JPS62216999A - Compound semiconductor single crystal and its production - Google Patents
Compound semiconductor single crystal and its productionInfo
- Publication number
- JPS62216999A JPS62216999A JP5658086A JP5658086A JPS62216999A JP S62216999 A JPS62216999 A JP S62216999A JP 5658086 A JP5658086 A JP 5658086A JP 5658086 A JP5658086 A JP 5658086A JP S62216999 A JPS62216999 A JP S62216999A
- Authority
- JP
- Japan
- Prior art keywords
- single crystal
- resistivity
- compound semiconductor
- specific resistivity
- semiconductor single
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000013078 crystal Substances 0.000 title claims abstract description 43
- 239000004065 semiconductor Substances 0.000 title claims abstract description 14
- 150000001875 compounds Chemical class 0.000 title claims description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 11
- 229910001218 Gallium arsenide Inorganic materials 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims description 5
- 229910000673 Indium arsenide Inorganic materials 0.000 claims description 2
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 claims description 2
- WPYVAWXEWQSOGY-UHFFFAOYSA-N indium antimonide Chemical compound [Sb]#[In] WPYVAWXEWQSOGY-UHFFFAOYSA-N 0.000 claims description 2
- RPQDHPTXJYYUPQ-UHFFFAOYSA-N indium arsenide Chemical compound [In]#[As] RPQDHPTXJYYUPQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910005540 GaP Inorganic materials 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 10
- 238000010791 quenching Methods 0.000 abstract 2
- 230000000171 quenching effect Effects 0.000 abstract 2
- 239000012535 impurity Substances 0.000 description 7
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 4
- 235000012431 wafers Nutrition 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 239000000370 acceptor Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000009828 non-uniform distribution Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、炭素濃度が極めて低くしかも固有抵抗率の高
い半絶縁性化合物半導体単結晶およびその製造方法に関
する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a semi-insulating compound semiconductor single crystal having extremely low carbon concentration and high specific resistivity, and a method for manufacturing the same.
（従来技術とその問題点）
■−■族化合物半導体、たとえばガリウム砒素（ＧａＡ
ｓ）単結晶は、電子移動度が大きいので、高速ディバイ
ス、高速集積回路などの材料として広く利用されている
が、この化合物半導体の半絶縁性はディバイス製造にお
いて要求される重要な特性である。この場合、不純物と
しての炭素はイオンインプラネーションなどにより、結
晶表面にｒｌ型の電気的活性層を作る場合のキラーとし
て作用し、活性層のキャリヤ濃度を著しく減少させるの
で、結晶中の炭素濃度はこれを極めて低くすることが望
まれている。(Prior art and its problems) ■-■ group compound semiconductors, such as gallium arsenide (GaA
s) Since single crystals have high electron mobility, they are widely used as materials for high-speed devices, high-speed integrated circuits, etc., and the semi-insulating property of this compound semiconductor is an important property required in device manufacturing. In this case, carbon as an impurity acts as a killer when an RL-type electrically active layer is formed on the crystal surface by ion implantation, etc., and significantly reduces the carrier concentration in the active layer, so the carbon concentration in the crystal decreases. It is desired to make this extremely low.
しかし、結晶中の炭素濃度を通常の値の２×１０１６原
子数／ｄから２ｘ ｌｏ １４原子数／ ａｄ程度にま
で減少させてゆくと、結晶の固有抵抗率が１、Ｘ１０１
１Ｑ訓のオーダーからＩ Ｘ Ｉ Ｏ’Ωσのオーダー
以下にまで低下し、ｎ型導電性に変化してしまう。However, when the carbon concentration in the crystal is reduced from the normal value of 2×1016 atoms/d to about 2× lo14 atoms/ad, the specific resistivity of the crystal becomes 1,×101
The conductivity decreases from the order of 1Q to below the order of I X I O'Ωσ, changing to n-type conductivity.
