Effect of growth pressure on the morphology evolution and doping characteristics in nonpolar a-plane GaN

Nonpolar a-plane GaN layers grown on r-plane sapphire substrates were examined by using a two-step growth process. The higher initial growth pressure for the nucleation layer resulted in the improved crystalline quality with lower density of both threading dislocations and basal stacking faults. This was attributed to the higher degree of initial roughening and recovery time via a growth mode transition from three-dimensional (3D) to quasi two-dimensional (2D) lateral growth. Using Hall-effect measurements, the overgrown Si doped GaN layers grown with higher initial growth pressure were found to have higher mobility. The scattering mechanism due to the dislocations was dominant especially at low temperature (<200 K) for the lower initial growth pressure, which was insignificant for the higher initial growth pressure. The temperature-dependent Hall-effect measurements for the Mg doped GaN with a higher initial growth pressure yielded the activation energy and the acceptor concentration to be 128 meV and 1.2 × 10¹⁹ cm⁻³, respectively, corresponding to about 3.6% of activation at room temperature. Two-step growth scheme with a higher initial growth pressure is suggested as a potential method to improve the performance of nonpolar a-plane GaN based devices.     

Comparative studies on structural and optical properties of ZnO films grown on c-plane sapphire and GaAs (001) by MOCVD

ZnO thin films were grown on c-plane sapphire and GaAs (001) substrates by metalorganic chemical vapor deposition. Atomic force microscopy and double-crystal X-ray diffractometry were utilized to investigate the structural properties of the ZnO films. The optical properties of ZnO films were also investigated in terms of time integrated and resolved photoluminescence (TIPL and TRPL). Large hexagonal crystallites and better crystalline quality were observed from the ZnO film on sapphire. Also, both the TIPL and TRPL showed a significant difference as the substrate changed. In particular, a detected sharp contrast in the result of TRPL measurement is due to the different defect structure and the lattice strain and stress of ZnO films on different substrates.     

Rare-earth chloride seeded growth of GaN nano- and micro-crystals

A novel rare-earth chloride seed was employed as a catalyst for growth of GaN nano- and micro-crystals on c-, a- and r-plane sapphire. The ErCl₃ seed on the substrate surface enhanced the growth rate and density of the GaN crystals. Distinctive green photoluminescence was measured, confirming that Er³⁺ ions were active in the GaN matrix. This technique can be adapted to selectively grow GaN crystals with emission tailored to the particular optical transitions of the rare-earth seed.     

The etching of a-plane GaN epilayers grown by metal--organic chemical vapour deposition

Morphology of nonpolar (1120) a-plane GaN epilayers on r-plane (1102) sapphire substrate grown by low-pressure metal-organic vapour deposition was investigated after KOH solution etching. Many micron-and nano-meter columns on the a-plane GaN surface were observed by scanning electron microscopy. An etching mechanism model is proposed to interpret the origin of the peculiar etching morphology. The basal stacking fault in the a-plane GaN plays a very important role in the etching process.     

Epitaxial ZnO films grown on ZnO-buffered c-plane sapphire substrates by hydrothermal method

ZnO films are hydrothermally grown on ZnO-buffered c-plane sapphire substrates at a low temperature of 70 °C. A radio-frequency (RF) reactive magnetron sputtering has been used to grow the ZnO buffer layers. X-ray diffraction, scanning electron microscopy, and room temperature photoluminescence are carried out to characterize the structure, morphology and optical property of the films. It is found that the films are stress-free. The epitaxial relationship between the ZnO film and the c-plane sapphire substrate is found to be ZnO (0 0 0 1)||Al₂O₃ (0 0 0 1) in the surface normal and in plane. Sapphire treatment, as such acid etching, nitridation, and oxidation are found to influence the nucleation of the film growth, and the buffer layers determine the crystalline quality of the ZnO films. The maximum PL quantum efficiency of ZnO films grown with hydrothermal method is found to be about 80% of single-crystal ZnO.     

