Computational Fluid Dynamic Analysis of a High-Pressure Spatial Chemical Vapor Deposition (HPS-CVD) Reactor for Flow Stability

High indium-content group-III nitrides are of interest to further expand upon our ability to produce highly efficient optical emitters at longer visible/IR wavelengths or to broaden bandgap engineering opportunities in the group-III nitride material system. Current synthesis approaches are limited in their capabilities, in part due to the low decomposition temperature of indium nitride. A new high-pressure spatial chemical vapor deposition (HPS-CVD) has been proposed which can operate at pressures up to 100 atmospheres, thereby significantly raising the growth temperature of indium nitride more than 100 kelvins and permitting the investigation of the impact of pressure on precursor stability and reactivity. This study systematically analyzes an HPS-CVD reactor design using computational fluid dynamic modeling in order to understand favorable operating conditions for growth of group III nitrides. Specifically, the relationship between inlet gas type (nitrogen, hydrogen, or ammonia), inlet gas velocity, gas flow rate, and rotational speed of the wafer carrier is evaluated for conditions under which a smooth and dominant vortex-free flow are obtained over the wafer. Heater power was varied to maintain a wafer temperature of 1250–1300 K. Favorable operating conditions were identified that were simultaneously met for all three gas types, providing a stable operating window for a wide range of gas chemistries for growth; at one atmosphere, a disk rotational speed of 50 rpm and a flow rate of 12 slm for all gas types is desired

Numerical Analysis of a High-Pressure Spatial Chemical Vapor Deposition (HPS-CVD) Reactor for Flow Stability at High Pressures

Highly indium-rich group-III nitrides are attracting attention for advancing our capacity to create highly effective optical emitters at extended visible/IR wavelengths or for enhancing bandgap engineering possibilities within the group-III nitride material framework. Current methods of synthesis are constrained in their efficacy, partially owing to the low decomposition temperature of indium nitride. Implementation of a new design of a vertical high-pressure spatial chemical vapor deposition (HPS-CVD) reactor with six separated precursor source zones and a rotating wafer carrier disk carrying four 2-inch wafers is proposed and analyzed using COMSOL Multiphysics as a commercial computational fluid dynamics (CFD) program to study the fluid phenomena inside the numerical domain. This study focuses on understanding the different flow patterns within the chambers at super-atmospheric conditions (5 atm to 30 atm) and identifying suitable operating conditions under which smooth and dominant vortex-free flow is achieved. Four 2-inch wafers are heated to maintain a temperature of 1200–1300 K at each pressure and gas type. Three different gas types (nitrogen, hydrogen, and ammonia) are used, and the impacts of different inlet flow velocities and rotational speeds are investigated and discussed. An operating matrix is presented for each analyzed system pressure providing suitable combinations of these operational variables for smooth flow in the chambers. Each gas type was identified to have a range of suitable rotational and inlet velocity regimes at each operating pressure. Overlap of these three gas-specific operating condition windows resulted in the identification of a generally suitable operating condition for smooth flow patterns in the system regardless of the gas type used, as required for the growth of group-III nitride materials

Infrared absorption of hydrogen-related defects in ammonothermal GaN

Polarization controlled Fourier transform infrared (FTIR) absorption measurements were performed on a high quality m-plane ammonothermal GaN crystal grown using basic chemistry. The polarization dependence of characteristic absorption peaks of hydrogen-related defects at 3000-3500 cm(-1) was used to identify and determine the bond orientation of hydrogenated defect complexes in the GaN lattice. Majority of hydrogen was found to be bonded in gallium vacancy complexes decorated with one to three hydrogen atoms (V-Ga-H-1,H-2,H-3) but also hydrogenated oxygen defect complexes, hydrogen in bond-center sites, and lattice direction independent absorption were observed. Absorption peak intensity was used to determine a total hydrogenated V-Ga density of approximately 4 x 10(18) cm(-3), with main contribution from V-Ga-H-1,H-2. Also, a significant concentration of electrically passive V-Ga-H-3 was detected. The high density of hydrogenated defects is expected to have a strong effect on the structural, optical, and electrical properties of ammonothermal GaN crystals. Published by AIP Publishing.Peer reviewe

Free electron concentration dependent sub-bandgap optical absorption characterization of bulk GaN crystals

