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The dilute GaNxAs1-x alloys (with x up to 0.05) have exhibited many unusual properties as compared to the conventional binary and ternary semiconductor alloys. We report on a new effect in the GaNxAs1-x alloy system in which electrically active substitutional group IV donors and isoelectronic N atoms passivate each other's activity. This mutual passivation occurs in dilute GaNxAs1-x doped with group IV donors through the formation of nearest neighbor IVGa- NAs pairs when the samples are annealed under conditions such that the diffusion length of the donors is greater than or equal to the average distance between donor and N atoms. The passivation of the shallow donors and the NAs atoms is manifested in a drastic reduction in the free electron concentration and, simultaneously, an increase in the fundamental bandgap. This mutual passivation effect is demonstrated in both Si and Ge doped GaNxAs1-x alloys. Analytical calculations of the passivation process based on Ga vacancy mediated diffusion show good agreement with the experimental results.

It has long been recognized that the introduction of a narrow band of states in a semiconductor band gap could be used to achieve improved power conversion efficiency in semiconductor-based solar cells. The intermediate band would serve as a “stepping stone” for photons of different energy to excite electrons from the valence to the conduction band. An important advantage of this design is that it requires formation of only a single p-n junction, which is a crucial simplification in comparison to multijunction solar cells. A detailed balance analysis predicts a limiting efficiency of more than 50% for an optimized, single intermediate band solar cell. This is higher than the efficiency of an optimized two junction solar cell. Using ion beam implantation and pulsed laser melting we have synthesized Zn1-yMnyOxTe1-x alloys with x1-yMnyOxTe1-x alloys. We observe an extension of the photovoltaic response towards lower photon energies, which is a clear indication of optical transitions from the valence to the intermediate band.

We have carried out a systematic study of the effects of irradiation on the electronic and optical properties of InGaN alloys over the entire composition range. High energy electrons, protons, and 4He+ were used to produce displacement damage doses (Dd) spanning over five orders of magnitude. The free electron concentrations in InN and In-rich InGaN increase with Dd and finally saturate after a sufficiently high Dd. The saturation of carrier density is attributed to the formation of native donors and the Fermi level pinning at the Fermi Stabilization Energy (EFS), as predicted by the amphoteric native defect model. Electrochemical capacitance-voltage (ECV) measurements reveal a surface electron accumulation whose concentration is determined by pinning at EFS.

High-energy particle irradiation has been used to control the free electron concentration and electron mobility in InN by introducing native point defects that act as donors. A direct comparison between theoretical calculations and the experimental electron mobility suggests that scattering by triply-charged donor defects limits the mobility in irradiated samples across the entire range of electron concentrations studied. Thermal annealing of irradiated films in the temperature range 425°C to 475°C results in large increases in the electron mobility that approach the values predicted for singly-ionized donor defect scattering. It is suggested that the radiation-induced donor defects are stable, singly-charged nitrogen vacancies, and triply-charged, relaxed indium vacancy complexes that are removed by the annealing.

Two ternary alloys based on III-nitride semiconductor alloys are explored as potential components of photoelectrochemical cells (PECs) for the direct generation of hydrogen using solar energy. For In1-xGaxN, it will be shown using prior measurements of band offsets that spontaneous water splitting can occur for x up to 0.2 and potentially higher. Flat band potential and photocurrent measurements from an n-type epilayer with x = 0.37 will be presented. This initial data appears to indicate that the flat band potential lies just below the H+/H2 from pH 0 – 14. In the case of GaAsxN1-x we will demonstrate that the replacement of a few percent of As in N sublattice drives the bandgap down from the GaN value (3.4 eV) into a range that is attractive for PEC cells [1]. This band gap reduction is explained by the valence band anticrossing that pushes the valence band maximum up initially by 0.5 eV. From the point of view of a PEC cell, this reduces the gap (desirable for efficiency) without compromising the desired H+/H2 overpotential.

