Method and Apparatus for Producing Group-13-Element Nitride Crystals

Abstract

A crystal growth apparatus includes a pressure-resistant vessel; a plurality of support tables arranged inside the pressure-resistant vessel; inner vessels each placed over the support tables, respectively; growth vessels contained the inner vessels, respectively; a heating means for heating the growth vessels; and a central rotating shaft connected to the support tables. The central rotating shaft is distant from central axes of the inner vessels, respectively. A seed crystal, a raw material of the Group 13 element and a flux are charged in each of the growth vessels, and the growth vessels are heated to form a melt and a nitrogen-containing gas is supplied to the melt to grow a crystal of a nitride of said Group 13 element while the central rotating shaft is rotated.

Claims

1. A crystal growth apparatus comprising: a pressure-resistant vessel; a plurality of support tables arranged inside said pressure-resistant vessel; inner vessels placed over said support tables, respectively; growth vessels contained in said inner vessels, respectively; a heating means for heating said growth vessels; and a central rotating shaft connected to said support tables, said central rotating shaft being distant from central axes of said inner vessels, respectively, wherein a seed crystal, a raw material of a Group 13 element and a flux are charged in each of said growth vessels, and wherein said growth vessels are heated to form a melt and a nitrogen-containing gas is supplied to said melt to grow a crystal of a nitride of said Group 13 element while said central rotating shaft is rotated.

2. The apparatus of claim 1, further comprising revolving shafts attached to said support tables, respectively, and wherein said revolving shafts are revolved while said crystal of said nitride of said Group 13 element is grown.

3. The apparatus of claim 2, wherein distances between said revolving shafts and said central rotating shaft are equal to one another.

4. The apparatus of claim 1, wherein said central axes of said inner vessels are arranged at positions which are point symmetrical with respect to said central rotating shaft.

5. The apparatus of claim 1, wherein a number of said inner vessels is two or more.

6. The apparatus of claim 1 further comprising a heating vessel provided with said heating means, said heating vessel being arranged inside said pressure-resistant vessel and containing said inner vessels.

7. A crystal growth method of growing a crystal of a nitride of a Group 13 element, said method using a crystal growth apparatus, said crystal growth apparatus comprising: a pressure-resistant vessel; a plurality of support tables arranged inside said pressure-resistant vessel; inner vessels placed over said support tables, respectively; growth vessels contained in said inner vessels, respectively; a heating means for heating said growth vessels; and a central rotating shaft connected to said support tables, said central rotating shaft being distant from central axes of said inner vessels, respectively, the method comprising the steps of charging a seed crystal, a raw material of said Group 13 element and a flux in each of said growth vessels; and heating said growth vessels to form a melt and supplying a nitrogen-containing gas to said melt to grow said crystal of said nitride of said Group 13 element while said central rotating shaft is rotated.

8. The method of claim 7, wherein said apparatus further comprising revolving shafts attached to said support tables, respectively, and wherein said revolving shafts are revolved while said crystal of said nitride of said Group 13 element is grown.

9. The method of claim 8, wherein distances between said revolving shafts and said central rotating shaft are equal to one another.

10. The method of claim 7, wherein said central axes of said inner vessels are arranged at positions which are point symmetrical with respect to said central rotating shaft.

11. The method of claim 7, wherein a number of said inner vessels is two or more.

12. The method of claim 7, wherein said apparatus further comprises a heating vessel provided with said heating means, said heating vessel being arranged inside said pressure-resistant vessel and containing said inner vessels.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0020] FIG. 1 is a schematic view illustrating a crystal growth apparatus according to an embodiment of the present invention.

[0021] FIG. 2 is a schematic view illustrating growth vessels, inner vessels, support tables, and a rotation mechanism.

[0022] FIG. 3 is a schematic view illustrating a positional relationship among a pressure-resistant vessel, a heating vessel, inner vessels, a central rotating shaft, and rotational axes, when two inner vessels are provided.

[0023] FIG. 4 is a schematic view illustrating a positional relationship among the pressure-resistant vessel, the heating vessel, the inner vessels, the central rotating shaft, and the rotational axes, when three inner vessels are provided.

EMBODIMENTS OF THE INVENTION

[0024] As shown in FIG.1, in a crystal growth apparatus according to an embodiment of the present invention, a heating vessel 7 is housed in an internal space G of a pressure-resistant vessel 9. The pressure-resistant vessel 9 is formed, for example, in a cylindrical shape having disc-shaped upper and lower surfaces. The heating vessel 7 comprises a heat insulating material 7b, a cover 7c that covers an external side of the heat insulating material, and a cover 7a that covers an internal side of the heat insulating material. Heaters 24 are arranged in a plurality of stages, for example, three stages, on a sidewall of the heating vessel 7, thereby enabling to control a temperature distribution in an internal space F of the heating vessel 7.

