Growth and characterization of GaN and AlN films on (1 1 1) and (0 0 1) Si substrates

GaN and AlN films were grown on (1 1 1) and (0 0 1) Si substrates by separate admittances of trimethylgallium (or trimethylaluminum) and ammonia (NH₃) at 1000°C. A high temperature (HT) or low temperature (LT) grown AlN thin layer was employed as the buffer layer between HT GaN (or HT AlN) film and Si substrate. Experimental results show that HT AlN and HT GaN films grown on the HT AlN-coated Si substrates exhibit better crystalline quality than those deposited on the LT AlN-coated Si substrates. Transmission electron microscopy (TEM) of the HT GaN/HT AlN buffer layer/(1 1 1)Si samples shows a particular orientation relationship between the (0 0 0 1) planes of GaN film and the (1 1 1) planes of Si substrate. High quality HT GaN films were achieved on (1 1 1) Si substrates using a 200 Å thick HT AlN buffer layer. Room temperature photoluminescence spectra of the high quality HT GaN films show strong near band edge luminescence at 3.41 eV with an emission linewidth of ∼110 meV and weak yellow luminescence.     

Growth of thick,continuous GaN layers on 4-in. Si substrates by metalorganic chemical vapor deposition

We report on the growth of thick GaN epilayers on 4-in. Si(1 1 1) substrates by metalorganic chemical vapor deposition. Using intercalated AlN layers that contribute to counterbalance the tensile strain induced by the thermal mismatch between gallium nitride and the silicon substrate, up to 6.7 μm thick crack-free group III-nitride layers have been grown. Root mean-squares surface roughness of 0.5 nm, threading dislocation densities of 1.1×10⁹ cm^?2, as well as X-ray diffraction (XRD) full widths at half-maximum (FWHM) of 406 arcsec for the GaN(0 0 2) and of 1148 arcsec for the GaN(3 0 2) reflection have been measured. The donor bound exciton has a low-temperature photoluminescence line width of 12 meV. The correlation between the threading dislocation density and XRD FWHM, as well as the correlation between the wafer curvature and the GaN in-plane stress is discussed. An increase of the tensile stress is observed upon n-type doping of GaN by silicon.     

Growth optimization and characterization of lattice-matched Al0.82In0.18N optical confinement layer for edge emitting nitride laser diodes

We present the growth optimization and the doping by the metal organic chemical vapor deposition of lattice-matched Al_0.82In_0.18N bottom optical confinement layers for edge emitting laser diodes. Due to the increasing size and density of V-shaped defects in Al_1?xIn_xN with increasing thickness, we have designed an Al_1?xIn_xN/GaN multilayer structure by optimizing the growth and thickness of the GaN interlayer. The Al_1?xIn_xN and GaN interlayers in the multilayer structure were both doped using the same SiH₄ flow, while the Si levels in both layers were found to be significantly different by SIMS. The optimized 8×(Al_0.82In_0.18N/GaN=54/6 nm) multilayer structures grown on free-standing GaN substrates were characterized by high resolution X-ray diffraction, atomic force microscopy and transmission electron microscopy, along with the in-situ measurements of stress evolution during growth. Finally, lasing was obtained from the UV (394 nm) to blue (436 nm) wavelengths, in electrically injected, edge-emitting, cleaved-facet laser diodes with 480 nm thick Si-doped Al_1?xIn_xN/GaN multilayers as bottom waveguide claddings.     

Growth of highly oriented crystalline α-Fe/AlN/Fe3N trilayer structures on Si(1 1 1) substrates by molecular beam epitaxy

We have realized highly oriented nitride-based α-Fe/AlN/Fe₃N ferromagnetic hybrid structures on Si(1 1 1) substrates by molecular beam epitaxy using AlN/SiC intermediate layers. A two-step hysteresis loop, typically observed in magnetic tunneling junctions, was clearly observed in magnetization versus magnetic field measurements. This result indicates the formation of ferromagnetic α-Fe and Fe₃N layers separated by 8-nm-thick AlN layers over approximately 1 cm² area, and also shows the difference in coercive field between the two ferromagnetic layers.     

