JPH0769531B2 - Method for producing transparent conductive film having insulating protective film - Google Patents
Method for producing transparent conductive film having insulating protective filmInfo
- Publication number
- JPH0769531B2 JPH0769531B2 JP60005400A JP540085A JPH0769531B2 JP H0769531 B2 JPH0769531 B2 JP H0769531B2 JP 60005400 A JP60005400 A JP 60005400A JP 540085 A JP540085 A JP 540085A JP H0769531 B2 JPH0769531 B2 JP H0769531B2
- Authority
- JP
- Japan
- Prior art keywords
- transparent conductive
- conductive film
- film
- insulating protective
- heat treatment
- 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
Landscapes
- Surface Treatment Of Glass (AREA)
- Physical Vapour Deposition (AREA)
- Non-Insulated Conductors (AREA)
- Manufacturing Of Electric Cables (AREA)
- Liquid Crystal (AREA)
Description
【発明の詳細な説明】 （技術分野） 本発明は、絶縁保護膜を有する透明導電膜の製造方法に
関するものである。TECHNICAL FIELD The present invention relates to a method for producing a transparent conductive film having an insulating protective film.
（従来技術） 透明導電膜は、可視光線に対して透明で電気伝導性を有
する薄膜であり、液晶表示装置の電極等に多く採用され
ている。(Prior Art) A transparent conductive film is a thin film that is transparent to visible light and has electrical conductivity, and is often used for electrodes and the like of liquid crystal display devices.
ところで、このような透明導電膜では、通常、その表面
を保護するために、ZrO2やAl2O3等の酸化物を絶縁保護
膜として設ける必要がある。そこで、従来では、ガラス
等の所定の基板上に成膜された透明導電膜に対して熱処
理（アニーリング）を施し、その熱処理後、その表面に
絶縁保護膜を形成するようになっていた。このようにし
て製造された絶縁保護膜を有する透明導電膜は、可視光
線透過率が高く、比抵抗も小さいという特長を備えてい
る。By the way, in such a transparent conductive film, it is usually necessary to provide an oxide such as ZrO 2 or Al 2 O 3 as an insulating protective film in order to protect the surface thereof. Therefore, conventionally, a transparent conductive film formed on a predetermined substrate such as glass is subjected to a heat treatment (annealing), and after the heat treatment, an insulating protective film is formed on the surface thereof. The transparent conductive film having the insulating protective film produced in this manner has the features of high visible light transmittance and low specific resistance.
（発明が解決しようとする問題点） しかし、上述の如き従来の手法で製造された透明導電膜
では、透明導電膜と絶縁保護膜との間の密着性が必ずし
も良好に得られているとは言い難く、未だ改善の余地が
ある。(Problems to be Solved by the Invention) However, in the transparent conductive film manufactured by the conventional method as described above, the adhesion between the transparent conductive film and the insulating protective film is not necessarily good. It is hard to say, and there is still room for improvement.
これに対し、特開昭51−111348号公報に記載されている
ように、透明導電膜を成膜後、Al2O3等の絶縁体をスパ
ッタ法により透明導電膜面に形成する技術が提案された
り、或いは実開昭53−151931号公報に記載されているよ
うに、透明導電膜上にSiO2膜を真空蒸着により成膜後、
500度程度の焼純を１時間程度施す技術が提案されてい
る。On the other hand, as disclosed in Japanese Patent Laid-Open No. 51-111348, a technique is proposed in which an insulating material such as Al 2 O 3 is formed on the surface of the transparent conductive film by a sputtering method after forming the transparent conductive film. Or, as described in Japanese Utility Model Publication No. 53-151931, after forming a SiO 2 film on the transparent conductive film by vacuum deposition,
A technique has been proposed in which a refining at about 500 degrees is performed for about 1 hour.
