Akira Kitamoto

Fabrication of low-curvature 2 in. GaN wafers by Na-flux coalescence growth technique

Low-curvature and large-diameter GaN wafers are in high demand for the development of GaN-based electronic devices. Recently, we have proposed the coalescence growth of GaN by the Na-flux method and demonstrated the possibility of enlarging the diameter of high-quality GaN crystals. In the present study, 2 in. GaN wafers with a radius of curvature larger than 100 m were successfully produced by the Na-flux coalescence growth technique. FWHMs of the 002 and 102 GaN X-ray rocking curves were below 30.6 arcsec, and the dislocation density was less than the order of 102 cm−2 for the entire area of the wafer.

Effects of Solution Stirring on the Growth of Bulk GaN Single Crystals by Na Flux Method

Recently, we succeeded in fabricating centimeter-sized bulk gallium nitride (GaN) crystals with large dislocation-free areas on a GaN point seed. However, problems of polycrystal formation, skeletal growth, and low growth rate still remained. In this study, to suppress skeletal growth, polycrystals formation and increase the growth rate, we introduced two types of solution-stirring techniques – rotating stirring and swinging stirring – in the growth on point seeds by the Na flux method. We found that increasing the reversal frequency of the rotating stirring and increasing the rate of the swinging stirring increased the growth rate and suppressed the formation of polycrystals and skeletal growth. Moreover, the maximum c-direction growth rate of 46 µm/h was achieved without the formation of polycrystals and skeletal growth. We conclude that solution stirring may be an effective technique for fabricating high-quality large bulk GaN crystals.

High Temperature Growth of Non-polar a-Plane GaN Film Grown Using Gallium-Oxide as Ga Source

In this study, we reported a decrease of oxygen concentration and an increase in the growth rate of a-plane gallium nitride (a-GaN) film grown using Ga2O gas and NH3 gas. The oxygen concentration in a-GaN film was decreased with increasing partial pressure of NH3 and growth temperature. An a-GaN film with the lowest oxygen concentration of 4 ×1018 atoms/cm3 and the growth rate of 18 µm/h was obtained under NH3 partial pressure of 84 kPa at 1250 °C. We concluded that growth under high partial pressure of NH3 at high temperature can produce a-plane GaN film with a high growth rate and low oxygen concentration.

The Effects of Substrate Surface Treatments on Growth of a-Plane GaN Single Crystals Using Na Flux Method

Nonpolar GaN substrates are necessary for the improvement of GaN device performance. The growth of high-quality nonpolar GaN crystals, however, has not yet been achieved. In this study, we grew a-plane GaN crystals using the Na flux method and investigated the effects of the substrate surface treatment on the crystallinity of grown GaN crystals. A-plane GaN substrates with chemical mechanical polishing (CMP) and with chemical etching using pyrophosphoric acid were used as the seed substrates. We found that full width at the half-maximum (FWHM) of the X-ray rocking curve (XRC) of GaN crystals grown on the substrate with chemical etching was smaller than that on the substrate with CMP. The results show that chemical etching is more effective than CMP for improving the crystallinity of a-plane GaN crystals.

Growth of GaN layers using Ga2O vapor obtained from Ga and H2O vapor

In this study, we performed growth of GaN layers using Ga2O vapor synthesized from Ga and H2O vapor. In this process, we employed H2O vapor instead of HCl gas in hydride vapor phase epitaxy (HVPE) to synthesize Ga source gas. In the synthesis reaction of Ga2O, a Ga2O3 whisker formed and covered Ga, which impeded the synthesis reaction of Ga2O. The formation of the Ga2O3 whisker was suppressed in H2 ambient at high temperatures. Then, we adopted this process to supply a group III precursor and obtained an epitaxial layer. X-ray diffraction (XRD) measurement revealed that the epitaxial layer was single-crystalline GaN. Growth rate increased linearly with Ga2O partial pressure and reached 104 µm/h.

The Effects of Ba-Additive on Growth of a-Plane GaN Single Crystals Using Na Flux Method

Large-area nonpolar GaN substrates with high crystallinity are necessary to improve the performance of GaN devices. Nonpolar GaN substrates of 2-in. diameter have been commercially fabricated by growing along the nonpolar direction on heterogeneous substrates. However, the crystallinity of the nonpolar GaN substrates requires improvement. Here, we grew a-plane GaN crystals using the Na flux method and investigated the effects of a Ba-additive on surface morphology and crystallinity. We found that the crystallinity of the crystals grown by the Na flux method was greatly improved compared with that of seed substrates. Moreover, the use of the Ba-additive suppressed the formation of voids that occurred during the Na flux growth without the Ba-additive. As a result, a-plane GaN crystals with high crystallinity were produced using the Na flux method with the Ba-additive.

Dependence of polarity inversion on V/III ratio in −c-GaN growth by oxide vapor phase epitaxy

One of the issues in bulk c-GaN growth is the decrease in the diameter of crystals with an increase in thickness owing to the appearance of inclined and facets. In this study, we performed −c-GaN growth by oxide vapor phase epitaxy (OVPE). As a result, truncated-inverted-pyramidal crystals were successfully grown on dot-patterned −c-GaN substrates. The diameter of the top surface of crystals was larger than that of windows. We further investigated the dependence of the ratio of inversion-domain area to growth area (R ID) on growth temperature, V/III ratio, and growth rate. The remained results revealed that R ID decreased with increasing growth temperature and V/III ratio, and kept constant for growth rate. Additionally, an epitaxial layer on −c-GaN substrates with a growth rate of 12.4 µm/h and an R ID as low as 3.8% was obtained under an NH3 partial pressure (P NH3) of 83 kPa at 1200 °C.

Improvement of crystallinity of GaN layers grown using Ga2O vapor synthesized from liquid Ga and H2O vapor

Growth methods using Ga2O vapor allow long-term growth of bulk GaN crystals. Ga2O vapor is generated by the reduction of Ga2O3 powder with H2 gas (Ga2O3–H2 process) or by the oxidation of liquid Ga with H2O vapor (Ga–H2O process). We investigated the dependence of the properties of grown GaN layers on the synthesis of Ga2O. In the Ga–H2O process, the polycrystal density and full width at half maximum (FWHM) GaN(0002) X-ray rocking curves (XRC) at a high growth rate were lower than those in the Ga2O3–H2 process, and a GaN layer with FWHM of 99 arcsec and growth rate of 216 µm/h was obtained. A low H2O partial pressure in the growth zone improved crystallinity in the Ga–H2O process, realized by the high efficiency of conversion from liquid Ga to Ga2O vapor. We concluded that using Ga2O vapor in the Ga–H2O process has the potential for obtaining higher crystallinity with high growth rate.

Homoepitaxial growth of a-plane GaN layers by reaction between Ga2O vapor and NH3 gas

Growth of high-quality a-plane GaN layers was performed by reaction between Ga2O vapor and NH3 gas at a high temperature. Smooth a-plane GaN epitaxial layers were obtained on a-plane GaN seed substrates sliced from thick c-plane GaN crystals. Growth rate increased with increasing Ga2O partial pressure. An a-plane GaN layer with a growth rate of 48 µm/h was obtained. The X-ray rocking curve (XRC) measurement showed that the full widths at half maximum (FWHMs) of GaN with the incident beam parallel and perpendicular to the [0001] direction were 29–43 and 29–42 arcsec, respectively. Secondary ion mass spectrometry (SIMS) measurement revealed that oxygen concentration decreased at a high temperature. These results suggest that growth of a-GaN layers using Ga2O vapor and NH3 gas at a high temperature enables the generation of high-quality crystals.

Control of the Growth Habit in the Na Flux Growth of GaN Single Crystals

Seeded growth of gallium nitride (GaN) crystals on a spontaneously nucleated small GaN by the Na flux method was performed. In this study, we attempted to control the growth habit by changing the flux composition (Ga/Na) and by introducing a small amount of additives (Ca and Li). Our experiment clarified that a low Ga composition was preferred to grow high-crystallinity prismatic GaN crystals with a high growth rate. Furthermore, the transparent GaN single crystals with prism shape could be grown by the addition of Ca and Li.