Valence band mixing of cubic GaN/AlN quantum dots

We study the spin purity of the hole ground state in nearly axially symmetric GaN/AlN quantum dots (QDs). To this end, we develop a six-band Burt-Foreman Hamiltonian describing the valence band structure of zinc blende nanostructures with cylindrical symmetry and calculate the effects of eccentricity variationally. We show that the aspect ratio is a key factor for spin purity. In typical QDs with small aspect ratio the ground state is essentially a heavy hole (HH) whose spin purity is even higher than that of InGaAs QDs of similar sizes. When the aspect ratio increases, mixing with light-hole (LH) and split-off (SO) subbands becomes important and, additionally, the ground state becomes sensitive to QD anisotropy, which further enhances the mixing. We finally show that, despite the large GaN hole effective mass, an efficient magnetic modulation is feasible in QDs with aspect ratio ~1, which can be used to modify the ground state symmetry and hence the optical spectrum properties.     

Lateral electric field effects on quantum size confinement in cylindrical quantum dot under parabolic potential

Within the effective mass approximation, we investigated theoretically the ground-state energy of a single particle and the binding energy of the neutral donor impurity (D⁰) affected by a lateral electric field in a parabolic quantum dot (QD). The results show that the electron and the hole ground-state energy and the band to band transition energies shift to lower values (red shift) by increasing the field intensity. The quantum Stark shift (QSS) for the electron increases rapidly in the quasi spherical QD (QSQD) by increasing the lateral field, whereas for the hole it increases monotony. In the cylindrical QDs (CQDs), we found that the QSS for electron and hole increase monotonically. The quantum size, lateral electric field and impurity position effect on the binding energy of neutral donor (D⁰) is studied. Unexpected behavior of D⁰ in quantum well limit (QW), the binding energy of D⁰ is increasing (blue shift) with increasing QD radius R$R$ at the presence of a lateral electric field. It appears that for a fixed size of the QD, the off-center binding energy decreases when the impurity ion is displaced from the center to the QD borders, while it is shifted to lower energy with increasing the field.     

White light-emitting quantum dot diodes and tuning of luminescence processes

A novel white light-emitting diode based on a large Stokes shift (~200 nm) and using pure green light-emitting CdSeS quantum dots (QDs) with an Ag/ZnSnO/QDs/spiro-TPD/ITO structure has been fabricated in which ZnSnO and spiro-TPD are served as the electron and hole transport layer, respectively. The large Stokes shift of the CdSeS QDs excludes potentially Förster resonance energy transfer process, which allows spiro-TPD to act as both an emitter and hole transport layer. The devices exhibit a wide EL spectrum consisting of three components: blue emission from spiro-TPD, green emission from QD band–band recombination, and red emission from QD surface-state recombination. We further found that as the intensity ratios among these three components vary with bias the color of the QD light-emitting diodes is tunable. The device displays a good white light-emitting characteristic with CIE coordinates of (0.281, 0.384) at an appropriate bias.     

Ab Initio Simulation of Charge Transfer at the Semiconductor Quantum Dot/TiO2 Interface in Quantum Dot‐Sensitized Solar Cells

Quantum dot‐sensitized solar cells (QDSSCs) have emerged as a promising solar architecture for next‐generation solar cells. The QDSSCs exhibit a remarkably fast electron transfer from the quantum dot (QD) donor to the TiO₂ acceptor with size quantization properties of QDs that allows for the modulation of band energies to control photoresponse and photoconversion efficiency of solar cells. To understand the mechanisms that underpin this rapid charge transfer, the electronic properties of CdSe and PbSe QDs with different sizes on the TiO₂ substrate are simulated using a rigorous ab initio density functional method. This method capitalizes on localized orbital basis set, which is computationally less intensive. Quite intriguingly, a remarkable set of electron bridging states between QDs and TiO₂ occurring via the strong bonding between the conduction bands of QDs and TiO₂ is revealed. Such bridging states account for the fast adiabatic charge transfer from the QD donor to the TiO₂ acceptor, and may be a general feature for strongly coupled donor/acceptor systems. All the QDs/TiO₂ systems exhibit type II band alignments, with conduction band offsets that increase with the decrease in QD size. This facilitates the charge transfer from QDs donors to TiO₂ acceptors and explains the dependence of the increased charge transfer rate with the decreased QD size.     

