Comparative Study on MOCVD Growth of a-Plane GaN Films on r-Plane Sapphire Substrates Using GaN, AlGaN, and AlN Buffer Layers

In this work, we have comparatively investigated the effects of the GaN, AlGaN, and AlN low-temperature buffer layers (BL) on the crystal quality of a-plane GaN thin films grown on r-plane sapphire substrates. Scanning electron microscopy images of the a-plane GaN epilayers show that using an AlGaN BL can significantly reduce the density of surface pits. The full-width at half-maximum values of the x-ray rocking curve (XRC) are 0.19°, 0.36°, and 0.48° for the films grown using Al_0.15Ga_0.85N, GaN, and AlN BLs, respectively, indicating that an AlGaN BL can effectively reduce the mosaicity of the films. Room-temperature photoluminescence shows that the AlGaN BL results in lower impurity incorporation in the subsequent a-plane GaN films, as compared with the case of GaN and AlN BLs. The higher crystal quality of a-plane GaN films produced by the Al_0.15Ga_0.85N BL could be due to improvement of BL quality by reducing the lattice mismatch between the BL and r-sapphire substrates, while still keeping the lattice mismatch between the BL and epitaxial a-plane GaN films relatively small.     

Correlation of biaxial strains, bound exciton energies, and defect microstructures in gan films grown on AlN/6H-SiC(0001) substrates

Biaxial strains resulting from mismatches in thermal expansion coefficients and lattice parameters in 22 GaN films grown on A1N buffer layers previously deposited on vicinal and on-axis 6H-SiC(0001) substrates were measured via changes in the c-axis lattice parameter. A Poisson’s ratio of ν = 0.18 was calculated. The bound exciton energy (E_BX) was a linear function of these strains. The shift in E_BX with film stress was 23 meV/GPa. Threading dislocations densities of ~10¹⁰/cm² and ~10⁸/em² were determined for GaN films grown on vicinal and on-axis SiC, respectively. A 0.9% residual compressive strain at the GaN/AIN interface was observed by high resolution transmission electron microscopy (HRTEM).     

Physical Properties of AlGaN/GaN Heterostructures Grown on Vicinal Substrates

We report on the growth of Al_0.25Ga_0.75N/GaN heterostructures grown on low dislocation density vicinal surfaces of semi-insulating c-axis GaN substrates. Atomic force microscopy (AFM), photoluminescence (PL), cathodoluminescence (CL), high-resolution x-ray diffraction (HRXRD), secondary-ion mass spectroscopy (SIMS), Hall effect, and Raman spectroscopy have been used to assess structural and electrical properties as a function of substrate offcut. Bulk GaN substrates with vicinal offcut between 0.5° and 1.4° are optimal with respect to surface roughness and dopant incorporation. AFM, PL, and CL show decreasing Mg incorporation with increasing offcut angle. Raman spectroscopy, used to analyze biaxial strain, confirms essentially strain-free heterostructure growth on vicinal substrates with offcut angles between 0.5° and 1.4° off [0001] toward [1[`1] 00] [1\overline{1} 00] . Aluminum (Al) incorporation in the Al _x Ga_1−x N barrier assessed by Raman vibration is in excellent agreement with trends found by HRXRD.     

Investigations of 3C-SiC inclusions in 4H-SiC epilayers on 4H-SiC single crystal substrates

Synchrotron white beam x-ray topography (SWBXT) and Nomarski optical microscopy (NOM) have been used to characterize 4H-SiC epilayers and to study the character of triangular inclusions therein. 4H-SiC substrates misoriented by a range of angles from (0001), as well as (1 100) and (1120) oriented substrates were used. For epilayers grown on substrates misoriented by 3.5° from (0001) toward <1120>, the triangular inclusions were identified as consisting of two 3C-SiC structural configurations which are related to each other by a 180° rotation about the [111] axis. The epitaxial relationships between the 3C inclusions and the 4H-SiC epilayers (or substrates) were also determined. No evidence was found for the nucleation of 3C-SiC inclusions at superscrew dislocations (along the [0001] axis) in the 4H-SiC substrates. Increasing the off-axis angle of the substrates from 3.5 to 6.5° was found to greatly suppress the formation of the triangular inclusions. In the case of substrates misoriented by 8.0° from (0001) toward <1120>, the triangular inclusions were virtually eliminated. The crystalline quality of 4H-SiC epilayers grown on the substrates misoriented by 8.0° from (0001) was very good. For the (1100) and (1120) samples, there is no indication of 3C-SiC inclusions in the epilayers. Possible formation mechanisms and the morphology of 3C-SiC inclusions are discussed.     

