
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where η0 and ηm are the optical a
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N_SiO2 = SiO2(2,2:3); t_SiO2 = 100;
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SFILCalc.m function data = SFILcalc
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function [a] = phase(lambda,N,H,thi
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Figure B.1: Picture of the surface
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An Omega type K thermocouple is con
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Figure B.2: Diagram of surface trea
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Figure B.3: User interface for the
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option when the program is started
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Figure B.7: Various subVIs called b
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Figure B.10: Program diagram for Ch
Page 257 and 258:
The Auto program uses these same su
Page 259 and 260:
Figure C.1: Force balance diagram f
Page 261 and 262:
Figure C.2: Plot of cos θ vs. γlv
Page 263 and 264:
Figure C.4: Plot of cos θ vs. γlv
Page 265 and 266:
Equation C.8 which upon rearrangeme
Page 267 and 268:
and electron-donor (γ - ) paramete
Page 269 and 270:
where θ0 is the contact angle in v
Page 271 and 272:
Kwok, et al reinforce the relation
Page 273 and 274:
Figure C.7: Correlation between mea
Page 275 and 276:
If one requires only an estimation
Page 277 and 278:
32. Kwok, D.Y., et al., Langmuir, 1
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a separate delimited text file for
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2 -2 M -1 1; AreaPerTest 1.20197e+0
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ins1 = strcat('< ',num2str(edges(2)
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n(2) = n(2) + 1; case 3 n(3) = n(3)
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Appendix E: Estimation of Downstrea
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Figure E.1: Experimental FTIR appar
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Figure E.2: Vapor pressure apparatu
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Absorbance 0.16 0.14 0.12 0.1 0.08
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Absorbance 0.3 0.25 0.2 0.15 0.1 0.
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Absorbance 2.45 1.95 1.45 0.95 0.45
Page 299 and 300:
Figure E.9: Comparison of experimen
Page 301 and 302:
ln(Psat (Torr)) 1.5 1 0.5 0 -0.5 -1
Page 303 and 304:
FOTS Concentration (mol/liter) 2.0E
Page 305 and 306:
Bouwhuis, G., et al., Principles of
Page 307 and 308:
Constantine, C., R. Westerman, and
Page 309 and 310:
Gun'ko, V.M., et al., Inter. J. Mas
Page 311 and 312:
Lee, L.-H., J. Coll. Int. Sci., 199
Page 313 and 314:
Pellerite, M.J., E.J. Wood, and V.W
Page 315 and 316:
The Aldrich Library of FT-IR Spectr
Page 317:
VITA Todd Christopher Bailey was bo
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