Spectroscopy of. Semiconductors. Luminescence OXFORD IVAN PELANT. Academy ofsciences of the Czech Republic, Prague JAN VALENTA

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1 Luminescence Spectroscopy of Semiconductors IVAN PELANT Institute ofphysics, v.v.i. Academy ofsciences of the Czech Republic, Prague JAN VALENTA Department of Chemical Physics and Optics Charles University, Prague OXFORD UNIVERSITY PRESS

2 1 Introduction l References 7 2 Experimental techniques of luminescence spectroscopy Emission and excitation spectra Types of photodetectors Monochromators and spectrographs Dispersion and resolving power Throughput of monochromators and spectrographs Signal detection methods in luminescence spectroscopy Phase-synchronous detection Photon counting Signal-to-noise ratio in a scanning monochromator Fourier luminescence spectroscopy Spectral corrections Influence of slit opening on the shape of emission spectra Time-resolved luminescence measurements Direct imaging of the luminescence response Phase-shift method Time-correlated photon counting Boxcar integrator Streak camera Problems 78 References 80 3 Kinetic description of luminescence processes Radiative and non-radiative recombination. Luminescence quantum yield Monomolecular process Bimolecular process Stretched exponential Multiple processes present simultaneously Problems 96 References 96

3 4 Phonons and their participation in optical phenomena Lattice vibrations phonons Electron-phonon and exciton-phonon interactions Lattice vibrations associated with point defects A localized optical centre in a solid matrix the configurational coordinate model The shape of absorption and emission spectra of a localized centre Thermal quenching of luminescence Problems 121 References Channels of radiative recombination in semiconductors Overview of luminescence processes in crystalline semiconductors Recombination of free electron-hole pairs Direct bandgap Indirect bandgap Recombination of a free electron with a neutral acceptor (e-a ) and of a free hole with a neutral donor (h-d ) Recombination of donor-acceptor pairs (D -A ) Luminescence excited by two-photon absorption Luminescence from transition metal and rare earth ion impurities Problems 146 References Non-radiative recombination Transformation of the excitation energy into heat Multiphonon recombination Auger and bimolecular recombination Creation of lattice defects Photochemical changes Problems 159 References Luminescence of excitons Concept of the Wannier exciton Absorption spectrum of the Wannier exciton Direct bandgap: resonant luminescence of free exciton-polaritons Direct bandgap: luminescence of free excitons with emission of optical phonons Luminescence of free excitons in indirect-bandgap semiconductors Bound excitons 180

4 7.2.1 Excitons bound to shallow impurities Quantitative luminescence analysis of shallow impurities in silicon Excitons bound to isoelectronic impurities Self-trapped excitons Problems 201 References Highly excited semiconductors Experimental considerations Excitonic molecule or biexciton Identification of the EM emission line Determination of biexciton parameters Collisions of free excitons Electron-hole liquid (EHL) Luminescence determination of EHL parameters Identification of the EHL emission band Coexistence of excitonic molecules with electron-hole liquid Electron-hole plasma (EHP) Mott transition Luminescence of EHP Bose-Einstein condensation of excitons Properties of the Bose-Einstein distribution Luminescence experiment: Bose-Einstein condensation yes or no? Problems 239 References Luminescence of disordered semiconductors Densities of states in bands Temperature dependence of luminescence Distribution of luminescence lifetimes Spectral shape of the emission band Some other properties of luminescence of disordered semiconductors Correlation effects Non-radiative recombination Luminescence of impurities and defects Luminescence 'fatigue' Problems 261 References Stimulated emission Spontaneous versus stimulated emission. Optical gain Optical gain in semiconductors 267

5 10.3 Spectral shape of the optical gain Stimulated emission in an indirect-bandgap semiconductor Participation of excitons in stimulated emission Experimental techniques for measuring the optical gain Variable stripe length (VSL) technique Pump and probe (P&P) method Problems 299 References Electroluminescence Historical notes High-field electroluminescence Experimental considerations Mechanisms of high-field electroluminescence Intensity, spectral and temporal characteristics Injection electroluminescence Electrical properties of a p-n junction Intensity, spectral and temporal characteristics of LEDs Electroluminescence of a p-n junction biased in the reverse direction Problems 336 References Electronic structure and luminescence of low-dimensional semiconductors Basic types of low-dimensional semiconductors Semiconductor heterostructures Basic types of quantum-well heterostructures Density of states in low-dimensional semiconductors Quantum wells (layers) two-dimensional semiconductors Single quantum well with infinite barriers Quantum well with finite barriers Excitons in a quantum well Optical transitions in a quantum well Luminescence of quantum wells Quantum wires Quantum dots nanocrystals Quantum dot with spherically symmetric potential Types of quantum dots according to the strength of the quantum confinement effect Luminescence of quantum dots Exciton-phonon interaction. Phonon bottleneck Some special phenomena Problems 378 References 379

6 13 Effects of high excitation in low-dimensional structures Excitonic molecule (biexciton) in a quantum well Trions in a quantum well Collisions of free excitons in a quantum well Electron-hole plasma (EHP) and electron-hole liquid (EHL) in 2D structures Biexcitons, EHP, and EHL in quantum wires Effects of high excitation in quantum dots (nanocrystals) Problems 398 References Stimulated emission and losing in low-dimensional structures Stimulated emission in quantum wells Localized excitons Radiative decay of an exciton with emission of an LO-phonon (X-LO) Stimulated emission in electron-hole plasma (EHP) Stimulated emission in quantum wires Stimulated emission in nanocrystals Nanocrystals dispersed in a matrix Heterostructures with ordered quantum dots Random lasing Problems 420 References Silicon nanophotonics Silicon nanocrystals Optical gain in silicon nanocrystals Active planar waveguides made of silicon nanocrystals Electroluminescence of silicon nanocrystals Silicon nanocrystals combined with Ei?+ ions Biological applications of silicon nanocrystals Problems 438 References Photonic structures Photonic crystals Spontaneous emission Stimulated emission Microresonators Microcavities Single photon sources 451

7 16.5 Problems 453 References Spectroscopy of single semiconductor nanocrystals Basic principles Experimental techniques Wide-field micro-spectroscopy Scanning techniques Preparation of samples Electron-and ion-beam lithography Colloidal dispersions Experimental observation of luminescence from individual nanocrystals Hidden fine structure of luminescence spectra Changes in spectra: jumps, shifts, blinking Stark effect Luminescence polarization Luminescence intermittency blinking Nanocrystals as sources of non-classical photon flux Measuring photon statistics Experimental manifestation of non-classical light emitted by a single nanocrystal Problems 490 References 491 Appendices 493 A Convolution 493 B Emission spectrum of free excitons including phonon broadening 495 C Luminescence of an excitonic molecule 497 D Kinetic model of exciton condensation 502 E Bose-Einstein condensation 503 F Emission band due to strong electron-phonon interaction 505 G Fitting the optical gain spectral shape in the model of k-relaxation 507 H Reabsorption of luminescence in semiconductors 511 I Oscillator strength 513 J Fitting with a double exponential (Kocka's summation) 514 K Absolute quantum yield of luminescent materials 515 L Basic description of statistics of light from classical and non-classical sources 521 M Behaviour of multi-component spectral mixtures: the isostilbic point 526 Subject index 530 Material index 538

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