JPH02217339A - 透明導電ガラス - Google Patents

透明導電ガラス

Info

Publication number
JPH02217339A
JPH02217339A JP1284846A JP28484689A JPH02217339A JP H02217339 A JPH02217339 A JP H02217339A JP 1284846 A JP1284846 A JP 1284846A JP 28484689 A JP28484689 A JP 28484689A JP H02217339 A JPH02217339 A JP H02217339A
Authority
JP
Japan
Prior art keywords
film
transparent conductive
glass
protective film
nitride
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
Application number
JP1284846A
Other languages
English (en)
Inventor
Hiroyasu Kojima
啓安 小島
Koichi Suzuki
巧一 鈴木
Masashi Tada
昌史 多田
Naoki Hashimoto
直樹 橋本
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.)
AGC Inc
Original Assignee
Asahi 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
Priority claimed from JP63076202A external-priority patent/JPH0682163B2/ja
Priority claimed from JP63144827A external-priority patent/JPH0626877B2/ja
Priority to AU30879/89A priority Critical patent/AU616736B2/en
Priority to CA000592521A priority patent/CA1338431C/en
Priority to KR1019890002663A priority patent/KR960000031B1/ko
Priority to DE89103796T priority patent/DE68906923T2/de
Priority to US07/318,330 priority patent/US5110637A/en
Priority to ES198989103796T priority patent/ES2041856T3/es
Priority to DE68928474T priority patent/DE68928474T2/de
Priority to EP89103796A priority patent/EP0331201B1/en
Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Priority to JP1284846A priority patent/JPH02217339A/ja
Publication of JPH02217339A publication Critical patent/JPH02217339A/ja
Pending legal-status Critical Current

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    • C03GLASS; MINERAL OR SLAG WOOL
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    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3411Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
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    • C03C3/00Glass compositions
    • C03C3/12Silica-free oxide glass compositions
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    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
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    • C03C2218/00Methods for coating glass
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Abstract

