JP4682473B2 - Substrate with tin oxynitride film and method for producing the same - Google Patents
Substrate with tin oxynitride film and method for producing the same Download PDFInfo
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- JP4682473B2 JP4682473B2 JP2001219477A JP2001219477A JP4682473B2 JP 4682473 B2 JP4682473 B2 JP 4682473B2 JP 2001219477 A JP2001219477 A JP 2001219477A JP 2001219477 A JP2001219477 A JP 2001219477A JP 4682473 B2 JP4682473 B2 JP 4682473B2
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/245—Oxides by deposition from the vapour phase
- C03C17/2453—Coating containing SnO2
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/225—Nitrides
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/28—Other inorganic materials
- C03C2217/281—Nitrides
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
- Surface Treatment Of Glass (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、酸窒化スズ膜付き基体に関し、詳しくは、熱線反射性、電波透過性および耐熱性に優れる酸窒化スズ膜付き基体に関する。また、本発明は、熱線反射性、電波透過性および耐擦傷性に優れる酸窒化スズ膜付き基体に関する。
【０００２】
【従来の技術】
以前より、酸窒化スズ膜は、熱線反射性、電波透過性等に優れる透明膜として知られている。酸窒化スズ膜は、ガラス等の基板上に設けられ、熱線反射ガラス、透明電極用基板等の種々の用途に用いられてきた。
【０００３】
【発明が解決しようとする課題】
本発明者は、そのような酸窒化スズ膜について鋭意研究した結果、特定の酸窒化スズ膜は、高温で熱処理した場合にも体積変化が極めて小さいことを見出した。
酸窒化スズ膜を有する基体を高温で熱処理した場合に、酸窒化スズ膜が収縮すると、膜面を内側とする反りが基体に生じ、一方、酸窒化スズ膜が膨張すると、膜面を外側とする反りが基体に生じる。そして、その収縮や膨張が大きいときには、酸窒化スズ膜にクラックが生じるという問題がある。
即ち、本発明者は、特定の酸窒化スズ膜が高温で熱処理した場合にも体積変化が極めて小さいことを見出し、この酸窒化スズ膜を有する基体は、熱処理により反りがほとんど生じず、かつ、酸窒化スズ膜にクラックが生じることもないことを見出し、本発明を完成した。
【０００４】
また、従来の酸窒化スズ膜は耐擦傷性に優れたものとはいえず、したがって各用途に用いるときには、酸窒化スズ膜の上に更に他の層を積層するなどして、耐擦傷性を向上させる必要があった。
【０００５】
したがって、本発明は、熱線反射性、電波透過性等に優れ、更に、耐熱性に優れる酸窒化スズ膜付き基体を提供することを目的とする。
【０００６】
【課題を解決するための手段】
本発明は、透明基体と、該透明基体の一方の側に積層してなる酸窒化スズ膜とを有する酸窒化スズ膜付き基体であって、
該酸窒化スズ膜が、Ｓｎ、ＯおよびＮの合計に対して、Ｎを２．５〜１５ａｔ％含有することを特徴とする酸窒化スズ膜付き基体を提供する。
【０００７】
また、本発明は、透明基体と、該透明基体の一方の側に積層してなる酸窒化スズ膜とを有する酸窒化スズ膜付き基体を反応性スパッタリング法により製造する方法であって、
該反応性スパッタリング法が、酸素ガスと窒素原子を含むガスとを含有する混合ガスを用い、該窒素原子を含むガスの分圧を０．２〜０．４Ｐａとし、該酸素ガスの分圧の該窒素原子を含むガスの分圧に対する比を０．２〜１として行うことを特徴とする酸窒化スズ膜付き基体の製造方法を提供する。
【０００８】
更に、本発明は、透明基体と、該透明基体の一方の側に積層してなる酸窒化スズ膜とを有する酸窒化スズ膜付き基体であって、
該透明基体が厚さ２ｍｍのソーダライムガラスであり、かつ、
１００ｍｍ×１００ｍｍの正方形の試験片を用いて、基体温度６５０℃、７分間の条件で熱処理した後における、正方形の対角線の交点での凹み量の絶対値が、酸窒化スズ膜の厚さ１００ｎｍあたり１．０ｍｍ以下であることを特徴とする酸窒化スズ膜付き基体を提供する。
【０００９】
更に、本発明は、前記酸窒化スズ膜付き基体または前記製造方法により得られる酸窒化スズ膜付き基体を熱処理して得られる酸窒化スズ膜付き基体を提供する。
【００１０】
更に、本発明は、透明基体と、該透明基体の一方の側に積層してなる酸窒化スズ膜とを有する酸窒化スズ膜付き基体を熱処理して得られ、
熱処理後の該酸窒化スズ膜が、Ｓｎ、ＯおよびＮの合計に対して、Ｎを０．５〜１０ａｔ％含有することを特徴とする酸窒化スズ膜付き基体を提供する。
【００１１】
更に、本発明は、前記酸窒化スズ膜付き基体または前記製造方法により得られる酸窒化スズ膜付き基体を熱処理して、酸窒化スズ膜が、Ｓｎ、ＯおよびＮの合計に対して、Ｎを０．５〜１０ａｔ％含有する酸窒化スズ膜付き基体を製造する酸窒化スズ膜付き基体の製造方法を提供する。
【００１２】
更に、本発明は、前記熱処理して得られる酸窒化スズ膜付き基体を用いた自動車用ガラスを提供する。
【００１３】
【発明の実施の形態】
以下に、本発明を詳細に説明する。
初めに、本発明のいずれの態様においても共通に用いられる透明基体について説明する。
本発明に用いられる透明基体は、無色透明の材料に限られず、透過率が本発明の目的を損なわない範囲で、着色している材料も用いることができる。例えば、ガラス、プラスチックが挙げられる。
ガラスは、特に限定されず、例えば、透明または着色のフロートガラス（フロート法で製造されたガラス）、着色させた熱線吸収ガラスが挙げられる。特に、本発明を自動車用ガラスとして用いる場合、直達の日射エネルギ低減の観点から、熱線吸収ガラスを用いるのが好ましい。また、強化ガラスを用いることもできる。
具体的には、ソーダライムガラスが好適に用いられる。
プラスチックは、例えば、透明または着色のポリカーボネート、ポリメチルメタクリレートが挙げられる。
【００１４】
本発明に用いられる透明基体は、第１の透明基体と中間膜と第２の透明基体との積層体であってもよい。第１および第２の透明基体としては、透明基体として上述したものをそれぞれ任意に組み合わせて用いることができる。中間膜は、例えば、透明または着色のポリビニルブチラール、エチレンビニルアセテートが挙げられる。本発明に用いられる積層体は、これらを任意に組み合わせることができる。例えば、第１および第２の透明基体としてガラスを用い、中間膜としてポリビニルブチラールを用いた合わせガラスが挙げられる。積層体の好適な具体例としては、第１および第２の透明基体として、それぞれ熱線吸収ガラス、高熱線吸収ガラス、紫外線吸収ガラスのいずれかを用い、中間膜としてポリビニルブチラールを用いた合わせガラスが挙げられる。
【００１５】
本発明の第１の態様は、透明基体と、該透明基体の一方の側に積層してなる酸窒化スズ膜とを有する酸窒化スズ膜付き基体であって、
該酸窒化スズ膜が、Ｓｎ、ＯおよびＮの合計に対して、Ｎを２．５〜１５ａｔ％含有することを特徴とする酸窒化スズ膜付き基体である。
本発明の第１の態様において、酸窒化スズ膜におけるＮの含有量は、Ｓｎ、ＯおよびＮの合計に対して、２．５〜１５ａｔ％である。上記範囲であると、酸窒化スズ膜付き基体を高温で熱処理した際に、基体に実用上問題となる程度の反りが生じたり、酸窒化スズ膜にクラックが生じたりすることがない。酸窒化スズ膜におけるＮの含有量は、Ｓｎ、ＯおよびＮの合計に対して、２．５〜１０ａｔ％であるのが好ましい。上記範囲であると、高温で熱処理をしても組成の変化が小さく、個体ごとのバラツキが小さいため、工業的生産が容易となる。より好ましくは、２．５〜６ａｔ％である。
