S. Porowski

Chemical polishing of bulk and epitaxial GaN

Abstract Bulk single crystals of GaN and heteroepitaxial GaN layers were subjected to free-etching and mechano-chemical polishing in aqueous solutions (10-1N) of KOH and NaOH. It has been established that free-etching of bulk crystals is kinetically controlled and strongly anisotropic, resulting in the formation of numerous stable pyramids. Etching is terminated when the {0 0 0 1}-oriented surface of GaN is completely covered by these pyramids. On the other hand, when a soft polishing pad and pressure above 2 kg/cm2 are employed, all surface irregularities (etch pyramids, roughness after mechanical polishing, growth hillocks on epitaxial layers) are removed. The procedure is very effective: removal of a few tenths of a micron from the surface are usually sufficient to polish out irregularities 200 nm in height. When optimized mechano-chemical polishing is used, atomically flat surfaces of bulk GaN have been reproducibly obtained (RMS= 0.1nm), as measured by Atomic Force Microscopy.

Investigation of longitudinal‐optical phonon‐plasmon coupled modes in highly conducting bulk GaN

We report a cross‐correlated investigation, performed by means of Raman scattering and infrared spectroscopy, of coupled LO phonon‐plasmon modes in bulk GaN. Using different samples with different (high) residual concentrations of free carriers, we find that the high‐energy Raman mode follows closely the plasma frequency resolved from the infrared data. On the opposite, the low‐frequency modes appears down shifted, with respect to the standard TO phonon frequency, by about 11 cm−1. Both findings agree satisfactorily with predictions of the linear response theory for undamped phonon‐plasmon modes and establish Raman scattering as a powerful and nondestructive tool to investigate the residual doping level of GaN up to about 1020 cm−3 .

Thermodynamical properties of III–V nitrides and crystal growth of GaN at high N2 pressure

Abstract In this paper, thermodynamical properties of AIN, GaN and InN are considered. It is shown that significant differences in melting conditions, thermal stability and solubilities in liquid group III metals lead to different possibilities of growing crystals from high temperature solutions, at N 2 pressure up to 20 kbar. It is shown that the best conditions for crystal growth at available pressure and temperature conditions can be achieved for GaN. High quality 6–10 mm single crystals of GaN have been grown at high N 2 pressure in 60–150 h processes. The mechanisms of nucleation and growth of GaN crystals are discussed on the basis of the experimental results. The crystallization of AlN is less efficient due to relatively low solubility of AlN in liquid Al. Possibility for the growth of InN crystals is strongly limited since this compound loses its stability at T > 600°C, even at 2 GPa N 2 pressure. The crystals of GaN grown at high pressure are the first crystals of this material used for homoepitaxial layer deposition. Both MOCVD and MBE methods have been successfully applied. Structural, electrical and optical properties of both GaN single crystals and homoepitaxial layers are reviewed.

Mechanism of yellow luminescence in GaN

We investigated the pressure behavior of yellow luminescence in bulk crystals and epitaxial layers of GaN. This photoluminescence band exhibits a blueshift of 30±2 meV/GPa for pressures up to about 20 GPa. For higher pressure we observe the saturation of the position of this luminescence. Both effects are consistent with the mechanism of yellow luminescence caused by electron recombination between the shallow donor (or conduction band) and a deep gap state of donor or acceptor character.

High pressure growth of GaN — new prospects for blue lasers

Abstract Recent significant progress in III–V semiconductor technology based on GaN has created widespread interest in GaN device applications. It is argued that the remaining obstacle to the fabrication of a GaN laser is a lack of thermally and lattice-matched substrates. The thermodynamic properties of III–V nitrides are reviewed and recent progress in the growth of GaN platelets under high pressure nitrogen is presented. It is shown that GaN crystals as grown at present have good structural properties, flat surfaces, small dislocation densities and cleavage planes perpendicular to the (0001) crystallographic plane. These properties suggest that GaN substrates offer new prospects for laser technology.

Thermal expansion of gallium nitride

Lattice constants of gallium nitride (wurzite structure) have been measured at temperatures 294–753 K. The measurements were performed by using x‐ray diffractometry. Two kinds of samples were used: (1) bulk monocrystal grown at pressure of 15 kbar, (2) epitaxial layer grown on a sapphire substrate. The latter had a smaller lattice constant in a direction parallel to the interface plane by about 0.03%. This difference was induced by a higher thermal expansion of the sapphire with respect to the GaN layer. However, this thermal strain was created mainly at temperatures below 500–600 K. Above these temperatures the lattice mismatch in parallel direction diminished to zero at a temperature of about 800 K.

Polarity determination for GaN films grown on (0001) sapphire and high-pressure-grown GaN single crystals

In order to resolve any doubt in lattice polarity calibrations, a given undoped GaN layer deposited on (0001) sapphire by metalorganic chemical vapor deposition and a given high-pressure-grown GaN single crystal have been studied by three different techniques: Hemispherically scanned x-ray photoelectron diffraction, convergent beam electron diffraction, and chemical etching. We conclude that Ga-polar surfaces are resistant to a 200 °C molten NaOH+KOH etching whereas N-polar surfaces are chemically active. All the observed flat GaN films grown on (0001) sapphire have Ga polarity. On the contrary, the native flat faces of undoped GaN bulk crystals have N polarity.

Temperature dependence of the energy gap in GaN bulk single crystals and epitaxial layer

We performed optical‐absorption studies of the energy gap in various GaN samples in the temperature range from 10 up to 600 K. We investigated both bulk single crystals of GaN and an epitaxial layer grown on a sapphire substrate. The observed positions of the absorption edge vary for different samples of GaN (from 3.45 to 3.6 eV at T=20 K). We attribute this effect to different free‐electron concentrations (Burstein–Moss effect) characterizing the employed samples. For the sample for which the Burstein shift is zero (low free‐electron concentration) we could deduce the value of the energy gap as equal to 3.427 eV at 20 K. Samples with a different free‐electron concentration exhibit differences in the temperature dependence of the absorption edge. We explain the origin of these differences by the temperature dependence of the Burstein–Moss effect.

Determination of the effective mass of GaN from infrared reflectivity and Hall effect

Infrared reflectivity and Hall effect measurements were performed on highly conducting n‐type GaN (n≊6×1019 cm−3) bulk crystals grown by the high‐pressure high‐temperature method. Values of electron‐plasma frequency and free‐electron concentration were determined for each sample of the set of seven crystals. It enabled us to calculate the perpendicular effective mass of electrons in the wurtzite structure of GaN as m*=0.22±0.02 m0. Effects of nonparabolicity and a difference between parallel and perpendicular components of the effective mass are small and do not exceed the experimental error.

Elastic and plastic properties of GaN determined by nano-indentation of bulk crystal

The major obstacle to the production of a blue laser is posed by difficulties with the preparation of defect-free GaN layers. A considerable amount of empirical work is presently being undertaken to achieve this goal. However, there is a lack of basic research on the reduction of residual stress and defects in these epilayers since the mechanical characteristics of GaN have not been measured yet. This is due to difficulties with experimental examination of thin films. This work addresses the mechanical properties of bulk GaN obtained by a high-pressure method. Young’s modulus (295 GPa), hardness (20 GPa), yield strength (15 GPa), and the stress–strain curve of GaN have been evaluated using nano-indentation. The cause of the sudden depth excursions during indentation of GaN epilayers has been clarified.