JP6827330B2 - Method for manufacturing group III nitride substrate - Google Patents
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- JP6827330B2 JP6827330B2 JP2017008188A JP2017008188A JP6827330B2 JP 6827330 B2 JP6827330 B2 JP 6827330B2 JP 2017008188 A JP2017008188 A JP 2017008188A JP 2017008188 A JP2017008188 A JP 2017008188A JP 6827330 B2 JP6827330 B2 JP 6827330B2
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- 239000000758 substrate Substances 0.000 title claims description 237
- 150000004767 nitrides Chemical class 0.000 title claims description 46
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 238000000034 method Methods 0.000 title description 45
- 239000013078 crystal Substances 0.000 claims description 54
- 239000007788 liquid Substances 0.000 claims description 51
- 229910052751 metal Inorganic materials 0.000 claims description 35
- 239000002184 metal Substances 0.000 claims description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 31
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 229910052738 indium Inorganic materials 0.000 claims description 8
- 229910052733 gallium Inorganic materials 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 230000000149 penetrating effect Effects 0.000 claims description 6
- 230000008016 vaporization Effects 0.000 claims description 5
- 238000009834 vaporization Methods 0.000 claims description 4
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 88
- 229910002601 GaN Inorganic materials 0.000 description 81
- 239000007789 gas Substances 0.000 description 75
- 238000006243 chemical reaction Methods 0.000 description 26
- 238000010438 heat treatment Methods 0.000 description 22
- 238000012545 processing Methods 0.000 description 17
- 238000005121 nitriding Methods 0.000 description 13
- 238000001947 vapour-phase growth Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 10
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- 238000010586 diagram Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 150000004678 hydrides Chemical class 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- NWAIGJYBQQYSPW-UHFFFAOYSA-N azanylidyneindigane Chemical compound [In]#N NWAIGJYBQQYSPW-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000005429 filling process Methods 0.000 description 2
- 239000003779 heat-resistant material Substances 0.000 description 2
- 238000002513 implantation Methods 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
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- 239000000203 mixture Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 238000000879 optical micrograph Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 102100036738 Guanine nucleotide-binding protein subunit alpha-11 Human genes 0.000 description 1
- 101100283445 Homo sapiens GNA11 gene Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- RNQKDQAVIXDKAG-UHFFFAOYSA-N aluminum gallium Chemical compound [Al].[Ga] RNQKDQAVIXDKAG-UHFFFAOYSA-N 0.000 description 1
- AJGDITRVXRPLBY-UHFFFAOYSA-N aluminum indium Chemical compound [Al].[In] AJGDITRVXRPLBY-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- XOYLJNJLGBYDTH-UHFFFAOYSA-M chlorogallium Chemical compound [Ga]Cl XOYLJNJLGBYDTH-UHFFFAOYSA-M 0.000 description 1
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- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
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- Crystals, And After-Treatments Of Crystals (AREA)
- Chemical Vapour Deposition (AREA)
Description
本発明は、ＩＩＩ族窒化物基板の製造方法およびＩＩＩ族窒化物基板に関する。 The present invention relates to a method for producing a group III nitride substrate and a group III nitride substrate.
発光素子や高速トランジスタ等の半導体デバイスを作製する際、例えば窒化ガリウム（ＧａＮ）等のＩＩＩ族窒化物の結晶からなる基板（以下、ＩＩＩ族窒化物基板、或いは、単に基板とも称する）を用意し、この基板の表面上に、結晶をさらにエピタキシャル成長させてデバイスを作製する処理が行われる場合がある（特許文献１参照）。 When manufacturing a semiconductor device such as a light emitting element or a high-speed transistor, a substrate made of a crystal of Group III nitride such as gallium nitride (GaN) (hereinafter, also referred to as a Group III nitride substrate or simply a substrate) is prepared. On the surface of this substrate, a process of further epitaxially growing crystals to produce a device may be performed (see Patent Document 1).
しかしながら、上述の基板は、貫通ピットや貫通クラック等の貫通孔を有する場合があり、真空ピンセット等の搬送冶具を使用する際、搬送冶具に真空吸着しなかったり、スピンコート法により基板上にレジスト膜を設けることが難しくなったりすることがある。本発明の目的は、ここに述べた課題を回避し、貫通孔を有するために不良品となっていたＩＩＩ族窒化物基板を再生させることが可能な技術を提供することにある。 However, the above-mentioned substrate may have through holes such as through pits and through cracks, and when a transfer jig such as vacuum tweezers is used, the substrate may not be vacuum-adsorbed to the transfer jig or resisted on the substrate by the spin coating method. It may be difficult to provide a film. An object of the present invention is to avoid the above-mentioned problems and to provide a technique capable of regenerating a group III nitride substrate which has been a defective product due to having through holes.
本発明の一態様によれば、
ＩＩＩ族窒化物の結晶からなり、表裏を貫通する貫通孔を有する基板を用意する準備工程と、
前記基板を、ＧａまたはＩｎのうち少なくともいずれかのＩＩＩ族金属を介して保持板上に配置する配置工程と、
前記保持板上に配置された前記基板を、少なくとも窒素源を含む雰囲気中で加熱して前記ＩＩＩ族金属を気化させ、前記基板の裏面側から表面側に向かって前記貫通孔内を流れる前記ＩＩＩ族金属の蒸気と、前記窒素源と、を前記貫通孔内で反応させることで、前記貫通孔を塞ぐ前記ＩＩＩ族金属の窒化物多結晶を前記貫通孔内の少なくとも一部に成長させる埋込工程と、
を有するＩＩＩ族窒化物基板の製造方法が提供される。
According to one aspect of the invention
A preparatory step of preparing a substrate made of group III nitride crystals and having through holes penetrating the front and back surfaces, and
An arrangement step of arranging the substrate on the holding plate via at least one group III metal of Ga or In,
The substrate arranged on the holding plate is heated in an atmosphere containing at least a nitrogen source to vaporize the group III metal, and the substrate III flows through the through hole from the back surface side to the front surface side of the substrate. By reacting the vapor of the group metal with the nitrogen source in the through hole, the nitride polycrystal of the group III metal that closes the through hole is embedded in at least a part of the through hole. Process and
A method for producing a group III nitride substrate having the above is provided.
本発明の他の態様によれば、
ＩＩＩ族窒化物の結晶からなり、
表裏を貫通する貫通孔を有し、
前記貫通孔内の少なくとも一部が、ＧａまたはＩｎのうち少なくともいずれかのＩＩＩ族金属の窒化物多結晶によって塞がれてなるＩＩＩ族窒化物結晶基板が提供される。
According to another aspect of the invention
Consists of group III nitride crystals
It has through holes that penetrate the front and back,
A group III nitride crystal substrate is provided in which at least a part of the through hole is closed by a nitride polycrystal of at least one of Group III metals, Ga or In.
本発明によれば、貫通孔を有するために不良品となっていたＩＩＩ族窒化物基板を再生させることが可能となる。 According to the present invention, it is possible to regenerate a group III nitride substrate which has been a defective product due to having through holes.
＜本発明の一実施形態＞
以下、本発明の一実施形態について図面を用いて説明する。
<One Embodiment of the present invention>
Hereinafter, an embodiment of the present invention will be described with reference to the drawings.
（１）ＧａＮ基板の製造方法
本実施形態では、一例として、
ＧａＮの結晶（以下、ＧａＮ結晶とも称する）からなり、表裏を貫通する貫通孔１０ｈを有する基板１０（以下、基板１０とも称する）を用意する準備ステップと、
基板１０を、ガリウム（Ｇａ）１１を介して保持板１２上に配置する配置ステップと、
貫通孔１０ｈを塞ぐＧａの窒化物多結晶（ＧａＮ多結晶）１４を、貫通孔１０ｈ内の少なくとも一部に成長させる埋込ステップと、
を行うことで、ＩＩＩ族窒化物基板としてのＧａＮ基板を作製する場合について説明する。以下、各ステップの詳細について説明する。
(1) Manufacturing method of GaN substrate In this embodiment, as an example,
A preparatory step for preparing a substrate 10 (hereinafter, also referred to as a substrate 10) which is composed of a GaN crystal (hereinafter, also referred to as a GaN crystal) and has through holes 10h penetrating the front and back surfaces.
An arrangement step of arranging the substrate 10 on the holding plate 12 via gallium (Ga) 11 and
An embedding step of growing Ga's nitride polycrystal (GaN polycrystal) 14 that closes the through hole 10h into at least a part of the through hole 10h.
A case where a GaN substrate as a group III nitride substrate is produced will be described. The details of each step will be described below.
（準備ステップ）
図１（ａ）、（ｂ）に、処理対象として用意した基板１０の平面、断面構成をそれぞれ例示する。ここに示した基板１０は、例えば、下地基板（種結晶基板）の表面上にＧａＮ結晶を厚くエピタキシャル成長させ、その後、成長させた結晶インゴットをスライスして自立化させることにより作製できる。本実施形態では、一例として、表面（成長面）が（０００１）面、すなわち、Ｇａ極性面（＋ｃ面）となるように成長させたＧａＮ結晶のインゴットをスライスし、これにより得られたアズグロウン状態の自立基板を基板１０として用いる例について説明する。
(Preparation step)
FIGS. 1 (a) and 1 (b) exemplify the plane and cross-sectional configurations of the substrate 10 prepared as a processing target, respectively. The substrate 10 shown here can be produced, for example, by epitaxially growing a GaN crystal thickly on the surface of a base substrate (seed crystal substrate), and then slicing the grown crystal ingot to make it self-supporting. In the present embodiment, as an example, an ingot of a GaN crystal grown so that the surface (growth surface) becomes the (0001) plane, that is, the Ga polar plane (+ c plane) is sliced, and the asgrown state obtained thereby is obtained. An example of using the self-supporting substrate of No. 1 as the substrate 10 will be described.
基板１０としては、例えば、直径が２〜６インチ程度の大きさであって、厚さが０．２〜１．０ｍｍの大きさである円板状の基板を用いることができる。基板１０の表面は、ＧａＮ結晶の（０００１）面に対して平行であるか、±５°以内、好ましくは±１°以内の傾斜を有する面として構成されている。基板１０は、シリコン（Ｓｉ）や鉄（Ｆｅ）、ゲルマニウム（Ｇｅ）等の添加物を、所定の割合で含有していてもよい。 As the substrate 10, for example, a disk-shaped substrate having a diameter of about 2 to 6 inches and a thickness of 0.2 to 1.0 mm can be used. The surface of the substrate 10 is configured as a surface parallel to the (0001) plane of the GaN crystal or having an inclination of ± 5 ° or less, preferably ± 1 ° or less. The substrate 10 may contain additives such as silicon (Si), iron (Fe), and germanium (Ge) in a predetermined ratio.