InxGa1-x N layers grown with compositions with the predicted miscibility gap have been studied using Transmission Electron Microscopy (TEM), x-ray diffraction and optical measurements (photoluminescence and absorption). The samples (0.34 < × < 0.8) were deposited by Molecular Beam Epitaxy at 800°C using 200 nm AlN buffer layer grown directly on sapphire substrates. Another sample with × = 0.34 was grown on a GaN buffer layer. Dislocation densities in the InGaN layers were typically in the mid-1010 cm−2 to1011 cm−2 range. Edge dislocations were the most prevalent. For In concentration × = 0.5 compositional ordering is observed leading to extra diffraction spots in electron and x-ray diffraction. The ordering was not observed for the sample with x=0.34 grown on GaN. Based on TEM measurements the estimated period of ordering Δ was about Δ = 45 Å for × = 0.5 and Δ = 65Å for × = 0.78. The sample with × = 0.5 had the highest dislocation density. In addition to the presence of threading dislocations two types of domain boundaries on (0001) and (0110) planes were also observed in this sample. This sample has a broader photoluminescence (PL) that is redshifted compared to the absorption edge (“Stokes shift”).

The hydrostatic pressure dependence of the optical transitions in InN, In-rich In1-xGaxN (0 < x < 0.5) and In1-xAlxN (x = 0.25) alloys is studied using diamond anvil cells. The absorption edges and the photoluminescence peaks shift to higher energy with pressure. The pressure coefficient of InN is determined to be 3.0±0.1 meV/kbar. Together with previous experimental results, our data suggest that the pressure coefficients of group-III nitride alloys have only a weak dependence on the alloy composition. Photoluminescence gives much smaller pressure coefficients, which is attributed to emission involving highly localized states. This indicates that photoluminescence might not be an accurate method to study the pressure dependence of the fundamental bandgaps of group III-nitrides.

Growth of non-polar III-nitrides has been an important subject recently due to its potential improvement on the efficiency of III-nitride-based opto-electronic devices. Despite study of non-polar GaN and GaN-based heterostructures, there are few reports on epitaxial growth of non-polar InN, which is also an important component of the III-nitride system. In this study, we report heteroepitaxial growth of non-polar InN on r-plane sapphire substrates using plasma-assisted molecular beam epitaxy. It is found that when a GaN buffer is used, the following InN film appears to be non-polar (1120) a-plane which follows the a-plane GaN buffer. The room temperature Hall mobility of undoped a-plane InN is around 250 cm2/Vs with a carrier concentration around 6×1018 cm-3. Meanwhile, if InN film is directly deposited on r-plane sapphire without any buffer, the InN layer is found to consist of a predominant zincblende (cubic) structure along with a fraction of the wurtzite (hexagonal) phase with increasing content with proceeding growth.

In this study, InN films with thickness up to 7.5 micron were prepared by molecular beam epitaxy (MBE) on (0001) sapphire and quasi-bulk GaN templates. Previously it has been challenging to grow InN film much beyond 1 micron because the growing surface tended to become rough. Techniques to overcome this limit have been developed. Various buffer techniques were used and compared to optimize the epitaxial growth. It was found that with increasing film thickness, Hall mobility will monotonically increase, while carrier concentration decreases. Hall mobility beyond 2100 cm2/Vs with carrier concentration close to 3×1017 cm−3 was obtained at room temperature. Compared with the lowest carrier concentration ∼2×1018 cm−3 obtained on thin InN films grown at the same condition, the conclusion is that impurities from the growth environment are not responsible for the high background doping of InN. Instead, some structural defects or substrate/buffer impurities may be the major source of the unintentional doping, which can be reduced by growing thicker films.Some results on Mg and Be doping of InN will be reported as well. To date, all Mg and Be doping attempts have resulted in n-type material.

