JP2681117B2 - Method for stabilizing compound semiconductor surface - Google Patents
Method for stabilizing compound semiconductor surfaceInfo
- Publication number
- JP2681117B2 JP2681117B2 JP1104477A JP10447789A JP2681117B2 JP 2681117 B2 JP2681117 B2 JP 2681117B2 JP 1104477 A JP1104477 A JP 1104477A JP 10447789 A JP10447789 A JP 10447789A JP 2681117 B2 JP2681117 B2 JP 2681117B2
- Authority
- JP
- Japan
- Prior art keywords
- compound semiconductor
- sulfur
- solution
- semiconductor surface
- compound
- 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.)
- Expired - Lifetime
Links
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- Drying Of Semiconductors (AREA)
- Weting (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、化合物半導体表面の安定化方法、特に、砒
化ガリウム（GaAs）、砒化アルミニウム（AlAs）あるい
は、それらの混晶（AlxGa1-xAs）によって形成される化
合物半導体表面の安定化方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to a method for stabilizing a compound semiconductor surface, particularly gallium arsenide (GaAs), aluminum arsenide (AlAs) or a mixed crystal thereof (Al x Ga 1 -x As) for stabilizing the compound semiconductor surface.
［従来の技術］ 砒化ガリウム、砒化アルミニウムあるいはそれらの混
晶系の化合物半導体の表面には、特有の活性・不安定性
がある。このため、雰囲気中の気体の吸着や酸化の進行
などにより、化合物半導体表面の電気的あるいは光学的
特性が経時変化する。このことは、これらの化合物半導
体装置の寿命、信頼性の向上の大きな妨げとなってい
る。[Prior Art] The surface of a compound semiconductor of gallium arsenide, aluminum arsenide or a mixed crystal thereof has peculiar activity and instability. Therefore, the electrical or optical characteristics of the compound semiconductor surface change over time due to the adsorption of gas in the atmosphere and the progress of oxidation. This is a major obstacle to improving the life and reliability of these compound semiconductor devices.
このため、これら半導体の表面を何らかの手法で不活
性化し、電気的・光学的特性を安定化させることが強く
求められている。Therefore, it is strongly required to inactivate the surface of these semiconductors by some method to stabilize the electrical and optical characteristics.
本発明者等は、先に砒化ガリウム表面を硫化アンモニ
ウムの水溶液で処理して、その表面を不活性化する方法
を、1988年８月に開催された「20th Conference on Sol
id State Devices and Materials,Tokyo,1988」にて発
表した。この方法によれば、砒化ガリウム表面に硫黄の
薄膜が形成され、この薄膜により、砒化ガリウム表面を
保護し、電気的・光学的特性を改善することができる。The present inventors have previously described a method of deactivating the surface of gallium arsenide by treating it with an aqueous solution of ammonium sulfide, which was held in August 1988, “20th Conference on Sol”.
id State Devices and Materials, Tokyo, 1988 ". According to this method, a thin film of sulfur is formed on the surface of gallium arsenide, and the thin film can protect the surface of gallium arsenide and improve the electrical / optical characteristics.
［発明が解決しようとする課題］ しかしながら、構成元素としてアルミニウムを含む砒
化アルミニウムや、砒化ガリウムと砒化アルミニウムと
の混晶では、大気との短時間の接触でも表面にアルミニ
ウム酸化物の薄膜が形成されてしまい、それが半導体表
面と硫黄薄膜との間の強固な付着を阻害する。更に、ア
ルミニウムを含まない化合物半導体であっても、大気と
の接触により、表面に酸化物の薄膜が形成されることが
ある。[Problems to be Solved by the Invention] However, in the case of aluminum arsenide containing aluminum as a constituent element or a mixed crystal of gallium arsenide and aluminum arsenide, a thin film of aluminum oxide is formed on the surface even when contacted with the atmosphere for a short time. Which hinders the firm adhesion between the semiconductor surface and the sulfur thin film. Furthermore, even a compound semiconductor containing no aluminum may form a thin oxide film on its surface when contacted with the atmosphere.
［課題を解決するための手段］ 本発明は、硫黄のハロゲン化合物またはその有機溶媒
溶液で、化合物半導体表面を処理することにより、半導
体の表面に形成されたアルミニウム酸化物の薄膜を除去
しつつ、同時に硫黄の薄膜を形成し、表面を不活性化即
ち、安定化することを特徴とする。[Means for Solving the Problems] The present invention removes an aluminum oxide thin film formed on the surface of a semiconductor by treating the compound semiconductor surface with a halogen compound of sulfur or an organic solvent solution thereof, At the same time, it is characterized by forming a thin film of sulfur to inactivate or stabilize the surface.
