JP4097908B2 - Manufacturing method of radio wave transmission wavelength selective membrane - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、透明基板、特に建造物、自動車などの窓ガラスに到来する電波、および可視光線を効率よく透過させることができるとともに、太陽の熱線を反射して充分な断熱性を発揮できる電波透過波長選択膜に関する。
【従来の技術】
近年、日射を遮蔽することを目的として、導電性薄膜を被覆したり、または導電性薄膜を含むフィルムを貼り付けた窓ガラスが普及し始めた。このような窓ガラスを高層ビルに施工するとＴＶ周波数帯域の電波を反射して、ＴＶ画面にゴーストを発生させる原因となるとともに室内アンテナで衛星放送を受信し難くなる。また、住宅用窓ガラス或いは自動車用窓ガラスとして用いた場合には、携帯電話が通じ難くなる可能性があったり、ガラスアンテナの利得が悪化したりする原因となり得る。
【０００３】
このような事情から現状では、ガラス基板に電気抵抗の比較的高い透明な熱線反射膜を被覆して、可視光線の透過を一部させるとともに、電波の反射を低減させて電波障害を防止することが行なわれている。また、導電性膜付きガラスの場合には、ガラス基板に被覆させた導電性膜を、入射電波の電界方向に平行な導電性膜の長さを電波の波長の１／２０倍以下になるように分割し、電波障害を防止することが特許第２６２０４５６号公報に示されている。
【０００４】
しかしながら、前記の電気抵抗の比較的高い透明な熱線反射膜を被覆する方法は、電波の反射を低減して電波障害を防止することは出来るが、熱線遮蔽性能が十分ではなく、生活の快適性において問題があった。また、特許第２６２０４５６号公報に示された導電性膜を分割する方法は、分割する長さが太陽光の大部分を占める可視光、近赤外光の波長より非常に大きいので、これらの光は全て反射してしまい、電波障害を防止し充分な日射遮蔽性能を有する電波透過性波長選択スクリーンガラスは得られるが、可視光の透過性が確保できないという問題がある。さらに、開口部のサイズが２ｍ×３ｍのように大きな窓では、例えば、衛星放送波を透過させるためには、衛星放送の波長約２５ｍｍの１／２０、少なくとも導電膜を１.２５ｍｍ平方に、好ましくは０.５ｍｍ平方に切断しなければならない。大面積の導電性膜をこのような小さいセグメントに、例えば、イットリウム−アルミニウム−ガーネットレーザで切断するには、長時間を要し現実的でない等の問題があった。
【０００５】
【発明が解決しようとする課題】
そこで本発明者等は、特開２０００−２８１３８８号公報に記載するように、ガラス基板表面、またはガラス基板上にＡｌＮ（窒化アルミ層）を被覆した表面に、スパッタリング法により連続層よりなるＡｇ層を成膜させたのち、熱処理することにより粒状のＡｇに変化生成させたＡｇ層を積層させた電波透過性波長選択ガラスについて出願した。さらに、特開２０００−３４４５４７公報に記載するように、加熱したガラス基板表面、またはガラス基板上にＡｌＮ（窒化アルミ層）を被覆した表面に、Ａｇを成膜することにより粒状のＡｇに変化生成させた電波透過性波長選択ガラスについて開発した。
【０００６】
ところが、更に研究を進めた結果、前記のガラス基板上にＡｌＮを被覆した表面に、Ａｇを成膜することにより粒状のＡｇに変化生成させる方法は、成膜の工程数が多いという不具合があった。
【０００７】
【課題を解決するための手段】
本発明者等は、このような事情に鑑みて鋭意研究した結果、窒化物とＡｇを混合した混合層を成膜したのち熱処理し、粒状のＡｇ層に変化生成させても良好な電波透過性波長選択膜が得られることが判明し、本発明をなすに至った。
【０００８】
すなわち、本発明の電波透過性波長選択膜は、透明基板上に形成された金属窒化物とＡｇの混合分散層と、その表面に生成された粒状のＡｇからなる複合層を少なくとも有することを特徴とする。
また、本発明の電波透過性波長選択膜は、混合分散層中のＡｇの濃度は、該混合分散層の表層側が大きいことを特徴とする。
【０００９】
さらに、本発明の電波透過性波長選択膜は、粒状のＡｇは、平均粒径が１００ｎｍ〜０．５ｍｍ、混合分散層の表面における占有面積率が０．２〜０．８の範囲であることを特徴とする。
【００１０】
さらにまた、本発明の電波透過性波長選択膜は、前記電波透過性波長選択膜の光線反射率は、波長が６００ｎｍ〜１５００ｎｍの範囲において最大値を有することを特徴とする。
【００１１】
またさらに、本発明の電波透過性波長選択膜は、前記複合層の下層および／または上層に誘電体層を設けたことを特徴とする。
【００１２】
さらに、本発明の電波透過性波長選択膜は、式（１）で定義する近赤外域の遮蔽率（Ｅｓ）が０.３以上であることを特徴とする。
【００１３】
【式２】
ここで、λ ： 透明基板（膜面側）に入射する電磁波の波長
Ｒdp： 波長λにおける透明基板（膜面側）の反射率
Ｉsr： 波長λにおけるエアーマス１.０における太陽の放射強度
さらに、本発明の電波透過性波長選択膜は、混合分散層の空孔率が０．０１〜０．５であることを特徴とする。
