Direct bandgap optical transitions in Si nanocrystals

JETP Letters - The effect of quantum confinement on the direct bandgap of spherical Si nanocrystals has been modelled theoretically. We conclude that the energy of the direct bandgap at the...     

The optical transition in porous Si: The effects of quantum confinement,surface states and hydrogen passivation

Summary We present a theoretical study of two infinite wires of Si with a different lateral size. The analysis is based on the linear muffin tin orbitals method in the atomic sphere approximation (LMTO-ASA). We consider free, partially and totally H-covered [001] Si quantum wires with rectangular cross-section. The results of this investigation prove the quantum wire nature of porous Si and interpret many of its physical features. In particular we show thata) as expected quantum confinement originates the opening of the LDA gap;b) the gap opening effect is asymmetric: 1/3 of the widening is in the valence band, while 2/3 in the conduction band;c) the near band gap states originate from Si atoms located at the center of the wire;d) the confinement is enhanced in the case of free surfaces;e) the imaginary part of the dielectric function shows a low-energy side structure strongly anisotropic, identified as responsible of the luminescence transition;f) the presence of dangling bonds destroys the luminescence properties;g) in spite of featurec), all Si atoms are collectively involved in the luminescence transition;h) the shift detected by the Si L_{2, 3}VV Auger signal is due to H-interaction effect and is not a measure of the quantum confinement effect;i) the Si atoms probed by the Si L_{2, 3}VV Auger are bonded with H and H₂. Paper presented at the III INSEL (Incontro Nazionale sul Silicio Emettitore di Luce), Torino, 12–13 October 1995.     

Formation and optical properties of CdSSe semiconductor nanocrystals in the silicate glass matrix

Technological conditions providing the formation of CdS _x Se_1−x semiconductor crystal grains with sizes ranging from 2 to 8 nm in a silicate glass matrix have been determined. As the temperature of forming annealing increases, the size of crystal grains increases without changes in their crystal structure and composition. The observed short-wavelength shift of the optical absorption edge indicates that the quantum confinement affects the energy band structure of the nanocrystals. Intense luminescence of the samples is due to radiative transitions involving defects at the semiconductor nanocrystal-silicate matrix interface or intrinsic defects of nanocrystals.     

Room temperature visible light emission from Si/SiO2 multilayers: Roles of interface electronic states and silicon phase

We have studied luminescence properties and microstructure of 20 patterns Si/SiO₂ multilayers. The photoluminescence spectra consist of two gaussian bands in the visible-infrared spectral region. It has been demonstrated that the strong PL band is caused by the radiative recombination in the Si/SiO₂ interfaces states, whereas the weaker band originates from radiative recombination in the nanosized Si layers. The peak shift of this latter band shows a discontinuity that corresponds to a crystalline-to-amorphous phase change when the Si layers are thinner than 30 Å. The peak energy as a function of the layer thickness is interpreted using a quantum confinement model in the case of amorphous Si layers.     

Raman investigation of silicon nanocrystals: quantum confinement and laser‐induced thermal effects

We present a detailed experimental and theoretical Raman investigation of quantum confinement and laser‐induced local thermal effects on hydrogenated nanocrystalline silicon with different nanocrystal sizes (3.6–6.2 nm). The local temperature was monitored by measuring the Stokes/anti‐Stokes peak ratio with the laser power density range from ~120 to 960 kW/cm². In combination with the three‐dimensional phonon confinement model and the anharmonic effect, which incorporates the three‐phonon and four‐phonon decay processes, we revealed an asymmetrical decay process with wavenumbers ~170 and 350 cm^–1, an increasing anharmonic effect with nanocrystal sizes, and a shortening lifetime with enhanced temperature and decreasing nanocrystal dimension. Furthermore, we demonstrated experimentally that for Si nanocrystals smaller than 6 nm, the quantum confinement effect is dominant for the peak shift and line broadening. Copyright © 2011 John Wiley & Sons, Ltd.     

