JPH0513119B2 - - Google Patents
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- Publication number
- JPH0513119B2 JPH0513119B2 JP61056580A JP5658086A JPH0513119B2 JP H0513119 B2 JPH0513119 B2 JP H0513119B2 JP 61056580 A JP61056580 A JP 61056580A JP 5658086 A JP5658086 A JP 5658086A JP H0513119 B2 JPH0513119 B2 JP H0513119B2
- Authority
- JP
- Japan
- Prior art keywords
- single crystal
- ωcm
- specific resistivity
- compound semiconductor
- group
- 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.)
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- Crystals, And After-Treatments Of Crystals (AREA)
- Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)
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
抗率の高い絶縁性−族の二元素以上からなる
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 (Field of Industrial Application) The present invention relates to a compound semiconductor single crystal composed of two or more insulating group elements, which has an extremely low carbon concentration and a high specific resistivity, and a method for producing 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
（GaAs）単結晶は、電子移動度が大きいので、
高速デイバイス、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
縁性はデイバイス製造において要求される重要な
特許である。この場合、不純物としての炭素はイ
オンインプラネーシヨンなどにより、結晶表面に
ｎ型の電気的活性層を作る場合のキラーとして作
用し、活性層のキヤ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 (GaAs) single crystals, have high electron mobility, so
Although it is widely used as a material for high-speed devices and high-speed integrated circuits, the semi-insulating property of this compound semiconductor is an important patent required in device manufacturing. In this case, carbon as an impurity acts as a killer when forming an n-type electrically active layer on the crystal surface by ion implantation, etc., and significantly reduces the carrier concentration in the active layer. is desired to be extremely low.
しかし、結晶中の炭素濃度を通常の値の２×
1016原子数／cm3から２×1014原子数／cm3程度にま
で減少させてゆくと、結晶の固有抵抗率が１×
108Ωcmのオーダーから１×106Ωcm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, the carbon concentration in the crystal is 2× the normal value.
When decreasing the number of atoms from 10 16 atoms/cm 3 to about 2×10 14 atoms/cm 3 , the specific resistivity of the crystal increases to 1×
The conductivity decreases from the order of 10 8 Ωcm to below the order of 1×10 6 Ωcm, 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
きには隠れて現われなかつた浅いドナー不純物お
よび結晶欠陥が相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 carbon acceptors decreases, so shallow donor impurities and crystal defects that were hidden and did not appear when the carbon concentration was high become relatively electrically active, and the crystal becomes n This is thought to be because it exhibits 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、炭素濃度の低い−族の二
元素以上からなる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 present inventors have found that even after heating a compound semiconductor single crystal consisting of two or more elements of the − group with a low carbon concentration, The present invention was achieved by discovering that the specific resistivity can be brought to a semi-insulating state by rapid cooling.
（発明の構成）
すなわち第１の発明は、炭素濃度が1.5×1015
原子数／cm3以下、固有抵抗率が２×107Ωcm以上
であることを特徴とする−族の二元素以上か
らなる化合物半導体単結晶であり、第２の発明
は、炭素濃度が1.5×1015原子数／cm3以下、固有
抵抗率が１×107Ωcm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２×107Ωcm
以上とすることを特徴とする−族の二元素以
上からな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 1.5×10 15
The second invention is a compound semiconductor single crystal consisting of two or more elements of the - group, characterized in that the number of atoms/cm 3 or less and the specific resistivity is 2×10 7 Ωcm or more, 10 15 atoms/cm 3 or less and a starting single crystal material with a specific resistivity of 1×10 7 Ωcm or less,
After heating to 750°C to 1100°C, it is rapidly cooled at a rate of 1.0°C or more per minute to reduce the specific resistivity of the single crystal to 2×10 7 Ωcm.
This is a method for manufacturing a compound semiconductor single crystal comprising two or more elements of the - group, characterized by the above.