【００１５】
本発明の透明基板上に形成された金属窒化物とＡｇの混合分散層と、その表面に生成された粒状のＡｇからなる複合層を少なくとも有する電波透過性波長選択膜の製法は、透明基板上に金属窒化物とＡｇとが混合されてなる混合層を成膜したのち、該膜を熱処理をすることにより、金属窒化物とＡｇの混合分散層と、その表面に生成された粒状のＡｇからなる複合層を形成してなることを特徴とする。
【００１６】
さらに、本発明の電波透過性波長選択膜の製法は、式（２）で定義する前記混合層におけるＡｇの体積含有量（Ｖag）は、０.５以下であることを特徴とする。
【００１７】
【式３】
ここで、Ｗag： 透明基板１ｍ2 当たりに積層されたＡｇの重量
Ｗn ： 透明基板１ｍ2 当たりに積層された金属窒化物の重量
ρag： Ａgバルクの密度 （単位：ｋｇ／ｍ3）
ρn ： 金属窒化物バルクの密度（単位：ｋｇ／ｍ3）
さらにまた、本発明の電波透過性波長選択膜の製法は、前記混合層を成膜した後の熱処理における加熱方法は、抵抗加熱、ガス燃焼加熱、レーザまたは電子線などのビームの照射、または誘導加熱の内の少なくとも１種を用いることを特徴とする。
【００２０】
【発明の実施の形態】
本発明の電波透過性波長選択膜は、透明基板上に形成された金属窒化物とＡｇの混合分散層と、その表面に生成された粒状のＡｇからなる複合層を少なくとも有することを特徴とする。
【００２１】
本発明の金属窒化物層は、Ａｌ、Ｓｉ、Ｔｉ、Ｔａの金属の内の少なくとも１種よりなる窒化物が好ましく、これらの窒化物とＡｇを混合した混合層を成膜したのち、熱処理することにより、金属窒化物とＡｇの混合分散層と、その表面に生成された粒状のＡｇからなる複合層を形成させることができる。
【００２２】
本発明の電波透過性波長選択膜は、前記複合層の下層及び／または上層に誘電体層を設けることが好ましい。この誘電体層としては、Ａｌ、Ｓｉ、Ｔｉ、Ｔａ、Ｇｅ、Ｉｎ、Ｗ、Ｖ、Ｍｎ、Ｃｒ、Ｎｉ、ステンレスのいずれかの窒化物、Ａｌ、Ｓｉ、Ｚｎ、Ｓｎ、Ｔｉ、Ｔａ、Ｇｅ、Ｉｎ、Ｗ、Ｖ、Ｍｎ、Ｃｒ、Ｎｉ、ステンレスのいずれかの酸化物、およびこれらを多層に積層したもの等を用いることができる。特に、Ａｌ、Ｓｉの窒化物、Ａｌ、Ｓｉ、Ｚｎ、Ｓｎ、Ｔｉ、Ｔａ、Ｉｎの酸化物は無色透明であるので、可視光透過率の高い電波透過性波長選択膜を必要とする建築用、車輌用窓ガラスに適している。なお、粒状のＡｇを表面に生成させた複合層上に、さらに誘電体層を被覆すると、透明基板上に成膜した誘電体層との相互作用によって可視光透過率を高められるとともに複合層の保護膜として作用するので好ましい。この場合には、誘電体層としてＡｌ、Ｓｉの窒化物、Ａｌ、Ｓｉ、Ｚｎ、Ｓｎ、Ｔｉ、Ｔａ、Ｉｎの酸化物または、これらを多層に積層したものが望ましい。
【００２３】
また、本発明の電波透過性波長選択膜は、式（１）で定義した近赤外域の遮蔽率（Ｅｓ）が０．３以上であることが好ましく、この特性を有する電波透過性波長選択膜を得るには、選択膜の反射率が６００ｎｍ〜１５００ｎｍの波長範囲で最大となるように混合分散層の表面に生成する粒状のＡｇの粒径を制御する必要がある。この目的に適合する粒状のＡｇの平均粒径は１００ｎｍ以上、占有面積率は０．２以上であることが好ましい。なお、粒状のＡｇの占有面積率とは、Ａｇ微粒子の外部形態を法線方向から電界放射型走査電子顕微鏡（ＦＥ−ＳＥＭ）で観察した像をＡｇ微粒子とそうでない背景部とに２値化して、Ａｇ微粒子の総面積を求め、ＳＥＭ画像全体の面積で除した値を示す。ここでいう２値化は、Ａｇ微粒子を白色、マトリックスを黒色に塗り分けて画像処理を行なう。
【００２４】
粒状のＡｇの占有面積率が０．２以下になると、粒状Ａｇ間の平均距離が粒径の２倍以上になり、粒子間の相互干渉が小さくなり、単独で粒子が存在している状態に近づく。そのため、光線反射率は占有面積率程度となり、反射率がたとえ６００ｎｍ〜１５００ｎｍの波長範囲で最大となっても、目標の近赤外線遮蔽率が得られない。粒状のＡｇの平均粒径が１００ｎｍ以下であると、いかなる占有面積率に対しても反射率が最大となる波長は６００ｎｍ以下となる。
【００２５】
一方、銀粒子の粒径は０.５ｍｍ以下が望ましい。その理由は、本発明者等が出願した特開２０００−２８１３８８号公報に記したように、粒径が０.５ｍｍ以上になると現在使用されている放送波の内、最も波長の短い衛星放送波の波長の１／２０以上になり、電波障害が問題となる（特許登録番号２６２０４５６参照）。
【００２６】
さらに、式（２）で定義した窒化物とＡｇを混合したＡｇの体積含有量（Ｖag）は、０.５以下であることが好ましい。この値が大きいほど平均粒径は大きくなるが、０.５を越えると粒状のＡｇが生成し難くなる。粒子の生成過程を知るために、Ａｇ体積含有量０．２５の試料について日本電子製ＪＡＭＰ−３０型オージェ電子分光法で膜表面から内部方向のＡｇ元素の分布を測定した。その結果、熱処理前の試料ではＡｇの濃度は深さ方向にほぼ一定で、均質であったが、熱処理後の試料ではＡｇの濃度は、混合分散層の表層側が大きく表面で極大となった。また、熱処理前の試料の比抵抗はＡｇの１００倍以上であった。これらのことから、混合層中におけるＡｇは、金属窒化物の三次元骨格で遮られて連続膜ではなく、クラスター状に存在している。このＡｇが金属窒化物の三次元骨格の隙間を拡散して、表層でＡｇ微粒子を生成したものと推定できる。
【００２７】
したがって、特開２０００−２８１３８８号公報に記載したＡｇ単層膜（連続膜）を熱処理して粒状Ａｇを生成させる方法に比べて本発明の窒化物とＡｇを混合した連続層を熱処理して粒状Ａｇを生成させる方法は少ないエネルギーで同様の構造の電波透過性波長選択膜を作製することができる。混合層におけるＡｇの一部が連続膜を形成するようなＡｇ体積含有量０.５以上では、熱処理後に粒状のＡｇが生成し難くなることが上記の実験結果から明らかである。
なお、１ｍ2 当たりに最低必要なＡｇ量は、３０ｍｇ／ｍ2〜５００ｍｇ／ｍ2の範囲とすることが好ましい。
【００２８】
金属窒化物とＡｇの混合分散層とその表面に生成された粒状のＡｇからなる窒化物と銀の複合層は、透明基板表面に直接被覆しても構わないし、透明基板の表面に誘電体層を被覆させた表面に該複合層を積層することもできる。なお、透明基板としては、ガラス基板、透明セラミック基板、耐熱性透明プラスチック等を用いることができ、目的に応じて適宜選択し得る。
【００２９】
得られた波長選択膜は、ＴＶ放送、衛星放送、携帯電話それぞれの周波数帯域の電波に対して反射率を低減させて、電波障害を防止するとともに、充分な日射遮蔽性能と可視光線透過性を有する電波透過性波長選択膜であり、前記基板表面に被覆することで、建築用窓ガラス、自動車用窓ガラス用等に用いることができる。
【００３０】
金属窒化物とＡｇの混合層、誘電体層を成膜する方法については、特に限定するものではなく、スパッタリング法、真空蒸着法、ＣＶＤ法、イオンプレーティング等の成膜法を用いて、金属窒化物の膜を常法で形成する際にＡｇをターゲット材として付加するなどの手段により成膜することが可能であるが、特に、ＤＣマグネトロンスパッタリング法は生成する層の均一性、生産性の点より好ましい。
【００３１】
また、成膜したのち熱処理を行うことにより、混合層中のＡｇは、窒化物層の表層に粒子状のＡｇを生成する。この粒径は、前記した０.５ｍｍより小さく、また、Ａｇ膜の厚み、熱処理条件などを制御することにより、近赤外線を選択的に反射する膜が得られる。なお、熱処理を行う加熱方法としては、抵抗加熱、ガス燃焼加熱、レーザまたは電子線などのビームの照射、または誘導加熱等を適宜用いることが可能である。そのうち、前記混合層には吸収されるが、基板とは相互作用のないレーザビームを短時間照射して熱処理を行うと、基板はほとんど加熱されないので、耐熱性透明プラスチックを基板とする系に対しては特に適している。また、導電性物質のみを選択的に加熱できる誘導加熱も同様である。
【００３２】
なお、熱処理条件については、熱処理温度は１５０℃以上で、抵抗加熱、ガス燃焼加熱の場合、透明基板が劣化しない温度以下とすることが好ましい。また、レーザまたは電子線などのビームの照射、または誘導加熱の場合の熱処理温度の上限は、Ａｇの沸点２２１２℃である。また、熱処理時間は、抵抗加熱、ガス燃焼加熱の場合、数秒から数時間、レーザまたは電子線などのビームの照射、または誘導加熱の場合、マイクロ秒から数秒とすることが好ましい。
【００３３】
また、Ａｇは紫外線領域にプラズマ振動数が存在し、さらに、この周波数の低周波数側に「銀の窓」と呼ばれるＡｇの消衰係数が無限小になる領域があるので、Ａｇ粒子の厚みと誘電体層膜の膜厚を制御すれば、可視光の透過性が確保できる。
【００３４】
【実施例】
以下、本発明の実施例を述べる。但し、本発明は、これに限定するものではない。
【００３５】
実施例１
本発明の電波透過性波長選択膜付きガラスは次に示す手順で製造した。
（１）洗浄した厚さ３ｍｍのフロートガラス板をＤＣマグネトロンスパッタリング装置内に入れ、槽内の真空度が２〜４×１０-4Ｐａに達するまで排気した。なお、ターゲット−ガラス基板間の距離は９０ｍｍに固定した。
（２）純Ａｌターゲット（直径１２９ｍｍ、厚み１０ｍｍ）のエロージョン域にＡｇチップ（１０ｍｍ×１０ｍｍ×１ｍｍの直方体）４個を等間隔に載置した。このターゲットにＤＣ２００Ｗを印加して放電させ、反応性スパッタで膜厚２００ｎｍのＡｌＮ−Ａｇ混合層を作製した。なお、異常放電を防止するために、周波数１０ｋＨｚの矩形パルス波をカソードに印加した。スパッタリング中、Ｎ2／Ａｒ混合ガスのガス流量比を２０／７に、圧力を１Ｐａに制御した。
（３）混合層を被覆した試料を雰囲気温度５００℃の恒温炉で５分間加熱し、金属窒化物とＡｇの混合分散層と、その表面に生成された粒状のＡｇからなる複合層を有する電波透過性波長選択膜付きガラスを作製した。
【００３６】
このようにして得られた電波透過性波長選択膜付きガラスの反射率を日立製作所製Ｕ−４０００型自記分光光度計を用いて波長３００〜２５００ｎｍの範囲で測定したところ、９００ｎｍで最大となった。測定値を式（１）に代入して算出した近赤外域の遮蔽率は０．５７となり、高い波長選択性を有するものが得られた。
【００３７】
生成したＡｇ微粒子の外部形態をＦＥ−ＳＥＭ（日立製作所製Ｓ−４５００）で法線方向から観察し、画像処理によって求めたＡｇ占有面積率、平均粒径は、それぞれ０．５１、２４３ｎｍであった。また、（２）の工程で得られた膜に含まれる金属Ａｇ、Ａｌの重量を原子吸光法で求め、測定値を式（２）に代入してＡｇ体積含有量を求めたところ、０．３５であった。
【００３８】
実施例２
実施例１と同様にしてＡｌＮ−Ａｇ混合層を作製した。なお、純Ａｌターゲットのエロージョン域に載置したＡｇチップの形状は８．７ｍｍ×８．７ｍｍ×１ｍｍの直方体で、載置数は実施例１と同様４個である。実施例１と同一の条件で混合層を熱処理して金属窒化物とＡｇの混合分散層と、その表面に生成された粒状のＡｇからなる複合層を有する電波透過性波長選択膜付きガラスを作製した。
【００３９】
このようにして得られた電波透過性波長選択膜付きガラスの反射率を波長３００〜２５００ｎｍの範囲で測定したところ、６９０ｎｍで最大となった。近赤外域の遮蔽率は０．４０、Ａｇ占有面積率は０．５１、平均粒径は２０６ｎｍであった。また、（２）の工程で得られた層のＡｇ体積含有量率は０．２５であった。
【００４０】
実施例３
実施例１と同一条件で成膜したＡｌＮ−Ａｇ混合層にＹＡＧレーザを照射して熱処理を行ったところ、窒化物層の表層に、ほぼ真円で、粒径の揃った粒状のＡｇが生成した複合層を有する電波透過性波長選択膜付きガラスが得られた。この膜の反射率は７３０ｎｍで最大となり、分光曲線は上に凸のシャープな形となった。遮蔽率は０．５１、Ａｇ占有面積率は０．５２、面積平均粒径は２７４ｎｍであった。なお、レーザ照射方法と条件を以下に示す。（１）混合膜を積層した基板をＸ−Ｙテーブルに固定し、レーザ照射中、テーブルを２００ｍｍ／秒の速度でＸ軸方向で往復させ、Ｙ軸方向のピッチを１０ｍｍに設定した。（２）東芝製ＹＡＧレーザ（ＬＡＹ−６１６Ｃ）で発振した波長１．０６μｍのレーザビームをコリメータなどの光学系で１０ｍｍ程度に広げて、垂直（法線）方向から試料に照射した。
【００４１】
比較例１
Ａｌターゲットのエロージョン域に載置するＡｇチップの数を調整してＡｇ体積含有量が０．６の混合膜を作製し、恒温炉で加熱したところ、遮蔽率０．０３であった。
【００４２】
遮蔽率が低くなる原因は、熱処理過程でＡｌＮが三次元マトリックスを形成できなかったため、Ａｇが表層に拡散して微粒子を生成するのを阻害したと考えられる。
【００４３】
【発明の効果】
本発明により得られた電波透過性波長選択膜は、ＴＶ放送、衛星放送、携帯電話それぞれの周波数帯域の電波に対して反射率を低減させるとともに、充分な日射遮蔽性能と可視光線透過性を有するので、ＴＶ画面にゴーストを発生させたり、携帯電話が通じなくなったり、或いはガラスアンテナの利得が悪くなったり等の電波障害がなく、且つ日射を充分に遮蔽される等快適な生活環境を提供することが可能である等の著効を有するので、特に自動車用窓ガラス、建築用窓ガラスとして好適である。[0001]
BACKGROUND OF THE INVENTION
The present invention is capable of efficiently transmitting radio waves coming to transparent substrates, particularly window glass of buildings, automobiles, and the like, and visible light, and also capable of exhibiting sufficient heat insulation by reflecting solar heat rays. The present invention relates to a wavelength selective film.
[Prior art]
In recent years, for the purpose of shielding solar radiation, window glass coated with a conductive thin film or attached with a film containing the conductive thin film has begun to spread. If such a window glass is installed in a high-rise building, it will cause radio waves in the TV frequency band to be reflected and cause ghost on the TV screen, and it will be difficult to receive satellite broadcasts with the indoor antenna. In addition, when used as a window glass for a house or a window glass for an automobile, there is a possibility that the mobile phone may become difficult to communicate, or the gain of the glass antenna may be deteriorated.
[0003]
Under such circumstances, at present, the glass substrate is covered with a transparent heat ray reflective film having a relatively high electrical resistance to partially transmit visible light and to reduce radio wave reflection to prevent radio interference. Has been done. In the case of glass with a conductive film, the length of the conductive film parallel to the direction of the electric field of the incident radio wave is 1/20 times or less the wavelength of the radio wave. Japanese Patent No. 2620456 discloses that it is divided into two parts to prevent radio interference.
[0004]
However, the method of coating a transparent heat ray reflective film having a relatively high electrical resistance can reduce radio wave reflection and prevent radio wave interference, but the heat ray shielding performance is not sufficient, and the comfort of life. There was a problem. In addition, the method of dividing the conductive film disclosed in Japanese Patent No. 2620456 is much longer than the wavelength of visible light and near infrared light that occupy most of sunlight, so that these light beams are divided. However, there is a problem in that visible light transmittance cannot be secured, although a radio wave transmissive wavelength selection screen glass having sufficient solar radiation shielding performance and preventing radio wave interference can be obtained. Furthermore, in a large window such as the size of the opening of 2 m × 3 m, for example, in order to transmit satellite broadcast waves, 1/20 of the wavelength of satellite broadcast is about 1/20, at least the conductive film is 1.25 mm square, Preferably it must be cut to 0.5 mm square. In order to cut a large-area conductive film into such small segments with, for example, an yttrium-aluminum-garnet laser, there is a problem that it takes a long time and is not practical.
[0005]
[Problems to be solved by the invention]
Therefore, as described in Japanese Patent Application Laid-Open No. 2000-281388, the present inventors have made an Ag layer made of a continuous layer by a sputtering method on a glass substrate surface or a surface coated with AlN (aluminum nitride layer) on a glass substrate. After the film was formed, an application was made for a radio wave-transmitting wavelength-selective glass in which an Ag layer changed into granular Ag by heat treatment was laminated. Furthermore, as described in JP-A-2000-344547, the Ag is formed on the surface of the heated glass substrate or the surface coated with AlN (aluminum nitride layer) on the glass substrate, thereby changing to granular Ag. We developed a radio wave transmitting wavelength selective glass.
[0006]
However, as a result of further research, the method of changing and generating granular Ag by forming Ag on the surface of the glass substrate coated with AlN has a problem that the number of film forming steps is large. It was.
[0007]
[Means for Solving the Problems]
As a result of intensive studies in view of such circumstances, the present inventors have formed a mixed layer of nitride and Ag, and then heat-treated to form a granular Ag layer. It has been found that a wavelength selective film can be obtained, and the present invention has been made.
[0008]
That is, the radio wave transmission wavelength selective film of the present invention has at least a mixed dispersion layer of metal nitride and Ag formed on a transparent substrate, and a composite layer made of granular Ag formed on the surface thereof. And
The radio wave transmission wavelength selective film of the present invention is characterized in that the concentration of Ag in the mixed dispersion layer is large on the surface layer side of the mixed dispersion layer.
[0009]
Further, in the radio wave transmitting wavelength selective film of the present invention, the granular Ag has an average particle diameter of 100 nm to 0.5 mm and an occupation area ratio on the surface of the mixed dispersion layer of 0.2 to 0.8. It is characterized by.
[0010]
Furthermore, the radio wave transmission wavelength selection film according to the present invention is characterized in that the light wave reflectance of the radio wave transmission wavelength selection film has a maximum value in a wavelength range of 600 nm to 1500 nm.
[0011]
Furthermore, the radio wave transmission wavelength selection film of the present invention is characterized in that a dielectric layer is provided in a lower layer and / or an upper layer of the composite layer.
[0012]
Furthermore, the radio wave transmitting wavelength selective film of the present invention is characterized in that the near-infrared shielding rate (Es) defined by the formula (1) is 0.3 or more.
[0013]
[ Formula 2 ]
Where λ: wavelength of the electromagnetic wave incident on the transparent substrate (film surface side) Rdp: reflectance of the transparent substrate (film surface side) at wavelength λ Isr: solar radiation intensity at air mass 1.0 at wavelength λ The radio wave transmission wavelength selective membrane of the invention is characterized in that the mixed dispersion layer has a porosity of 0.01 to 0.5.
[0015]
A method for producing a radio wave transmission wavelength selective film having at least a composite layer composed of a mixed layer of metal nitride and Ag formed on a transparent substrate of the present invention and granular Ag formed on the surface thereof is provided on the transparent substrate. After forming a mixed layer in which the metal nitride and Ag are mixed together, the film is subjected to a heat treatment, so that the mixed dispersion layer of the metal nitride and Ag and the granular Ag generated on the surface thereof are formed. It is characterized by forming a composite layer.
[0016]
Furthermore, the method for producing a radio wave transmitting wavelength selective film of the present invention is characterized in that the volume content (Vag) of Ag in the mixed layer defined by the formula (2) is 0.5 or less.
[0017]
[ Formula 3 ]
Here, Wag: transparent substrate 1m 2 hit the layered the Ag Weight Wn: the weight of the transparent substrate 1m metal nitride stacked per 2 ρag: Ag bulk density (unit: kg / m 3)
ρn: density of metal nitride bulk (unit: kg / m 3 )
Furthermore, in the method for producing a radio wave transmissive wavelength selective film of the present invention, the heating method in the heat treatment after forming the mixed layer is resistance heating, gas combustion heating, irradiation of a beam such as a laser or an electron beam, or induction. It is characterized by using at least one of heating.
[0020]
DETAILED DESCRIPTION OF THE INVENTION
The radio wave transmissive wavelength selective film of the present invention has at least a mixed dispersion layer of metal nitride and Ag formed on a transparent substrate, and a composite layer made of granular Ag formed on the surface thereof. .
[0021]
The metal nitride layer of the present invention is preferably a nitride composed of at least one of Al, Si, Ti, and Ta metals, and a heat treatment is performed after forming a mixed layer in which these nitrides and Ag are mixed. Thus, a composite dispersion layer composed of a mixed dispersion layer of metal nitride and Ag and granular Ag generated on the surface thereof can be formed.
[0022]
In the radio wave transmitting wavelength selective film of the present invention, it is preferable to provide a dielectric layer in the lower layer and / or the upper layer of the composite layer. As this dielectric layer, Al, Si, Ti, Ta, Ge, In, W, V, Mn, Cr, Ni, any nitride of stainless steel, Al, Si, Zn, Sn, Ti, Ta, Ge , In, W, V, Mn, Cr, Ni, stainless steel, and those obtained by stacking these in multiple layers can be used. In particular, since nitrides of Al and Si and oxides of Al, Si, Zn, Sn, Ti, Ta, and In are colorless and transparent, they require a radio wave-transmitting wavelength selective film having high visible light transmittance. Suitable for vehicle window glass. In addition, when a dielectric layer is further coated on the composite layer in which granular Ag is formed on the surface, the visible light transmittance can be increased by interaction with the dielectric layer formed on the transparent substrate, and the composite layer Since it acts as a protective film, it is preferable. In this case, the dielectric layer is preferably Al, Si nitride, Al, Si, Zn, Sn, Ti, Ta, In oxide, or a laminate of these.
[0023]
In addition, the radio wave transmission wavelength selection film of the present invention preferably has a near-infrared shielding rate (Es) defined by the formula (1) of 0.3 or more, and the radio wave transmission wavelength selection film having this characteristic. In order to obtain the above, it is necessary to control the particle size of the granular Ag generated on the surface of the mixed dispersion layer so that the reflectance of the selective film becomes maximum in the wavelength range of 600 nm to 1500 nm. The average particle diameter of granular Ag suitable for this purpose is preferably 100 nm or more and the occupied area ratio is preferably 0.2 or more. Note that the occupied area ratio of the granular Ag is binarized from an image obtained by observing the external form of the Ag fine particles with a field emission scanning electron microscope (FE-SEM) from the normal direction to the Ag fine particles and the background portion that is not. Then, the total area of the Ag fine particles is obtained, and a value obtained by dividing by the area of the entire SEM image is shown. In this binarization, image processing is performed by separately coating Ag fine particles in white and matrix in black.
[0024]
When the occupied area ratio of granular Ag becomes 0.2 or less, the average distance between granular Ag becomes twice or more of the particle diameter, the mutual interference between the particles becomes small, and the particles exist alone. Get closer. Therefore, the light reflectance is about the occupied area ratio, and even if the reflectance is maximum in the wavelength range of 600 nm to 1500 nm, the target near-infrared shielding ratio cannot be obtained. When the average particle diameter of the granular Ag is 100 nm or less, the wavelength at which the reflectance is maximum for any occupied area ratio is 600 nm or less.
[0025]
On the other hand, the particle size of the silver particles is desirably 0.5 mm or less. The reason for this is that, as described in Japanese Patent Application Laid-Open No. 2000-281388, filed by the present inventors, a satellite broadcast wave having the shortest wavelength among the currently used broadcast waves when the particle size becomes 0.5 mm or more. The wavelength becomes 1/20 or more, and radio wave interference becomes a problem (see Patent Registration No. 2620456).
[0026]
Furthermore, the volume content (Vag) of Ag obtained by mixing the nitride defined by the formula (2) and Ag is preferably 0.5 or less. The larger the value, the larger the average particle diameter, but when it exceeds 0.5, it becomes difficult to form granular Ag. In order to know the formation process of the particles, the distribution of Ag element in the internal direction from the film surface was measured with a JAMP-30 type Auger electron spectroscopy made by JEOL on a sample with an Ag volume content of 0.25. As a result, in the sample before the heat treatment, the Ag concentration was almost constant in the depth direction and uniform, but in the sample after the heat treatment, the Ag concentration was large on the surface layer side of the mixed dispersion layer and maximized on the surface. The specific resistance of the sample before the heat treatment was 100 times or more of Ag. From these facts, Ag in the mixed layer is interrupted by the three-dimensional skeleton of the metal nitride and is present in a cluster rather than a continuous film. It can be presumed that this Ag diffused through the gaps in the three-dimensional skeleton of the metal nitride and produced Ag fine particles on the surface layer.
[0027]
Therefore, the continuous layer obtained by mixing the nitride of the present invention and Ag is heat-treated compared to the method in which the Ag single-layer film (continuous film) described in JP 2000-281388 A is heat-treated to produce granular Ag. The method of generating Ag can produce a radio wave transmissive wavelength selective film having the same structure with less energy. From the above experimental results, it is clear that when the Ag volume content is 0.5 or more so that a part of Ag in the mixed layer forms a continuous film, it is difficult to form granular Ag after heat treatment.
Note that minimum required amount of Ag per 1 m 2 is preferably in the range of 30mg / m 2 ~500mg / m 2 .
