JP4305817B2 - Alkali-free glass substrate - Google Patents
Alkali-free glass substrate Download PDFInfo
- Publication number
- JP4305817B2 JP4305817B2 JP2002359046A JP2002359046A JP4305817B2 JP 4305817 B2 JP4305817 B2 JP 4305817B2 JP 2002359046 A JP2002359046 A JP 2002359046A JP 2002359046 A JP2002359046 A JP 2002359046A JP 4305817 B2 JP4305817 B2 JP 4305817B2
- Authority
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- glass
- glass substrate
- alkali
- transmittance
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Links
- 239000011521 glass Substances 0.000 title claims description 104
- 239000000758 substrate Substances 0.000 title claims description 53
- 238000002834 transmittance Methods 0.000 claims description 32
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 4
- 238000006124 Pilkington process Methods 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- 238000007500 overflow downdraw method Methods 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 18
- 239000010408 film Substances 0.000 description 13
- 239000002253 acid Substances 0.000 description 8
- 238000004031 devitrification Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 230000007423 decrease Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000004973 liquid crystal related substance Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000001259 photo etching Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 239000006059 cover glass Substances 0.000 description 3
- 239000006025 fining agent Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000003384 imaging method Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- -1 alkalis Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- 238000007088 Archimedes method Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 206010040925 Skin striae Diseases 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000003280 down draw process Methods 0.000 description 1
- 229910052634 enstatite Inorganic materials 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000156 glass melt Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- BBCCCLINBSELLX-UHFFFAOYSA-N magnesium;dihydroxy(oxo)silane Chemical compound [Mg+2].O[Si](O)=O BBCCCLINBSELLX-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007372 rollout process Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C03C4/00—Compositions for glass with special properties
