JPH0317912A - Manufacture of transparent conductive thin film - Google Patents
Manufacture of transparent conductive thin filmInfo
- Publication number
- JPH0317912A JPH0317912A JP15182589A JP15182589A JPH0317912A JP H0317912 A JPH0317912 A JP H0317912A JP 15182589 A JP15182589 A JP 15182589A JP 15182589 A JP15182589 A JP 15182589A JP H0317912 A JPH0317912 A JP H0317912A
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- oxygen
- transparent conductive
- substrate
- ion irradiation
- 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.)
- Pending
Links
- 239000010409 thin film Substances 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 23
- 239000007789 gas Substances 0.000 claims abstract description 13
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000001678 irradiating effect Effects 0.000 claims abstract description 5
- 238000000151 deposition Methods 0.000 claims abstract 3
- 150000002500 ions Chemical class 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 7
- 239000000758 substrate Substances 0.000 abstract description 25
- 239000010408 film Substances 0.000 abstract description 10
- 238000007747 plating Methods 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- -1 oxygen ion Chemical class 0.000 description 10
- 238000010586 diagram Methods 0.000 description 6
- 229910001128 Sn alloy Inorganic materials 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 3
- 229910000846 In alloy Inorganic materials 0.000 description 2
- 229910002064 alloy oxide Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000007751 thermal spraying Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明｛上 電子工業における機能素子などに用いられ
る透明導電薄膜の製造方法に関するものであも
従来の技術
従来の透明導電膜の製造方法として、例えばインジウム
・錫の合金酸化物（ＩＴＯ）からなる透明導電膜を作製
する場合、 １ｍＴｏｒｒ以下に減圧した酸素雰囲気中
で、 Ｉｎ酸化物・Ｓｎ酸化物を混合したターゲットニ
電子ビームを照射・加熱してターゲットを蒸発させ
たり（ＥＢ蒸着法）、．イオンを照射してターゲットを
スパッタリングしたり（スパッタ蒸着法）することによ
って、 Ｉｎ・Ｓｎの合金酸化物の分子・クラスターを
生威し所定の位置に置かれた基板にＩＴＯ薄膜を形或す
るという方法が用いられていた
発明力｛解決しようとする課題
従来の透明導電薄膜の製造方法に用いられるＥＢ蒸着法
やスパッタ蒸着法で（上 大面積に均一な膜質の透゛明
導電膜を形或することが困難であもまた基板を２００℃
程度の高温に加熱しなげればならないた△ 使用できる
基板の種類が限られるという問題があった
課題を解決するための手段
以上の課題を解決するために 本発明は基体上にＩｎ及
びＳｎからなる薄膜を堆積し その後にイオン照射装置
によって、少なくとも酸素を含む気体の放電分解による
生戊物を前記薄膜に照射するという手段を用いる。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for manufacturing a transparent conductive thin film used for functional elements in the electronics industry. When producing a transparent conductive film made of indium-tin alloy oxide (ITO), a target containing a mixture of In oxide and Sn oxide is irradiated with an electron beam and heated in an oxygen atmosphere with a pressure reduced to 1 mTorr or less. Evaporate the target (EB evaporation method), . By irradiating the target with ions and sputtering (sputter deposition method), molecules and clusters of In-Sn alloy oxide are generated to form an ITO thin film on a substrate placed at a predetermined position. The inventiveness of the method [Problem to be solved] The EB evaporation method and sputter evaporation method used in the conventional manufacturing method of transparent conductive thin film (in addition, it is possible to form a transparent conductive film with uniform film quality over a large area. If it is difficult to heat the substrate to 200℃
In order to solve the problem more than a means to solve the problem that the types of substrates that can be used are limited. A method is used in which a thin film is deposited, and then the thin film is irradiated with a product produced by discharge decomposition of a gas containing at least oxygen using an ion irradiation device.