基板１０は、上述したように、基板１０の表裏を貫通する（基板１０を厚さ方向に貫く）貫通ピットや貫通クラック等の貫通孔１０ｈを１つ以上有している。貫通孔１０ｈの大きさは、特に限定されるものではなく、基板１０は、例えばアズグロウン状態の基板１０が有し得る最大の大きさの貫通孔１０ｈを有していてもよい。 As described above, the substrate 10 has one or more through holes 10h such as through pits and through cracks that penetrate the front and back surfaces of the substrate 10 (penetrate the substrate 10 in the thickness direction). The size of the through hole 10h is not particularly limited, and the substrate 10 may have, for example, the maximum size of the through hole 10h that the substrate 10 in the asgrown state can have.
（配置ステップ）
準備ステップを実施したら、配置ステップを実施する。本ステップでは、貫通孔１０ｈを有する基板１０を、Ｇａ１１を介して保持板（支持板）１２上に配置する。言い換えると、基板１０と保持板１２との間には、Ｇａ１１からなる層が設けられている。
(Placement step)
After performing the preparatory step, perform the placement step. In this step, the substrate 10 having the through hole 10h is arranged on the holding plate (support plate) 12 via Ga11. In other words, a layer made of Ga 11 is provided between the substrate 10 and the holding plate 12.
後述する埋込ステップにおける取り扱いを容易とするため、基板１０は、例えば平板として構成された保持板１２上に配置する。基板１０は、裏面（Ｎ極性面、−ｃ面）がＧａ１１と接するように保持板１２上に配置する。図１（ｂ）に、Ｇａ１１を介して基板１０を保持板１２上に配置した様子を示す模式図を例示する。 In order to facilitate handling in the embedding step described later, the substrate 10 is arranged on a holding plate 12 configured as, for example, a flat plate. The substrate 10 is arranged on the holding plate 12 so that the back surface (N-polar surface, −c surface) is in contact with Ga 11. FIG. 1B exemplifies a schematic view showing a state in which the substrate 10 is arranged on the holding plate 12 via Ga11.
Ｇａ（融点約３０℃）は、一度加熱して融解した後は、室温（常温、２０〜３０℃の範囲内の所定の温度、例えば３００Ｋ（ケルビン）、約２７℃）において、過冷却状態で液状を維持することができる。本ステップでは、基板１０は、室温下で、融解させたＧａ１１（以下、液状Ｇａ１１ともいう）を介して保持板１２上に配置する。液状Ｇａ１１は、後述する埋込ステップにおいて、貫通孔１０ｈ内に成長させるＧａＮ多結晶１４を形成する材料すなわち埋込材のうちの１つとして機能する。また、液状Ｇａ１１は、保持板１２と基板１０とを一時的に接着する接着剤としても機能する。すなわち、液状Ｇａ１１は、埋込ステップにおいて、反応室２０１内へ基板１０（保持板１２上に配置した基板１０）を搬入し、貫通孔１０ｈ内へのＧａＮ多結晶１４の成長が開始されるまでの間、保持板１２上における基板１０の位置ずれを防止するように機能する。 Ga (melting point of about 30 ° C.) is supercooled at a predetermined temperature within the range of room temperature (normal temperature, 20 to 30 ° C., for example, 300 K (Kelvin), about 27 ° C.) after being heated and melted once. It can be kept liquid. In this step, the substrate 10 is placed on the holding plate 12 via the melted Ga 11 (hereinafter, also referred to as liquid Ga 11) at room temperature. The liquid Ga 11 functions as one of the materials for forming the GaN polycrystal 14 to be grown in the through hole 10h, that is, the embedding material in the embedding step described later. The liquid Ga 11 also functions as an adhesive that temporarily adheres the holding plate 12 and the substrate 10. That is, in the embedding step, the liquid Ga 11 carries the substrate 10 (the substrate 10 arranged on the holding plate 12) into the reaction chamber 201 until the growth of the GaN polycrystal 14 into the through hole 10h is started. During that time, it functions to prevent the displacement of the substrate 10 on the holding plate 12.
本ステップでは、図１（ｂ）に例示するように、液状Ｇａ１１を介して保持板１２上に基板１０を配置する際、貫通孔１０ｈ内に液状Ｇａ１１が侵入する（入り込む）ことがないように、保持板１２上に塗布する液状Ｇａ１１の量を調整する。上述のようにＧａは室温において過冷却状態で液状を維持することができることから、室温下で、所定量の液状Ｇａ１１を、保持板１２上の所定位置に塗布することができる。液状Ｇａ１１の塗布量が多すぎると、液状Ｇａ１１を介して保持板１２上に基板１０を配置する際、図１（ｄ）に例示するように貫通孔１０ｈ内に液状Ｇａ１１が侵入することがある。 In this step, as illustrated in FIG. 1 (b), when the substrate 10 is placed on the holding plate 12 via the liquid Ga 11, the liquid Ga 11 does not enter (enter) into the through hole 10h. , Adjust the amount of liquid Ga 11 to be applied on the holding plate 12. Since Ga can be maintained in a liquid state in a supercooled state at room temperature as described above, a predetermined amount of liquid Ga 11 can be applied to a predetermined position on the holding plate 12 at room temperature. If the amount of the liquid Ga 11 applied is too large, the liquid Ga 11 may enter the through hole 10h as illustrated in FIG. 1 (d) when the substrate 10 is placed on the holding plate 12 via the liquid Ga 11. ..
また、本ステップでは、貫通孔１０ｈ内に液状Ｇａ１１が侵入することがないように、保持板１２上に塗布する液状Ｇａ１１の塗布位置を調整してもよい。例えば、図１（ｃ）に示すように、液状Ｇａ１１を介して保持板１２上に基板１０を配置する際、貫通孔１０ｈが位置することとなる保持板１２上の箇所に液状Ｇａ１１が存在しないように、液状Ｇａ１１の塗布位置を調整してもよい。 Further, in this step, the coating position of the liquid Ga 11 to be applied on the holding plate 12 may be adjusted so that the liquid Ga 11 does not enter the through hole 10h. For example, as shown in FIG. 1C, when the substrate 10 is placed on the holding plate 12 via the liquid Ga 11, the liquid Ga 11 does not exist at the position on the holding plate 12 where the through hole 10h is located. As described above, the coating position of the liquid Ga 11 may be adjusted.
なお、ここでいう「貫通孔１０ｈ内に液状Ｇａ１１が侵入することがない」とは、液状Ｇａ１１が貫通孔１０ｈ内に全く侵入しない場合だけでなく、液状Ｇａ１１が貫通孔１０ｈ内にわずかに侵入する場合を含むものとする。但し、液状Ｇａ１１が貫通孔１０ｈ内に侵入した場合であっても、その量は、後述する埋込ステップを実施した際、貫通孔１０ｈ内に窒化不充分なＧａがそのまま残ることがない量、すなわち窒化不充分なＧａを内包しない量とする。本明細書で用いる「窒化不充分なＧａ」という用語は、窒化が不充分なＧａだけでなく、窒化されていないＧａも含み得る。 The phrase "the liquid Ga 11 does not invade the through hole 10h" here means not only when the liquid Ga 11 does not invade the through hole 10h at all, but also when the liquid Ga 11 slightly invades the through hole 10h. It shall include the case of. However, even when the liquid Ga 11 invades the through hole 10h, the amount thereof is such that insufficient nitriding Ga does not remain in the through hole 10h as it is when the embedding step described later is performed. That is, the amount is set so as not to include Ga with insufficient nitriding. As used herein, the term "insufficient nitriding Ga" may include not only poorly nitriding Ga, but also unnitrided Ga.
また、液状Ｇａ１１の塗布量は、上述の要件を満たす範囲内で、貫通孔１０ｈの平面積（貫通孔１０ｈが複数存在する場合は、貫通孔１０ｈの総平面積）等によって適宜設定することが好ましい。というのも、液状Ｇａ１１の塗布量に応じて、後述する埋込ステップにおいて生成されるＧａ蒸気の量が変わり、このＧａ蒸気の生成量が少なすぎると、貫通孔１０ｈをＧａＮ多結晶１４で塞ぐ（埋め込む）ことができない場合があるためである。 Further, the coating amount of the liquid Ga 11 may be appropriately set according to the flat area of the through holes 10h (if there are a plurality of through holes 10h, the total flat area of the through holes 10h) within the range satisfying the above requirements. preferable. This is because the amount of Ga vapor generated in the embedding step described later changes according to the amount of liquid Ga 11 applied, and if the amount of Ga vapor generated is too small, the through hole 10h is closed with the GaN polycrystal 14. This is because it may not be possible to (embed).
保持板１２の材料としては、後述する埋込ステップでの処理温度、処理雰囲気に耐えられる耐熱性、耐蝕性を有する材料を用いる必要がある。但し、保持板１２上に塗布する液状Ｇａ１１は、埋込ステップを実施することで自然と消滅する。このため、本実施形態で用いる保持板１２の材料はその線膨張係数を不問とすることができる。また、保持板１２を、基板１０よりも表層が剥離しやすい材料で形成する必要もない。保持板１２の材料として、等方性黒鉛、異方性黒鉛（パイロリティックグラファイト（ＰＧ））、パイロリティックボロンナイトライド（ＰＢＮ）、シリコン（Ｓｉ）、石英、炭化ケイ素（ＳｉＣ）、サファイア等を用いることができる。また、保持板１２の材料として、等方性黒鉛、Ｓｉ、石英、ＳｉＣ等の平板基材の表面を、ＰＧ等の耐蝕性に優れた材料により被覆（コーティング）してなる複合材料を用いてもよい。 As the material of the holding plate 12, it is necessary to use a material having heat resistance and corrosion resistance that can withstand the treatment temperature and the treatment atmosphere in the embedding step described later. However, the liquid Ga 11 applied on the holding plate 12 disappears naturally by carrying out the embedding step. Therefore, the material of the holding plate 12 used in the present embodiment can have any linear expansion coefficient. Further, it is not necessary to form the holding plate 12 with a material whose surface layer is more easily peeled off than the substrate 10. As the material of the holding plate 12, isotropic graphite, anisotropic graphite (pyrolic graphite (PG)), pyrolytic boron nitride (PBN), silicon (Si), quartz, silicon carbide (SiC), sapphire and the like are used. Can be used. Further, as the material of the holding plate 12, a composite material obtained by coating the surface of a flat plate base material such as isotropic graphite, Si, quartz, or SiC with a material having excellent corrosion resistance such as PG is used. May be good.
（埋込ステップ）
配置ステップを実施したら、貫通孔１０ｈ内の少なくとも一部に、貫通孔１０ｈを塞ぐＧａＮ多結晶１４を成長させる処理を実施する。
(Embedding step)
After performing the arrangement step, a process of growing a GaN polycrystal 14 that closes the through hole 10h is performed in at least a part of the through hole 10h.