MOCVD growth of GaN on Si(1 1 1) substrates using an ALD-grown Al2O3 interlayer

GaN thin films have been grown on Si(1 1 1) substrates using an atomic layer deposition (ALD)-grown Al₂O₃ interlayer. This thin Al₂O₃ layer reduces strain in the subsequent GaN layer, leading to lower defect densities and improved material quality compared to GaN thin films grown by the same process on bare Si. XRD ω-scans showed a full width at half maximum (FWHM) of 549 arcsec for GaN grown on bare Si and a FWHM as low as 378 arcsec for GaN grown on Si using the ALD-grown Al₂O₃ interlayer. Raman spectroscopy was used to study the strain in these films in more detail, with the shift of the E₂(high) mode showing a clear dependence of strain on Al₂O₃ interlayer thickness. This dependence of strain on Al₂O₃ thickness was also observed via the redshift of the near bandedge emission in room temperature photoluminescence (RT-PL) spectroscopy. The reduction in strain results in a significant reduction in both crack density and screw dislocation density compared to similar films grown on bare Si. Screw dislocation density of the films grown on Al₂O₃/Si substrates approaches that of typical GaN layers on sapphire. This work shows great promise for the use of oxide interlayers for growth of GaN-based LEDs on Si.     

Growth and characterization of GaSb/AlGaSb multi-quantum well structures on Si (0 0 1) substrates

GaSb/AlGaSb multi-quantum well (MQW) structures with an AlSb initiation layer and a relatively thick GaSb buffer layer grown on Si (0 0 1) substrates were prepared by molecular beam epitaxy (MBE). Transmission electron microscopy (TEM) images and high-resolution X-ray diffraction (XRD) patterns indicated definite MQW structures. The photoluminescence (PL) emission around 1.55 μm wavelength was observed for 10.34 nm GaSb/30 nm Al_0.6Ga_0.4Sb MQW structure at room temperature. Dependence of PL emission energy on GaSb well width was well explained by finite square well potential model.     

Cathodoluminescence study of the excitons localization in AlGaN/GaN and InGaN/GaN quantum wells grown on sapphire

Al_0.1Ga_0.9N(5 nm)/GaN(2 nm) and In_0.2Ga_0.8N/GaN quantum wells (QWs) grown on GaN/sapphire have been studied by cathodoluminescence (CL) spectroscopy and imaged using an experimental setup especially developed for scanning near-field CL microscopy, which combines a scanning force microscope and a scanning electron microscope. The CL spectra show the characteristic band edge emission peak of GaN at λ= 364 nm and the emission peaks related to the presence of QWs, at λ= 353 and 430 nm for the AlGaN/GaN and the InGaN/GaN samples, respectively. Monochromatic CL images reveal that the emission of the AlGaN/GaN and InGaN/GaN QWs is localized at the level of the grains observed by SFM. A cross sectional analysis of the InGaN/GaN sample gives insight into its growth and an estimation of the exciton diffusion length of about L=180 nm.     

High quality MOCVD GaN film grown on sapphire substrates using HT-AlN buffer layer

In this work we report on the growth and characterization of high quality MOCVD GaN film grown on Al₂O₃ substrates by using a HT (>1150 °C)-AlN buffer layer. We have investigated the most favorable growth conditions in terms of temperature, thickness and growth rate of AlN buffer layer in order to optimize the high temperature GaN layer. The improved morphological and structural properties of GaN layer were verified by AFM and XRD measurements. The optimized GaN layer presents a smooth surface with a rms value of 1.4 Å. The full width at half maximum (FWHM) for 800 nm thick GaN films is 144″. Furthermore PL measurements and C–V analysis confirm that in GaN layer grown on HT-AlN buffer layer defect density is drastically reduced.     