これは、炭素濃度の減少に伴い炭素による浅いアクセプ
ターが減少するため、炭素濃度が高いときには隠九で現
われなかった浅いドナー不純物および結晶欠陥力叫目対
的に電気的活性を示すようになり、結晶がｎ型導電性を
示すためと考えられる。This is because as the carbon concentration decreases, the number of shallow acceptors due to carbon decreases, so it becomes electrically active toward shallow donor impurities and crystal defects, which did not appear when the carbon concentration was high. This is thought to be because the crystal exhibits n-type conductivity.
しかして、結晶の半絶縁性を確保する目的において、従
来クロムなどの不純物を添加する方法が知られているが
、この方法はクロムが単結晶中に取り込まれるときに不
均一に分布し、電気特性のバラツキの原因となるので好
ましくない。このため低炭素含有率で、かつクロムなど
の不純物を添加せずに半絶縁性とする方法が久しく望ま
れていた。Conventionally, a method of adding impurities such as chromium is known for the purpose of ensuring semi-insulating properties of the crystal, but this method results in non-uniform distribution of chromium when it is incorporated into the single crystal. This is not preferable because it causes variations in characteristics. For this reason, there has long been a desire for a method of achieving semi-insulating properties with a low carbon content and without adding impurities such as chromium.
（問題点を解決するための手段）
本発明者らは、上述の問題点を解決すべく鋭意検討を重
ねた結果、炭素１度の低い化合物半導体単結晶でも加熱
後急冷すれば、固有抵抗率を半絶縁性の状態にすること
ができることを見出し本発明に到達した。(Means for Solving the Problems) As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have found that even a compound semiconductor single crystal with a low carbon 1 degree can have a specific resistivity of The present invention was achieved by discovering that it is possible to make a semi-insulating state.
（発明の構成）
すなわち第１の発明は、炭素濃度が１．５×１０１Ｊ）
？（子ａ／ｃｎ？以下、固Ｔｆｇ抗率ｆｆ１２ ｘ １
０’Ω■以上であることを特徴とする化合物半導体単結
晶であり、第２の発明は、炭素濃度が１．５×１０”ｆ
ｊｆｉ子数／ｄ以下、固有抵抗率がＩ Ｘ Ｉ Ｑ７Ω
備以下の始発単結晶材料を、７５０℃〜１１００℃に加
熱後、毎分１．０℃以上の速度で急冷却し、該単結晶の
固有抵抗率を２ Ｘ １０’Ω口以上とすることを特徴
とする化合物半導体単結晶の製造方法である。(Structure of the invention) That is, the first invention has a carbon concentration of 1.5×101J)
? (Child a/cn? Below, solid Tfg resistance ff12 x 1
The second invention is a compound semiconductor single crystal characterized by having a carbon concentration of 0'Ω■ or more, and a carbon concentration of 1.5×10"f
jfi number of children/d or less, specific resistivity is I X I Q7Ω
After heating the starting single crystal material below to 750°C to 1100°C, rapidly cool it at a rate of 1.0°C or more per minute to make the specific resistivity of the single crystal 2 x 10'Ω or more. A method for manufacturing a compound semiconductor single crystal, characterized by the following.
以下本発明をＧ ａ Ａ ｓ単結晶を例にとり詳しく説
明する。The present invention will be explained in detail below using a GaAs single crystal as an example.
ＧａＡｓ単結晶は炭素濃度を低減してゆくとｎ型導電性
を示すようになる。もちろんここではＳｉやＳなどのｎ
型導電性不純物は添加していない。GaAs single crystals come to exhibit n-type conductivity as the carbon concentration is reduced. Of course, here we use n such as Si and S.
No conductive impurities are added.
この結晶を加熱炉に入れ７５０℃から１１００℃の間、
好ましくは９５０℃に３０分乃至数時間加熱保持し、そ
の後加熱炉内で徐冷却しても固有抵抗率は結晶成長直後
とほとんど変化がない。しかるに、この加熱処理した単
結晶を加熱炉から取り出し、１．０℃／分以上の割合で
急冷却することによって固有抵抗率は数桁上昇し、２Ｘ
１０’乃至２×１０８Ω国になった。このように、高温
からの急冷によって固有抵抗率が半絶縁性の領域にまで
高くなることは、今迄到底考えられないことであった。This crystal was placed in a heating furnace between 750°C and 1100°C.
