JP3079535B2 - Manufacturing method of semiconductor thin film - Google Patents
Manufacturing method of semiconductor thin filmInfo
- Publication number
- JP3079535B2 JP3079535B2 JP02028030A JP2803090A JP3079535B2 JP 3079535 B2 JP3079535 B2 JP 3079535B2 JP 02028030 A JP02028030 A JP 02028030A JP 2803090 A JP2803090 A JP 2803090A JP 3079535 B2 JP3079535 B2 JP 3079535B2
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- tio
- semiconductor thin
- substrate
- film
- 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 - Fee Related
Links
Description
【発明の詳細な説明】 a. 産業上の利用分野 本発明は半導体ガスセンサー、水の分解用電極,NOx還
元触媒，光燃料電池等々に用いられる半導体薄膜の製造
方法に関する。The present invention relates to a method for producing a semiconductor thin film used for a semiconductor gas sensor, an electrode for decomposing water, a NOx reduction catalyst, a photofuel cell, and the like.
b. 従来の技術 半導体薄膜の製造方法及びその性質の研究について
は、たとえば、次のような技術が知られている。すなわ
ち、表面改質技術の一つとしてセラミックコーテング法
があるが、このコーテング法には蒸着法,CVD法，スパッ
タリング法や気相を介しておこなうプラズマCVD法，光C
VD法等があり、また単に液体をスプレーする方法，塗布
する方法などが知られている。さらに金属有機化合物や
金属塩を加水分解することによって得られる酸化物前駆
体高分子を含む溶液（ゾル）に、基板を浸漬して引き上
げることによって基板をコーテングし、その後、ゲル
化，焼成を経てセラミックコーテング膜とする、所謂ゾ
ル・ゲル法がある。b. Conventional technology The following technologies are known, for example, for research on a method of manufacturing a semiconductor thin film and its properties. That is, there is a ceramic coating method as one of the surface modification techniques, and the coating method includes a vapor deposition method, a CVD method, a sputtering method, a plasma CVD method performed through a gas phase, and a photo-C coating method.
There are a VD method and the like, and a method of simply spraying a liquid and a method of applying a liquid are known. Further, the substrate is coated by dipping the substrate in a solution (sol) containing an oxide precursor polymer obtained by hydrolyzing a metal organic compound or a metal salt and then pulling it up. There is a so-called sol-gel method for forming a coating film.
また、このゾル・ゲル法を用いることによって、アン
チモンをドーピングしたTiO2薄膜を調整し、そのTiO2薄
膜の電気化学的性質について論じた文献がある（日本化
学会誌No.11,1946−51（1987））。In addition, there is a document that prepares a TiO 2 thin film doped with antimony by using this sol-gel method and discusses the electrochemical properties of the TiO 2 thin film (Chemical Society of Japan No. 11, 1946-51 ( 1987)).
c. 発明が解決しようとする課題 前記ゾル・ゲル法による薄膜の形成は、極めて簡単な
装置で大面積のコーテング膜が容易に得られ、かつゾル
状態では分子レベルで均一なので不純物元素のドーピン
グができる。そして、この従来のゾル・ゲル法には低温
加熱法が用いられ、その温度は500〜700℃の範囲で処理
されているが、これによって比較的低い抵抗（10Ω・cm
オーダー）をもつTiO2薄膜を作成した例はみられない。
その理由としては、形成する薄膜の抵抗を低下させるた
めには、被処理物を高温加熱処理をして結晶粒の成長を
促進し、TiO2粒子内に不純物元素を固溶させる必要があ
るが、この高温加熱処理によって膜と、この膜を形成す
るための基板とが反応してしまったり、また両者の熱膨
張係数の差によって、膜にクラックあるいは粒子接触の
不備が発生するためと思われる。c. Problems to be Solved by the Invention In the formation of a thin film by the sol-gel method, a large-area coating film can be easily obtained with an extremely simple apparatus, and in the sol state, it is uniform at the molecular level. it can. A low-temperature heating method is used in the conventional sol-gel method, which is performed at a temperature in the range of 500 to 700 ° C.
There is no example in which a TiO 2 thin film having (order) was prepared.
The reason is that, in order to reduce the resistance of the thin film to be formed, it is necessary to heat-treat the object to be treated at a high temperature to promote the growth of crystal grains, and to dissolve the impurity element in the TiO 2 particles. It is considered that the film and the substrate for forming this film react with each other due to the high-temperature heat treatment, and a difference in thermal expansion coefficient between the film and the film causes cracks or defects in particle contact. .
