Dynamics of Atomic Steps on GaN (0001) during Vapor Phase Epitaxy
Guangxu Ju, Dongwei Xu, Carol Thompson, Matthew J. Highland, Jeffrey A. Eastman, Weronika Walkosz, Peter Zapol, G. Brian Stephenson
备注：
18 pages, 30 figures, 12 tables, 3 appendices. This is long paper to accompany "Do A or B Steps Have Faster Kinetics during Hexagonal Crystal Growth?" by same author list
Images of the morphology of GaN (0001) surfaces often show half-unit-cell-height steps separating a sequence of terraces having alternating large and small widths. This can be explained by the $αβαβ$ stacking sequence of the wurtzite crystal structure, which results in steps with alternating $A$ and $B$ edge structures for the lowest energy step azimuths, i.e. steps normal to $[0 1 \bar{1} 0]$ type directions. Predicted differences in the adatom attachment kinetics at $A$ and $B$ steps would lead to alternating $α$ and $β$ terrace widths. However, because of the difficulty of experimentally identifying which step is $A$ or $B$, it has not been possible to determine the absolute difference in their behavior, e.g. which step has higher adatom attachment rate constants. Here we show that surface X-ray scattering can measure the fraction of $α$ and $β$ terraces, and thus unambiguously differentiate the growth dynamics of $A$ and $B$ steps. We first present calculations of the intensity profiles of GaN crystal truncation rods (CTRs) that demonstrate a marked dependence on the $α$ terrace fraction $f_α$. We then present surface X-ray scattering measurements performed \textit{in situ} during homoepitaxial growth on (0001) GaN by vapor phase epitaxy. By analyzing the shapes of the $(1 0 \bar{1} L)$ and $(0 1 \bar{1} L)$ CTRs, we determine that the steady-state $f_α$ increases at higher growth rate, indicating that attachment rate constants are higher at $A$ steps than at $B$ steps. We also observe the dynamics of $f_α$ after growth conditions are changed. The results are analyzed using a Burton-Cabrera-Frank model for a surface with alternating step types, to extract values for the kinetic parameters of $A$ and $B$ steps. These are compared with predictions for GaN (0001).
To develop a quantitative reaction simulator, data assimilation was performed using high-resolution time-of-flight mass spectrometry (TOF-MS) data applied to GaN metalorganic vapor phase epitaxy system. Incorporating ab initio knowledge into the optimization successfully reproduces not only the concentration of CH$_4$ (an impurity precursor) as an objective variable but also known reaction pathways. The simulation results show significant production of GaH$_3$, a precursor of GaN, which has been difficult to detect in TOF-MS experiments. Our proposed approach is expected to be applicable to ot…
We report on the optical characterization of non-polar a-plane InGaN quantum dots (QDs) grown by metal-organic vapor phase epitaxy using a short nitrogen anneal treatment at the growth temperature. Spatial and spectral mapping of sub-surface QDs have been achieved by cathodoluminescence at 8 K. Microphotoluminescence studies of the QDs reveal resolution limited sharp peaks with typical linewidth of 1 meV at 4.2 K. Time-resolved photoluminescence studies suggest the excitons in these QDs have a typical lifetime of 538 ps, much shorter than that of the c-plane QDs, which is strong evidence of th…
Several ten $μ$m GaN have been deposited on a silicon substrate using a two-step hydride vapor phase epitaxy (HVPE) process. The substrates have been covered by AlN layers and GaN nanostructures grown by plasma-assisted molecular-beam epitaxy. During the first low-temperature (low-T) HVPE step, stacking faults (SF) form, which show distinct luminescence lines and stripe-like features in cathodoluminescence images of the cross-section of the layers. These cathodoluminescence features allow for an insight into the growth process. During a second high-temperature (high-T) step, the SFs disappear,…