Theory of Raman light scattering by nanocrystal acoustic vibrations

A theory of Raman scattering of light by acoustic phonons in spherical nanocrystals of zinc-blende and wurtzite semiconductors has been developed with the inclusion of the complex structure of the valence band. The deformation-potential approximation was used to describe the exciton-phonon interaction. It is shown that this approximation allows only Raman scattering processes involving spheroidal acoustic phonons with a total angular momentum F=0 or 2. The effect of phonon quantum confinement on linewidth in Raman scattering spectra and scattered polarization is analyzed. An expression for the shape of the spectral line corresponding to nonresonant scattering from F=0 phonons was obtained. Fiz. Tverd. Tela (St. Petersburg) 41, 1473–1483 (August 1999)     

The chemical zeno effect in exchange-coupled radical Pairs: 1. Triplet radical pairs

It was shown that spin-selective intracage recombination could influence the limiting triplet-singlet conversion stage and, therefore, the whole chemical dynamics. An increase in the rate constant for intracage recombination w decreases the S-T evolution frequency and changes its character by transforming the oscillating spin conversion mode into “kinetic.” As a result, an increase in w can decrease the yield of intracage recombination products and increase the yields of products formed in competing extracellular radical reaction channels. The chemical Zeno effect and its consequences are an analogue of the quantum Zeno effect (quantum evolution “deceleration” caused by successive measurements), and spin-selective recombination is similar to quantum state measurements.     

CdxHg(1−x)Te Alloy Colloidal Quantum Dots: Tuning Optical Properties from the Visible to Near‐Infrared by Ion Exchange

The energy gap between valence and conduction levels in colloidal semiconductor quantum dots can be tuned via the nanoparticle diameter when this is comparable to or less than the Bohr radius. In materials such as cadmium mercury telluride, which readily forms a single phase ternary alloy, this quantum confinement tuning can also be augmented by compositional tuning, which brings a further degree of freedom in the bandgap engineering. Here it is shown that compositional control of 2.3 nm diameter Cd_xHg_(1?x)Te nanocrystals by exchange of Hg²⁺ in place of Cd²⁺ ions can be used to tune their optical properties across a technologically useful range, from 500 nm to almost 1200 nm. Data on composition‐dependent changes in the optical properties are provided, including bandgap, extinction coefficient, emission energy and spectral shape, Stokes shift, quantum efficiency, and radiative lifetimes as the exchange process occurs, which are highly relevant for those seeking to use these technologically important QD materials.     

Eu<Superscript>3+</Superscript> doped yttrium oxysulfide quantum structures—structural,optical and electronic properties

Small particles of trivalent europium doped yttrium oxysulfide nanocrystals (ϕ ∼ 7 nm) were synthesized using sol–gel polymer thermolysis. The nanocrystals show significant change in the excitation bands corresponding to fundamental absorption and charge transfer absorption bands. The optical spectra essentially comprise of two parts: fundamental absorption (∼260 nm) and Eu³⁺–X²⁻ ligand (O²⁻/S²⁻) charge transfer (∼290 nm) bands. They show significant blue shifts (0.24–0.30 eV), respectively, with respect to the bulk counterpart. These may be explained by considering possible size dependent changes associated with quantum confinement effect in this large bandgap semiconductor system. FT-IR spectra revealed the difference in chemisorbed species between bulk and nanocrystalline samples. The results of the solid-state photo-induced electrical impedance spectroscopy studies are reported.     

Si–Si optical phonon behavior in localized Si clusters of Si<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Ge<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript> alloy nanocrystals

Raman spectra acquired from Si _x Ge_1−x -nanocrystal-embedded SiO₂ films show dependence of the Si–Si optical phonon frequency on Si content. The frequency upshifts, and peak intensity increases as the silicon concentration increases. For a given Si content, the frequency remains unchanged with annealing temperature. Spectral analysis and density functional theory calculation reveal that the optical Si–Si phonon is related to the formation of localized Si clusters surrounded by Si/Ge atomic layers in the Si _x Ge_1−x nanocrystals and the intensity enhancement arises from the larger cluster size. The synergetic effect of surface tensile stress and phonon confinement determines the Si–Si optical phonon behavior.     

Luminescence of amorphous silicon nanoclusters

Films of amorphous silicon suboxide α-SiO _x containing amorphous silicon nanoclusters have been grown by direct current magnetron sputtering. It has been found that two radiation bands are observed in the photoluminescence spectra of relatively large amorphous nanoclusters (a size of ∼2 nm) unlike one photoluminescence band of silicon nanocrystals of the same size. The form of the spectra upon the change in the nanocluster sizes agrees with that predicted in theoretical works, in which the energy spectrum of amorphous nanoclusters has been calculated taking into account quantum confinement of delocalized, weakly localized, and strongly localized states.     