この処理は、例えば、図２に示す加熱装置２００を用いて行うことができる。加熱装置２００は、石英等の耐熱性材料からなり、反応室（結晶成長室）２０１が内部に構成された気密容器２０３を備えている。反応室２０１内には、１つまたは複数の基板１０を保持する保持具２０８が設けられている。保持具２０８は、１つまたは複数の基板１０を、それぞれの基板１０が液状Ｇａ１１を介して保持板１２上に配置された状態で、垂直方向に多段に保持するように構成されている。気密容器２０３の一端には、反応室２０１内へ窒素源としてのアンモニア（ＮＨ３）ガス、窒素（Ｎ２）ガスを供給するガス供給管２３２ａ，２３２ｂが接続されている。ガス供給管２３２ａ，２３２ｂには、上流側から順に、流量制御器２４１ａ，２４１ｂ、バルブ２４３ａ，２４３ｂがそれぞれ設けられている。ガス供給管２３２ａ，２３２ｂの下流側には、これらのガス供給管から供給された各種ガスを保持具２０８上に保持した基板１０に向けて供給するノズル２４９ａ，２４９ｂが、それぞれ接続されている。気密容器２０３の他端には、反応室２０１内を排気する排気管２３０が設けられている。排気管２３０にはポンプ２３１が設けられている。気密容器２０３の外周には、保持具２０８に保持した基板１０を所望の温度に加熱するヒータ２０７が設けられている。気密容器２０３内には、反応室２０１内の温度を測定する温度センサ２０９が設けられている。加熱装置２００が備える各部材は、コンピュータとして構成されたコントローラ２８０に接続されており、コントローラ２８０上で実行されるプログラムによって、後述する処理手順や処理条件が制御されるように構成されている。 This process can be performed, for example, by using the heating device 200 shown in FIG. The heating device 200 includes an airtight container 203 made of a heat-resistant material such as quartz and having a reaction chamber (crystal growth chamber) 201 inside. A retainer 208 for holding one or more substrates 10 is provided in the reaction chamber 201. The holder 208 is configured to hold one or more substrates 10 in multiple stages in the vertical direction in a state where each of the substrates 10 is arranged on the holding plate 12 via the liquid Ga 11. Gas supply pipes 232a and 232b for supplying ammonia (NH 3 ) gas and nitrogen (N 2 ) gas as nitrogen sources into the reaction chamber 201 are connected to one end of the airtight container 203. The gas supply pipes 232a and 232b are provided with flow rate controllers 241a and 241b and valves 243a and 243b in this order from the upstream side. On the downstream side of the gas supply pipes 232a and 232b, nozzles 249a and 249b that supply various gases supplied from these gas supply pipes toward the substrate 10 held on the holder 208 are connected, respectively. At the other end of the airtight container 203, an exhaust pipe 230 for exhausting the inside of the reaction chamber 201 is provided. A pump 231 is provided in the exhaust pipe 230. A heater 207 that heats the substrate 10 held by the holder 208 to a desired temperature is provided on the outer periphery of the airtight container 203. Inside the airtight container 203, a temperature sensor 209 for measuring the temperature inside the reaction chamber 201 is provided. Each member included in the heating device 200 is connected to a controller 280 configured as a computer, and is configured so that a processing procedure and processing conditions described later are controlled by a program executed on the controller 280.
埋込ステップでは、上述の加熱装置２００により、例えば以下の処理手順が実施される。まず、液状Ｇａ１１を介して保持板１２上に配置した基板１０を保持具２０８上に保持（載置）する。そして、反応室２０１内の加熱および排気を実施しながら、反応室２０１内へ、ＮＨ３ガス、或いはＮＨ３ガスとＮ２ガスとの混合ガスを供給する。 In the embedding step, for example, the following processing procedure is carried out by the heating device 200 described above. First, the substrate 10 arranged on the holding plate 12 via the liquid Ga 11 is held (placed) on the holder 208. Then, while heating and exhausting the inside of the reaction chamber 201, NH 3 gas or a mixed gas of NH 3 gas and N 2 gas is supplied into the reaction chamber 201.
このように、液状Ｇａ１１を介して保持板１２上に配置した基板１０を、少なくともＮＨ３ガスを含む雰囲気中で加熱することで、まず、液状Ｇａ１１が、反応室２０１内の昇温に伴って徐々に気化してＧａ蒸気となる。そして、このＧａ蒸気が基板１０の裏面側から表面側に向かって貫通孔１０ｈ内を流れる（通過する）際、貫通孔１０ｈ内で、Ｇａ蒸気と、基板１０の表面側から供給したＮＨ３ガスと、を反応させてＧａを窒化させ、貫通孔１０ｈ内にＧａＮ多結晶１４を成長させる。これにより、貫通孔１０ｈがＧａＮ多結晶１４で埋め込まれて気密に塞がれる。図３（ａ）に貫通孔１０ｈがＧａＮ多結晶１４で塞がれた基板１０の平面構成図を示し、図３（ｂ）にその断面構成図を示す。なお、液状Ｇａ１１は、埋込ステップを実施することで、例えば埋込ステップの昇温中に、その殆ど、或いは、全てが蒸発し、自然と消滅する。 By heating the substrate 10 arranged on the holding plate 12 via the liquid Ga 11 in an atmosphere containing at least NH 3 gas, the liquid Ga 11 first becomes warmer in the reaction chamber 201 as the temperature rises. It gradually vaporizes into Ga vapor. Then, when the Ga vapor flows (passes) in the through hole 10h from the back surface side to the front surface side of the substrate 10, the Ga vapor and the NH 3 gas supplied from the front surface side of the substrate 10 in the through hole 10h. And are reacted to nitrid Ga, and the GaN polycrystal 14 is grown in the through hole 10h. As a result, the through hole 10h is embedded with the GaN polycrystal 14 and is airtightly closed. FIG. 3A shows a plan view of the substrate 10 in which the through hole 10h is closed with the GaN polycrystal 14, and FIG. 3B shows a cross-sectional view thereof. By carrying out the embedding step, the liquid Ga 11 evaporates almost or all of the liquid Ga 11 during the temperature rise of the embedding step, and disappears naturally.
ＧａＮ多結晶１４の成長は、液状Ｇａ１１の気化の開始（Ｇａ蒸気の生成の開始）とほぼ同時に開始する。したがって、本ステップでは、貫通孔１０ｈの埋め込みに寄与せずに、反応室２０１内から排出されるＧａ蒸気の量を減らすため、液状Ｇａ１１の気化が始まる前から反応室２０１内（雰囲気中）へＮＨ３ガスを供給するのが好ましい。また、本ステップでは、基板１０を構成する結晶の分解を防止するため、例えば反応室２０１内の加熱前から反応室２０１内へＮＨ３ガスを供給するのがより好ましい。 The growth of the GaN polycrystal 14 starts almost at the same time as the start of vaporization of the liquid Ga 11 (the start of the formation of Ga vapor). Therefore, in this step, in order to reduce the amount of Ga vapor discharged from the reaction chamber 201 without contributing to the embedding of the through hole 10h, the liquid Ga 11 enters the reaction chamber 201 (in the atmosphere) before the vaporization of the liquid Ga 11 starts. It is preferable to supply NH 3 gas. Further, in this step, in order to prevent degradation of the crystal constituting the substrate 10, for example, it is more preferable to supply NH 3 gas before the heating in the reaction chamber 201 into the reaction chamber 201.
本ステップでは、基板１０の温度が例えば５５０℃以上１２００℃以下、好ましくは９００℃以上１０００℃以下の温度となるように、ヒータ２０７により調整することが望ましい。 In this step, it is desirable to adjust the temperature of the substrate 10 by the heater 207 so that the temperature of the substrate 10 is, for example, 550 ° C or higher and 1200 ° C or lower, preferably 900 ° C or higher and 1000 ° C or lower.
基板１０の温度が５５０℃未満では、Ｇａの窒化が進行しにくく、貫通孔１０ｈ内にＧａＮ多結晶１４を成長させることができないことがある。基板１０の温度を５５０℃以上とすることでＧａの窒化を進行させることができ、９００℃以上とすることで、Ｇａの窒化を確実に進行させることができる。基板１０の温度が１２００℃を超えると、基板１０の表面がサーマルエッチングされたり、基板１０を構成する結晶の分解が促進されたりして、基板１０の表面から窒素（Ｎ）原子が抜けて（飛んで）しまう、すなわちＮ原子が脱落することがある。その結果、基板１０の表面が荒れたり、欠陥が増加したりすることがある。基板１０の温度を１２００℃以下とすることでこれらの問題を解決でき、１０００℃以下とすることで、これらの問題を確実に解決することができる。 If the temperature of the substrate 10 is less than 550 ° C., nitriding of Ga is difficult to proceed, and the GaN polycrystal 14 may not be able to grow in the through hole 10h. Nitriding of Ga can be advanced by setting the temperature of the substrate 10 to 550 ° C. or higher, and nitriding of Ga can be reliably promoted by setting the temperature of the substrate 10 to 900 ° C. or higher. When the temperature of the substrate 10 exceeds 1200 ° C., the surface of the substrate 10 is thermally etched or the decomposition of the crystals constituting the substrate 10 is promoted, so that nitrogen (N) atoms are released from the surface of the substrate 10 ( It may fly), that is, the N atom may drop out. As a result, the surface of the substrate 10 may be roughened or defects may increase. By setting the temperature of the substrate 10 to 1200 ° C. or lower, these problems can be solved, and by setting the temperature to 1000 ° C. or lower, these problems can be surely solved.
埋込ステップの処理条件としては、以下が例示される。
処理温度（基板１０の温度）：５５０〜１２００℃、好ましくは、９００〜１０００℃
処理圧力（反応室２０１内の圧力）：９０〜１０５ｋＰａ、好ましくは、９０〜９５ｋＰａ
ＮＨ３ガスの分圧：９〜２０ｋＰａ
The following are examples of processing conditions for the embedding step.
Processing temperature (temperature of substrate 10): 550 to 1200 ° C., preferably 900 to 1000 ° C.
Processing pressure (pressure in reaction chamber 201): 90-105 kPa, preferably 90-95 kPa
Partial pressure of NH 3 gas: 9 to 20 kPa
本ステップでは、図３（ｂ）に例示するように、貫通孔１０ｈ内の全てをＧａＮ多結晶１４で埋め込む必要はない。本ステップでは、後述の研磨ステップを行うことから、図３（ｂ）（ｄ）に例示するように、基板１０の表面とＧａＮ多結晶の表面とが非面一の面であってもよく、また、貫通孔１０ｈをＧａＮ多結晶１４で気密に塞ぐことができれば、図３（ｃ）（ｄ）に例示するように、貫通孔１０ｈ内の少なくとも一部にのみＧａＮ多結晶１４を成長させてもよい。 In this step, as illustrated in FIG. 3B, it is not necessary to embed the entire inside of the through hole 10h with the GaN polycrystal 14. In this step, since the polishing step described later is performed, the surface of the substrate 10 and the surface of the GaN polycrystal may be non-planetary as illustrated in FIGS. 3 (b) and 3 (d). Further, if the through hole 10h can be airtightly closed with the GaN polycrystal 14, the GaN polycrystal 14 is grown only in at least a part of the through hole 10h as illustrated in FIGS. 3C and 3D. May be good.