Influence of nanomechanical force on the electronic structure of InAs/GaAs quantum dots

We show nanomechanical force is useful to dynamically control the optical response of self-assembled quantum dots, giving a method to shift electron and heavy hole levels, interval of electron and heavy hole energy levels, and the emission wavelength of quantum dots (QDs). The strain, the electron energy levels, and heavy hole energy levels of InAs/GaAs(001) quantum dots with vertical nanomechanical force are investigated. Both the lattice mismatch and nanomechanical force are considered at the same time. The results show that the hydrostatic and the biaxial strains inside the QDs subjected to nanomechanical force vary with nanomechanical force. That gives the control for tailoring band gaps and optical response. Moreover, due to strain-modified energy, the band edge is also influenced by nanomechanical force. The nanomechanical force is shown to influence the band edge. As is well known, the band offset affects the electronic structure, which shows that the nanomechanical force is proven to be useful to tailor the emission wavelength of QDs. Our research helps to better understand how the nanomechanical force can be used to dynamically control the optics of quantum dots.     

Synthesis and characterization of binary and ternary III–V quantum dots

Quantum dots of InP, GaP, GaInP₂, and GaAs with diameters ranging from 20–80 Å can be synthesized as well-crystallized nanoparticles with bulk zinc blende structure. The synthesis is achieved by heating appropriate organometallic precursors with stabilizers in high boiling solvents for several days to produce QDs, which can then be dissolved in nonpolar organic solvents to form transparent colloidal QD dispersions. The high sample quality of the InP and Gap QDs results in excitonic features in the absorption spectra; excitonic features could not be observed for GaAs or GaInP₂ QDs. The GaP and GaInP₂ QD colloids exhibit very intense (quantum yields of 15–25%) visible photoluminescence at room temperature. The photoluminescence for InP QDs preparations show two emission bands: one band is in the visible at the band edge of the QD, and a second band appears above 800 nm. The near-IR PL is attributed to deep traps, presumably phosphorus vacancies on the QD surface. This band can be removed after controlled addition of etchant; subsequently, very intense band-edge emission (quantum yield 30%), which is tunable with particle size, is obtained. The QDs were characterized by TEM, SAXS, AFM, powder X-ray diffraction, steady-state optical absorption and photoluminescence spectroscopy, ps to ns transient photoluminescence spectroscopy, and fs to ps pump-probe absorption (i.e., hole-burning) spectroscopy.     

Electronic structure and optical properties of zinc-blende GaN quantum dots

The energy levels of zinc-blende GaN quantum dots (QDs) are studied within the framework of the effective-mass envelope-function approximation. The dependence of the energy of electron and hole states on the quantum dot (QD) size is presented. The selection rules for optical transitions are given and the oscillator strengths of the dipole-allowed transitions for various QD radii are calculated with the wavefunctions of quantized energy levels. The theoretical absorption spectrum of GaN QDs is in good agreement with the existing experimental result.     

All‐optical modulation based on silicon quantum dot doped SiOx:Si‐QD waveguide

All‐optical modulation based on silicon quantum dot doped SiO_x:Si‐QD waveguide is demonstrated. By shrinking the Si‐QD size from 4.3 nm to 1.7 nm in SiO_x matrix (SiO_x:Si‐QD) waveguide, the free‐carrier absorption (FCA) cross section of the Si‐QD is decreased to 8 × 10⁻¹⁸ cm² by enlarging the electron/hole effective masses, which shortens the PL and Auger lifetime to 83 ns and 16.5 ps, respectively. The FCA loss is conversely increased from 0.03 cm⁻¹ to 1.5 cm⁻¹ with the Si‐QD size enlarged from 1.7 nm to 4.3 nm due to the enhanced FCA cross section and the increased free‐carrier density in large Si‐QDs. Both the FCA and free‐carrier relaxation processes of Si‐QDs are shortened as the radiative recombination rate is enlarged by electron–hole momentum overlapping under strong quantum confinement effect. The all‐optical return‐to‐zero on‐off keying (RZ‐OOK) modulation is performed by using the SiO_x:Si‐QD waveguides, providing the transmission bit rate of the inversed RZ‐OOK data stream conversion from 0.2 to 2 Mbit/s by shrinking the Si‐QD size from 4.3 to 1.7 nm.     

基于量子点-CBP混合层的量子点LED的制备

采用一锅法制备出高质量的具有核壳结构的Cd Se@Zn S、Cd Zn S/Zn S量子点。将量子点混入空穴传输材料CBP中形成复合的有源材料,经过几步简单的旋涂操作,制备出相应的绿光、蓝光量子点LED器件。这种方法利用了油溶性量子点和CBP材料的相容性,减少了旋涂操作的步骤,有利于快速制备基于量子点的电致发光器件。基于两步旋涂操作制备的量子点LED,由于阴极与复合有源层之间的能级差较大,导致需要较高的开启电压。在CBP材料中,注入的载流子有可能会被量子点表面缺陷捕获,形成表面态的发光。表面态发光的相对强度依赖于载流子浓度。     

The influence of ligand type on self-organization and optical properties of cadmium selenide quantum dots

A method for successive replacement of organic shells of colloidal cadmium selenide quantum dots (QDs) of different sizes is proposed. It is found that the spectral parameters of QD samples depend on the type of organic shells. It is shown that the structural morphology is independent of the QD size and is determined by the chemical composition of the organic shell. Spectral analysis of the luminescence of QD-based superstructures shows that the luminescence wavelength and intensity strongly depend on the degree of QD surface passivation.     

Energy-selective charging of type-II GaSb/GaAs quantum dots

The hole confinement in type-II self-organized GaSb/GaAs quantum dots (QDs) was investigated by combining optical excitation and time-resolved capacitance spectroscopy. The experimental results indicate energy-selective charging even for type-II QDs. With increasing excitation energy the apparent hole activation energy decreases, which is attributed to light absorption in sub-ensembles of QDs with decreasing hole localization. The large localization energy of about 450 meV and the possibility of optical-multiplexing makes type-II GaSb/GaAs QDs a potential material system for QD memory concepts.     

Resonant Raman scattering from CdTe/ZnTe self-assembled quantum dot structures

We report resonant Raman scattering results of CdTe/ZnTe self-assembled quantum dot (QD) structures. Photoluminescence spectra reveal that the band gap energies of the CdTe QDs decrease with the increase of CdTe thickness from 2.0 to 3.5 monolayers, which indicates that the size of the QDs increases. When the CdTe/ZnTe QD structures are excited by non-resonant excitation, a longitudinal optical (LO) phonon response from the ZnTe barrier material is observed at 206 cm⁻¹. In contrast, when the CdTe/ZnTe QD structures are resonantly excited near the band gap energy of the QDs, additional phonon modes emerge at 167 and 200 cm⁻¹, while the ZnTe LO phonon response completely disappears. The 167 cm⁻¹ mode corresponds to the LO phonon of the CdTe QDs. A spatially resolved Raman scattering from the cleaved edge of the QD sample reveals that the 200 cm⁻¹ mode is strongly localized at the interface between the CdTe QDs and ZnTe cap layer. This phonon mode is attributed to the interface optical (IO) phonon. The analytically calculated value of the IO phonon energy using a dielectric continuum approach, assuming a spherical dot boundary, agrees well with the experimental value.     

Electronic energy alignment at the PbSe quantum dots/ZnO(101̅0) interface

A number of solar energy conversion strategies depend on exciton dissociation across interfaces between semiconductor quantum dots (QDs) and other electron or hole conducting materials. A critical factor governing exciton dissociation and charge transfer in these systems is the alignment of electronic energy levels across the interface. We probe interfacial electronic energy alignment in a model system, sub-monolayer films of PbSe QDs adsorbed on single crystal ZnO(101?0) surfaces using ultraviolet photoemission spectroscopy. We establish electronic energy alignment as a function of quantum dot size and surface chemistry. We find that replacing insulating oleic-acid capping molecules on the QDs by the short hydrazine or ethanedithiol molecules results in pinning of the valence band maximum (VBM) of QDs to ZnO substrate states, independent of QD size. This is in contrast to similar measurements on TiO₂(110) where the alignment of the PbSe QD VBM to that of the TiO₂ substrate depends on QD size. We interpret these findings as indicative of strong electronic coupling of QDs with the ZnO surface but less with the TiO₂ surface. Based on the measured energy alignment, we predict that electron injection from the 1s_e level in photo-excited PbSe QDs to ZnO can occur with small QDs (diameter ? = 3.4 nm), but energetically unfavorably for larger dots (? = 6.7 nm). In the latter, hot electrons above the 1s_e level are necessary for interfacial electron injection.     

Optimum Quantum Yield of the Light Emission from 2 to 10 nm Hydrosilylated Silicon Quantum Dots

Optimizing the light‐emitting efficiency of silicon quantum dots (Si QDs) has been recently intensified by the demand of the practical use of Si QDs in a variety of fields such as optoelectronics, photovoltaics, and bioimaging. It is imperative that an understanding of the optimum light‐emitting efficiency of Si QDs should be obtained to guide the design of the synthesis and processing of Si QDs. Here an investigation is presented on the characteristics of the photoluminescence (PL) from hydrosilylated Si QDs in a rather broad size region (≈2–10 nm), which enables an effective mass approximation model to be developed, which can very well describe the dependence of the PL energy on the QD size for Si QDs in the whole quantum‐confinement regime, and demonstrates that an optimum PL quantum yield (QY) appears at a specific QD size for Si QDs. The optimum PL QY results from the interplay between quantum‐confinement effect and surface effect. The current work has important implications for the surface engineering of Si QDs. To optimize the light‐emission efficiency of Si QDs, the surface of Si QDs must be engineered to minimize the formation of defects such as dangling bonds at the QD surface and build an energy barrier that can effectively prevent carriers in Si QDs from tunneling out.     

Surface-plasmon-assisted electromagnetic field enhancement in semiconductor quantum dots

The temporal development of incident electromagnetic plane waves across semiconductor quantum dots (QDs) is analyzed by the finite-difference time-domain method. By coating the QDs using thin metal films, surface plasmon polaritons (SPPs) can be created. As illustration, our modeling approach is applied to fluorescent multiphoton quantum dots made of cadmium sulphide of particular size (3.7 nm) and energy band gap (2.67 eV). When such a QD is coated by a metal film, a dipole-formed SPP is generated at the external surface of the coated QD by the incident electromagnetic wave with a photon energy of 1.34 eV corresponding to a two-photon process. When the thickness of the metal film is 0.37 nm, the peak intensity of the SPP oscillates through both the thin metal film and the core QD, resulting in an electromagnetic field inside the QD enhanced by a factor of 10, and thus an increased two-photon excitation that can be useful for bioimaging applications. Further increasing the metal film thickness blockades the SPP initially generated at the external surface of the coated QD from penetrating through the metal film, reducing the electromagnetic field inside the QD. PACS 73.22.-f; 78.67.Hc     

The effect of bio-conjugation on aging of the photoluminescence in CdSeTe–ZnS core–shell quantum dots

The aging of the photoluminescence (PL) in bio-conjugated and non-conjugated CdSeTe–ZnS core–shell quantum dots (QDs) is studied by the micro-PL, micro-Raman and X-ray diffraction (XRD) in the samples of buffered QD solution dried on a crystalline Si wafer and stored in the atmospheric ambience for about 2 years. The aging of the PL consists in a “blue” spectral shift of the PL band, an increase in PL band half-width and the decrease in the PL intensity. These changes are more pronounced in the conjugated QD samples. The XRD analysis of the aged samples revealed that the QD core diameter is reduced by ∼1.5 nm in the conjugated QDs as compared to the non-conjugated ones. The possible mechanism of PL spectrum aging is the oxidation that decreases the QD core dimension. It is concluded that the bio-conjugation promotes QD oxidation and the mechanism of the effect is proposed.     

