JPS5845176B2 - 3↓-Plasma anodic oxidation method for group 5 compound semiconductors - Google Patents
3↓-Plasma anodic oxidation method for group 5 compound semiconductorsInfo
- Publication number
- JPS5845176B2 JPS5845176B2 JP54024525A JP2452579A JPS5845176B2 JP S5845176 B2 JPS5845176 B2 JP S5845176B2 JP 54024525 A JP54024525 A JP 54024525A JP 2452579 A JP2452579 A JP 2452579A JP S5845176 B2 JPS5845176 B2 JP S5845176B2
- Authority
- JP
- Japan
- Prior art keywords
- semiconductor
- plasma
- oxide film
- atoms
- anodic oxidation
- 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
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/36—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases using ionised gases, e.g. ionitriding
Description
【発明の詳細な説明】
本発明はＤＩ−Ｖ族化合物半導体表面一絶縁膜の界面に
準位の少ない、優れた電気特性を有する絶縁膜の形成法
に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for forming an insulating film having excellent electrical properties with few levels at the interface between the surface of a DI-V compound semiconductor and the insulating film.
従来から、プラズマ陽極酸化法は半導体表面に酸化膜を
形成する手法として使用されてきたものであるが、ｍ−
ｖ族化合物半導体、たとえば、ＧａＡｓ表面を酸化した
場合に得られる半導体−酸化膜界面は必らずしも良好な
特性を示さなかった。Conventionally, plasma anodic oxidation has been used as a method to form an oxide film on the surface of a semiconductor, but m-
The semiconductor-oxide film interface obtained when the surface of a V-group compound semiconductor, for example, GaAs, is oxidized does not necessarily exhibit good characteristics.
これはプラズマ陽極酸化を０□ガスのプラズマ放電で進
行させているため、Ｏ原子が化合物半導体表面のダング
リングボンドに結合しにくいからである。This is because plasma anodic oxidation is progressed by plasma discharge of 0□ gas, so O atoms are less likely to bond to dangling bonds on the surface of the compound semiconductor.
５ｉ−８ｉ０２が安定した界面特性をもつのは、膜中の
Ｏ原子がＳｉ表面層原子のダングリングボンドと結合し
、準位密度を著しく低減しているからである。The reason why 5i-8i02 has stable interface properties is that the O atoms in the film combine with the dangling bonds of the Si surface layer atoms, significantly reducing the level density.
以上の理由で、０２プラズマ放電で作製した■−■族化
合物半導体表面−酸化膜界面には準位密度が太きいとい
う電気特性の悪ざがあった。For the reasons mentioned above, the interface between the surface of the ■-■ group compound semiconductor and the oxide film produced by 02 plasma discharge had a bad electrical characteristic such as a high level density.
本発明はこれらの欠点を解決するために、Ｉ−Ｖ族化合
物半導体上に酸化膜を形成する場合に、半導体結晶表面
のダングリングボンドと結合しやすい水素ガスをプラズ
マ陽極酸化の過程に導入しとくに酸化膜中に水素原子を
含有させることを特徴とし、その目的は■−■族化合物
半導体表面と酸化膜界面の準位を減らして良質の電気特
性を示す界面をもった半導体装置を得ることにある。In order to solve these drawbacks, the present invention introduces hydrogen gas, which easily combines with dangling bonds on the semiconductor crystal surface, into the plasma anodization process when forming an oxide film on a group IV compound semiconductor. It is particularly characterized by containing hydrogen atoms in the oxide film, and its purpose is to reduce the levels at the interface between the ■-■ group compound semiconductor surface and the oxide film, thereby obtaining a semiconductor device with an interface that exhibits good electrical characteristics. It is in.
以下に本発明を実施例により詳細に説明する。The present invention will be explained in detail below using examples.
Ｈ原子が結晶表面層原子のダングリングボンドと強い結
合をすることはよく知られている。It is well known that H atoms form strong bonds with dangling bonds of crystal surface layer atoms.
本発明はｍ −、、−ｖ族化合物半導体のプラズマ陽極
酸化の過程において、■−■原子の活性な作用を有効に
利用しようとするものである。The present invention aims to effectively utilize the active action of the -■ atoms in the process of plasma anodic oxidation of m-, -v group compound semiconductors.
すなわち、本発明は酸化膜中にＨ原子を取り込むように
酸化膜の形成を進行させる方法を提供するものである。That is, the present invention provides a method for advancing the formation of an oxide film so as to incorporate H atoms into the oxide film.
第１図は本発明に使用するプラズマ放電装置であり、１
はチャンバ、２はチャンバ１へのガス導入管、３は水蒸
気溜め、４はＦＩ２ガス溜め、５は真空ポンプに連結さ
れた排気管、６は高周波コイル、７は試料８を載置する
下部電極、９は−Ｌ部電極、１０は減速調整電極である
。FIG. 1 shows a plasma discharge device used in the present invention.
is a chamber, 2 is a gas introduction pipe to chamber 1, 3 is a water vapor reservoir, 4 is an FI2 gas reservoir, 5 is an exhaust pipe connected to a vacuum pump, 6 is a high frequency coil, and 7 is a lower electrode on which a sample 8 is placed. , 9 is a −L part electrode, and 10 is a deceleration adjustment electrode.