貫通孔１０ｈがＧａＮ多結晶１４で塞がれたら、反応室２０１内へＮＨ３ガス、或いはＮＨ３ガスとＮ２ガスとの混合ガスを供給しつつ、反応室２０１内を排気した状態で、ヒータ２０７による加熱を停止する。そして、反応室２０１内の温度が５００℃以下となったらＮＨ３ガスの供給を停止し、その後、反応室２０１内の雰囲気をＮ２ガスへ置換して大気圧に復帰させるとともに、反応室２０１内を搬出可能な温度にまで降温させた後、反応室２０１内から基板１０を搬出する。 When the through hole 10h is closed with the GaN polycrystal 14, NH 3 gas or a mixed gas of NH 3 gas and N 2 gas is supplied into the reaction chamber 201, and the inside of the reaction chamber 201 is exhausted. The heating by the heater 207 is stopped. Then, when the temperature in the reaction chamber 201 becomes 500 ° C. or lower, the supply of NH 3 gas is stopped, and then the atmosphere in the reaction chamber 201 is replaced with N 2 gas to restore the atmospheric pressure, and the reaction chamber 201 is restored. After the temperature is lowered to a temperature at which the inside can be carried out, the substrate 10 is carried out from the inside of the reaction chamber 201.
（研磨ステップ）
埋込ステップを実施したら、スラリー等を用いて基板１０の表裏面を研磨する処理を実施する。本ステップを行うことで、図３（ｂ）〜（ｄ）に例示するように貫通孔１０ｈがＧａＮ多結晶１４で塞がれた基板１０は、図４に断面構成図を示すように、基板１０の表面とＧａＮ多結晶１４の表面とが面一の面となるとともに、基板１０の裏面とＧａＮ多結晶１４の裏面とが面一の面となる。なお、本ステップでは、必ずしも基板１０の表裏面を研磨する必要はなく、少なくとも基板１０の表面を研磨する処理を実施すればよい。
(Polishing step)
After performing the embedding step, a process of polishing the front and back surfaces of the substrate 10 with a slurry or the like is performed. By performing this step, as illustrated in FIGS. 3 (b) to 3 (d), the substrate 10 in which the through holes 10h are closed with the GaN polycrystal 14 is a substrate as shown in FIG. The front surface of 10 and the surface of the GaN polycrystal 14 are flush with each other, and the back surface of the substrate 10 and the back surface of the GaN polycrystal 14 are flush with each other. In this step, it is not always necessary to polish the front and back surfaces of the substrate 10, and at least the surface of the substrate 10 may be polished.
（２）本実施形態で得られる効果
本実施形態によれば、以下に示す１つまたは複数の効果が得られる。
(2) Effects obtained in the present embodiment According to the present embodiment, one or more of the following effects can be obtained.
（ａ）本実施形態では、貫通孔１０ｈを有する基板１０を、液状Ｇａ１１を介して保持板１２上に配置し、この状態で、反応室２０１内に少なくともＮＨ３ガスを供給しながら基板１０を加熱することで、貫通孔１０ｈ内の少なくとも一部にＧａＮ多結晶１４を成長させ、貫通孔１０ｈを塞ぐことができる。図５は、上述の配置ステップ、埋込ステップの実施後であって研磨ステップの実施前の貫通孔をＧａＮ多結晶で塞いだＧａＮ基板の貫通孔近傍を撮影した写真である。このように、配置ステップ、埋込ステップを実施することで、貫通孔を気密に塞ぐことができることを、本発明者は確認済みである。 (A) In the present embodiment, a substrate 10 having a through hole 10h, located on the holding plate 12 via a liquid GA11, in this state, the substrate 10 while supplying at least the NH 3 gas into the reaction chamber 201 By heating, the GaN polycrystal 14 can be grown in at least a part of the through hole 10h, and the through hole 10h can be closed. FIG. 5 is a photograph of the vicinity of the through hole of the GaN substrate in which the through hole after the above-mentioned arrangement step and embedding step is performed and before the polishing step is performed is closed with a GaN polycrystal. The present inventor has confirmed that the through hole can be airtightly closed by carrying out the placement step and the embedding step in this way.
（ｂ）ＧａＮ多結晶１４で貫通孔１０ｈを塞ぐことで、例えば、真空ピンセット等の搬送冶具を使用する際、貫通孔１０ｈから空気が漏れて上記搬送冶具への基板１０の真空吸着が阻害されることを防ぐことができる。また例えば、基板１０の表面上にスピンコート法等によりレジスト膜を設ける際、レジスト液が貫通孔１０ｈを介して基板１０に吸い込まれたり、真空吸着用のポンプが貫通孔１０ｈを介して基板１０に吸い込まれたレジスト液を吸い込んでポンプが故障したりすることを回避できる。 (B) By closing the through hole 10h with the GaN polycrystal 14, for example, when a transfer jig such as vacuum tweezers is used, air leaks from the through hole 10h and the vacuum adsorption of the substrate 10 to the transfer jig is hindered. Can be prevented. Further, for example, when a resist film is provided on the surface of the substrate 10 by a spin coating method or the like, the resist liquid is sucked into the substrate 10 through the through holes 10h, or a pump for vacuum suction passes through the through holes 10h. It is possible to prevent the pump from malfunctioning by sucking in the resist liquid sucked into the pump.
このように、本実施形態では、貫通孔１０ｈを有するために上述のような基板１０上にデバイスを作製する後工程を実施することができず、従来では不良品となっていた基板１０を再生させることができる。 As described above, in the present embodiment, since the through hole 10h is provided, the post-process of manufacturing the device on the substrate 10 as described above cannot be performed, and the substrate 10 which has been a defective product in the past cannot be regenerated. Can be made to.
なお、貫通孔１０ｈをＧａＮ多結晶１４で塞いだ基板１０上に例えばＧａＮ結晶膜を成長させると、基板１０の主面（すなわちＧａＮの単結晶）上にはＧａＮ単結晶がエピタキシャル成長し、ＧａＮ多結晶１４上にはＧａＮ多結晶がさらに成長する。この場合、ＧａＮ多結晶上にはデバイスを作製することはできないが、ＧａＮ単結晶上にはデバイスを問題なく作製することができる。 When, for example, a GaN crystal film is grown on the substrate 10 in which the through holes 10h are closed with the GaN polycrystal 14, the GaN single crystal grows epitaxially on the main surface of the substrate 10 (that is, the GaN single crystal), and the GaN polycrystal is present. A GaN polycrystal grows further on the crystal 14. In this case, the device cannot be formed on the GaN polycrystal, but the device can be formed on the GaN single crystal without any problem.
（ｃ）本実施形態によれば、基板１０の裏面側から表面側に向かってＧａ蒸気が貫通孔１０ｈ内を流れる際、Ｇａ蒸気と、基板１０の表面側から供給したＮＨ３ガスと、を貫通孔１０ｈ内で反応させて、貫通孔１０ｈ内にＧａＮ多結晶１４を成長させることが可能となる。これにより、貫通孔１０ｈ内をＧａＮ多結晶１４のみで塞ぐことができる。 (C) According to the present embodiment, when Ga vapor flows in the through hole 10h from the back surface side to the front surface side of the substrate 10, Ga vapor and NH 3 gas supplied from the front surface side of the substrate 10 are mixed. It is possible to grow the GaN polycrystal 14 in the through hole 10h by reacting in the through hole 10h. As a result, the inside of the through hole 10h can be closed only with the GaN polycrystal 14.
この手法に対し、貫通孔内にあらかじめＧａ（液状Ｇａ）を注入した基板を、窒素源を含む雰囲気中で加熱してＧａと窒素源とを反応させ、貫通孔内に窒化物多結晶を成長させる手法も考えられる。しかしながら、この代替手法では、貫通孔内がＧａで埋め込まれた状態となっている。このため、このような基板に対してＧａの窒化処理を行っても、窒素源を含む雰囲気中に露出しているＧａ（基板の表面側付近に位置するＧａ）しか窒化せず、貫通孔の内部に位置するＧａを窒化させることが困難となる。この代替手法で貫通孔が塞がれた基板は、一見すると、貫通孔がＧａＮ多結晶で塞がれているが、貫通孔の内部には窒化不充分なＧａがそのまま残ることを本発明者は確認済みである。このような基板に対して例えば塩化水素（ＨＣｌ）を用いた洗浄処理を行い、ＧａＮ多結晶をエッチングすると、貫通孔内の窒化不充分なＧａが流れ出て、その結果、ＧａＮ基板に貫通孔が再度出現することがある。また、このような基板を用いて上述の後工程が行われた際、窒化不充分なＧａがコンタミネーションの発生源になる場合もある。例えば、このような基板上にＧａＮ結晶膜をエピタキシャル成長させると、貫通孔内から窒化不充分なＧａが出てきてＧａＮ結晶膜の品質が低下することがある。さらにまた、このような基板に対してワックス等を用いた研磨処理が施された際、貫通孔内にワックス等が残りやすくなる。 In contrast to this method, a substrate in which Ga (liquid Ga) is previously injected into the through hole is heated in an atmosphere containing a nitrogen source to react Ga with the nitrogen source, and a nitride polycrystal grows in the through hole. A method of making it possible is also conceivable. However, in this alternative method, the inside of the through hole is filled with Ga. Therefore, even if Ga nitriding treatment is performed on such a substrate, only Ga (Ga located near the surface side of the substrate) exposed in the atmosphere containing a nitrogen source is nitrided, and the through hole It becomes difficult to nitrid the Ga located inside. At first glance, in a substrate in which the through holes are closed by this alternative method, the through holes are closed with GaN polycrystals, but the present inventor presents that Ga with insufficient nitriding remains inside the through holes as it is. Has been confirmed. When such a substrate is cleaned with, for example, hydrogen chloride (HCl) and the GaN polycrystal is etched, insufficient Ga in the through holes flows out, and as a result, through holes are formed in the GaN substrate. It may reappear. Further, when the above-mentioned post-process is performed using such a substrate, Ga with insufficient nitriding may become a source of contamination. For example, when a GaN crystal film is epitaxially grown on such a substrate, insufficient Ga nitriding may come out from the through holes and the quality of the GaN crystal film may deteriorate. Furthermore, when such a substrate is subjected to a polishing treatment using wax or the like, wax or the like tends to remain in the through holes.
これに対し、本実施形態では、ＧａＮ多結晶１４の成長を、貫通孔１０ｈ内にＧａ蒸気を流すことで行っていることから、上述の課題を回避することが可能となる。 On the other hand, in the present embodiment, since the GaN polycrystal 14 is grown by flowing Ga vapor through the through hole 10h, the above-mentioned problem can be avoided.
また例えば、塩化ガリウム（ＧａＣｌ）ガスとＮＨ３ガスとを反応させることで、貫通孔１０ｈ内にＧａＮ多結晶１４を成長させる手法も考えられる。しかしながら、この代替手法では、ハイドライド気相成長（ＨＶＰＥ）装置等の気相成長装置を用いて埋込ステップを実施する必要がある。また、この代替手法では、ＧａＮ多結晶１４を成長させる際、気相成長装置の反応炉（成長室）内にもＧａＮ等が付着することから、反応炉内のクリーニングを頻繁に行う必要があり、メンテナンス頻度が高くなるという課題もある。 Further, for example, by reacting a gallium chloride (GaCl) gas and NH 3 gas, a method of growing a GaN polycrystal 14 in the through hole 10h is also conceivable. However, in this alternative method, it is necessary to carry out the implantation step using a vapor phase growth device such as a hydride vapor phase growth (HVPE) device. Further, in this alternative method, when the GaN polycrystal 14 is grown, GaN and the like also adhere to the inside of the reaction furnace (growth chamber) of the vapor phase growth apparatus, so that it is necessary to frequently clean the inside of the reaction furnace. There is also a problem that the maintenance frequency becomes high.
