The authors have performed first-principles calculations to examine the effects of biaxial strain and chemical ordering on the band gap of wurtzite In{sub x}Ga{sub 1{minus}x}N in the range 0 {le} x {le} 0.5. The results for unstrained, random alloys are in good agreement with theoretical estimates and measurements on unstrained zinc-blende alloys, but are in poor agreement with recent measurements on strained wurtzite alloys which display significantly lower gaps. Biaxial strain is found to have a non-linear effect on calculated alloy gaps, increasing them for x < 0.25 and decreasing them for x > 0.25. However, the overall agreement with measured wurtzite values remains poor. Chemical ordering along the [0001] direction in strained alloys is found to decrease the band gaps considerably, yielding much improved agreement with measurements. They discuss their results with regard to current theories concerning the optical properties of wurtzite InGaN alloys.
The diffusion, uptake, and release of H in p-type GaN are modeled employing state energies from density-function theory and compared with measurements of deuterium uptake and release using nuclear-reaction analysis. Good semiquantitative agreement is found when account is taken of a surface permeation barrier.
Formation energies and vibrational frequencies for H in wurtzite GaN were calculated from density functional theory and used to predict equilibrium state occupancies and solid solubilities for p-type, intrinsic, and n-type material. The solubility of deuterium (D) was measured at 600--800 C as a function of D{sub 2} pressure and doping and compared with theory. Agreement was obtained by reducing the H formation energies 0.2 eV from ab-initio theoretical values. The predicted stretch-mode frequency for H bound to the Mg acceptor lies 5% above an observed infrared absorption attributed to this complex. It is concluded that currently recognized H states and physical processes account for the equilibrium behavior of H examined in this work.
The LDRD entitled ``Role of Defects in III-Nitride Based Devices'' is aimed to place Sandia National Laboratory at the forefront of the field of GaN materials and devices by establishing a scientific foundation in areas such as material growth, defect characterization/modeling, and processing (metalization and etching) chemistry. In this SAND report the authors summarize their studies such as (1) the MOCVD growth and doping of GaN and AlGaN, (2) the characterization and modeling of hydrogen in GaN, including its bonding, diffusion, and activation behaviors, (3) the calculation of energetic of various defects including planar stacking faults, threading dislocations, and point defects in GaN, and (4) dry etching (plasma etching) of GaN (n- and p-types) and AlGaN. The result of the first AlGaN/GaN heterojunction bipolar transistor is also presented.
The behavior of H in p-GaN(Mg) at temperatures >400 C is modeled by using energies and vibrational frequencies from density-functional theory to parameterize transport and reaction equations. Predictions agree semiquantitatively with experiment for the solubility, uptake, and release of the H when account is taken of a surface barrier. Hydrogen is introduced into GaN during growth by metal-organic chemical vapor deposition (MOCVD) and subsequent device processing. This impurity affects electrical properties substantially, notably in p-type GaN doped with Mg where it reduces the effective acceptor concentration. Application of density-functional theory to the zincblende and wurtzite forms of GaN has indicated that dissociated H in interstitial solution assumes positive, neutral, and negative charge states. The neutral species is found to be less stable than one or the other of the charged states for all Fermi energies. Hydrogen is predicted to form a bound neutral complex with Mg, and a local vibrational mode ascribed to this complex has been observed. The authors are developing a unified mathematical description of the diffusion, reactions, uptake, and release of H in GaN at the elevated temperatures of growth and processing. Their treatment is based on zero-temperature energies from density functional theory. One objective is to assess the consistency of theory with experiment at a more quantitative level than previously. A further goal is prediction of H behavior pertinent to device processing. Herein is discussed aspects relating to p-type GaN(Mg).
The authors have used ion channeling to examine the lattice configuration of deuterium in Mg doped GaN grown by MOCVD. The deuterium is introduced both by exposure to deuterium gas and to ECR plasmas. A density functional approach including lattice relaxation, was used to calculate total energies for various locations and charge states of hydrogen in the wurtzite Mg doped GaN lattice. Computer simulations of channeling yields were used to compare results of channeling measurements with calculated yields for various predicted deuterium lattice configurations.
Charge-state calculations based on density-functional theory are used to study the formation energy of hydrogen in wurtzite and zinc-blende GaN as a function of Fermi level Comparison of these results reveals notable differences including a 0.56 eV lower formation energy for H2 in wurtzite, and different configurations for H2 and H- in the two crystal structures. Furthermore, H+ is found to be equally stable at bond-centered and anti-bonding sites in wurtzite, whereas it is unstable at a bond-centered site in zinc blende. These differences are due to distinct features of the two crystal structures including: the lower symmetry of wurtzite which provides a wider selection of bonding sites for H+, and the existence of extended three-fold symmetric channels oriented along the c-axis in wurtzite which provide more favorable bonding configurations for H2 and H-.N-H+ stretch-mode vibration frequencies, clustering of ?3+ in p-type material, and diffusion barriers for H" are also investigated in wurtzite GaN. A diffusion barrier of 1.6 eV is found for H- in wurtzite GaN, significantly lower than a previous estimate, and a tendency for H+ clustering in p-type material is found.
We have investigated two types of extended defects commonly found in AlN, GaN and InN films using density-functional techniques. First, basal-plane stacking faults have been studied for all three compounds. Stacking-fault energies were found to be largest in AlN and smallest in GaN consistent with density-functional results for their wurtzite/zinc-blende energy differences. In addition, the 4H and 6H structures were found to have lower energies than zinc blende for all three compounds. Second, we have investigated the electronic structure and formation energy for an edge dislocation in AlN. The full-core dislocation structure was found to have a filled electronic level approximately 0.55 eV above the valence-band edge and an empty level 1.4 eV below the conduction-band edge. An open-core structure was found to have filled and empty electronic levels closer to the middle of the energy gap. Formation energies for these two geometries suggest that the full-core structure would be expected to form in p-type material whereas both are expected in n-type material.
First-principles density-functional calculations utilizing ab initio pseudopotentials and plane- wave expansions are used to determine lattice parameters, bulk moduli, and band structures for AlN, GaN, and InN. It is found that large numbers of plane waves are necessary to resolve the nitrogen 2p wave functions and that explicit treatment of the gallium 3d and indium 4d electrons is important for an accurate description of GaN and InN. Several properties of ternary zinc-blende alloys are determined including their bond-length and bond-angle relaxation and their energy-gap bowing parameters. The similarity of the calculated zinc- blende and wurtzite direct gaps also allows estimates to be made of the energy gap versus composition for wurtzite alloys.