ここで、前記のイオン照射装置と（よ 絶縁物で形戊さ
れた面を有する第１の真空槽と、真空槽の絶縁物で形或
された面に沿って前記真空槽の外部に設けらｈ １３
． ５６ＭＨｚの高周波を印加する高周波電極を少な
くとも備えてなる放電室と、基板台を備えて前記放電室
と接続された第２の真空槽からなる基板室とを有し 基
板室及び放電室との間に前記基板室及び前記放電室と電
気的に絶縁され 直流或は交流電源と接続され 開口部
を有した第１の電極を（ＭＬ さらに第１の電極と対
向する位置に 放電により生じたプラズマを挟んで第１
の電極と同電位とされて設けられた第２の電極を放電室
内に備えてなるイオン照射処理装置のことを指す。Here, the above-mentioned ion irradiation device, a first vacuum chamber having a surface formed with an insulator, and a first vacuum chamber provided outside the vacuum chamber along the surface formed with an insulator of the vacuum chamber are provided. h 13
．． A discharge chamber comprising at least a high frequency electrode for applying a high frequency of 56 MHz, and a substrate chamber comprising a second vacuum chamber equipped with a substrate stand and connected to the discharge chamber, between the substrate chamber and the discharge chamber. A first electrode (ML) is electrically insulated from the substrate chamber and the discharge chamber, connected to a DC or AC power source, and has an opening (ML). 1st sandwich
Refers to an ion irradiation processing apparatus that is equipped with a second electrode in the discharge chamber that is provided at the same potential as the electrode.
作 用
蒸着・メッキなどによりＩ ｎ ＸＳ ｎ ｙ （ｘ＋
ｙ＝ １，ｙ≦１）からなる薄膜を大面積に対して容易
に堆積することが可能であり、かつ上記イオン照射装置
により、少なくとも酸素を含む気体の放電分解による生
成物を大面積に対して照射することが可能であることか
転 透明で導電性のＩ ｎｘｓｎｕの酸化物薄膜が大面
積基板上に均一に形戊できもまた 高いエネルギーのイ
オンの照射によって薄膜の表面付近が高温となるた＆
１００℃以下の基板温度にかかわらず薄膜の表面付近
が化学的に活性な状態となり、低温での透明導電膜の形
或が可能となん
実施例
以下図面を用いて本発明についてさらに詳しく説明する
。I n XS ny (x+
It is possible to easily deposit a thin film consisting of y = 1, y≦1) over a large area, and the above ion irradiation device can deposit products from discharge decomposition of gas containing at least oxygen over a large area. Although it is possible to form a transparent and conductive Inxsnu oxide thin film uniformly on a large-area substrate, the high-energy ion irradiation also causes a high temperature near the surface of the thin film. Ta&
The vicinity of the surface of the thin film becomes chemically active regardless of the substrate temperature of 100° C. or less, making it possible to form a transparent conductive film at low temperatures.Examples The present invention will be explained in more detail with reference to the drawings.
第１図（友 本発明の第１実施例における透明導電薄膜
の製造方法を実施するイオン照射処理装置の概略構戊図
であも ガスボンベ１０１の酸素ガスを、放電室１０２
へガス流量制御装置１０３を介してガス導入管１０４か
ら導入すも このガスを、高周波電極１０５によって供
給する高周波電力によって放電分解する。そして第１の
電極１０６、第２の電極１０７に印加される直流電圧に
よって、放電分解により生じた高励起の酸素プラズマに
正の電位を与丸 プラズマ中のイオンを第２の電極１０
７の開口部１０８から押し出し加速すも そして酸素イ
オン流１０９を基板室１１０内の基板１１１に照射・注
入する。FIG. 1 is a schematic diagram of an ion irradiation treatment apparatus for carrying out the method for producing a transparent conductive thin film in the first embodiment of the present invention.
The gas introduced from the gas introduction pipe 104 via the gas flow rate control device 103 is discharge decomposed by high frequency power supplied by the high frequency electrode 105. Then, a DC voltage applied to the first electrode 106 and the second electrode 107 gives a positive potential to the highly excited oxygen plasma generated by discharge decomposition.Ions in the plasma are transferred to the second electrode 10.