Interface of GaN grown on Ge(1 1 1) by plasma assisted molecular beam epitaxy

Early efforts to grow GaN layers on germanium substrates by plasma assisted molecular beam epitaxy led to GaN domains, rotated by 8° relative to each other. Increased insight in the growth of GaN on germanium resulted in the suppression of these domain and consequently high quality layers. In this study the interface of these improved layers is investigated with transmission electron microscopy. The GaN layers show high crystal quality and an atomically abrupt interface with the Ge substrate. A thin, single crystalline Ge₃N₄ layer is observed in between the GaN layer and Ge substrate. This Ge₃N₄ layer remains present even at growth temperatures (850 °C) far above the decomposition temperature of Ge₃N₄ in vacuum (600 °C). Triangular voids in the Ge substrate are observed after growth. Reducing the Ga flux at the onset of GaN growth helps to reduce the triangular defect size. This indicates that the formation of voids in the Ge substrate strongly depends on the presence of Ga atoms at the onset of growth. However complete elimination was not achieved. The formation of voids in the germanium substrate leads to diffusion of Ge into the GaN layer. Therefore we examined the diffusion of Ge atoms into the GaN layer and Ga atoms into the Ge substrate. It was found that the diffusion of Ge into the GaN layer and Ga into the Ge substrate can be influenced by the growth temperature but cannot be completely suppressed. Our results suggest that Ga atoms diffuse through small imperfections in the Ge₃N₄ interlayer and locally etch the Ge substrate, leading to the diffusion of Ga and Ge atoms.     

The growth of high-quality and self-separation GaN thick-films by hydride vapor phase epitaxy

About 1.2 mm thick GaN bulk crystals were obtained by combining a pulsed NH₃-flow modulation (PFM) method and a self-separation method of short-shutting NH₃ flow when using hydride vapor phase epitaxy (HVPE). High crystal quality of bulk GaN was evaluated by X-ray rocking curves (XRC) and the full width at half maximum (FWHM) values were 110, 72 and 83 arcsec for (002), (102) and (100) reflection planes, respectively. The PFM method is proved to be effective in reducing cracks and keeping the surface smooth. And the method of short-shutting NH₃ flow can lead to GaN thick layer separate from sapphire substrate when cooling from the high growth temperature. Growth and separation mechanisms were investigated. Two states were found in PFM method. With PFM method modulating between high quality state and low stress state, 300 μm thick GaN layers without cracks were obtained. Study of spontaneous separation mechanism revealed that the separation attributed to formation of voids inside the GaN layer.     

Properties and structure of (1 − x)Li2O–xNa2O–Al2O3–4SiO2 glass systems

(1 − x)Li₂O–xNa₂O–Al₂O₃–4SiO₂ glasses were studied for the progressive percentage substitution of Na₂O for Li₂O at the constant mole of Al₂O₃ and SiO₂. The crystallization temperature at the exothermic peak increased from 898 to 939 °C when the Na₂O content increases from 0 to 0.6 mol. The coefficient of thermal expansion and density of these as-quenched glasses increase from 6.54 × 10⁻⁶ °C⁻¹ to 10.1 × 10⁻⁶ °C⁻¹ and 2.378 g cm⁻³ to 2.533 g cm⁻³ when the Na₂O content increases from 0 to 0.4 mol, respectively. The electrical resistivity has a maximum value at Na₂O · (Li₂O + Na₂O)⁻¹ = 0.4. The activation energy of crystallization decreases from 444 to 284 kJ mol⁻¹ when the Na₂O content increased from 0 to 0.4 mol. Moreover, the activation energy increases from 284 kJ mol⁻¹ to 446 kJ mol⁻¹ when the Na₂O content increased from 0.4 to 0.6 mol. The FT-IR spectra show that the symmetric stretching mode of the SiO₄ tetrahedra (1035–1054 cm⁻¹) and AlO₄ octahedra (713–763 cm⁻¹) exhibiting that the network structure is built by SiO₄ tetrahedra and AlO₄.     

Fabrication of 3-in GaN substrates by hydride vapor phase epitaxy using void-assisted separation method

By using the hydride vapor phase epitaxy and a void-assisted separation method, freestanding 3-in GaN substrates were successfully fabricated for the first time, and the process showed an excellent reproducibility. A thick GaN layer 3.2 in in diameter was easily separated from the base substrate. No cracks were generated during the separation process. The dislocation density was of the order of 10⁶ cm^–2. The carrier density was approximately 1×10¹⁸ cm^–3 and the mobility was 3.4×10² cm² V^–1 s^–1. The concentrations of impurities, estimated by secondary-ion mass spectrometry, were below the limit of detection, except for Si. The Si concentration was approximately 1×10¹⁸ cm^–3, which is in good agreement with the carrier density.     

