JPH0274597A - Chromium-doped semi-insulative gallium-arsenic single crystal and production thereof - Google Patents
Chromium-doped semi-insulative gallium-arsenic single crystal and production thereofInfo
- Publication number
- JPH0274597A JPH0274597A JP22515288A JP22515288A JPH0274597A JP H0274597 A JPH0274597 A JP H0274597A JP 22515288 A JP22515288 A JP 22515288A JP 22515288 A JP22515288 A JP 22515288A JP H0274597 A JPH0274597 A JP H0274597A
- Authority
- JP
- Japan
- Prior art keywords
- single crystal
- concentration
- nsi
- chromium
- crystal
- 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 58
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 title claims description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 229910001218 Gallium arsenide Inorganic materials 0.000 claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000010703 silicon Substances 0.000 claims abstract description 6
- 239000011651 chromium Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims 1
- 239000002019 doping agent Substances 0.000 claims 1
- 229910052733 gallium Inorganic materials 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- 239000010453 quartz Substances 0.000 abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 9
- 238000009736 wetting Methods 0.000 abstract description 9
- 230000009466 transformation Effects 0.000 abstract 1
- 238000000137 annealing Methods 0.000 description 12
- 239000012535 impurity Substances 0.000 description 10
- 230000007423 decrease Effects 0.000 description 5
- 239000011734 sodium Substances 0.000 description 4
- 239000011572 manganese Substances 0.000 description 3
- 235000012431 wafers Nutrition 0.000 description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- 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 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 101100080277 Caenorhabditis elegans ncr-1 gene Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
- Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、クロムドープ半絶縁性ガリウム・ヒ素（Ｇａ
Ａｓ）単結晶およびその製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention is directed to a chromium-doped semi-insulating gallium arsenide (Ga
As) It relates to a single crystal and its manufacturing method.
［従来の技術］
横形ボート法を用いて得られるクロム（Ｃｒ）ドープ半
絶縁性ＧａＡｓ結晶中＼は、比抵抗が高い（〜１０８Ω
・ＣＩ）、転位密度が小さい（〜５０００Ｃ１１−３）
等の特徴があり、液体封止引上法（ＬＥＣ法）を用いて
得られるウエノ１と競合して用いられている。ＧａＡｓ
にＣｒをドープする理由は、石英ボートから混入する浅
いドナーレベルを有するシリコン（Ｓｉ）に対し、深い
アクセプタレベルを有するＣｒをより多く添加すること
によりＳｉによる不純物の影響を補償するためである。[Prior art] Chromium (Cr)-doped semi-insulating GaAs crystal obtained using the horizontal boat method has a high specific resistance (~108Ω
・CI), low dislocation density (~5000C11-3)
It has the following characteristics and is used in competition with Ueno 1, which is obtained using the liquid-enclosed drawing method (LEC method). GaAs
The reason for doping Cr with Cr is to compensate for the influence of impurities caused by Si by adding more Cr having a deep acceptor level to silicon (Si) having a shallow donor level mixed in from the quartz boat.
半絶縁性、すなわち比抵抗ｐ〉１０６Ω・ｃｍの関係を
得るには（ｅ）式の関係を満足する必要がある。In order to obtain semi-insulating property, that is, the relationship of specific resistance p>106 Ω·cm, it is necessary to satisfy the relationship of equation (e).
ｎ ｃｒ＞ ｎ ｓ＋ −
（ｃ）但し、ｎｃｒ：Ｃｒの濃度、ｎｓｉ：Ｓｔの濃度
。n cr> n s+ −
(c) However, ncr: concentration of Cr, nsi: concentration of St.
［発明が解決しようとする課題］
上述したように石英ボートを用いて半絶縁性のＧａＡｓ
単結晶を製造する場合は、ボートから混入するＳｉの電
子レベルを補償するためＣｒドブが行なわれているが、
混入する５ｉｆｆｉが多い場合はさらに多量のＣｒを添
加しなければならない。[Problem to be solved by the invention] As described above, semi-insulating GaAs can be fabricated using a quartz boat.
When manufacturing single crystals, Cr doping is performed to compensate for the electronic level of Si mixed in from the boat.