Then, the oxygen ion flow 109 is pushed out through the opening 108 of the substrate chamber 110 and irradiated and injected into the substrate 111 in the substrate chamber 110.
第２図は 同製造方法における要部の概略図である。基
板１１１上に 蒸着・溶射・メッキ等によってＩ’ｎｘ
Ｓ ｎｖ（ｘ＋ｙ＝ １、 ｙ≦１）の合金薄膜１１
２をあらかじめ形或しておく。その後に 第１図の装置
によって、 １００℃以下の温度に保たれた基板１１１
に対して酸素イオン・ラジカルの上記照射を行う。この
とき酸素イオン１ ０ ９ ｃＬ少なくとも１ ｋｅＶ
以上に加速すも この様な高いエネルギーのイオンの照
射によって薄膜１１２の表面付近が高温となる。そのた
敗 １００℃以下の基板温度にかかわらず薄膜１１２の
表面付近が化学的に活性な状態となる。この様な状態の
もとで、酸素ラジカルの照射及び酸素イオンの注入を行
なうことによって、 Ｉｎ及びＳｎの合金薄膜１１２の
表面及び内部を酸化Ｌ Ｉ ｎｘｓ ｎ，（ｘ＋’ｊ
＝１．’ｌ≦１）の合金酸化物からなる透明導電膜１１
３を形戒することができも
第３図（上 本発明の第２実施例における透明導電薄膜
の製造方法を実施するイオン照射処理装置の概略構或図
であも 基板室２１０に設けた誘導加熱蒸着源２１４に
よってＩ ｎｘＳ ｎ ｖ （ｘ＋ｙ＝ １，ｙ≦１）
合金の分子・クラスター流２１５を発生させ、基板２１
１に照射することによって、基板２１１上にＩｎｘＳｎ
ｖ（ｘ＋ｙ＝１，ｙ≦１）合金薄膜２１２を形威すも
これと同時に 酸素イオン２０９を、基板２１４に対し
て照射・注入すも なお第１実施例と同様に 酸素イオ
ン２ ０ ９ ｆ；Ｌ ガスボンベ２０１の酸素ガス
をガス流量制御装置２０３を介してガス導入管２０４か
ら放電室２０２に導入し 高周波電極２０５によって供
給する高周波電力によって放電分解することにより発生
させも さらに酸素イオン２０９の照射・注入（上第１
の電極２０６、第２の電極２０７に印加される直流電圧
によって、放電分解により生じた高励起の酸素プラズマ
に正の電位を与え、プラズマ中のイオンを第２の電極２
０７の開口部２０８から押し出し加速することによって
行う。FIG. 2 is a schematic diagram of the main parts of the manufacturing method. I'nx is applied on the substrate 111 by vapor deposition, thermal spraying, plating, etc.
Alloy thin film 11 of S nv (x+y=1, y≦1)
2 in advance. Thereafter, the substrate 111 was kept at a temperature of 100°C or less using the apparatus shown in FIG.
The above-mentioned irradiation with oxygen ions and radicals is performed on the target. At this time, oxygen ion 1 0 9 cL at least 1 keV
Due to the irradiation of such high-energy ions, the vicinity of the surface of the thin film 112 becomes high temperature. Failure: The vicinity of the surface of the thin film 112 becomes chemically active regardless of the substrate temperature of 100° C. or less. Under such conditions, by irradiating oxygen radicals and implanting oxygen ions, the surface and interior of the In and Sn alloy thin film 112 are oxidized L I nxs n, (x+'j
=1. Transparent conductive film 11 made of alloy oxide with 'l≦1)
Figure 3 (above) is a schematic diagram of the ion irradiation processing apparatus for carrying out the method for producing a transparent conductive thin film in the second embodiment of the present invention. I nxS n v (x+y= 1, y≦1) by the heating evaporation source 214
A molecular/cluster flow 215 of the alloy is generated, and the substrate 21
1, InxSn is deposited on the substrate 211.
v (x+y=1, y≦1) The alloy thin film 212 is formed
At the same time, oxygen ions 209 are irradiated and injected into the substrate 214. As in the first embodiment, oxygen gas from the gas cylinder 201 is introduced via the gas flow rate control device 203. Oxygen ions 209 are introduced into the discharge chamber 202 from the tube 204 and generated by discharge decomposition by high frequency power supplied by the high frequency electrode 205.