Dilute III-Nx-V1-x alloys were successfully synthesized by nitrogen implantation in GaAs and InP. The fundamental band gap energy for the ion beam synthesized III-Nx-V1-x alloys was found to decrease with increasing N implantation dose in a manner similar to that commonly observed in epitaxially grown GaNxAs1-x and InNxP1-x thin films. The fraction of N occupying anion sites (“active” N) in the GaNxAs1-x layers formed by N implantation was thermally unstable and decreased with increasing annealing temperature. In contrast, thermally stable InNxP1-x alloys with N mole fraction as high as 0.012 were synthesized by N implantation in InP. Moreover, the N activation efficiency in InP was at least a factor of two higher than in GaAs under similar processing conditions. The low N activation efficiency (

We present results of photoluminescence (PL) studies of GaN, InxGa1-xN and AlxGa1-xN alloys, as well as related thin film heterostructures under hydrostatic pressure using the diamond-anvil-cell technique. The GaN PL spectra are dominated by strong and sharp near-band-edge luminescence associated with annihilations of bound excitons and intrinsic free excitons in the crystals. The spectrally well-resolved emission lines allow us to accurately determine their pressure. The PL spectra of InxGa1-xN and AlxGa1-xN epitaxial films were found to exhibit strong near-band-edge luminescence emissions. By examining the pressure dependence of these spectral features, the pressure coefficients for the PL emissions associated with the direct Γ band gap of InxGa1-xN and AlxGa1-xN were determined for the first time.

We propose a new approach for modeling of impurity diffusion at semiconductor heterointerfaces. The approach is based on the notion of a common energy reference for highly localized defects. It is shown that in the kick-out process, the segregation of group II acceptors is controlled by the valence band offsets among different constituent layers of the heterostructure. Extensive numerical modeling of the diffusion provides an explanation for the experimentally observed strong segregation of Zn and Be acceptors in the lattice matched InP/InGaAs, InP/InGaAsP and GaAs/AlGaAs heterostructures.

We report on the observation of optical quenching of persistent photoconductivity (PPC) in unintentionally doped n-type GaN films. The PPC is induced by subbandgap illumination between room temperature and 77K. The corresponding decay, which.is thermally activated, is substantially increased upon low energy illumination, e.g. illumination by wavelengths between 1O50nm and 700nm. We measure the saturation conductivity under simultaneous illumination with excitation and quenching light and find that some wavelengths can induce both excitation and quenching of photoconductivity. Additionally, we present a preliminary investigation of the spectral dependence of the quenching effect. A simulation indicates only a weak spectral dependence of the quenching cross-sections in the wavelength range from 470nm–1050nm.

We have calculated the electron mobilities in GaN and InN taking into consideration scattering by short range potentials, in addition to all standard scattering mechanisms. These potentials are produced by the native defects which are responsible for the high electron concentrations in nominally undoped nitrides. Comparison of the calculated mobilities with experimental data shows that scattering by short range potentials is the dominant mechanism limiting the electron mobilities in unintentionally doped nitrides with large electron concentrations. In the case of AlxGal1−xN alloys, the reduction in the electron concentration due to the upward shift of the conduction band relative to the native defect level can account for the experimentally measured mobilities. Resonant scattering is shown to be important when the defect and Fermi levels are close in energy.

GaN plays a key role in the exploration of the properties of group-Ill nitrides. As grown GaN often shows a high electron concentration, e.g. 1019 cm−3, of as yet unidentified origin. Applying large hydrostatic pressure we studied the behavior of these donors and a frequently observed strong luminescence band at 3.42 eV. We find a drop of the electron concentration to 3×1017 cm−3 at 27 GPa and derive a binding energy of 126 meV for the neutral singlet donor level at this pressure. Such a pressure behavior of a donor is consistent with the model of strongly localized defects. Within the framework of a bandstructure calculation we predict the neutral level of this donor at 0.40 ± 0.10 eV above the conduction band edge at ambient pressure.