If a large amount of 5iffi is mixed, a larger amount of Cr must be added.
しかしＣｒの偏析係数は約６Ｘ１０”−’と小さいため
結晶中に混入し難＜、Ｃｒ濃度が高くなった結晶成長の
後半では濃縮過大となって析出を生じてしまう。However, since the segregation coefficient of Cr is as small as about 6×10''-', it is difficult to mix into the crystal, and in the latter half of crystal growth when the Cr concentration becomes high, it becomes excessively concentrated and precipitates.
そこで、Ｓｌの混入を抑制する必要があるが、現在Ｓｉ
の量を低減する方法としては、酸素を添加する方法やＰ
ＢＮ （パイロリティック窒化ボロン）ボートを使用す
る方法等が採用されている。Therefore, it is necessary to suppress the contamination of Sl, but currently Si
Methods for reducing the amount of P include adding oxygen and
Methods such as using a BN (pyrolytic boron nitride) boat have been adopted.
しかし、酸素を添加する方法において石英ボートを使用
した場合、単結晶後端においてＳｉ濃度か著しく低下す
るため、石英ボートと単結晶後端との間に「ぬれ」 （
焼付き現象）を生ずることが確認されており、この「ぬ
れ」の発生はＳｉ濃度ｎｓｊ≦４． ４ Ｘ １０１５
ｃｍ−３（＝０． １ｐｐｍａ）のときに顕著である。However, when a quartz boat is used in the method of adding oxygen, the Si concentration at the rear end of the single crystal decreases significantly, resulting in "wetting" between the quartz boat and the rear end of the single crystal.
It has been confirmed that this "wetting" occurs when the Si concentration nsj≦4. 4 x 1015
It is noticeable at cm-3 (=0.1 ppma).
またＳｉ／ａ７１１１１：ｎｓｉがｎｓｉ≧８． ８
Ｘ １０ ”’ｃｍ−３（０、２ｐｐｍａ）の場合は、
アニール後表面比抵抗か低下することが知られている。Also, Si/a71111: nsi is nsi≧8. 8
In the case of X 10'''cm-3 (0.2ppma),
It is known that the surface resistivity decreases after annealing.
これは、Ｃｒか表面から外部拡散（ｏｕｔ ｄｉ「ｒｕ
ｓｉｏｎ ）することにより、（Ｃ）式を満足できない
場合が生じたためである。この傾向はＣｒｌａ度ｎｃｒ
が低くなる程顕著となり、安定した品質が得られない恐
れがある。This is caused by external diffusion from the Cr surface.
This is because there were cases where equation (C) could not be satisfied due to the following. This trend is Crla degree ncr
The lower the value, the more noticeable this becomes, and there is a risk that stable quality may not be obtained.
本発明の目的は、熱的に安定なりロムドープ半絶縁性ガ
リウム・ヒ素単結晶およびその製造方法を提供すること
にある。An object of the present invention is to provide a thermally stable ROM-doped semi-insulating gallium arsenide single crystal and a method for producing the same.
［課題を解決するための手段］
本発明は、ＧａＡｓ単結晶中に残留する残留シリコン濃
度ｎｓｉに対し、
１Ｘ１０ｃｍ ≦ｎｃ ＜ ｎｓｉ −（ａ）
ｎｓｉ−ｎｃ≦４ 、 ４ Ｘ １０１５ｃｍ−３−（
ｂ）の両式を満足する濃度ｎｃのカーボンを倉荷し、１
０６Ω・ｃｍ以上の比抵抗を有する第１の発明と、横形
ボート法によるＣｒドープ半絶縁性ＧａＡｓ単結晶の製
造方法において、上記（ａ）式及び（ｂ）式を満足する
濃度ｎｃとなるのに必要な量のカーボンをドープして製
造するようにした第２の発明とにより、熱的に安定なＣ
ｒドープ半絶縁性ＧａＡｓ単結晶が得られるようにして
目的の達成を計っている。[Means for Solving the Problems] The present invention provides the following for the residual silicon concentration nsi remaining in the GaAs single crystal: 1X10cm ≦nc < nsi −(a)
nsi-nc≦4, 4×1015cm-3-(
Carbon with a concentration nc that satisfies both formulas of b) is loaded, and 1
In the first invention having a specific resistance of 0.6 Ω cm or more and the method for manufacturing a Cr-doped semi-insulating GaAs single crystal by the horizontal boat method, the concentration nc that satisfies the above equations (a) and (b) is obtained. According to the second invention, in which carbon is doped in the required amount to produce thermally stable carbon.