本発明は前記事情に鑑みてなされたもので、前記課題
を解消してなる半導体薄膜の製造方法を提供することを
目的とする。The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method of manufacturing a semiconductor thin film that solves the above-mentioned problems.
d. 課題を解決するための手段 前記目的に添い、本発明は、半導体薄膜を形成する基
板に、TiO2の熱膨張係数と同じ、あるいは上記半導体薄
膜の製造工程時における焼結によって上記半導体にクラ
ックを生じさせない程度のTiO2に近い熱膨張係数を持つ
材料を用い、この基板に中間層としてSiO2を被覆したあ
と、この基板にTiO2のゲル膜を形成し、これを還元雰囲
気中で、温度1200〜1300℃で常圧焼結することを特徴と
することによって前記課題を解消した。d. Means for Solving the Problems In accordance with the above object, the present invention provides a method for forming a semiconductor thin film on a substrate having the same thermal expansion coefficient as that of TiO 2 or by sintering during the manufacturing process of the semiconductor thin film. Using a material with a thermal expansion coefficient close to TiO 2 that does not cause cracks, coat this substrate with SiO 2 as an intermediate layer, then form a TiO 2 gel film on this substrate, and place it in a reducing atmosphere. The above problem was solved by performing normal pressure sintering at a temperature of 1200 to 1300 ° C.
以下、本発明について図面を参照しながら、詳細に説
明する。Hereinafter, the present invention will be described in detail with reference to the drawings.
本発明によって得られたTiO2半導体薄膜は、第１図に
示すように基板１上にSiO2膜２をアンダーコート（中間
層）し、その上にTiO2半導体薄膜３を形成してなるもの
である。As shown in FIG. 1, the TiO 2 semiconductor thin film obtained by the present invention is obtained by undercoating (intermediate layer) an SiO 2 film 2 on a substrate 1 and forming a TiO 2 semiconductor thin film 3 thereon. It is.
薄膜の製造工程で、薄膜成分TiO2の抵抗を低下させる
ために高温処理（1200〜1300℃）を処すが、この処理に
よって薄膜成分と反応しない物質、すなわち、SiO2を用
いて、これを基板上に0.1〜0.5μｍのSiO2膜をまず形成
する。In the manufacturing process of the thin film, a high temperature treatment (1200-1300 ° C.) is performed to reduce the resistance of the thin film component TiO 2 , but a substance that does not react with the thin film component by this treatment, that is, SiO 2, is used for the substrate. First, a 0.1 to 0.5 μm SiO 2 film is formed thereon.
なお、基板には薄膜成分TiO2の熱膨張係数に近く、か
つアンダーコートとなるSiO2と反応しない材料を用い
る。たとえば、TiO2磁器などである。Note that a material that is close to the thermal expansion coefficient of the thin film component TiO 2 and does not react with SiO 2 serving as an undercoat is used for the substrate. For example, TiO 2 porcelain and the like.
次に、所定のゾル溶液を調整し、スプレー法，スピナ
ー法あるいは浸漬法（デイップ法）等を用いて前記処理
を旋した基板にゲル膜を形成する。このゾル溶液は、半
導体化元素NbをTiO2に対し、所定の組成となるように金
属アルコキシド｛Ti（Ｏ−ｉ−C3H7）4,Nb（OC
2H5）５｝をC2H5OHに溶解し、さらに触媒とH2Oを加えて
調整したものである。Next, a predetermined sol solution is prepared, and a gel film is formed on the substrate on which the above-described processing is swirled by using a spray method, a spinner method, a dipping method (dip method), or the like. The sol solution, a semiconductive dopant Nb relative to TiO 2, metal alkoxides to make a predetermined composition {Ti (O-i-C 3 H 7) 4, Nb (OC
2 H 5 ) 5 ｝ was dissolved in C 2 H 5 OH and further adjusted by adding a catalyst and H 2 O.
このようにして前記ゲル膜を形成した基板は約500℃
で加熱分解し、さらに前記操作を繰り返し、所定厚のNb
添加TiO2薄膜を形成する。The substrate on which the gel film has been formed in this way is about 500 ° C.
And decompose by heating, and repeat the above operation to obtain a predetermined thickness of Nb.
Form an additive TiO 2 thin film.
次にこれを還元雰囲気中で1200〜1300℃で常圧焼結す
ればよい。Next, this may be sintered under normal pressure at 1200 to 1300 ° C. in a reducing atmosphere.
実施例 半導体化元素NbをTiO2に対し1mol％Nb2O5の組成とな
るように金属アルコキシド｛Ti（Ｏ−ｉ−C3H7）4,Nb
（OC2H5）５｝をC2H5OHに溶解し、さらに触媒とH2Oを加
えてゾル溶液を調整し、第２図に示すようなデイップコ
ーテング装置によって基板にゲル膜を形成した。図にお
いて５はTiO2ゾル溶液、６はTiO2ゾル溶液を収容する容
器、１はTiO2ゾル溶液５に浸漬された基板、７は基板１
を保持するクリップ、８はクリップを吊下げ保持するフ
ァイバーであり、駆動装置９を駆動することによってフ
ァイバー８を昇降させ基板１を浸漬したり引きあげたり
するようになっている。Example The metal alkoxide ｛Ti (OiC 3 H 7 ) 4 , Nb was used so that the semiconductor element Nb had a composition of 1 mol% Nb 2 O 5 with respect to TiO 2.