Ferromagnetic properties of In1-xMnxAs thin films were investigated. Room temperature ferromagnetic order was observed in nominally single-phase films with x = 0.01-0.10. Magnetization measurements indicated that these In1-xMnxAs samples had a Curie temperature of 333 K. The Curie temperature was independent of Mn concentration. The temperature dependent magnetization along with the magnitude of the saturation magnetization and microstructural data indicate that the source of the high-temperature ferromagnetism in single-phase films is not attributable to MnAs nanoprecipitates. The high transi…
N-polar GaN p-n diodes are realized on single-crystal N-polar GaN bulk wafers by plasma-assisted molecular beam epitaxy growth. The current-voltage characteristics show high-quality rectification and electroluminescence characteristics with a high on/off current ratio and interband photon emission. The measured electroluminescence spectrum is dominated by strong near-band edge emission, while deep level luminescence is greatly suppressed. A very low dislocation density leads to a high reverse breakdown electric field. The low leakage current N-polar diodes open up several potential application…
We demonstrate the self-assembled growth of vertically aligned GaN nanowire ensembles on a flexible Ti foil by plasma-assisted molecular beam epitaxy. The analysis of single nanowires by transmission electron microscopy reveals that they are single crystalline. Low-temperature photoluminescence spectroscopy demonstrates that, in comparison to standard GaN nanowires grown on Si, the nanowires prepared on the Ti foil exhibit a equivalent crystalline perfection, a higher density of basal-plane stacking faults, but a reduced density of inversion domain boundaries. The room-temperature photolumines…
In1-xMnxAs diluted magnetic semiconductor (DMS) thin films have been grown using metalorganic vapor phase epitaxy (MOVPE). Tricarbonyl(methylcyclopentadienyl)manganese was used as the Mn source. Nominally single-phase, epitaxial films were achieved with Mn content as high as x=0.14 using growth temperatures Tg>475 C. For lower growth temperatures and higher Mn concentrations, nanometer scale MnAs precipitates were detected within the In1-xMnxAs matrix. Magnetic properties of the films were investigated using a superconducting quantum interference device (SQUID) magnetometer. Room-temperature f…
The effect of film morphology on its surface chemistry and band structure has been analyzed for gallium nitride epitaxial films grown by molecular beam epitaxy. The film morphology has been studied using scanning electron microscopy and atomic force microscopy, and the bandstructure, defect and emission properties have been studied by X ray photoelectron spectroscopy and cathodoluminescence spectroscopy. It was found that the highly porous GaN nanowall network shows the highest relative conductivity and does not have defect related luminescence. The flatter films were more resistive and showed…
The present study elucidates the correlation between the structural and optical properties of GaN nanowires grown on Si(111) substrate by plasma assisted molecular beam epitaxy (PA-MBE) technique under various growth conditions. GaN NWs exhibiting different shapes, sizes and distribution were grown at various substrate temperatures with same Ga-N (III-V) ratio of 0.4. We observe that sample grown at lower substrate temperature (~700 degC) results 2-dimensional island like structure with almost very little (~30%) circularity while increasing substrate temperature (>770 degC) leads to growth of …
We propose a novel solid-phase epitaxy technique applicable to high annealing temperatures up to 1000 C without re-vaporization of alkali metal elements with high vapor pressures. This technique is demonstrated through the successful growth of high-quality KFe2As2 epitaxial films. The key factors are employing a custom-designed alumina vessel/cover and sealing it in a stainless tube with a large amount of atmospheric KFe2As2 powder in tightly closed sample spaces. This technique can also be effective for other materials composed of elements with very high vapor pressures, such as alkali metals…