[0028]
The mixed dispersion layer of metal nitride and Ag and the composite layer of nitride and silver made of granular Ag formed on the surface thereof may be directly coated on the surface of the transparent substrate, or the dielectric layer on the surface of the transparent substrate. The composite layer can also be laminated on the surface coated with. In addition, as a transparent substrate, a glass substrate, a transparent ceramic substrate, a heat resistant transparent plastic, etc. can be used, and it can select suitably according to the objective.
[0029]
The obtained wavelength selective film reduces the reflectivity for radio waves in each frequency band of TV broadcast, satellite broadcast, and mobile phone to prevent radio wave interference and provide sufficient solar radiation shielding performance and visible light transmittance. It has a radio wave transmission wavelength selection film, and can be used for architectural window glass, automobile window glass and the like by covering the substrate surface.
[0030]
The method for forming a mixed layer of metal nitride and Ag and a dielectric layer is not particularly limited, and a metal film formed by sputtering, vacuum deposition, CVD, ion plating, or the like can be used. It is possible to form a nitride film by means such as adding Ag as a target material when forming a nitride film by a conventional method. In particular, the DC magnetron sputtering method has the uniformity and productivity of a layer to be produced. It is more preferable than the point.
[0031]
Further, by performing heat treatment after film formation, Ag in the mixed layer generates particulate Ag in the surface layer of the nitride layer. The particle diameter is smaller than 0.5 mm, and a film that selectively reflects near infrared rays can be obtained by controlling the thickness of the Ag film, heat treatment conditions, and the like. Note that as a heating method for performing the heat treatment, resistance heating, gas combustion heating, irradiation with a beam such as a laser or an electron beam, induction heating, or the like can be used as appropriate. Among them, when the heat treatment is carried out by irradiating the mixed layer with a laser beam that does not interact with the substrate for a short time, the substrate is hardly heated. Is particularly suitable. The same applies to induction heating in which only a conductive substance can be selectively heated.
[0032]
Regarding the heat treatment conditions, the heat treatment temperature is preferably 150 ° C. or more, and in the case of resistance heating or gas combustion heating, it is preferable to set the temperature to a temperature at which the transparent substrate does not deteriorate. In addition, the upper limit of the heat treatment temperature in the case of irradiation with a beam such as a laser or an electron beam or induction heating is a boiling point of 2212 ° C. of Ag. In addition, the heat treatment time is preferably several seconds to several hours in the case of resistance heating and gas combustion heating, and is preferably from microseconds to several seconds in the case of irradiation with a beam such as a laser or an electron beam or induction heating.
[0033]
Further, Ag has a plasma frequency in the ultraviolet region, and there is a region called “silver window” where the extinction coefficient of Ag is infinitesimal on the low frequency side of this frequency. By controlling the film thickness of the dielectric layer film, it is possible to ensure visible light transmission.
[0034]
【Example】
Examples of the present invention will be described below. However, the present invention is not limited to this.
[0035]
Example 1
The glass with a radio wave transmitting wavelength selective film of the present invention was produced by the following procedure.
(1) The washed 3 mm thick float glass plate was put in a DC magnetron sputtering apparatus and evacuated until the degree of vacuum in the tank reached 2-4 × 10 −4 Pa. The distance between the target and the glass substrate was fixed at 90 mm.
(2) Four Ag chips (10 mm × 10 mm × 1 mm rectangular parallelepiped) were placed at equal intervals in the erosion region of a pure Al target (diameter 129 mm, thickness 10 mm). The target was discharged by applying DC 200 W, and an AlN-Ag mixed layer having a thickness of 200 nm was formed by reactive sputtering. In order to prevent abnormal discharge, a rectangular pulse wave with a frequency of 10 kHz was applied to the cathode. During sputtering, the gas flow rate ratio of N 2 / Ar mixed gas was controlled to 20/7, and the pressure was controlled to 1 Pa.
(3) A sample coated with a mixed layer is heated for 5 minutes in a constant temperature furnace having an atmospheric temperature of 500 ° C., and a radio wave having a mixed dispersion layer of metal nitride and Ag and a composite layer made of granular Ag formed on the surface thereof. A glass with a transparent wavelength selective film was prepared.
[0036]
The reflectance of the glass with a radio wave transmitting wavelength selective film thus obtained was measured in the wavelength range of 300 to 2500 nm using a Hitachi U-4000 type self-recording spectrophotometer. . The near-infrared shielding rate calculated by substituting the measured value into Equation (1) was 0.57, and a high wavelength selectivity was obtained.
[0037]
The external form of the generated Ag fine particles was observed with a FE-SEM (S-4500 manufactured by Hitachi, Ltd.) from the normal direction, and the Ag occupation area ratio and the average particle diameter obtained by image processing were 0.51 and 243 nm, respectively. It was. Further, the weight of the metal Ag and Al contained in the film obtained in the step (2) was determined by atomic absorption method, and the measured value was substituted into the equation (2) to determine the Ag volume content. 35.
[0038]
Example 2
In the same manner as in Example 1, an AlN-Ag mixed layer was produced. The shape of the Ag chip placed in the erosion area of the pure Al target is a cuboid of 8.7 mm × 8.7 mm × 1 mm, and the number of placement is four as in the first embodiment. The mixed layer is heat-treated under the same conditions as in Example 1 to produce a glass with a radio wave-transmitting wavelength selective film having a mixed dispersion layer of metal nitride and Ag and a composite layer made of granular Ag formed on the surface of the mixed layer. did.
[0039]
When the reflectance of the glass with a radio wave transmitting wavelength selective film thus obtained was measured in the wavelength range of 300 to 2500 nm, it was maximum at 690 nm. The shielding ratio in the near infrared region was 0.40, the Ag occupation area ratio was 0.51, and the average particle size was 206 nm. Moreover, Ag volume content rate of the layer obtained at the process of (2) was 0.25.
[0040]
Example 3
When an AlN-Ag mixed layer formed under the same conditions as in Example 1 was subjected to heat treatment by irradiating a YAG laser, granular Ag with a uniform particle size was formed on the surface of the nitride layer. Thus, a glass with a radio wave-transmitting wavelength selective film having a composite layer was obtained. The reflectance of this film was maximum at 730 nm, and the spectral curve had a sharp shape that was convex upward. The shielding ratio was 0.51, the Ag occupation area ratio was 0.52, and the area average particle diameter was 274 nm. The laser irradiation method and conditions are shown below. (1) The substrate on which the mixed film was laminated was fixed to an XY table, and during laser irradiation, the table was reciprocated in the X-axis direction at a speed of 200 mm / second, and the pitch in the Y-axis direction was set to 10 mm. (2) A laser beam with a wavelength of 1.06 μm oscillated by a YAG laser (LAY-616C) manufactured by Toshiba was expanded to about 10 mm by an optical system such as a collimator, and the sample was irradiated from the vertical (normal) direction.
[0041]
Comparative Example 1
When the number of Ag chips placed in the erosion region of the Al target was adjusted to produce a mixed film with an Ag volume content of 0.6 and heated in a constant temperature furnace, the shielding rate was 0.03.
[0042]
The reason for the low shielding rate is considered that AlN was unable to form a three-dimensional matrix during the heat treatment process, and therefore, Ag was prevented from diffusing into the surface layer to form fine particles.
[0043]
【The invention's effect】
The radio wave transmissive wavelength selective film obtained by the present invention reduces the reflectance with respect to radio waves in the frequency bands of TV broadcast, satellite broadcast, and mobile phone, and has sufficient solar radiation shielding performance and visible light transmittance. Therefore, there is no radio wave interference such as ghosting on the TV screen, cellular phone becoming inaccessible, or the gain of the glass antenna being deteriorated, and providing a comfortable living environment that is sufficiently shielded from sunlight. Therefore, it is particularly suitable as an automotive window glass and an architectural window glass.
Claims (3)
【式１】
Ｗn ： 透明基板１ｍ2 当たりに積層された金属窒化物の重量
ρag： Ａgバルクの密度 （単位：ｋｇ／ｍ3）
ρn ： 金属窒化物バルクの密度（単位：ｋｇ／ｍ3）The volume content of Ag before the heat treatment in the mixed layer (Vag) is preparation of a radio wave transmitting wavelength selective film of claim 1, wherein a is 0.5 or less defined in formula (2).
[Formula 1]
ρn: density of metal nitride bulk (unit: kg / m 3 )
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001132236A JP4097908B2 (en) | 2001-04-27 | 2001-04-27 | Manufacturing method of radio wave transmission wavelength selective membrane |
| US10/128,516 US6673462B2 (en) | 2001-04-27 | 2002-04-24 | Frequency selective plate and method for producing same |
| DE60208258T DE60208258T2 (en) | 2001-04-27 | 2002-04-26 | Frequency-selective plate and method for its production |
| EP02009575A EP1254871B1 (en) | 2001-04-27 | 2002-04-26 | Frequency selective plate and method for producing same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001132236A JP4097908B2 (en) | 2001-04-27 | 2001-04-27 | Manufacturing method of radio wave transmission wavelength selective membrane |
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| JP2002328220A JP2002328220A (en) | 2002-11-15 |
| JP4097908B2 true JP4097908B2 (en) | 2008-06-11 |
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| JP2001132236A Expired - Fee Related JP4097908B2 (en) | 2001-04-27 | 2001-04-27 | Manufacturing method of radio wave transmission wavelength selective membrane |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1058681C (en) * | 1996-03-21 | 2000-11-22 | 中国石油化工总公司石油化工科学研究院 | Process of producing fine-grain model. A zeolite |
| RU2448197C1 (en) * | 2011-04-05 | 2012-04-20 | Российская Федерация, от имени которой выступает Министерство промышленности и торговли Российской Федерации (Минпромторг России) | Application method of transparent electrically conducting coating |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4371690B2 (en) * | 2003-04-11 | 2009-11-25 | セントラル硝子株式会社 | Radio wave transmissive wavelength selective plate and method for producing the same |
| FR2950878B1 (en) * | 2009-10-01 | 2011-10-21 | Saint Gobain | THIN LAYER DEPOSITION METHOD |
| FR2969391B1 (en) * | 2010-12-17 | 2013-07-05 | Saint Gobain | METHOD FOR MANUFACTURING OLED DEVICE |
| CN115233159B (en) * | 2022-08-05 | 2023-11-17 | 中国科学院光电技术研究所 | Silver film with low roughness and controllable dielectric constant and preparation method thereof |
-
2001
- 2001-04-27 JP JP2001132236A patent/JP4097908B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1058681C (en) * | 1996-03-21 | 2000-11-22 | 中国石油化工总公司石油化工科学研究院 | Process of producing fine-grain model. A zeolite |
| RU2448197C1 (en) * | 2011-04-05 | 2012-04-20 | Российская Федерация, от имени которой выступает Министерство промышленности и торговли Российской Федерации (Минпромторг России) | Application method of transparent electrically conducting coating |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2002328220A (en) | 2002-11-15 |
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