JPH05313111A - Production of transparent conductive glass for liquid crystal display element - Google Patents

Production of transparent conductive glass for liquid crystal display element

Info

Publication number
JPH05313111A
JPH05313111A JP11443592A JP11443592A JPH05313111A JP H05313111 A JPH05313111 A JP H05313111A JP 11443592 A JP11443592 A JP 11443592A JP 11443592 A JP11443592 A JP 11443592A JP H05313111 A JPH05313111 A JP H05313111A
Authority
JP
Japan
Prior art keywords
glass
film
transparent conductive
alkali elution
chamber
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.)
Granted
Application number
JP11443592A
Other languages
Japanese (ja)
Other versions
JP3232646B2 (en
Inventor
Kenzou Sono
健三 曾野
Koji Nakanishi
功次 中西
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Sheet Glass Co Ltd
Original Assignee
Nippon Sheet Glass Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nippon Sheet Glass Co Ltd filed Critical Nippon Sheet Glass Co Ltd
Priority to JP11443592A priority Critical patent/JP3232646B2/en
Publication of JPH05313111A publication Critical patent/JPH05313111A/en
Application granted granted Critical
Publication of JP3232646B2 publication Critical patent/JP3232646B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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  • Surface Treatment Of Glass (AREA)

Abstract

PURPOSE:To efficiently produce a transparent conductive glass for the liq. crystal display element by using an in-line sputtering device. CONSTITUTION:A first coating chamber 2, a heating chamber 3 and a second coating chamber 4 are connected in this order to constitute an in-line sputtering device. A glass sheet is heated to <=200 deg.C in the first coating chamber 2 and coated with an alkali elution preventive film consisting of silicon dioxide, then the glass sheet is heated to >=300 deg.C in the heating chamber 3, densified and simultaneously heat-contracted, and the glass sheet is heated to >=300 deg.C in the second coating chamber 4 and coated with an ITO film.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は、ガラス板上にアルカリ
溶出防止膜と透明電導膜が順次被覆された透明電導ガラ
ス、とりわけソーダライムシリカ組成のフロートガラス
をガラス基板とした液晶表示素子用に好適に用いられる
透明電導ガラスを製造する方法に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is applied to a liquid crystal display device having a glass substrate made of transparent conductive glass in which an alkali elution preventive film and a transparent conductive film are sequentially coated on a glass plate, particularly float glass having a soda lime silica composition. The present invention relates to a method for producing a transparent conductive glass that is preferably used.

【0002】[0002]

【従来の技術】単純マトリックスタイプの液晶表示素子
用の透明電導ガラスには、ソーダライムシリカ組成のフ
ロートガラス板にアンダーコートとしてアルカリ溶出防
止膜が被覆され、透明電導膜としてITO(錫をドープ
した酸化インジウム)膜が被覆されたものが知られてい
る。上記の透明電導ガラスの製造方法としては、洗浄し
たガラス板を珪弗素酸溶液に漬けてガラス板上に約35
〜50nmの二酸化珪素膜からなるアルカリ溶出防止膜
を室温度で被覆(図3の工程1)し、その後ガラスを再
度洗浄(図3の工程2)した後、スパッタリングなどの
真空成膜(図3の工程3)によりITO膜を被覆する方
法が知られている。また、上記の珪弗素酸溶液の代わり
にポリシロキサンのような有機珪素化合物の希釈液にガ
ラス板を漬け、その後ガラス板を空気中で加熱して有機
成分を分解除去して厚みが100〜200nmの二酸化
珪素膜とし、しかるのちITO膜を被覆する方法が知ら
れている。
2. Description of the Related Art A transparent conductive glass for a liquid crystal display device of a simple matrix type is a float glass plate of soda lime silica composition coated with an alkali elution preventive film as an undercoat and ITO (tin-doped) as a transparent conductive film. A film coated with an (indium oxide) film is known. As the method for producing the transparent conductive glass, the washed glass plate is dipped in a fluorosilicic acid solution to form about 35
After coating an alkali elution preventive film consisting of a silicon dioxide film of ˜50 nm at room temperature (step 1 in FIG. 3) and then cleaning the glass again (step 2 in FIG. 3), vacuum deposition such as sputtering (FIG. 3). There is known a method of coating the ITO film by the step 3). Further, instead of the above silicofluoric acid solution, the glass plate is dipped in a diluting solution of an organosilicon compound such as polysiloxane, and then the glass plate is heated in air to decompose and remove the organic component to a thickness of 100 to 200 nm. There is known a method of forming a silicon dioxide film, and then covering the ITO film.