チャンバ１内に水蒸気（）、−Ｉ ２０ ）溜め３、あ
るいはこれとＨ２ガス溜め４からＨ２Ｏ、あるいは■Ｉ
２ガスとＦＩ２０の混合ガス（ただし、混合比は幅があ
るので制限しない）を導入し、高周波放電を開始すれば
、チャンバ１内の雰囲気ガスは次式のような成分でプラ
ズマ放電する。In the chamber 1, water vapor (), -I 20 ) is supplied from the reservoir 3, or from this and the H2 gas reservoir 4, H2O, or ■I
When a mixed gas of 2 gas and FI20 (however, the mixing ratio is not limited as there is a range) is introduced and high frequency discharge is started, the atmospheric gas in the chamber 1 generates a plasma discharge with components as shown in the following equation.
（■■２＋Ｈ２０）→（Ｈ＋０＋ＯＨ）
いま、半導体試料８を載置した下部電極７をアノード、
上部電極９をカソードとして放電させれば、０原子によ
り酸化が進行する。(■■2+H20) → (H+0+OH) Now, the lower electrode 7 on which the semiconductor sample 8 is placed is the anode,
When the upper electrode 9 is used as a cathode and discharge is caused, oxidation progresses due to zero atoms.
たとえば、半導体試料８としてＧａＡｓ結晶を用いれば
、（酸化ガリウム、酸化ヒ素）を主成分とする酸化膜が
結晶表面に形威されて行く。For example, if a GaAs crystal is used as the semiconductor sample 8, an oxide film containing (gallium oxide, arsenic oxide) as a main component is formed on the crystal surface.
この場合、従来の方法と違って、本発明の方法ではプラ
ズマ雰囲気内にＨ原子が多量に存在するため、形成され
る酸化膜内には■４原子が多量に取り込まれるという特
徴がある。In this case, unlike the conventional method, the method of the present invention is characterized in that a large amount of 4 atoms are incorporated into the formed oxide film because a large amount of H atoms are present in the plasma atmosphere.
雰囲気内にＨ２ガスを混入しなくても、Ｈ原子はＨ２０
ガスの分解から得られるので、あえて混入する必要もな
いが、しかし、多量にＩ−１原子を酸化膜中に取り込む
ためには、Ｆ■２ガスを混入することが必要である。Even if H2 gas is not mixed into the atmosphere, H atoms are H20
Since it is obtained from the decomposition of the gas, there is no need to intentionally mix it in. However, in order to incorporate a large amount of I-1 atoms into the oxide film, it is necessary to mix F2 gas.
このようにして酸化膜中に取り込まれた）（原子は半導
体結晶−酸化膜の界面で重要な働きをする。The atoms thus incorporated into the oxide film play an important role at the semiconductor crystal-oxide film interface.
すなわち、従来、結晶表面層原子のダングリングボンド
は半導体表面に準位を形威し、電気特性を低下させてき
たが、本発明においては、酸化膜中に取り込まれたＨ原
子がこのダングリングボンドと結合し、準位密度を著し
く減少させる。In other words, in the past, dangling bonds of atoms in the crystal surface layer formed levels on the semiconductor surface and deteriorated electrical properties, but in the present invention, H atoms incorporated into the oxide film form dangling bonds. It combines with bonds and significantly reduces the level density.
この結果として、本発明で作成された半導体結晶−酸化
膜界面は優れた電気特性を示すようになった。As a result, the semiconductor crystal-oxide film interface created according to the present invention showed excellent electrical properties.
酸化膜形成前の半導体結晶面は、通常種々の理由で汚染
されている。A semiconductor crystal surface before an oxide film is formed is usually contaminated for various reasons.
したがって、酸化膜形成前に表向を清浄化することは価
値がある。Therefore, it is worthwhile to clean the surface before forming the oxide film.
これは、本発明においては、同一雰囲気のまま、下部電
極γと上部電極９の電位を逆にすれはよい。In the present invention, it is preferable to reverse the potentials of the lower electrode γ and the upper electrode 9 while keeping the same atmosphere.
このエツチング過程で、結晶の表面は清浄化される。This etching process cleans the surface of the crystal.
従来の方法では、この過程で結晶表面層に多くのダング
リングボンドができてしまうが、本発明では、この段階
ですでに雰囲気中のＨ原子がダングリングボンドと結合
するという利点がある。In the conventional method, many dangling bonds are formed in the crystal surface layer during this process, but the present invention has the advantage that H atoms in the atmosphere are already bonded to the dangling bonds at this stage.