[0025] Further, the pressure-resistant vessel 9 is connected to a nitrogen gas pipe 20 from a nitrogen gas cylinder 21 as well as a vacuum suction pipe 11 from a vacuum pump 12. The nitrogen gas pipe 20 penetrates through the pressure-resistant vessel 9 and the heating vessel 7 and is opened to the internal space F of the heating vessel. The nitrogen gas pipe 20 is branched on its way and also opened to a space G between the pressure-resistant vessel 9 and the heating vessel. The heating vessel 7 is not completely sealed, however nitrogen gas is supplied to both an outside space and an inside space of the heating vessel in order to prevent a large pressure difference between the inside and the outside of the heating vessel. A branch pipe of the nitrogen gas pipe 20 leading to the internal space F of the heating vessel 7 is equipped with a mass flow controller 19 capable of adjusting a flow rate.

[0026] The vacuum suction pipe 11 penetrates through the pressure-resistant vessel 9 and is opened to a space between the pressure-resistant vessel 9 and the heating vessel 7.

[0027] As mainly shown in FIG. 2, the apparatus has, for example, two inner vessels 1A and 1B each placing growth vessels 2. The number of the growth vessels housed in each inner vessel is not limited, however a plurality of the growth vessels are preferably housed in each inner vessel from the standpoint of productivity. Each growth vessel 2 comprises a body 2b and a lid 2a. During the growth of crystals, a melt 3 is formed in each growth vessel 2 and seed crystals 4 is immersed in the melt 3.

[0028] Inlet ports 5 of a nitrogen-containing gas are provided to the inner vessels 1A and 1B, respectively. Further, each of cradles 10 arranged under each inner vessel is supported by one of support tables 13 and revolving shafts 14. The revolving shafts 14 are each attached to a supporting structure 15 so as to be rotatable in directions of arrows A and B. Further, as shown in FIG. 1, each of the revolving shafts 14 penetrates through the heating vessel 7, and the supporting structure 15 is arranged between the heating vessel and the pressure-resistant vessel 9.

[0029] Further, the whole supporting structure 15 is attached to a central rotating shaft 16. The central rotating shaft is provided with an internal magnet 17. Further, a driving magnet 18 is provided outside the internal magnet 17, allowing each of the support tables 13 to rotate in directions of an arrow D.

[0030] During the growth of crystals, each growth vessel is supplied with the seed crystals 4 and materials of the melt 3. The materials of the melt 3 include a raw material of a Group 13 element, a flux, and optionally an additive and a trace substance.

[0031] The Group 13 element refers to a Group 13 element in the periodic table determined by IUPAC. Specific examples of the Group 13 element include gallium, aluminum, indium, thallium and the like. As a nitride of the Group 13 element, gallium nitride, aluminum nitride, and gallium aluminum nitride are particularly preferable. Further, examples of the additive include carbon, a metal having a low melting point (tin, bismuth, silver, and gold), and a metal having a high melting point (a transition metal such as iron, manganese, titanium, and chromium).

[0032] The seed crystals may constitute a self-standing body of the seed crystal or may be a seed crystal film formed on a supporting body.

[0033] When the seed crystal film is formed on the supporting body, although a single crystal substrate formed on the supporting body is not limited, examples thereof include sapphire, an AlN template, a GaN template, a GaN self-standing body, a silicon single crystal, a SiC single crystal, an MgO single crystal, spinel (MgAl.sub.2O.sub.4), LiAlO.sub.2, LiGaO.sub.2, a perovskite-type composite oxide, such as LaAO.sub.3, LaGaO.sub.3, and NdGaO.sub.3, and SCAM (ScAlMgO.sub.4). Also, it is possible to use a perovskite-type mixed oxide of a cubic crystal system represented by a composition formula [A.sub.1-y(Sr.sub.1-xBa.sub.x).sub.7] [(Al.sub.1-zGa.sub.z).sub.1-y.D]O.sub.3 (where A is a rare-earth element; D is one or more elements selected from the group consisting of niobium and tantalum; y=0.3 to 0.98; x=0 to 1; z=0 to 1; u=0.15 to 0.49; and x+z=0.1 to 2).

[0034] Although a production method of the seed crystals are not particularly limited, examples thereof include a vapor phase method such as a metal organic chemical vapor deposition (MOCVD) method, a hydride vapor phase epitaxy (HYPE) method, a pulse excited deposition (PXD) method, an MBE method, and a sublimation method, and a liquid phase method such as a flux method.

[0035] In a preferred embodiment, the Group 13 element nitride can be grown by the flux method. In this method, a type of a flux is not particularly limited as long as it can generate the Group 13 element nitride. In a preferred embodiment, a flux containing at least one of an alkali metal and an alkaline earth metal is used, and a flux containing sodium metal is particularly preferable.

[0036] As a raw material of the Group 13 element, simple metal, an alloy, or a metal compound may be used, although the simple metal of the Group 13 element is preferable from the standpoint of handling

[0037] A ratio (molar ratio) of the Group 13 element/flux (e.g., sodium) in the melt is preferably high from the viewpoint of the present invention, and it is preferably 13 mol % or more, further preferably 18 mol % or more. However, when this ratio becomes too high, the crystal quality tends to be deteriorated. Thus, the ratio is preferably 40 mol % or less.