【００１６】
なお、本発明においては、酸素窒素スズ膜のＮ、ＯおよびＳｎの組成はＸ線光電子分光法（ＸＰＳ）により分析することができる。具体的にはＸＰＳ測定装置（ＰＨＩ社製ＥＳＣＡ５４００）を用いて以下の条件で測定することができる。
＜ＸＰＳ測定条件＞
Ｘ線源：ＭｇＫα線、ビーム径２ｍｍ、出力１５ｋＶ、４００Ｗ
Ａｒ+ イオンビーム（４ｋｅＶ、２５ｍＡ／ｃｍ2 ）を用いて、サンプル面上３ｍｍ×３ｍｍの領域をラスタースキャンし、表面層をスパッタエッチングした面を測定する。
光電子の検出角度：４５°、
光電子分析器のパスエネルギー幅：７１．５５ｅＶ
上記条件で測定したＮ1s、Ｏ1s、Ｓｎ3d5/2 ピークの各ピーク面積を求め、相対感度係数を用いて表面原子数比を算出し、窒素の含有割合ａｔ％（原子％）を求める。相対感度係数は、Ｎ1sは０．４９９、Ｏ1sは０．７３３、Ｓｎ3d5/2 は４．８９０である。
以下においても同様である。
【００１７】
本発明の第１の態様の酸窒化スズ膜付き基体の製造方法は、特に限定されないが、スパッタリング法で酸窒化スズ膜を基体上に成膜するのが好ましい。スパッタリング法は、例えば、ＤＣ（直流）スパッタリング方式、高周波スパッタリング方式、マグネトロンスパッタリング方式が挙げられる。中でも、プロセスが安定しており、大面積への成膜が容易であるという利点があるので、ＤＣマグネトロンスパッタリング法が好ましい。
本発明において、スパッタリング法を用いる場合、ターゲットとしてスズを用い、スパッタガスとして酸素ガスと窒素原子を含むガスとを含有するガスを用いて、反応性スパッタリング法を行う。
ターゲットは、スズ単独でもよいが、Ａｌ、Ｓｉ、Ｚｎ等公知のドーパントを本発明の特徴を損なわない範囲でドープしてもよい。
【００１８】
スパッタガスは、酸素ガスと窒素原子を含むガスとを含有するものであれば特に限定されない。例えば、酸素ガスおよび窒素ガスの混合ガス、酸素ガス、窒素ガスおよび不活性ガスの混合ガスを用いることができる。また、窒素原子を含むガスとしては、窒素ガス（Ｎ2 ）以外にも、Ｎ2 Ｏ、ＮＯ、ＮＯ2 、ＮＨ3 等を用いることができる。
不活性ガスは、例えば、ヘリウム、ネオン、アルゴン、クリプトン、キセノン等の希ガスが挙げられる。中でも、経済性および放電のしやすさの点から、アルゴンが好ましい。これらは、単独でまたは２種以上を混合して用いられる。
【００１９】
スパッタガスにおける酸素ガスおよび窒素原子を含むガスの分圧、ならびに、スパッタガスの全圧は、特に限定されず、グロー放電が安定に行われる圧力であればよい。
【００２０】
ＤＣマグネトロンスパッタリング法を行う場合、スパッタリングチャンバーの大きさは特に限定されない。基体の大きさ等を考慮し、適当な大きさのスパッタリングチャンバーを用いることができる。例えば、０．１〜３５ｍ3 のスパッタリングチャンバーが好適に用いられる。
ＤＣマグネトロンスパッタリング法を行う場合、ＤＣ電力密度は、０．９〜３．６Ｗ／ｃｍ2 であるのが好ましく、０．９〜１．８Ｗ／ｃｍ2 であるのがより好ましい。
成膜時間は、成膜速度および所望の膜厚に応じて決定すればよい。
【００２１】
本発明の第２の態様は、透明基体と、該透明基体の一方の側に積層してなる酸窒化スズ膜とを有する酸窒化スズ膜付き基体を反応性スパッタリング法により製造する方法であって、
該反応性スパッタリング法が、酸素ガスと窒素原子を含むガスとを含有する混合ガスを用い、該窒素原子を含むガスの分圧を０．２〜０．４Ｐａとし、該酸素ガスの分圧の該窒素原子を含むガスの分圧に対する比を０．２〜１として行うことを特徴とする酸窒化スズ膜付き基体の製造方法である。
本発明の第２の態様における反応性スパッタリング法は、上述した本発明の第１の態様に用いる方法と同様であるが、混合ガスにおける窒素原子を含むガスの分圧は０．２〜０．４Ｐａであり、酸素ガスの分圧の窒素原子を含むガスの分圧に対する比は０．２〜１である。窒素原子を含むガスの分圧、および、酸素ガスの分圧の窒素原子を含むガスの分圧に対する比が上記範囲であると、得られる酸窒化スズ膜付き基体を高温で熱処理した際に、実用上問題となる程度の反りが生じたり、酸窒化スズ膜にクラックが生じたりすることがないうえに、組成の変化が小さく、個体ごとのバラツキが小さいため、工業的生産が容易となる。混合ガスにおける窒素原子を含むガスの分圧が０．２５〜０．３５Ｐａであるのが好ましい。
【００２２】
本発明の第３の態様は、透明基体と、該透明基体の一方の側に積層してなる酸窒化スズ膜とを有する酸窒化スズ膜付き基体であって、
該透明基体が厚さ２ｍｍのソーダライムガラスであり、かつ、
１００ｍｍ×１００ｍｍの正方形の試験片を用いて、基体温度６５０℃、７分間の条件で熱処理した後における、正方形の対角線の交点での凹み量の絶対値が、酸窒化スズ膜の厚さ１００ｎｍあたり１．０ｍｍ以下であることを特徴とする酸窒化スズ膜付き基体である。
本発明の第３の態様の酸窒化スズ膜付き基体における熱処理の条件は、基体温度６５０℃、７分間の条件である。これは、基体温度が経時的に上昇する場合には、基体最高温度が６５０℃であり、基体最高温度の保持時間が７分間であることを意味する。
【００２３】
本発明の第３の態様の酸窒化スズ膜付き基体は、透明基体が厚さ２ｍｍのソーダライムガラスであり、かつ、１００ｍｍ×１００ｍｍの正方形の試験片を用いて、上記条件で熱処理した後において、正方形の対角線の交点での凹み量の絶対値が、酸窒化スズ膜の厚さ１００ｎｍあたり１．０ｍｍ以下である。
正方形の対角線の交点での凹み量とは、熱処理に起因する反りにより酸窒化スズ膜付き基体に生じた膜面を内側とする凹みの深さを、正方形の対角線の交点で測定した量をいう。
酸窒化スズ膜付き基体の熱処理による反りは、通常、膜面を内側とするが、本発明においては膜面を外側とする反りも含まれる。膜面を外側とする反りの場合には、前記正方形の対角線の交点での凹み量は負の値となる。
本発明の第３の態様の酸窒化スズ膜付き基体は、熱処理した場合の反りが小さく、好適に用いられる。
【００２４】
本発明においては、第１および第３の態様に該当する酸窒化スズ膜付き基体は好ましい態様の一つである。また、本発明においては、第１および／または第３の態様に該当する酸窒化スズ膜付き基体は、第２の態様により製造するのが好ましい。
例えば、透明基体と、該透明基体の一方の側に積層してなる酸窒化スズ膜とを有する酸窒化スズ膜付き基体であって、
該酸窒化スズ膜が、酸素ガスと窒素原子を含むガスとを含有する混合ガスを用い、該窒素原子を含むガスの分圧を０．２〜０．４Ｐａとし、該酸素ガスの分圧の該窒素原子を含むガスの分圧に対する比を０．２〜１として行う反応性スパッタリング法により形成され、Ｓｎ、ＯおよびＮの合計に対して、Ｎを２．５〜１５ａｔ％含有することを特徴とする酸窒化スズ膜付き基体は好ましい態様の一つであり、更に、該透明基体が厚さ２ｍｍのソーダライムガラスであり、かつ、１００ｍｍ×１００ｍｍの正方形の試験片を用いて、基体温度６５０℃、７分間の条件で熱処理した後における、正方形の対角線の交点での凹み量の絶対値が、酸窒化スズ膜の厚さ１００ｎｍあたり１．０ｍｍ以下であることを特徴とする酸窒化スズ膜付き基体は、特に好ましい態様の一つである。
【００２５】
本発明の第１および第３の態様の酸窒化スズ膜付き基体ならびに第２の態様により得られる酸窒化スズ膜付き基体は、上述したように、高温で熱処理を行うことができる。したがって、熱処理によって、曲げ加工または強化加工をすることができる。
曲げ加工は、例えば、自動車のフロントガラス等に本発明の酸窒化スズ膜付き基体を用いる場合に、平面状の酸窒化スズ膜付き基体を３次元曲面形状に変形して酸窒化スズ膜が室内側になるように、熱処理しつつまたは熱処理の直後に行う加工である。
強化加工は、例えば、自動車のリアガラス、ドアガラス等に本発明の酸窒化スズ膜付き基体を用いる場合に、平面状の酸窒化スズ膜付き基体を酸窒化スズ膜が室内側になるように、熱処理した直後に急冷し、ガラス表面に圧縮応力層を施す加工である。
曲げ加工および強化加工において、熱処理は、通常、基体最高温度が６２０〜６８０℃となるように、大気雰囲気で行う。