(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。

Description

【発明の詳細な説明】 [産業上の利用分野] 本発明は、透明導電ガラスに関するもので。
特に耐久性に優れた透明導電ガラスに関するものである
[従来の技術] ガラスなどの透明基体上に導電性の膜を形成したものは
、液晶表示素子の基板、冷凍ショーケースの防曇ガラス
、CRTのフェースプレートなどの帯電防止ガラス(ホ
コリが付きにく(するため)、タッチパネルガラスなど
に用いられている、その他、最近では電磁シールドガラ
スとしての用途も出てきた。これらにはITO(錫を含
んだ酸化インジウム)、導電性Snowなどが通常使わ
れている。ITOは通常真空蒸着法又はスパッタリング
法で、Snugはスプレー法などで成膜される。
[発明の解決しようとする課題] ITOは、比抵抗的には最も優れた材料の一つであるが
、一般的に酸に対して溶解し、これがパターニングのと
きには利点となるが、耐久性的には劣る。一方、抵抗値
的に有利なメタル膜はその性質上、可視光線の吸収が強
(、高い透過率を得るためにはかなり薄い膜にしなけれ
ばならない、このような膜は、経時的に安定でな(酸化
により抵抗値が上昇したり、光学的特性が変化してしま
う。更に一般に酸に対しての耐久性も充分でない。
酸化錫にフッ素、アンチモンなどをドープした導電性酸
化錫は、一般にスプレー法などで成膜される。この膜は
耐久性的には前述のものより優れているが、スプレー法
は原料の熱分解のために通常400℃以上の基体加熱を
必要とし、また膜厚分布の均一性や低抵抗化が難しいと
いう問題点がある。
[課題を解決するための手段] 本発明は、前述の問題点を解決すべ(なされたものであ
り、ガラス基板上に、透明導電膜、その上に保護膜を順
次積層した透明導電ガラスであって、該保護膜がCrと
Bとを含む窒化膜であることを特徴とする透明導電ガラ
スを提供するものである。
第1図は、本発明の実施例を示す1例の断面図である。
 11はガラス基板、13はITOlSnug。
ZnOなどからなる透明導電膜、15はCrとBを含む
窒化膜からなる保護膜である。
ガラス基板11としては、フロー・トガラス、熱線吸収
ガラス等が用いられ、特に限定されない。又、合せガラ
ス、強化ガラス等も使用できる。
保護膜15は透明導電膜13を保護するものであり、緻
密で、硬(、かつ耐久性の高いものが要求されるが、C
rとBとを含む窒化膜(crsxNy)が、極めて硬く
ご緻密で、耐久性も高いので、本発明における保護膜1
5として好適である。
CrとBを含む窒化膜は、窒化クロムの格子中にホウ素
が入り込んで密度が高く緻密な構造になっており、この
ため、耐擦傷性や、耐酸性等の化学的耐久性も高くなっ
ていると考えられる。又、窒化物は、可視光線の一部を
吸収するため、膜厚や窒素含有量を調整することにより
、透明導電ガラス全体の可視光線透過率を制御できる。
これは、例えば、窒素の存在下に、ボロン合金を反応性
スパッタリングあるいはイオンブレーティングし、窒化
膜とすることによって形成することができる。又、蒸着
法、イオンブレーティングの場合は、蒸発源として混合
窒化物をベレット化したものなどを用いれば良い、ボロ
ン(B)合金におけるCrとBとの比は特に制限はない
が、Cr:Bが原子比で50:50以下、特に70:3
0以下のす11合でBが含まれていることが好ましい。
これ以上Bの割合が多いと、窒化クロムの格子がひずん
でかえって不安定となり、耐酸性や耐擦傷性が低下する
。又、下限としては、95:5以上、特に90:10以
以下が含有されるのが好ましい。これ以下だと窒化クロ
ムに対する優位性、Bの耐久性に対する効果が認められ
なくなる。
保護膜15の膜厚としてはあまり薄いと十分な化学的耐
久性、硬度、耐擦傷性等が得られに(くなり、保護膜と
しての性能が十分でなくなるので、少なくとも30Å以
上、好ましくは100Å以上、特に150Å以上が良い
、厚い方は特に制限はないが、あまり厚すぎると膜剥離
も生じやすくなるため、400Å以下が好ましい。保護
膜の屈折率、及びこの干渉による外観変化、可視光線透
過率、生産性等を考慮して決めれば良い。
ITOをはじめとして透明導電膜は比較的耐薬品性に乏
しく、n出した状態で使用する場合には、耐アルカリ性
に比べて特に耐酸性に問題が生じやすいが、上記保護膜
は実用上十分な耐薬品性を付与することができる。又、
上記保護膜は、赤外域の光を反射し、熱線反射膜として
の役割を果たすことも出来る。
透明導電膜13は酸化錫を含んだ酸化インジウム(IT