Elevated-Temperature Annealing Effects on AlGaN/GaN Heterostructures

The effect of high-temperature annealing of undoped AlGaN/GaN heterostructures on different substrates was systematically studied between 1100°C and 1230°C. An AlN spacer layer was found to add stability to structures on sapphire substrates. AlGaN/GaN heterostructures on SiC substrates demonstrated excellent robustness for the temperature range studied, maintaining their mobility, sheet resistance, and sheet concentration values, even after annealing. A silicon nitride, SiN _x , capping layer was found to assist in minimizing surface roughness during annealing and maintaining the electrical characteristics of the heterostructures. AlGaN/GaN heterostructures on SiC substrates showed a 20% decrease in mobility for uncapped samples compared with SiN _x -capped samples.     

Activation of silicon ion-implanted gallium nitride by furnace annealing

Ion implantation into III–V nitride materials is animportant technology for high-power and high-temperature digital and monolithic microwave integrated circuits. We report the results of the electrical, optical, and surface morphology of Si ion-implanted GaN films using furnace annealing. We demonstrate high sheet-carrier densities for relatively low-dose (n_atoms=5×10¹⁴ cm⁻²) Si implants into AlN/GaN/sapphire heteroepitaxial films. The samples that were annealed at 1150°C in N₂ for 5 min exhibited a smooth surface morphology and a sheet electron concentration n_s ∼9.0×10¹³ cm⁻², corresponding to an estimated 19% electrical activation and a 38% Si donor activation in GaN films grown on sapphire substrates. Variable-temperature Hall-effect measurem entsindicate a Si donor ionization energy ∼15 meV.     

Step structure during organometallic vapor phase epitaxial growth of ordered GaInP

The nature of the steps on the nominally (00l)-oriented surface of Ga_0.5In_0.5P lattice matched to GaAs has been studied using high resolution atomic force microscopy. The layers were grown by organometallic vapor phase epitaxy (OMVPE) at a temperature of 620°C on substrates misoriented by angles,?_m, from 0 to 9° toward the $[\bar 110]$ direction in the lattice. An array of bunched steps from 25 to 50Å in height, depending on the substrate misorientation angle, is observed on the surface. An unusual feature of these bunched or super-steps, as compared to those seen for GaAs surfaces, is that they have relatively short lengths of a few thousand Angstroms. In addition, not all of the steps congregate into the surface steps. Thus, the surface consists of three “phases”: (001) flats, (11n) facets, and misoriented areas covered by an array of monolayer steps. The fraction of steps contained in the supersteps decreases monotonically as ?_m increases from 3 to 9°. Again, this differs from reports of the nature of GaAs surfaces grown under similar conditions where essentially all of the steps congregate into supersteps. The value of n for the (lln) facets also varies with misorientation angle: The angle between the (001) and the (lln) facets increases from approximately 11-12° for ?_m = 3° to nearly 30? for ?_m = 9°. An attempt was made to correlate the surface structure with ordering, which is observed to vary significantly with misorientation angle. The degree of order is found to increase monotonically with the fraction of steps forming supersteps.     

ZnSe heteroepitaxy on GaAs (110) substrate

ZnSe heteroepitaxial layers have been grown on GaAs (100), (110) on axis, and (110) 6° miscut substrates by molecular beam epitaxy. ZnSe on GaAs (110) shows smooth and featureless spectra from Rutherford backscattering channeling measurements taken along major crystalline directions, whereas ZnSe on GaAs (100) without pre-growth treatments exhibit large interface disorder in channeling spectra. ZnSe films grown on GaAs (110) on axis show facet formation over a wide range of growth conditions. The use of (110) 6° miscut substrates is shown to suppress facet formation; and under the correct growth conditions, facet-free surfaces are achieved. Etch pit density measurements give dislocation densities for ZnSe epitaxial layers grown on GaAs (100), (110) on axis, and (110) 6° miscut substrates of 10⁷/cm², 3 × 10⁵/cm² and 5 × 10⁴/cm², respectively. These results suggest that with further improvements to ZnSe growth on GaAs (110)-off substrates it may be possible to fabricate defect free ZnSe based laser devices.     