【００２６】
本発明の第１および第３の態様の酸窒化スズ膜付き基体ならびに第２の態様により得られる酸窒化スズ膜付き基体においては、酸窒化スズ膜の上に更に１または２以上の機能性膜を積層して、多層膜としてもよい。
機能性膜は、特に限定されないが、例えば、窒化チタン膜、酸化ケイ素膜が挙げられる。また、基体に積層された酸窒化スズ膜と組成が同一のまたは異なる酸窒化スズ膜を機能性膜としていずれかの層に有していてもよい。
多層膜とした本発明の酸窒化スズ膜付き基体を熱処理する場合には、酸窒化スズ膜は熱処理による体積変化が極めて小さいため、酸窒化スズ膜に起因して層間剥離が生じることがない。
【００２７】
本発明の第１および第３の態様の酸窒化スズ膜付き基体ならびに第２の態様により得られる酸窒化スズ膜付き基体は、熱線反射性および電波透過性に優れ、かつ、耐熱性に優れる。
本発明の第１および第３の態様の酸窒化スズ膜付き基体ならびに第２の態様により得られる酸窒化スズ膜付き基体の用途は、特に限定されず、例えば、熱線反射性を要求される車両用窓、建築用窓等として好適に用いられるが、特に、後述するように電波透過性の要求される自動車用の窓ガラス（特に、フロントガラス、リアガラス、ドアガラス）として好適に用いられる。
本発明の第１および第３の態様の酸窒化スズ膜付き基体ならびに第２の態様により得られる酸窒化スズ膜付き基体は、特に、耐熱性に優れ、熱処理によって、曲げ加工または強化加工をすることができるので、自動車用ガラス等に用いられる本発明の第４または第５の態様の酸窒化スズ膜付き基体の製造に好適に用いられる。
【００２８】
本発明の第４の態様は、本発明の第１および第３の態様の酸窒化スズ膜付き基体ならびに第２の態様により得られる酸窒化スズ膜付き基体を熱処理して得られる酸窒化スズ膜付き基体である。熱処理により、耐擦傷性が向上するので、種々の用途に好適に用いられる。
【００２９】
熱処理は、特に限定されず、所望の特性に応じて条件を変動させることができる。中でも、好適な具体例の一つとして、酸素ガスを含有する雰囲気（例えば、大気雰囲気）の中で、５００〜７００℃で３〜５分間熱処理することが挙げられる。
【００３０】
本発明の酸窒化スズ膜付き基体は、自動車等の車両等に好適に用いられる。自動車の車両等に用いられるガラスは、曲げ加工または強化加工をする場合、６３０〜６９０℃で３〜７分間程度の熱処理を行う。この際の基体最高温度は、通常、６２０〜６８０℃である。
したがって、本発明の第４の態様の酸窒化スズ膜付き基体は、本発明の第１および第３の態様の酸窒化スズ膜付き基体ならびに第２の態様により得られる酸窒化スズ膜付き基体を曲げ加工または強化加工に供し、その際の熱処理を利用することによって得ることもできる。
【００３１】
本発明の第５の態様は、透明基体と、該透明基体の一方の側に積層してなる酸窒化スズ膜とを有する酸窒化スズ膜付き基体を熱処理して得られ、
熱処理後の該酸窒化スズ膜が、Ｓｎ、ＯおよびＮの合計に対して、Ｎを０．５〜１０ａｔ％含有することを特徴とする酸窒化スズ膜付き基体である。
本発明の第５の態様において、熱処理後の酸窒化スズ膜におけるＮの含有量は、Ｓｎ、ＯおよびＮの合計に対して、０．５〜１０ａｔ％である。上記範囲であると、耐擦傷性に優れる。
本発明の第５の態様に用いられる酸窒化スズ膜付き基体は、特に限定されず、従来公知の酸窒化スズ膜付き基体を用いることができるが、本発明の第１または第２の態様により得られる酸窒化スズ膜付き基体を用いると、熱処理後の酸窒化スズ膜におけるＮの含有量が上記範囲となりやすいので好ましい。
本発明の第５の態様における熱処理は、上述した本発明の第４の態様と同様である。
【００３２】
本発明の好適な態様は、第４の態様および第５の態様のいずれにも該当する酸窒化スズ膜付き基体である。
即ち、本発明の第１および第３の態様の酸窒化スズ膜付き基体ならびに第２の態様により得られる酸窒化スズ膜付き基体を熱処理して得られ、熱処理後の該酸窒化スズ膜が、Ｓｎ、ＯおよびＮの合計に対して、Ｎを０．５〜１０ａｔ％含有することを特徴とする酸窒化スズ膜付き基体が好ましい。
また、本発明の第１および第３の態様の酸窒化スズ膜付き基体ならびに第２の態様により得られる酸窒化スズ膜付き基体を熱処理して、酸窒化スズ膜が、Ｓｎ、ＯおよびＮの合計に対して、Ｎを０．５〜１０ａｔ％含有する酸窒化スズ膜付き基体を製造する酸窒化スズ膜付き基体の製造方法は、本発明の第６の態様である。本発明の第６の態様における熱処理は、上述した本発明の第４の態様と同様である。
【００３３】
本発明の第４および第５の態様の酸窒化スズ膜付き基体においては、本発明の第１、第２および第３の態様と同様に、多層膜としてもよい。
【００３４】
本発明の第４および第５の態様の酸窒化スズ膜付き基体は、熱線反射性および電波透過性に優れ、かつ、耐擦傷性に優れる。
本発明の第４および第５の態様の酸窒化スズ膜付き基体の用途は、特に限定されず、例えば、熱線反射性を要求される車両用窓、建築用窓等として好適に用いられるが、特に、後述するように電波透過性の要求される自動車用の窓ガラス（特に、フロントガラス、リアガラス、ドアガラス）として好適に用いられる。
本発明の第４および第５の態様の酸窒化スズ膜付き基体は、特に、熱処理の際に曲げ加工または強化加工をすれば、自動車用ガラス等に好適に用いられる。その際には、酸窒化スズ膜が室内側になるようにして用いるのが好ましい。
また、耐擦傷性にも優れるので、建築用等にも好適に用いられる。
【００３５】
本発明の第７の態様は、本発明の第４または第５の態様の酸窒化スズ膜付き基体を用いた自動車用ガラスである。
自動車用ガラスは、一般的な要求性能として熱線反射性を要求されるうえ、携帯電話、有料道路自動料金収受システム（ＥＴＣシステム）等の利用において、電波透過性を要求される。
一方、自動車用ガラスは、曲げ加工により所望の３次元曲面形状に加工されるが、従来は基体となるガラスを所望の形状に加工した後に成膜をしており、生産効率が悪かった。
本発明の自動車用ガラスは、熱線反射性および電波透過性に優れるだけでなく、曲面形状のガラスに成膜することなく、平板状のガラスに成膜した後、曲げ加工により３次元曲面形状とすることができるため、生産効率にも優れる。
【００３６】
本発明の自動車用ガラスを自動車のフロントガラスに用いる場合には、２枚のガラスと中間膜としてのポリビニルブチラールとからなる合わせガラスを透明基体として用いるのが好ましい。なお、合わせガラスを製造する場合には、前記したように本発明の酸窒化スズ膜付きガラスを曲げ加工した後、別の同形状のガラスと中間膜を介して酸窒化スズ膜面が車内側に露出するように合わせガラス化する方法が好ましく用いられる。
【００３７】
【実施例】
つぎに、本発明を実施例により具体的に説明するが、本発明はこれら実施例に限定されるものではない。
１．酸窒化スズ膜付き基体の製造
（実施例１）
真空槽内に、縦４３１ｍｍ、横１２７ｍｍの平板形状の金属スズ（Ｓｎ）をスパッタターゲットとしてカソード上に設置し、真空槽（ＩＬＳ１６００、Ａｉｒｃｏ社製）を圧力が２．６×１０-3Ｐａとなるまで排気した。真空槽内に設置した無着色のソーダライムガラス基板（厚み２ｍｍ）上に次のようにして酸窒化スズの単層膜を形成した。
まず、放電ガスとして酸素ガスと窒素ガスの混合ガスを導入し、圧力が６．５×１０-1Ｐａになるようコンダクタンスを調整した。このときの酸素ガスおよび窒素ガスの分圧は、第１表に示した通りである。
ついで、Ｓｎのカソードに１．５ｋＷ（２．７Ｗ／ｃｍ2 ）の負のＤＣ電力を印加し放電させた。放電中のＳｎカソードの下側に、ガラス基板をローラー搬送させ、ガラス基板上にＳｎターゲットのＤＣマグネトロンスパッタリングにより、酸窒化スズ膜を成膜した。
酸窒化スズ膜の膜厚は、１００ｎｍ前後とした。
【００３８】
（実施例２〜５）
酸素ガスおよび窒素ガスの分圧を第１表に示した通りとした以外は、実施例１と同様の方法により、ガラス基板上に酸窒化スズ膜を成膜した。
（比較例１）
放電ガスとして酸素ガスと窒素ガスの混合ガスの代わりに酸素ガスのみを導入し、酸素ガスの分圧を第１表に示した通りとした以外は、実施例１と同様の方法により、ガラス基板上に、酸化スズ膜を成膜した。
【００３９】
（実施例６および７ならびに比較例３および４）
酸素ガスおよび窒素ガスの分圧を第２表に示した通りとし、膜厚を２００ｎｍ前後とした以外は、実施例１と同様の方法により、ガラス基板上に酸窒化スズ膜を成膜した。