しかしながら、上記の技術を用いて、透明導電膜上に絶
縁保護膜を形成し、その絶縁保護膜の密着性を高めるた
めに不活性ガス雰囲気中でアニールを施すと、上記透明
導電膜の比抵抗が増加するという欠点があった。However, when an insulating protective film is formed on the transparent conductive film using the above technique and annealing is performed in an inert gas atmosphere to enhance the adhesion of the insulating protective film, the specific resistance of the transparent conductive film is increased. Has the drawback of increasing.
本発明は以上の事情を背景として為されたものであり、
その目的とするところは、透明導電膜の比抵抗を増加さ
せることなく、高い剥離強度および耐磨耗性を有する絶
縁保護膜を有する透明導電膜の製造方法を提供すること
にある。The present invention has been made in the background of the above circumstances,
It is an object of the invention to provide a method for producing a transparent conductive film having an insulating protective film having high peel strength and abrasion resistance without increasing the specific resistance of the transparent conductive film.
（問題点を解決するための手段） かかる目的を達成するための本発明の要旨とするところ
は、透明導電膜を成膜後、ZrO2またはAl2O3から成る絶
縁保護膜をスパッタリング法を用いてその透明導電膜面
に形成し、その絶縁保護膜を形成した透明導電膜に対し
て、10-1Pa以下の真空中において300℃以上の温度で２
〜６時間加熱する熱処理を行うことにある。(Means for Solving Problems) The gist of the present invention for achieving such an object is that a transparent conductive film is formed and then an insulating protective film made of ZrO 2 or Al 2 O 3 is formed by a sputtering method. The transparent conductive film formed on the surface of the transparent conductive film with the insulating protective film formed thereon is heated at a temperature of 300 ° C. or higher in a vacuum of 10 −1 Pa or lower.
It is to perform a heat treatment of heating for 6 hours.
なお、上記熱処理は、10-1Pa以下の真空中において300
℃以上の温度で２〜６時間加熱するのがよい。300℃以
上の熱処理では、アルゴンのような不活性ガス雰囲気よ
りも真空中の方が透明導電膜の抵抗値変化率が好適に抑
制され、その真空度は10-1Paを越えるとその抵抗値変化
率抑制効果が得られ難くなる。また、上記真空中におけ
る熱処理では、後述の第３図に示すように、その温度が
300℃を下まわると、不活性ガス雰囲気中における熱処
理による抵抗値変化率に対して効果が認められ難くな
る。また、その加熱時間が２〜６時間の範囲を越えても
同様である。また、上記熱処理温度は、透明導電膜の抵
抗値変化率に関してはかなり高くてもよいが、それが高
くなるにともなって透明導電膜の可視光線透過率が低下
するので、実用上は500℃を下まわる温度がよい。The heat treatment is performed at a vacuum of 10 -1 Pa or less for 300
It is preferable to heat at a temperature of ℃ or more for 2 to 6 hours. With heat treatment at 300 ° C or higher, the rate of change in resistance of the transparent conductive film is more preferably suppressed in a vacuum than in an inert gas atmosphere such as argon, and when the degree of vacuum exceeds 10 -1 Pa, the resistance changes. It becomes difficult to obtain the effect of suppressing the rate of change. Further, in the heat treatment in the vacuum, as shown in FIG.
Below 300 ° C, it becomes difficult to recognize the effect on the rate of change in resistance value due to heat treatment in an inert gas atmosphere. The same applies when the heating time exceeds the range of 2 to 6 hours. Further, the heat treatment temperature may be considerably high with respect to the rate of change in resistance of the transparent conductive film, but the visible light transmittance of the transparent conductive film decreases as it increases, so 500 ° C. is practically used. The lower temperature is good.
また、前記絶縁保護膜としてはCeO2、MgAlO4、SiO2、Ti
O2、ZrO2、Al2O3等を採用し得るけれども、高い密着性
を得るためにはZrO2、Al2O3が優れている。Further, as the insulating protective film, CeO 2 , MgAlO 4 , SiO 2 , Ti
Although O 2 , ZrO 2 , Al 2 O 3 and the like can be adopted, ZrO 2 and Al 2 O 3 are excellent in order to obtain high adhesion.