AlGaN/GaN HEMTs regrown by MBE on epi-ready semi-insulating GaN-on-sapphire with inhibited interface contamination

In this work, we show that, by carefully designing the subsurface Fe doping profile in SI-GaN templates grown by MOVPE and by optimizing the MBE regrowth conditions, a highly resistive GaN buffer can be achieved on these epi-ready GaN-on-sapphire templates without any addition of acceptors during the regrowth. As a result, high-quality high electron mobility transistors can be fabricated. Furthermore, we report on the excellent properties of two-dimensional electron gas and device performances with electron mobility greater than 2000 cm²/V s at room temperature and off-state buffer leakage currents as low as 5 μA/mm at 100 V.     

Characterization of deep levels in a-plane GaN epi-layers grown using various growth techniques

To study the correlation between defects and deep levels in a-plane GaN films grown on r-plane sapphire substrates, transmission electron microscopy (TEM) and deep level transient spectroscopy (DLTS) have been performed on three types of a-plane GaN samples grown using modified two-step growth (sample I), SiN_x interlayer (sample II), and patterned insulator on sapphire substrate (sample III). From the microstructure evolution in cross-sectional TEM images, it was shown that combination of growth techniques is highly efficient in the reduction of dislocation densities. Average dislocation densities of samples I, II, and III were about 2.2×10⁹ cm^?2, 1.1×10⁹ cm^?2, and 3.4×10⁸ cm^?2, respectively. The trap a_t E_c–E_t～0.13 eV (E1) was observed in only sample I, and three electron traps at 0.28–0.33 eV (E2), 0.52–0.58 eV (E3), and 0.89–0.95 eV (E4) from the conduction band edge were measured common to all the samples. The analysis of trap properties indicated that E2 and E3 trap levels are strongly associated with the partial dislocations in a-plane GaN films.     

Dielectric relaxation of Al/Lu2O3/Al thin film structures from 10 μHz to 10 MHz

Results of dielectric studies of lutetium sesquioxide layers examined in Al/Lu₂O₃/Al thin film sandwiches are reported. The dielectric measurements were carried out in the frequency range 10⁻⁵–10⁷ Hz and for temperatures from 292 K to 500 K. Results are presented as plots of frequency functions: the capacitance, the dielectric loss factor, tan δ(f) and also on the complex plane as Cole–Cole plots and Nyquist plots. The influence of the external voltage on C(U) and tan δ(U) was examined. Experimental data were analyzed taking into account thin insulating Lu₂O₃ film, near-electrode regions of Al/Lu₂O₃ and Lu₂O₃/Al interfaces and series resistance of electrodes and leads. The parameters of Lu₂O₃ film, near-electrode regions and resistance of contacts and leads were determined.     

High quality InAlN/GaN heterostructures grown on sapphire by pulsed metal organic chemical vapor deposition

High quality InAlN/GaN heterostructures are successfully grown on the (0 0 0 1) sapphire substrate by pulsed metal organic chemical vapor deposition. The InAlN barrier layer with an indium composition of 17% is observed to be nearly lattice matched to GaN layer, and a smooth surface morphology can be obtained with root mean square roughness of 0.3 nm and without indium droplets and phase separation. The 50 mm InAlN/GaN heterostructure wafer exhibits a mobility of 1402 cm²/V s with a sheet carrier density of 2.01×10¹³  cm^?2, and a low average sheet resistance of 234 Ω/cm² with a sheet resistance nonuniformity of 1.22%. Compared with the conventional continual growth method, PMOCVD reduces the growth temperature of the InAlN layer and the Al related prereaction in the gas phase, and consequently enhances the surface migration, and improves the crystallization quality. Furthermore, indium concentration of InAlN layer can be controlled by adjusting the pulse time ratio of TMIn to TMAl in a unit cycle, the growth temperature and pressure, as well as the InAlN layer thickness by the number of unit cycle repeats.     