O)、フッ素、アンチモンなどをドープした酸化錫、ア
ルミニウムやフッ素をドープした酸化亜鉛、CdgSn
04など透明で導電性があるものであれば構わない。膜
厚は用途に応じて、また用いる導電膜の比抵抗を考慮し
て選べば良い。
たとえば帯電防止には数十にΩ/口から数百にΩ/口程
度のシート抵抗の膜を、電磁波シールドには数Ω/口程
度のシート抵抗の膜を用いる。膜厚が厚ければ表面抵抗
が小さくなり帯電防止や電磁波シールド性能は向上する
が、あまり厚すぎると膜はがれや膜の着色が起こってし
まう恐れがあるので、20000Å以下が好ましい、透
明導電膜の形成法も特に限定はな(真空蒸着法、イオン
ブレーティング法、スパッタリング法、CVD法いずれ
でも良いことはいうまでもないことである。透明導電膜
と基体との密着力は、特に透明導電膜の膜厚が厚い場合
は問題になるが、このときは透明導電膜13と基体1と
の間に接着力向上のためにクロム等の薄膜を下地膜とし
て形成するのは好ましい、また、透明導電膜13と保護
膜15との間に接着性向上のための薄膜を介在させても
よい。
第2図は、本発明の他の構成例を示す断面図であり、基
板11上に、下地膜17、透明導電膜13および保護膜
15が順次積層されている。
下地膜17は、ガラス基板11との密着性を高めるため
に用いられるものであるが、吸収膜を用いて透過率を制
御したり、干渉効果を利用して色調を調整したり、ある
いは熱線反射特性を持たすこともできる。
下地膜17としては、Cr、Ti、Zr、Ta、Snの
うち少なくとも1種からなる金属膜;その酸化膜又はそ
の窒化膜; Cr、Ti、Zr、Ta、Snのうち少な
くとも1種とBとの合金膜; Cr、 Ti、 Zr、
 Ta、 Snのうち少なくとも1種とBを含む酸化膜
; Cr、Ti、Zr、Ta。
Snのうち少なくとも1種とBを含む窒化膜等が好適な
例として挙げられる。
かかる下地膜17の膜厚としては、透過率を制御する目
的で、金属膜、合金膜、窒化膜を用いる場合には10〜
300人程度が好適である。干渉を利用して色調を調整
する目的で、酸化膜を用いる場合には、該下地膜の上に
形成される透明導電膜や保護膜の屈折率や膜厚にも依る
が、20〜10000人程度が好適でああ。
各層の膜厚を制御することにより、種々の特性を調整す
ることができる。例えば、可視光透過率40%、ITO
膜表面抵抗4Ω/口の場合を例にとると、下地膜17と
して20人±5%のCr層を形成し、透明導電膜として
8000人±5%の110層を形成し、保護膜として2
00人±5%のCr B N x層を形成すればよい、
このように、実測した屈折率を元に各層の膜厚を選定す
ることにより、可視光の透過率、ガラス側(膜形゛成面
の反対側)の反射特性などを自由に変えることができる
さらに、第1図および第2図には、透明導電膜13が単
層の場合を示したが、透明導電膜を他の膜と交互に積層
して、光の干渉効果を利用して光学的特性、色調等を調
整してデザイン性を持たせることも可能である。第4図
には透明導電膜13を3層、他の膜19を2層形成した
例の断面図が示されている。他の膜19としては、特に
限定されるものでは′なく、TiOx、 Zr0t、 
5i02゜Snug等の誘電体膜、金属膜等を使用でき
る。膜の屈折率等の光学特性により、適宜の材料を選択
すれば良い。又、下地膜17や保護膜15と同様の膜を
用いることもできる。例えばガラス/Cr/ ITO/
 Cr層 ITO/ CrBxNyのようにすることも
できる。又、第4図には、下地膜17の上に、透明導電
膜13と他の膜19を交互に積層した構成を示したが、
下地膜を介さずに、透明導電膜13と他の膜19を積層
し、最外層に保護膜I5を形成して、本発明の透明導電
ガラスを構成することもできる。例えば、ガラス/ I
TO/ Cr層 ITO/CrBxNyのようにするこ
ともできる。
膜19の膜厚については、所望の光学的特性に合わせて
適宜選択すればよい。
このように、透明導電膜と他の膜を交互に積層する場合
には、複数の透明導電膜の合計膜厚による抵抗値が目的
に合うようにすればよい。
以上のように、透明導電膜と他の膜を交互に積層する場
合、空気側最外層には保護膜15を形成する。
以上、本発明の透明導電ガラスを説明したが、保護膜1
5、透明導電膜13、下地膜17、他の膜19の成膜方
法としては、真空蒸着法、DC。
RFスパッタ法、イオンブレーティング法等のいずれも
が採用できるが、特に、スパッタ法は組成変動が少なく
、又、大面積にわたり均一な膜を形成できるので、透明
導電膜13、保護膜15、下地膜17、膜19等の成膜
法として好ましい。