Optical and structural investigation of a-plane GaN layers on r-plane sapphire with nucleation layer optimization

Nonpolar a-plane GaN epilayers are grown on several r-plane sapphire substrates by metal organic chemical vapour deposition using different nucleation layers:(A) a GaN nucleation layer deposited at low temperature(LT);(B) an AlN nucleation layer deposited at high temperature;or(C) an LT thin AlN nucleation layer with an AlN layer and an AlN/AlGaN superlattice both subsequently deposited at high temperature.The samples have been characterized by Xray diffraction(XRD),atomic force microscopy and photoluminescence.The GaN layers grown using nucleation layers B and C show narrower XRD rocking curves than that using nucleation layer A,indicating a reduction in crystal defect density.Furthermore,the GaN layer grown using nucleation layer C exhibits a surface morphology with triangular defect pits eliminated completely.The improved optical property,corresponding to the enhanced crystal quality,is also confirmed by temperature-dependent and excitation power-dependent photoluminescence measurements.     

金属有机物化学气相沉积生长的$lt;i$gt;a$lt;/i$gt;(1120)面GaN三角坑缺陷的消除研究

用金属有机物化学气相沉积方法在r面蓝宝石上生长了非极性a面GaN薄膜,通过采用AlGaN多量子阱插入层,得到了高质量的非极性GaN材料. 用原子力显微镜和高分辨X射线衍射仪研究了a面GaN的表面形貌和结晶质量,发现非极性材料上典型的三角坑缺陷被消除,（1120）面X射线双晶摇摆曲线的半峰宽为680″. 关键词： GaN 原子力显微镜 高分辨X射线衍射仪 非极性     

Characterization of a-plane orientation ZnO film grown on GaN/Sapphire template by pulsed laser deposition

In this study, the authors have investigated the structural and optical properties of ZnO layer grown by pulsed laser deposition on GaN/r-plane sapphire. X-ray diffraction results demonstrate the ZnO film to be highly preferentially deposited at a-axis orientation; the different rocking curve values along the two orthogonal directions indicate the low C_2v symmetry in the growth a-plane ZnO. From free stress to large tensile stress (about 1.34 × 10⁹ Pa) distribution along the growth direction of ZnO is revealed by visible Raman mapping spectra. The enhanced significantly high-order longitudinal-optical (LO) phonon modes up to 4th and no TO phonons have been observed in Raman spectrum under UV 325 nm by resonance conditions; an intense and broad disorder activated surface phonon mode is also observed, resulting from the increased disorder on the film surface with stripe-like growth features. Low-temperature photoluminescence measurements reveal that the band-edge emission of ZnO is dominated by neutral donor-bound exciton and free electrons to neutral acceptor emissions. Interfacial microstructure of ZnO/GaN has been examined by transmission electron microscopy, with the epitaxial relationship () ZnO//() GaN. All these results indicated that GaN template played an important role in the growth of ZnO film, with full advantage of small lattice mismatch.     

Control of a- and c-plane preferential orientations of ZnO thin films

We report orientation-controllable growth of ZnO thin films and their orientation-dependent electrical characteristics. ZnO thin films were deposited on single-crystalline (1 0 0) LaAlO₃ and (1 0 0) SrTiO₃ substrates using pulsed laser deposition (PLD) at different substrate temperatures (400-800 °C). It was found that the orientation of ZnO films could be controlled by using different substrates of single-crystalline (1 0 0) LaAlO₃ and (1 0 0) SrTiO₃. The a-plane () and c-plane (0 0 0 2) oriented ZnO films are formed on LaAlO₃ and SrTiO₃, respectively. In both cases, the degree orientation increased with increasing deposition temperature T_s. Both the surface free energy and the degree of lattice mismatch are ascribed to play an important role for the orientation-controllable growth. Further characterization show that the grain size of the films with both orientations increases for a substrate temperature increase (i.e. from T_s = 400 °C to T_s = 800 °C), whereas the electrical properties of ZnO thin films depend upon their crystalline orientation, showing lower electrical resistivity values for a-plane oriented ZnO films.     

Surface morphology of GaN nanorods grown by catalyst-free hydride vapor phase epitaxy

GaN nanorods were grown on c-plane sapphire substrates by using catalyst-free hydride vapor phase epitaxy (HVPE). The effects of substrate temperature, Ga boat temperature, and Ga pretreatment on the surface morphology of GaN nanorods were investigated. From the dependence of a radial and axial growth rate on the substrate temperature, the kinetically limited process was found to be a rate determining step in the growth of GaN nanorods in HVPE. In addition, the activation energy of the growth along the both axial and radial directions were estimated. The dependence of a Ga boat temperature and the Ga pretreatment effect revealed that the density of nanorods were dependent on the flux of Ga species on the substrate.     

Investigation of GaN layer grown on different low misoriented sapphire by MOCVD

GaN layer on c-plane misoriented sapphire, grown by metal organic chemical vapor deposition, has been studied. It was observed that the random and non-uniform distribution of the step was caused by the step reconstruction for GaN grown on 0° sapphire by atomic force microscopy. The image quality parameter analysis of electron back-scatter diffraction indicated that the strains were reduced for GaN grown on 0.2° and 0.3° sapphire, and optical and electrical properties were improved. The electroluminescence intensity of LED grown on 0.2° and 0.3° sapphire was 2 times as that of 0° sapphire.     

Stress and morphology of a nonpolar a-plane GaN layer on r-plane sapphire substrate

The anisotropic strain of a nonpolar (1120) a-plane GaN epilayer on an r-plane (1102) sapphire substrate, grown by low-pressure metal-organic vapour deposition is investigated by Raman spectroscopy. The room-temperature Raman scattering spectra of nonpolar a-plane GaN are measured in surface and edge backscattering geometries. The lattice is contracted in both the c- and the m-axis directions, and the stress in the m-axis direction is larger than that in the c-axis direction. On the surface of this sample, a number of cracks appear only along the m-axis, which is confirmed by the scanning electron micrograph. Atomic force microscopy images reveal a significant decrease in the root-mean-square roughness and the density of submicron pits after the stress relief.     

Study on the relationships between Raman shifts and temperature range for a-plane GaN using temperature-dependent Raman scattering

In this paper, Raman shifts of a-plane GaN layers grown on r-plane sapphire substrates by low-pressure metal-organic chemical vapor deposition (LPMOCVD) are investigated. We compare the crystal qualities and study the relationships between Raman shift and temperature for conventional a-plane GaN epilayer and insertion AlN/AlGaN superlattice layers for a-plane GaN epilayer using temperature-dependent Raman scattering in a temperature range from 83 K to 503 K. The temperature-dependences of GaN phonon modes (A₁ (TO), E₂ (high), and E₁ (TO)) and the linewidths of E₂ (high) phonon peak are studied. The results indicate that there exist two mechanisms between phonon peaks in the whole temperature range, and the relationship can be fitted to the pseudo-Voigt function. From analytic results we find a critical temperature existing in the relationship, which can characterize the anharmonic effects of a-plane GaN in different temperature ranges. In the range of higher temperature, the relationship exhibits an approximately linear behavior, which is consistent with the analyzed results theoretically.     

Optical properties of nonpolar -plane GaN layers

We have studied optical properties of nonpolar a-plane GaN layers grown on r-plane sapphire by metalorganic chemical vapor deposition and hydride vapor phase epitaxy using different nucleation schemes. Several emission bands, which are not typical for c-plane GaN, are observed in the photoluminescence spectra and their excitation-intensity, temperature, and polarization dependencies are examined. In addition, the spatial distribution of the emissions was examined by cathodoluminescence imaging and relations of the different emissions with particular structural features in the layers are revealed. The results are discussed with emphasis on the origin of the emission line and particular recombination mechanisms.     