（比較例２）
放電ガスとして酸素ガスと窒素ガスの混合ガスの代わりに酸素ガスのみを導入し、酸素ガスの分圧を第２表に示した通りとし、膜厚を２００ｎｍ前後とした以外は、実施例１と同様の方法により、ガラス基板上に、酸化スズ膜を成膜した。
【００４０】
２．熱処理
各実験例および比較例で得られた酸窒化スズ膜付き基体等を１００ｍｍ×１００ｍｍの正方形に切断し、小型のマッフル炉で熱処理を行った。熱処理条件は、設定温度６５０℃、熱処理時間は１０分間で行った。基板最高温度は、６５０℃、基板が最高温度に到達していた時間は７分であった。
【００４１】
３．酸窒化スズ膜付き基体の評価
熱処理前および熱処理後の酸窒化スズ膜付き基体等について、下記の評価を行った。なお実施例および比較例で形成した酸窒化スズ膜中のＳｎ、ＯおよびＮ量（ａｔ％）は前述したＸＰＳ測定装置および測定条件により分析した。
（１）膜厚
熱処理前において、触針式膜厚測定機（ＤＥＫＴＡＫ ＩＩＩａ）により膜厚を測定した。
（２）光学特性
熱処理前および熱処理後において、自記分光光度計（ＵＶ３１００ＰＣ、島津製作所社製）で光学特性を測定した。光学特性としては、可視光線透過率（ＴV ）および膜面側の可視光線反射率を測定し、これらから可視光線吸収率を算出した。実用上は、可視光線透過率が７０％以上であることが好ましい。
また、日射透過率（ＴE ）も測定した。
（３）膜抵抗
熱処理前および熱処理後において、膜抵抗を二探針抵抗計（ハイレスタＨＰ、三菱化学社製）で測定した。
【００４２】
（４）組成
熱処理前および熱処理後において、ＥＳＣＡにより膜の深さ方向の組成を分析した。
（５）反りおよびクラック（耐熱性）
熱処理後において、デジタルノギスを用い、膜面を内側とした反りの凹み量を正方形の対角線の交点において測定し、酸窒化スズ膜１００ｎｍあたりの反りの量を算出した。すべての実施例および比較例において、反りは膜面を内側とするものであった。実用上は、酸窒化スズ膜１００ｎｍあたりの反りの量を１．０ｍｍ以下とする。
また、膜にクラックが生じているか否かを目視観察した。
（６）耐擦傷性
熱処理後において、テーバー磨耗試験機を用い、膜面を回転磨耗輪で擦り、試験後の膜剥離の状態を観察し、膜剥離をしていないものについてはヘイズ値を測定した。テーバー試験条件は、荷重４．９Ｎ×１０００回転で行った。ヘイズ値が小さいほど耐擦傷性に優れることを示す。実用上、ヘイズ値は、５％以下、特に３％以下であるのが好ましい。
【００４３】
評価の結果を第１表および第２表に示す。
第１表から、本発明の第２の態様により得られた第１の態様の酸窒化スズ膜付き基体に該当する実施例１〜５は、いずれも熱処理による反りが小さく、本発明の第３の態様にも該当することが分かる。特に、実施例１〜４は、熱処理による組成の変化が小さく、工業的生産に適している。また、膜抵抗は、実施例１〜５のいずれにおいても１×１０9 Ω／□以上であり、十分な電波透過性を示した。
これに対し、比較例１の酸化スズ膜付き基体は、反りが大きい。
【００４４】
第２表から、本発明の第２の態様により得られた第１の態様の酸窒化スズ膜付き基体に該当する実施例６および７は、いずれも熱処理による反りが小さく、本発明の第３の態様にも該当し、クラックも発生せず、得られた本発明の第４および第５の態様に該当する酸窒化スズ膜付き基体は、耐擦傷性に優れることが分かる。
これに対し、比較例２の酸化スズ膜付き基体は、反りが大きく、クラックを生じ、膜剥離を生じる。また、比較例３および４の酸窒化スズ膜付き基体は、クラックを生じ、膜剥離を生じる。
【００４５】
【表１】
【表２】
４．多層膜を有する酸窒化スズ膜付き基体の製造
（実施例１３）
真空槽内に金属スズ（Ｓｎ）、金属チタン（Ｔｉ）、および比抵抗１．２Ω・ｃｍのｎ型Ｓｉ（リンドープ単結晶）をターゲットとしてカソード上に設置し、真空槽（ＩＬＳ１６００）を圧力が２．６×１０-3Ｐａとなるまで排気した。真空槽内に設置した着色ソーダライムガラス基板（旭硝子社製「ＵＶクールグリーン」、厚み４ｍｍ）上に次のようにして多層膜からなる断熱膜をガラス基板上に形成した。
まず、放電ガスとして酸素ガスと窒素ガスの混合ガス（酸素ガスの分圧０．２９Ｐａ、窒素ガスの分圧０．３６Ｐａ）を導入し、圧力が６．５×１０-1Ｐａになるようコンダクタンスを調整した。ついで、Ｓｎのカソードに１．０ｋＷ（１．８Ｗ／ｃｍ2 ）の負のＤＣ電力を印加し、ＳｎターゲットのＤＣマグネトロンスパッタリングにより、７６ｎｍの酸窒化スズ膜を成膜した。
【００４８】
ガス導入を停止し、真空槽内を高真空とした後、放電ガスとしてアルゴンと窒素ガスの混合ガス（窒素ガスの分圧８０％）を導入し、圧力が２．６×１０-1Ｐａになるようコンダクタンスを調整した。ついで、Ｔｉのカソードに２．０ｋＷ（３．０Ｗ／ｃｍ2 ）の負のＤＣ電力を印加し、ＴｉターゲットのＤＣマグネトロンスパッタリングにより、３ｎｍの窒化チタン膜を成膜した。
つぎに、上述したのと同様の方法により、５４ｎｍの酸窒化スズ膜を成膜した。
【００４９】
ガス導入を停止し、真空槽内を高真空とした後、放電ガスとして酸素ガス（１００％）を導入し、圧力が２．６×１０-1Ｐａになるようコンダクタンスを調整した。ついで、Ｓｉのカソードに２．０ｋＷ（３．０Ｗ／ｃｍ2 ）の負のＤＣ電力を印加し、ＳｉターゲットのＤＣスパッタリングにより、１０ｎｍの酸化ケイ素膜を形成した。
得られた多層膜を有する酸窒化スズ膜付き基体の総膜厚は、１４３ｎｍであった。
【００５０】
得られた多層膜を有する酸窒化スズ膜付き基体を上述した単層膜の場合と同様の方法により、熱処理をした。
熱処理後の酸窒化スズ膜付き基体について、上述した単層膜の場合と同様に、光学特性、耐熱性および耐擦傷性の評価を行った。なお、光学特性については、可視光線および太陽エネルギーについての透過率、ガラス面側の反射率および膜面側の反射率を測定し、熱線反射性について評価した。
また、熱処理後の酸窒化スズ膜付き基体について、以下のようにして耐薬品性試験も行った。
（７）耐薬品性試験
▲１▼耐酸性試験
０．１ｍｏｌ／Ｌ硫酸に２時間浸せきした。
▲２▼耐アルカリ性試験
０．１ｍｏｌ／Ｌ水酸化ナトリウム水溶液に２時間浸せきした。
▲１▼および▲２▼を実施し、それぞれ試験前後において、上述したのと同様の方法により、可視光線および太陽エネルギーの透過率および反射率を測定し、外観観察を実施した。
【００５１】
光学特性の結果を第３表に示す。
本発明の第２の態様により得られた酸窒化スズ膜付き基体を熱処理して得られた本発明の第４および第５の態様に該当する酸窒化スズ膜付き基体は、可視光線透過率を高く保持しつつも、太陽エネルギー透過率が低く、優れた熱線反射性を示すことが分かる。
耐熱性の評価においては、反りは小さく、クラックの発生もなかった。耐擦傷性の評価においては、膜剥離は発生せず、ヘイズ値も小さかった。耐薬品性の評価においては、耐酸性試験および耐アルカリ性試験の前後において、透過率、反射率および外観に変化は見られなかった。
【００５２】
【表３】
【発明の効果】
本発明の酸窒化スズ膜付き基体は、熱線反射性、電波透過性および耐熱性に優れ、熱処理により曲げ加工または強化加工をすることができ、また、本発明の熱処理後の酸窒化スズ膜付き基体は、熱線反射性、電波透過性および耐擦傷性に優れるので、広範な用途に用いることができ、特に、自動車用ガラスに好適に用いることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a substrate with a tin oxynitride film, and more particularly to a substrate with a tin oxynitride film that is excellent in heat ray reflectivity, radio wave transmission, and heat resistance. The present invention also relates to a substrate with a tin oxynitride film that is excellent in heat ray reflectivity, radio wave permeability, and scratch resistance.
