Dilute nitride semiconductors : band structure, scattering and high field transport

The substitution of a small fraction x of nitrogen atoms, for the group V elements in conventional III-V semiconductors such as GaAs and GaSb strongly perturbs the conduction band of the host semiconductor. In this thesis we investigate the effects of nitrogen states on the band dispersion, carrier scattering and mobility of dilute nitride alloys. In the supercell model we solve the single particle Hamiltonian for a very large supercell containing randomly placed nitrogen. This model predicts a gap in the density of states of GaNxAs1−x, where this gap is filled in the Green’s function model. Therefore we develop a self-consistent Green’s function (SCGF) approach, which provides excellent agreement with supercell calculations and reveals a gap in the DOS, in contrast with the results of previous non-self-consistent Green’s function calculations. However, including the distribution of N states destroys this gap, as seen in experiment. We then examine the high field transport of carriers by solving the steadystate Boltzmann transport equation and find that it is necessary to include the full distribution of N levels in order to account for the small, low-field mobility and the absence of a negative differential velocity regime observed experimentally with increasing x. Overall the results account well for a wide range of experimental data. We also investigate the band structure, scattering and mobility of carriers by finding the poles of the SCGF, which gives lower carrier mobility for GaNxAs1−x, compared to those already calculated, in better agreement with experiments. The calculated optical absorption spectra for InyGa1−yNxAs1−x and GaNxSb1−x using the SCGF agree well with the experimental data, confirming the validity of this approach to study the band structure of these materials.

A tight-binding analysis of the electronic properties of III-nitride semiconductors

This thesis divides into two distinct parts, both of which are underpinned by the tight-binding model. The first part covers our implementation of the tight-binding model in conjunction with the Berry phase theory of electronic polarisation to probe the atomistic origins of spontaneous polarisation and piezoelectricity as well as attempting to accurately calculate the values and coefficients associated with these phenomena. We first develop an analytic model for the polarisation of a one-dimensional linear chain of atoms. We compare the zincblende and ideal wurtzite structures in terms of effective charges, spontaneous polarisation and piezoelectric coefficients, within a first nearest neighbour tight-binding model. We further compare these to real wurtzite structures and conclude that accurate quantitative results are beyond the scope of this model but qualitative trends can still be described. The second part of this thesis deals with implementing the tight-binding model to investigate the effect of local alloy fluctuations in bulk AlGaN alloys and InGaN quantum wells. We calculate the band gap evolution of Al1_xGaxN across the full composition range and compare it to experiment as well as fitting bowing parameters to the band gap as well as to the conduction band and valence band edges. We also investigate the wavefunction character of the valence band edge to determine the composition at which the optical polarisation switches in Al1_xGaxN alloys. Finally, we examine electron and hole localisation in InGaN quantum wells. We show how the built-in field localises the carriers along the c-axis and how local alloy fluctuations strongly localise the highest hole states in the c-plane, while the electrons remain delocalised in the c-plane. We show how this localisation affects the charge density overlap and also investigate the effect of well width fluctuations on the localisation of the electrons.

Earth-Abundant Zinc-IV-Nitride Semiconductors

This investigation is motivated by the need for new visible frequency direct bandgap semiconductor materials that are abundant and low-cost to meet the increasing demand for optoelectronic devices in applications such as solid state lighting and solar energy conversion. Proposed here is the utilization of zinc-IV-nitride materials, where group IV elements include silicon, germanium, and tin, as earth-abundant alternatives to the more common III-nitrides in optoelectronic devices. These compound semiconductors were synthesized under optimized conditions using reactive radio frequency magnetron sputter deposition. Single phase ZnSnN₂, having limited experimental accounts in literature, is validated by identification of the wurtzite-derived crystalline structure predicted by theory through X-ray and electron diffraction studies. With the addition of germanium, bandgap tunability of ZnSn_xGe_1-xN₂ alloys is demonstrated without observation of phase separation, giving these materials a distinct advantage over In_xGa_1-xN alloys. The accessible bandgaps range from 1.8 to 3.1 eV, which spans the majority of the visible spectrum. Electron densities, measured using the Hall effect, were found to be as high as 10²² cm⁻³ and indicate that the compounds are unintentionally degenerately doped. Given these high carrier concentrations, a Burstein-Moss shift is likely affecting the optical bandgap measurements. The discoveries made in this thesis suggest that with some improvements in material quality, zinc-IV-nitrides have the potential to enable cost-effective and scalable optoelectronic devices.