Direct MBE growth of GaN on GaAs substrates for integrated short wavelength emitters

The growth and material properties of GaN heteroepitaxial layers on vicinal (1 0 0) and exact (1 1 1)B substrates have been investigated, using molecular beam epitaxy (MBE) with N₂ RF-plasma source. We examined the approach to grow GaN directly on the oxide desorbed GaAs, without the incidence of an As beam during oxide desorption or the following stages of growth. Perfect smooth surfaces were obtained on (1 1 1)B GaAs but excellent luminescence properties were observed on vicinal (1 0 0) GaAs. Four growth temperatures (T_G) were compared for the (1 0 0) orientation and a monotonic increase of photoluminescence intensity with increasing T_G, in the range of 570–680°C, was observed. The best surface morphology of less than 10 nm rms roughness was also determined, by atomic force microscopy, for the maximum (680°C) temperature. The layers exhibited up to 10¹⁷ cm⁻³ electron concentration and it could be compensated by Mg impurities. Metallizations of Pt and Pd gave ohmic contacts on GaN/GaAs (1 0 0) but a Schottky diode contact was achieved by Ir metallization. The obtained material properties are probably sufficient for realizing efficient GaN light emitters on (1 0 0) GaAs substrates.     

Step structure of GaInAsSb grown by organometallic vapor phase epitaxy

The surface step structure of Ga_1−xIn_xAs_ySb_1−y grown by organometallic vapor phase epitaxy on GaSb substrates has been studied by atomic force microscopy. Epilayers were grown at 525°C and 575°C on (001) GaSb substrates misoriented 2° toward (101) or 6° toward (1 1)B. For Ga_0.88In_0.12As_0.1Sb_0.9 grown at 575°C, the surface exhibits step-bunching on both types of substrates. When the composition is increased to Ga_0.86In_0.14As_0.12Sb_0.88, the periodic step structure breaks down and the surface becomes irregular. The deterioration of the step structure is a consequence of phase separation at the surface of the metastable GaInAsSb epilayer, which leads to the formation of GaAs- and InSb-rich regions. The photoluminescence (PL) of such layers show significant broadening due to carrier recombination in the lower energy gap InSb-rich quaternary regions. On the other hand, the surface of GaInAsSb epilayers grown at a lower temperature of 525°C is vicinal with steps heights of one to two monolayers. The PL FWHM values are considerably smaller for these layers. This improvement in material quality is related to smaller adatom lifetimes at the lower growth temperature. The importance of surface kinetics as it influences the step structure and thermodynamically driven phase separation is discussed.     

Scanning electron microscopy and cathodoluminescence study of the epitaxial lateral overgrowth (ELO) process for gallium nitride

Traditional epitaxial growth of GaN by metalorganic vapor phase epitaxy (MOVPE) on mismatched substrates such as sapphire or SiC produces a columnar material consisting of many hexagonal grains ∼0.2–1.0 μm in diameter. The epitaxial-lateral-overgrowth (ELO) process for GaN creates a new material: single-crystal GaN. We have studied the ELO process for GaN grown by MOVPE in a vertical flow rotating substrate reactor. Characterization consisted of plan-view SEM and vertical-cross-section TEM studies, which revealed a large reduction in dislocation density in the overgrown regions of the GaN. Panchromatic and monochromatic cathodoluminescence images and spectra were used to study the spatial variation of the optical properties within the GaN ELO samples. The effects of growth temperature and stripe material on the overgrown layers were examined. Through the use of a higher substrate temperature during growth and the use of a SiN_x stripe material, the overgrown crystal shape has a smooth 2D top surface with vertical sidewalls. Applying a second ELO step, rotated by 60°, over a fully coalesced ELO layer yields a further reduction of defects in GaN overgrown surfaces.     

