JP5729182B2 - n型III族窒化物単結晶の製造方法、n型III族窒化物単結晶および結晶基板 - Google Patents
n型III族窒化物単結晶の製造方法、n型III族窒化物単結晶および結晶基板 Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims description 310
- 150000004767 nitrides Chemical class 0.000 title claims description 85
- 239000000758 substrate Substances 0.000 title claims description 56
- 238000004519 manufacturing process Methods 0.000 title claims description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 66
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 66
- 238000006243 chemical reaction Methods 0.000 claims description 51
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 50
- 239000001301 oxygen Substances 0.000 claims description 50
- 229910052760 oxygen Inorganic materials 0.000 claims description 50
- 239000007789 gas Substances 0.000 claims description 42
- 229910052757 nitrogen Inorganic materials 0.000 claims description 28
- 229910052796 boron Inorganic materials 0.000 claims description 27
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 26
- 229910052810 boron oxide Inorganic materials 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 24
- 150000001340 alkali metals Chemical class 0.000 claims description 17
- 229910052783 alkali metal Inorganic materials 0.000 claims description 15
- 230000008018 melting Effects 0.000 claims description 15
- 238000002844 melting Methods 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 5
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 80
- 229910002601 GaN Inorganic materials 0.000 description 72
- 239000002994 raw material Substances 0.000 description 15
- 239000011734 sodium Substances 0.000 description 12
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 11
- 239000012895 dilution Substances 0.000 description 11
- 238000010790 dilution Methods 0.000 description 11
- 238000007716 flux method Methods 0.000 description 11
- 229910052733 gallium Inorganic materials 0.000 description 11
- 238000010586 diagram Methods 0.000 description 9
- 229910001873 dinitrogen Inorganic materials 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 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 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 239000002585 base Substances 0.000 description 6
- 229910052732 germanium Inorganic materials 0.000 description 6
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 6
- 239000002019 doping agent Substances 0.000 description 5
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 4
- -1 Pyrolytic-BN (P-BN) Chemical class 0.000 description 4
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 229910052594 sapphire Inorganic materials 0.000 description 4
- 239000010980 sapphire Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 229910052582 BN Inorganic materials 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000009434 installation Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 description 2
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 238000002109 crystal growth method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000000927 vapour-phase epitaxy Methods 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
- C30B29/403—AIII-nitrides
- C30B29/406—Gallium nitride