Quantitative analysis of the phonon confinement effect in arbitrarily shaped Si nanocrystals decorated on Si nanowires and its correlation with the photoluminescence spectrum

Arrays of single‐crystalline Si nanowires (NWs) decorated with arbitrarily shaped Si nanocrystals (NCs) are grown by a metal‐assisted chemical etching process using silver (Ag) as the noble metal catalyst. The metal‐assisted chemical etching‐grown Si NWs exhibit strong photoluminescence (PL) emission in the visible and near infrared region at room temperature. Quantum confinement of carriers in the Si NCs is believed to be primarily responsible for the observed PL emission. Raman spectra of the Si NCs decorated on Si NWs exhibit a red shift and an asymmetric broadening of first‐order Raman peak as well as the other multi‐phonon modes when compared with that of the bulk Si. Quantitative analysis of confinement of phonons in the Si NCs is shown to account for the measured Raman peak shift and asymmetric broadening. To eliminate the laser heating effect on the phonon modes of the Si NWs/NCs, the Raman measurement was performed at extremely low laser power. Both the PL and Raman spectral analysis show a log‐normal distribution for the Si NCs, and our transmission electron microscopy results are fully consistent with the results of PL and Raman analyses. We calculate the size distribution of these Si NCs in terms of mean diameter (D₀) and skewness (σ) by correlating the PL spectra and Raman spectra of the as‐grown Si NCs decorated on Si NWs. Copyright © 2015 John Wiley & Sons, Ltd.     

Effect of confinement on the Eu emission band D0→F0 in Eu-doped nano-glass-ceramics

We report a non-linear blue shift of the zero-phonon emission line ⁵D₀→⁷F₀ of Eu³⁺-dopant in Eu³⁺-doped nano-glass-ceramics in magnetic field up to 50 T. The shift is significantly larger in nano-glass-ceramics compared to its precursor glass, suggesting that the nanoceraming of the precursor glass decreases the effective mass of the f-electrons bands of Eu³⁺ resulting in their enhanced magnetic confinement. Moreover, the non-linear character of the magnetic field dependence of this blue energy shift denotes a spatial confinement of f-electrons wave-functions of Eu³⁺ dopants in the PbF₂-based nanocrystals of the nano-glass-ceramics where up to 90% of the dopants partition. The spatial confinement seems to be due to an admixture to the f-states of Eu³⁺ of its higher lying states of opposite parity which fall in the quantum well comprising of Eu³⁺-doped PbF₂ crystalline nanoparticles embedded in the surrounding glass network.     

Observation of a shift of the mobility threshold in the D − band of silicon in an electric field according to the photoconductivity spectra

We have discovered that the extrinsic photoconductivity spectrum of doped, uncompensated crystalline Si at liquid-helium temperatures is qualitatively different in electric fields E above a critical value E _c . Specifically, the red edge of the photoconductivity, associated with photoionization of a neutral impurity, is shifted strongly to lower frequencies. This result is explained by the appearance of a mobility threshold in the D ⁻-band (upper Hubbard band) and the shift of this threshold as E increases. Pis’ma Zh. éksp. Teor. Fiz. 63, No. 2, 89–94 (25 January 1996)     

a-Si/SiN<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> multilayered light absorber for solar cell

40 alternate a-Si/SiN _x multilayer are incorporated as an absorber layer in a p–i–n solar cell. The device is fabricated using hot-wire chemical vapor deposition (HWCVD) technique. The structure of the multilayer film is examined by high resolution transmission electron microscopy (HR-TEM) which shows distinct formation of alternate a-Si and SiN _x layers. The a-Si and SiN _x layers have thickness of ~3.5 and 4 nm, respectively. The photoluminescence (PL) of multilayer film shows bandgap energy of ~2.52 eV, is larger than that of the c-Si and a-Si. Dark and illuminated current–voltage (I–V) characterization of the ML films shows that these ML are photosensitive. In the present work, it is seen that the p–i–n structure with i-layer as ML quantum well (QW) structures show photovoltaic effect with relatively high open-circuit voltage (V _OC). The increment of bandgap energy in PL and high V _OC of the device is attributed to the quantum confinement effect (QCE).     