The objective is to be achieved by obtaining an r-doped semi-insulating GaAs single crystal.
［作用］
本発明のＣｒドープ半絶縁性ＧａＡｓ単結晶およびその
製造方法では、浅いアクセプタレベルを有するカーボ〉
Ｃを前記の（ａ）式および（ｂ）式を満足するように添
加することにより、ＣがＳｉを補償するため、Ｃｒの添
加量を少なくすることができる。[Function] In the Cr-doped semi-insulating GaAs single crystal and the manufacturing method thereof of the present invention,
By adding C so as to satisfy the above formulas (a) and (b), the amount of Cr added can be reduced because C compensates for Si.
ＣはＳｉと同様熱処理により動きにくい元素で、ウェハ
上へのエピタキシャル層形成時に成長層への拡散も少な
いため、熱的に安定なＣｒドープ半絶縁性ＧａＡｓ単結
晶であると言うことができる。Like Si, C is an element that does not easily move during heat treatment, and it also diffuses little into the growth layer when an epitaxial layer is formed on the wafer, so it can be said that it is a thermally stable Cr-doped semi-insulating GaAs single crystal.
また、Ｓｉｎが８． ８ Ｘ １０ ”’ｃｍ−３以上
の場合は石英ボートとの「ぬれ」は発生しに＜＜、低転
位単結晶が得られ易い。Also, Sin is 8. If it is 8 x 10'''cm-3 or more, "wetting" with the quartz boat will not occur and a low dislocation single crystal will be easily obtained.
なお、ＳｉはＧａＡｓ結晶中で浅いドナー不純物および
浅いアクセプタ不純物の両方になり得る両性不純物であ
り、従ってＧａＡｓ中の８１の全てを浅いドナー不純物
として扱うわけにはいかない。すなわち、正確には、浅
いドナー不純物として機能するＳｔ濃度（Ｓｌ ）は、
Ｓｌ本−（浅・本
いドナーレベルの５ｉｉａ度）−（浅いアクセプタレベ
ルのＳｉ＃ａ度）となり、上述の（ａ）、（ｂ）式中の
ｎｓｉは、厳密にはｎｓ＋’とすべきものである。Note that Si is an amphoteric impurity that can serve as both a shallow donor impurity and a shallow acceptor impurity in the GaAs crystal, and therefore, all of 81 in GaAs cannot be treated as a shallow donor impurity. That is, to be more precise, the St concentration (Sl) that functions as a shallow donor impurity is:
Sl book - (shallow/large donor level 5iia degree) - (shallow acceptor level Si#a degree), and nsi in the above formulas (a) and (b) should strictly be ns+'. It is.
また、浅いドナーレベルの不純物ｎＤのほとんどはＳ
ｉ （ｎＤ ＃ｎｓｉ” ）であり、浅いアクセプタ
ーレベルの不純物ｎＡの場合は、原料から混入するもの
としてナトリウム（Ｎａ）、カリウム（Ｃａ）、マンガ
ン（Ｍｎ）およびＣ等があげられるが、通常ボート法を
用いてＧａＡｓ単結晶を装造する場合のｎへの総量は１
×１０１５ＣＩＩ＋−３以下である。従ってＳｉｆｌｍ
が比較的多量に含まれる結晶（＞ ８． ８ Ｘ １０
１５ｃ＋ｎ−３）の場合でも前記（ａ）。Also, most of the shallow donor level impurity nD is S
i (nD #nsi”), and in the case of shallow acceptor level impurities nA, sodium (Na), potassium (Ca), manganese (Mn), and C can be cited as contaminants from raw materials, but usually When mounting a GaAs single crystal using the boat method, the total amount of n is 1.
