CHEM01200604009 Sreejith Kaniyankandy - Homi Bhabha ...

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160 isolated CdTe QD over graphene sheet. CdTe QD sizes are approximately 2nm. The lattice fringes in HRTEM images show a d-spacing of 0.24nm which matched well with (220) plane for cubic CdTe. SAED shows 2 rings which could be assigned to (220) and (311) planes of Cubic CdTe. 6.3.2. Steady State UV-Vis Absorption and Emission Studies Figure 6.2 shows optical absorption spectra of CdTe and Graphene-CdTe (G-CdTe). The clear discerning feature in the spectrum is a band at 440nm for both the samples and is assigned to 1S e -1S 3/2 exciton. Since under the synthesis conditions the particles are spherical, the position of optical absorption feature can be used to arrive at a size of 2.2nm for quantum dot from sizing curves as reported previously [6.21]. This size obtained from optical absorption spectrum matches well with the size obtained from TEM. A closer look at the absorption spectra reveals a feature at ~300nm which matches well with the Graphene π- π * absorption. The similar peak position of CdTe and G-CdTe clearly show that the sizes are similar for both. This observation enables us in a direct one to one comparison between CdSe and G-CdTe. The photoluminescence spectrum in figure 6.2 shows just a single feature in the visible region at 500nm illustrating similar particle sizes. This emission is assigned to radiative recombination of the 1S 3/2 -1S e exciton. The peaks position for both the samples are ~500nm indicating the similar size of the quantum dots in both the cases confirming the conclusions based on optical absorption. The emission spectra from absorbance matched samples show a clear ~90% quenching of the G-CdTe emission as compared to pure CdTe. This observation could be an indication of electron transfer from CdTe to graphene on photoexcitation which will be confirmed later by femtosecond studies.
161 Intensity (a.u.) 5 4 3 2 1 CdTe G-CdTe c d Absorbance (a.u.) 1.5 1.0 0.5 0.0 a b 450 600 750 Wavelength (nm) 0 400 500 600 700 Wavelength (nm) Figure 6.2: Photoluminescence Spectra of a) CdTe and b) G-CdTe after exciting the sample at 380 nm. Inset: optical absorption spectra of c) CdTe and d) G-CdTe. 6.3.3. TCSPC Studies TCSPC studies was also carried out on G-CdTe by monitoring the peak position. Figure 6.3 shows the emission decay kinetics of CdTe in water and on graphene surface.
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Charge Transfer Dynamics in Quantum
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DECLARATION I, hereby declare that
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ACKNOWLEDGEMENTS It is my privilege
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1.3.5. Defect Mediated Relaxation 2
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2. 8. 4. White Light Generation- 45
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6.2. Experimental 6.2.1.Synthesis o
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devices based on QDs it has been sh
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Furthermore generation of pump (~40
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shell). This clearly indicated that
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12. V. I. Klimov, J. Phys. Chem. B,
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1.13 Reactant and Product Potential
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light. Inset: Kinetic traces monito
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6.5 Transient decay kinetics of gra
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at 670 nm after exciting at 400 nm
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ABBREVIATIONS BET BQ CB CCD CdS CdT
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1 Chapter 1
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3 size dependent optical properties
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5 1.2. Physics of Semiconductors 1.
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7 As seen from the schematic, poten
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9 Substituting this in Schrödinger
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11 ( r, r ) ( r ) ( r ) (1.13) e
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13 E E E 2 2 2 EX ne, le nh,
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15 spherical symmetry of field. The
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17 gE ( ) 2Em 2 3 3 (1.25) For a
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19 1.3.2. Electron-Hole energy tran
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21 Impact Ionization Figure 1.7. Sc
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23 understanding on mechanistic asp
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25 carriers are unable to sample th
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27 CB VB QD Metal Figure. 1. 10. Sc
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29 energy barrier. Therefore it is
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31 1 f q 2 A qB (1.30) 2 In equa
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33 Vibrational contribution can be
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35 1. 7. 1. Electron Injection ET i
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37 Under assumption of invariance o
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39 distribution. To achieve good si
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41 initially achieved monodispersit
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43 and rate of charge transfer acro
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45 1.32 P. V. Kamat, J. Phys. Chem.