［作 用］ 硫黄のハロゲン化合物またはその有機溶媒溶液がアル
ミニウム酸化物をエッチングする作用を有することを見
出した。この作用により、硫黄のハロゲン化合物または
その有機溶媒溶液を用いて化合物半導体表面を処理する
と、化合物半導体表面に酸化物の薄膜が形成されていて
も、この酸化物薄膜を除去して、硫黄の薄膜を化合物半
導体表面に被着することができる。また、形成された硫
黄の薄膜は、化合物半導体表面と強固な結合を持つの
で、雰囲気中の酸素などの吸着が阻害され、表面での化
学反応が抑えられる。その結果、長期間安定化した電気
的・光学的特性が得られる。[Operation] It was found that a halogen compound of sulfur or an organic solvent solution thereof has a function of etching aluminum oxide. By this action, when a compound semiconductor surface is treated with a halogen compound of sulfur or an organic solvent solution thereof, even if an oxide thin film is formed on the compound semiconductor surface, the oxide thin film is removed to remove the sulfur thin film. Can be deposited on the compound semiconductor surface. Further, since the formed thin film of sulfur has a strong bond with the surface of the compound semiconductor, the adsorption of oxygen and the like in the atmosphere is hindered and the chemical reaction on the surface is suppressed. As a result, stable electrical and optical characteristics can be obtained for a long period of time.
［実施例１］ ｎ型の砒化ガリウム基板（不純物濃度約５×10+15cm
-3）を用意し、硫酸（H2SO4）：過酸化水素（H2O2）：
水（H2O）を5:1:1の混合比とした溶液でエッチングす
る。次いで、同試薬を用い混合比のみ5:1:40とした溶液
で軽くエッチング後、水洗して取り出す。その後、付着
している水を窒素（N2）ガスを吹き付けて飛ばす。[Example 1] n-type gallium arsenide substrate (impurity concentration of about 5 x 10 +15 cm
-3 ), and prepare sulfuric acid (H 2 SO 4 ): hydrogen peroxide (H 2 O 2 ):
Etch with a solution of water (H 2 O) at a mixing ratio of 5: 1: 1. Then, using the same reagent, lightly etching with a solution having a mixing ratio of 5: 1: 40, washing with water, and taking out. Then, the attached water is blown off by blowing nitrogen (N 2 ) gas.
このようにして清浄化した基板を、室温の二塩化硫黄
（SCl2）液に約10分間浸した後取り出す。取り出した基
板を四塩化炭素（CCl4）で数回すすぎ、二塩化硫黄を表
面から洗い流す。その後、四塩化炭素洗液から取り出し
て窒素ガスを吹き付けて洗液をとばし、さらに減圧雰囲
気に10分間放置して、洗液、残存している未反応の二塩
化硫黄を完全に除去し、表面に強固に結合した硫黄のみ
を残す。The substrate thus cleaned is immersed in a room temperature sulfur dichloride (SCl 2 ) solution for about 10 minutes and then taken out. Rinse the removed substrate several times with carbon tetrachloride (CCl 4 ) to rinse sulfur dichloride from the surface. After that, remove from the carbon tetrachloride washing liquid, blow nitrogen gas to skip the washing liquid, and leave it in a reduced pressure atmosphere for 10 minutes to completely remove the washing liquid and residual unreacted sulfur dichloride. Leaving only sulfur that is tightly bound to.
［実施例２］ ｎ型の砒化ガリウム基板（不純物濃度約５×10+15cm
-3）を用意し、通常の前処理の後、分子線エピタキシャ
ル成長（MBE）装置内に導入する。そして、上記基板の
上に、アルミニウムとガリウムの組成比が1:9である砒
化アルミニウムと砒化ガリウムの混晶（Al0.1Ga0.9As）
を、MBE法により、厚さ３μｍ成長する。Example 2 N-type gallium arsenide substrate (impurity concentration of about 5 × 10 +15 cm
-3 ) is prepared, and after ordinary pretreatment, it is introduced into a molecular beam epitaxial growth (MBE) device. Then, a mixed crystal of aluminum arsenide and gallium arsenide (Al 0.1 Ga 0.9 As) having a composition ratio of aluminum and gallium of 1: 9 is formed on the substrate.
Are grown to a thickness of 3 μm by the MBE method.
このようにして調製したAl0.1Ga0.9As混晶化合物半導
体試料を、MBE装置より取り出し、室温の二塩化硫黄（S
Cl2）液に約10分間浸す。基板を取り出し、実施例１と
同様に、四塩化炭素（CCl4）ですすぎ、減圧雰囲気下に
放置して表面に強固に結合した硫黄のみを残す。The Al 0.1 Ga 0.9 As mixed crystal compound semiconductor sample prepared in this manner was taken out from the MBE apparatus and was stored at room temperature in sulfur dichloride (S
Immersing Cl 2) solution for about 10 minutes. The substrate was taken out, rinsed with carbon tetrachloride (CCl 4 ) as in Example 1, and left under a reduced pressure atmosphere to leave only sulfur firmly bonded to the surface.
