http://ronald-wagner.de/diss/html/lit/share/surfsci411(98)186.pdf

The surface energy of metals

In this review, the structural, mechanical, thermal, and chemical properties of substrates used for gallium nitride (GaN) epitaxy are compiled, and the properties of GaN films deposited on these substrates are reviewed. Among semiconductors, GaN is unique; most of its applications uses thin GaN films deposited on foreign substrates (materials other than GaN); that is, heteroepitaxial thin films. As a consequence of heteroepitaxy, the quality of the GaN films is very dependent on the properties of the substrate—both the inherent properties such as lattice constants and thermal expansion coefficients, and process induced properties such as surface roughness, step height and terrace width, and wetting behavior. The consequences of heteroepitaxy are discussed, including the crystallographic orientation and polarity, surface morphology, and inherent and thermally induced stress in the GaN films. Defects such as threading dislocations, inversion domains, and the unintentional incorporation of impurities into the epitaxial GaN layer resulting from heteroepitaxy are presented along with their effect on device processing and performance. A summary of the structure and lattice constants for many semiconductors, metals, metal nitrides, and oxides used or considered for GaN epitaxy is presented. The properties, synthesis, advantages and disadvantages of the six most commonly employed substrates (sapphire, 6H-SiC, Si, GaAs, LiGaO 2 , and AlN) are presented. Useful substrate properties such as lattice constants, defect densities, elastic moduli, thermal expansion coefficients, thermal conductivities, etching characteristics, and reactivities under deposition conditions are presented. Efforts to reduce the defect densities and to optimize the electrical and optical properties of the GaN epitaxial film by substrate etching, nitridation, and slight misorientation from the (0 0 0 1) crystal plane are reviewed. The requirements, the obstacles, and the results to date to produce zincblende GaN on 3C-SiC/Si(0 0 1) and GaAs are discussed. Tables summarizing measures of the GaN quality such as XRD rocking curve FWHM, photoluminescence peak position and FWHM, and electron mobilities for GaN epitaxial layers produced by MOCVD, MBE, and HVPE for each substrate are given. The initial results using GaN substrates, prepared as bulk crystals and as free-standing epitaxial films, are reviewed. Finally, the promise and the directions of research on new potential substrates, such as compliant and porous substrates are described.

Substrates for gallium nitride epitaxy

Electron mobilities in GaN and InN are calculated, by variational principle, as a function of temperature for carrier concentrations of 1016, 1017, and 1018 cm−3 with compensation ratio as a parameter. Both GaN and InN have maximum mobilities between 100 and 200 K, depending on the electron density and compensation ratio, with lower electron density peaking at lower temperature. This is due to the interplay of piezoelectric acoustic phonon scattering at low carrier concentrations and ionized impurity scattering at higher carrier concentrations. Above 200 K, polar mode optical phonon scattering is the mobility limiting process. The 300 and 77 K electron and Hall mobilities as functions of carrier concentration in the range of 1016–1020 cm−3 and compensation ratio are also calculated. The theoretical maximum mobilities in GaN and InN at 300 K are about 1000 and 4400 cm2 V−1 s−1, respectively, while at 77 K the limits are beyond 6000 and 30 000 cm2 V−1 s−1, respectively. We compare the results with experimental data and find reasonable correlation, but with evidence that structural imperfection and heavy compensation play important roles in the material presently available. Only phonon limited scattering processes are considered in the calculation of the mobility in AlN since it is an insulator of extremely low carrier concentration. We find a phonon limited electron mobility of about 300 cm2 V−1 s−1 at 300 K.

Electron mobilities in gallium, indium, and aluminum nitrides

Reactive‐ion molecular‐beam epitaxy has been used to grow epitaxial hexagonal‐structure α‐GaN on Al2O3(0001) and Al2O3(0112) substrates and metastable zinc‐blende‐structure β‐GaN on MgO(001) under the following conditions: growth temperature Ts=450–800 °C; incident N+2/Ga flux ratio JN+2/JGa=1–5; and N+2 kinetic energy EN+2=35–90 eV The surface structure of the α‐GaN films was (1×1), with an ≊3% contraction in the in‐plane lattice constant for films grown on Al2O3(0001), while the β‐GaN films exhibited a 90°‐rotated two‐domain (4×1) reconstruction Using a combination of in situ reflection high‐energy electron diffraction, double‐crystal x‐ray diffraction, and cross‐sectional transmission electron microscopy, the film/substrate epitaxial relationships were determined to be: (0001)GaN∥ (0001)Al2O3 with [2110]GaN∥[1100]Al2O3 and [1100]GaN∥[1210]Al2O3, (2110)GaN∥(0112)Al2O3 with [0001]GaN∥[0111]Al2O3 and [0110]GaN∥[2110]Al2O3, and (001)GaN∥(001)MgO with [001]GaN∥[001]MgOFilms with the lowest e