RF plasma assisted MBE growth of Scandium Nitride (ScN) thin films on GaN (0001)/SiC, AlN (0001)/Al2O3 and on 6H-SiC (0001) hexagonal substrates is found to lead to a face centered cubic (rock-salt) crystal structure with (111) out-of-plane orientation instead of hexagonal orientation. For the first time, cubic (111) twinned patterns in ScN are observed by in-situ electron diffraction during epitaxy, and the twin domains in ScN are detected by electron backscattered diffraction, and further corroborated with X-ray diffraction. The epitaxial ScN films display very smooth, sub nanometer surface …
N-polar (In,Ga)N/GaN quantum wells prepared on freestanding GaN substrates by plasma-assisted molecular beam epitaxy at conventional growth temperatures of about 650 °C do not exhibit any detectable luminescence even at 10 K. In the present work, we investigate (In,Ga)N/GaN quantum wells grown on Ga- and N-polar GaN substrates at a constant temperature of 730 °C. This exceptionally high temperature results in a vanishing In incorporation for the Ga-polar sample. In contrast, quantum wells with an In content of 20% and abrupt interfaces are formed on N-polar GaN. Moreover, these quantum wells e…
Using in situ grazing-incidence x-ray scattering, we have measured the diffuse scattering from islands that form during layer-by-layer growth of GaN by metal-organic vapor phase epitaxy on the (1010) m-plane surface. The diffuse scattering is extended in the (0001) in-plane direction in reciprocal space, indicating a strong anisotropy with islands elongated along [1 $\overline{2}$ 10] and closely spaced along [0001]. This is confirmed by atomic force microscopy of a quenched sample. Islands were characterized as a function of growth rate G and temperature. The island spacing along [0001] obser…
Dependence of the Mn sticking coefficient on Ga-rich, N-rich, and Ga/N-flux-free conditions in GaN grown by plasma-assisted molecular beam epitaxy
Cornell University（康奈尔大学）；Paul-Drude-Institut für Festkörperelektronik (PDI), Leibniz-Institut im Forschungsverbund Berlin e.V.（柏林莱布尼茨联合会保罗·德鲁德固态电子学研究所）
Molecular beam epitaxy of GaN/AlGaN quantum wells on bulk GaN substrate in the step-flow or step meandering regime: influence on indirect exciton diffusion
本文在块体 GaN 衬底上通过分子束外延生长 GaN/AlxGa1-xN 量子阱，通过优化生长温度等条件最小化光致发光峰展宽，利用微光致发光装置测量间接激子扩散，提取扩散常数并确定了研究间接激子液体量子集体效应的最佳生长条件。
We report on the growth and characterization of metalorganic vapor-phase epitaxy-grown \b{eta}-(AlxGa1-x)2O3/\b{eta}-Ga2O3 modulation-doped heterostructures. Electron channel is realized in the heterostructure by utilizing a delta-doped \b{eta}-(AlxGa1-x)2O3 barrier. Electron channel characteristics are studied using transfer length method, capacitance-voltage and Hall measurements. Hall sheet charge density of 1.06 x 1013 cm-2 and mobility of 111 cm2/Vs is measured at room temperature. Fabricated transistor showed peak current of 22 mA/mm and on-off ratio of 8 x 106. Sheet resistance of 5.3 k…
An HVPE reactor for the growth of bulk GaN crystals with a diameter of 50 mm was developed. Growth rate non-uniformity of 1% was achieved using an axisymmetric vertical gas injector with stagnation point flow. Chemically-resistant refractory materials were used instead of quartz in the reactor hot zone. High-capacity external gallium precursor sources were developed for the non-stop growth of the bulk GaN layers. A load-lock vacuum chamber and a dry in-situ growth chamber cleaning were implemented to improve the growth process reproducibility. Freestanding GaN crystals with a diameter of 50 mm…
Silicon is the dominant semiconductor in many semiconductor device applications for a variety of reasons, including both performance and cost. III-V materials have improved performance compared to silicon, but currently they are relegated to applications in high-value or niche markets due to the absence of a low-cost, high-quality production technique. Here we present an advance in III-V materials synthesis using hydride vapor phase epitaxy that has the potential to lower III-V semiconductor deposition costs by orders of magnitude while maintaining the requisite optoelectronic material quality…