[効 果1 本発明によれば、ガラス基板上に形成したITO等の導
電膜の上に、保護膜としてCrB、N、膜を形成するこ
とにより、酸、アルカリ、水、紫外線に対して安定な耐
候性に優れた透明導電ガラスができるのみでな(、耐擦
傷性等の物理的耐久性にも優れている。よって、液晶表
示素子やCRT等のデイスプレーのパネルや冷凍ショー
ケース用防曇ガラス、帯電防止ガラス、電磁シールドガ
ラス等の用途に好適な透明導電ガラスを提供できる。
又、B、Nの含有量を変え、屈折率や吸収率等が調節で
きるので光学設計をして外観的にもある程度の希望の透
過率、反射率、色調を得ることが可能である。このこと
は複写機の天板ガラスの帯電防止などでは透過率アップ
のため重要である。また液晶表示素子などの電極パター
ン見え防止にも応用できる。この時同時に異物などによ
る上下電極間の短絡防止(・クロストーク防止)も達成
できる。
又、透明導電膜の電磁波遮蔽能を利用した場合には、単
板での電磁遮蔽ガラスを実現できる。この単板電磁遮蔽
ガラスは、従来の金属メツシュを挟み込んだ複層ガラス
と比較して非常に低価格であり、目障りな埋め込み物も
ない。
施工に際しても、サツシまわりの間隔を太き(変更する
ことなしに取付けが可能となる。又、保護膜や下地膜に
熱線反射機能をもたせて多機能化を実現でき、実用上極
めて有利である。さらに、保護膜や下地膜に光の干渉効
果をもたせたり、透明導電膜と他の膜を交互に積層した
りして、デザイン性を付与することもできる。
又、金属膜、窒化膜等の光吸収性の下地膜を形成した場
合には、膜厚をコントロールすることにより、可視光透
過率を目的に応じて任意に変化させることができる。こ
の電磁波遮蔽ガラスは、建築用のみでな(、自動車用、
航空機用などに対しても応用できる。
[実施例] 洗浄乾燥したフロートガラス板を、スパッタターゲット
と蒸着源が並設されたチャンバーに入れて高真空とした
のち、Arガスを導入して2x 10−”Torrとし
、ターゲット電圧0.5KV −’C−D Cスパッタ
を行ない、下地層として20人のCr層を形成した。次
に基板を蒸着チャンバーに移し、0□ガスを導入して7
 X 10−’Torrとし、ルツボ内のITO膜ペレ
ットを蒸発させ、透明導電膜として8000人のITO
膜を形成した。なお、このITO膜の表面抵抗は4Ω/
口であった。
次に、更にスパッタチャンバーに移し、CrBの合金タ
ーゲット[Cr: B =9 : 1 (原子比)]を
用いて、N、とArの混合ガス(N2 : Ar= 7
0 :30)で2 X 10−”Torrに雰囲気を調
整し、ターゲット電圧2XVの条件でDCスパッタし、
保護膜として 200人のCrBxNy層(x =0.
2.y =  0.5)を形成して、透明導電ガラス(
サンプルA)を得た。
この透明導電ガラスの分光特性を第3図に示す。
次に比較例として、サンプルAと同様にして、下地膜、
透明導電膜を形成した後、SnO2膜(200人)を形
成し、サンプルBとした。
次に、比較例として、サンプルAと同様にして、下地膜
、透明導電膜を形成した後、TiO□膜(200人)を
形成し、サンプルCとした。
又、サンプルAと同様にして下地膜、透明導電膜を形成
しただけのものをサンプルDとした。
これらサンプルA’−Dについて、以下の通り耐酸テス
トを行ない、その結果を表−1に示す。
サンプルB、C,Dに比べ、本発明の実施例のサンプル
Aでは非常に耐薬品性が向上していることが判かる。
耐酸テスト l規定塩酸中に、25℃で、各供試保護膜付き透明導電
ガラスを入れ、経過時間毎に膜の状態を観察し、以下の
基準で耐酸性を評価した。
O:変化なし ×:膜の表面が荒れる (以下余白) 表−1=耐酸テスト結果 別に、サンプルANDについて耐アルカリ性試験(1規
定水酸化ナトリウムの常温溶液に6時間浸漬)を行なっ
たが、外観変化はほとんど認められなかった。
又、別にサンプルA−Dについて耐湿性試験(50℃×
98%RH雰囲気に7日放置)を行なったが、どれも外
観変化は認められなかった。
また、砂けしゴムでコート面をひっかいても傷はつきに
くく、優れた耐久性を示した。
また、実施例の透明導電ガラス(サンプルA)は、周波
数I Gl(zの電磁波に関して試験したところ、シー
ルド性能は約35dB程度で、良好な電磁波遮蔽性能を
示した。
【図面の簡単な説明】
第1図、第2図、および第4図は本発明の構成例の層構
成を示す断面図である。 第3図は、実施例の分光特性を示すグラフである。 11・・・ガラス基板   13・・・透明導電膜15
・・・保護膜  17・・・下地膜  19・・・他の
膜第1図 第2因 波 優−1nml−一−