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- C01B21/00—Nitrogen; Compounds thereof
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- C01B21/0632—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with gallium, indium or thallium
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- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
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Description
図1は、本実施の形態にかかるn型III族窒化物単結晶を製造する結晶製造装置1の構成例を示す概略図である。
(1)原料等の調製
本実施の形態にかかるn型III族窒化物単結晶の結晶製造方法では、III族窒化物の針状結晶を種結晶として用いて、当該針状結晶をフラックス法によりさらに成長させることにより、窒化物結晶基板を製造するための単結晶インゴットを製造する。
上述のように原料等を耐圧容器11内にセッティングした後、ヒーター13に通電して、耐圧容器11およびその内部の反応容器12を加熱する。上述のように酸化ホウ素の融点は本実施形態の結晶成長温度よりも低温であるため、反応容器12を結晶成長温度まで加熱する過程において、反応容器12の温度は酸化ホウ素の融点に達し、これにより、酸化ホウ素は融解して液化する(融解工程)。
上述のようにして得られたn型III族窒化物単結晶27を成形加工することによって、本実施の形態にかかるn型III族窒化物の結晶基板を製造する。図4は、本実施の形態にかかる結晶基板28m、28c(以降、特に限定しない場合には結晶基板28と称する。)を製造する製造工程を示す工程図である。
本実施例では、GaNの針状結晶25を種結晶として用いて、酸素がドープされたn型GaN単結晶27を結晶成長させた。尚、符号は図1を参照して説明した結晶製造装置1の構成に対応している。
本実施例では、酸化ホウ素(B2O3)の添加量はガリウムの量に対し0.04mol%とし、その他の実験条件は実施例1と同様としてn型GaN単結晶を結晶成長させた。
図5は、実施例3にかかる結晶製造装置2の構成を示す概略図である。本実施例では、耐圧容器11内に内径17mmの反応容器12(12a〜12e)を5個設置し、各々の反応容器12a〜12e内にGaNの針状結晶25(25a〜25e)を設置して、各針状結晶25a〜25eを結晶成長させた。
図6に示すように、酸化ホウ素(B2O3)を添加せずに結晶成長させたGaN単結晶27中の酸素濃度は、本測定時における酸素のバックグラウンド値である8×1016cm−3以下であった。また、酸化ホウ素(B2O3)を0.01mol%添加した場合には、GaN単結晶27中の酸素濃度は1017cm−3程度であり、酸化ホウ素(B2O3)を0.22mol%添加した場合には、GaN単結晶27中の酸素濃度は4×1020cm−3であった。従って、酸化ホウ素(B2O3)を0.01mol%ないし0.22mol%添加して結晶成長させることによって、GaN単結晶27中に酸素を1017cm−3ないし4×1020cm−3程度までドープできることが分かった。
図6に示すように、酸化ホウ素(B2O3)を0.01mol%添加した場合には、GaN単結晶27中のホウ素濃度は1017cm−3程度であり、酸化ホウ素(B2O3)を0.1mol%添加した場合には、GaN単結晶27中のホウ素濃度は3×1018cm−3程度であった。従って、酸化ホウ素(B2O3)を0.01mol%ないし0.22mol%添加して結晶成長させることによって、GaN単結晶27中にホウ素を1017cm−3ないし3×1018cm−3程度までドープできることが分かった。
さらに、GaN単結晶27(27a〜27e)について電気伝導度の測定を行った。その結果、GaN単結晶27はn型の電気伝導性を示し、酸化ホウ素(B2O3)の添加量が増えるにつれて電気伝導度が増加し、低抵抗となることが分かった。これは、GaN単結晶27中にドープされた酸素がドナーとして寄与していることに起因していると考えられる。
11 耐圧容器
12、12a、12b、12c、12d、12e 反応容器
13 ヒーター
14 ガス供給管
15、18、21 バルブ
16、19 圧力制御装置
17 窒素供給管
20 希釈ガス供給管
22 圧力計
23 内部空間
24 混合融液
25、25a 針状結晶(種結晶)
26 設置台
27、27a n型III族窒化物単結晶(n型GaN単結晶)
28、28m、28c 結晶基板
Claims (7)
- 反応容器内に、少なくともIII族元素を含む物質と、アルカリ金属と、酸化ホウ素と、を投入する材料投入工程と、
前記反応容器を前記酸化ホウ素の融点まで加熱することにより、前記酸化ホウ素を融解させる融解工程と、
前記反応容器をIII族窒化物の結晶成長温度まで加熱することにより、前記反応容器内に、前記III族元素と、前記アルカリ金属と、前記酸化ホウ素と、を含む混合融液を形成する混合融液形成工程と、
前記混合融液に窒素を含む気体を接触させて、前記混合融液中に窒素を溶解させる窒素溶解工程と、
前記混合融液中に溶解した前記III族元素と、前記窒素と、前記酸化ホウ素中の酸素とから、前記酸素がドナーとしてドープされたn型のIII族窒化物単結晶を結晶成長させる結晶成長工程と、
を含むことを特徴とするn型III族窒化物単結晶の製造方法。 - 前記結晶成長工程において、前記酸化ホウ素中のホウ素を前記n型III族窒化物単結晶にドープすること、を特徴とする請求項1記載のn型III族窒化物単結晶の製造方法。
- 請求項1または2に記載の製造方法で製造され、10 17 cm −3 以上の酸素および10 17 cm −3 以上のホウ素を含むことを特徴とするn型III族窒化物単結晶。
- 六角柱状の結晶を内部に備えることを特徴とする、請求項3記載のn型III族窒化物単結晶。
- 前記六角柱状の結晶は、前記n型III族窒化物単結晶よりも小さい酸素濃度およびホウ素濃度を有することを特徴とする請求項4に記載のn型III族窒化物単結晶。
- 請求項3または4に記載のn型III族窒化物単結晶からなり、m面またはc面を主面とすることを特徴とするn型III族窒化物の結晶基板。
- 前記c面を主面とし、エッチピット密度が10 3 cm −2 以下であることを特徴とする請求項6記載のn型III族窒化物の結晶基板。
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US14/474,924 US9464367B2 (en) | 2010-08-31 | 2014-09-02 | Method for producing N-type group III nitride single crystal, N-type group III nitride single crystal, and crystal substrate |
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