- C03C4/0085—Compositions for glass with special properties for UV-transmitting glass
-
- 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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/004—Refining agents
-
- 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
-
- 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
- C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
-
- 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Liquid Crystal (AREA)
- Electroluminescent Light Sources (AREA)
- Glass Compositions (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は、液晶ディスプレイ、エレクトロルミネッセンスディスプレイ、フィールドエミッションディスプレイ等のフラットパネルディスプレイやセンサー等の基板、固体撮像素子のカバーガラスに用いられる無アルカリガラス基板に関するものである。
【０００２】
【従来の技術】
従来より、フラットパネルディスプレイやセンサー等の基板、固体撮像素子のカバーガラスとしては、矩形状のガラス基板が広く使用されている。
【０００３】
この種のガラス基板の表面には、透明導電膜、絶縁膜、半導体膜、金属膜等が成膜され、しかもフォトリソグラフィーエッチング（フォトエッチング）によって種々の回路やパターンが形成される。これらの成膜、フォトエッチング工程において、ガラス基板は、数百度の熱処理を受けると共に、硫酸、塩酸、アルカリ溶液、フッ酸、バッファードフッ酸等の種々の薬品による処理を受ける。
【０００４】
この種のガラス基板には、以下のような特性が要求される。
（１）ガラス中にアルカリ金属酸化物が含有されていると、熱処理時に成膜された半導体物質中にアルカリイオンが拡散し、膜特性の劣化を招くため、実質的にアルカリ金属酸化物を含有しないこと。
（２）フォトエッチング工程において使用される種々の酸、アルカリ等の薬品によって劣化しないような耐薬品性を有すること。
（３）成膜等のＴＦＴ（薄膜トランジスタ）素子製造工程でガラス基板が熱収縮してパターンずれを起こさないように、高い歪点、具体的には、６４０℃以上の歪点を有すること。例えば多結晶シリコンＴＦＴ−ＬＣＤの場合、その工程温度が６００℃以上であるため、このような用途のガラス基板には、歪点が６４０℃以上であることが要求される。
【０００５】
また、これ以外にも、次のような特性が要求される。
（４）ガラス中に基板として好ましくない溶融欠陥が発生しないよう溶融性に優れていること。
（５）耐熱衝撃性を向上させて、熱処理工程中での破損を低減させるために、熱膨張係数が小さいこと。
【０００６】
更に、これらのデバイスではガラス基板の透過率はきわめて重要であり、紫外域から可視域において、高い透過率を有するガラス基板が望まれている。
【０００７】
例えば、液晶ディスプレイの場合、非発光型ディスプレイであり、光の利用効率が悪いため、可視域におけるガラス基板の透過率は高い方が良い。また、ＴＦＴ（薄膜トランジスタ）素子は、ガラス基板上に透明導電膜、絶縁膜、半導体膜、金属膜等を成膜した後、ガラス基板の裏面より波長３００ｎｍ付近の紫外線を照射する背面露光法によるフォトリソグラフィによって形成される。そのため、紫外域におけるガラス基板の透過率も高い方が良い。
【０００８】
また、近年、注目されている有機エレクトロルミネッセンスディスプレイの場合、赤、緑、青の有機蛍光体を発光させて表示を行うが、青色の光を発する蛍光体の発光効率が他の蛍光体に比べて低い。そのため、青色の光に対応する波長域におけるガラスの透過率は高い方が良い。
【０００９】
【特許文献１】
特開平７−２０２２０８号公報
【特許文献２】
特開２００１−２６１３６６号公報
【００１０】
【発明が解決しようとする課題】
Ｆｅ2Ｏ3は、ガラス中でＦｅ3+又はＦｅ2+の状態で存在し、特に、Ｆｅ3+は、３８０ｎｍ付近に吸収ピークを持ち、紫外域、短波長側の可視域における透過率を低下させる。一般に、安価で大量生産されるガラスは、ガラス原料や製造工程中から多量のＦｅ2Ｏ3がガラス中に混入している。そのため、このようなガラスをディスプレイやセンサーの基板として用いると、紫外域、短波長側の可視域における透過率が低いため、ディスプレイやセンサーとしての性能の低下が懸念されている。
【００１１】
ガラス中へのＦｅ2Ｏ3の混入を完全に排除するには、高純度ガラス原料を用い、且つ、原料調合設備等から原料へＦｅ2Ｏ3が混入しないような特別に設計された製造設備を使用する必要があり、製造コストが非常に高くなるため、現実的ではない。
【００１２】
本発明の目的は、上記した要求特性項目（１）〜（５）の全てを満足し、しかも、コストを上げることなく、透過率の高い無アルカリガラス基板を提供することである。
【００１３】
【課題を解決するための手段】
本発明者は、種々の実験を繰り返した結果、ガラス中にＳｎＯ2を添加することで所望の透過率が得られることを見いだし本発明として提案するものである。
【００１４】
即ち、本発明の無アルカリガラス基板は、実質的にアルカリ金属酸化物を含まず、質量％で、ＳｎＯ2 ０．０１〜０．３％、Ａｓ2Ｏ3 ０〜０．１％、Ｓｂ2Ｏ3 ０〜１．０％であり、且つ、ガラス中のＦｅの含有量が、Ｆｅ2Ｏ3に換算して、質量％で０．００５〜０．０３％であることを特徴とする。
【００１５】
【作用】
一般に、ガラス基板上のＴＦＴを作製する際に用いられる紫外線は、主として３００ｎｍを中心とした波長の紫外線が使用される。このため、波長３００ｎｍにおけるガラス基板の透過率は、できるだけ高い方が良く、少なくとも５０％以上（好ましくは６０％以上）であることが重要である。この透過率が５０％未満であると背面露光を行ってＴＦＴを形成する際に時間がかかり、生産性に支障をきたす虞がある。
【００１６】
また、液晶ディスプレイは非発光型ディスプレイであるため、光の利用効率の損失は少ないほうが良い。このため、液晶ディスプレイ用ガラス基板の可視域における透過率はできるだけ高い方が良く、板厚０．７ｍｍで波長４００〜８００ｎｍにおける透過率は８９％以上（好ましくは９０％以上）であることが重要である。この透過率が８９％未満であるとディスプレイの性能が低下する虞がある。
【００１７】
そこで、本発明の無アルカリガラス基板においては、ガラス中のＡｓ２Ｏ３を０．１％以下に制限し、ＳｎＯ２を０．０１〜０．３％添加する。これによりＦｅの価数を３価（Ｆｅ３＋）から２価（Ｆｅ２＋）へ変化させて、板厚０．７ｍｍで波長３００ｎｍにおける透過率を５０％以上に保ち、且つ、波長４００〜８００ｎｍにおける透過率を８９％以上にしている。
【００１８】
ガラス中にＳｎＯ2を０．０１〜０．３％含有させると、Ｓｎ2+＋２Ｆｅ3+→Ｓｎ4+＋２Ｆｅ2+の反応が起こり、Ｆｅの価数が変化して、Ｆｅ2+が増加し、Ｆｅ3+が減少すると考えられ、紫外域や短波長側の可視域の透過率が上昇する。ＳｎＯ2の含有量が０．０１％より少ないと、価数変化するＦｅの量が少なくなり、紫外域や短波長側の可視域の透過率が低くなるため好ましくない。一方、０．３％より多いとＳｎＯ2の結晶が析出しやすくなるため好ましくない。ＳｎＯ2の好ましい範囲は０．０５〜０．３％である。尚、Ｓｎと同様にＦｅの価数変化を起こすものとして、ＣｅやＴｉ等が存在するが、これらは、紫外域に吸収を持つため、好ましくない。
【００１９】
また、清澄剤として広く使用されているＡｓ2Ｏ3は紫外域に吸収ピークを持つ。更に、ＳｎＯ2によるＦｅ2+への価数変化を阻害する働きがある。このため、Ａｓ2Ｏ3の含有量は０．１％以下に制限される。Ａｓ2Ｏ3の含有量が０．１％より多いと、紫外域の透過率が低下するため好ましくない。好ましくは０．０５％以下である。尚、無アルカリガラスにおいて、清澄剤として用いられているＡｓ2Ｏ3の含有量を減らすと、泡のないガラスを得ることは難しくなるが、透過率を高めるために添加しているＳｎＯ2が清澄剤としても働くため、Ｓｂ2Ｏ3やＣｌを適宜組み合せることで泡のないガラスを得ることができる。但し、Ｓｂ2Ｏ3もＡｓ2Ｏ3と同様に紫外域に吸収ピークを持つため、その含有量は１．０％以下に抑えるべきである。
【００２０】
また、ＳｎＯ2の添加によって、Ｆｅ2+が増加しすぎると、Ｆｅ2+は１０８０ｎｍ付近に吸収ピークを持つため、長波長側の可視透過率が低下し、波長４００〜８００ｎｍにおける透過率を８９％以上に保つことができなくなる虞がある。これを防止するには、全Ｆｅ量を調整する必要があり、Ｆｅ2Ｏ3に換算して０．００５〜０．０３％の範囲内に入るようにすることが重要である。Ｆｅ2Ｏ3の含有量が０．０３％より多くなると、長波長側の可視透過率が低下するため好ましくない。一方、０．００５％より少なくしようとすると、コストが高くなりすぎるため好ましくない。Ｆｅ2Ｏ3の好ましい範囲は、０．００７〜０．０３％である。
【００２１】
本発明において使用するガラスは無アルカリガラスである。その理由は、ガラス中にアルカリ金属酸化物（Ｎａ2Ｏ、Ｋ2Ｏ、Ｌｉ2Ｏ）を含有すると、ガラス中のアルカリ成分が、ガラス基板上に形成された各種の膜やＴＦＴ素子の特性を劣化させるばかりか、アルカリ成分と各種の膜が反応することで白濁し、基板の透過率を低下させる虞があるからである。
【００２２】
また、本発明のガラス基板の具体的な組成は、耐薬品性、熱収縮性、溶融性、成形性、熱膨張係数等を考慮して、用途に応じて適宜決定すればよい。好適な組成例として、質量百分率で、ＳｉＯ2 ５５〜７０％、Ａｌ2Ｏ3 １２〜２０％、Ｂ2Ｏ3 ５〜１５％、ＭｇＯ ０〜５％、ＣａＯ ０〜１２％、ＳｒＯ ０〜１０％、ＢａＯ ０〜１０％、ＺｎＯ ０〜５％、ＺｒＯ2 ０〜５％、Ｃｌ ０〜０．５％の無アルカリガラスがあげられる。