[0002]
[Prior art]
Conventionally, a tin oxynitride film has been known as a transparent film excellent in heat ray reflectivity, radio wave permeability, and the like. The tin oxynitride film is provided on a substrate such as glass and has been used for various applications such as heat ray reflective glass and a substrate for transparent electrodes.
[0003]
[Problems to be solved by the invention]
As a result of intensive studies on such a tin oxynitride film, the present inventor has found that a specific tin oxynitride film has a very small volume change even when heat-treated at a high temperature.
When a substrate having a tin oxynitride film is heat-treated at a high temperature, if the tin oxynitride film shrinks, a warp with the film surface on the inside occurs in the substrate, while when the tin oxynitride film expands, the film surface becomes the outside. Warping occurs in the substrate. And when the shrinkage | contraction and expansion | swelling are large, there exists a problem that a crack arises in a tin oxynitride film | membrane.
That is, the present inventors have found that the volume change is extremely small even when a specific tin oxynitride film is heat-treated at a high temperature, and the substrate having this tin oxynitride film is hardly warped by the heat treatment, and The present invention was completed by finding that no cracks occur in the tin oxynitride film.
[0004]
Further, the conventional tin oxynitride film is not excellent in scratch resistance. Therefore, when it is used for each application, another layer is further laminated on the tin oxynitride film to improve the scratch resistance. There was a need to improve.
[0005]
Accordingly, an object of the present invention is to provide a substrate with a tin oxynitride film that is excellent in heat ray reflectivity, radio wave permeability, and the like, and further excellent in heat resistance.
[0006]
[Means for Solving the Problems]
The present invention is a substrate with a tin oxynitride film having a transparent substrate and a tin oxynitride film laminated on one side of the transparent substrate,
Provided is a substrate with a tin oxynitride film, wherein the tin oxynitride film contains 2.5 to 15 at% of N with respect to the total of Sn, O, and N.
[0007]
Further, the present invention is a method for producing a substrate with a tin oxynitride film having a transparent substrate and a tin oxynitride film laminated on one side of the transparent substrate by a reactive sputtering method,
The reactive sputtering method uses a mixed gas containing oxygen gas and a gas containing nitrogen atoms, the partial pressure of the gas containing nitrogen atoms is 0.2 to 0.4 Pa, and the partial pressure of the oxygen gas is Provided is a method for producing a substrate with a tin oxynitride film, wherein the ratio of the nitrogen-containing gas to the partial pressure is 0.2 to 1.
[0008]
Furthermore, the present invention is a substrate with a tin oxynitride film comprising a transparent substrate and a tin oxynitride film laminated on one side of the transparent substrate,
The transparent substrate is soda-lime glass having a thickness of 2 mm, and
Using a 100 mm × 100 mm square test piece, the absolute value of the dent amount at the intersection of the square diagonal lines after heat treatment under the condition of the substrate temperature of 650 ° C. for 7 minutes is the thickness per 100 nm of the tin oxynitride film. Provided is a substrate with a tin oxynitride film, which is 1.0 mm or less.
[0009]
Furthermore, the present invention provides a substrate with a tin oxynitride film obtained by heat-treating the substrate with a tin oxynitride film or the substrate with a tin oxynitride film obtained by the production method.
[0010]
Furthermore, the present invention is obtained by heat-treating a substrate with a tin oxynitride film having a transparent substrate and a tin oxynitride film laminated on one side of the transparent substrate,
Provided is a substrate with a tin oxynitride film, characterized in that the tin oxynitride film after the heat treatment contains 0.5 to 10 at% of N with respect to the total of Sn, O and N.
[0011]
Further, in the present invention, the substrate with a tin oxynitride film or the substrate with a tin oxynitride film obtained by the manufacturing method is subjected to a heat treatment so that the tin oxynitride film has N as a sum of Sn, O and N. Provided is a method for producing a substrate with a tin oxynitride film, which produces a substrate with a tin oxynitride film containing 0.5 to 10 at%.
[0012]
Furthermore, this invention provides the glass for motor vehicles using the base | substrate with a tin oxynitride film | membrane obtained by the said heat processing.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below.
First, a transparent substrate that is commonly used in any aspect of the present invention will be described.
The transparent substrate used in the present invention is not limited to a colorless and transparent material, and a colored material can be used as long as the transmittance does not impair the object of the present invention. Examples thereof include glass and plastic.
The glass is not particularly limited, and examples thereof include transparent or colored float glass (glass produced by a float process) and colored heat ray absorbing glass. When using this invention as glass for motor vehicles especially, it is preferable to use heat ray absorption glass from a viewpoint of direct solar radiation energy reduction. Tempered glass can also be used.
Specifically, soda lime glass is preferably used.
Examples of the plastic include transparent or colored polycarbonate and polymethyl methacrylate.
[0014]
The transparent substrate used in the present invention may be a laminate of a first transparent substrate, an intermediate film, and a second transparent substrate. As the first and second transparent substrates, those described above as the transparent substrates can be used in any combination. Examples of the interlayer film include transparent or colored polyvinyl butyral and ethylene vinyl acetate. These can be arbitrarily combined in the laminate used in the present invention. For example, a laminated glass using glass as the first and second transparent substrates and polyvinyl butyral as the intermediate film can be mentioned. As a suitable specific example of the laminate, laminated glass using polyvinyl butyral as an intermediate film is used as the first and second transparent substrates, respectively, one of heat ray absorbing glass, high heat ray absorbing glass and ultraviolet ray absorbing glass. Can be mentioned.
[0015]
A first aspect of the present invention is a substrate with a tin oxynitride film having a transparent substrate and a tin oxynitride film laminated on one side of the transparent substrate,
The tin oxynitride film is a substrate with a tin oxynitride film characterized by containing 2.5 to 15 at% of N with respect to the total of Sn, O and N.
In the first aspect of the present invention, the content of N in the tin oxynitride film is 2.5 to 15 at% with respect to the total of Sn, O and N. Within the above range, when the substrate with a tin oxynitride film is heat-treated at a high temperature, the substrate will not be warped to a practical degree, and the tin oxynitride film will not crack. The N content in the tin oxynitride film is preferably 2.5 to 10 at% with respect to the total of Sn, O and N. Within the above range, even if heat treatment is performed at a high temperature, the change in composition is small, and the variation among individuals is small, so that industrial production becomes easy. More preferably, it is 2.5 to 6 at%.
[0016]
In the present invention, the composition of N, O and Sn in the oxygen-nitrogen tin film can be analyzed by X-ray photoelectron spectroscopy (XPS). Specifically, it can be measured under the following conditions using an XPS measuring apparatus (ESCA5400 manufactured by PHI).
<XPS measurement conditions>
X-ray source: MgKα ray, beam diameter 2 mm, output 15 kV, 400 W
Ar + Ion beam (4 keV, 25 mA / cm 2 ), A raster scan of a 3 mm × 3 mm region on the sample surface is performed, and the surface on which the surface layer is sputter-etched is measured.
Photoelectron detection angle: 45 °,
Photoelectron analyzer path energy width: 71.55 eV
N measured under the above conditions 1s , O 1s , Sn 3d5 / 2 The area of each peak is obtained, the surface atomic ratio is calculated using the relative sensitivity coefficient, and the nitrogen content ratio at% (atomic%) is obtained. The relative sensitivity coefficient is N 1s Is 0.499, O 1s Is 0.733, Sn 3d5 / 2 Is 4.890.
The same applies to the following.
[0017]
The method for producing a substrate with a tin oxynitride film according to the first aspect of the present invention is not particularly limited, but it is preferable to form a tin oxynitride film on the substrate by a sputtering method. Examples of the sputtering method include a DC (direct current) sputtering method, a high frequency sputtering method, and a magnetron sputtering method. Among these, the DC magnetron sputtering method is preferable because the process is stable and the film can be easily formed on a large area.
In the present invention, when the sputtering method is used, the reactive sputtering method is performed using tin as a target and a gas containing oxygen gas and a gas containing nitrogen atoms as a sputtering gas.
