Gallium nitride crystal growth method, gallium nitride crystal substrate, epi-wafer manufacturing method, and epi-wafer
Affords gallium nitride crystal growth methods, gallium nitride crystal substrates, epi-wafers, and methods of manufacturing the epi-wafers, that make it possible to curb cracking that occurs during thickness reduction operations on the crystal, and to grow gallium nitride crystal having considerable thickness. A gallium nitride crystal growth method in one aspect of the present invention is a method of employing a carrier gas, a gallium nitride precursor, and a gas containing silicon as a dopant, and by hydride vapor phase epitaxy (HVPE) growing gallium nitride crystal onto an undersubstrate. The gallium nitride crystal growth method is characterized in that the carrier-gas dew point during the gallium nitride crystal growth is −60° C. or less.
1. A method of growing silicon-doped gallium nitride crystal by HVPE, the growth method comprising:
(a) preparing carrier gasses for carrying gallium nitride precursors;
(b) preparing a gas containing silicon as a dopant;
(c) purifying the prepared carrier gasses so that the carrier gasses have a dew point of not greater than −60° C.;
(d) preparing a gallium source and an undersubstrate suitable for gallium nitride growth and placing the gallium source and the undersubstrate within an HVPE reactor;
(e) supplying the gallium nitride precursors via the carrier gasses, at a predetermined total partial pressure, into the HVPE reactor and thereby to the gallium source, supplying the doping gas into the HVPE reactor, and heating the HVPE reactor interior to vapor-phase epitaxially grow gallium nitride crystal onto the undersubstrate;
(f) growing the gallium nitride crystal to a thickness of at least 200 μm; and
(g) repeating (a) through (f) a plurality of times to yield a production run of silicon-doped gallium nitride crystals, wherein
said total partial pressure of the carrier gasses is predetermined together with said carrier-gas dew point in such a way as to impart to the grown gallium nitride crystal a silicon dopant concentration of not less than 2.2×10 18 cm −3 correlating to a cracking frequency of not greater than 7% in the production run, given that an occurrence of cracking is taken to be 30 or more crack lines of 100 μm or greater length appearing over the entirety of a 45.8 mm-diameter area of each of the crystals grown in the production run.
2. A gallium nitride crystal growth method as set forth in claim 1 , wherein the partial pressure of the carrier gas during the gallium nitride crystal growth in (e) is between 0.56 atm and 0.92 atm inclusive.
3. An epi-wafer manufacturing method, comprising:
the gallium nitride crystal growth method as set forth in claim 1 ;
a step of removing at least the undersubstrate to form a substrate composed of gallium nitride crystal and therein having a silicon dopant concentration of not less than 2.2×10 18 cm −3 and a thickness of at least 200 μm;
a step of forming an epitaxially grown layer onto said substrate; and
a step of processing for thickness reduction a surface of the substrate on the side opposite from that surface of the substrate onto which the epitaxially grown layer is formed.
4. An epi-wafer comprising:
a substrate of the production run in (q) of the gallium nitride crystal growth method set forth in claim 1 ; and
an epitaxially grown layer formed onto said substrate;
the epi-wafer characterized in being mechanically thickness-reduced to a thickness of 100 μm.
5. A method of growing silicon-doped gallium nitride crystal by HVPE, the growth method comprising:
(a) preparing carrier gasses for carrying gallium nitride precursors and for carrying a doping gas;
(b) preparing as the doping gas a gas containing dopant silicon;
(c) passing the prepared carrier gasses across a molecular film to purify them so that the carrier gasses have a dew point of not greater than −60° C.;
(d) preparing a gallium source and an undersubstrate suitable for gallium nitride growth and placing the gallium source and the undersubstrate within an HVPE reactor;
(e) via the carrier gasses supplying, at a predetermined total partial pressure, the gallium nitride precursors into the HVPE reactor, and thereby to the gallium source, and supplying the doping gas into the HVPE reactor, and heating the HVPE reactor interior to vapor-phase epitaxially grow gallium nitride crystal onto the undersubstrate;
(f) growing the gallium nitride crystal to a thickness of at least 200 μm; and
(g) repeating (a) through (f) a plurality of times to yield a production run of silicon-doped gallium nitride crystals, wherein
said total partial pressure of the carrier gasses is predetermined together with said carrier-gas dew point in such a way as to impart to the grown gallium nitride crystal a silicon dopant concentration of not less than 2.2×10 18 cm −3 correlating to a cracking frequency of not greater than 7% in the production run, given that an occurrence of cracking is taken to be 30 or more crack lines of 100 μm or greater length appearing over the entirety of a 45.8 mm-diameter area of each of the crystals grown in the production run.
6. A gallium nitride crystal growth method as set forth in claim 5 , wherein the partial pressure of the carrier gas during the gallium nitride crystal growth in (e) is between 0.56 atm and 0.92 atm inclusive.
7. A silicon-doped gallium nitride crystal substrate of the gallium nitride crystal growth method set forth in claim 3 , wherein the gallium nitride crystal has a thickness of at least 4 mm.
8. An epi-wafer manufacturing method as set forth in claim 3 , wherein the crystal is grown onto the undersubstrate to a thickness of at least 4 mm.