Preferably, even if the material is heated and maintained at 950.degree. C. for 30 minutes to several hours and then slowly cooled in a heating furnace, the specific resistivity hardly changes from immediately after crystal growth. However, by taking out this heat-treated single crystal from the heating furnace and rapidly cooling it at a rate of 1.0°C/min or more, the specific resistivity increases by several orders of magnitude, increasing 2X.
It became a 10' to 2 x 108Ω country. In this way, it was completely unthinkable until now that the specific resistivity could be increased to a semi-insulating region by rapid cooling from a high temperature.
本発明の方法では、単結晶は棒状、ブロック状に成形し
たもの、ウェーハにスライスしたものいずれでも同様な
結果が得られる。また、この結晶の急冷却前後のエッチ
ピット分布を比較したが。In the method of the present invention, similar results can be obtained whether the single crystal is formed into a rod shape, a block shape, or sliced into wafers. We also compared the etch pit distribution before and after rapid cooling of this crystal.
転位の発生増加がないことも確かめられた。It was also confirmed that there was no increase in the occurrence of dislocations.
なお１本発明の技術は単結晶の製法の種類を問わず、液
体封止法、ブリッジマン法あるいは蒸気圧制御法のいず
れで製造されたものでも適用可能である。Note that the technique of the present invention is applicable to single crystals manufactured by any of the liquid sealing method, Bridgman method, or vapor pressure control method, regardless of the type of manufacturing method.
また５本発明の対象とする化合物半導体はｍ −■族の
二元前以上からなる化合物半導体すべてに適用すること
ができ、ＧａＡｓ 、ＧａＰ 、ＧａＡｓＰ。Furthermore, the compound semiconductors to which the present invention is applied can be applied to all compound semiconductors consisting of binary or more m -■ group, such as GaAs, GaP, and GaAsP.
ＩｎＡｓ 、ＩｎＰ 、ＩｎＳｂあるいはこれらの結
晶構成成分の二成分以上の混合体、例えばＧａＡｓ−Ｉ
ｎＡｓなどもその対象として挙げられる。InAs, InP, InSb or a mixture of two or more of these crystal components, such as GaAs-I
nAs and the like are also included as targets.
つぎに本発明の実施例を述べる。Next, embodiments of the present invention will be described.
（実施例１）
炭素不純物濃度が１．Ｉ Ｘ １０”ｉ子数／ｄ、固有
抵抗率が１．４ Ｘ １０’Ω国であるＧ ａ Ａ ｓ
単結晶のウェーハを加熱炉に入れ、８５０℃で３０分保
持し、その後炉外に取り出し、毎分５℃以上の速度で急
冷却し、固有抵抗率を測定したところ、２．７ Ｘ １
０’Ω個であった。つぎに温度を変えて９００℃、９５
０℃、１０００℃で同様の処理をしたところ、固有抵抗
率はそれぞれ、５．２ｘ１０７、 Ｇ、６ Ｘ １０７
．７．９ ｘ １０７ΩＱであった。(Example 1) Carbon impurity concentration is 1. I x 10''i number of children/d, specific resistivity is 1.4 x 10'Ω
A single crystal wafer was placed in a heating furnace and held at 850°C for 30 minutes, then taken out of the furnace and rapidly cooled at a rate of 5°C or more per minute.The specific resistivity was measured and found to be 2.7 x 1.
The number was 0'Ω. Next, change the temperature to 900℃, 95℃
When similar treatments were performed at 0°C and 1000°C, the specific resistivities were 5.2 x 107, G, and 6 x 107, respectively.
．． It was 7.9 x 107ΩQ.
（実施例２） 炭素不純物濃度が０．６ Ｘ Ｉ Ｏ”原子数／ｄ。(Example 2) Carbon impurity concentration is 0.6 x IO'' atoms/d.
固有抵抗率が３．４ΩｃｍであるＧａＡｓ単結晶のイン
ゴットを加熱炉に入れ、９００℃で２４時間保持した後
、毎分０．５℃の速度で冷却したところ、固有抵抗率は
８．５Ωｃｍであった。A GaAs single crystal ingot with a specific resistivity of 3.4 Ωcm was placed in a heating furnace, held at 900°C for 24 hours, and then cooled at a rate of 0.5°C per minute.The specific resistivity was 8.5Ωcm. there were.