Optical transmission measurements were performed on high quality bulk gallium nitride (GaN) crystals grown by sodium flux, hydride vapor phase epitaxy, and the ammonothermal method with varying free electron concentrations ranging from 4×1016 cm-3 to 9×1018 cm-3. The quality of the crystals was analyzed by x-ray diffraction, threading dislocation density determination, impurity concentrations, and Hall mobility measurements. The sub-bandgap absorption coefficient and index of refraction was determined based on illumination wavelengths ranging from 360 nm to 800 nm. Phonon-assisted free carrier absorption was determined to be the dominant absorption mechanism above approximately 0.1 cm-1. The absorption coefficient at 450 nm varied linearly from 0.1 cm- 1 to 5 cm-1 for free electron concentrations ranging from 1×1017 cm-3 to 9×1018 cm-3. The ammonothermal GaN samples exhibited a strong defect related onset of absorption above 2.9 eV which can be explained by the presence of appreciable hydrogenated gallium vacancies having defect states close to the valance band within the electric bandgap of GaN. The presence of hydrogenated gallium vacancies was experimentally confirmed by Fourier transform infrared absorbance measurements and double hydrogenated gallium vacancy defect are speculated to be prominent in ammonothermal GaN.Peer reviewe

Incorporation and effects of impurities in different growth zones within basic ammonothermal GaN

The ammonothermal method is one of the most promising candidates for large-scale bulk GaN growth due to its scalability and high crystalline quality. However, emphasis needs to be put on understanding the incorporation and effects of impurities during growth. This article discusses how impurities are incorporated in different growth zones in basic ammonothermal GaN, and how they affect the structural, electrical and optical properties of the grown crystal. The influence of growth time on the impurity incorporation is also studied. We measure the oxygen, silicon, and carbon impurity concentrations using secondary ion mass spectrometry, and measure their effect on the lattice constant by high resolution x-ray diffraction (HR-XRD). We determine the resulting free carrier concentration by spatially resolved Fourier transform infrared spectroscopy and study the optical properties by spatially resolved low-temperature photoluminescence. We find that oxygen is incorporated preferentially in different growth regions and its incorporation efficiency depends on the growth direction. The oxygen concentration varies from 6.3×1020 cm-3 for growth on the 112-2 planes to 2.2×1019 cm-3 for growth on the (0001) planes, while silicon and carbon concentration variation is negligible. This results in a large variation in impurity concentration over a small length scale, which causes significant differences in the strain within the boule, as determined by HR-XRD on selected areas. The impurity concentration variation induces large differences in the free carrier concentration, and directly affects the photoluminescence intensity.Peer reviewe

Ammonothermal Crystal Growth of Functional Nitrides for Semiconductor Devices: Status and Potential

The state-of-the-art ammonothermal method for the growth of nitrides is reviewed here, with an emphasis on binary and ternary nitrides beyond GaN. A wide range of relevant aspects are covered, from fundamental autoclave technology, to reactivity and solubility of elements, to synthesized crystalline nitride materials and their properties. Initially, the potential of emerging and novel nitrides is discussed, motivating their synthesis in single crystal form. This is followed by a summary of our current understanding of the reactivity/solubility of species and the state-of-the-art single crystal synthesis for GaN, AlN, AlGaN, BN, InN, and, more generally, ternary and higher order nitrides. Investigation of the synthesized materials is presented, with a focus on point defects (impurities, native defects including hydrogenated vacancies) based on GaN and potential pathways for their mitigation or circumvention for achieving a wide range of controllable functional and structural material properties. Lastly, recent developments in autoclave technology are reviewed, based on GaN, with a focus on advances in development of in situ technologies, including in situ temperature measurements, optical absorption via UV/Vis spectroscopy, imaging of the solution and crystals via optical (visible, X-ray), along with use of X-ray computed tomography and diffraction. While time intensive to develop, these technologies are now capable of offering unprecedented insight into the autoclave and, hence, facilitating the rapid exploration of novel nitride synthesis using the ammonothermal method

A new system for sodium flux growth of bulk GaN

Though several methods exist to produce bulk crystals of gallium nitride (GaN), none have been commercialized on a large scale. The sodium flux method, which involves precipitation of GaN from a sodium-gallium melt supersaturated with nitrogen, offers potentially lower cost production due to relatively mild process conditions while maintaining high crystal quality. We successfully developed a novel apparatus for conducting crystal growth of bulk GaN using the sodium flux method which has advantages with respect to prior reports. A key task was to prevent sodium loss or migration from the growth environment while permitting N2 to access the growing crystal. We accomplished this by implementing a reflux condensing stem along with a reusable capsule containing a hermetic seal. The reflux condensing stem also enabled direct monitoring of the melt temperature, which has not been previously reported for the sodium flux method. Furthermore, we identified and utilized molybdenum and the molybdenum alloy TZM as a material capable of directly containing the corrosive sodium-gallium melt. This allowed implementation of a crucible-free system, which may improve process control and potentially lower crystal impurity levels. Nucleation and growth of parasitic GaN ("PolyGaN") on non-seed surfaces occurred in early designs. However, the addition of carbon in later designs suppressed PolyGaN formation and allowed growth of single crystal GaN. Growth rates for the (0001) Ga face (+c-plane) were up to 14μm/h while X-ray omega rocking (ω-XRC) curve full width half-max values were 731″ for crystals grown using a later system design. Oxygen levels were high, >1019 atoms/cm3, possibly due to reactor cleaning and handling procedures.Peer reviewe