We investigate the influence of modified growth conditions during the spontaneous formation of GaN nanowires on Si(111) in plasma-assisted molecular beam epitaxy. We find that a two-step growth approach, where the substrate temperature is increased during the nucleation stage, is an efficient method to gain control over the area coverage, average diameter, and coalescence degree of GaN nanowire ensembles. Furthermore, we also demonstrate that the growth conditions employed during the incubation time that precedes nanowire nucleation do not influence the properties of the final nanowire ensembl…
We report on silicon delta doping of metalorganic vapor-phase epitaxy-grown \b{eta}-Ga2O3 thin films using silane precursor. Delta-doped \b{eta}-Ga2O3 epitaxial films are characterized using capacitance-voltage profiling and secondary-ion mass spectroscopy. Electron sheet charge density in the range of 2.9e12 cm-2 to 8e12 cm-2 with a half width at half maximum ranging from 6.2 nm to 3.5 nm is measured. We also demonstrate a high density (6.4e12 cm-2) degenerate two-dimensional electron gas using a delta-doped \b{eta}-(Al0.26Ga0.74)2O3/\b{eta}-Ga2O3 heterostructure.The total charge could also i…
We present a systematic study of the morphology of homoepitaxial InP films grown by metalorganic vapor-phase epitaxy which are imaged with ex situ atomic force microscopy. These films show a dramatic range of different surface morphologies as a function of the growth conditions and substrate (growth temperature, V/III ratio, and miscut angle < 0.6deg and orientation toward A or B sites), ranging from stable step flow to previously unreported strong step bunching, over 10 nm in height. These observations suggest a window of growth parameters for optimal quality epitaxial layers. We also present…
GaN/SiO2 core/shell nanowires are grown by cobalt phthalocyanine catalyst assisted vapor-liquid-solid route, in which Si wafer coated with a mixture of gallium and indium is used as the source for Ga and Si and ammonia is used as the precursor for nitrogen and hydrogen. Gallium in the presence of indium and hydrogen, which results from the dissociation of ammonia, forms Si-Ga-In alloy at the growth temperature around 910 degree Celsius. This alloy acts as the source of Si, Ga and In. A detailed study using a variety of characterization tools reveals that these wires, which are several tens of …
We describe an instrument that exploits the ongoing revolution in synchrotron sources, optics, and detectors to enable in situ studies of metal-organic vapor phase epitaxy (MOVPE) growth of III-nitride materials using coherent x-ray methods. The system includes high-resolution positioning of the sample and detector including full rotations, an x-ray transparent chamber wall for incident and diffracted beam access over a wide angular range, and minimal thermal sample motion, giving the sub-micron positional stability and reproducibility needed for coherent x-ray studies. The instrument enables …
Strain-released epitaxy of GaN enabled by compliant single-crystalline metal foils
Zhejiang University（浙江大学）；Westlake University（西湖大学）；Zhongke Crystal Materials (Dongguan) Technology Co., Ltd.（中科晶材（东莞）科技有限公司）；Institute of Semiconductors, Chinese Academy of Sciences（中国科学院半导体研究所）；Westlake Smoky-mountain Technologies（西湖烟山科技有限公司）；Peking University（北京大学）；University of Toronto（多伦多大学）；BOE Technology Group Co., Ltd.（京东方科技集团股份有限公司）
Chiral Epitaxy: Enantioselective Growth of Chiral Nanowires on Low-Symmetry Two-Dimensional Materials
Weizmann Institute of Science（魏茨曼科学研究所）；Massachusetts Institute of Technology（麻省理工学院）；Université Paris-Saclay（巴黎萨克雷大学）；Federal University of ABC（ABC联邦大学）；State University of Campinas（坎皮纳斯州立大学）；De Shalit High School（德沙拉希特高中）；Tel Aviv University（特拉维夫大学）
We report on some surprising optical properties of diluted nitride InGaAs_(1-y)N_y /GaAs (y<<1) pyramidal site-controlled quantum dots, grown by metalorganic vapor phase epitaxy on patterned GaAs (111)B substrates. Microphotoluminescence characterizations showed antibinding exciton/ biexciton behavior, a spread of exciton lifetimes in an otherwise very uniform sample, with unexpected long neutral exciton lifetimes (up to 7 ns) and a nearly zero fine structure splitting on a majority of dots.