つぎに、同インゴットをウェーハにし、加熱炉しこ入れ
、８５０℃で３０分保持後、毎分５℃以上の速度で急冷
却した結果、固有抵抗率は、２．０ＸＩＯ７Ωｃｍであ
った。Next, the same ingot was made into a wafer, put into a heating furnace, held at 850° C. for 30 minutes, and then rapidly cooled at a rate of 5° C./min or more. As a result, the specific resistivity was 2.0×IO7 Ωcm.
（実施例３）
Ｉ ｒｌＡ ｓを重量で２％含むＧ ａ Ａ ｓ無転位
単結晶で。(Example 3) A GaAs dislocation-free single crystal containing 2% by weight of IrlAs.
炭素濃度が１．７ Ｘ Ｉ Ｏ”Ｊ７Ｉ子数／ ａｎｔ
、固有抵抗率が５．６Ｘ１０３Ωσのインゴットを加熱
炉に入れ、８５０℃で２４時間加熱保持し、毎分０．８
℃の速度で冷却した結果、固有抵抗率は２．６×１０’
Ωαであった。このインゴットをウェーハにし、加熱炉
に入れ、８５０℃で５時間保持した後取出し、毎分１．
２℃で冷却したところ、固有抵抗率は２．ＯＸ １０７
Ω印であった。Carbon concentration is 1.7 X I O”J7I number of children/ant
, an ingot with a specific resistivity of 5.6 x 103 Ωσ was placed in a heating furnace, heated and held at 850°C for 24 hours, and the resistivity was 0.8/min.
As a result of cooling at a rate of ℃, the specific resistivity is 2.6 x 10'
It was Ωα. This ingot was made into a wafer, placed in a heating furnace, held at 850°C for 5 hours, and then taken out, at a rate of 1.
When cooled to 2°C, the specific resistivity was 2. OX107
It was marked Ω.
（発明の効果）
本発明による化合物半導体単結晶は、含まれる炭素濃度
が１．５Ｘ１０”原子数／ ａｄと少ないにもかかわら
ず、固有抵抗率が２ Ｘ Ｉ Ｏ’Ωｍ以上と高い半絶
縁性のもので、高速ディバイス、高速集積回路用として
、きわめて優れた材料である。(Effects of the Invention) The compound semiconductor single crystal according to the present invention has a high semi-insulating property with a specific resistivity of 2 X I O'Ωm or more, even though the carbon concentration contained is as low as 1.5 X 10" atoms/ad. It is an extremely excellent material for high-speed devices and high-speed integrated circuits.
Claims (1)
以下、固有抵抗率が２×１０＾７Ωｃｍ以上であること
を特徴とする化合物半導体単結晶。 ２）炭素濃度が１．５×１０＾１＾５原子数／ｃｍ＾３
以下、固有抵抗率が１×１０＾７Ωｃｍ以下の始発単結
晶材料を、７５０℃〜１１００℃に加熱後、毎分１．０
℃以上の速度で急冷却し、該単結晶の固有抵抗率を２×
１０＾７Ωｃｍ以上とすることを特徴とする化合物半導
体単結晶の製造方法。 ３）始発単結晶材料が棒状もしくはブロック状インゴッ
トあるいはウェーハである特許請求の範囲第２項記載の
方法。 ４）化合物半導体単結晶がＧａＡｓ、ＧａＰ、ＧａＡｓ
Ｐ、ＩｎＡｓ、ＩｎＰ、ＩｎＳｂのいずれか一種、もし
くはこれらの混合である特許請求の範囲第１項、第２項
、第３項いずれかに記載の単結晶体。[Claims] 1) Carbon concentration is 1.5 x 10^1^5 atoms/cm^3
Hereinafter, a compound semiconductor single crystal characterized by having a specific resistivity of 2×10^7 Ωcm or more. 2) Carbon concentration is 1.5 x 10^1^5 atoms/cm^3
Below, a starting single crystal material with a specific resistivity of 1 x 10^7 Ωcm or less is heated to 750°C to 1100°C, and then heated at 1.0°C per minute.