×1015CII+-3 or less. Therefore Siflm
Crystals containing a relatively large amount of (> 8.8 x 10
15c+n-3) also applies to (a) above.
（Ｌ＋）式を満足するようにＣを添加することにより低
転位で熱的に安定なＣｒドープ半絶縁性単結晶を１）る
ことかできる。By adding C so as to satisfy the equation (L+), a thermally stable Cr-doped semi-insulating single crystal with low dislocations can be produced (1).
［実施例］ 以下、本発明の一実施例について説明する。[Example] An embodiment of the present invention will be described below.
実施例１
反応管内の一端に、Ｇａ：１０００ｇ、Ｃｒ：４３０ｍ
ｇ、酸化ガリウム（Ｇａ２ｏ３）： ４０ｍｇおよび種
結晶を入れた石英ボートを置き、他端にはＡｓ：１１１
０ｇを配置する。次に、反応管内を５ Ｘ １０−６Ｔ
ｏｒｒ以下の圧力で１時間以上真空に吸引した後封止す
る。真空状態に封止した反応管を横形二連式電気炉の中
に設置して高温炉の志度を１２００℃、低温炉の温度を
６１０℃まで上昇させこの状態で定温制御を行なう。こ
のようにしてボート内でＧａＡｓの合成反応を行なイ〕
せた後、温度勾配一定の状態でＧａＡｓ融液に種結晶を
若干溶解させ、ボート側温度をこれより高くした状態で
一定温度で降温させて単結晶の成長を行なわせる。単結
晶が全部固化したならば１００℃／時の割合で室温まで
冷却して取り出す；
このようにして成長させたＧａＡｓ単結晶について固化
率−０，１の部分でスライスしてウェハを取り出し不純
物濃度をＡｌｌ＋定した結果、ｎｅｒ＝１、 ３Ｘ１０
Ｉ５ ｃａｌ” ｎ５ｉ＝８． ８Ｘ１０”ｃ１３
ｎｃ＜１０１１０１４ｃ１テあツタ。Example 1 Ga: 1000g, Cr: 430m at one end of the reaction tube
g. Place a quartz boat containing 40 mg of gallium oxide (Ga2O3) and a seed crystal, and place As: 111 at the other end.
Place 0g. Next, the inside of the reaction tube was heated to 5 x 10-6T.
After vacuuming for more than 1 hour at a pressure of orr or less, the tube is sealed. A reaction tube sealed in a vacuum state is placed in a horizontal double-barrel electric furnace, and the temperature of the high temperature furnace is raised to 1200°C and the temperature of the low temperature furnace is raised to 610°C, and constant temperature control is performed in this state. In this way, the GaAs synthesis reaction is carried out inside the boat.]
After this, a seed crystal is slightly dissolved in the GaAs melt with a constant temperature gradient, and the temperature is lowered at a constant temperature while the boat side temperature is higher than this to grow a single crystal. Once the single crystal is completely solidified, it is cooled down to room temperature at a rate of 100°C/hour and taken out; the GaAs single crystal grown in this way is sliced at a solidification rate of -0 and 1, and the wafer is taken out and the impurity concentration determined. As a result of setting All+, ner=1, 3X10
I5 cal” n5i=8.8X10”c13
nc<1011014c1 Teatsuta.
また、隣接するウェハを取り出し二端子法を用いて比抵
抗ρを測定した結果、アニール前は２×１０８Ω・Ｃｌ
１１であったが、温度８５０℃、水素中で３０分間Ｆ
Ｆ Ｃｒａｃａ ｔｏ ｆａｃｅ）法によりアニルした
後は、ρ−５Ｘ１０６Ω・Ｃｌ１１となり、比抵抗が低
下する現象がみられた。In addition, as a result of taking out adjacent wafers and measuring the specific resistance ρ using the two-terminal method, it was found that the resistivity ρ was 2×108Ω・Cl before annealing.
11, but at a temperature of 850°C and F for 30 minutes in hydrogen.
After annealing by F Craca to face) method, it became ρ-5×10 6 Ω·Cl 11 , and a phenomenon in which the specific resistance decreased was observed.