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47 Chapter 2
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49 chemical species. Since a partic
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51 fluorescence forms an important
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53 eliminated by use of standard wh
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55 sample. Raman spectroscopy is ba
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57 will appear bright and region wi
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59 volatile solvent is drop casted
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61 spots arise from diffraction fro
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63 The electrical signal is then ch
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65 delayed and inverted. The two si
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67 Pump-probe technique is one of t
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69 Amplifier Jade Stretcher fs Osci
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71 Figure 2.6. Optical layout of Ti
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73 Grating Convex Mirror Concave Mi
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75 changes the polarization from ho
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77 Grating Output Input Mirror Grat
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79 μJ has a very high peak power.
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81 2.6. Dynamical Theory of X-Ray D
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83 Chapter 3
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85 Therefore the study of interfaci
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87 3. 2. Experimental Section 3.2.1
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89 and intensity show absence of ot
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91 which is also neutral; therefore
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93 electron transfer times. This re
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95 r B a * 0 3.1 me / me Now the
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97 nonadiabatic case the electron t
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99 drastically reduced leading to a
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101 While the study of injection dy
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103 study. Based on the injection d
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105 17. L. E. Brus, J. Phys. Chem.
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107 Chapter 4
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109 of the QDs. As a result surface
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111 4.2.2. Synthesis: The CdTe QDs
Page 158 and 159: 113 lower hole state. In CdSe the l
Page 160 and 161: 115 4.2 inset. The kinetic traces a
Page 162 and 163: 117 growth of the bleach kinetics (
Page 164 and 165: 119 previous section we have discus
Page 166 and 167: 121 lived charge transfer complex w
Page 168 and 169: 123 100 times concentration of the
Page 170 and 171: 125 4.5. References 4.1. Efros, Al.
Page 173: 127 Chapter 5
Page 176 and 177: 129 been made in the synthesis of t
Page 178 and 179: 131 metallic synthesis by arrested
Page 180 and 181: 133 5.3. Result and discussion: 5.3
Page 182 and 183: 135 indicating a confinement induce
Page 184 and 185: 137 absorption studies that on form
Page 186 and 187: 139 1000 c b PL Intensity 100 10 a
Page 188 and 189: 141 samples due to a very weak exci
Page 190 and 191: 143 dynamical spectrum is negligibl
Page 192 and 193: 145 Earlier authors [5.4] reported
Page 194 and 195: 147 Sample t r(ps) t 1(ps) t 2(ps)
Page 196 and 197: 149 In addition to the cooling dyna
Page 198 and 199: 151 pulse-width time scale followed
Page 200 and 201: 153 5.20. Sreejith Kaniyankandy, Sa
Page 203 and 204: 155 CHAPTER 6 Charge Separation in
Page 205 and 206: 157 Studies by Wang et. al. [6.15]
Page 207: 159 graphene in a 1M NaOH solution.
Page 211 and 212: 163 dynamics of graphene oxide and
Page 213 and 214: 165 GO as shown in the Figure 3 rev
Page 215 and 216: 167 electron acceptor for Graphene.
Page 217 and 218: 169 governs the recombination dynam
Page 219 and 220: 171 Sample τ 1 (ps) τ 2 (ps) τ 3
Page 221 and 222: 173 A (mO.D) 10.0 0.0 -10.0 -20.0 0
Page 223 and 224: 175 involved in the relaxation may
Page 225 and 226: 177 Electron quencher (benzoquinone
Page 227 and 228: 179 Scheme 6.1. Schematic of Electr
Page 229 and 230: 181 6.6. Reina, A.; Jia, X.; Ho, J.
Page 231: 183 6.26. Kaiser, A. B.; Navarro, C
Page 234 and 235: 185 assigned to injection into diff
Page 236 and 237: 187 transfer from CdSe core to ZnTe
Page 238 and 239: 189 However the position of bands i
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