Luminescence studies on nitride quaternary alloys double quantum wells

We present theoretical photoluminescence (PL) spectra of undoped and p-doped Al(x)In(1-xy)Ga(y)N/Al(X)In(1) (X) (Y)Ga(Y)N double quantum wells (DQWs). The calculations were performed within the k.p method by means of solving a full eight-band Kane Hamiltonian together with the Poisson equation in a plane wave representation, including exchange-correlation effects within the local density approximation. Strain effects due to the lattice mismatch are also taken into account. We show the calculated PL spectra, analyzing the blue and red-shifts in energy as one varies the spike and the well widths, as well as the acceptor doping concentration. We found a transition between a regime of isolated quantum wells and that of interacting DQWs. Since there are few studies of optical properties of quantum wells based on nitride quaternary alloys, the results reported here will provide guidelines for the interpretation of forthcoming experiments. (C) 2008 Elsevier B.V. All rights reserved.

Effects of growth temperature on nonpolar a-plane InN grown by molecular beam epitaxy

Nonpolar a-plane InN films were grown on r-plane sapphire substrate by plasma assisted molecular beam epitaxy with GaN underlayer. Effect of growth temperature on structural, morphological, and optical properties has been studied. The growth of nonpolar a-plane (1 1 -2 0) orientation was confirmed by high resolution X-ray diffraction study. The film grown at 500 degrees C shows better crystallinity with the rocking curve FWHM 0.67 degrees and 0.85 degrees along 0 0 0 1] and 1 - 1 0 0] directions, respectively. Scanning electron micrograph shows formation of Indium droplets at higher growth temperature. Room temperature absorption spectra show growth temperature dependent band gap variation from 0.74-0.81 eV, consistent with the expected Burstein-Moss effect. The rectifying behaviour of the I-V curve indicates the existence of Schottky barrier at the InN and GaN interface. (C) 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Spectra analysis of a novel Ti-doped LiAlO2 single crystal

LiAlO2 single crystals doped with Ti at concentration 0.2 at.% are grown by the Czochralskl technique with dimensions Phi 42 x 55 mm. Ti ions in the crystal are quadrivalence proven by comparing the absorption and fluorescence spectra of pure LiAlO2 and Ti: LiAlO2. After air and Li-rich atmosphere annealing, the absorption peaks in the range of 600-800nm disappear. We conclude that 682 and 756nm absorption peaks are attributed to the V-Li and V-O absorptions, respectively. The peaks at 716nm and 798nm may stem from the V-Li(+) and F+ absorptions. The colour-centre model can be applied to explain the experimental phenomena. Ti4+-doping produces more lithium vacancies in the LiAlO2 crystal. The intensities of [LiO4] and the associated bonds remain unchanged, which improves the anti-hydrolyzation and thermal stability of LiAlO2 crystals.

Blue-green optically pumped GaN-based vertical cavity surface emitting laser

Blue-green GaN-based vertical cavity surface emitting lasers (VCSELs) were fabricated with two dielectric Ta2O5/SiO2 distributed Bragg reflectors. Lasing action was observed at a wavelength of 498.8 nm at room temperature under optical pumping. Threshold energy density and emission linewidth were 189 mJ/cm(2) and 0.15 nm, respectively. The result demonstrates that blue-green VCSELs can be realised using III-nitride semiconductors.

Spin-Polarized Localized Exciton Photoluminescence Dynamics in GaInNAs Quantum Wells

We have investigated spin polarization-related localized exciton photoluminescence (PL) dynamics in GaInNAs quantum wells by time-resolved PL spectroscopy. The emission energy dependence of PL polarization decay time as well as polarization-independent PL decay time suggests that the acoustic phonon scattering in the process of localized exciton transfer from the high-energy localized states to the low-energy ones dominates the PL polarization relaxation. By increasing the excitation power from 1 to 10 mW, the PL polarization decay time is changed from 0.17 to more than 1 ns, which indicates the significant effect of the trapping of localized electrons by nonradiative recombination centers. These experimental findings indicate that the spin-related PL polarization in diluted nitride semiconductors can be manipulated through carrier scattering and recombination process. (C) 2009 The Japan Society of Applied Physics

Structural characterization of AlGaN/GaN superlattices by x-ray diffraction and Rutherford backscattering

We report on structural characterization of AlGaN/GaN superlattices grown on sapphire. The superlattice formation is evidenced by high-resolution x-ray diffraction and transmission electron microscopy. The high resolution x-ray diffraction spectra exhibit a pattern of satellite peaks. The in-plane lattice constants of the superlattices indicate the coherent growth of the AlGaN layer onto GaN. The average At composition in the superlattices is determined to be 0.08 by Rutherford backscattering spectroscopy. The average parallel and perpendicular elastic strains for the SLs are determined to be (e(parallel to)) = +0.25% and (e(perpendicular to)) = -0.17%. (c) 2006 Elsevier Ltd. All rights reserved.