Etching temperature dependence of optical properties of the electrochemically etched n-GaAs

The GaAs granular films have been prepared by electrochemical anodic etching of n-GaAs in HCl electrolyte at different etching temperatures. The microstructure and optical properties of the films were investigated by micro-Raman spectrum, atomic force microscopy (AFM) and photoluminescence (PL) spectroscopy. Raman spectra reveal marked redshift and broadening, which could be explained by phonon confinement model. Results show the GaAs nanocrystalline films have formed during the anodic etching process under certain chemical conditions. Two “infrared” PL bands at ∼860 nm and ∼920 nm and a strongly enhanced visible PL band envelope around 550 nm were observed in the film prepared at etching temperature of 50 °C. The “green” PL band envelope is attributed to both quantum confinement in GaAs nanocrystals and PL of Ga₂O₃ and As₂O₃. The results reveal that the energy band structure of GaAs granular films is closely related to the etching temperatures. PACS 81.07.Bc; 78.30.Fs; 78.55.Cr     

Time-resolved spectroscopy of soantaneous luminescence of CdSSe1−x quantum dots

Picosecond time-resolved spectroscopy of the edge luminescence band of CdS _x Se_1–x quantum dots with crystallite diameters as small as a few nanometers under band-to-band excitation reveals strong enhancement of the radiative recombination rate compared to bulk CdS owing to quantum confinement. The splitting of the luminescence band into two lines originates from near-band-gap absorption. Analysis of the temperature as well as the spectral dependence of the decay time (leading to a red shift of the luminescence with increasing time) and of the total-light-decay law result in a new model for the dominant radiative recombination channel: donor-acceptor pair recombination instead of an excitonic mechanism as claimed in previous publications.Dedicated to H.-J. Queisser on the occasion of his 60th birthday     

2N qubit “mirror states” for optimal quantum communication

We introduce a new genuinely 2N qubit state, known as the “mirror state” with interesting entanglement properties. The well known Bell and the cluster states form a special case of these “mirror states”, for N = 1 and N = 2 respectively. It can be experimentally realized using SWAP and multiply controlled phase shift operations. After establishing the general conditions for a state to be useful for various communicational protocols involving quantum and classical information, it is shown that the present state can optimally implement algorithms for the quantum teleportation of an arbitrary N qubit state and achieve quantum information splitting in all possible ways. With regard to superdense coding, one can send 2N classical bits by sending only N qubits and consuming N ebits of entanglement. Explicit comparison of the mirror state with the rearranged N Bell pairs and the linear cluster states is considered for these quantum protocols. We also show that mirror states are more robust than the rearranged Bell pairs with respect to a certain class of collisional decoherence.     

Stability of Charged Exciton States in Quantum Wires

We show that the order of energies of negative (X⁻) and positive (X⁺) trions in quantum wires is determined by the relative electron and hole lateral confinements. For equal electron and hole confinement, X⁺ has a larger binding energy, but a small imbalance towards a stronger hole localization changes the order of the X⁻ and X⁺ recombination lines in the photoluminescence spectrum.     

Tunneling conductivity oscillations in a magnetic field in metal-insulator-narrow-gap-HgCdTe structures: The energy spectrum and spin-orbit splitting of 2D states

We study tunneling conductivity oscillations in a magnetic field in narrow-gap p-HgCdTe-oxide-metal (Yb, Al) structures. In tunnel structures with Yb we detect two types of tunneling conductivity oscillations. The first is related to the crossing of the Landau levels of two-dimensional (2D) states localized in the surface quantum well of the semiconductor, and has an energy E _F+eV, where E _F is the Fermi energy of the semiconductor and V is the bias voltage; the second has an energy E _F. We find that in such structures with an asymmetric quantum well there is strong spin-orbit splitting in the spectrum of the 2D states. In p-HgCdTe-oxide-Al tunnel structures the surface potential is much weaker and only oscillations of the first type are observed. We find that in such structures there is only one spin state of the 2D carriers, while the second is pushed into the continuous spectrum because of strong spin-orbit coupling. To analyze the experimental results we calculate the spectrum of 2D states localized in the surface quantum well in a semiconductor with a Kane dispersion law. We find that all the experimental results are in good agreement with the results of calculations. Finally, we discuss the features of “kinematically coupled” states in an asymmetric quantum well. Zh. éksp. Teor. Fiz. 112, 537–550 (August 1997)