実施例２
Ｇａ２０３を８０１１ｇに増量した以外は実施例１と同
一条件で結晶の成長を行なわせた結果、ｎｅｒ＝１．３
Ｘ１０ ｃａ＋ 、 ｎ５ｌ−４，４Ｘ１０１５
ｃａ＝ ｎ ｃ ＜ １０１４ｅａ＋−”ノＧ ａ
Ａ ｓ単結晶が得られた。また比抵抗ρは、アニール前
が５×１０８Ω・ｃＩＢ、アニール後が８×１０７Ω＠
ｅ７−１実施例１に比べるとアニール後の比抵抗の低下
は少なかったが、単結晶が成長するとき単結晶とボート
との間に「ぬれ」が発生して結晶の後端部に割れが生ず
る現象がみられた。Example 2 Crystal growth was performed under the same conditions as in Example 1 except that the amount of Ga203 was increased to 8011 g. As a result, ner=1.3
X10ca+, n5l-4,4X1015
ca=n c <1014ea+-"ノGa
An As single crystal was obtained. Also, the specific resistance ρ is 5×108Ω・cIB before annealing and 8×107Ω@cIB after annealing.
e7-1 The decrease in specific resistance after annealing was smaller than in Example 1, but when the single crystal grew, "wetting" occurred between the single crystal and the boat, causing cracks at the rear end of the crystal. This phenomenon was observed.
実施例３
この実施例が実施例１．２と異なる点はＣを０．１ｎｇ
添加した点にあり、この条件で実施例１と同様の方法で
単結晶を成長させた結果、ｎｃｒ−１、３Ｘ１０ ｃ
ｍ 、 ｎ５ｌ−８，８Ｘ１０１５ｅ＋ｎ−３ｎｃ
＝ ４． ４ Ｘ １０１５ｃＩ１１−”であり、ま
た比抵抗ρはアニール前が５×１０８Ω・Ｃ１１、アニ
ール後が７Ｘ１０７Ω・ｃａｌでアニール後僅かに減少
している。単結晶とボートとの間に「ぬれ」は生じてい
ない。Example 3 This example differs from Example 1.2 in that 0.1 ng of C was added.
As a result of growing a single crystal in the same manner as in Example 1 under these conditions, ncr-1, 3X10 c
m, n5l-8,8X1015e+n-3nc
= 4. 4 x 1015cI11-", and the specific resistance ρ is 5 x 108 Ω・C11 before annealing and 7×107 Ω・cal after annealing, which decreases slightly after annealing. There is no "wetting" between the single crystal and the boat. It has not occurred.
実施例４
本実施例は上記実施例に対しＧａ２Ｏ３を３０ｍｇに減
少させ、Ｃを０．１４ｍｇに増量して添加した場合であ
る。上記実施例と同様にして単結晶を成長させた結果、
ｎｅｒ −１，３ｘ １０ ”ｃｏ＋−３ｎ、５ｉ−Ｉ
ＸＩＯＣＩｌ 、ｎｃ−６Ｘ１０Ｉ５ｃｍ−３であり、
比抵抗ρはアニール前６Ｘ１０８Ω・ｃｍ、アニール後
８Ｘ１０７Ω・ｅｌｍで、アニール後の比抵抗の減少は
僅少であった。また単結晶とボートとの間に「ぬれ」は
生じていない。Example 4 This example is a case where Ga2O3 was reduced to 30 mg and C was increased to 0.14 mg compared to the above example. As a result of growing a single crystal in the same manner as in the above example,
ner -1,3x 10"co+-3n,5i-I
XIOCIl, nc-6X10I5cm-3,
The specific resistance ρ was 6×10 8 Ω·cm before annealing and 8×10 7 Ω·elm after annealing, and the decrease in specific resistance after annealing was slight. Furthermore, no "wetting" occurs between the single crystal and the boat.