【００２３】
このようにガラス組成を限定した理由は、次のとおりである。
【００２４】
ＳｉＯ2は、ガラスのネットワークフォーマーとなる成分であり、ガラスの耐酸性を向上させたり、ガラスの歪点を上昇させてガラス基板の熱収縮を小さくする効果がある。含有量が５５〜７０％であれば、耐酸性が高く、熱収縮の小さいガラス基板を得ることができる。好ましい範囲は、５７〜６７％である。尚、ＳｉＯ2の含有量が多くなると、ガラスの高温粘度が高くなり、溶融性が悪化すると共にクリストバライトの失透ブツが析出しやすくなる傾向にある。また、含有量が少なくなると、ガラスの耐酸性や歪点が低下する傾向にある。
【００２５】
Ａｌ2Ｏ3は、ガラスの歪点を上昇させたり、クリストバライトの失透ブツの析出を抑える成分である。含有量が１２〜２０％であれば、液相温度が低いガラス基板を得ることができる。好ましい範囲は、１３〜１８％である。尚、Ａｌ2Ｏ3の含有量が多くなると、ガラスの耐バッファードフッ酸性が悪化したり、液相温度が上昇して成形しにくくなる傾向にある。また、含有量が少なくなると、ガラスの歪点が低下する傾向にある。
【００２６】
Ｂ2Ｏ3は、融剤として作用し、ガラスの粘性を下げ、溶融性を改善する成分である。含有量が５〜１５％であれば、上記効果を得ることができる。好ましい範囲は、７〜１４％である。尚、Ｂ2Ｏ3の含有量が多くなると、ガラスの歪点が低下したり、耐酸性が悪化する傾向にある。また、含有量が少なくなると、融剤として十分に作用せず溶融性が低下する傾向にある。
【００２７】
ＭｇＯは、ガラスの歪点を低下させずに高温粘性のみを低下させて、ガラスの溶融性を改善する成分である。含有量が５％以下であれば、ガラスの溶融性を改善することができる。好ましい範囲は、０〜３％である。尚、ＭｇＯの含有量が多くなると、エンステタイトの失透ブツが析出しやすくなる。また、耐バッファードフッ酸性が低下し、フォトエッチング工程において、ガラス基板表面が侵食されて、反応生成物がガラス基板表面に付着し、ガラス基板が白濁し易くなる。
【００２８】
ＣａＯは、ガラスの歪点を低下させずに高温粘性のみを低下させて、ガラスの溶融性を著しく改善する成分である。含有量が１２％以下であれば、ガラスの溶融性を改善することができる。好ましい範囲は、３〜１０％である。尚、ＣａＯの含有量が多くなると、耐バッファードフッ酸性が悪化する傾向にある。
【００２９】
ＳｒＯは、ガラスの耐薬品性と耐失透性を向上させる成分である。含有量が１０％以下であれば、上記効果を得ることができる。好ましい範囲は０〜７％である。尚、ＳｒＯの含有量が多くなると、ガラスの密度や熱膨張係数が大きくなったり、溶融性が悪化する傾向にある。
【００３０】
ＢａＯは、ＳｒＯと同様にガラスの耐薬品性と耐失透性を向上させる成分である。含有量が１０％以下であれば、上記効果を得ることができる。好ましい範囲は０〜５％である。尚、ＢａＯの含有量が多くなると、ガラスの密度や熱膨張係数が大きくなったり、溶融性が著しく悪化する傾向にある。
【００３１】
ＺｎＯは、ガラスの耐バッファードフッ酸性や溶融性を改善する成分である。含有量が３％以下であれば、上記効果を得ることができる。好ましい範囲は、０〜２．５％である。尚、ＺｎＯの含有量が多くなると、ガラスの耐失透性や歪点が低下する傾向にある。
【００３２】
尚、ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯのアルカリ土類金属酸化物は、混合して含有させることで、ガラスの溶融性と耐失透性を向上させることができるが、これら成分の合量が多くなると、ガラスの密度が上昇する傾向にあり、ガラス基板の軽量化が困難となるため、合量で１１％未満にすることが望ましい。
【００３３】
ＺｒＯ2は、ガラスの耐酸性を改善する成分である。含有量が１％以下であれば、ガラスの耐酸性を向上させることができる。好ましい範囲は、０〜０．７％である。尚、ＺｒＯ2の含有量が多くなると、ジルコンの失透ブツが析出する傾向にある。
【００３４】
Ｃｌは、ガラスの清澄剤として働く成分である。含有量が多くなると、ガラス融液からの揮発が多くなり、脈理が発生しやすくなるが、含有量が０．５％以下であれば、問題なく上記効果が得られる。好ましい範囲は、０〜０．４％である。
【００３５】
次に、本発明の無アルカリガラス基板を製造する方法を説明する。
【００３６】
まず、不純物として含まれるＦｅの量を考慮しながら、無アルカリガラスの原料を選択し、その原料を用いて上記のガラス組成範囲となるように調合する。続いて、調合した原料を連続溶融炉で１５２０〜１６８０℃の温度で溶融する。その後、溶融ガラスをスロットダウンドロー法、オーバーフローダウンドロー法、フロート法、ロールアウト法等の方法で板状に成形し徐冷することで無アルカリガラス基板を得ることができる。
【００３７】
【実施例】
以下、本発明を実施例に基づいて詳細に説明する。
【００３８】
表１〜４は、本発明の実施例（試料Ｎｏ．１〜２０）を、表５は、比較例（試料Ｎｏ．２１、２２）をそれぞれ示している。
【００３９】
【表１】
【表２】
【表３】
【表４】
【表５】