【0003】[0003]

【発明が解決しようとする課題】しかしながら、上記の
従来技術においては、アルカリ溶出防止膜の被覆と透明
電導膜の被覆を行うにあたり、それぞれデイッピング設
備および真空成膜設備を必要としたので、工程間に不可
欠であるガラスの運搬に基因する傷やガラスエッジの欠
け等の欠点が生じ易い、広い設備スペースが必要であ
る、各工程に作業者が必要であるなどの問題点があり、
効率よく、かつ、高歩留まりで透明電導ガラスを生産す
ることが困難であった。また、ガラス中のナトリウムイ
オンの存在は、液晶表示素子の信頼性を確保する上で好
ましくないことが知られており、よりアルカリ溶出防止
性能を有する透明電導ガラスが必要とされ、そのような
透明電導ガラスを効率よく製造する方法の開発が望まれ
ていた。
However, in the above-mentioned prior art, since the alkali elution preventing film and the transparent conductive film are covered with the dipping equipment and the vacuum film forming equipment, respectively, the inter-process There are problems such as defects such as scratches and glass edge chipping that are indispensable for glass transportation, large equipment space is required, an operator is required for each process, etc.
It has been difficult to efficiently produce transparent conductive glass with a high yield. Further, it is known that the presence of sodium ions in the glass is not preferable in ensuring the reliability of the liquid crystal display element, and a transparent conductive glass having a more alkaline elution prevention performance is required. It has been desired to develop a method for efficiently producing conductive glass.

【0004】本発明は、上記問題点を解決するためにな
されたものであって、アルカリ防止性能が大きい液晶表
示素子用の電導ガラスを経済性よく製造する方法を提供
することを目的とする。
The present invention has been made in order to solve the above problems, and an object of the present invention is to provide a method for economically producing a conductive glass for a liquid crystal display device having a high alkali prevention performance.

【0005】また、上記従来技術の透明電導ガラスを用
いて液晶表示素子を製作する場合、電極パターン加工さ
れた透明電導ガラスは、通常配向膜処理工程などで40
0〜480℃、30〜60分程度の加熱処理を受けるの
で、このときガラスに熱収縮が発生し、ガラス寸法がわ
ずかに小さくなり、これにより電極パターンにずれが生
じるといった問題点があった。このガラスの熱収縮によ
る電極パターンのずれは、とりわけ大きな表示面積で高
精細液晶表示素子を製作するときに問題となっていた。
特に液晶表示をカラーで行うとき、あるいはモノクロ表
示であっても高精細の表示を行うときは、液晶表示セル
の透明電極の線巾は、100〜200μm程度と細くな
る。このとき、透明電極パターン巾のズレを少なくとも
1/2〜1/3以下にする必要があり、そのために通
常、液晶セルの組立プロセス中で生じるガラス基板の熱
収縮を30ppm以下にすることが必要とされている。
When a liquid crystal display device is manufactured using the above-mentioned transparent conductive glass of the prior art, the transparent conductive glass on which an electrode pattern is processed is usually manufactured by an alignment film treatment step or the like.
Since the glass is subjected to heat treatment at 0 to 480 ° C. for about 30 to 60 minutes, heat shrinkage occurs in the glass at this time, and the size of the glass is slightly reduced, which causes a problem that the electrode pattern is displaced. The displacement of the electrode pattern due to the thermal contraction of the glass has been a problem when manufacturing a high-definition liquid crystal display device with a particularly large display area.
In particular, when the liquid crystal display is performed in color, or when high-definition display is performed even in monochrome display, the line width of the transparent electrode of the liquid crystal display cell becomes as thin as about 100 to 200 μm. At this time, it is necessary that the deviation of the width of the transparent electrode pattern is at least 1/2 to 1/3 or less, and therefore, the heat shrinkage of the glass substrate that normally occurs during the assembly process of the liquid crystal cell is required to be 30 ppm or less. It is said that.

【0006】本発明の第2の目的は、上記の液晶表示素
子組立工程で受ける熱処理によって生じるガラス基板の
熱収縮を減じた、すなわち、電極パターンのズレが生じ
ない透明電導ガラスを経済性良く製造する方法を提供す
るにある。
A second object of the present invention is to economically manufacture a transparent conductive glass in which the heat shrinkage of the glass substrate caused by the heat treatment in the liquid crystal display element assembling step is reduced, that is, the electrode pattern is not displaced. To provide a way to do it.

【課題を解決するための手段】本発明は、減圧した雰囲
気が調節可能な第1の被覆室と前記第1の被覆室とは開
閉可能なゲートバルブで接続され減圧した雰囲気が調節
可能な加熱室と前記加熱室とは開閉可能なゲートバルブ
で接続され減圧した雰囲気が調節可能な第2の被覆室と
を少なくとも有するインライン型スパッタリング装置を
用いて、ガラス基板上にアルカリ溶出防止膜および透明
電導膜が順次被覆された透明電導ガラスを製造する方法
であって、 a)前記第1の被覆室では、前記ガラス基板の温度を2
00℃以下とした状態で透明金属酸化物または透明金属
窒化物からなるアルカリ溶出防止膜をスパッタリングに
より被覆すること、 b)前記加熱室では、被覆された前記アルカリ溶出防止
膜を300℃以上に加熱することにより緻密化するこ
と、 c)前記第2の被覆室では、前記アルカリ溶出防止膜が
被覆されたガラス基板を300℃以上に加熱した状態で
透明電導膜を被覆すること、 を連続して行う液晶表示素子用透明電導ガラスの製造方
法である。
According to the present invention, there is provided a first coating chamber in which a reduced pressure atmosphere can be adjusted and a heating valve in which the reduced pressure atmosphere can be adjusted by connecting the first coating chamber with an openable gate valve. Using an in-line type sputtering apparatus having at least a second coating chamber in which the chamber and the heating chamber are connected by an openable / closable gate valve and the depressurized atmosphere can be adjusted, an alkali elution preventing film and a transparent conductive film are formed on a glass substrate. A method for producing a transparent conductive glass in which films are sequentially coated, comprising: a) setting the temperature of the glass substrate to 2 in the first coating chamber.
Covering the alkali elution preventive film composed of a transparent metal oxide or a transparent metal nitride by sputtering at a temperature of 00 ° C or lower, b) heating the coated alkali elution preventive film to 300 ° C or higher in the heating chamber. To densify, c) coating the transparent conductive film in the second coating chamber in a state where the glass substrate coated with the alkali elution preventing film is heated to 300 ° C. or higher. This is a method for producing a transparent conductive glass for a liquid crystal display element.

【0007】本発明は、アルカリ溶出防止膜と透明電導
膜が別個の装置で実施することを排除し、単一の設備で
連続的にアルカリ溶出膜防止の被覆工程とアルカリ溶出
防止膜の緻密化工程と透明電導膜の被覆工程とを行うこ
とを特徴としている。
The present invention eliminates the case where the alkali elution preventive film and the transparent conductive film are carried out by separate devices, and continuously coats the alkali elution preventive film with a single facility and densifies the alkali elution preventive film. It is characterized in that the step and the step of coating the transparent conductive film are performed.

【0008】本発明に用いられるアルカリ溶出防止膜と
しては、可視光線の波長域で透明な透明金属酸化物また
は透明金属窒化物が用いられ、具体的には窒化珪素、窒
化タンタル、二酸化珪素、二酸化ジルコニウム、五酸化
タンタル、酸化アルミニウムが挙げられる。こお中で
も、とりわけ二酸化珪素が最も好んで用いられる。これ
らのアルカリ溶出防止膜の厚みは、10〜200nmと
するのが好ましい。10nm以下ではアルカリの溶出防
止性能が低下するので好ましくなく、200nm以上の
厚みに被覆しても膜の厚みに応じてアルカリ防止性能が
向上しない。
As the alkali elution preventive film used in the present invention, a transparent metal oxide or a transparent metal nitride, which is transparent in the wavelength range of visible light, is used. Specifically, silicon nitride, tantalum nitride, silicon dioxide, or dioxide is used. Examples include zirconium, tantalum pentoxide, and aluminum oxide. Of these, silicon dioxide is most preferably used. The thickness of these alkali elution preventive films is preferably 10 to 200 nm. If the thickness is 10 nm or less, the alkali elution prevention performance is deteriorated, which is not preferable, and even if the thickness is 200 nm or more, the alkali prevention performance is not improved depending on the thickness of the film.

【0009】特に、二酸化珪素膜については、10〜5
0nmの比較的薄い厚みでその目的が達成できるので好
ましい。上記のアルカリ溶出防止膜は、公知の高周波ス
パッタリングや金属ターゲットを酸素あるいは窒素を含
む雰囲気下でスパッタリングする直流反応性スパッタリ
ングにより成膜することができる。
Particularly, for the silicon dioxide film, 10 to 5
It is preferable because the object can be achieved with a relatively thin thickness of 0 nm. The above alkali elution preventing film can be formed by known high frequency sputtering or direct current reactive sputtering in which a metal target is sputtered in an atmosphere containing oxygen or nitrogen.

【0010】アルカリ溶出防止膜を被覆するときのガラ
ス板の温度を200℃以下とすることは、次工程の緻密
化処理工程での膜の焼きしめ効果を大きくし、よりアル
カリ溶出防止性能を向上させるために必要である。ガラ
ス板の温度を150℃以下とすることは、ガラス中のナ
トリウムイオンがガラス表面に拡散してくるのを抑制す
るので、より好ましい。
When the temperature of the glass plate at the time of coating the alkali elution preventing film is set to 200 ° C. or less, the effect of baking the film in the subsequent densification treatment step is increased and the alkali elution preventing performance is further improved. It is necessary to make it. Setting the temperature of the glass plate to 150 ° C. or lower is more preferable because it suppresses the diffusion of sodium ions in the glass onto the glass surface.

【0011】本発明にかかる加熱室で行う熱処理温度
は、300℃以上であることが必要である。加熱温度の
上限は、ガラス板が曲がったり、反ったりすることによ
りガラス表面の平坦度が損なわれない温度とすることが
できる。また、加熱時間はアルカリ溶出防止膜の厚み、
透明電導膜の厚みなどと関連してきめられる。
The heat treatment temperature performed in the heating chamber according to the present invention needs to be 300 ° C. or higher. The upper limit of the heating temperature can be set to a temperature at which the flatness of the glass surface is not deteriorated due to the bending or warping of the glass plate. The heating time depends on the thickness of the alkali elution prevention film,
It is determined in relation to the thickness of the transparent conductive film.

【0012】本発明においては、アルカリ溶出防止膜の
緻密化処理と同時にガラス板の熱収縮処理を行うことが
できる。ガラスの熱収縮は、ソーダライムシリカ組成の
ガラスでは380℃以上に加熱することにより行われ
る。短時間で熱収縮処理をするには、ガラスの加熱温度
は450℃以上とするのが好ましく、さらに500℃以
上とするのがより好ましい。また、熱収縮を行うときの
雰囲気は、減圧した雰囲気中で行われる。
In the present invention, the heat shrinkage treatment of the glass plate can be performed simultaneously with the densification treatment of the alkali elution preventive film. The heat shrinkage of the glass is performed by heating the glass of the soda lime silica composition to 380 ° C. or higher. In order to perform the heat shrinkage treatment in a short time, the heating temperature of the glass is preferably 450 ° C. or higher, more preferably 500 ° C. or higher. Further, the atmosphere for the heat shrinkage is a reduced pressure atmosphere.

【0013】本発明にかかるガラス板の熱収縮のための
加熱温度は、そのガラス板を用いて液晶表示素子を製作
するときのプロセス中の加熱温度を越えることを必ずし
も必要としない。ガラス基板にソーダライムシリカ組成
のガラス板を用いる場合、加熱室での熱収縮の収縮率を
50ppm以上とすることは、液晶表示素子製作工程中
の加熱処理によって生ずるガラス寸法の収縮量を低減
し、電極パターンのずれを実質的に生じにくくさせる上
で好ましく、さらに150ppm以上とするのがより好
ましい。
The heating temperature for the heat shrinkage of the glass plate according to the present invention does not necessarily need to exceed the heating temperature during the process of manufacturing a liquid crystal display device using the glass plate. When a glass plate having a soda lime silica composition is used as the glass substrate, setting the shrinkage ratio of the heat shrinkage in the heating chamber to 50 ppm or more reduces the shrinkage amount of the glass size caused by the heat treatment during the liquid crystal display element manufacturing process. It is preferable that the deviation of the electrode pattern is substantially unlikely to occur, and it is more preferably 150 ppm or more.

【0014】本発明に用いられる透明電導膜は、錫をド
ープした酸化インジウム(ITO)膜、フッ素あるいは
アンチモンをドープした酸化錫膜などが用いられ、それ
らの被覆方法としては、合金または酸化物をターゲット
に用いて高周波スパッタリングや直流反応性スパッタリ
ングなどの公知の方法が用いられる。とりわけITO膜
が低抵抗率を有し、かつ微細電極の加工が容易であるの
で好ましい。
The transparent conductive film used in the present invention may be a tin-doped indium oxide (ITO) film, a fluorine- or antimony-doped tin oxide film, or the like. A known method such as high frequency sputtering or direct current reactive sputtering is used for the target. In particular, the ITO film is preferable because it has a low resistivity and the fine electrode can be easily processed.

【0015】また、液晶表示素子用のガラス板として
は、ソーダライムシリカ組成のフロートガラス(主成分
として重量%でSiO2が70〜73%、Al23が1
〜1.8%、CaOが7〜12%、MgOが1〜4.5
%、Na2Oが13〜15%、Fe23が0.08〜
0.14%含まれる)が安価で大量に入手できることか
ら最もよく用いられる。本発明においては、とりわけソ
ーダライムシリカ組成のガラスに対して、アルカリ溶出
防止性能の改善と熱収縮によるガラス板の寸法の安定化
を同時に、かつ、効果的に行うことができる。
As a glass plate for a liquid crystal display device, a float glass having a soda lime silica composition (70% to 73% by weight of SiO 2 and 1% of Al 2 O 3 as main components by weight%) is used.
~ 1.8%, CaO 7-12%, MgO 1-4.5
%, Na 2 O 13 to 15%, Fe 2 O 3 0.08 to
0.14% included) is most commonly used because it is cheap and available in large quantities. In the present invention, particularly with respect to the glass having the soda lime silica composition, the improvement of the alkali elution prevention performance and the stabilization of the dimension of the glass plate by heat shrinkage can be simultaneously and effectively performed.

【0016】また、低膨張率を有するいわゆる低膨張ガ
ラスである、たとえばホーヤ社製商品名NAー45ガラ
ス、旭硝子社製AXガラス、コーニングガラス社製70
59ガラスなどのガラス基板を用いることができる。
Further, it is a so-called low expansion glass having a low expansion coefficient, for example, NA-45 glass manufactured by Hoya Co., AX glass manufactured by Asahi Glass Co., 70 manufactured by Corning Glass Co., Ltd.
A glass substrate such as 59 glass can be used.

【実施例】以下に本発明を実施例に基づいて説明する。
図1は本発明の実施に用いたインライン型スパッタリン
グ装置の側面断面図、図2は図1のAA断面図、図3は
従来技術による透明電導ガラスの製造方法を説明するた
めの製造フローチャートである。 実施例 洗浄乾燥されたソーダライムシリカ組成の厚みが1.1
mmのフロートガラス板を上下に爪を有しその間にガラ
ス基板を支持できる金属製のキャリア13に取付け、開
閉可能なゲートバルブ14A、14Bで仕切られた真空
予備室1内にセットした。真空予備室1内が所定の減圧
状態になってからキャリア13を第1の被覆室2に移し
た。そしてヒータ9によりガラス板温度を150℃に維
持して、0.4Pa(パスカル)のアルゴンガスの雰囲
気下で、高周波電力が印加されてスパッタリングされて
いる石英ガラスターゲット7、7の前面を0.45m/
分のスピードで搬送しながら、二酸化珪素(SiO2
膜を35nm被覆した。さらに、ゲートバルブ14Cの
開閉操作によりキャリア13を加熱室3へ搬送するとと
もに、ヒータ10およびヒータ11によりキャリア13
が加熱室13にあるときにガラスの温度が500℃にな
るようにして、アルカリ溶出防止膜の緻密化とガラス板
の熱収縮を行った。このときの加熱室の雰囲気は0.4
Pa以下とした。その後、開閉可能なゲートバルブ14
Dを開けて、キャリア13を第2の被覆室4内に搬送
し、ヒータ11Aおよびヒータ12によりガラス板温度
が400℃になるように調節して、酸素1%アルゴン9
9%からなる0.3Paの減圧雰囲気下で直流電力が印
加されてスパッタリングされているITO(10%の酸
化錫と90%の酸化インジウムの混合物)ターゲットを
貼りつけたカソード8、8、8、8の前面を0.45m
/分のスピードで搬送しながら、ITO膜を150nm
被覆した。その後、開閉可能なゲートバルブ14E、1
4F、14Gを操作して、第2の被覆室の減圧された雰
囲気状態を変えることなく、キャリア13を第2の被覆
室4から順次、バッフア室5、取り出し室6に移し、最
後にインラインスパッタリング装置15からキャリア1
3を外部に取り出した。
EXAMPLES The present invention will be described below based on examples.
1 is a side sectional view of an in-line type sputtering apparatus used for carrying out the present invention, FIG. 2 is a sectional view taken along the line AA of FIG. 1, and FIG. 3 is a manufacturing flow chart for explaining a method for manufacturing a transparent conductive glass according to a conventional technique. .. Example The washed and dried soda lime silica composition has a thickness of 1.1.
A mm float glass plate was attached to a metal carrier 13 having upper and lower claws and capable of supporting a glass substrate between them, and set in a vacuum preliminary chamber 1 partitioned by openable and closable gate valves 14A and 14B. The carrier 13 was transferred to the first coating chamber 2 after the inside of the vacuum preliminary chamber 1 became a predetermined depressurized state. The temperature of the glass plate is maintained at 150 ° C. by the heater 9 and the front surface of the quartz glass targets 7, 7 to which high frequency power is applied and is sputtered in an atmosphere of argon gas of 0.4 Pa (Pascal) is set to 0. 45m /
Silicon dioxide (SiO 2 ) while transporting at the speed of a minute
The film was coated to 35 nm. Further, the carrier 13 is conveyed to the heating chamber 3 by opening / closing the gate valve 14C, and the carrier 13 is driven by the heater 10 and the heater 11.
The temperature of the glass was set to 500 ° C. when the sample was in the heating chamber 13, and the alkali elution preventing film was densified and the glass plate was heat-shrinked. At this time, the atmosphere in the heating chamber is 0.4.
It was set to Pa or less. After that, the gate valve 14 that can be opened and closed
Open D, convey the carrier 13 into the second coating chamber 4, adjust the glass plate temperature to 400 ° C. by the heater 11A and the heater 12, and add oxygen 1% argon 9
Cathodes 8, 8 and 8 to which an ITO (mixture of 10% tin oxide and 90% indium oxide) target, which is sputtered by applying DC power in a reduced pressure atmosphere of 9% of 0.3 Pa, is attached. 0.45m in front of 8
While transporting at a speed of / min, the ITO film is 150 nm
Coated. After that, the gate valve 14E that can be opened and closed, 1
By operating 4F and 14G, the carrier 13 is sequentially transferred from the second coating chamber 4 to the buffer chamber 5 and the take-out chamber 6 without changing the decompressed atmosphere state of the second coating chamber, and finally in-line sputtering is performed. Device 15 to carrier 1
3 was taken out.

【0017】得られた透明電導ガラスの可視光線透過率
は90%、ITO膜の面積抵抗は8オーム/平方であっ
た。このガラスのITO膜を酸でエッチング除去した
後、100℃の沸騰した純水中に24時間漬け、この純
水中のアルカリ量を定量して、アルカリ溶出防止性能を
測定したところ、0.01μg/cm2であった。ま
た、この透明電導ガラスを480℃、30分の大気中で
の加熱処理をしたときのガラスの熱収縮率は、26.5
ppmであった。 比較例1 洗浄され乾燥されたソーダライムシリカ組成の厚みが
1.1mmのフロートガラス板を珪弗素酸水溶液に漬
け、35℃でSiO2膜を35nm被覆した。このガラ
スのSiO2膜上に、実施例で用いたのと同じ装置で、
第1被覆室でのSiO2膜の被覆を行わなかったことお
よびヒータ11による加熱を行わなかったこと以外は、
実施例と同じようにしてITO膜を被覆した。
The visible light transmittance of the obtained transparent conductive glass was 90%, and the sheet resistance of the ITO film was 8 ohm / square. After the ITO film of this glass was removed by etching with an acid, it was immersed in boiling pure water at 100 ° C. for 24 hours, the amount of alkali in this pure water was quantified, and the alkali elution prevention performance was measured. Was / cm 2 . The heat shrinkage rate of the transparent conductive glass when it was heat-treated in the atmosphere at 480 ° C. for 30 minutes was 26.5.
It was ppm. Comparative Example 1 A washed and dried float glass plate having a soda-lime-silica composition having a thickness of 1.1 mm was immersed in an aqueous solution of silicofluoric acid, and a SiO 2 film was coated to a thickness of 35 nm at 35 ° C. On the SiO 2 film of this glass, with the same device used in the example,
Except that the SiO 2 film was not coated in the first coating chamber and that the heater 11 was not used for heating,
The ITO film was coated in the same manner as in the example.

【0018】得られた透明電導ガラスの可視光線透過率
は90%、ITO膜の面積抵抗は8オーム/平方であっ
た。このガラスのITO膜を酸でエッチング除去した
後、100℃の沸騰した純水中に24時間漬け、この純
水中のアルカリ量を定量して、アルカリ溶出防止性能を
測定したところ、0.05μg/cm2とアルカリ溶出
防止性能は実施例の1/5に低下していた。また、この
透明電導ガラスを480℃、30分の大気中での加熱処
理をしたときのガラスの熱収縮率は、48.3ppmで
あった。 比較例2 加熱室3のヒータ11に電力を投入しなかったこと以外
は実施例と全く同様にして透明電導ガラスを製作した。
The transparent conductive glass obtained had a visible light transmittance of 90%, and the ITO film had a sheet resistance of 8 ohms / square. After the ITO film of this glass was removed by etching with an acid, it was immersed in boiling pure water at 100 ° C. for 24 hours, the amount of alkali in this pure water was quantified, and the alkali elution prevention performance was measured. / Cm 2 and the alkali elution prevention performance were reduced to 1/5 of those of the examples. The heat shrinkage rate of the transparent conductive glass was 48.3 ppm when heat-treated at 480 ° C. for 30 minutes in the atmosphere. Comparative Example 2 A transparent conductive glass was manufactured in exactly the same manner as in Example except that the heater 11 in the heating chamber 3 was not powered.

【0019】得られた透明電導ガラスの可視光線透過率
は90%、透明電導膜の面積抵抗は8オーム/平方であ
った。このガラスのITO膜を酸でエッチング除去した
後、100℃の沸騰した純水中に24時間漬け、この純
水中のアルカリ量を定量して、アルカリ溶出防止性能を
測定したところ、0.05〜1μg/cm2とアルカリ
溶出防止性能は実施例の1/5〜1/10に低下してい
た。また、この透明電導ガラスを480℃、30分の大
気中での加熱処理をしたときのガラスの熱収縮率は、4
2.6ppmであった。
The visible light transmittance of the obtained transparent conductive glass was 90%, and the sheet resistance of the transparent conductive film was 8 ohm / square. After the ITO film of this glass was removed by etching with an acid, it was immersed in boiling pure water at 100 ° C. for 24 hours and the amount of alkali in this pure water was quantified to measure the alkali elution prevention performance. As a result, the alkali elution prevention performance was about 1 μg / cm 2, which was 1/5 to 1/10 that of the examples. The heat shrinkage rate of the transparent conductive glass when it is heat-treated in the atmosphere at 480 ° C. for 30 minutes is 4
It was 2.6 ppm.

【0020】上記のように、実施例で得られた透明電導
ガラスは、比較例で得られたものよりも、1/5〜1/
10の低いアルカリ溶出量であることが分かる。さら
に、実施例で得られた透明電導ガラスは、液晶表示素子
製作工程(液晶セル組立工程)で受けるのとほぼ同じ熱
処理条件である480℃、30分の大気中での熱処理を
行っても、熱収縮率が30ppm以下に抑えられ、比較
例で得られた透明電導ガラスよりも熱収縮が大巾に減少
していることが分かる。
As described above, the transparent conductive glass obtained in the examples is 1/5 to 1 / th of that obtained in the comparative examples.
It can be seen that the alkali elution amount is as low as 10. Furthermore, even if the transparent conductive glass obtained in the example is subjected to heat treatment in the atmosphere for 30 minutes at 480 ° C., which is almost the same heat treatment condition as received in the liquid crystal display element manufacturing process (liquid crystal cell assembling process), It can be seen that the heat shrinkage was suppressed to 30 ppm or less, and the heat shrinkage was greatly reduced as compared with the transparent conductive glass obtained in Comparative Example.

【0021】[0021]

【発明の効果】本発明によると、優れたアルカリ溶出防
止性能を有するアンダーコートと低抵抗の透明電導膜と
を単一設備で連続してガラス板上に被覆することができ
るので、液晶表示素子用の透明電導ガラスを、高歩留ま
りで能率よく製造することができる。また、被覆したア
ルカリ溶出防止膜の緻密化とガラス板の熱収縮処理を同
時に行うことができるので、液晶表示素子製作工程中の
加熱処理におけるガラスの熱収縮量が低減され、透明電
極のパターンずれが生じない透明電導ガラスを単一の設
備で効率よく製造することができる。
According to the present invention, a glass plate can be continuously coated with an undercoat having an excellent alkali elution preventing property and a low resistance transparent conductive film, so that a liquid crystal display device can be obtained. It is possible to efficiently manufacture the transparent conductive glass for use with high yield. Further, since the densification of the coated alkali elution preventing film and the heat shrinkage treatment of the glass plate can be performed at the same time, the heat shrinkage amount of the glass in the heat treatment during the liquid crystal display element manufacturing process is reduced, and the pattern shift of the transparent electrode is reduced. It is possible to efficiently manufacture a transparent conductive glass that does not cause a phenomenon with a single facility.

【図面の簡単な説明】[Brief description of drawings]

【図1】本発明の実施に用いたインライン型スパッタリ
ング装置の側面断面図である。
FIG. 1 is a side sectional view of an in-line type sputtering apparatus used for carrying out the present invention.

【図2】図1のAA断面図である。FIG. 2 is a sectional view taken along the line AA in FIG.

【図3】従来の技術を説明するための製造フローチャー
トである。
FIG. 3 is a manufacturing flowchart for explaining a conventional technique.

【符号の説明】 1・・・真空予備室、2・・・第1の被覆室、3・・・
加熱室、4・・・第2の被覆室、5・・・バッフア室、
6・・・取り出し室、7、8・・・カソード、9、1
0、11、11A、12・・・ヒータ、13・・・キャ
リア、14・・・ゲートバルブ、15・・・インライン
型スパッタリング装置
[Explanation of Codes] 1 ... vacuum reserve chamber, 2 ... first coating chamber, 3 ...
Heating chamber, 4 ... second coating chamber, 5 ... buffer chamber,
6 ... take-out chamber, 7, 8 ... cathode, 9, 1
0, 11, 11A, 12 ... Heater, 13 ... Carrier, 14 ... Gate valve, 15 ... In-line type sputtering device

Claims (5)

【特許請求の範囲】[Claims] 【請求項1】減圧した雰囲気が調節可能な第1の被覆室
と前記第1の被覆室とは開閉可能なゲートバルブで接続
され減圧した雰囲気が調節可能な加熱室と前記加熱室と
は開閉可能なゲートバルブで接続され減圧した雰囲気が
調節可能な第2の被覆室とを少なくとも有するインライ
ン型スパッタリング装置を用いて、ガラス基板上にアル
カリ溶出防止膜および透明電導膜が順次被覆された透明
電導ガラスを製造する方法であって、 a)前記第1の被覆室では、前記ガラス基板の温度を2
00℃以下とした状態で透明金属酸化物または透明金属
窒化物からなるアルカリ溶出防止膜をスパッタリングに
より被覆すること、 b)前記加熱室では、被覆された前記アルカリ溶出防止
膜を300℃以上に加熱することにより緻密化するこ
と、 c)前記第2の被覆室では、前記アルカリ溶出防止膜が
被覆されたガラス基板を300℃以上に加熱した状態で
透明電導膜を被覆すること、 を連続して行う液晶表示素子用透明電導ガラスの製造方
法。
1. A first coating chamber in which the reduced pressure atmosphere can be adjusted and the first coating chamber are connected by a gate valve that can be opened and closed, and a heating chamber in which the reduced pressure atmosphere can be adjusted and the heating chamber are opened and closed. A transparent conductive film in which an alkali elution-preventing film and a transparent conductive film are sequentially coated on a glass substrate by using an in-line type sputtering device which has at least a second coating chamber which is connected by a gate valve and is capable of adjusting a depressurized atmosphere. A method for producing glass, comprising: a) setting the temperature of the glass substrate to 2 in the first coating chamber.
Covering the alkali elution preventive film composed of a transparent metal oxide or a transparent metal nitride by sputtering at a temperature of 00 ° C or lower, b) heating the coated alkali elution preventive film to 300 ° C or higher in the heating chamber. To densify, c) coating the transparent conductive film in the second coating chamber in a state where the glass substrate coated with the alkali elution preventing film is heated to 300 ° C. or higher. A method for producing a transparent conductive glass for a liquid crystal display device.
【請求項2】前記加熱室での前記ガラス板の加熱を38
0℃以上とすることにより、前記アルカリ溶出防止膜の
緻密化と前記ガラス基板の熱収縮とを同時に行うことを
特徴とする請求項1に記載の方法。
2. Heating the glass plate in the heating chamber
The method according to claim 1, wherein the alkali elution preventing film is densified and the glass substrate is thermally contracted at the same time by setting the temperature to 0 ° C. or higher.
【請求項3】前記アルカリ溶出防止膜を、10〜200
nmの厚みの二酸化珪素としたことを特徴とする請求項
1または2に記載の方法。
3. The alkali elution preventive film comprises 10 to 200
3. The method according to claim 1 or 2, characterized in that it is silicon dioxide with a thickness of nm.
【請求項4】前記ガラス基板をソーダライムシリカ組成
のガラス板とし、その熱収縮率を50ppm以上とする
ことを特徴とする請求項2または3に記載の方法。
4. The method according to claim 2, wherein the glass substrate is a glass plate having a soda lime silica composition, and the heat shrinkage rate is 50 ppm or more.
【請求項5】前記透明電導膜が錫をドープした酸化イン
ジウム膜であることを特徴とする請求項1乃至4に記載
の方法。
5. The method according to claim 1, wherein the transparent conductive film is a tin-doped indium oxide film.
JP11443592A 1992-05-07 1992-05-07 Method for producing transparent conductive glass for liquid crystal display element Expired - Lifetime JP3232646B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP11443592A JP3232646B2 (en) 1992-05-07 1992-05-07 Method for producing transparent conductive glass for liquid crystal display element