以下本発明をGaAs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 begin to exhibit n-type conductivity as the carbon concentration is reduced. Of course, no n-type conductive impurities such as Si or S are added here.
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つて固有
抵抗率はは数桁上昇し、２×107乃至２×108Ωcm
になつた。このように、高温からの急冷によつて
固有抵抗率が半絶縁性の領域まで高くなること
は、今迄到底考えられないことであつた。 This crystal is placed in a heating furnace between 750℃ and 1100℃.
Preferably, heat and hold at 950°C for 30 minutes to several hours,
After that, even if it is slowly cooled in a heating furnace, the specific resistivity hardly changes from immediately after crystal growth. However, when this heat-treated single crystal was taken out of the heating furnace and
By rapidly cooling at a rate of ℃/min or more, the specific resistivity increases by several orders of magnitude, and reaches 2×10 7 to 2×10 8 Ωcm.
It became. Thus, until now, it was completely unthinkable that rapid cooling from a high temperature would increase the specific resistivity to a semi-insulating range.
本発明の方法では、単結晶は棒状、ブロツク状
に成形したもの、ウエ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
の急冷却前後のエツチピツト分布を比較したが、
転位の発生増加がないことも確かめられた。 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 a single crystal sliced into wafers. We also compared the etchipite distribution of this crystal before and after rapid cooling.
It was also confirmed that there was no increase in the occurrence of dislocations.
なお、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、ブリツ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, Bridgeman method, or vapor pressure control method, regardless of the type of manufacturing method.
また、本発明の対象とする−族の二元素以
上からなる化合物半導体としては、GaAs，
GaP，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−InAsなどもその対象として挙げられる。 In addition, the compound semiconductors made of two or more - group elements that are the object of the present invention include GaAs,
GaP, GaAsP, InAs, InP, InSb or a mixture of two or more of these crystal constituents, e.g.
GaAs-InAs 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1.1×1015原子／cm3、固有抵
抗率が1.4×106ΩcmであるGaAs単結晶のウエー
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、2.7×107Ωcm
であつた。つぎに温度を変えて900℃、950℃、
1000℃で同様の処理をしたところ、固有抵抗率は
それぞれ、5.2×107、6.6×107、7.9×107Ωcmであ
つた。Example 1 A GaAs single crystal wafer with a carbon impurity concentration of 1.1×10 15 atoms/cm 3 and a specific resistivity of 1.4×10 6 Ωcm was placed in a heating furnace, held at 850°C for 30 minutes, and then removed from the furnace. When taken out and rapidly cooled at a rate of 5°C per minute or more, the specific resistivity was measured and found to be 2.7×10 7 Ωcm.
It was hot. Next, change the temperature to 900℃, 950℃,
When the same treatment was performed at 1000°C, the specific resistivities were 5.2×10 7 , 6.6×10 7 , and 7.9×10 7 Ωcm, respectively.
実施例 ２
炭素不純物濃度が0.6×1015原子／cm3、固有抵
抗率が3.4ΩcmであるGaAs単結晶のインゴツトを
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8.5
Ωcmであつた。Example 2 A GaAs single crystal ingot with a carbon impurity concentration of 0.6 x 10 15 atoms/cm 3 and a specific resistivity of 3.4 Ωcm was placed in a heating furnace, kept at 900°C for 24 hours, and then heated every minute.
When cooled at a rate of 0.5℃, the specific resistivity was 8.5
It was Ωcm.
つぎに、同インゴツトをウエーハにし、加熱炉
に入れ、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、2.0×107Ω
cmであつた。 Next, the same ingot was made into a wafer, placed in a heating furnace, held at 850°C for 30 minutes, and rapidly cooled at a rate of 5°C or more per minute. As a result, the specific resistivity was 2.0 × 10 7 Ω.
It was cm.