(OC 2 H 5 ) 5 ｝ was dissolved in C 2 H 5 OH, and a catalyst and H 2 O were added to prepare a sol solution. A gel film was formed on the substrate by a dip coating apparatus as shown in FIG. did. In the figure, 5 is a TiO 2 sol solution, 6 is a container for containing the TiO 2 sol solution, 1 is a substrate immersed in the TiO 2 sol solution 5, and 7 is a substrate 1.
Is a fiber for suspending and holding the clip. By driving a driving device 9, the fiber 8 is moved up and down so that the substrate 1 is immersed or pulled up.
なお、この基板１は、Si（OC2H5）４を用いて同様な
方法によって予めSiO2薄膜（0.1〜0.5μｍ）を被覆して
あるTiO2磁器を用いた。ゲル膜は500℃で加熱分解し、
ディップ操作を繰り返して膜厚約１μｍのNb添加TiO2薄
膜を作成した。次にこれを還元雰囲気中で常圧焼結し
た。薄膜の焼結は、1200℃付近より急激に進行し、1300
℃では粒径0.8〜2.0μｍとなり30Ωcmの低抵抗半導体薄
膜がえられた。The substrate 1 was a TiO 2 porcelain previously coated with a SiO 2 thin film (0.1 to 0.5 μm) using Si (OC 2 H 5 ) 4 by the same method. The gel film decomposes by heating at 500 ° C,
The dip operation was repeated to form an Nb-doped TiO 2 thin film having a thickness of about 1 μm. Next, this was sintered at normal pressure in a reducing atmosphere. The sintering of the thin film progresses rapidly from around 1200 ° C,
At ℃, the grain size was 0.8 to 2.0 μm, and a low-resistance semiconductor thin film of 30 Ωcm was obtained.
なお、基板としてSiO2ガラスを用いて同様に処理した
場合、Nb添加TiO2薄膜にはクラックが生じた。When the same treatment was performed using SiO 2 glass as the substrate, cracks occurred in the Nb-added TiO 2 thin film.
e. 発明の効果 本発明によれば、半導体薄膜の製造工程時における焼
結によって上記半導体薄膜にクラックを生じさせないの
で、大面積をもち、しかも低抵抗のTiO2半導体薄膜がえ
られる。e. Effects of the Invention According to the present invention, a TiO 2 semiconductor thin film having a large area and low resistance can be obtained because cracks are not generated in the semiconductor thin film due to sintering during the manufacturing process of the semiconductor thin film.
第１図は本発明に係る製造方法で製作した半導体、第２
図は本発明に係る半導体薄膜の製造要領を説明する図で
ある。 １……基板、２……SiO2膜、 ３……TiO2半導体薄膜。FIG. 1 shows a semiconductor manufactured by the manufacturing method according to the present invention, and FIG.
The figure is a view for explaining the manufacturing procedure of the semiconductor thin film according to the present invention. 1 ...... substrate, 2 ...... SiO 2 film, 3 ...... TiO 2 semiconductor thin film.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) H01L 21/203,21/368 C04B 41/87 C23C 18/00 - 20/08 ──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. 7 , DB name) H01L 21 / 203,21 / 368 C04B 41/87 C23C 18/00-20/08
Claims (1)
張係数と同じ、あるいは上記半導体薄膜の製造工程時に
おける焼結によって上記半導体にクラックを生じさせな
い程度のTiO2に近い熱膨張係数を持つ材料を用い、この
基板に中間層としてSiO2を被覆したあと、この基板にTi
O2のゲル膜を形成し、これを還元雰囲気中で、温度1200
〜1300℃で常圧焼結することを特徴とする半導体薄膜の
製造方法。To 1. A substrate for forming a semiconductor thin film, the thermal expansion coefficient close same as the thermal expansion coefficient of the TiO 2, or by sintering during the manufacturing process of the semiconductor thin film to TiO 2 to the extent that does not cause cracks in the semiconductor After covering this substrate with SiO 2 as an intermediate layer,
A gel film of O 2 is formed, which is heated at a temperature of 1200 in a reducing atmosphere.
A method for producing a semiconductor thin film, comprising sintering under normal pressure at 1300 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02028030A JP3079535B2 (en) | 1990-02-07 | 1990-02-07 | Manufacturing method of semiconductor thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02028030A JP3079535B2 (en) | 1990-02-07 | 1990-02-07 | Manufacturing method of semiconductor thin film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03232222A JPH03232222A (en) | 1991-10-16 |
| JP3079535B2 true JP3079535B2 (en) | 2000-08-21 |
Family
ID=12237346
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP02028030A Expired - Fee Related JP3079535B2 (en) | 1990-02-07 | 1990-02-07 | Manufacturing method of semiconductor thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3079535B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1976019B1 (en) | 2007-03-29 | 2011-06-15 | Korea Advanced Institute of Science and Technology | Thin film transistor including titanium oxides as active layer and method of manufacturing the same |
| KR100983544B1 (en) * | 2009-11-16 | 2010-09-27 | 한국과학기술원 | method for manufacturing thin film transistors based on titanium oxides as active layer and structure thereof |
-
1990
- 1990-02-07 JP JP02028030A patent/JP3079535B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03232222A (en) | 1991-10-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |