Spectroscopic ellipsometry of layer by layer deposited colloidal HgTe nanocrystals exhibiting quantum confinement

We have explored the optical properties of bilayers of Mercury telluride (HgTe) nanocrystals (NCs) embedded in polymer which were prepared from a colloidal solution. These NCs show strong luminescence in the near infrared at room temperature, which makes them an interesting material for the telecommunication area. The emission wavelength can efficiently be tuned by controlling the size of the NCs. We report spectroscopic ellipsometry measurements, which clearly show an energy shift of the critical points (CPs) in the dielectric function to higher energies compared to the HgTe bulk properties. This is caused by quantum confinement in the crystals. The exact peak energies of the transitions are fitted with line-shape models for CPs. Surprisingly, concepts coming from semiconductor bulk optics, as CPs, can be applied to NCs with a diameter of less than 5 unit cells.     

Auger relaxation processes in semiconductor nanocrystals and quantum wells

Auger recombination rates in mesoscopic semiconductor structures have been studied as a function of energy band parameters and heterostructure size. It is shown that nonthreshold Auger processes stimulated by the presence of heteroboundaries become the dominant nonradiative recombination channel in nanometer size semiconductor structures. The size dependence of luminescence quantum yields in nanostructures and microcrystals are discussed. Auger-like collisions of electrons and heavy holes are shown to serve as “accelerators” of thermalization processes in semiconductor quantum dots.     

Persistent hole burning in semiconductor nanocrystals

The persistent spectral hole burning (PSHB) phenomenon was found to occur in many kinds of nanocrystalline semiconductors, such as CdSe, CdS, CuCl, CuBr and CuI, embedded in crystals, glass or polymers. In inhomogeneously broadened exciton absorption spectra of these nanocrystals, the spectral hole and its associated structure were created by the narrow-band laser excitation and were conserved for more than several hours at 2 K. Hole depth grew in proportion to the logarithm of the burning fluence. Thermally-annealing and light-induced hole-filling phenomena were observed. The hole burning takes place by the tunneling process through potential barriers with broadly distributed barrier height and thickness. Unusual luminescence behaviors related to the PSHB phenomena were also observed. They are luminescence elongation with increase of the light exposure and hole burning in the luminescence spectrum. The observed PSHB phenomena are explained by the exciton localization and the succeeding ionization of nanocrystals. The energy of the photoionized nanocrystal is released from the original energy and the new energies depend on the spatial arrangement of the trapped carriers. Quantum confinement of carriers and resulting strong Coulomb interaction between confined carriers and trapped carriers are essential for the energy change. Possible applications of the PSHB phenomenon is discussed.     

Photoluminescence polarization of semiconductor nanocrystals

We review the polarization properties of photoluminescence (PL) in nanocrystals (NCs) from both theoretical and experimental points of view. We show that, under linearly polarized excitation, NCs emit partly polarized light owing to their uniaxial structure or their anisotropic shape. In elongated NCs, the anisotropy may have two origins, the electronic confinement or the effect of depolarizing field created by the light-induced charges on the interfaces. Results of polarization studies in porous silicon are presented. They are explained by the shape of the Si NCs. Experiments in CdSe NCs reveal the fine structure of the excitonic levels and show evidence of the enhancement of the electron-hole exchange energy with decreasing NC size. Spin orientation in wurtzite-type NCs is achieved by optical pumping with circularly polarized light. The effect of a magnetic field on the degree of circular polarization and the mechanisms of spin relaxation are discussed. Results in large-size NCs are presented.     

Phonon confinement and substitutional disorder in Cd1−xZnxS nanocrystals

1‐longitudinal optical (LO) phonons in free‐standing mixed Cd_1−xZn_xS nanocrystals, synthesized using chemical precipitation, are investigated using Raman spectroscopy. As expected for the nanocrystals, the 1‐LO modes are found to appear at slightly lower wavenumbers than those in the bulk mixed crystals and exhibit one‐mode behavior. On the other hand, the line broadening is found to be much more than that can be accounted on the basis of phonon confinement. From the detailed line‐shape analysis it turns out that the substitutional disorder in the mixed crystals contributes much more to the line broadening than the phonon confinement. The linewidth arising from these mechanisms are also extracted from the analysis. Copyright © 2009 John Wiley & Sons, Ltd.     

Theory of radiative and nonradiative transitions for semiconductor nanocrystals

Existing calculations on the radiative and nonradiative transitions in semiconductor crystallites are reviewed with particular emphasis on indirect band-gap materials like silicon for which the quantum confinement effects are more spectacular. It is shown that the crystallite gaps and radiative recombination rates can be predicted with fair accuracy. Effects related to atomic relaxation in the excited state (Stokes shift) are calculated and it is shown that small enough crystallites lead to self-trapped excitons which provide another source of luminescence, much less dependent on size effects. Nonradiative processes are then examined: intrinsic, due to Auger recombination, and extrinsic, due to dangling bond surface states. Both are found to play an essential role in the interpretation of experimental data. Finally, dielectric screening is studied, justifying the use of a reduced internal dielectric constant and providing an estimate of the Coulomb shift due to charging effects.     

