GaN crystals without cracks were successfully grown on a MOCVD-GaN/6H-SiC (MGS) substrate with a low V/III ratio of 20 at initial growth. With a high V/III ratio of 80 at initial growth, opaque GaN polycrystals were obtained. The structural analysis and optical characterization reveal that stress has a great influence on the growth of the epitaxial films. An atomic level model is used to explain these phenomena during crystal growth. It is found that atomic mobility is retarded by compressive stress and enhanced by tensile stress.
GaN has long been considered a most promising material for applications in short wavelength optoelectronics and high-power high-frequency electronics due to its excellent properties, such as a wide direct bandgap,high thermal stability and high electron velocities1,2,3. Currently, most GaN-based devices like light emitting diodes (LEDs) and laser diodes (LDs) have been commercialized by using hetero-epitaxial growth on sapphire, due to the lack of more compatible cost effective substrates. However, the large lattice mismatch (13.8%) and the large thermal expansion coefficient difference between GaN and sapphire results in a high dislocation density and residual stress, both of which seriously affect the optical and electrical performance of the fabricated devices4. A SiC substrate offers the advantages of small lattice mismatch, similar thermal expansion coefficent to GaN, and higher thermal conductivity. Thus, epitaxial growth of GaN on a SiC substrates is considered to be a very promising approach to solving these problems. The thermal expansion coefficients, lattice constants, and thermal conductivity for GaN, 6H-SiC and sapphire are listed inTable 1.
Lin et al. first reported the growth of 2.5–3.5 μm GaN films on a SiC substrate by molecular beam epitaxy (MBE) with a high electron mobility of 580 cm2/Vs10. The microstructure and defects in GaN films grown on a SiC substrate were also investigated11,12. Nikolaev et al. reported on GaN/6H-SiC p-n heterojunctions fabricated by the HVPE of GaN on p-doped 6H-SiC epitaxial layers grown by low temperature liquid phase epitaxy13. Insulating GaN layers doped with Zn were grown by HVPE on SiC substrates and the temperature dependence of the specific resistivity of the GaN:Zn layers was measured over the temperature range from 200 to 500 K14. H. Lahrèche et al. presented a three-step growth process that enabled them to grow high quality mirror-like GaN layers without using AlN buffer layers by MOCVD15. GaN/4H-SiC heterodiodes were fabricated where the GaN is directly grown by HVPE on off-axis 4H-SiC16. Lee et al. found that H-etching of the SiC substrate was important to eliminate stacking disorder in the GaN grown by MBE, and a high growth temperature reduced the density of screw dislocations in particular17. K. Jeganathan et al. demonstrated the growth of unstrained GaN layers on SiC-6H (0001) substrate by MBE using a double-step AlN buffer process grown at two different high temperatures with a difference of 30–50°C18. Our research group reported that GaN films were grown by HVPE on MOCVD-GaN/Al2O3(MGA) and MOCVD-GaN/6H-SiC (MGS) samples. The strain variations were microscopically identified using Z scan Raman spectroscopy. The Raman peak (E2) shift indicates that the stress increased gradually as a function of increase in measurement depth19. The reported references mainly focused on the microstructures or defects of GaN films on a SiC substrate and the characteristics of GaN/6H-SiC p-n heterojunctions or heterodiodes grown by MBE or MOCVD. However, the influences of growth conditions and stress on GaN crystal growth with a MGS substrate grown by HVPE have not been reported. In this work, different growth conditions were tried for the growth of GaN on MGS substrates. The aim is to study the influence of stress in GaN crystals growth. We believe that this work may be helpful in understanding GaN crystal growth by HVPE on an MGS substrate.
GaN films were grown in a home-made vertical HVPE reactor. A template with a 5 μm GaN layer grown by MOCVD on the 6H-SiC substrates was employed as the starting substrate. Ga and NH3 were used as respective gallium and nitrogen sources. HCl gas was reacted with liquid Ga at 820°C to form GaCl, which was transported to the growth zone of the reactor and reacted with NH3 at 1030°C to form GaN molecules. Nitrogen was used as the carrier gas. The reactor pressure was kept at around atmospheric pressure. In this study, two different growth conditions (A and B, shown in Table 2) were used for the growth of GaN on the MGS substrate.
Two sets of samples were grown under identical conditions on MGA and MGS templates. The growth temperature was 1030°C. The GaN layers on the MGA and MGS templates have the same dislocation density (6 × 108 cm−1). The gas flow rates of NH3 (800 mL/min, 1000 mL/min), HCl (10 mL/min, 20 mL/min), NH3 carrier gas (1000 mL/min), HCl carrier gas (1000 mL/min) and N2 (2000 mL/min) for growth condition A on MGA and MGS templates were the same. The gas flow rates of NH3 (400 mL/min, 1000 mL/min), HCl (20 mL/min, 20 mL/min, NH3 carrier gas (1000 mL/min), HCl carrier gas (1000 mL/min) and N2 (2000 mL/min) for growth condition B on MGA and MGS templates were the same. The heating rate and cooling rates were also the same. The surface morphology and structural quality of the as-grown GaN films were investigated by a variety of characterization techniques. AFM (Digital Instrument Dimension 3100) and FE-SEM (Hitachi S-4800) were used to investigate the surface morphology. Raman spectra of the samples were obtained by the LabRAM HR system of Horiba Jobin Yvon at room temperature using a 532 nm solid state laser as the excitation source. Photoluminescence (PL) measurements were carried out at room temperature using a 325 nm He–Cd laser as the excitation source. All samples were evaluated by high-resolution X-ray diffraction (HRXRD). The lattice parameters were determined by measuring the (002), (004) and (102), (204) peaks in a multi-diffraction ω-2θ scan.
Results and Discussion
Fig. 1 shows photographs of the GaN films grown on the MGS substrate under (a) condition A (high V/III ratio 80 at initial growth) and (b) condition B (low V/III ratio 20 at initial growth). Under growth condition A, (Fig. 1a) the surface is black and many small polycrystalline grains are observed. As shown in Fig. 1b, a 40 μm thick GaN layer with a mirror-like smooth surface was obtained on the MGS substrate under growth condition B.