なお、上記二つの実施例においては、硫黄のハロゲン
化合物として、二塩化硫黄を使用したが、二塩化二硫黄
（S2Cl2）や二臭化二硫黄（S2Br2）なども使用できる。Although sulfur dichloride was used as the halogen compound of sulfur in the above two examples, disulfur dichloride (S 2 Cl 2 ) and disulfur dibromide (S 2 Br 2 ) can also be used. .
さらに、これらのハロゲン化合物（液体）は、そのま
ま用いても、また有機溶媒に希釈した形で用いてもよ
い。この場合、有機溶媒としては、ベンゼン、トルエ
ン、キシレンなどの芳香族炭化水素、エチルエーテル、
テトラヒドロフラン、ジオキサンなどのエーテル類、四
塩化炭素、エタノール、および二硫化炭素が使用でき
る。Further, these halogen compounds (liquid) may be used as they are, or may be used in a form diluted with an organic solvent. In this case, as the organic solvent, benzene, toluene, aromatic hydrocarbon such as xylene, ethyl ether,
Ethers such as tetrahydrofuran, dioxane, carbon tetrachloride, ethanol, and carbon disulfide can be used.
［発明の効果］ 以上説明したように、本発明においては、化合物半導
体を硫黄のハロゲン化合物あるいはその有機溶媒溶液で
処理し、その表面に硫黄薄膜を強固に被着させているの
で、処理を行なった化合物半導体試料のフォトルミネッ
センス強度には、処理を行なわない場合と比較して、数
倍の強度の改善が見られ、基板表面が安定化されている
ことが示された。[Effects of the Invention] As described above, in the present invention, the compound semiconductor is treated with a halogen compound of sulfur or an organic solvent solution thereof, and the sulfur thin film is firmly adhered to the surface of the compound semiconductor. Regarding the photoluminescence intensity of the compound semiconductor sample, the intensity of the photoluminescence was improved several times as compared with the case where no treatment was performed, and it was shown that the substrate surface was stabilized.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平１−217917（ＪＰ，Ａ) 特開 平２−187029（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A 1-217917 (JP, A) JP-A 2-187029 (JP, A)
Claims (4)
物溶液で処理することを特徴とする化合物半導体表面の
安定化方法。1. A method for stabilizing a surface of a compound semiconductor, which comprises treating the surface of the compound semiconductor with a halogen compound solution of sulfur.
二硫黄、二塩化硫黄、および二臭化二硫黄の内の一つで
あることを特徴とする請求項（１）記載の化合物半導体
表面の安定化方法。2. The compound semiconductor surface according to claim 1, wherein the halogen compound solution of sulfur is one of disulfur dichloride, sulfur dichloride, and disulfur dibromide. Stabilization method.
物の有機溶媒溶液で処理することを特徴とする化合物半
導体表面の安定化方法。3. A method for stabilizing a surface of a compound semiconductor, which comprises treating the surface of the compound semiconductor with a solution of a halogen compound of sulfur in an organic solvent.
テル類、四塩化炭素、エタノール、および二硫化炭素の
内の一つであることを特徴とする請求項（３）記載の化
合物半導体表面の安定化方法。4. The compound semiconductor surface according to claim 3, wherein the organic solvent solution is one of aromatic hydrocarbons, ethers, carbon tetrachloride, ethanol, and carbon disulfide. Stabilization method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1104477A JP2681117B2 (en) | 1989-04-26 | 1989-04-26 | Method for stabilizing compound semiconductor surface |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1104477A JP2681117B2 (en) | 1989-04-26 | 1989-04-26 | Method for stabilizing compound semiconductor surface |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02284420A JPH02284420A (en) | 1990-11-21 |
| JP2681117B2 true JP2681117B2 (en) | 1997-11-26 |
Family
ID=14381650
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1104477A Expired - Lifetime JP2681117B2 (en) | 1989-04-26 | 1989-04-26 | Method for stabilizing compound semiconductor surface |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2681117B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR0176715B1 (en) * | 1990-07-30 | 1999-04-15 | 오가 노리오 | Dry etching method |
| US5393680A (en) * | 1990-08-01 | 1995-02-28 | Sumitomo Electric Industries, Ltd. | MIS electrode forming process |
| JPH04288828A (en) * | 1991-03-18 | 1992-10-13 | Sony Corp | Dry etching method |
| JP3198586B2 (en) * | 1992-02-14 | 2001-08-13 | ソニー株式会社 | Dry etching method |
| KR20020006735A (en) * | 2000-07-13 | 2002-01-26 | 이형도 | Surface treating material and surface treating method of micro-device |
| KR101973974B1 (en) * | 2015-02-12 | 2019-04-30 | 후지필름 가부시키가이샤 | Method and apparatus for removing oxides of III-V elements, process liquids of compounds of group III-V elements, antioxidants of group III-V elements, process liquid of semiconductor substrates, and method of manufacturing semiconductor substrate products |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01217917A (en) * | 1988-02-26 | 1989-08-31 | Hitachi Ltd | Dry etching method |
-
1989
- 1989-04-26 JP JP1104477A patent/JP2681117B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02284420A (en) | 1990-11-21 |
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