表中の各試料は、次のようにして作製した。
【００４５】
まず表の組成となるようにガラス原料を調合し、白金ポットで１６００℃で２４時間溶融した後、カーボン板上に流し出し、板状に成形した。次いでこれらの板状ガラスの両面を光学研磨することによって、縦寸法が３００ｍｍ、横寸法が３００ｍｍ、厚みが０．７ｍｍの大型で薄肉のガラス基板を作製した。
【００４６】
このようにして作製した各試料について、各種の特性を評価した。結果を表に示す。
【００４７】
表から明らかなように、実施例である試料Ｎｏ．１〜２０はいずれも波長３００ｎｍにおける透過率が５５％以上と高く、波長４００〜８００ｎｍにおける透過率も９０％以上と高かった。密度は２．４３ｇ／ｃｍ3以下と低く、基板の軽量化を図ることができる。熱膨張係数は３０〜３４×１０-7／℃であった。歪点は６６５℃以上と高いため、熱収縮の小さいガラス基板が得られる。また、１０2.5ポイズに相当する温度は１６１０℃以下、液相温度は、１１２０℃以下であるため、溶融性、成形性にも優れていた。更に、耐酸性、耐ＢＨＦにも優れていた。
【００４８】
一方、比較例である試料Ｎｏ．２１及び２２は、波長３００ｎｍにおける透過率が４０％以下と低かった。
【００４９】
透過率については、分光光度計にて波長３００ｎｍ、４００ｎｍ、６００ｎｍ、８００ｎｍにおける試料の透過率を測定した。
【００５０】
密度については、周知のアルキメデス法によって測定した。
【００５１】
熱膨張係数は、ディラトメーターを用いて、３０〜３８０℃における平均熱膨張係数を測定したものである。
【００５２】
歪点は、ＡＳＴＭ Ｃ３３６−７１の方法に基づいて測定し、この値が高いほど、ガラスの熱収縮は小さくなる。ｌｏｇη ａｔ １０2.5は、高温粘度である１０2.5ポイズの粘度に相当する温度を示すものであり、この温度が低いほど、溶融性に優れていることになる。
【００５３】
液相温度については、以下の要領で行った。まず、各試料をそれぞれ３００〜５００μｍの大きさに粉砕、洗浄し、これを白金製のボートに入れて１０００〜１３００℃の温度勾配炉に移して２４時間保持し、温度勾配炉より白金製のボートを取り出した。その後、白金製のボートからガラスを取り出した。このようにして得られたサンプルを偏光顕微鏡で観察し、結晶の析出点を測定し、これを液相温度とした。
【００５４】
耐ＨＣｌ性は、各試料を８０℃に保持された１０質量％塩酸水溶液に３時間浸漬した後、それらの表面状態を目視で観察することによって評価した。また、耐バッファードフッ酸性は、各試料を２０℃に保持された３０質量％弗化アンモニウム、６質量％フッ酸からなるバッファードフッ酸に３０分間浸漬した後、それらの表面状態を目視で観察することによって評価した。ガラス基板の表面に全く変化のないものは○、変色したものは×で示した。
【００５５】
【発明の効果】
以上のように、本発明の無アルカリガラス基板は、可視域全体に亘って透過率が高いため、フラットパネルディスプレイやセンサー等の基板、固体撮像素子のカバーガラスに用いられるガラス基板として好適である。また、紫外域における透過率も高いため、特に、背面露光によってＴＦＴ素子を製作するＴＦＴ型アクティブマトリックス液晶ディスプレイに使用される無アルカリガラス基板として好適である。[0001]
[Industrial application fields]
The present invention relates to a flat panel display such as a liquid crystal display, an electroluminescence display, and a field emission display, a substrate such as a sensor, and a non-alkali glass substrate used for a cover glass of a solid-state imaging device.
[0002]
[Prior art]
2. Description of the Related Art Conventionally, rectangular glass substrates have been widely used as substrates for flat panel displays and sensors, and cover glasses for solid-state imaging devices.
[0003]
A transparent conductive film, an insulating film, a semiconductor film, a metal film, and the like are formed on the surface of this type of glass substrate, and various circuits and patterns are formed by photolithography etching (photoetching). In these film forming and photoetching steps, the glass substrate is subjected to heat treatment of several hundred degrees and various treatments such as sulfuric acid, hydrochloric acid, alkaline solution, hydrofluoric acid, and buffered hydrofluoric acid.