また、本発明は特に透明導電膜としてのITO（In2O3-SnO
2）膜を製造するのに良好な結果を発揮するものである
が、これに限定されるものではない。Further, the present invention is particularly applicable to ITO (In 2 O 3 -SnO) as a transparent conductive film.
2 ) It gives good results in producing the membrane, but is not limited thereto.
（発明の効果） 本発明の方法により製造された透明導電膜は、10-1Pa以
下の真空中において300℃以上の温度で２〜６時間加熱
する熱処理により、絶縁保護膜の抵抗値変化率が抑制さ
れて比較的低い比抵抗となるとともに、充分な密着性が
得られる。したがって、その密着性の向上により透明導
電膜の信頼性が一層高められる。すなわち、10-1Pa以下
の真空中における300℃以上の熱処理温度によりZrO2ま
たはAl2O3から成る絶縁保護層の結晶性が高められて低
いヘーズ値すなわち高い剥離強度および耐摩耗性を有す
る絶縁保護膜が得られるのである。(Effect of the invention) The transparent conductive film produced by the method of the present invention is subjected to a heat treatment of heating at a temperature of 300 ° C or higher for 2 to 6 hours in a vacuum of 10 -1 Pa or lower, and thereby the resistance change rate of the insulating protective film Is suppressed, resulting in a relatively low specific resistance and sufficient adhesion. Therefore, the reliability of the transparent conductive film is further enhanced by the improvement of the adhesiveness. That is, the crystallinity of the insulating protective layer made of ZrO 2 or Al 2 O 3 is enhanced by a heat treatment temperature of 300 ° C. or higher in a vacuum of 10 −1 Pa or lower, and a low haze value, that is, high peel strength and abrasion resistance. An insulating protective film can be obtained.
以下、本発明の実施例を説明するが、これは多数の実施
例の中の一部であり、本発明がここに例示の実施例の記
載によって限定されるものでないことは勿論である。Examples of the present invention will be described below, but it is a matter of course that the present invention is part of a large number of examples, and the present invention is not limited to the description of the examples.
（実施例） スパッタリング装置を用い、到達真空度10-4Pa,酸素導
入圧1.3×10-3Pa,Ar導入圧2.6×10-1Paの雰囲気内にお
いて、印加電力1kWで、第１図に示すように、ガラス基
板10上に透明導電膜であるITO膜12を約１μｍ成膜し
た。次いで、そのITO膜12の表面に絶縁保護膜であるCeO
2，MgAl2O4，SiO2，ZrO2，Al2O3等の酸化膜14を約0.3μ
ｍの厚さで成膜し、その成膜後、真空電気炉を用いて10
-3Pa以下に真空排気した雰囲気内において、500℃で約
４時間熱処理（アニーリング）した。そして、そのよう
にして製造した酸化膜14を有するITO膜12に対してJIS R
3212に準じた耐摩耗試験を行い、ヘーズ値を測定した。
また、酸化膜14の成膜後の熱処理温度を200℃,300℃お
よび400℃に変え、同様にしてヘーズ値を測定した。そ
れらの結果を下記第１表に示す。(Example) Using a sputtering apparatus, in an atmosphere of ultimate vacuum of 10 -4 Pa, oxygen introduction pressure of 1.3 × 10 -3 Pa, Ar introduction pressure of 2.6 × 10 -1 Pa, with applied power of 1 kW, as shown in FIG. As shown, the ITO film 12, which is a transparent conductive film, was formed on the glass substrate 10 to a thickness of about 1 μm. Next, CeO, which is an insulating protective film, is formed on the surface of the ITO film 12.
2 , oxide film 14 of MgAl 2 O 4 , SiO 2 , ZrO 2 , Al 2 O 3 etc.
After forming a film with a thickness of 10 m, a vacuum electric furnace is used for 10
Heat treatment (annealing) was performed at 500 ° C. for about 4 hours in an atmosphere evacuated to −3 Pa or less. Then, for the ITO film 12 having the oxide film 14 thus manufactured, JIS R
A wear resistance test according to 3212 was performed and the haze value was measured.