Realization of intrinsic surface dominant transport in a wide temperature region for a topological insulators (TIs) is an important frontier research in order to promote the progresses of TIs towards the future electronics. We report here systematic measurements of longitudinal electrical transport, Shubnikov-de-Haas (SdH) quantum oscillations, Hall coefficient (R_H^2D), and Seebeck coefficient as a function of film thickness (d) and temperature using high quality Bi2-xSbxTe3-ySey (BSTS) single crystal thin films grown by physical vapor-phase deposition. The thickness dependence of sheet condu…
We studied the persistent photoconductivity (PPC) effect in AlGaN/AlN/GaN heterostructures with two different Al-compositions (x=0.15 and x=0.25). The two-dimensional electron gas formed at the AlN/GaN heterointerface was characterized by Shubnikov-de Haas and Hall measurements. Using optical illumination, we were able to increase the carrier density of the Al0.15Ga0.85N/AlN/GaN sample from 1.6x10^{12} cm^{-2} to 5.9x1012 cm^{-2}, while the electron mobility was enhanced from 9540 cm2/Vs to 21400 cm2/Vs at T = 1.6 K. The persistent photocurrent in both samples exhibited a strong dependence on …
In this work, we report on the growth of high-mobility $β$-Ga$_2$O$_3$ homoepitaxial thin films grown at a temperature much lower than the conventional growth temperature window for metalorganic vapor phase epitaxy. Low-temperature $β$-Ga$_2$O$_3$ thin films grown at 600$^{\circ}$C on Fe-doped (010) bulk substrates exhibits remarkable crystalline quality which is evident from the measured room temperature Hall mobility of 186 cm$^2$/Vs for the unintentionally doped films. N-type doping is achieved by using Si as a dopant and controllable doping in the range of 2$\times$10$^{16}$ - 2$\times$10$…
Doping of III-nitride based compound semiconductor nanowires is still a challenging issue to have a control over the dopant distribution in precise locations of the nanowire optoelectronic devices. Knowledge of the dopant incorporation and its pathways in nanowires for such devices is limited by the growth methods. We report the direct evidence of incorporation pathway for Mg dopants in p-type nonpolar GaN nanowires grown via vapour-liquid-solid (VLS) method in a chemical vapour deposition technique for the first time. Mg incorporation is confirmed using X-ray photoelectron (XPS) and electron …
We present a model for the interplay between the fundamental phenomena responsible for the formation of nanostructures by metalorganic vapour phase epitaxy on patterned (001)/(111)B GaAs substrates. Experiments have demonstrated that V-groove quantum wires and pyramidal quantum dots form as a consequence of a self-limiting profile that develops, respectively, at the bottom of V-grooves and inverted pyramids. Our model is based on a system of reaction-diffusion equations, one for each crystallographic facet that defines the pattern, and include the group III precursors, their decomposition and …
Blue light-emitting diodes (LEDs) consisting of a buried n+-p+ GaN tunnel junction, (In,Ga)N multiple quantum wells (MQWs) and a n+-GaN top layer are grown on single-crystal Ga-polar n+-GaN bulk wafers by plasma-assisted molecular beam epitaxy. The (In,Ga)N MQW active regions overgrown on the p+-GaN show chemically abrupt and sharp interfaces in a wide range of compositions and are seen to have high structural and optical properties as verified by X-ray diffraction and spatially resolved cathodoluminescence measurements. The processed LEDs reveal clear rectifying behavior with a low contact an…
Cubic (zinc-blende) Ga1-xMnxN layers were grown by plasma-assisted molecular beam epitaxy on GaAs (001) substrates. Some of the structures also contained cubic AlN buffer layers. Auger Electron Spectroscopy and Secondary Ion Mass Spectroscopy studies clearly confirmed the incorporation of Mn into cubic GaN, the Mn being uniformly distributed through the layer. X-ray diffraction studies demonstrated that the Mn-doped GaN films are cubic and do not show phase separation up to a Mn concentrations of x<0.1. P-type conductivity for the cubic Ga1-xMnxN layers was observed for a wide range of the Mn …