これに対し、本実施形態では、上述のように気相成長装置よりも簡易かつ低価な加熱装置２００で埋込ステップを実施することができる。また、加熱装置２００を用いることで、複数の基板１０の貫通孔１０ｈの穴埋めを同時に実施できる。これらの結果、気相成長装置を用いて埋込ステップを行う場合よりも処理コストを低減することができる。また、本実施形態では、基板１０の裏面側に液状Ｇａ１１を配置した状態で、ＧａＣｌガスを流すことなく、ＮＨ３ガスを流すことで、ＧａＮ多結晶１４を成長させている。このため、ＧａＣｌガスを流す場合よりも、反応室２０１内（気密容器２０３の内壁等）に付着するＧａＮ等の量を少なくすることができ、反応室２０１内のクリーニングの頻度を低くする、すなわち、加熱装置２００のメンテナンス頻度を低くすることができる。その結果、基板１０の穴埋め処理のスループットを高めることができる。 On the other hand, in the present embodiment, as described above, the embedding step can be carried out by the heating device 200, which is simpler and less expensive than the vapor deposition device. Further, by using the heating device 200, it is possible to simultaneously fill the through holes 10h of the plurality of substrates 10. As a result, the processing cost can be reduced as compared with the case where the embedding step is performed using the vapor phase growth apparatus. Further, in the present embodiment, in the state in which the liquid Ga11 on the back side of the substrate 10, without flowing the GaCl gas, by flowing the NH 3 gas, thereby growing a GaN polycrystal 14. Therefore, the amount of GaN or the like adhering to the inside of the reaction chamber 201 (the inner wall of the airtight container 203, etc.) can be reduced as compared with the case where the GaCl gas is flowed, and the frequency of cleaning inside the reaction chamber 201 is reduced, that is, , The maintenance frequency of the heating device 200 can be reduced. As a result, the throughput of the hole filling process of the substrate 10 can be increased.
（ｄ）本実施形態によれば、貫通孔１０ｈ内に液状Ｇａ１１が侵入することがないので、貫通孔１０ｈがＧａＮ多結晶１４で塞がれた基板１０は、窒化不充分なＧａを内包しない。すなわち、本実施形態によれば、貫通孔１０ｈ内をＧａＮ多結晶１４のみで確実に塞ぐことができる。 (D) According to the present embodiment, since the liquid Ga 11 does not enter the through hole 10h, the substrate 10 in which the through hole 10h is closed with the GaN polycrystal 14 does not contain Ga with insufficient nitriding. .. That is, according to the present embodiment, the inside of the through hole 10h can be reliably closed only by the GaN polycrystal 14.
（ｅ）本実施形態の手法によれば、アズグロウン状態の基板１０が有し得る最大サイズの貫通孔１０ｈを塞ぐことができる。例えば、図６に光学顕微鏡像で示すような、ＧａＮ単結晶では埋め込むことができないような大きな貫通孔１０ｈ（例えば基板１０の表面側から見たときの最小幅（差し渡し最小幅）が３００μｍより大きい貫通孔１０ｈ）であっても塞ぐことができる。なお、基板１０の表面側から見たときの貫通孔１０ｈの最大幅（差し渡し最大幅）については特に限定されないが、アズグロウン状態の基板１０が有し得る貫通孔１０ｈの最大幅は通常３ｍｍ程度である。本実施形態によれば、最大幅が３ｍｍの貫通孔１０ｈであっても、ＧａＮ多結晶１４で塞ぐことができる。 (E) According to the method of the present embodiment, it is possible to close the through hole 10h having the maximum size that the substrate 10 in the asgrown state can have. For example, as shown in the optical microscope image in FIG. 6, a large through hole 10h that cannot be embedded by a GaN single crystal (for example, the minimum width (minimum width across) when viewed from the surface side of the substrate 10 is larger than 300 μm). Even the through hole 10h) can be closed. The maximum width of the through hole 10h (maximum width across the board) when viewed from the surface side of the substrate 10 is not particularly limited, but the maximum width of the through hole 10h that the substrate 10 in the asgrown state can have is usually about 3 mm. is there. According to this embodiment, even a through hole 10h having a maximum width of 3 mm can be closed with the GaN polycrystal 14.
（ｆ）基板１０の表面（主面）がｃ面であって、基板１０と、貫通孔１０ｈ内に成長させたＩＩＩ族金属の多結晶と、が同じ窒化物結晶で構成されている場合（例えばともにＧａＮ結晶で構成されている場合）、これらは殆ど同等の線膨張係数、同等の熱伝導率、同等の耐加工性（研磨耐性）を有する。 (F) When the surface (main surface) of the substrate 10 is the c-plane, and the substrate 10 and the polycrystal of the Group III metal grown in the through hole 10h are composed of the same nitride crystal ( For example, when both are composed of GaN crystals), they have almost the same coefficient of linear expansion, the same thermal conductivity, and the same work resistance (polishing resistance).
このように基板１０と貫通孔１０ｈ内の多結晶とが殆ど同等の線膨張係数を有することで、基板１０に温度変化が生じた際、基板１０と貫通孔１０ｈ内の多結晶との膨張量を揃えることができ、基板１０と貫通孔１０ｈ内の多結晶との界面から基板１０にクラックが入ることを抑制できる。また、これらが殆ど同等の熱伝導率を有することで、加熱による基板１０等の昇降温時において、基板１０の表面温度を面内均一にしやすくなる。さらにまた、これらが殆ど同等の耐加工性を有することで、上述の研磨ステップを実施することが容易となり、基板１０等の表裏面を、それぞれの領域区分（単結晶領域、多結晶領域）によらず連続した平滑な表面とすることが容易となる。 As described above, since the substrate 10 and the polycrystal in the through hole 10h have almost the same coefficient of linear expansion, the amount of expansion of the substrate 10 and the polycrystal in the through hole 10h when the temperature of the substrate 10 changes. It is possible to prevent cracks from entering the substrate 10 from the interface between the substrate 10 and the polycrystals in the through holes 10h. Further, since these have almost the same thermal conductivity, it becomes easy to make the surface temperature of the substrate 10 uniform in the plane when the substrate 10 or the like is raised or lowered by heating. Furthermore, since these have almost the same processing resistance, it becomes easy to carry out the above-mentioned polishing step, and the front and back surfaces of the substrate 10 and the like are divided into respective region divisions (single crystal region, polycrystalline region). Therefore, it becomes easy to obtain a continuous smooth surface.
（ｇ）本実施形態によれば、保持板１２上に塗布した液状Ｇａ１１上に基板１０を配置し、この状態で窒素源を含む雰囲気中で基板１０を加熱するという簡便な手法で貫通孔１０ｈを塞ぐことができることから、基板１０の穴埋めの処理コストを抑えることができる。 (G) According to the present embodiment, the through hole 10h is a simple method in which the substrate 10 is placed on the liquid Ga 11 coated on the holding plate 12 and the substrate 10 is heated in an atmosphere containing a nitrogen source in this state. It is possible to suppress the processing cost of filling the holes in the substrate 10 because the substrate 10 can be closed.
（ｈ）本実施形態によれば、上述のように、液状Ｇａ１１が基板１０と保持板１２とを一時的に接着する接着剤として機能することから、基板１０と保持板１２との接着が、加熱装置２００内への搬入（投入）前に行われる。このため、基板１０を例えば加熱装置２００内へ搬送（移送）する際、保持板１２上における基板１０の位置ずれや、貫通孔１０ｈ内への液状Ｇａ１１の侵入を抑制できる。また基板１０の位置ずれを抑制できることから、貫通孔１０ｈを有する基板１０が複数得られるまで、液状Ｇａ１１を介して保持板１２上に配置した状態で基板１０を保管することが容易になる。また、Ｇａは一度融解した後であっても、室温未満の所定温度となると過冷却状態を維持できず、再び固化する。このため、液状Ｇａ１１を介して保持板１２上に配置した基板１０を所定温度以下まで冷却して液状Ｇａ１１を固化させることで、基板１０と保持板１２との接着強度を高めることができ、その結果、上述の基板１０の搬送時における位置ずれ等を確実に抑制することができる。また、液状Ｇａ１１を固化させることで、保持板１２上に配置した基板１０を傾けたり、基板１０の主面が垂直となるように立てたりすることも可能となる。その結果、保持板１２上に配置した基板１０を保管する際、基板１０の主面が水平になるように保管する必要がなく、基板１０の保管がさらに容易となるとともに、保管場所の制限も少なくすることができる。 (H) According to the present embodiment, as described above, since the liquid Ga 11 functions as an adhesive for temporarily adhering the substrate 10 and the holding plate 12, the adhesion between the substrate 10 and the holding plate 12 can be achieved. This is performed before the loading (loading) into the heating device 200. Therefore, when the substrate 10 is transported (transferred) into, for example, the heating device 200, it is possible to suppress the displacement of the substrate 10 on the holding plate 12 and the invasion of the liquid Ga 11 into the through hole 10h. Further, since the misalignment of the substrate 10 can be suppressed, it becomes easy to store the substrate 10 in a state of being arranged on the holding plate 12 via the liquid Ga 11 until a plurality of substrates 10 having through holes 10h are obtained. Further, even after Ga has been melted once, it cannot maintain the supercooled state when it reaches a predetermined temperature lower than room temperature, and it solidifies again. Therefore, the adhesive strength between the substrate 10 and the holding plate 12 can be increased by cooling the substrate 10 arranged on the holding plate 12 via the liquid Ga 11 to a predetermined temperature or lower to solidify the liquid Ga 11. As a result, it is possible to reliably suppress the misalignment of the substrate 10 during transportation. Further, by solidifying the liquid Ga 11, it is possible to tilt the substrate 10 arranged on the holding plate 12 or to stand the substrate 10 so that the main surface of the substrate 10 is vertical. As a result, when the substrate 10 arranged on the holding plate 12 is stored, it is not necessary to store the substrate 10 so that the main surface of the substrate 10 is horizontal, which makes it easier to store the substrate 10 and also limits the storage location. Can be reduced.
（ｉ）また、貫通孔１０ｈ内を単結晶で埋め込む場合には、埋込ステップを実施する前に、貫通孔１０ｈの内面をエッチングし、貫通孔１０ｈの内面に付着した異物および貫通孔１０ｈの内面に形成されたダメージ層のうち少なくともいずれかを除去する洗浄工程が必要である。これに対し、本実施形態では、貫通孔１０ｈを多結晶（ＧａＮ多結晶１４）で埋め込むため、上述の洗浄工程は不要である。 (I) When embedding the inside of the through hole 10h with a single crystal, the inner surface of the through hole 10h is etched before the embedding step is performed, and the foreign matter adhering to the inner surface of the through hole 10h and the through hole 10h A cleaning step is required to remove at least one of the damaged layers formed on the inner surface. On the other hand, in the present embodiment, since the through holes 10h are embedded with polycrystals (GaN polycrystals 14), the above-mentioned cleaning step is unnecessary.