Further, the heat treatment temperature after forming the oxide film 14 was changed to 200 ° C., 300 ° C. and 400 ° C., and the haze value was measured in the same manner. The results are shown in Table 1 below.
また、それらの測定結果と比較するために、従来の方
法、すなわちITO膜12を成膜後熱処理し、その後酸化膜1
4を成膜することにより製造したものについて同様の試
験を行い、その結果を第１表に併せて示した。Further, in order to compare with the measurement results, the conventional method, that is, the ITO film 12 is heat-treated after forming, and then the oxide film 1 is formed.
The same test was conducted on the one manufactured by depositing 4 and the results are also shown in Table 1.
第１表から明らかなように、酸化膜14がCeO2，MgAl
2O4，SiO2等のものについては、従来の方法で製造した
ものでは剥離が認められたが、本発明方法によって製造
したものでは剥離が認められず、密着性が大幅に向上し
ていることが認められた。また、酸化膜14がZrO2，Al2O
3のものについては、従来の方法によって製造されたも
のについてもかなり良好な密着性を有していることが認
められたが、本発明方法に従って製造されたものでは、
密着性が一層向上していることが認められた。さらに、
酸化膜14の種類に拘わらず、熱処理温度が高いほど良好
な密着性が得られることが認められた。また、第１表の
結果から、密着性が高いことから、絶縁保護膜としては
ZrO2またはAl2O3が望ましいことが認められた。 As is clear from Table 1, the oxide film 14 is composed of CeO 2 , MgAl.
As for 2 O 4 , SiO 2 and the like, peeling was observed in the one manufactured by the conventional method, but peeling was not recognized in the one manufactured by the method of the present invention, and the adhesiveness is significantly improved. Was confirmed. Further, the oxide film 14 is formed of ZrO 2 , Al 2 O
It was observed that, as for 3 , those having a fairly good adhesion were also produced by the conventional method, but in the case of the method produced by the method of the present invention,
It was confirmed that the adhesion was further improved. further,
It was confirmed that the higher the heat treatment temperature, the better the adhesion, regardless of the type of the oxide film 14. Further, from the results in Table 1, since the adhesiveness is high, the insulating protective film is
It has been found that ZrO 2 or Al 2 O 3 are desirable.
また、2.7×10-1PaのAr雰囲気中および10-3Paの真空雰
囲気中において熱処理温度を変えて製造した酸化膜14を
有するITO膜12に対し、可視光線透過率を測定した。そ
の測定結果を第２図に示す。なお、加熱時間は約４時間
である。Further, the visible light transmittance was measured for the ITO film 12 having the oxide film 14 manufactured by changing the heat treatment temperature in an Ar atmosphere of 2.7 × 10 -1 Pa and a vacuum atmosphere of 10 -3 Pa. The measurement result is shown in FIG. The heating time is about 4 hours.
第２図から明らかなように、200℃程度以上の熱処理温
度において、いずれも良好な可視光線透過率が得られる
ことが認められた。As is clear from FIG. 2, it was confirmed that good visible light transmittance can be obtained at any heat treatment temperature of about 200 ° C. or higher.
さらに、上述と同様にして製造したITO膜12、および空
気雰囲気中において同様の条件下で製造したITO膜12の
熱処理前後の抵抗値を測定した。第３図にその測定の結
果得られた熱処理前後の抵抗値の変化率（R/R0）を示
す。なお、第３図中、R0は熱処理前の抵抗値であり、Ｒ
は熱処理後の抵抗値である。また、第３図においては、
R0が１のときが約４×10-4Ωcmの比抵抗に対応してい
る。Furthermore, the resistance values before and after the heat treatment of the ITO film 12 manufactured in the same manner as described above and the ITO film 12 manufactured under the same conditions in the air atmosphere were measured. FIG. 3 shows the rate of change (R / R 0 ) in the resistance value before and after the heat treatment obtained as a result of the measurement. In FIG. 3, R 0 is the resistance value before heat treatment, and R 0 is
Is the resistance value after heat treatment. Also, in FIG.