以上説明したように、本発明による水蒸気あるいは水蒸
気と水素の雰囲気中のプラズマ放電を利用した■−Ｖ族
化合物半導体の陽極酸化は、（１）ダングリングボンド
の激減した良質の半導体−酸化膜界面が得られる、
（２）結晶表向の清浄化が電極電位の反転のみで行なう
ことができる。As explained above, the anodic oxidation of a ■-V group compound semiconductor using plasma discharge in an atmosphere of water vapor or water vapor and hydrogen according to the present invention achieves (1) a high-quality semiconductor-oxide film interface with a sharp reduction in dangling bonds; (2) Cleaning of the crystal surface can be performed only by reversing the electrode potential.
そして、結晶表面のダングリングボンド密度を大幅に抑
えることを可能とする、
などの特徴があり、本方法は、■Ｉ−■族化合物半導体
のＭＯＳＦＥＴのゲート酸化膜の作製に有効であり、こ
れにより、ＩＩ−Ｖ族化合物半導体の反転領域が実現で
きる。This method has the following characteristics: it is possible to significantly suppress the dangling bond density on the crystal surface, and this method is effective for manufacturing gate oxide films of MOSFETs of group I-■ compound semiconductors. Accordingly, an inversion region of a II-V compound semiconductor can be realized.
第１図は本発明に使用するプラズマ放電装置の概略図で
ある。
図において、１・・・・・・チャンバ、２・・・・・・
ガス導入管、３・・・・・・水蒸気溜め、４・・・・・
・ＦＩ２ガス溜め、５・・・・・・排気管、６・・・・
・・高周波コイル、７・・・・・・下部電極、８・・・
・・・試料、９・・・・・・−１部電極、１０・・・・
・・減速調整電極。FIG. 1 is a schematic diagram of a plasma discharge device used in the present invention. In the figure, 1...chamber, 2...
Gas introduction pipe, 3... Steam reservoir, 4...
・FI2 gas reservoir, 5...exhaust pipe, 6...
...High frequency coil, 7...Lower electrode, 8...
...Sample, 9...--1 part electrode, 10...
...Deceleration adjustment electrode.
Claims (1)
ズマ放電させ、ＩＩＩ−Ｖ族化合物半導体をアノード側
に配置して、前記半導体の表面を酸化させることを特徴
とする■−■族化合物半導体のプラズマ陽極酸化法。 ２ 水蒸気あるいは水蒸気と水素との混合雰囲気をプラ
ズマ放電させ、■−■族化合物半導体をカソード側に配
置して前記該半導体の表面をプラズマエツチングし、し
かる後、前記と同一雰囲気をプラズマ放電させ、前記半
導体をアノード側に配置して前記半導体の表面を酸化さ
せることを特徴とする■−■族化合物半導体のプラズマ
陽極酸化法。[Claims] 1. A method characterized in that: 1. A plasma discharge is performed in a water vapor or a mixed atmosphere of water vapor and hydrogen, a III-V compound semiconductor is placed on the anode side, and the surface of the semiconductor is oxidized. Plasma anodic oxidation method for group compound semiconductors. 2 Plasma discharge is performed in water vapor or a mixed atmosphere of water vapor and hydrogen, a ■-■ group compound semiconductor is placed on the cathode side, and the surface of the semiconductor is plasma etched, and then the same atmosphere as described above is plasma discharged; A method for plasma anodization of a (1)-(2) group compound semiconductor, characterized in that the semiconductor is placed on the anode side and the surface of the semiconductor is oxidized.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP54024525A JPS5845176B2 (en) | 1979-03-05 | 1979-03-05 | 3↓-Plasma anodic oxidation method for group 5 compound semiconductors |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP54024525A JPS5845176B2 (en) | 1979-03-05 | 1979-03-05 | 3↓-Plasma anodic oxidation method for group 5 compound semiconductors |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS55117244A JPS55117244A (en) | 1980-09-09 |
| JPS5845176B2 true JPS5845176B2 (en) | 1983-10-07 |
Family
ID=12140564
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP54024525A Expired JPS5845176B2 (en) | 1979-03-05 | 1979-03-05 | 3↓-Plasma anodic oxidation method for group 5 compound semiconductors |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5845176B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61279180A (en) * | 1985-06-04 | 1986-12-09 | Semiconductor Energy Lab Co Ltd | Manufacture of photoelectric conversion device |
| EP0419693A1 (en) * | 1989-09-25 | 1991-04-03 | Siemens Aktiengesellschaft | Process for passivating crystal defects in a polycrystalline silicon material |
| FR2741361B3 (en) * | 1995-11-22 | 1998-04-17 | Balzers Hochvakuum | PROCESS FOR THERMOCHEMICAL SURFACE TREATMENT BY IMMERSION IN PLASMA, PLANT FOR THIS PROCESS, USES AND PARTS OBTAINED |
-
1979
- 1979-03-05 JP JP54024525A patent/JPS5845176B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS55117244A (en) | 1980-09-09 |
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