[0004]
This type of glass substrate is required to have the following characteristics.
(1) If an alkali metal oxide is contained in the glass, alkali ions diffuse into the semiconductor material formed during the heat treatment, resulting in deterioration of the film characteristics. Don't do it.
(2) To have chemical resistance that does not deteriorate due to various acids, alkalis, and other chemicals used in the photoetching process.
(3) It has a high strain point, specifically, a strain point of 640 ° C. or higher so that the glass substrate does not shrink due to heat shrinkage in the TFT (thin film transistor) element manufacturing process such as film formation. For example, in the case of a polycrystalline silicon TFT-LCD, since the process temperature is 600 ° C. or higher, the glass substrate for such use is required to have a strain point of 640 ° C. or higher.
[0005]
In addition, the following characteristics are required.
(4) The glass has excellent meltability so as not to cause undesirable melting defects as a substrate in the glass.
(5) The coefficient of thermal expansion is small in order to improve the thermal shock resistance and reduce breakage during the heat treatment process.
[0006]
Further, in these devices, the transmittance of the glass substrate is extremely important, and a glass substrate having a high transmittance from the ultraviolet region to the visible region is desired.
[0007]
For example, in the case of a liquid crystal display, since it is a non-light-emitting display and the light use efficiency is poor, the transmittance of the glass substrate in the visible region is preferably high. A TFT (Thin Film Transistor) element is a photo by back exposure method in which a transparent conductive film, an insulating film, a semiconductor film, a metal film, etc. are formed on a glass substrate and then irradiated with ultraviolet rays having a wavelength of about 300 nm from the back surface of the glass substrate. Formed by lithography. Therefore, it is better that the transmittance of the glass substrate in the ultraviolet region is also high.