Formation of InAs quantum dots and wetting layers in GaAs and AlAs analyzed by cross-sectional scanning tunneling microscopy

We have used cross-sectional scanning-tunneling microscopy (X-STM) to compare the formation of self-assembled InAs quantum dots (QDs) and wetting layers on AlAs (1 0 0) and GaAs (1 0 0) surfaces. On AlAs we find a larger QD density and smaller QD size than for QDs grown on GaAs under the same growth conditions (500 °C substrate temperature and 1.9 ML indium deposition). The QDs grown on GaAs show both a normal and a lateral gradient in the indium distribution whereas the QDs grown on AlAs show only a normal gradient. The wetting layers on GaAs and AlAs do not show significant differences in their composition profiles. We suggest that the segregation of the wetting layer is mainly strain-driven, whereas the formation of the QDs is also determined by growth kinetics. We have determined the indium composition of the QDs by fitting it to the measured outward relaxation and lattice constant profile of the cleaved surface using a three-dimensional finite element calculation based on elasticity theory.     

Growth of three-dimensional quantum dot crystals on patterned GaAs (0 0 1) substrates

The growth of a three-dimensional (3D) InAs quantum dot (QD) crystal on a patterned GaAs (0 0 1) substrate is demonstrated. The morphology of QDs grown on a surface patterned with shallow holes is studied as a function of the amount of deposited InAs. We observe that the QDs form in the patterned holes close to each other forming lateral QD bimolecules for InAs coverages below the commonly observed critical thickness of 1.6 monolayers. When the coverage increases, the QD bimolecules coalesce to form larger single QDs. The QDs in the holes are then capped with a Ga(Al)As spacer. The buried QD array serves as a strain template for controlling the formation site of the QDs in the second layer. By tuning the growth conditions for the second and subsequent layers, we achieve a 3D InAs QD crystal with a high degree of perfection. A detail investigation of the growth on hole patterns with different periodicities is presented.     

Composition of the “GaAs” quantum dot,grown by droplet epitaxy

Self-assembled strain-free quantum dot (QD) structures were grown on AlGaAs surface by the droplet epitaxal method. The QDs were developed from pure Ga droplets under As pressure. The QDs were investigated by atomic force microscopy (AFM) and transmission electron microscopy (TEM). Both techniques show that the QDs are very uniform in size and their distribution on the surface is also homogeneous. The high resolution cross-sectional TEM investigation shows perfect lattice matching between the QD and the substrate, and also the faceting of the side walls of QD can be identified exactly by lattice planes. Analytical TEM (elemental mapping by EELS) unambiguously identifies the presence of Al in the QD.     

1.5 μm emission from InAs quantum dots with InGaAsSb strain-reducing layer grown on GaAs substrates

InGaAsSb strain-reducing layers (SRLs) are applied to cover InAs quantum dots (QDs) grown on GaAs substrates. The compressive strain induced in InAs QDs from the GaAs is reduced due to the tensile strain induced by the InGaAsSb SRL, because the lattice constant of InGaAsSb is closer to InAs lattice constant than that of GaAs, resulting in a significant red shift of photoluminescence peaks of the InAs QDs. The emission wavelength from InAs QDs can be controlled by changing the Sb composition of the InGaAsSb SRL. The 1.5 μm band emissions were achieved in the sample with an InGaAsSb SRL whose Sb compositions were above 0.3. The calculation of the electron and the hole wave functions using the transfer matrix method indicates that the electron and the hole were localized around InAs QDs and InGaAsSb SRL.