第１表および第１図は上記各実施例の結果を纏めたもの
で、Ｃが添加されその濃度ｎｃが大きい実施例３，４の
場合が比抵抗ρの変化が少なく、また「ぬれ」も発生せ
ず良好な結果が得られている。Table 1 and Figure 1 summarize the results of each of the above examples. Examples 3 and 4, in which C is added and the concentration nc is large, have a small change in resistivity ρ, and also have no "wetting". Good results were obtained without any occurrence.
第１図は横軸がＳｉ濃度ｎｓＬ縦軸が比抵抗ρを示すも
ので、同図実線はＣが無添加の場合、点線がＣを添加し
た場合を示す。両者を比較するとＣ添加の場合の方が明
らかに比抵抗ρの変化が少なく絶縁性に優れていること
が認められる。In FIG. 1, the horizontal axis shows the Si concentration ns and the vertical axis shows the specific resistance ρ, and the solid line in the figure shows the case where C is not added, and the dotted line shows the case where C is added. Comparing the two, it can be seen that the case of C addition has clearly less change in specific resistance ρ and is superior in insulation properties.
なお、前記の実施例３，４ではＣを添加する場合につい
て示したか、Ｃの代りにＳｉより浅いアクセプタ量を有
する不純物、例えばナトリウム（Ｎａ） カリウム（Ｃ
ａ）、マンガン（Ｍ ｎ ）等を添加する方法も考えら
れる。In addition, in Examples 3 and 4 above, the case where C is added is shown, or instead of C, impurities having a shallower acceptor amount than Si, such as sodium (Na) potassium (C
a), a method of adding manganese (M n ), etc. is also considered.
Ｃ発明の効果コ
」二連したように本発明によれば次のような効果か得ら
れる。C. Effects of the Invention C. As mentioned above, according to the present invention, the following effects can be obtained.
（＋） Ｃの添加により結晶中のＳｔを低減させなく
とも熱的に安定なＣｒドープ半絶縁性単結晶を得ること
ができる。By adding (+)C, a thermally stable Cr-doped semi-insulating single crystal can be obtained without reducing the amount of St in the crystal.
（２）結晶と石英ボートとの間に「ぬれ」が生じないの
で、結晶の割れや歪み、転位等が発生せず高品質の単結
晶を得ることができる。(2) Since "wetting" does not occur between the crystal and the quartz boat, a high-quality single crystal can be obtained without cracking, distortion, dislocation, etc. of the crystal.
（３）品質の向上により製品の歩留りが」二昇しコスト
低減を計ることができる。(3) Improved quality can increase product yield and reduce costs.
第１図は本発明の製造方法による一実施例を示す特性図
で、カーボン添加有りおよび無しの場合におけるシリコ
ン濃度対比抵抗変化特性図を示す。
ｎｓ、、／′ｃｍ３FIG. 1 is a characteristic diagram showing an example of the manufacturing method of the present invention, and shows a characteristic diagram of resistance change versus silicon concentration with and without carbon addition. ns,,/'cm3
Claims (2)
晶において、該単結晶中に残留する残留シリコンの濃度
ｎｓｉに対し、 １×１０＾１＾５ｃｍ＾−＾３≦ｎｃ＜ｎｓｉ・・・（
ａ）ｎｓｉ−ｎｃ≦４．４×１０＾１＾５ｃｍ＾−＾３
・・・（ｂ）の両式を満足する濃度ｎｃのカーボンを含
有し、１０＾６Ω−ｃｍ以上の比抵抗を有することを特
徴とするクロムドープ半絶縁性ガリウム・ヒ素単結晶。(1) In a semi-insulating gallium arsenide single crystal doped with chromium, the concentration nsi of residual silicon remaining in the single crystal is 1×10^1^5 cm^-^3≦nc<nsi... (
a) nsi-nc≦4.4×10^1^5cm^-^3
A chromium-doped semi-insulating gallium arsenide single crystal containing carbon at a concentration nc that satisfies both equations (b) and having a resistivity of 10^6 Ω-cm or more.