The target may be tin alone, but may be doped with a known dopant such as Al, Si, Zn or the like within a range not impairing the characteristics of the present invention.
[0018]
The sputtering gas is not particularly limited as long as it contains oxygen gas and a gas containing nitrogen atoms. For example, a mixed gas of oxygen gas and nitrogen gas, a mixed gas of oxygen gas, nitrogen gas, and inert gas can be used. As the gas containing nitrogen atoms, nitrogen gas (N 2 ), N 2 O, NO, NO 2 , NH Three Etc. can be used.
Examples of the inert gas include rare gases such as helium, neon, argon, krypton, and xenon. Of these, argon is preferable from the viewpoint of economy and ease of discharge. These may be used alone or in admixture of two or more.
[0019]
The partial pressure of the gas containing oxygen gas and nitrogen atoms in the sputtering gas, and the total pressure of the sputtering gas are not particularly limited, and may be any pressure that allows stable glow discharge.
[0020]
When performing the DC magnetron sputtering method, the size of the sputtering chamber is not particularly limited. In consideration of the size of the substrate, a sputtering chamber of an appropriate size can be used. For example, 0.1-35m Three The sputtering chamber is preferably used.
When performing the DC magnetron sputtering method, the DC power density is 0.9 to 3.6 W / cm. 2 Preferably, 0.9 to 1.8 W / cm 2 It is more preferable that
The film formation time may be determined according to the film formation speed and the desired film thickness.
[0021]
A second aspect of the present invention is a method for producing a substrate with a tin oxynitride film having a transparent substrate and a tin oxynitride film laminated on one side of the transparent substrate by a reactive sputtering method. ,
The reactive sputtering method uses a mixed gas containing oxygen gas and a gas containing nitrogen atoms, the partial pressure of the gas containing nitrogen atoms is 0.2 to 0.4 Pa, and the partial pressure of the oxygen gas is A method for producing a substrate with a tin oxynitride film, wherein the ratio of the nitrogen atom-containing gas to the partial pressure is 0.2 to 1.
The reactive sputtering method in the second aspect of the present invention is the same as the method used in the first aspect of the present invention described above, but the partial pressure of the gas containing nitrogen atoms in the mixed gas is 0.2-0. 4 Pa, and the ratio of the partial pressure of oxygen gas to the partial pressure of a gas containing nitrogen atoms is 0.2 to 1. When the ratio of the partial pressure of the gas containing nitrogen atoms and the partial pressure of the oxygen gas to the partial pressure of the gas containing nitrogen atoms is within the above range, when the resulting substrate with a tin oxynitride film is heat-treated at a high temperature, Since there is no warp to the extent that is a problem in practice or cracks are generated in the tin oxynitride film, the change in composition is small and the variation among individuals is small, so that industrial production becomes easy. The partial pressure of the gas containing nitrogen atoms in the mixed gas is preferably 0.25 to 0.35 Pa.
[0022]
A third aspect of the present invention is a substrate with a tin oxynitride film having a transparent substrate and a tin oxynitride film laminated on one side of the transparent substrate,
The transparent substrate is soda-lime glass having a thickness of 2 mm, and
Using a 100 mm × 100 mm square test piece, the absolute value of the dent amount at the intersection of the square diagonal lines after heat treatment under the condition of the substrate temperature of 650 ° C. for 7 minutes is the thickness per 100 nm of the tin oxynitride film. The substrate with a tin oxynitride film is 1.0 mm or less.
The conditions for the heat treatment in the substrate with a tin oxynitride film according to the third aspect of the present invention are the substrate temperature of 650 ° C. and 7 minutes. This means that when the substrate temperature rises with time, the substrate maximum temperature is 650 ° C., and the substrate maximum temperature holding time is 7 minutes.
[0023]
In the substrate with a tin oxynitride film according to the third aspect of the present invention, the transparent substrate is soda lime glass having a thickness of 2 mm, and after heat treatment under the above conditions using a 100 mm × 100 mm square test piece. The absolute value of the dent amount at the intersection of the square diagonal lines is 1.0 mm or less per 100 nm thickness of the tin oxynitride film.
The amount of dents at the intersection of square diagonal lines refers to the amount measured at the intersection of square diagonal lines, with the depth of the dents on the inner surface of the tin oxynitride film-coated substrate caused by warpage caused by heat treatment. .
The warp due to the heat treatment of the substrate with the tin oxynitride film usually has the film surface on the inside, but in the present invention, the warp with the film surface on the outside is also included. In the case of warping with the film surface on the outside, the amount of depression at the intersection of the square diagonal lines is a negative value.
The substrate with a tin oxynitride film according to the third aspect of the present invention has a small warp when heat-treated, and is preferably used.
[0024]
In the present invention, the substrate with a tin oxynitride film corresponding to the first and third embodiments is one of the preferred embodiments. Moreover, in this invention, it is preferable to manufacture the base | substrate with a tin oxynitride film | membrane applicable to a 1st and / or 3rd aspect by a 2nd aspect.
For example, a substrate with a tin oxynitride film having a transparent substrate and a tin oxynitride film laminated on one side of the transparent substrate,
The tin oxynitride film uses a mixed gas containing oxygen gas and a gas containing nitrogen atoms, the partial pressure of the gas containing nitrogen atoms is 0.2 to 0.4 Pa, and the partial pressure of the oxygen gas is It is formed by a reactive sputtering method in which the ratio of the nitrogen atom-containing gas to the partial pressure is 0.2 to 1, and contains 2.5 to 15 at% N with respect to the total of Sn, O and N. The substrate with a featured tin oxynitride film is one of preferred embodiments, and further, the transparent substrate is soda lime glass having a thickness of 2 mm, and a substrate having a substrate temperature of 100 mm × 100 mm is used. The tin oxynitride characterized in that the absolute value of the dent at the intersection of square diagonal lines after heat treatment at 650 ° C. for 7 minutes is 1.0 mm or less per 100 nm thickness of the tin oxynitride film The substrate with film is Which is the one preferred embodiment.
[0025]
As described above, the substrate with the tin oxynitride film according to the first and third aspects of the present invention and the substrate with the tin oxynitride film obtained according to the second aspect can be heat-treated at a high temperature. Therefore, bending or strengthening can be performed by heat treatment.
For example, when the substrate with a tin oxynitride film of the present invention is used for a windshield of an automobile, for example, the planar substrate with a tin oxynitride film is deformed into a three-dimensional curved surface so that the tin oxynitride film is contained in the chamber. It is a process performed while performing heat treatment or immediately after the heat treatment so as to be inside.
For example, when the substrate with a tin oxynitride film of the present invention is used for a rear glass of an automobile, a door glass, or the like, the substrate with a planar tin oxynitride film is placed indoors so that the tin oxynitride film is on the indoor side. This is a process of quenching immediately after heat treatment and applying a compressive stress layer to the glass surface.
In bending and strengthening, the heat treatment is usually performed in an air atmosphere so that the maximum temperature of the substrate is 620 to 680 ° C.
[0026]
In the base with a tin oxynitride film of the first and third aspects of the present invention and the base with a tin oxynitride film obtained by the second aspect, one or more functional films are further formed on the tin oxynitride film. May be laminated to form a multilayer film.
The functional film is not particularly limited, and examples thereof include a titanium nitride film and a silicon oxide film. Further, a tin oxynitride film having the same composition as or different from that of the tin oxynitride film laminated on the substrate may have a functional film in any layer.
When heat-treating the substrate with a tin oxynitride film of the present invention as a multilayer film, the tin oxynitride film undergoes a very small volume change due to the heat treatment, so that delamination does not occur due to the tin oxynitride film.
[0027]
The substrate with a tin oxynitride film according to the first and third aspects of the present invention and the substrate with a tin oxynitride film obtained by the second aspect are excellent in heat ray reflectivity and radio wave permeability and excellent in heat resistance.
The uses of the base with a tin oxynitride film according to the first and third aspects of the present invention and the base with a tin oxynitride film obtained according to the second aspect are not particularly limited, for example, a vehicle that requires heat ray reflectivity Although it is suitably used as a window for buildings, a window for construction, etc., it is particularly suitably used as a window glass for automobiles (especially windshield, rear glass, door glass) that requires radio wave transmission as described later.
The substrate with a tin oxynitride film according to the first and third aspects of the present invention and the substrate with a tin oxynitride film obtained by the second aspect are particularly excellent in heat resistance and are subjected to bending or strengthening by heat treatment. Therefore, it can be suitably used for the production of a substrate with a tin oxynitride film according to the fourth or fifth aspect of the present invention used for automobile glass or the like.
[0028]
According to a fourth aspect of the present invention, there is provided a tin oxynitride film obtained by heat-treating a substrate with a tin oxynitride film according to the first and third aspects of the present invention and a substrate with a tin oxynitride film obtained according to the second aspect. It is an attached substrate. Since the scratch resistance is improved by the heat treatment, it is suitably used for various applications.