The DC voltage applied to the electrode 206 and the second electrode 207 gives a positive potential to the highly excited oxygen plasma generated by discharge decomposition, and the ions in the plasma are transferred to the second electrode 207.
This is done by extruding from the opening 208 of 07 and accelerating.
第４図（よ 同製造方法における要部の概略図であも
第３図のようなＩｎ及びＳｎ薄膜２１２を形戒するため
に蒸着あるいは溶射を行う機構を基板室２１０に備えた
装置内Ｆ，１００℃以下の温度の基板２１１上に 蒸着
源２１４によってＩｎ及びＳｎの合金薄膜２１２を形或
すると同時に酸素イオン・ラジカルの照射を行う。この
とき酸素イオン２ ０ ９ ＋＆ １ ０ ｋ ｅ
Ｖ以下に加速すも第１実施例と同様に イオン照射によ
って膜形或中の薄膜表面付近が高温となり、化学的に活
性な状態となん この様な状態のもとで、酸素ラジカル
の照射及び酸素イオンの注入を行なうことによつて、堆
積中のＩｎ及びＳｎの合金薄膜２１２の表面及び内部を
酸化Ｌ Ｉ ｎｘｓ ｎｕ （ｘ十ｙ＝ １，ｙ≦１
）の合金酸化物からなる透明導電膜２１３を形戊するこ
とができも
発明の効果
本発明により得られる効果（上 以下のようにまとめら
れも
蒸着・メッキなどによりＩ ｎ Ｘ Ｓ ｎ ｖ （ｘ
＋’ｙ＝ １、ｙ≦１）からなる薄膜を大面積に対して
容易に堆積することが可能であり、かつ上記イオン照射
装置により、少なくとも酸素を含む気体の放電分解によ
る生戊物を大面積に対して照射することが可能であるこ
とか板 透明で導電性の高いＩｎｘＳｎＩ１の酸化物薄
膜が大面積基板上に均一に形或できもまた 高いエネル
ギーのイオンの照射によって薄膜の表面付近が高温とな
るた＆ １００℃以下の基板温度にかかわらず薄膜の
表面付近が化学的に活性な状態となり、低温での透明導
電膜の形或が可能となん
以上のことか板 本発明に依って大面積のガラス・プラ
スチック等の様々な基板上に透明導電膜を形或すること
が可能となる。Figure 4 (also a schematic diagram of the main parts of the same manufacturing method)
In a device equipped with a mechanism for vapor deposition or thermal spraying in a substrate chamber 210 to form an In and Sn thin film 212 as shown in FIG. At the same time as forming the Sn alloy thin film 212, irradiation with oxygen ions and radicals is performed. At this time, oxygen ions 2 0 9 + & 1 0 ke
As in the first embodiment, the ion irradiation raises the temperature near the surface of the thin film in the membrane shape, making it chemically active.Under these conditions, oxygen radical irradiation and By implanting oxygen ions, the surface and interior of the In and Sn alloy thin film 212 being deposited is oxidized L I nxs nu (x + y= 1, y≦1
Effects of the Invention The transparent conductive film 213 made of an alloy oxide of
+'y = 1, y≦1) can be easily deposited over a large area, and the above-mentioned ion irradiation device can greatly reduce the amount of debris produced by discharge decomposition of gas containing at least oxygen. It is possible to irradiate a transparent and highly conductive InxSnI1 oxide thin film on a large-area substrate. The present invention makes it possible to form a transparent conductive film at low temperatures because the surface area of the thin film becomes chemically active regardless of the substrate temperature of 100°C or less. It becomes possible to form transparent conductive films on various substrates such as large-area glass and plastic.