High-efficiency,thin-film InP concentrator solar cells

High-efficiency, thin-film InP solar cells grown heteroepitaxially on GaAs and Si single-crystal bulk substrates are being developed as a means of eliminating the problems associated with using single-crystal InP substrates (e.g., high cost, fragility, high mass density and low thermal conductivity). A novel device structure employing a compositionally graded Ga _x In_1−x As layer (∼8 μm thick) between the bulk substrate and the InP cell layers is used to reduce the dislocation density and improve the minority carrier properties in the InP. The structures are grown in a continuous sequence of steps using computer-controlled atmospheric-pressure metalorganic vapor-phase epitaxy (AP-MOVPE). Dislocation densities as low as 3×10⁷ cm⁻² and minority carrier lifetimes as high as 3.3 ns are achieved in the InP layers with this method using both GaAs or Si substrates. Structures prepared in this fashion are also completely free of microcracks. These results represent a substantial improvement in InP layer quality when compared to heteroepitaxial InP prepared using conventional techniques such as thermally cycled growth and post-growth annealing. The present work is concerned with the fabrication and characterization of thin-film InP solar cells designed for operation at high solar concentration (∼100 suns) which have been prepared from similar device structures grown on GaAs substrates. The cell performance is characterized as a function of the air mass zero (AM0) solar concentration ratio (1–100 suns) and operating temperature (25°–80° C). From these data, the temperature coefficients of the cell performance parameters are derived as a function of the concentration ratio. Under concentration, the cells exhibit a dramatic increase in efficiency and an improved temperature coefficient of efficiency. At 25° C, a peak conversion efficiency of 18.9% (71.8 suns, AM0 spectrum) is reported. At 80° C, the peak AM0 efficiency is 15.7% at 75.6 suns. These are the highest efficiencies yet reported for InP heteroepitaxial cells. Approaches for further improving the cell performance are discussed.     

Fabrication and Optical Characteristics of Position‐Controlled ZnO Nanotubes and ZnO/Zn0.8Mg0.2O Coaxial Nanotube Quantum Structure Arrays

The position‐controlled growth and structural and optical characteristics of ZnO nanotubes and their coaxial heterostructures are reported. To control both the shape and position of ZnO nanotubes, hole‐patterned SiO₂ growth‐mask layers on Si(111) substrates with GaN/AlN intermediate layers using conventional lithography are prepared. ZnO nanotubes are grown only on the hole patterns at 600 °C by catalyst‐free metal–organic vapor‐phase epitaxy. Furthermore, the position‐controlled nanotube growth method allows the fabrication of artificial arrays of ZnO‐based coaxial nanotube single‐quantum‐well structures (SQWs) on Si substrates. In situ heteroepitaxial growth of ZnO and Zn_0.8Mg_0.2O layers along the circumference of the ZnO nanotube enable an artificial formation of quantum‐well arrays in a designed fashion. The structural and optical characteristics of the ZnO nanotubes and SQW arrays are also investigated using synchrotron radiation X‐ray diffractometry and photoluminescence and cathodoluminescence spectroscopy.     

Cathodoluminescence of ZnO/GaN/α-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> heteroepitaxial structures grown by chemical vapor deposition

The cathodoluminescent properties of ZnO films in ZnO/GaN/α-Al₂O₃ and ZnO/α-Al₂O₃ heteroepitaxial structures grown by chemical vapor deposition in a low-pressure flowing-gas reactor were studied and compared. A superlinear dependence of the excitonic-band intensity in the cathodoluminescence spectrum of the ZnO/GaN/α-Al₂O₃ structures on the electron-beam current is ascertained, which indicates that the emission is stimulated for relatively low thresholds of the excitation intensity. It is shown that the ZnO films grown on the GaN substrates exhibit a much more effective cathodoluminescence compared to the cathodoluminescence in the films grown on α-Al₂O₃. It was observed that the luminescent properties of ZnO layers in the ZnO/GaN/α-Al₂O₃ structures subjected to long-term heat treatment at 750°C in an oxygen atmosphere exhibit a high thermal stability.     

The effects of oxygen,nitrogen, and hydrogen annealing on Mg acceptors in GaN as monitored by electron paramagnetic resonance spectroscopy

Electron paramagnetic resonance (EPR) spectroscopy is used to study the unpassivated Mg-related acceptor in GaN films. As expected, the trends observed before and after O₂, N₂, or forming-gas anneals at temperatures <800°C are similar to those typically reported for electrical measurements. However, annealing at temperatures >850°C in O₂ or N₂ permanently removes the signal, contrary to the results of conductivity measurements. Approximately 10¹⁹ cm⁻³ Mg acceptors were detected in some GaN films grown by chemical vapor deposition (CVD) before acceptor activation, suggesting that it is possible to have electrically active Mg in as-grown CVD material.     

Control of ordering in GaInP and effect on bandgap energy

Ga_xIn_1-x P layers with x ≈ 0.5 have been grown by atmospheric pressure organometallic vapor phase epitaxy on GaAs substrates with 10 micron wide, [110]-oriented grooves produced photolithographically on the surface. The [110] steps and the misorientation produced at the edges of the grooves have been found to have important effects on the formation of the Cu-Pt ordered structure (ordering on {111} planes) in the GaInP layers during growth. In this work, the groove shape is demonstrated to be critically important. For the optimum groove shape, with a maximum angle to the (001) surface of between 10 and 16°, single domains of the (-111) and (1-11) variants of the Cu-Pt ordered structure are formed on the two sides of the groove. Shallow (≤0.25 μm deep) grooves, with maximum angles of <10°, are less effective. Within the large domains on each side of the groove, small domains of the other variant are observed. The boundary between the two domains is seen to wander laterally by a micron or more during growth, due to the change in shape of the groove during growth. For deep (1.5 μm) grooves, with maximum angles to the (001) plane of 35°, only a single variant is formed on each side of the groove. However, the domains are small, dispersed in a disordered matrix. For substrates with deep grooves on a GaAs substrate misoriented by 9° toward the [-110] direction, an interesting and useful pattern is produced. One half of the groove is a single domain which shrinks in size as the growth proceeds. The other half of the groove, where the misorientation is larger, is disordered. Thus, every groove contains large (>1 μm² cross-sectional area and several mm long) regions of highly ordered and completely disordered material separated by no more than a few microns. This allows a direct determination of the effect of ordering on the bandgap of the material using cathodoluminescence (CL) spectroscopy. The 10K photoluminescence (PL) consists of three distinct peaks at 1.94, 1.88, and 1.84 eV. High resolution CL images reveal that the peaks come from different regions of the sample. The high energy peak comes from the disordered material and the low energy peak comes from the large ordered domains. Electron microprobe measurements of the solid composition demonstrate that the shift in emission energy is not due to changes in solid composition. This is the firstdirect verification that ordering causes a reduction in bandgap of any III/V alloy. Decreasing the Ga_0.5In_0.5P growth rate from the normal 2.0 to 0.5 μ/h is found to enhance ordering in layers grown on planar GaAs substrates. Transmission electron diffraction results show that the domain size also increases significantly. For material grown on exactly (001)-oriented substrates, a pronounced [001] streaking of the superlattice spots is observed. This is correlated with the presence of a dense pattern of fine lines lying in the (001) plane in the transmission electron micrographs. The PL of this highly ordered material consists of a single peak that shifts to higher energy by > 110 meV as the excitation intensity is increased by several orders of magnitude.     

Influence of growth temperature and growth rate of p-GaN layers on the characteristics of green light emitting diodes

We investigated the electrical and structural qualities of Mg-doped p-type GaN layers grown under different growth conditions by metalorganic chemical vapor deposition (MOCVD). Lower 300 K free-hole concentrations and rough surfaces were observed by reducing the growth temperature from 1,040°C to 930°C. The hole concentration, mobility, and electrical resistivity were improved slightly for Mg-doped GaN layers grown at 930°C with a lower growth rate, and also an improved surface morphology was observed. In_0.25Ga_0.75N/GaN multiple-quantum-well light emitting diodes (LEDs) with p-GaN layers grown under different conditions were also studied. It was found from photoluminescence studies that the optical and structural properties of the multiple quantum wells in the LED structure were improved by reducing the growth temperature of the p-layer due to a reduced detrimental thermal annealing effect of the active region during the GaN:Mg p-layer growth. No significant difference in the photoluminescence intensity depending on the growth time of the p-GaN layer was observed. However, it was also found that the electroluminescence (EL) intensity was higher for LEDs having p-GaN layers with a lower growth rate. Further improvement of the p-GaN layer crystalline and structural quality may be required for the optimization of the EL properties of long-wavelength (∼540 nm) green LEDs.     

High-Quality GaN heteroepitaxial films grown by metalorganic chemical vapor deposition

In this paper, we describe the growth and characterization of high-quality GaN heteroepitaxial films grown on basal-plane sapphire substrates using metalorganic chemical vapor deposition. The quality of these films is analyzed by a variety of methods, including high-resolution x-ray diffraction, optical transmission spectroscopy, transmission electron microscopy (TEM), room temperature photoluminescence, and room-temperature Hall measurements. The x-ray diffraction full width at half maximum value of ΔΘ ～37 arc s is the narrowest reported to date for any III-V nitride film on any substrate. The x-ray rocking curves for ～0.48 μm thick GaN/Al₂O₃ heteroepitaxial layers exhibit Pendellösung fringes, indicating that even relatively thin films can be of high quality. High-resolution TEM lattice images further attest to the excellent structural quality, showing the films to be completely free of stacking faults. Furthermore, no evidence of columnar growth is observed.     

In situ control of gan growth by molecular beam epitaxy

Methods to determine GaN surface temperature, surface composition, and growth rates using in situ desorption mass spectroseopy (DMS) and reflection high energy electron diffraction (RHEED) are demonstrated for molecular beam epitaxial growth of GaN using NH₃. Using these methods, the GaN surface temperature, T_s, and GaN growth rates as a function of T_s, Ga flux, and NH₃ flux were obtained. Surface temperatures were determined from DMS and RHEED measurements of the temperature at which Ga condenses on GaN. NH₃-limited and Ga-limited growth regimes are identified and the transition between these regimes is shown to be abrupt. NH₃-limited samples have a weakly reconstructed (2 × 2) RHEED pattern, while Ga-limited samples reveal a transmission pattern. Atomic force microscopy showed that NH₃-limited samples exhibit atomic steps while Ga-limited samples exhibit faceting.     

Analysis of reactor geometry and diluent gas flow effects on the metalorganic vapor phase epitaxy of AIN and GaN thin films on α(6H)-SiC substrates

The influence of diluent gas on the metalorganic vapor phase epitaxy of AlN and GaN thin films has been investigated. A computational fluid dynamics model using the finite element method was employed to improve film uniformity and to analyze transport phenomena. The properties of AlN and GaN thin films grown on α(6H)-SiC(0001) substrates in H₂ and N₂ diluent gas environments were evaluated. Thin films of AlN grown in H₂ and N₂ had root mean square (rms) roughness values of 1.5 and 1.8 nm, respectively. The surface and defect microstructures of the GaN thin films, observed by scanning and transmission electron microscopy, respectively, were very similar for both diluents. Low temperature (12K) photoluminescence measurements of GaN films grown in N₂ had peak intensities and full widths at half maximum equal to or better than those films grown in H₂. A room temperature Hall mobility of 275 cm²/V·s was measured on 1 μm thick, Si-doped, n-type (1×10¹⁷ cm⁻³) GaN films grown in N₂. Acceptor-type behavior of Mg-doped GaN films deposited in N₂ was repeatably obtained without post-growth annealing, in contrast to similar films grown in H₂. The GaN growth rates were ∼30% higher when H₂ was used as the diluent. The measured differences in the growth rates of AlN and GaN films in H₂ and N₂ was attributed to the different transport properties of these mixtures, and agreed well with the computer model predictions. Nitrogen is shown to be a feasible alternative diluent to hydrogen for the growth of AlN and GaN thin films.