（ｊ）基板１０として、基板１０の主面のうち貫通孔１０ｈを含まない連続する領域の面積が１００ｍｍ２以上である基板を用意するとより好ましい。これにより、貫通孔１０ｈがＧａＮ多結晶１４で塞がれた基板１０上にデバイスを作製する際における、有効面積が減少しにくくなる。 (J) It is more preferable to prepare as the substrate 10 a substrate having an area of 100 mm 2 or more in a continuous region of the main surface of the substrate 10 that does not include the through hole 10h. This makes it difficult to reduce the effective area when the device is formed on the substrate 10 in which the through holes 10h are closed with the GaN polycrystal 14.
（３）変形例
本実施形態は、上述の態様に限定されず、以下に示す変形例のように変更することが可能である。
(3) Modified Example This embodiment is not limited to the above-described embodiment, and can be modified as shown in the modified example below.
（変形例１）
準備ステップでは、基板１０として、自然に発生した貫通孔を有する基板だけでなく、故意に貫通孔を形成した基板を用意してもよい。例えば、基板１０として、結晶の母相に比べて酸素濃度が局所的に大きくなっている領域や、極性反転領域や転位密集領域等がレーザ等により打ち抜かれて形成された貫通孔を有する基板を用意してもよい。この場合、基板１０の表面、裏面については、それぞれ、アズグロウン状態であってもよく、また、所定の表面処理（研磨処理やエッチング処理）が施されていてもよい。本変形例によっても、上述の実施形態と同様の効果が得られる。
(Modification example 1)
In the preparation step, as the substrate 10, not only a substrate having naturally generated through holes but also a substrate having through holes intentionally formed may be prepared. For example, as the substrate 10, a substrate having a through hole formed by punching out a region where the oxygen concentration is locally higher than that of the matrix of the crystal, a polarity inversion region, a dislocation dense region, and the like by a laser or the like. You may prepare it. In this case, the front surface and the back surface of the substrate 10 may be in an as-grown state, respectively, or may be subjected to a predetermined surface treatment (polishing treatment or etching treatment). The same effect as that of the above-described embodiment can be obtained by this modification.
（変形例２）
配置ステップでは、ＩＩＩ族金属であるインジウム（Ｉｎ）を介して保持板１２上に基板１０を配置するようにしてもよい。Ｉｎ（融点約１５０℃）は室温において固体であるため、本変形例では、平坦な基板支持（保持）面を有するホットプレート等の加熱装置を用いて保持板１２を所定温度に加熱することでＩｎを融解して液状Ｉｎとし、この液状Ｉｎ上に基板１０を配置する。本変形例では、埋込ステップを実施することで、貫通孔１０ｈがＩｎの窒化物多結晶（ＩｎＮ多結晶）で埋め込まれて塞がれる。本変形例によっても、上述の実施形態と同様の効果が得られる。また本変形例によれば、Ｇａを用いる場合よりも埋込ステップを低温条件で行うことができることから、上述のＮ原子の脱落を確実に抑制できる。
(Modification 2)
In the arrangement step, the substrate 10 may be arranged on the holding plate 12 via indium (In) which is a group III metal. Since In (melting point of about 150 ° C.) is solid at room temperature, in this modification, the holding plate 12 is heated to a predetermined temperature by using a heating device such as a hot plate having a flat substrate supporting (holding) surface. In is melted into a liquid In, and the substrate 10 is placed on the liquid In. In this modification, by carrying out the embedding step, the through hole 10h is embedded with the In nitride polycrystal (InN polycrystal) and closed. The same effect as that of the above-described embodiment can be obtained by this modification. Further, according to this modification, since the embedding step can be performed under low temperature conditions as compared with the case of using Ga, the above-mentioned loss of N atoms can be reliably suppressed.
（変形例３）
準備ステップでは、窒化アルミニウム（ＡｌＮ）、窒化アルミニウムガリウム（ＡｌＧａＮ）、窒化インジウム（ＩｎＮ）、窒化インジウムガリウム（ＩｎＧａＮ）、窒化アルミニウムインジウムガリウム（ＡｌＩｎＧａＮ）等のＩＩＩ族窒化物結晶、すなわち、ＡｌｘＩｎｙＧａ１−ｘ―ｙＮ（０≦ｘ≦１、０≦ｙ≦１、０≦ｘ＋ｙ≦１）の組成式で表されるＩＩＩ族窒化物の単結晶からなり、その表面が（０００１）面である基板を用意してもよい。これらの基板であっても、ＧａＮ基板と同様、表裏を貫通する貫通孔を有する場合があるからである。これらの場合においても、準備ステップ〜埋込ステップに至る一連のステップを実施することで、ＧａＮ多結晶又はＩｎＮ多結晶で貫通孔を塞ぐことができ、上述の実施形態と同様の効果が得られる。
(Modification 3)
In the preparatory step, group III nitride crystals such as aluminum nitride (AlN), aluminum gallium nitride (AlGaN), indium nitride (InN), indium gallium nitride (InGaN), and aluminum indium gallium nitride (AlInGaN), that is, Al x In. It is composed of a single crystal of Group III nitride represented by the composition formula of y Ga 1-x-y N (0 ≦ x ≦ 1, 0 ≦ y ≦ 1, 0 ≦ x + y ≦ 1), and its surface is (0001). A substrate that is a surface may be prepared. This is because even these substrates may have through holes penetrating the front and back surfaces as in the case of GaN substrates. Also in these cases, by carrying out a series of steps from the preparation step to the embedding step, the through hole can be closed with the GaN polycrystal or the InN polycrystal, and the same effect as that of the above-described embodiment can be obtained. ..
＜本発明の他の実施形態＞
以上、本発明の実施形態を具体的に説明した。しかしながら、本発明は上述の実施形態に限定されるものではなく、その要旨を逸脱しない範囲で種々変更可能である。
<Other Embodiments of the Present Invention>
The embodiments of the present invention have been specifically described above. However, the present invention is not limited to the above-described embodiment, and various modifications can be made without departing from the gist thereof.
（ａ）上述の実施形態では、準備ステップ〜埋込ステップに至る一連のステップを実施することで１枚のＧａＮ基板を取得する手法について説明した。しかしながら、本発明はこのような態様に限定されない。例えば、準備ステップ〜埋込ステップに至る一連のステップを実施した後、図７（ａ）に示すように、貫通孔１０ｈがＧａＮ多結晶１４で塞がれた基板１０の表面上にハイドライド気相成長法（ＨＶＰＥ法）等の気相成長法によりＧａＮ結晶膜２１を厚くエピタキシャル成長させる本格成長ステップを実施し、その後、このＧａＮ結晶膜２１をスライスすることにより、図７（ｂ）に示すように、１枚以上のＩＩＩ族窒化物基板（ＧａＮ基板）２０を取得するようにしてもよい。この場合であっても、上述の実施形態と同様の効果が得られる。 (A) In the above-described embodiment, a method of acquiring one GaN substrate by carrying out a series of steps from the preparation step to the embedding step has been described. However, the present invention is not limited to such aspects. For example, after performing a series of steps from the preparation step to the embedding step, as shown in FIG. 7A, the hydride vapor phase is placed on the surface of the substrate 10 in which the through holes 10h are closed with the GaN polycrystal 14. A full-scale growth step of thickly epitaxially growing the GaN crystal film 21 by a vapor phase growth method such as a growth method (HVPE method) is carried out, and then the GaN crystal film 21 is sliced as shown in FIG. 7 (b). One or more group III nitride substrates (GaN substrates) 20 may be acquired. Even in this case, the same effect as that of the above-described embodiment can be obtained.
本格成長ステップは、図８に示すハイドライド気相成長（ＨＶＰＥ）装置を用いて行うことができる。ＨＶＰＥ装置３００は、石英等の耐熱性材料からなり、成膜室３０１が内部に構成された気密容器３０３を備えている。成膜室３０１内には、基板１０を保持するサセプタ３０８が設けられている。サセプタ３０８は、回転機構３１６が有する回転軸３１５に接続されており、回転自在に構成されている。気密容器３０３の一端には、成膜室３０１内へＨＣｌガス、ＮＨ３ガス、Ｎ２ガスを供給するガス供給管３３２ａ〜３３２ｃが接続されている。ガス供給管３３２ｃにはＨ２ガスを供給するガス供給管３３２ｄが接続されている。ガス供給管３３２ａ〜３３２ｄには、上流側から順に、流量制御器３４１ａ〜３４１ｄ、バルブ３４３ａ〜３４３ｄがそれぞれ設けられている。ガス供給管３３２ａの下流には、原料としてのＧａ融液を収容するガス生成器３３３ａが設けられている。ガス生成器３３３ａには、ＨＣｌガスとＧａ融液との反応により生成された原料ガス（原料のハロゲン化物）であるＧａＣｌガスを、サセプタ３０８上に保持された基板１０に向けて供給するノズル３４９ａが接続されている。ガス供給管３３２ｂ，３３２ｃの下流側には、これらのガス供給管から供給された各種ガスをサセプタ３０８上に保持された基板１０に向けて供給するノズル３４９ｂ，３４９ｃがそれぞれ接続されている。気密容器３０３の他端には、成膜室３０１内を排気する排気管３３０が設けられている。排気管３３０にはポンプ３３１が設けられている。気密容器３０３の外周にはガス生成器３３３ａ内やサセプタ３０８上に保持された基板１０を所望の温度に加熱するゾーンヒータ３０７が、気密容器３０３内には成膜室３０１内の温度を測定する温度センサ３０９が、それぞれ設けられている。ＨＶＰＥ装置３００が備える各部材は、コンピュータとして構成されたコントローラ３８０に接続されており、コントローラ３８０上で実行されるプログラムによって、後述する処理手順や処理条件が制御されるように構成されている。 The full-scale growth step can be performed using the hydride vapor phase growth (HVPE) apparatus shown in FIG. The HVPE apparatus 300 includes an airtight container 303 made of a heat-resistant material such as quartz and having a film forming chamber 301 inside. A susceptor 308 for holding the substrate 10 is provided in the film forming chamber 301. The susceptor 308 is connected to the rotation shaft 315 of the rotation mechanism 316 and is rotatably configured. Gas supply pipes 332a to 332c for supplying HCl gas, NH 3 gas, and N 2 gas into the film forming chamber 301 are connected to one end of the airtight container 303. A gas supply pipe 332d for supplying H 2 gas is connected to the gas supply pipe 332c. The gas supply pipes 332a to 332d are provided with flow rate controllers 341a to 341d and valves 343a to 343d in this order from the upstream side. A gas generator 333a for accommodating a Ga melt as a raw material is provided downstream of the gas supply pipe 332a. The gas generator 333a has a nozzle 349a that supplies GaCl gas, which is a raw material gas (halide of the raw material) generated by the reaction of HCl gas and Ga melt, toward the substrate 10 held on the susceptor 308. Is connected. On the downstream side of the gas supply pipes 332b and 332c, nozzles 349b and 349c that supply various gases supplied from these gas supply pipes toward the substrate 10 held on the susceptor 308 are connected, respectively. At the other end of the airtight container 303, an exhaust pipe 330 for exhausting the inside of the film forming chamber 301 is provided. A pump 331 is provided in the exhaust pipe 330. A zone heater 307 that heats the substrate 10 held in the gas generator 333a or the susceptor 308 to a desired temperature is provided on the outer periphery of the airtight container 303, and the temperature in the film forming chamber 301 is measured in the airtight container 303. A temperature sensor 309 is provided for each. Each member included in the HVPE apparatus 300 is connected to a controller 380 configured as a computer, and is configured so that a processing procedure and processing conditions described later are controlled by a program executed on the controller 380.