Thickness-dependent structural transition in GaAs nanocrystals grown on Si (1 1 1) surface

Structural stabilities in GaAs nanocrystals grown on the Si (1 1 1) substrate have been studied by transmission electron microscopy in order to see the structure and growth mechanism. The GaAs nanocrystals grown epitaxially on the Si (1 1 1) surface kept at 573 K have thin shapes consisting of a flat surface which is parallel to the Si (1 1 1) surface. The crystalline structure of the initial growth layer approximately below 5 nm in thickness is the zincblend structure, but with increasing thickness the structure changes to the wurtzite structure by formation of orderly-arranged stacking faults. The small difference in the driving force between the wurtzite structure and the zincblende structure could bring about a situation, where the kinetic rate of nucleus formation is high for the wurtzite structure than for the zincblende structure. It would highly increase the probability that the wurtzite structure is formed as a non-equilibrium state.     

Study of the effects of Ga3+ co-doping on the Lu0.8Sc0.2BO3:Ce scintillation crystals

Transparent Lu_0.8Sc_0.2BO₃ crystals doped with 1 at%Ce³⁺ and co-doped with 1 at% and 3 at%Ga³⁺ were grown by the Czochralski method. We applied absorption spectrum, luminescence spectra under UV and X-ray excitation, fluorescence decay curve, three dimensional thermoluminescene and X-ray absorption near edge spectroscopy to study the effect of Ga³⁺ co-doping on the Lu_0.8Sc_0.2BO₃:Ce scintillation crystals. Experimental results indicated that no positive contribution of the Ga³⁺ ion doping on the scintillation efficiency was found. The causes for the deterioration of scintillation efficiency by co-doping Ga³⁺ were revealed. The decrease of practical cerium content and the Ce³⁺/Ce⁴⁺ ratio in crystals, and the increase of the trap concentrations, although the corresponding trap types still maintained the same, played a joint influence on the degrading of scintillation efficiency of Lu_0.8Sc_0.2BO₃:Ce crystals.     

Epitaxial lateral overgrowth of non-polar GaN(1 1̄ 0 0) on Si(1 1 2) patterned substrates by MOCVD

m-Plane GaN was grown selectively by metal–organic chemical vapor deposition (MOCVD) on patterned Si(1 1 2) substrates, where grooves aligned parallel to the Si〈1 1 0〉 direction were formed by anisotropic wet etching to expose the vertical Si{1 1 1} facets for growth initiation. The effect of growth conditions (substrate temperature, chamber pressure, and ammonia and trimethylgallium flow rates) on the growth habits of GaN was studied with the aim of achieving coalesced m-plane GaN films. The epitaxial relationship was found to be GaN(1 1? 0 0) || Si(1 1 2), GaN[0 0 0 1] || Si[1 1 –1], GaN[1? 1? 2 0] || Si[1 1? 0]. Among all growth parameters, the ammonia flow rate was revealed to be the critical factor determining the growth habits of GaN. The distribution of extended defects, such as stacking faults and dislocations, in the selectively grown GaN were studied by transmission electron microscopy in combination with spatially resolved cathodoluminescence and scanning electron microscopy. Basal-plane stacking faults were found in the nitrogen-wing regions of the laterally overgrown GaN, while gallium-wings were almost free of extended defects, except for the regions near the GaN/Si{1 1 1} vertical sidewall interface, where high dislocation density was observed.     

Synthesis and luminescent properties of novel RENbO4:Ln3+ (RE = Y, Gd, Lu; Ln = Eu, Tb) micro-crystalline phosphors

Using rare earth coordination polymers with aromatic carboxylic acids as the precursors of rare earth oxide components, with polyethylene glycol (PEG) as the dispersing media, micro-crystalline phosphors RENbO₄:Ln³⁺ (RE = Y, Gd, Lu; Ln = Eu, Tb) have been synthesized by an in situ co-precipitation method. Both X-ray diffraction and scanning electron microscopy have shown that the resultant samples present are crystalline with ‘rice glue ball’ micro-morphology and crystalline grain sizes in the range of 1–2 μm. The luminescent properties of these phosphors have been studied, which show that the best photoluminescent performance is achieved for GdNbO₄:Tb³⁺ or Eu³⁺. This was because Gd³⁺ plays an important role to enhance the luminescence of Tb³⁺ or Eu³⁺ in an energy transfer process. In addition, the influence of the doping concentration on the fluorescence behaviors has been examined. With increase of the doping concentration from 1 mol% to 5 mol%, both the red emission intensity of Eu³⁺ and the green emission intensity of Tb³⁺ increase.