[0029]
The heat treatment is not particularly limited, and the conditions can be changed according to desired characteristics. Among these, as a preferable specific example, heat treatment is performed at 500 to 700 ° C. for 3 to 5 minutes in an atmosphere (for example, an air atmosphere) containing oxygen gas.
[0030]
The substrate with a tin oxynitride film of the present invention is suitably used for vehicles such as automobiles. When bending or strengthening glass used for automobile vehicles, heat treatment is performed at 630 to 690 ° C. for about 3 to 7 minutes. In this case, the maximum substrate temperature is usually 620 to 680 ° C.
Therefore, the substrate with a tin oxynitride film according to the fourth aspect of the present invention includes the substrate with the tin oxynitride film according to the first and third aspects of the present invention and the substrate with the tin oxynitride film obtained according to the second aspect. It can also be obtained by subjecting it to bending or strengthening and utilizing heat treatment at that time.
[0031]
A fifth aspect of the present invention is obtained by heat-treating a substrate with a tin oxynitride film having a transparent substrate and a tin oxynitride film laminated on one side of the transparent substrate,
The tin oxynitride film after heat treatment is a substrate with a tin oxynitride film characterized by containing 0.5 to 10 at% of N with respect to the total of Sn, O and N.
In the fifth aspect of the present invention, the content of N in the tin oxynitride film after the heat treatment is 0.5 to 10 at% with respect to the total of Sn, O and N. Within the above range, the scratch resistance is excellent.
The substrate with a tin oxynitride film used in the fifth aspect of the present invention is not particularly limited, and a conventionally known substrate with a tin oxynitride film can be used, but according to the first or second aspect of the present invention. It is preferable to use the obtained substrate with a tin oxynitride film because the N content in the tin oxynitride film after heat treatment tends to be in the above range.
The heat treatment in the fifth aspect of the present invention is the same as in the fourth aspect of the present invention described above.
[0032]
A preferred aspect of the present invention is a substrate with a tin oxynitride film corresponding to both the fourth aspect and the fifth aspect.
Specifically, the tin oxynitride film-coated substrate of the first and third aspects of the present invention and the tin oxynitride film-coated substrate obtained by the second aspect are obtained by heat treatment, and the heat-treated tin oxynitride film is A substrate with a tin oxynitride film characterized by containing 0.5 to 10 at% of N with respect to the total of Sn, O and N is preferable.
Also, the substrate with tin oxynitride film of the first and third aspects of the present invention and the substrate with tin oxynitride film obtained by the second aspect are heat-treated, so that the tin oxynitride film has Sn, O and N The method for manufacturing a substrate with a tin oxynitride film, which manufactures a substrate with a tin oxynitride film containing 0.5 to 10 at% N with respect to the total, is the sixth aspect of the present invention. The heat treatment in the sixth aspect of the present invention is the same as in the fourth aspect of the present invention described above.
[0033]
The substrate with tin oxynitride film of the fourth and fifth aspects of the present invention may be a multilayer film as in the first, second and third aspects of the present invention.
[0034]
The bases with a tin oxynitride film of the fourth and fifth aspects of the present invention are excellent in heat ray reflectivity and radio wave permeability and excellent in scratch resistance.
The use of the substrate with a tin oxynitride film according to the fourth and fifth aspects of the present invention is not particularly limited, and for example, it is suitably used as a vehicle window, a building window, etc. that require heat ray reflectivity. In particular, as will be described later, it is suitably used as a window glass for automobiles (in particular, a windshield, a rear glass, and a door glass) that requires radio wave transmission.
The substrate with a tin oxynitride film according to the fourth and fifth aspects of the present invention is suitably used for automotive glass or the like, particularly if bending or strengthening is performed during heat treatment. In that case, it is preferable to use the tin oxynitride film on the indoor side.
Moreover, since it is excellent also in abrasion resistance, it is used suitably also for building use etc.
[0035]
A seventh aspect of the present invention is an automotive glass using the substrate with a tin oxynitride film according to the fourth or fifth aspect of the present invention.
Glass for automobiles is required to have heat ray reflectivity as a general required performance, and is also required to transmit radio waves in the use of mobile phones, toll road automatic toll collection systems (ETC systems) and the like.
On the other hand, glass for automobiles is processed into a desired three-dimensional curved surface shape by bending, but conventionally, film formation is performed after processing the glass as a substrate into a desired shape, and the production efficiency is poor.
The glass for automobiles of the present invention is not only excellent in heat ray reflectivity and radio wave transmission, but also formed into a flat glass without being formed on a curved glass, and then formed into a three-dimensional curved shape by bending. Therefore, production efficiency is also excellent.
[0036]
When the automotive glass of the present invention is used for a windshield of an automobile, it is preferable to use a laminated glass composed of two glasses and polyvinyl butyral as an intermediate film as a transparent substrate. In addition, when manufacturing a laminated glass, after bending the glass with a tin oxynitride film of the present invention as described above, the surface of the tin oxynitride film is inside the vehicle through another glass having the same shape and an intermediate film. A method of forming glass so as to expose the film is preferably used.
[0037]
【Example】
EXAMPLES Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
1. Production of substrate with tin oxynitride film
Example 1
In the vacuum chamber, flat metal tin (Sn) having a length of 431 mm and a width of 127 mm was placed on the cathode as a sputtering target, and the pressure in the vacuum chamber (ILS1600, manufactured by Airco) was 2.6 × 10. -3 It exhausted until it became Pa. A monolayer film of tin oxynitride was formed on an uncolored soda lime glass substrate (thickness 2 mm) placed in a vacuum chamber as follows.
First, a mixed gas of oxygen gas and nitrogen gas is introduced as a discharge gas, and the pressure is 6.5 × 10. -1 The conductance was adjusted to be Pa. The partial pressures of oxygen gas and nitrogen gas at this time are as shown in Table 1.
Next, 1.5 kW (2.7 W / cm) was applied to the Sn cathode. 2 ) Negative DC power was applied and discharged. A glass substrate was conveyed by a roller under the Sn cathode during discharge, and a tin oxynitride film was formed on the glass substrate by DC magnetron sputtering of a Sn target.
The film thickness of the tin oxynitride film was about 100 nm.
[0038]
(Examples 2 to 5)
A tin oxynitride film was formed on the glass substrate by the same method as in Example 1 except that the partial pressures of oxygen gas and nitrogen gas were as shown in Table 1.
(Comparative Example 1)
A glass substrate was obtained in the same manner as in Example 1 except that only oxygen gas was introduced as the discharge gas instead of the mixed gas of oxygen gas and nitrogen gas, and the partial pressure of oxygen gas was as shown in Table 1. A tin oxide film was formed thereon.
[0039]
(Examples 6 and 7 and Comparative Examples 3 and 4)
A tin oxynitride film was formed on the glass substrate in the same manner as in Example 1 except that the partial pressures of oxygen gas and nitrogen gas were as shown in Table 2 and the film thickness was about 200 nm.
(Comparative Example 2)
Example 1 except that only oxygen gas was introduced as the discharge gas instead of the mixed gas of oxygen gas and nitrogen gas, the partial pressure of oxygen gas was as shown in Table 2, and the film thickness was about 200 nm. A tin oxide film was formed on the glass substrate by the same method.
[0040]
2. Heat treatment
The substrate with tin oxynitride film obtained in each experimental example and comparative example was cut into a square of 100 mm × 100 mm and heat-treated in a small muffle furnace. The heat treatment conditions were a set temperature of 650 ° C. and a heat treatment time of 10 minutes. The substrate maximum temperature was 650 ° C., and the time during which the substrate reached the maximum temperature was 7 minutes.
[0041]
3. Evaluation of substrate with tin oxynitride film
The following evaluation was performed on the substrate with a tin oxynitride film before and after heat treatment. The Sn, O, and N amounts (at%) in the tin oxynitride films formed in the examples and comparative examples were analyzed using the XPS measurement apparatus and measurement conditions described above.
(1) Film thickness
Before the heat treatment, the film thickness was measured with a stylus type film thickness measuring machine (DEKTAK IIIa).
(2) Optical characteristics
Before and after the heat treatment, optical characteristics were measured with a self-recording spectrophotometer (UV3100PC, manufactured by Shimadzu Corporation). As optical characteristics, visible light transmittance (T V ) And the visible light reflectance on the film surface side, and the visible light absorptance was calculated from these. Practically, the visible light transmittance is preferably 70% or more.
Also, solar radiation transmittance (T E ) Was also measured.
(3) Membrane resistance
Before and after heat treatment, the film resistance was measured with a two-probe resistance meter (Hiresta HP, manufactured by Mitsubishi Chemical Corporation).
[0042]
(4) Composition
Before and after heat treatment, the composition in the depth direction of the film was analyzed by ESCA.