Environment-dependent blinking of single semiconductor nanocrystals and statistical aging of ensembles

We compare decreasing fluorescence signals from ensembles with the blinking statistics of individual nanocrystals in various environments. For most substrates, the ensemble decay follows a power-law of time, the exponent being the difference of the power-law exponents of on- and off-time distributions. The decay exponent is also found to depend on substrate. We discuss possible mechanisms for this dependence, in conjunction with previously published models.     

Two-photon spectroscopy and microscopy of II–VI semiconductor nanocrystals

We review our recent nonlinear spectroscopies of nanocrystals and synthetic efforts to improve their luminescence properties. A two-photon spectroscopic study of CdSe nanocrystals as a function of size is presented and compared with predictions from the effective mass model with spherical confinement. We also detail our efforts at improving the luminescence properties of nanocrystals which have culminated in a 50% fluorescence quantum yield for inorganic capping of some sizes of CdSe nanocrystals. Finally, we present the application of two-photon microscopy to resolve fluorescence from single nanocrystals at room temperature and cryogenic temperatures.     

Optical spectroscopy of lanthanides doped in wide band-gap semiconductor nanocrystals

Currently, tripositive lanthanide (Ln³⁺) ions doped wide band-gap semiconductor nanocrystals (NCs) have been the focus of research interest due to their distinct optical properties and potential applications in optical devices and luminescent biolabels. Because of the low absorptions of parity-forbidden 4f-4f transitions for Ln³⁺, it is highly anticipated that the luminescence of Ln³⁺ ions embedded in wide band-gap NC lattices can be sensitized efficiently via exciton recombination in the host. For this purpose, the successful incorporation of Ln³⁺ into the lattices of semiconductor NCs is of utmost importance, which still remains intractable via conventional wet chemical methods. Here, the most recent progress in the optical spectroscopy of Ln³⁺ ions doped wide band-gap semiconductor NCs is discussed. Much attention was focused on the optical properties including electronic structures, luminescence dynamics, energy transfer as well as the up-conversion emissions of Ln³⁺ ions in ZnO, TiO₂, SnO₂ and In₂O₃ NCs that were synthesized in our laboratory using wet chemical methods.     

Quantum confinement and surface chemistry of 0.8–1.6 nm hydrosilylated silicon nanocrystals

In the framework of density functional theory(DFT), we have studied the electronic properties of alkene/alkynehydrosilylated silicon nanocrystals(Si NCs) in the size range from 0.8 nm to 1.6 nm. Among the alkenes with all kinds of functional groups considered in this work, only those containing –NH2and –C4H3S lead to significant hydrosilylationinduced changes in the gap between the highest occupied molecular orbital(HOMO) and the lowest unoccupied molecular orbital(LUMO) of an Si NC at the ground state. The quantum confinement effect is dominant for all of the alkenehydrosilylated Si NCs at the ground state. At the excited state, the prevailing effect of surface chemistry only occurs at the smallest(0.8 nm) Si NCs hydrosilylated with alkenes containing –NH2and –C4H3S. Although the alkyne hydrosilylation gives rise to a more significant surface chemistry effect than alkene hydrosilylation, the quantum confinement effect remains dominant for alkyne-hydrosilylated Si NCs at the ground state. However, at the excited state, the effect of surface chemistry induced by the hydrosilylation with conjugated alkynes is strong enough to prevail over that of quantum confinement.     

Water-soluble, cyclodextrin-functionalized semiconductor nanocrystals: Preparation and pH-dependent aggregation and emission properties

Using peramino-functionalized β-cyclodextrin molecules for phase.transfer of hydrophobic CdSe multishell nanocrystals into water, we obtained hydrophilic nanoparticles with high quantum yield (up to 50%). At pH > 9, the aqueous solution of these nanocrystals remained stable for several months. The nanoparticles showed a strong influence of the pH of the aqueous solution on the emission of the nanocrystals: the quantum yield varied reversible from ∼10% at pH=6 to ∼50% at pH=14, an effect which according to particle size characterization by dynamic light-scattering and asymmetric flow field-flow fractionation has mainly been attributed to reversible partial aggregation of the hydrophilic nanocrystals at lower pH-values. Additionally, prolonged irradiation in the presence of oxygen led to a strong enhancement of the photoluminescence intensity of the nanocrystals.     

Strongly confined semiconductor quantum dots: Pair excitations and optical properties

This paper reviews a microscopic model of basic electron-hole pair excitation processes in strongly confined semiconductor quantum dots (QD) and their influence on the optical QD properties. The effects of valence band mixing, Coulomb interaction, and surface polarization are taken into account. The exciton and biexciton wave functions and energies are obtained using a numerical diagonalization method. The computed optical spectra, such as absorption, gain, pump-probe, and two-photon absorption, agree well with experiments.     

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.     