Interfaces in heterostructures of AlInGaN/GaN/Al2O3

Rutherford backscattering/channeling (RBS/C) and X-ray diffraction (XRD) are used to comprehensively characterize a heterostructure of AlInGaN/GaN/Al2O3(0001). The AlInGaN quaternary layer was revealed to process a high crystalline quality with a minimum yield of 1.4% from RBS/C measurements. The channeling spectrum of (1 (2) under bar 13) exhibits higher dechanneling than that of (0001) at the interface of AlInGaN/GaN. XRD measurements prove a coherent growth of AlInGaN on the GaN template layer. Combining RBS/C and XRD measurements, we found that the interface of GaN/Al2O3 is a nucleation layer, composed of a large amount of disorders and cubic GaN slabs, while the interface of AlInGaN/GaN is free of extra disordering (i.e. compare with the GaN layer). The conclusion is further evidenced by transmission electron microscopy (TEM). (c) 2005 Elsevier Ltd. All rights reserved.

Anomalous strains in the cubic-phase GaN films grown on GaAs (001) by metalorganic chemical vapor deposition

Strains in cubic GaN films grown on GaAs (001) were measured by a triple-axis x-ray diffraction method. Residual strains in the as-grown epitaxial films were in compression, contrary to the predicted tensile strains caused by large lattice mismatch between epilayers and GaAs substrates (20%). It was also found that the relief of strains in the GaN films has a complicated dependence on the growth conditions. We interpreted this as the interaction between the lattice mismatch and thermal mismatch stresses. The fully relaxed lattice constants of cubic GaN are determined to be 4.5038 +/- 0.0009 Angstrom, which is in excellent agreement with the theoretical prediction of 4.503 Angstrom. (C) 2000 American Institute of Physics. [S0021-8979(00)07918-4].

Electronic properties of zinc-blende GaN, AlN, and their alloys Ga1-xAlxN

The electronic properties of wide-energy gap zinc-blende structure GaN, A1N, and their alloys Ga(1-x)A1(x)N are investigated using the empirical pseudopotential method. Electron and hole effective mass parameters, hydrostatic and shear deformation potential constants of the valence band at Gamma and those of the conduction band at Gamma and X are obtained for GaN and AIN, respectively. The energies of Gamma, X, L conduction valleys of Ga(1-x)A1(x)N alloy versus Al fraction x are also calculated. The information will be useful for the design of lattice mismatched heterostructure optoelectronic devices based on these materials in the blue light range application. (C) 1995 American Institute of Physics.

Band structure parameters of zinc-blende GaN, AlN and their alloys Ga1-xAlxN

The electronic properties of wide energy gap zinc-blende structure GaN, AlN and their alloys Ga1-xAlxN are investigated using the empirical pseudopotential method. Electron and hole Effective mass parameters, hydrostatic and shear deformation potential constants of the valence band at Gamma and those of the conduction band at Gamma and X are obtained. The energies of Gamma, X, L conduction valleys of Ga1-xAlxN alloy versus Al fraction x are also calculated. The information will be useful for the design of lattice mismatched heterostructure optoelectronic devices in the blue light range.

Growth and photoluminescence of InAlGaN films

Two quaternary InAlGaN films were grown by metal-organic chemical-vapor deposition (MOCVD) on sapphire (0001) substrates with and without high-temperature GaN interlayer, respectively. The structural and optical properties of the quaternary films were investigated by high-resolution X-ray diffraction (HRXRD), high-resolution electron microscopy (HREM), temperature-dependent photoluminescence (PL) spectroscopy and time-resolved photoluminescence (TRPL) spectroscopy. According to the HRXRD and PL results, it is demonstrated that two samples have the same crystal quality. The TRPL signals of both samples were fitted well as a stretched exponential decay from 14 K to 250 K, indicating significant disorder in the materials, which is attributed to recombination of excitons localized in disorder quantum nanostructures such as quantum dots or quantum disks originating from indium (In) clusters or In composition fluctuation. The cross-section HREM measurement further proves that there exist disorder quantum nanostructures in the quaternary. By investigating the temperature dependence of the dispersive exponent beta, it is shown that the stretched exponential decays of the two samples originate from different mechanisms. (C) 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reduction in crystallographic tilt of lateral epitaxial overgrown GaN by using new patterned shape mask

We proposed a new method to suppress the crystallographic tilt in the lateral epitaxial overgrowth of GaN by using an oxide mask with a newly designed pattern. A rhombus mask with edges oriented in the direction of <10 - 10>(GaN) was used instead of the traditional stripe mask. The morphology evolution during the LEO GaN with the rhombus mask was investigated by SEM, and the crystallographic tilt in the LEO GaN was measured by DC-XRD. It is found that using the new rhombus mask can decrease the crystallographic tilt in the LEO GaN. In addition, this method makes the ELO GaN stripes easy to coalesce. (C) 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.