(5) Warpage and crack (heat resistance)
After the heat treatment, using a digital caliper, the amount of warp indentation with the film surface on the inside was measured at the intersection of square diagonal lines, and the amount of warpage per 100 nm of the tin oxynitride film was calculated. In all the examples and comparative examples, the warpage was the film surface inside. Practically, the amount of warpage per 100 nm of the tin oxynitride film is 1.0 mm or less.
Further, it was visually observed whether or not the film had cracks.
(6) Scratch resistance
After the heat treatment, using a Taber abrasion tester, the film surface was rubbed with a rotating wear ring, the state of film separation after the test was observed, and the haze value was measured for those without film peeling. The Taber test condition was performed with a load of 4.9 N × 1000 rotations. It shows that it is excellent in abrasion resistance, so that a haze value is small. Practically, the haze value is preferably 5% or less, particularly 3% or less.
[0043]
The results of evaluation are shown in Tables 1 and 2.
From Table 1, Examples 1 to 5 corresponding to the substrate with a tin oxynitride film of the first aspect obtained by the second aspect of the present invention are all less warped by heat treatment, and the third aspect of the present invention. It can be seen that this also applies to the embodiment. In particular, Examples 1 to 4 have a small change in composition due to heat treatment and are suitable for industrial production. Further, the membrane resistance is 1 × 10 in any of Examples 1 to 5. 9 It was Ω / □ or more, and sufficient radio wave permeability was shown.
In contrast, the substrate with the tin oxide film of Comparative Example 1 has a large warp.
[0044]
From Table 2, Examples 6 and 7 corresponding to the substrate with a tin oxynitride film of the first aspect obtained according to the second aspect of the present invention have small warpage due to heat treatment, and the third of the present invention. It can be seen that the substrate with a tin oxynitride film corresponding to the fourth and fifth aspects of the present invention obtained is also excellent in scratch resistance.
On the other hand, the substrate with the tin oxide film of Comparative Example 2 has a large warp, cracks, and film peeling. In addition, the bases with the tin oxynitride film of Comparative Examples 3 and 4 cause cracks and film peeling.
[0045]
[Table 1]
[Table 2]
4). Fabrication of a substrate with a multi-layered tin oxynitride film
(Example 13)
In the vacuum chamber, metal tin (Sn), metal titanium (Ti), and n-type Si (phosphorus-doped single crystal) with a specific resistance of 1.2 Ω · cm were set as targets on the cathode, and the vacuum chamber (ILS1600) was pressurized. 2.6 × 10 -3 It exhausted until it became Pa. A heat insulating film made of a multilayer film was formed on a glass substrate on a colored soda lime glass substrate (“UV Cool Green” manufactured by Asahi Glass Co., Ltd., thickness 4 mm) installed in a vacuum chamber as follows.
First, a mixed gas of oxygen gas and nitrogen gas (partial pressure of oxygen gas 0.29 Pa, partial pressure of nitrogen gas 0.36 Pa) is introduced as a discharge gas, and the pressure is 6.5 × 10 6. -1 The conductance was adjusted to be Pa. Next, 1.0 kW (1.8 W / cm) is applied to the Sn cathode. 2 ) Negative DC power was applied, and a 76 nm tin oxynitride film was formed by DC magnetron sputtering of a Sn target.
[0048]
After the gas introduction was stopped and the inside of the vacuum chamber was made high vacuum, a mixed gas of argon and nitrogen gas (nitrogen gas partial pressure 80%) was introduced as a discharge gas, and the pressure was 2.6 × 10 -1 The conductance was adjusted to be Pa. Next, 2.0 kW (3.0 W / cm) was applied to the Ti cathode. 2 ) Negative DC power was applied, and a 3 nm titanium nitride film was formed by DC magnetron sputtering of a Ti target.
Next, a 54 nm tin oxynitride film was formed by the same method as described above.
[0049]
After the gas introduction was stopped and the inside of the vacuum chamber was made high vacuum, oxygen gas (100%) was introduced as a discharge gas, and the pressure was 2.6 × 10 -1 The conductance was adjusted to be Pa. Next, 2.0 kW (3.0 W / cm) was applied to the Si cathode. 2 ) Negative DC power was applied, and a 10 nm silicon oxide film was formed by DC sputtering of the Si target.
The total film thickness of the obtained substrate with a tin oxynitride film having a multilayer film was 143 nm.
[0050]
The obtained substrate with a tin oxynitride film having a multilayer film was heat-treated by the same method as in the case of the single-layer film described above.
About the base | substrate with a tin oxynitride film | membrane after heat processing, the optical characteristic, heat resistance, and abrasion resistance were evaluated similarly to the case of the single layer film | membrane mentioned above. In addition, about the optical characteristic, the transmittance | permeability about visible light and solar energy, the reflectance on the glass surface side, and the reflectance on the film surface side were measured, and heat ray reflectivity was evaluated.
Further, the chemical resistance test was also conducted on the substrate with the tin oxynitride film after the heat treatment as follows.
(7) Chemical resistance test
(1) Acid resistance test
It was immersed in 0.1 mol / L sulfuric acid for 2 hours.
(2) Alkali resistance test
It was immersed in a 0.1 mol / L aqueous sodium hydroxide solution for 2 hours.
(1) and (2) were carried out, and before and after each test, the transmittance and reflectance of visible light and solar energy were measured by the same method as described above, and the appearance was observed.
[0051]
Table 3 shows the results of optical characteristics.
The substrate with tin oxynitride film corresponding to the fourth and fifth embodiments of the present invention obtained by heat-treating the substrate with tin oxynitride film obtained by the second embodiment of the present invention has a visible light transmittance. It can be seen that while maintaining high, the solar energy transmittance is low and excellent heat ray reflectivity is exhibited.
In the evaluation of heat resistance, warpage was small and no cracks were generated. In the evaluation of scratch resistance, film peeling did not occur and the haze value was small. In the evaluation of chemical resistance, there was no change in transmittance, reflectance and appearance before and after the acid resistance test and alkali resistance test.
[0052]
[Table 3]
【The invention's effect】
The substrate with a tin oxynitride film of the present invention is excellent in heat ray reflectivity, radio wave permeability and heat resistance, can be bent or strengthened by heat treatment, and has a tin oxynitride film after the heat treatment of the present invention. Since the substrate is excellent in heat ray reflectivity, radio wave permeability and scratch resistance, it can be used for a wide range of applications, and particularly suitable for automotive glass.
Claims (7)
該酸窒化スズ膜が、Ｓｎ、ＯおよびＮの合計に対して、Ｎを２．７〜８．６ａｔ％含有することを特徴とする酸窒化スズ膜付き基体。A substrate with a tin oxynitride film having a transparent substrate and a tin oxynitride film laminated on one side of the transparent substrate,
A substrate with a tin oxynitride film, wherein the tin oxynitride film contains 2.7 to 8.6 at% of N with respect to the total of Sn, O, and N.
該反応性スパッタリング法が、金属スズをスパッタリングターゲットとして、酸素ガスと窒素原子を含むガスとを含有する混合ガスを用い、該窒素原子を含むガスの分圧を０．２〜０．４Ｐａとし、該酸素ガスの分圧の該窒素原子を含むガスの分圧に対する比を０．２〜１として行うことを特徴とする酸窒化スズ膜付き基体の製造方法。A method for producing a substrate with a tin oxynitride film having a transparent substrate and a tin oxynitride film laminated on one side of the transparent substrate by a reactive sputtering method,
The reactive sputtering method uses metal tin as a sputtering target, a mixed gas containing oxygen gas and a gas containing nitrogen atoms, and the partial pressure of the gas containing nitrogen atoms is 0.2 to 0.4 Pa, A method for producing a substrate with a tin oxynitride film, wherein the ratio of the partial pressure of the oxygen gas to the partial pressure of the gas containing nitrogen atoms is 0.2 to 1.
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| JPH02259062A (en) * | 1989-03-31 | 1990-10-19 | Matsushita Electric Ind Co Ltd | Production of thin oxide film |
| JP2811917B2 (en) * | 1990-06-05 | 1998-10-15 | 日本板硝子株式会社 | Heat shielding glass |
| JPH04243935A (en) * | 1991-01-30 | 1992-09-01 | Central Glass Co Ltd | Low electric wave-reflecting and thermal ray-reflecting glass and production thereof |
| JP2518129B2 (en) * | 1991-10-30 | 1996-07-24 | 旭硝子株式会社 | Heat-treated coated glass and method for producing the same |
| JPH0664940A (en) * | 1992-08-19 | 1994-03-08 | Central Glass Co Ltd | Electric ray-transmitting and heat ray-shielding glass |
| JPH07291668A (en) * | 1994-04-22 | 1995-11-07 | Central Glass Co Ltd | Electric wave transmission type heat ray-shielding glass |
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