上述の本格成長ステップをこのＨＶＰＥ装置３００を用いて行う場合、例えば以下の処理手順で実施することができる。まず、ガス生成器３３３ａ内に原料としてＧａ融液を収容し、また、貫通孔１０ｈがＧａＮ多結晶１４で塞がれた基板１０を、気密容器３０３内へ投入（搬入）し、サセプタ３０８上に保持する。そして、成膜室３０１内の加熱および排気を実施しながら、成膜室３０１内へ、Ｈ２ガス（或いは、Ｈ２ガスとＮ２ガスとの混合ガス）を供給する。そして、成膜室３０１内が所望の成膜温度、成膜圧力に到達し、また、成膜室３０１内の雰囲気が所望の雰囲気となった状態で、ガス供給管３３２ａ，３３２ｂからガス供給を行い、基板１０の主面に対し、成膜ガスとしてＧａＣｌガスとＮＨ３ガスとを供給する。これにより、図７（ａ）に示すように、基板１０の主面上にＧａＮ結晶膜２１が成長する。このとき、基板１０の表面（すなわちＧａＮの単結晶）上にはＧａＮ単結晶がエピタキシャル成長し、ＧａＮ多結晶１４上にはＧａＮ多結晶がさらに成長する。ＧａＮ結晶膜２１の成長が完了したら、成膜室３０１内へＮＨ３ガス、Ｎ２ガスを供給し、成膜室３０１内を排気した状態で、ガス生成器３３３ａ内へのＨＣｌガス、成膜室３０１内へのＨ２ガスの供給、ヒータ３０７による加熱をそれぞれ停止する。そして、成膜室３０１内の温度が５００℃以下となったらＮＨ３ガスの供給を停止し、その後、成膜室３０１内の雰囲気をＮ２ガスへ置換して大気圧に復帰させるとともに、成膜室３０１内を搬出可能な温度にまで低下させた後、成膜室３０１内からＧａＮ結晶膜２１が成長された基板１０を搬出する。 When the above-mentioned full-scale growth step is performed using the HVPE apparatus 300, it can be carried out by, for example, the following processing procedure. First, the Ga melt is housed in the gas generator 333a as a raw material, and the substrate 10 whose through hole 10h is closed with the GaN polycrystal 14 is put (carried) into the airtight container 303 and placed on the susceptor 308. Hold on. Then, H 2 gas (or a mixed gas of H 2 gas and N 2 gas) is supplied into the film forming chamber 301 while heating and exhausting the inside of the film forming chamber 301. Then, gas is supplied from the gas supply pipes 332a and 332b in a state where the film forming temperature and the film forming pressure in the film forming chamber 301 are reached and the atmosphere in the film forming chamber 301 is a desired atmosphere. perform, with respect to the main surface of the substrate 10, and supplies the GaCl gas and the NH 3 gas as the film forming gas. As a result, as shown in FIG. 7A, the GaN crystal film 21 grows on the main surface of the substrate 10. At this time, the GaN single crystal grows epitaxially on the surface of the substrate 10 (that is, the GaN single crystal), and the GaN polycrystal further grows on the GaN polycrystal 14. When the growth of the GaN crystal film 21 is completed, NH 3 gas and N 2 gas are supplied into the film forming chamber 301, and the HCl gas and the film are formed in the gas generator 333a with the inside of the film forming chamber 301 exhausted. The supply of H 2 gas into the chamber 301 and the heating by the heater 307 are stopped. Then, when the temperature in the film forming chamber 301 becomes 500 ° C. or less, the supply of NH 3 gas is stopped, and then the atmosphere in the film forming chamber 301 is replaced with N 2 gas to restore the atmospheric pressure, and the film is formed. After lowering the temperature inside the film chamber 301 to a temperature at which it can be carried out, the substrate 10 on which the GaN crystal film 21 is grown is carried out from the film forming chamber 301.
なお、上述と同様の理由から、本格成長ステップでは、ＨＣｌガスよりも先行して（例えば成膜室３０１内の加熱前から）ＮＨ３ガスを供給するのが好ましい。また、基板１０上に成長させるＧａＮ結晶膜２１の面内膜厚均一性を高めるため、本格成長ステップは、サセプタ３０８を回転させた状態で行うことが好ましい。 Incidentally, for the same reason as described above, in the full growth step, (before heating, for example film forming chamber 301) ahead of the HCl gas preferably supplied NH 3 gas. Further, in order to improve the in-plane film thickness uniformity of the GaN crystal film 21 to be grown on the substrate 10, it is preferable that the full-scale growth step is performed in a state where the susceptor 308 is rotated.
本格成長ステップを実施する際の処理条件としては、以下が例示される。
処理温度（基板１０の温度）：９８０〜１１００℃
処理圧力（成膜室３０１内の圧力）：９０〜１０５ｋＰａ、好ましくは、９０〜９５ｋＰａ
ＧａＣｌガスの分圧：１．５〜１５ｋＰａ
ＮＨ３ガスの分圧／ＧａＣｌガスの分圧：４〜２０
Ｎ２ガスの分圧／Ｈ２ガスの分圧：０〜１
The following are examples of processing conditions when carrying out the full-scale growth step.
Processing temperature (temperature of substrate 10): 980 to 1100 ° C.
Processing pressure (pressure in the film forming chamber 301): 90 to 105 kPa, preferably 90 to 95 kPa.
Partial pressure of GaCl gas: 1.5 to 15 kPa
Partial pressures of / GaCl gas of the NH 3 gas: 4-20
Partial pressure of N 2 gas / Partial pressure of H 2 gas: 0 to 1
なお、本格成長ステップで基板１０上に成長させる結晶膜は、ＧａＮ結晶膜に限定されず、ＡｌｘＩｎｙＧａ１−ｘ―ｙＮ（０≦ｘ≦１、０≦ｙ≦１、０≦ｘ＋ｙ≦１）の組成式で表されるＩＩＩ族窒化物の結晶膜を成長させることができる。 The crystal film grown on the substrate 10 in the full-scale growth step is not limited to the GaN crystal film, and Al x In y Ga 1-xy N (0 ≦ x ≦ 1, 0 ≦ y ≦ 1, 0 ≦). A crystal film of a group III nitride represented by the composition formula of x + y ≦ 1) can be grown.
（ｂ）また例えば、埋込ステップを、上述のＨＶＰＥ装置３００を用いて行ってもよい。これによっても、貫通孔１０ｈをＧａＮ多結晶１４で塞ぐことができ、上述の実施形態と同様の効果が得られる。但し、埋込ステップを、上述の加熱装置２００を用いて実施する方が、ＨＶＰＥ装置３００を用いて実施する場合よりも、装置コストを低減できる点、一度に複数の基板１０の貫通孔１０ｈの埋め込みを行うことができる点、基板１０の穴埋め処理のスループットを高めることができる点等で好ましいことは上述の通りである。 (B) Further, for example, the embedding step may be performed using the above-mentioned HVPE device 300. Also by this, the through hole 10h can be closed with the GaN polycrystal 14, and the same effect as that of the above-described embodiment can be obtained. However, when the embedding step is carried out using the above-mentioned heating device 200, the device cost can be reduced as compared with the case where the embedding step is carried out using the HVPE device 300, and the through holes 10h of a plurality of substrates 10 at a time. As described above, it is preferable in that it can be embedded and that the throughput of the hole filling process of the substrate 10 can be increased.
ＨＶＰＥ装置３００を用いて埋込ステップを行う場合、基板１０の温度が所定温度になったら、成膜室３０１内へのＮＨ３ガスの供給を維持した状態で、ガス供給管３３２ａからガス供給を行い、基板１０の主面に対しＧａＣｌガスを供給してもよい。これにより、貫通孔１０ｈがＧａＮ多結晶１４で塞がれる前に液状Ｇａ１１が全て気化してしまった場合であっても、貫通孔１０ｈ内にＧａＮ多結晶１４を成長させることができ、貫通孔１０ｈをＧａＮ多結晶１４で塞ぐことができる。 When the embedding step is performed using the HVPE apparatus 300, when the temperature of the substrate 10 reaches a predetermined temperature, the gas is supplied from the gas supply pipe 332a while maintaining the supply of NH 3 gas into the film forming chamber 301. Then, GaCl gas may be supplied to the main surface of the substrate 10. As a result, even if all the liquid Ga 11 is vaporized before the through hole 10h is closed by the GaN polycrystal 14, the GaN polycrystal 14 can be grown in the through hole 10h, and the through hole can be grown. 10h can be closed with GaN polycrystal 14.
また、この場合、埋込ステップと本格成長ステップとを同一のＨＶＰＥ装置３００を用い連続して行うことが好ましい。これにより、これらのステップ間に、基板１０を成膜室３０１外へ搬出する必要がなくなるため、基板１０の表面への不純物の付着が抑制され、その結果、基板１０上に成膜されるＧａＮ結晶膜２１の品質を高めることができる。 Further, in this case, it is preferable that the embedding step and the full-scale growth step are continuously performed using the same HVPE device 300. As a result, it is not necessary to carry the substrate 10 out of the film forming chamber 301 between these steps, so that the adhesion of impurities to the surface of the substrate 10 is suppressed, and as a result, the GaN formed on the substrate 10 is suppressed. The quality of the crystal film 21 can be improved.
（ｃ）また例えば、本実施形態では、本格成長ステップ、埋込ステップにおいて気相成長法としてＨＶＰＥ法を用いる場合について説明したが、本発明はこのような態様に限定されない。例えば、本格成長ステップ等において、有機金属気相成長法（ＭＯＣＶＤ法）や酸化物気相成長法（ＯＶＰＥ法）等のＨＶＰＥ法以外の気相成長法を用いるようにしてもよい。また例えば、本格成長ステップにおいて、フラックスとしてナトリウム（Ｎａ）等を用いるフラックス法、高圧高温化で行う融液成長法、アモノサーマル法等の手法を用いて液相成長を行うようにしてもよい。 (C) Further, for example, in the present embodiment, the case where the HVPE method is used as the vapor phase growth method in the full-scale growth step and the implantation step has been described, but the present invention is not limited to such an aspect. For example, in the full-scale growth step or the like, a vapor phase growth method other than the HVPE method such as the organic metal vapor phase growth method (MOCVD method) or the oxide vapor phase growth method (OVPE method) may be used. Further, for example, in the full-scale growth step, liquid phase growth may be carried out by using a method such as a flux method using sodium (Na) as a flux, a melt growth method performed at high pressure and high temperature, or an amonothermal method. ..