Claims (4)

    【特許請求の範囲】
  1. (1)ガラス基板上に、透明導電膜、その上に保護膜を
    順次積層した透明導電ガラスであつ て、該保護膜がCrとBとを含む窒化膜であることを特
    徴とする透明導電ガラス。
  2. (2)ガラス基板上に、下地膜として、Cr、Ti、Z
    r、Ta、Snのうち少なくとも1種からなる金属膜、
    又はその酸化膜又はその窒化膜、あるいは、Cr、Ti
    、Zr、Ta、Snのうち少なくとも1種とBとの合金
    膜、又は上記金属のうち少なくとも1種とBを含む酸化
    膜、又は、上記金属のうち少なくとも1種とBを含む窒
    化膜を形成し、該下地膜上に透明導電膜を形成し、その
    上に、CrとBとを含む窒化膜を保護膜として形成した
    ことを特徴とする透明導電ガラス。
  3. (3)透明導電膜を、透明導電膜と、金属あるいは誘電
    体からなる他の膜を交互に積層した複数層により形成し
    たことを特徴とする請求項1又は2記載の透明導電ガラ
    ス。
  4. (4)透明導電膜が、錫を含む酸化インジウム、フッ素
    又はアルミニウムを含む酸化錫、あるいは、フッ素又は
    アルミニウムを含む酸化亜鉛のうち1種を主成分とする
    膜であることを特徴とする請求項1〜3いずれか1項記
    載の透明導電ガラス。
JP1284846A 1988-03-03 1989-11-02 透明導電ガラス Pending JPH02217339A (ja)

Priority Applications (9)

Application Number Priority Date Filing Date Title
AU30879/89A AU616736B2 (en) 1988-03-03 1989-03-01 Amorphous oxide film and article having such film thereon
CA000592521A CA1338431C (en) 1988-03-03 1989-03-02 Amorphous oxide film and article having such film thereon
EP89103796A EP0331201B1 (en) 1988-03-03 1989-03-03 Amorphous oxide film and article having such film thereon
DE68928474T DE68928474T2 (de) 1988-03-03 1989-03-03 Amorpher Oxid-Film und Gegenstand mit einem solchen Film
DE89103796T DE68906923T2 (de) 1988-03-03 1989-03-03 Amorpher Oxid-Film und Gegenstand mit einem solchen Film.
KR1019890002663A KR960000031B1 (ko) 1988-03-03 1989-03-03 비정질 산화물 필름 및 표면상에 그러한 필름을 갖는 제품
US07/318,330 US5110637A (en) 1988-03-03 1989-03-03 Amorphous oxide film and article having such film thereon
ES198989103796T ES2041856T3 (es) 1988-03-03 1989-03-03 Pelicula amorfa de oxido y articulo que tiene dicha pelicula en su superficie.
JP1284846A JPH02217339A (ja) 1988-03-03 1989-11-02 透明導電ガラス

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
JP4876588 1988-03-03
JP63076202A JPH0682163B2 (ja) 1988-03-03 1988-03-31 耐久性の優れた光学体
JP63144827A JPH0626877B2 (ja) 1988-06-14 1988-06-14 熱線遮断ガラス
JP26416388 1988-10-21
JP27730588 1988-11-04
JP63-277305 1988-11-04
JP1284846A JPH02217339A (ja) 1988-03-03 1989-11-02 透明導電ガラス

Publications (1)

Publication Number Publication Date
JPH02217339A true JPH02217339A (ja) 1990-08-30

Family

ID=39683722

Family Applications (1)

Application Number Title Priority Date Filing Date
JP1284846A Pending JPH02217339A (ja) 1988-03-03 1989-11-02 透明導電ガラス

Country Status (8)

Country Link
US (1) US5110637A (ja)
EP (1) EP0331201B1 (ja)
JP (1) JPH02217339A (ja)
KR (1) KR960000031B1 (ja)
AU (1) AU616736B2 (ja)
CA (1) CA1338431C (ja)
DE (2) DE68906923T2 (ja)
ES (1) ES2041856T3 (ja)

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Also Published As

Publication number Publication date
EP0331201B1 (en) 1993-06-09
KR960000031B1 (ko) 1996-01-03
US5110637A (en) 1992-05-05
DE68906923D1 (de) 1993-07-15
EP0331201A1 (en) 1989-09-06
DE68928474T2 (de) 1998-04-02
AU3087989A (en) 1989-09-07
DE68906923T2 (de) 1994-02-03
AU616736B2 (en) 1991-11-07
KR890014397A (ko) 1989-10-23
DE68928474D1 (de) 1998-01-15
CA1338431C (en) 1996-07-02
ES2041856T3 (es) 1993-12-01

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