When R 0 is 1, it corresponds to a specific resistance of about 4 × 10 −4 Ωcm.
第３図から明らかように、特に真空雰囲気中において低
い比抵抗が安定して得られ、300℃以上の温度、特に400
℃以上の温度で熱処理をした場合において比抵抗が極め
て小さくなることが認められた。As is clear from FIG. 3, a low specific resistance can be stably obtained especially in a vacuum atmosphere, and a temperature of 300 ° C. or higher, especially 400
It was confirmed that the specific resistance becomes extremely small when the heat treatment is performed at a temperature of ℃ or higher.
第１図は本発明方法によって製造される透明導電膜の一
例を説明するための断面図であり、第２図は本発明の一
例の方法によって製造された透明導電膜の熱処理温度と
可視光線透過率との関係を示すグラフであり、第３図は
同じく本発明の一例の方法によって製造された透明導電
膜の熱処理温度と比抵抗との関係を示すグラフである。 12:ITO膜、14:酸化膜FIG. 1 is a cross-sectional view for explaining an example of a transparent conductive film manufactured by the method of the present invention, and FIG. 2 is a heat treatment temperature and visible light transmission of the transparent conductive film manufactured by the method of the present invention. FIG. 3 is a graph showing the relationship with the rate, and FIG. 3 is a graph showing the relationship between the heat treatment temperature and the specific resistance of the transparent conductive film similarly manufactured by the method of the present invention. 12: ITO film, 14: Oxide film
Claims (1)
ら成る絶縁保護膜をスパッタリング法を用いて該透明導
電膜面に形成し、該絶縁保護膜を形成した透明導電膜に
対して、10-1Pa以下の真空中において300℃以上の温度
で２〜６時間加熱する熱処理を行うことを特徴とする絶
縁保護膜を有する透明導電膜の製造方法。1. A transparent conductive film in which an insulating protective film made of ZrO 2 or Al 2 O 3 is formed on the surface of the transparent conductive film by a sputtering method after the transparent conductive film is formed, and the insulating protective film is formed. On the other hand, a method for producing a transparent conductive film having an insulating protective film, which comprises performing a heat treatment of heating at a temperature of 300 ° C. or higher for 2 to 6 hours in a vacuum of 10 −1 Pa or lower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60005400A JPH0769531B2 (en) | 1985-01-16 | 1985-01-16 | Method for producing transparent conductive film having insulating protective film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60005400A JPH0769531B2 (en) | 1985-01-16 | 1985-01-16 | Method for producing transparent conductive film having insulating protective film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61165731A JPS61165731A (en) | 1986-07-26 |
| JPH0769531B2 true JPH0769531B2 (en) | 1995-07-31 |
Family
ID=11610093
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60005400A Expired - Lifetime JPH0769531B2 (en) | 1985-01-16 | 1985-01-16 | Method for producing transparent conductive film having insulating protective film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0769531B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4906524A (en) * | 1987-05-29 | 1990-03-06 | Orient Watch Co., Ltd. | Surface-coated article and a method for the preparation thereof |
| JPH0432555A (en) * | 1990-05-30 | 1992-02-04 | Nippon Steel Corp | Metallic substrate coated with insulating material excellent in insulating property |
| IT1276536B1 (en) * | 1995-04-18 | 1997-11-03 | Siv Soc Italiana Vetro | PROCEDURE TO IMPROVE THE ABRASION RESISTANCE AND CHEMICAL INERTIA PROPERTIES OF THIN TRANSPARENT COATINGS. |
| KR100710276B1 (en) * | 1999-12-31 | 2007-04-23 | 엘지.필립스 엘시디 주식회사 | Method of Fabricating Liquid Crystal Display Device |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51111348A (en) * | 1975-03-26 | 1976-10-01 | Fujitsu Ltd | Liquid crystal cell |
| JPS53151931U (en) * | 1978-03-30 | 1978-11-30 |
-
1985
- 1985-01-16 JP JP60005400A patent/JPH0769531B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61165731A (en) | 1986-07-26 |
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