＜本発明の好ましい態様＞
以下、本発明の好ましい態様について付記する。
<Preferable Aspect of the Present Invention>
Hereinafter, preferred embodiments of the present invention will be added.
（付記１）
本発明の一態様によれば、
ＩＩＩ族窒化物の結晶からなり、表裏を貫通する貫通孔を（１つ以上）有する基板を用意する準備工程と、
前記基板を、ＧａまたはＩｎのうち少なくともいずれかのＩＩＩ族金属を介して保持板上に配置する配置工程と、
前記保持板上に配置した前記基板を、少なくとも窒素源を含む雰囲気中で加熱して前記ＩＩＩ族金属を気化させ、前記基板の裏面側から表面側に向かって前記貫通孔内を流れる前記ＩＩＩ族金属の蒸気と、前記窒素源と、を前記貫通孔内で反応させることで、前記貫通孔を塞ぐ前記ＩＩＩ族金属の窒化物多結晶を前記貫通孔内の少なくとも一部に成長させる埋込工程と、
を有するＩＩＩ族窒化物基板の製造方法が提供される。
(Appendix 1)
According to one aspect of the invention
A preparatory step for preparing a substrate which is composed of group III nitride crystals and has (one or more) through holes penetrating the front and back surfaces.
An arrangement step of arranging the substrate on the holding plate via at least one group III metal of Ga or In,
The substrate arranged on the holding plate is heated in an atmosphere containing at least a nitrogen source to vaporize the group III metal, and the group III flows through the through hole from the back surface side to the front surface side of the substrate. An embedding step in which a nitride polycrystal of a group III metal that closes the through hole is grown in at least a part of the through hole by reacting the metal vapor and the nitrogen source in the through hole. When,
A method for producing a group III nitride substrate having the above is provided.
（付記２）
付記１の方法であって、好ましくは、
前記配置工程では、前記ＩＩＩ族金属を介して前記保持板上に前記基板を配置する際、前記貫通孔内に前記ＩＩＩ族金属が侵入することがないように、前記保持板上に塗布する前記ＩＩＩ族金属の量を調整する。
(Appendix 2)
The method of Appendix 1, preferably
In the arrangement step, when the substrate is arranged on the holding plate via the group III metal, the substrate is applied onto the holding plate so that the group III metal does not enter the through hole. Adjust the amount of group III metals.
（付記３）
付記１または２の方法であって、好ましくは、
前記配置工程では、前記ＩＩＩ族金属を介して前記保持板上に前記基板を配置する際、前記貫通孔内に前記ＩＩＩ族金属が侵入することがないように、前記保持板上に塗布する前記ＩＩＩ族金属の位置を調整する。
(Appendix 3)
The method of Appendix 1 or 2, preferably
In the arrangement step, when the substrate is arranged on the holding plate via the group III metal, the substrate is applied onto the holding plate so that the group III metal does not enter the through hole. Adjust the position of group III metals.
（付記４）
付記１〜３のいずれかの方法であって、好ましくは、
前記埋込工程では、前記ＩＩＩ族金属の気化が始まる前から前記雰囲気中に前記窒素源を供給する。
(Appendix 4)
Any of the methods of Appendix 1 to 3, preferably.
In the embedding step, the nitrogen source is supplied into the atmosphere even before the vaporization of the group III metal starts.
（付記５）
付記１〜４のいずれかの方法であって、好ましくは、
前記埋込工程では、前記基板の温度を５５０℃以上１２００℃以下、好ましくは９００℃以上１０００℃以下の範囲内の所定温度にする。
(Appendix 5)
Any of the methods of Appendix 1 to 4, preferably.
In the embedding step, the temperature of the substrate is set to a predetermined temperature within the range of 550 ° C. or higher and 1200 ° C. or lower, preferably 900 ° C. or higher and 1000 ° C. or lower.
（付記６）
付記１〜５のいずれかの方法であって、好ましくは、
前記準備工程では、前記基板として、前記基板の表面側から見たときの前記貫通孔の最小幅が３００μｍより大きい基板を用意する。好ましくは、前記貫通孔の最大幅が３ｍｍ以下である。
(Appendix 6)
The method according to any one of Supplementary notes 1 to 5, preferably.
In the preparation step, as the substrate, a substrate having a minimum width of the through hole larger than 300 μm when viewed from the surface side of the substrate is prepared. Preferably, the maximum width of the through hole is 3 mm or less.
（付記７）
付記１〜６のいずれかの方法であって、好ましくは、
前記準備工程では、前記基板として、ＡｌｘＩｎｙＧａ１−ｘ―ｙＮ（０≦ｘ≦１、０≦ｙ≦１、０≦ｘ＋ｙ≦１）の単結晶からなり、その表面が（０００１）面である基板を用意する。
(Appendix 7)
The method according to any one of Supplementary notes 1 to 6, preferably.
In the preparatory step, the substrate is made of a single crystal of Al x In y Ga 1-x-y N (0 ≦ x ≦ 1, 0 ≦ y ≦ 1, 0 ≦ x + y ≦ 1), and its surface is (0001). ) Prepare a substrate that is a surface.
（付記８）
付記１〜７のいずれかの方法であって、好ましくは、
前記埋込工程を実施することで得られたＩＩＩ族窒化物基板上に、ＩＩＩ族金属の窒化物結晶からなる結晶膜を成長させる本格成長工程と、
前記結晶膜から１枚以上のＩＩＩ族窒化物基板を切り出すスライス工程と、をさらに備える。
(Appendix 8)
The method according to any one of Supplementary notes 1 to 7, preferably.
A full-scale growth step of growing a crystal film composed of a nitride crystal of a group III metal on a group III nitride substrate obtained by carrying out the embedding step, and a full-scale growth step.
Further comprising a slicing step of cutting out one or more group III nitride substrates from the crystal film.
（付記９）
本発明の他の態様によれば、
ＩＩＩ族窒化物の結晶からなり、
表裏を貫通する貫通孔を（１つ以上）有し、
前記貫通孔内の少なくとも一部が、ＧａまたはＩｎのうち少なくともいずれかのＩＩＩ族金属の窒化物多結晶によって塞がれてなるＩＩＩ族窒化物基板が提供される。
(Appendix 9)
According to another aspect of the invention
Consists of group III nitride crystals
Has (one or more) through holes that penetrate the front and back
A group III nitride substrate is provided in which at least a part of the through hole is closed by a nitride polycrystal of at least one group III metal of Ga or In.
（付記１０）
本発明のさらに他の態様によれば、
ＩＩＩ族窒化物の結晶からなる基板であって、
前記基板は、表裏を貫通する貫通孔を（１つ以上）有し、
前記貫通孔内の少なくとも一部には、ＧａまたはＩｎのうち少なくともいずれかのＩＩＩ族金属を加熱することで気化して生成されて前記基板の裏面側から表面側に向かって前記貫通孔内を流れる前記ＩＩＩ族金属の蒸気と、窒素源と、が前記貫通孔内で反応することで、前記貫通孔を塞ぐ前記ＩＩＩ族金属の窒化物多結晶が成長されているＩＩＩ族窒化物基板が提供される。
(Appendix 10)
According to yet another aspect of the invention.
A substrate made of group III nitride crystals.
The substrate has (one or more) through holes penetrating the front and back surfaces.
At least a part of the through hole is generated by vaporizing at least one of the group III metals of Ga or In by heating, and the inside of the through hole is formed from the back surface side to the front surface side of the substrate. Provided is a group III nitride substrate in which a nitride polycrystal of the group III metal that closes the through hole is grown by reacting the flowing vapor of the group III metal with a nitrogen source in the through hole. Will be done.
（付記１１）
付記９または１０の基板であって、好ましくは、
前記貫通孔は、前記ＩＩＩ族金属の窒化物多結晶のみで塞がれている。
(Appendix 11)
The substrate of Appendix 9 or 10, preferably
The through hole is closed only with the nitride polycrystal of the group III metal.
（付記１２）
付記９〜１１のいずれかの基板であって、好ましくは、
前記貫通孔内には、窒化不充分な前記ＩＩＩ族金属が存在しない。
(Appendix 12)
The substrate according to any one of Appendix 9 to 11, preferably
The group III metal having insufficient nitriding is not present in the through hole.
（付記１３）
付記９〜１２のいずれかの基板であって、好ましくは、
前記基板の表面側から見たときの前記貫通孔の最小幅が３００μｍより大きい。
(Appendix 13)
The substrate according to any one of Appendix 9 to 12, preferably
The minimum width of the through hole when viewed from the surface side of the substrate is larger than 300 μm.
（付記１４）
付記９〜１３のいずれかの基板であって、好ましくは、
前記基板は、ＡｌｘＩｎｙＧａ１−ｘ―ｙＮ（０≦ｘ≦１、０≦ｙ≦１、０≦ｘ＋ｙ≦１）の単結晶からなる。
(Appendix 14)
The substrate according to any one of Appendix 9 to 13, preferably
The substrate is composed of a single crystal of Al x In y Ga 1-xy N (0 ≦ x ≦ 1, 0 ≦ y ≦ 1, 0 ≦ x + y ≦ 1).
１０ ＧａＮ基板（貫通孔を有する処理対象基板）
１０ｈ 貫通孔
１４ ＧａＮ多結晶（ＩＩＩ族金属の窒化物多結晶）
２０ ＧａＮ基板（ＩＩＩ族窒化物基板）
10 GaN substrate (processed substrate with through holes)
10h through hole 14 GaN polycrystal (nitride polycrystal of group III metal)
20 GaN substrate (group III nitride substrate)
Claims (6)
前記基板を、ＧａまたはＩｎのうち少なくともいずれかの液状のＩＩＩ族金属を介して保持板上に配置する配置工程と、
前記保持板上に配置した前記基板を、少なくとも窒素源を含む雰囲気中で加熱して前記ＩＩＩ族金属を気化させ、前記基板の裏面側から表面側に向かって前記貫通孔内を流れる前記ＩＩＩ族金属の蒸気と、前記窒素源と、を前記貫通孔内で反応させることで、前記貫通孔を塞ぐ前記ＩＩＩ族金属の窒化物多結晶を前記貫通孔内の少なくとも一部に成長させる埋込工程と、
を有するＩＩＩ族窒化物基板の製造方法。 A preparatory step of preparing a substrate made of group III nitride crystals and having through holes penetrating the front and back surfaces, and
An arrangement step of arranging the substrate on the holding plate via at least one liquid group III metal of Ga or In,
The substrate arranged on the holding plate is heated in an atmosphere containing at least a nitrogen source to vaporize the group III metal, and the group III flows through the through hole from the back surface side to the front surface side of the substrate. An embedding step in which a nitride polycrystal of a group III metal that closes the through hole is grown in at least a part of the through hole by reacting the metal vapor and the nitrogen source in the through hole. When,
A method for producing a group III nitride substrate having the above.
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