The specific resistivity of the single crystal is reduced to 2× by rapid cooling at a rate of ℃ or higher.
A method for manufacturing a compound semiconductor single crystal, characterized in that the resistance is 10^7 Ωcm or more. 3) The method according to claim 2, wherein the starting single crystal material is a rod-shaped or block-shaped ingot or wafer. 4) Compound semiconductor single crystal is GaAs, GaP, GaAs
The single crystal body according to any one of claims 1, 2, and 3, which is any one of P, InAs, InP, and InSb, or a mixture thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5658086A JPS62216999A (en) | 1986-03-14 | 1986-03-14 | Compound semiconductor single crystal and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5658086A JPS62216999A (en) | 1986-03-14 | 1986-03-14 | Compound semiconductor single crystal and its production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62216999A true JPS62216999A (en) | 1987-09-24 |
| JPH0513119B2 JPH0513119B2 (en) | 1993-02-19 |
Family
ID=13031100
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5658086A Granted JPS62216999A (en) | 1986-03-14 | 1986-03-14 | Compound semiconductor single crystal and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62216999A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6445126A (en) * | 1987-08-13 | 1989-02-17 | Furukawa Electric Co Ltd | Manufacture of gaas compound semiconductor substrate |
| JPS6472999A (en) * | 1987-09-14 | 1989-03-17 | Nippon Mining Co | Heat treatment of compound semiconductor single crystal |
| JPH01102932A (en) * | 1987-10-16 | 1989-04-20 | Showa Denko Kk | Manufacture of semi-insulating gaas substrate |
| JPH01257200A (en) * | 1988-04-08 | 1989-10-13 | Furukawa Electric Co Ltd:The | Production of substrate for gaas compound semiconductor |
| US5209811A (en) * | 1988-03-25 | 1993-05-11 | Shin-Etsu Handotai Company Limited Of Japan | Method for heat-treating gallium arsenide monocrystals |
| JP2545477B2 (en) * | 1988-02-24 | 1996-10-16 | 株式会社ジャパンエナジー | Compound semiconductor single crystal, manufacturing method thereof, and semiconductor device using the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60210591A (en) * | 1984-04-05 | 1985-10-23 | Hitachi Cable Ltd | Production of semiinsulating gaas single crystal |
| JPS6144800A (en) * | 1984-08-09 | 1986-03-04 | Sumitomo Electric Ind Ltd | Method for improving crystal quality |
-
1986
- 1986-03-14 JP JP5658086A patent/JPS62216999A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60210591A (en) * | 1984-04-05 | 1985-10-23 | Hitachi Cable Ltd | Production of semiinsulating gaas single crystal |
| JPS6144800A (en) * | 1984-08-09 | 1986-03-04 | Sumitomo Electric Ind Ltd | Method for improving crystal quality |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6445126A (en) * | 1987-08-13 | 1989-02-17 | Furukawa Electric Co Ltd | Manufacture of gaas compound semiconductor substrate |
| JPS6472999A (en) * | 1987-09-14 | 1989-03-17 | Nippon Mining Co | Heat treatment of compound semiconductor single crystal |
| JPH01102932A (en) * | 1987-10-16 | 1989-04-20 | Showa Denko Kk | Manufacture of semi-insulating gaas substrate |
| JP2545477B2 (en) * | 1988-02-24 | 1996-10-16 | 株式会社ジャパンエナジー | Compound semiconductor single crystal, manufacturing method thereof, and semiconductor device using the same |
| US5209811A (en) * | 1988-03-25 | 1993-05-11 | Shin-Etsu Handotai Company Limited Of Japan | Method for heat-treating gallium arsenide monocrystals |
| JPH01257200A (en) * | 1988-04-08 | 1989-10-13 | Furukawa Electric Co Ltd:The | Production of substrate for gaas compound semiconductor |
| JPH058156B2 (en) * | 1988-04-08 | 1993-02-01 | Furukawa Electric Co Ltd |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0513119B2 (en) | 1993-02-19 |
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