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It was revealed that the metastable region, in which liquid phase epitaxy (LPE) of GaN single crystals proceeds without the generation of polycrystals, expands with growth temperature in the Na flux method. The metastable region appears when LPE growth proceeds at temperatures above 1073 K, although generation of polycrystals inevitably occurs on a crucible at temperatures less than 1073 K. The highest growth rate of 14 μm/h in a small experimental setup was achieved at a temperature of 1163 K with a nitrogen pressure of 5.5 MPa due to complete suppression of the growth of polycrystals on a crucible, even though the supersaturation at this condition reached a fairly high level. Also, an LPE crystal with a flat surface could easily be obtained under high-temperature conditions.

We found that a carbon additive could suppress the unfavorable generation of polycrystals in a crucible without reduction in the yield of GaN in the Na flux method. The suppression of polycrystals due to the effect of carbon significantly increased the growth rate of liquid phase epitaxy (LPE), which has been the biggest problem of the Na flux LPE, and enabled an increase in the growth rate above 20 μm/h. A 3 mm-thick 2 in GaN crystal was obtained for the first time. In addition, the carbon additive was found to have another effect in that the nonpolar face could be widely developed. SIMS measurements revealed that carbon added into a Ga–Na mixed melt was hardly taken into LPE crystals, although carbon did have some favorable effects.

The effect of the addition of Li or Ca to Ga–Na melt on the promotion of nitrogen dissolution was examined quantitatively in the growth of GaN single crystals using the sodium flux method. The addition of Li or Ca to Ga–Na melt increased both the solubility of solid GaN and that of gaseous nitrogen against the solution. The increase in the solubility of gaseous nitrogen seems to be caused by additives having a high binding energy with nitrogen. We measured the solubility of GaN and that of gaseous nitrogen against Ga–Na, Ga–Na–Li and Ga–Na–Ca melt in this study. On the basis of these data, we clarified the relationship between the N/Ga ratio in the solution and the coloration of GaN crystals grown in each system, and between changes in the yield of GaN and the absolute value of supersaturation.

The dependency of LPE growth rate and dislocation density on supersaturation in the growth of GaN single crystals in the Na flux was investigated. When the growth rate was low during the growth of GaN at a small value of supersaturation, the dislocation density was much lower compared with that of a substrate grown by the Metal Organic Chemical Vapor Deposition method (MOCVD). In contrast, when the growth rate of GaN was high at a large value of supersaturation, the crystal was hopper including a large number of dislocations. The relationship between the growth conditions and the crystal color in GaN single crystals grown in Na flux was also investigated. When at 800 °C the nitrogen concentration in Na–Ga melt was low, the grown crystals were always tinted black. When the nitrogen concentration at 850 °C was high, transparent crystals could be grown.

We investigated the threshold pressure necessary for heterogeneous nucleation of GaN using pure nitrogen gas and nitrogen gas mixed with ammonia in the Na-flux method. In our investigation, we found the appropriate pressure region for nucleating GaN and growing GaN seed crystals without additional heterogeneous nucleation. This study revealed that the threshold pressure to nucleate GaN decreases as the ratio of ammonia increases. We also succeeded in reducing the nucleation threshold pressure from 30 to 10 atm by using nitrogen gas with 25–40% ammonia gas instead of pure nitrogen gas. We confirmed that seed growth without additional nucleation is possible in both pure nitrogen and nitrogen gas mixed with ammonia at pressures below those required for nucleation.