A luminescence band centered around 3.42 eV is commonly observed in GaN. Its appearance has been tentatively assigned to an oxygen donor level. Stimulated laser activity has also been reported at this energy. We present a study of this band in GaN grown by high temperature vapor phase epitaxy (HTVPE). The high quality of this material, with an excitonic line width as narrow as 3 meV, allows us to distingish four different peak positions of this luminescence band. They appear at 3.4066, 3.4121, 3.4186, and 3.4238 eV (T = 6 K). Within the experimental error the lines exhibit an equidistant spacing of 6 meV. They show a pressure behavior similar to shallow levels described by effective mass theory. We discuss our results in the context of incorporation of oxygen and structural defects in GaN.

We have synthesized dilute magnetic semiconductor (DMS) thin films of CdMnTe and ZnMnSe using the ion beam technique. High doses of Mn ions (∼2–5×1016/cm 2) were implanted into single crystal CdTe and into ZnSe epilayers on GaAs, forming subsurface layers of Cdl.xMnxTe and Znl-xMnxSe alloys, respectively, with x∼0.15–0.22. Fluorescence extended x-ray absorption fine structure (EXAFS) measurements on these materials reveal that the Mn atoms in the CdMnTe and ZnMnSe layers, both as-implanted and annealed, have local environments similar to their corresponding bulk-grown DMS alloys. While the anion-cation distances (Ra-c) in the annealed samples are equivalent to those in the corresponding bulk-grown DMS, the Ra-c in the asimplanted samples are slightly larger (∼0.01Å) than those in the bulk-grown DMS. This is most likely due to the implantation damage in the as-implanted materials. Our results on the Ra-c of the ion beam synthesized layers deviate significantly from Vegard's law, but are consistent with the bimodal distribution model. The EXAFS results are corroborated with results from ion beam analysis and Raman spectroscopy.

The effects of heavy doping on the formation of charged point defects are considered. It is shown that the Fermi level dependent part of the formation energy of highly localized defects can be determined using a universal energy reference, common to all III-V compound semiconductors. The concept is used to analyze the electrical activity and diffusion of dopant impurities in these compounds. We present model calculations which explain the correlation between the maximum hole concentrations and the acceptor impurity diffusion in InP and in InGaAs alloys, doped with group II acceptors. The calculations account for the redistribution of the impurity atoms at the lattice matched InP/InGaAs interface. It is also demonstrated that an abrupt enhancement of the Fermi level induced defect formation is observed at the onset of highly degenerate statistics in heavily doped semiconductors.

Annealing of oxygen-rich Czochralski silicon at temperatures between 700°C and 1000°C introduces a new scattering mechanism which correlates very well with the presence of oxide precipitates. In lightly doped crystals (n,p ∼1015cm−3) this mechanism becomes dominant at T0.5. This dependence was explained in terms of scattering of free carriers by spacially slowly varying potential associated with oxide precipitates of varying size.

We report the results of DLTS experiments under uniaxial stress on the second ionization level of EL2(++/+) in p-type GaAs. We measured the shift in the hole emission rate as a function of stress applied in the [100] and [110] directions. By modeling the valence band with two independently displacing bands and appropriately derived effective masses, we obtain a small absolute hydrostatic pressure derivative for the defect, 39 ±15 meV GPa-1. The shear contribution is negligible. This result is very different than for the first ionization level, EL2(+/o) with a emission energy pressure derivative of 90 ±15 meV GPa-1. The difference can be accounted for by the pressure dependence of the electron capture barrier of EL2(+/o), 49 ±15meV GPa-1. The absolute pressure derivatives of the two levels are then comparable and in good agreement with simple theory for Ga site point defects.

Based on transition metal reference levels, we present absolute pressure derivatives for band-edges in GaAs and InP and defects in GaAs. The defect deformation potentials are directly related to the electron-lattice coupling which drives lattice relaxation around the defects. We find an exceedingly large inward lattice relaxation of the EL2 defect in GaAs upon electron emission.