OPTICAL PROPERTIES AND SPECTROSCOPY OF NANOAAATERIALS. Jin Zhong Zhang. World Scientific TECHNISCHE INFORMATIONSBIBLIOTHEK
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1 OPTICAL PROPERTIES AND SPECTROSCOPY OF NANOAAATERIALS Jin Zhong Zhang University of California, Santa Cruz, USA TECHNISCHE INFORMATIONSBIBLIOTHEK Y World Scientific NEW JERSEY. t'on.don SINGAPORE «'BEIJING SHANGHAI HONG KONG TAIPEI CHENNAI
2 Contents Preface vii Acknowledgments ix 1. Introduction 1 2. Spectroscopic Techniques for Studying Optical Properties 11 of Nanomaterials 2.1. UV-visible electronic absorption spectroscopy Operating principle; Beer's law Instrument: UV-visible spectrometer Spectrum and interpretation Photoluminescence and electroluminescence 18 spectroscopy Operating principle Instrumentation: spectrofluorometer Spectrum and interpretation Electroluminescence (EL) Infrared (1R) and Raman vibrational spectroscopy IR spectroscopy Raman spectroscopy Time-resolved optical spectroscopy Nonlinear optical spectroscopy: harmonic generation 38 and up-conversion 2.6. Single nanoparticle and single molecule spectroscopy Dynamic light scattering (DLS) Summary 42 xi
3 xii Optical Properties and Spectroscopy of Nanomaterials 3. Other Experimental Techniques: Electron Microscopy 47 and X-ray 3.1. Microscopy: AFM, STM, SEM and TEM Scanning probe microscopy (SPM): 48 AFM and STM Electron microscopy: SEM and TEM X-ray: XRD, XPS, and XAFS, SAXS Electrochemistry and photoelectrochemistry Nuclear magnetic resonance (NMR) and electron 67 spin resonance (ESR) Nuclear magnetic resonance (NMR) Electron spin resonance (ESR) Summary Synthesis and Fabrication of NanomateriaLs Solution chemical methods General principle for solution-based 77 colloidal nanoparticle synthesis Metal nanomaterials Semiconductor nanomaterials Metal oxides Complex nanostructures Composite and hetero-junction 95 nanomaterials 4.2. Gas or vapor-based methods of synthesis: CVD, 96 MOCVD and MBE Metals Semiconductors Metal oxides Complex and composite structures Nanolithography techniques Bioconjugation Toxicity and green chemistry approaches 103 for synthesis 4.6. Summary 104
4 Cimlcnt.s xiii 5. Optical Properties of Semiconductor Nanomaterials Some basic concepts about semiconductors Crystal structure and phonons Electronic energy bands and bandgap Electron and hole effective masses Density-of-states, Fermi energy, and carrier 121 concentration Charge carrier mobility and conductivity Exciton, exciton binding energy, and exciton 123 Bohr radius Fundamental optical absorption due to 125 electronic transitions Trap states and large surface-to-volume ratio Energy levels and density of states in reduced 127 dimension systems Energy levels Density of states (DOS) in nanomaterials Size dependence of absorption coefficient, 132 oscillator strength, and exciton lifetime 5.3. Electronic structure and electronic properties Electronic structure of nanomaterials Eleclron-phonoii interaction Optical properties of semiconductor nanomaterials Absorption: direct and indirect bandgap 135 transitions Emission: photoluminescence and Raman 142 scattering Fjnission: chemiluminescence and 147 electroluminescence Optical properties of assembled 148 nanostructures: interaction between nanoparticles Shape dependent optical properties Doped semiconductors: absorption and 153 luminescence
5 xiv Optical Properties and Spectroscopy of Nanomaterials 5.6. Nonlinear optical properties Absorption saturation and harmonic 157 generation Luminescence up-conversion Optical properties of single particles Summary Optical Properties of Metal Oxide Nanomaterials Optical absorption Optical emission Other optical properties: doped and sensitized metal 194 oxides 6.4. Nonlinear optical properties: up-conversion (LUC) luminescence Summary Optical Properties of Metal Nanomaterials Strong absorption and lack of photoemission Surface plasmon resonance (SPR) Correlation between structure and SPR: a theoretical 214 perspective Effects of size and surface on SPR of metal 214 nanoparticles The effect of shape on SPR The effect of substrate on SPR Effect of particle-particle interaction on SPR Surface enhanced Raman scattering (SERS) Background of SERS Mechanism of SERS Distance dependence of SERS Location and orientation dependence 225 of SERS Dependence of SERS on substrate Single nanoparticle and single molecule SERS Summary 229
6 Contents xv 8. Optical Properties of Composite Nanostructures Inorganic semiconductor-insulator and 239 semiconductor-semiconductor 8.2. Inorganic metal-insulator Inorganic semiconductor-metal Inorganic-organic (polymer) Nonconjugated polymers Conjugated polymers Inorganic-biological materials Summary Charge Carrier Dynamics in Nanomaterials Experimental techniques for dynamics studies 261 in nanomaterials 9.2. Electron and photon relaxation dynamics in metal 262 nanomaterials Electronic dephasing and spectral line shape Electronic relaxation due to 264 electron-phonon interaction Photon relaxation dynamics Charge carrier dynamics in semiconductor 271 nanomaterials Spectral line width and electronic 272 dephasing Intraband charge carrier energy relaxation Charge carrier trapping Interband electron-hole recombination 276 or single excitonic delay Charge carrier dynamics in doped 282 semiconductor nanomaterials Nonlinear charge carrier dynamics Charge carrier dynamics in metal oxide and 288 insu 1 ator nanomaterials 9.5. Photoinduced charge transfer dynamics Summary 297
7 xvi Optical Properties and Spectroscopy of Nanomaterials 10. Applications of Optical Properties of Nanomaterials Chemical and biomedical detection, imaging 306 and therapy Luminescence-based detection Surface plasmon resonance (SPR) detection SERS for detection Chemical and biochemical imaging Biomedical therapy Energy conversion: PV and PEC PV solar cells Photoelectrochemical cells (PEC) Environmental protection: photocatalytic and 331 photochemical reactions Lasers, LEDs, and solid state lighting Lasing and lasers Light emitting diodes (LEDs) Solid state lighting: ACPEL Optical detectors Optical filters: photonic bandgap materials 341 or photonic crystals Summary 344 Index 359
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