実施例 ３
InAsを重量で２％含むGaAs無転位単結晶で、
炭素濃度が1.7×1015原子数／cm3、固有抵抗率が
5.6×103Ωcmのインゴツトを加熱炉に入れ、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2.6×106Ωcmであつた。
このインゴツトをウエーハにし、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2.0×107Ωcmであ
つた。Example 3 GaAs dislocation-free single crystal containing 2% InAs by weight,
The carbon concentration is 1.7×10 15 atoms/cm 3 and the specific resistivity is
Put a 5.6×10 3 Ωcm ingot into a heating furnace and
As a result of heating and holding at ℃ for 24 hours and cooling at a rate of 0.8 ℃ per minute, the specific resistivity was 2.6×10 6 Ωcm.
This ingot is made into wafers and placed in a heating furnace.
After being held at 850°C for 5 hours, it was taken out and cooled at 1.2°C per minute, and the specific resistivity was 2.0×10 7 Ωcm.
（発明の効果）
本発明による−族の二元素以上からなる化
合物半導体単結晶は、含まれる炭素濃度が1.5×
1015原子数／cm3と少ないにもかかわらず、固有抵
抗率が２×107Ωcm以上と高い半絶縁性のもので、
高速デイバイス、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 composed of two or more - group elements according to the present invention has a carbon concentration of 1.5×
Despite having a small number of 10 15 atoms/cm 3 , it is a semi-insulating material with a high specific resistivity of over 2×10 7 Ωcm.
It is an extremely excellent material for high-speed devices and high-speed integrated circuits.
Claims (1)
抵抗率が２×107Ωcm以上であることを特徴とす
る−族の二元素以上からなる化合物半導体単
結晶。 ２ −族の二元素以上からなる化合物半導体
単結晶がGaAs，GaP，GaAsP，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項に記載の単結晶。 ３ 炭素濃度が1.5×1015原子数／cm3以下、固有
抵抗率が１×107Ωcm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２×107Ωcm
以上とすることを特徴とする−族の二元素以
上からなる化合物半導体単結晶の製造方法。 ４ 始発単結晶材料が棒状もしくはブロツク状イ
ンゴツトあるいはウエハーである特許請求の範囲
第３項に記載の方法。 ５ −族の二元素以上からなる化合物半導体
単結晶がGaAs，GaP，GaAsP，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３項に記載の方法。[Scope of Claims] 1. A compound semiconductor single crystal consisting of two or more - group elements, characterized by having a carbon concentration of 1.5×10 15 atoms/cm 3 or less and a specific resistivity of 2×10 7 Ωcm or more. . Compound semiconductor single crystals consisting of two or more elements of group 2-2 are GaAs, GaP, GaAsP, InAs, InP,
The single crystal according to claim 1, which is any one type of InSb or a mixture thereof. 3 A starting single crystal material with a carbon concentration of 1.5×10 15 atoms/cm 3 or less and a specific resistivity of 1×10 7 Ωcm or less,
After heating to 750°C to 1100°C, it is rapidly cooled at a rate of 1.0°C or more per minute to reduce the specific resistivity of the single crystal to 2×10 7 Ωcm.
A method for producing a compound semiconductor single crystal comprising two or more - group elements, characterized by the above. 4. The method according to claim 3, wherein the starting single crystal material is a rod-shaped or block-shaped ingot or wafer. Compound semiconductor single crystals consisting of two or more elements of the 5-group are GaAs, GaP, GaAsP, InAs, InP,
The method according to claim 3, which is any one type of 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 JPS62216999A (en) | 1987-09-24 |
| JPH0513119B2 true 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) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0787187B2 (en) * | 1987-08-13 | 1995-09-20 | 古河電気工業株式会社 | Method for manufacturing GaAs compound semiconductor substrate |
| JPS6472999A (en) * | 1987-09-14 | 1989-03-17 | Nippon Mining Co | Heat treatment of compound semiconductor single crystal |
| JP2505222B2 (en) * | 1987-10-16 | 1996-06-05 | 昭和電工株式会社 | Method for manufacturing 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 |
Family Cites Families (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
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62216999A (en) | 1987-09-24 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |