GaN is a promising semiconductor of wide band gap of 3.4 eV at room temperature and can be used as a substrate material for blue/green/UV light-emitting diode (LED) and laser diode (LD) [1]. Sapphire has been the most widely used substrate for manufacturing GaN-based LEDs. However, GaN films grown on sapphire substrates include many critical defects owing to the large lattice mismatch (~15%) and large difference of thermal expansion coefficients (~25%) between GaN and sapphire. Thus, GaN substrates are needed for fabrication of the high power LEDs and LDs.

Two typical routes, ammono-basic and ammono-acidic, have been studied in the ammonothermal growth of GaN crystals. Addition of alkali (Li, Na, and K) elements to ammonia typically results in a basic ammonia solution, whereas addition of halogens (F, Cl, Br, and I) to ammonia typically results in an acidic ammonia solution. The acidic ammonothermal method has a fast crystal growth rate but requires installation of Pt liner due to the corrosive environment. Thus, the basic ammonothermal method is regarded as more appropriate for mass production of GaN crystals [2].

Only a few types of basic mineralizer including NaNH₂ [3] and KNH₂ [4] have been used previously for the crystal growth of GaN. The reports of comparison with other sodium-based mineralizers for ammonothermally grown GaN crystals have not to be achieved. Potassium mineralizers were not included in this study because they are more sensitive to oxygen and moisture and corrosive to autoclave compared to sodium mineralizers.

In this study, we demonstrate the growth rate, crystal quality, and surface morphology of the as-grown GaN single crystals according to sodium amide, sodium azide, and sodium metal as mineralizer. Also, we describe the morphology and properties of approximately 2 inch GaN crystals grown by ammonothermal method using sodium metal mineralizer.

Reference

[1] S. Nakamura, G. Fosol, The Blue Laser Diode, Springer, Berlin, 1997, chap. 1.

[2] R. Dwilinski, R. Doradzinski, J. Garczynski, L. P. Sierzputowski, A. Puchalski, Y. Kanbara, K. Yagi, H. Minakuchi, H. Hayashi, J. Cryst. Growth 311 (2009) 3015.

[3] T. Hashimoto, F. Wu, J. S. Speck, S. Nakamura, J. Cryst. Growth 310 (2008) 3907.

[4] R. Dwilinski, R. Doradzinski, J. Garczynski, L. P. Sierzputowski, A. Puchalski, Y. Kanbara, K. Yagi, H. Minakuchi, H. Hayashi, J. Cryst. Growth 310 (2008) 3911.