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP11443592A JP3232646B2 (en) 1992-05-07 1992-05-07 Method for producing transparent conductive glass for liquid crystal display element

Publications (2)

Publication Number Publication Date
JPH05313111A true JPH05313111A (en) 1993-11-26
JP3232646B2 JP3232646B2 (en) 2001-11-26

Family

ID=14637658

Family Applications (1)

Application Number Title Priority Date Filing Date
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Country Link
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2364068A (en) * 1998-12-21 2002-01-16 Cardinal Ig Co Glass with water-sheeting coating of silica
KR100707960B1 (en) * 2005-03-31 2007-04-16 (주)플라웍스 An Inline sputter apparatus for manufacturing a multi-layered ITO for transparent electrode
JP2012522137A (en) * 2009-03-31 2012-09-20 エスエヌユー プレシジョン カンパニー リミテッド Thin film deposition apparatus, thin film deposition method and thin film deposition system
US8281618B2 (en) 2005-12-16 2012-10-09 Nippon Electric Glass Co., Ltd. Alkali-free glass substrate and process for producing the same
JP2013533922A (en) * 2010-06-10 2013-08-29 エスエヌユー プレシジョン カンパニー リミテッド Thin film deposition apparatus and thin film deposition system
JP2015187749A (en) * 2009-03-31 2015-10-29 ビュー, インコーポレイテッド Film formation system and methods for manufacturing electrochromic layer and inorganic electrochromic device
US9454053B2 (en) 2011-12-12 2016-09-27 View, Inc. Thin-film devices and fabrication
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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2364068B (en) * 1998-12-21 2003-01-29 Cardinal Ig Co Soil-resistant coating for glass surfaces
GB2364068A (en) * 1998-12-21 2002-01-16 Cardinal Ig Co Glass with water-sheeting coating of silica
KR100707960B1 (en) * 2005-03-31 2007-04-16 (주)플라웍스 An Inline sputter apparatus for manufacturing a multi-layered ITO for transparent electrode
US8281618B2 (en) 2005-12-16 2012-10-09 Nippon Electric Glass Co., Ltd. Alkali-free glass substrate and process for producing the same
JP2015187749A (en) * 2009-03-31 2015-10-29 ビュー, インコーポレイテッド Film formation system and methods for manufacturing electrochromic layer and inorganic electrochromic device
JP2012522137A (en) * 2009-03-31 2012-09-20 エスエヌユー プレシジョン カンパニー リミテッド Thin film deposition apparatus, thin film deposition method and thin film deposition system
US9429809B2 (en) 2009-03-31 2016-08-30 View, Inc. Fabrication of low defectivity electrochromic devices
US9477129B2 (en) 2009-03-31 2016-10-25 View, Inc. Fabrication of low defectivity electrochromic devices
US9664974B2 (en) 2009-03-31 2017-05-30 View, Inc. Fabrication of low defectivity electrochromic devices
JP2017138628A (en) * 2009-03-31 2017-08-10 ビュー, インコーポレイテッド Method for manufacturing electrochromic element
US9904138B2 (en) 2009-03-31 2018-02-27 View, Inc. Fabrication of low defectivity electrochromic devices
US11947232B2 (en) 2009-03-31 2024-04-02 View, Inc. Fabrication of low defectivity electrochromic devices
JP2013533922A (en) * 2010-06-10 2013-08-29 エスエヌユー プレシジョン カンパニー リミテッド Thin film deposition apparatus and thin film deposition system
US9454053B2 (en) 2011-12-12 2016-09-27 View, Inc. Thin-film devices and fabrication
US10310150B2 (en) 2015-01-14 2019-06-04 AGC Inc. Near-infrared cut filter and solid-state imaging device

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