Apparatus for obtaining a bulk single crystal using supercritical ammonia

• US 7,335,262 B2
• Filed: 12/11/2002
• Issued: 02/26/2008
• Est. Priority Date: 05/17/2002
• Status: Expired due to Term

• Current Assignee: Ammono Sp. Z O.O., Nichia Corporation
• Original Assignee: Ammono Sp. Z O.O., Nichia Corporation
• Inventors: Kanbara, Yasuo, Doradzinski, Roman, Garczynski, Jerzy, Dwilinski, Robert, Sierzputowski, Leszek P.
• Primary Examiner(s): Hiteshew; Felisa
• Application Number:
  US10/514,639
• Publication Number:
  US 20060191472A1
• Time in Patent Office: 1,903 Days
• Field of Search: 422/245.1, 117/200, 117/205, 117/206
• US Class Current: 117/206
• CPC Class Codes: C30B 29/406 Gallium nitride
• CPC Class Codes: C30B 7/00 Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions from molten solvents C30B9/00; by normal or gradient freezing C30B11/00; under a protective fluid C30B27/00
• CPC Class Codes: C30B 7/08 by cooling of the solution
• CPC Class Codes: C30B 7/10 by application of pressure, e.g. hydrothermal processes
• CPC Class Codes: Y10T 117/10 Apparatus
• CPC Class Codes: Y10T 117/102 for forming a platelet shape or a small diameter, elongate, generally cylindrical shape [e.g., whisker, fiber, needle, filament]
• CPC Class Codes: Y10T 117/1024 for crystallization from liquid or supercritical state

Abstract

An apparatus includes an autoclave for preparing a supercritical solvent, a convection controller for establishing a convection flow, a dissolution zone where a feedstock is located above the convection controller and a crystallization zone where a seed is located below the convection controller are formed. A convection flow rate of the supercritical solution between the dissolution zone and the crystallization zone is determined by the degree of opening of the convection controller and the temperature difference between the dissolution zone and the crystallization zone. Accordingly, the supercritical solution, in which the nitride has a negative temperature coefficient of solubility, is supplied from the dissolution zone to the crystallization zone in which a seed is located through the convection controller so that nitride crystal is selectively grown on the seed by maintaining supersaturation of the supercritical solution with respect to the seed at a raised temperature.

Claims

1. An apparatus for obtaining a bulk single crystal comprising an autoclave for preparing a supercritical solvent equipped with a convection control means for establishing a convection flow, and mounted inside a furnace unit equipped with a heating device and a cooling device,

wherein the furnace unit is controlled to obtain a temperature gradient within said autoclave by said heating device and/or cooling device,

wherein the convection control means comprises at least one horizontal baffle having a central opening and/or a space between the baffle and an inner wall of the autoclave, and separating the dissolution zone where a feedstock is located above said baffle from said crystallization zone where a seed is located below said baffle,

wherein nitride is dissolved in the supercritical solvent containing ammonia and at least alkali metal ions to make the supercritical solution, in which the nitride has a negative temperature coefficient of solubility and the supercritical solution is supplied from said dissolution zone to said crystallization zone in which a seed is located through said convection control means so that nitride crystal is grown on the seed arranged in the autoclave,

wherein a lining of metal such as Ag, Mo, Fe or Ta, or alloy thereof is applied to an inner wall of the autoclave.

2. The apparatus for obtaining a bulk single crystal according to claim 1, wherein the cooling device is placed so as to cool an area where said convection control means is located, thereby to provide the temperature difference between said dissolution zone and said crystallization zone.

3. The apparatus for obtaining a bulk single crystal according to claim 1, wherein the cooling device which can cool the bottom of the flowing area of said crystallization zone is placed in the autoclave and thereby rapid cooling function is operated after crystallization.

4. The autoclave according to claim 1, wherein said convection control means is located within the range from ⅓

to ⅔

of the total length of the inner autoclave in a longitudinal direction, to thereby adjust the ratio between said dissolution zone and said crystallization zone to a desirable value.

5. The autoclave according to claim 1, wherein the ratio of a diameter of the autoclave in a direction perpendicular to a longitudinal direction relative to a total length of the autoclave is set from 1/15 to 7/15, the ratio of opening in said horizontal baffle on the cross-sectional area is set at 30% or less and a growth rate on a seed is 10 μ

m/hr or more.

6. The autoclave for obtaining a bulk single crystal according to claim 1, wherein a convection flow rate of the supercritical solution between said dissolution zone and said crystallization zone is determined by a degree of opening of said convection control means and a temperature difference between said dissolution zone and said crystallization zone.

7. An apparatus for obtaining a bulk single crystal comprising an autoclave for preparing a supercritical solvent equipped with a convection control means for establishing a convection flow, and mounted inside a furnace unit equipped with a heating device and a cooling device,

wherein the furnace unit is controlled to obtain a temperature gradient within said autoclave by said heating device and/or cooling device,

wherein the convection control means comprises at least one horizontal baffle having a central opening and/or a space between the baffle and an inner wall of the autoclave, and separating the dissolution zone where a feedstock is located above said baffle from said crystallization zone where a seed is located below said baffle,

wherein nitride is dissolved in the supercritical solvent containing ammonia and at least alkali metal ions to make the supercritical solution, in which the nitride has a negative temperature coefficient of solubility and the supercritical solution is supplied from said dissolution zone to said crystallization zone in which a seed is located through said convection control means so that nitride crystal is grown on the seed arranged in the autoclave,

wherein the feedstock made of gallium metal is placed in said dissolution zone and the filling ratio of the feedstock is less than half of said dissolution zone.

8. The autoclave for obtaining a bulk single crystal according to claim 7, wherein a convection flow rate of the supercritical solution between said dissolution zone and said crystallization zone is determined by a degree of opening of said convection control means and a temperature difference between said dissolution zone and said crystallization zone.