Raman spectra of CdS nanocrystals in Nafion: longitudinal optical and confined acoustic phonon modes

Quantum confinement effects on the longitudinal optical and acoustic phonons in CdS nanocrystals in the strongly confined regime in the polymer matrix Nafion are studied using Raman spectroscopy. The LO-phonon modes show size-dependent asymmetric broadening though the broadening and asymmetry are less than those predicted by the phonon confinement models. Two types of confined acoustic modes corresponding to n=1, l=0 and n=1, l=2 spheroidal vibrations are observed. Softening of the spheroidal modes is observed in the strongly confined regime.     

Electron—phonon interactions in semiconductor nanocrystals

The electron—phonon interactions in semiconductor nanocrystals, especially concerning the acoustic phonon modes are derived and the size dependence of the coupling strength is clarified for typical coupling mechanisms. On the basis of these results, the commonly observed linearly temperature-dependent term of the excitonic dephasing rate and the proportionality of its magnitude to the inverse square of the nanocrystal size are attributed to the pure dephasing due to the deformation-potential coupling. The luminescence Stokes shift and the Huang-Rhys factor due to acoustic phonon modes in Si nanocrystals are discussed in conjunction with the origin of the recently observed luminescence onset energy.     

Photoluminescence properties of Mn-doped II–VI semiconductor nanocrystals

Our recent photoluminescence studies on ZnS:Mn²⁺- and CdS:Mn²⁺-nanocrystals dispersed in polyvinyl alcohol polymer films are reviewed. Both nanocrystal samples show Mn²⁺ 3d intrashell luminescence with high quantum efficiencies of about 20% at room temperature under the interband excitation. Noticeable characteristics of our nanocrystal samples are that the luminescence involving some trap state is much weaker than the Mn²⁺ luminescence, unlike other reports, and that thermal quenching of the Mn²⁺ luminescence is remarkably weak, compared with the corresponding bulky crystal powder. These two characteristics lead to the above high quantum efficiencies of the Mn²⁺ luminescence at room temperature. In addition, we examine the dominant excitation mechanism of Mn²⁺ in the nanocrystals under the interband excitation and the validity of the sp–d mixing model proposed previously to explain the high luminescence quantum efficiency.     

Quantum confinement and interface structure of Si nanocrystals of sizes 3–5 nm embedded in a-SiO2

Spectroscopic ellipsometry and Monte Carlo simulations are employed to answer the fundamental question whether the energy gaps of Si nanocrystals with sizes in the range of 3–5 nm, which are embedded in amorphous silica, follow or deviate from the quantum confinement model, and to examine their interfacial structure. It is shown that the optical properties of these nanocrystals are well described by the Forouhi–Bloomer interband model. Analysis of the optical measurements over a photon-energy range of 1.5–5 eV shows that the gap of embedded nanocrystals with a mean size of 3.9 nm follows closely quantum confinement theory. A large band gap expansion (0.65 eV) compared to bulk Si is observed. The Monte Carlo simulations reveal a non-abrupt interface and a large fraction of interface oxygen bonds. This, in conjunction with the experimental observations, indicates that oxygen states and the chemical disorder at the interface have a negligible influence on the optical properties of the material in this size regime.     

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.     

Resonant Raman scattering in CdSxSe1−x nanocrystals: effects of phonon confinement,composition, and elastic strain

Optical phonon modes, confined in CdS_xSe_1−x nanocrystal (NC) quantum dots (≈2 nm in radius) grown in a glass matrix by the melting‐nucleation method, were studied by resonant Raman scattering (RRS) spectroscopy and theoretical modeling. The formation of nanocrystalline quantum dots (QDs) is evidenced by the observation of absorption peaks and theoretically expected resonance bands in the RRS excitation spectra. This system, a ternary alloy, offers the possibility to investigate the interplay between the effects of phonon localization by disorder and phonon confinement by the NC/matrix interface. Based on the concept of propagating optical phonons, which is accepted for two‐mode pseudo‐binary alloys in their bulk form, we extended the continuous lattice dynamics model, which has successfully been used for nearly spherical NCs of binary materials, to the present case. After determining the alloy composition for NCs (that was evaluated with only 2–3% uncertainty using the bulk longitudinal optical phonon wavenumbers) and the NC size (using atomic force microscopy and optical absorption data), the experimental RRS spectra were described rather well by this theory, including the line shape and polarization dependence of the scattering intensity. Even though the presence of a compressive strain in the NCs (introduced by the matrix) masks the expected downward shift owing to the phonons' spatial quantization, the asymmetric broadening of both Raman peaks is similar to that characteristic of NCs of pure binary materials. Although with some caution, we suggest that both CdSe‐like and CdS‐like optical phonon modes indeed are propagating within the NC size unless the alloy is considerably heterogeneous. Copyright © 2011 John Wiley & Sons, Ltd.     

Si nanocrystals in silicon nitride: An ellipsometric study using parametric semiconductor models

Low-pressure chemical vapour deposited Si₃N₄/nc-Si/Si₃N₄ layers prepared on Si substrates were characterized by spectroscopic ellipsometry. Model Dielectric Function (MDF) was applied to obtain the thickness and the dielectric spectra of the middle nc-Si layer. Sensitive effect of the deposition time was obtained on the MDF parameters. A comparison is presented between the studied samples and reference materials.