GaN-based resonators supporting whispering gallery modes are suggested as a promising approach for fabrication of efficient nanophotonic applications. A modification of excitonic emission due to coupling with cavity modes is observed experimentally in the GaN planar hexagonal microcavities grown by a selective area metal-organic vapor phase epitaxy. Low temperature cathodoluminescence spectra measured in-situ scanning electron microscope show two or three emission peaks split by 100 meV or 160 meV for the resonators formed by double- and single-wall micro-nuts, respectively. The results are co…
TBA-enabled spin-coating of a percolatively connected GO nanosieve for thru-hole epitaxy: tuning GO flake stacking and coverage to control GaN nucleation
We report the influence of the In mole fraction on the material and electrical characteristics of p-i-n InxGa1-xN homojunctions (x = 0.10-0.40) synthesized by plasma-assisted molecular-beam epitaxy on GaN-on-sapphire substrates. Junctions terminated with p-InGaN present improved carrier extraction efficiency in comparison with devices capped with p-GaN, due to the deleterious effect of polarization discontinuities on the device performance. We demonstrate that the presence of Mg does not perturb the In incorporation in InGaN, and it leads to a significant reduction of the stacking fault densit…
We report on low-temperature MOVPE growth of silicon delta-doped \b{eta}-Ga2O3 films with low FWHM. The as-grown films are characterized using Secondary-ion mass spectroscopy, Capacitance-Voltage and Hall techniques. SIMS measurements show that surface segregation is the chief cause of large FWHM in MOVPE-grown films. The surface segregation coefficient (R) is observed to reduce with reduction in the growth temperature. Films grown at 600 °C show an electron concentration of 9.7 x 1012 cm-2 and a FWHM of 3.2 nm. High resolution scanning/transmission electron microscopy of the epitaxial film di…
Growth of GaN nanowires are carried out via metal initiated vapor-liquid-solid mechanism, with Au as the catalyst. In chemical vapour deposition technique, GaN nanowires are usually grown at high temperatures in the range of 900-1100 ^oC because of low vapor pressure of Ga below 900 ^oC. In the present study, we have grown the GaN nanowires at a temperature, as low as 700 ^oC. Role of indium in the reduction of growth temperature is discussed in the ambit of Raoult's law. Indium is used to increase the vapor pressure of the Ga sufficiently to evaporate even at low temperature initiating the gr…
Recently theorized hybrid II-IV-N{_2} / III-N heterostructures, based on current commercialized (In,Ga)N devices, are predicted to significantly advance the design space of highly efficient optoelectronics in the visible spectrum, yet there are few epitaxial studies of II-IV-N{_2} materials. In this work, we present heteroepitaxial ZnGeN{_2} grown on GaN buffers and AlN templates. We demonstrate that a GaN nucleating surface is crucial for increasing the ZnGeN{_2} crystallization rate to combat Zn desorption, extending the stoichiometric growth window from 215 {\degree}C on AlN to 500 {\degree…
We explore and systematically compare the morphological, structural and optical properties of GaN/(Al,Ga)N multiple quantum wells (MQWs) grown by plasma-assisted molecular beam epitaxy (PA-MBE) on freestanding GaN$(0001)$ and GaN$(000\bar{1})$ substrates. Samples of different polarity are found to be comparable in terms of their morphological and structural perfection and exhibit essentially identical quantum well widths and Al content. Regardless of the crystal orientation, the exciton decay in the MQWs at 10 K is dominantly radiative and the photoluminescence (PL) energy follows the quantum …
Large area epitaxy of two-dimensional (2D) layered materials with high material quality is a crucial step in realizing novel device applications based on 2D materials. In this work, we report high-quality, crystalline, large-area gallium selenide (GaSe) films grown on bulk substrates such as c-plane sapphire and gallium nitride (GaN) using a valved cracker source for Se. (002)-oriented GaSe with random in-plane orientation of domains was grown on sapphire and GaN substrates at a substrate temperature of 350-450 C with complete surface coverage and smooth surface morphology. Higher growth tempe…