Structural and electrical properties of single crystalline and bi-crystalline ZnO thin films grown by molecular beam epitaxy

C-oriented ZnO epitaxial thin films are grown separately on the a-plane and c-plane sapphire substrates by using a molecular-beam epitaxy technique. In contrast to single crystalline ZnO films grown on a-plane sapphire, the films grown on c-plane sapphire are found to be bi-crystalline; some domains have a 30o rotation to reduce the large mismatch between the film and the substrate. The presence of these rotation domains in the bi-crystalline ZnO thin film causes much more carrier scatterings at the boundaries, leading to much lower mobility and smaller mean free path of the mobile carriers than those of the single crystalline one. In addition, the complex impedance spectra are also studied to identify relaxation mechanisms due to the domains and/or domain boundaries in both the single crystalline and bi-crystalline ZnO thin films.     

Luminescence of a GaN grain with a nonpolar and semipolar plane in relation to microstructural characterization

We report on the growth of the high-quality GaN grain on a r-plane sapphire substrate by using a self-organized SiN interlayer as a selective growth mask.Transmission electron microscopy,scanning electron microscopy,and Raman spectroscopy are used to reveal the effect of SiN on the overgrown a-plane GaN growth.The SiN layer effectively terminates the propagation of the threading dislocation and basal plane stacking faults during a-plane GaN regrowth through the interlayer,resulting in the window region shrinking from a rectangle to a "black hole".Furthermore,strong yellow luminescence(YL) in the nonpolar plane and very weak YL in the semipolar plane on the GaN grain is revealed by cathodoluminescence,suggesting that C-involved defects are responsible for the YL.     

Effects of V/III ratio on the growth of a-plane GaN films

The non-polar a-plane GaN is grown on an r-plane sapphire substrate directly without a buffer layer by metal-organic chemical vapour deposition and the effects of V/III ratio growth conditions are investigated. Atomic force microscopy results show that triangular pits are formed at a relatively high V/III ratio, while a relatively low V/III ratio can enhance the lateral growth rate along the c-axis direction. The higher V/III ratio leads to a high density of pits in comparison with the lower V/III ratio. The surface morphology is improved greatly by using a low V/III ratio of 500 and the roughness mean square of the surface is only 3.9 nm. The high resolution X-ray diffraction characterized crystal structural results show that the rocking curve full width at half maximum along the m axis decreases from 0.757° to 0.720°, while along the c axis increases from 0.220° to 0.251° with the V/III increasing from 500 μmol/min to 2000 μmol/min, which indicates that a relatively low V/III ratio is conducible to the c-axis growth of a-plane GaN.     

Optical spectroscopy of a-plane-oriented ZnO epilayers grown by plasma-assisted molecular beam epitaxy

a-plane ZnO layers were successfully grown, by plasma-assisted molecular beam epitaxy, on r-plane (011–2) sapphire substrates. Several features attributed to the A, B and C free excitonic transitions are identified through temperature-dependent photoluminescence (PL) and reflectivity measurements. The temperature dependence of the peak energy positions of these transitions was studied from 8 K to 300 K. So, the PL peak energy of the A free exciton was plotted and fitted with a Varshni empirical equation. In the σ polarization (E⊥c), for which A and B are allowed, the reflectivity spectrum measured at 8 K was fitted by using a program based on the theory of the spatial resonance dispersion Hopfield model. Our results indicate that the A and B free excitonic features are at a higher energy than those in ZnO on c-oriented sapphire and show a good PL even at 250 K. These results also show that the new and intense emission peak observed in the region of the first phonon replica (3.33–3.28 eV) and identified as a stacking fault in the epilayer disappears at high temperature above 150 K.     

Giant optical anisotropy in M-plane GaN/AlGaN quantum wells due to crystal-field effect

The optical polarization of GaN/AlGaN wurtzite quantum wells in various orientations is studied using an arbitrarily-oriented [hkil] Hamiltonian potential matrix. The optical matrix elements in the wurtzite quantum wells are calculated using the k⋅p finite difference scheme. The results reveal the presence of giant in-plane optical anisotropy (polarized normal to [0001]) in the M-plane (i.e., the -oriented layer plane) GaN/Al_0.2Ga_0.8N quantum well, due to the positive crystal-field split energy effect (ΔCR>0). The present theoretical results are consistent with the photoluminescence measurements presented in the literature [B. Rau, et al., Appl. Phys. Lett. 77 (2000) 3343].