リウム・ヒ素条結晶とドーパントであるクロムを入れた
横形ボートを反応管の一端に配置し、該反応管の他端に
はヒ素を配置し前記反応管内を加熱して前記横形ボート
内にガリウム・ヒ素融液を生成させた後、該ガリウム・
ヒ素融液に前記種結晶を接触させつつ冷却して前記ガリ
ウム・ヒ素の単結晶を育成するクロムドープ半絶縁性ガ
リウム・ヒ素単結晶の製造方法において、前記単結晶中
に残留する残留シリコンの濃度ｎｓｉに対し、 １×１０＾１＾５ｃｍ＾−＾３≦ｎｃ＜ｎｓｉ・・・
（ａ）ｎｓｉ−ｎｃ≦４．４×１０＾１＾５ｃｍ＾−３
・・・（ｂ）の両式を満足する濃度ｎｃとなるのに必要
な量のカーボンをドープすることを特徴とするクロムド
ープ半絶縁性ガリウム・ヒ素単結晶の製造方法。(2) A horizontal boat containing a seed crystal at one end, a raw material of gallium or gallium arsenide strip crystals, and a dopant of chromium is placed at one end of the reaction tube, and arsenic is placed at the other end of the reaction tube. After heating the inside of the reaction tube to produce a gallium arsenic melt in the horizontal boat, the gallium arsenic
In a method for producing a chromium-doped semi-insulating gallium arsenide single crystal, in which the seed crystal is brought into contact with an arsenic melt and cooled to grow the gallium arsenide single crystal, the concentration of residual silicon remaining in the single crystal is nsi. For, 1×10^1^5cm^-^3≦nc<nsi...
(a) nsi-nc≦4.4×10^1^5cm^-3
A method for producing a chromium-doped semi-insulating gallium arsenide single crystal, comprising doping carbon in an amount necessary to obtain a concentration nc that satisfies both equations (b).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63225152A JPH08758B2 (en) | 1988-09-08 | 1988-09-08 | Method for producing chromium-doped semi-insulating gallium arsenide single crystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63225152A JPH08758B2 (en) | 1988-09-08 | 1988-09-08 | Method for producing chromium-doped semi-insulating gallium arsenide single crystal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0274597A true JPH0274597A (en) | 1990-03-14 |
| JPH08758B2 JPH08758B2 (en) | 1996-01-10 |
Family
ID=16824760
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63225152A Expired - Fee Related JPH08758B2 (en) | 1988-09-08 | 1988-09-08 | Method for producing chromium-doped semi-insulating gallium arsenide single crystal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08758B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6007622A (en) * | 1996-04-26 | 1999-12-28 | Sumitomo Electric Industries, Ltd. | Method of preparing group III-V compound semiconductor crystal |
| US6045767A (en) * | 1997-11-21 | 2000-04-04 | American Xtal Technology | Charge for vertical boat growth process and use thereof |
| USRE40662E1 (en) | 1998-03-25 | 2009-03-17 | Sumitomo Electric Industries, Ltd. | Method of preparing a compound semiconductor crystal |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01215799A (en) * | 1988-02-24 | 1989-08-29 | Nippon Mining Co Ltd | Semi-insulating gaas compound semiconductor single crystal and production thereof |
-
1988
- 1988-09-08 JP JP63225152A patent/JPH08758B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01215799A (en) * | 1988-02-24 | 1989-08-29 | Nippon Mining Co Ltd | Semi-insulating gaas compound semiconductor single crystal and production thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6007622A (en) * | 1996-04-26 | 1999-12-28 | Sumitomo Electric Industries, Ltd. | Method of preparing group III-V compound semiconductor crystal |
| USRE39778E1 (en) * | 1996-04-26 | 2007-08-21 | Sumitomo Electric Industries, Ltd. | Method of preparing group III-V compound semiconductor crystal |
| USRE41551E1 (en) * | 1996-04-26 | 2010-08-24 | Sumitomo Electric Industries, Ltd. | Method of preparing group III-V compound semiconductor crystal |
| US6045767A (en) * | 1997-11-21 | 2000-04-04 | American Xtal Technology | Charge for vertical boat growth process and use thereof |
| USRE40662E1 (en) | 1998-03-25 | 2009-03-17 | Sumitomo Electric Industries, Ltd. | Method of preparing a compound semiconductor crystal |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08758B2 (en) | 1996-01-10 |
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