第１図は本発明の第１実施例における透明導電薄膜の製
造方法を実施するイオン照射処理装置の概略構或阻 第
２図は同製造方法における要部の概略諷 第３図は本発
明の第２実施例における透明導電薄膜の製造方法を実施
するイオン照射処理装置の概略構戒阻 第４図は同製
造方法における要部の概略図であも
１０２、 ２０２・・・放電塞 １０９、 ２０９・・
・酸素イオン胤 １１１、 ２１１・・・基坂 １１２
、２ １ ２ ・・・Ｉ ｎｘｓ ｎ，（ｘ十ｙ＝ １
， ｙ≦１）の合金薄［１１３、２１３・・・透明導
電！ ２１４・・・誘導加熱蒸着Ｉ！２ １ ５ ・
・４ ｎｘＳｎｖ （ｘ十ｙ＝ １，ｙ≦１）合金の分
子・クラスター嵐FIG. 1 shows a schematic structure of an ion irradiation treatment apparatus for carrying out the method for manufacturing a transparent conductive thin film according to the first embodiment of the present invention. FIG. 2 shows a schematic diagram of the main parts of the manufacturing method. A schematic diagram of an ion irradiation processing apparatus for carrying out the method for manufacturing a transparent conductive thin film in the second embodiment. FIG.・・・
・Oxygen ion seed 111, 211... Motosaka 112
, 2 1 2 ... I nxs n, (x 1 y = 1
, y≦1) alloy thin [113, 213...transparent conductive! 214...Induction heating vapor deposition I! 2 1 5 ・
・4 nxSnv (x + y = 1, y≦1) Alloy molecules/cluster storm
Claims (3)
）からなる薄膜を堆積し、その後にイオン照射装置によ
って、少なくとも酸素を含む気体の放電分解による生成
物を前記薄膜に照射することを特徴とする透明導電薄膜
の製造方法。(1) In_xSn_y (x+y=1, y≦1
), and then irradiating the thin film with a product of discharge decomposition of a gas containing at least oxygen using an ion irradiation device.
）からなる薄膜を堆積すると同時に、イオン照射装置に
よって、少なくとも酸素を含む気体の放電分解による生
成物を前記薄膜に照射することを特徴とする透明導電薄
膜の製造方法。(2) In_xSn_y (x+y=1, y≦1
1.) A method for manufacturing a transparent conductive thin film, which comprises depositing a thin film consisting of the following: and simultaneously irradiating the thin film with a product of discharge decomposition of a gas containing at least oxygen using an ion irradiation device.
を、０．５ｋｅＶ以上、１０ｋｅＶ以下とすることを特
徴とする請求項１または２記載の透明導電薄膜の製造方
法。(3) The method for producing a transparent conductive thin film according to claim 1 or 2, characterized in that the energy of ions of the products of discharge decomposition is set to 0.5 keV or more and 10 keV or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15182589A JPH0317912A (en) | 1989-06-14 | 1989-06-14 | Manufacture of transparent conductive thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15182589A JPH0317912A (en) | 1989-06-14 | 1989-06-14 | Manufacture of transparent conductive thin film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0317912A true JPH0317912A (en) | 1991-01-25 |
Family
ID=15527141
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15182589A Pending JPH0317912A (en) | 1989-06-14 | 1989-06-14 | Manufacture of transparent conductive thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0317912A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7540505B2 (en) | 2002-02-06 | 2009-06-02 | Toyota Jidosha Kabushiki Kaisha | Stabilizer system |
-
1989
- 1989-06-14 JP JP15182589A patent/JPH0317912A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7540505B2 (en) | 2002-02-06 | 2009-06-02 | Toyota Jidosha Kabushiki Kaisha | Stabilizer system |
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