Heteroepitaxial wurtzite and zinc‐blende structure GaN grown by reactive‐ion molecular‐beam epitaxy: Growth kinetics, microstructure, and properties

We discuss surface alloy phases and their stability based on surface phase diagrams constructed from the surface energy as a function of the surface composition. We show that in the simplest cases of pseudomorphic overlayers there are four generic classes of systems, characterized by the sign of the heat of segregation from the bulk and the sign of the excess interactions between the atoms in the surface (the surface mixing energy). We also consider the more complicated cases with ordered surface phases, nonpseudomorphic overlayers, second layer segregation, and multilayers. The discussion is based on density-functional calculations using the coherent-potential approximation and on effective-medium theory. We give self-consistent density-functional results for the segregation energy and surface mixing energy for all combinations of the transition and noble metals. Finally we discuss in detail the cases Ag/Cu(100), Pt/Cu(111), Ag/Pt(111), Co/Cu(111), Fe/Cu(111), and Pd/Cu(110) in connection with available experimental results.

/pdf/phase-diagrams-for-surface-alloys-3ijpv1rsgf.pdf

Phase diagrams for surface alloys

A first-principles total-energy calculation is performed on gallium nitride (GaN). The equilibrium lattice parameters, the bulk modulus, and the cohesive energy of GaN in the wurtzite structure is calculated and compared with experimental values. In our calculation, the ground state of GaN is a zinc-blende structure, and the difference between these two phases is around 1.4 mRy.

/pdf/first-principles-total-energy-calculation-of-gallium-nitride-3mfdl1kapl.pdf

First-principles total-energy calculation of gallium nitride.

An intriguing growth morphology of Pb islands on a Si(111) surface is observed in our STM experiments: the growth of a Pb layer on Pb islands with unstable heights starts from the periphery and moves towards the center, while the nucleation of the next layer on stable Pb islands starts away from the periphery. Using first-principles total energy calculations, we have studied the diffusion barriers of Pb adatoms on a freestanding Pb(111) film as a function of film thickness. The diffusion barriers are found to be very low (<60 meV), and a bi-layer oscillation due to the quantum size effect (QSE) is observed, with a lower barrier on the odd-layered, relatively unstable Pb films. The diffusion barrier difference between the odd- and even-layered film is as large as 40 meV. The observed unusual growth can be attributed to this big difference in the diffusion barriers due to QSE.

Quantum Size Effect on the Diffusion Barriers and Growth Morphology of Pb/Si(111)

Quantum size effect on the diffusion barriers and growth morphology of Pb/Si(111)

The oxygen adsorption on the Zr(0001) surface is studied using first-principles total-energy and force calculations. We calculated the atomic structure, heat of adsorption, work function, and electronic structure for oxygen occupying various surface and subsurface sites for both the Zr(0001)-(1\ifmmode\times\else\texttimes\fi{}1)-O and Zr(0001)- (2\ifmmode\times\else\texttimes\fi{}1)-O system. We found that the energetically most favorable occupation sites for oxygen are the octahedral sites between the second and the third layer. The change in the work function induced by oxygen adsorption depends strongly on the position of the adsorbed oxygen atoms and the calculated change of work function at the energetically most favorable site is consistent with previous experiments. A large difference in the electronic structure between the overlayer and subsurface adsorption is also found. \textcopyright{} 1996 The American Physical Society.

/pdf/first-principles-calculation-of-oxygen-adsorption-on-zr-0001-2mmw802ely.pdf

First-principles calculation of oxygen adsorption on Zr(0001) surface: Possible site occupation between the second and the third layer.

We studied the initial growth mode of Au on Ag(110) using first-principles total energy calculations. We found that a recently observed bilayer growth mode in this system is not energetically favorable and thus may not be an equilibrium process. The most favorable initial growth process up to 1 monolayer Au coverage is found to proceed via subsurface substitution, which is an interesting growth mode for a metal-on-metal system

/pdf/initial-growth-mode-of-au-on-ag-110-studied-with-first-13jvv05gbv.pdf

K.M. Ho

Papers

First-principles total-energy calculation of gallium nitride.

Quantum Size Effect on the Diffusion Barriers and Growth Morphology of Pb/Si(111)

Quantum size effect on the diffusion barriers and growth morphology of Pb/Si(111)

First-principles calculation of oxygen adsorption on Zr(0001) surface: Possible site occupation between the second and the third layer.

Initial growth mode of Au on Ag(110) studied with first-principles calculations