[0038] After the materials to be melted are supplied in the growth vessels, the growth vessels are put in the inner vessels, respectively. The inner vessels are then placed over the support tables 13, respectively. Next, the pressure-resistant vessel 9 is turned into vacuum state by driving the vacuum pump 12, and the nitrogen-containing gas is supplied into the pressure-resistant vessel 9 and the heating vessel 7 via the pipe 20 from the nitrogen gas-containing cylinder 21 to pressurize the insides of the pressure-resistant vessel 9 and the heating vessel 7. Then, under the pressurized atmosphere, the heating space F is heated at a prescribed temperature to form the melt. The nitrogen-containing gas is released into the internal space of the heating vessel from discharge ports 22 of the pipe 20, taken into the inner vessels from the inlet ports 5 attached to the inner vessels, and then supplied into the respective growth vessels.

[0039] In the present example, the central rotating shaft 16 is rotated as the arrow D, as shown in FIG. 1 and FIG. 3, at least during the growth of crystals. As a result, the supporting structure 15 rotates according to the rotation of the central rotating shaft 16, and the support tables 1A and 1B rotate around the central rotating shaft 16 as the arrow D. During this operation, central axes CA and CB of the inner vessels 1A and 1B are distant from the central rotating shaft 16, thus the inner vessels are configured to revolve around the central rotating shaft. As a result, the flow of the melt can be made uniform in the respective growth vessels present inside the inner vessels.

[0040] Further, in the present embodiment, the revolving shafts 14 are rotated as arrows A and B, respectively. As a result, the support tables 13 and the inner vessels 1A and 1B placed thereon are also revolved as the arrows A and B, respectively. In this manner, the inner vessels are configured to further rotate, which can additionally promote the stirring of the melt in the respective growth vessels and facilitate the growth of the nitride crystals.

[0041] Further, in the example shown in FIG. 4, three support tables 13 are provided and the inner vessels 1A, 1B, and 1C are each placed over one of the support tables 13. Then, the central rotating shaft 16 is rotated as the arrow D at least during the growth of crystals. As a result, the supporting structure 15 revolves according to the rotation of the central rotating shaft 16, and the support tables 1A, 1B, and 1C each rotate around the central rotating shaft 16 as the arrow D. During this operation, central axes of the inner vessels 1A, 1B and 1C are distant from the central rotating shaft 16, thus the inner vessels are configured to revolve around the central rotating shaft. As a result, the flow of the melt is made uniform in the respective growth vessels present inside the inner vessels.

[0042] Further, in the present embodiment, the revolving shafts 14 are rotated as arrows A, B, and C, respectively. As a result, the support tables 13 and the inner vessels 1A, 1B, and 1C placed thereon are also revolved as the arrows A, B, and C, respectively. In this manner, the inner vessels are configured to further revolve, which can additionally promote the stirring of the melt in the respective growth vessels and facilitate the growth of the nitride crystals.

[0043] In the present invention, the central rotating shaft and each rotating shaft can be independently and individually controlled. Further, the central rotating shaft and each rotating shaft can be rotated in the following manners.

[0044] (1) Rotated at constant speed.

[0045] (2) Changed in rotational speed.

[0046] (3) Reversed in rotational direction.

[0047] (4) After stopping rotation, resume rotation, in other words, rotated intermittently.

[0048] (5) Performing combination of (1) to (4) above.

[0049] The number of the support tables arranged inside the pressure-resistant vessel is not limited, but it is preferably two or more. Further, an upper limit of the number of the support tables is not particularly limited, but it is preferably eight or less.

[0050] The present invention comprises the central rotating shaft 16 connected to a plurality of the support tables, the central rotating shaft 16 being distant from the central axes CA, CB, and CC of the inner vessels. Distances between the central rotating shaft and the central axes of the inner vessels are preferably 30 mm or more from the viewpoint of making the flow of the melt uniform in each inner vessel. Further, an upper limit of the distances between the central rotating shaft and the central axes of the inner vessels is not particularly limited and varies depending on the device scale.

[0051] Further, the distances between the central rotating shaft and the central axes of the inner vessels are preferably close to one another from the viewpoint of making the growth of the crystals uniform among the melt. Regarding this, a difference between a maximum value and a minimum value of the distances between the central rotating shaft and the central axes of the inner vessels is preferably 20 mm or less. It is particularly preferred that the distances between the central rotating shaft and the central axes of the inner vessels are equal to one another.

[0052] In a preferred embodiment, the central axes of the plurality of the inner vessels are arranged at positions having point symmetrical with respect to the central rotating shaft.

[0053] Further, in a preferred embodiment, for example, as shown in FIG. 1, the apparatus comprises the heating vessel 7 provided with the heating means 24. Such a heating vessel 7 is arranged inside the pressure-resistant vessel 9 and houses the plurality of the inner vessels.