[0008]
In recent years, in the case of organic electroluminescence displays that have been attracting attention, display is performed by emitting red, green, and blue organic phosphors, but the luminous efficiency of phosphors that emit blue light is higher than that of other phosphors. Low. Therefore, it is better that the transmittance of the glass in the wavelength region corresponding to blue light is high.
[0009]
[Patent Document 1]
JP-A-7-202208 [Patent Document 2]
JP 2001-261366 A
[Problems to be solved by the invention]
Fe 2 O 3 exists in glass in the state of Fe 3+ or Fe 2+ , and in particular, Fe 3+ has an absorption peak in the vicinity of 380 nm and has a transmittance in the visible region in the ultraviolet region and short wavelength side. Reduce. In general, a glass that is inexpensive and mass-produced contains a large amount of Fe 2 O 3 in the glass from the glass raw material and the manufacturing process. Therefore, when such glass is used as a substrate for a display or a sensor, there is a concern that the performance as a display or a sensor is lowered because the transmittance in the visible region on the ultraviolet or short wavelength side is low.
[0011]
Specially designed production equipment that uses high-purity glass raw material and does not mix Fe 2 O 3 into the raw material from raw material preparation equipment, etc., to completely eliminate the mixing of Fe 2 O 3 into the glass This is not practical because the manufacturing cost becomes very high.
[0012]
An object of the present invention is to provide an alkali-free glass substrate that satisfies all of the above-described required characteristic items (1) to (5) and has high transmittance without increasing the cost.
[0013]
[Means for Solving the Problems]
As a result of repeating various experiments, the present inventor has found that a desired transmittance can be obtained by adding SnO 2 into glass, and proposes the present invention.
[0014]
That is, the alkali-free glass substrate of the present invention contains substantially no alkali metal oxide, and is in mass%, SnO 2 0.01 to 0.3%, As 2 O 3 0 to 0.1%, Sb 2. O 3 is 0 to 1.0%, and the Fe content in the glass is 0.005 to 0.03% by mass in terms of Fe 2 O 3 .
[0015]
[Action]
In general, ultraviolet rays having a wavelength centered at 300 nm are mainly used for producing TFTs on a glass substrate. For this reason, the transmittance of the glass substrate at a wavelength of 300 nm should be as high as possible, and it is important that it is at least 50% or more (preferably 60% or more). If the transmittance is less than 50%, it takes time to form a TFT by performing back exposure, which may impair productivity.
[0016]
Further, since the liquid crystal display is a non-luminous display, it is better that the loss of light use efficiency is small. For this reason, the transmittance in the visible region of the glass substrate for liquid crystal display should be as high as possible. It is important that the transmittance at a wavelength of 400 to 800 nm is 89% or more (preferably 90% or more) with a plate thickness of 0.7 mm. It is. If the transmittance is less than 89%, the display performance may be degraded.
[0017]
Therefore, in the alkali-free glass substrate of the present invention, As 2 O 3 in the glass is limited to 0.1% or less, and SnO 2 is added in an amount of 0.01 to 0.3%. As a result, the valence of Fe is changed from trivalent (Fe 3+ ) to divalent (Fe 2+ ), the transmittance at a wavelength of 300 nm is maintained at 50% or more with a plate thickness of 0.7 mm , and at a wavelength of 400 to 800 nm. The transmittance is 89% or more.
[0018]
When 0.01 to 0.3% of SnO 2 is contained in the glass, the reaction of Sn 2+ + 2Fe 3+ → Sn 4+ + 2Fe 2+ occurs, the valence of Fe changes, and Fe 2+ increases. was believed to Fe 3+ is reduced, the transmittance in the visible range of ultraviolet or short wavelength side is increased. When the content of SnO 2 is less than 0.01%, the amount of Fe that changes in valence decreases, and the transmittance in the ultraviolet region and the visible region on the short wavelength side is lowered, which is not preferable. On the other hand, if it exceeds 0.3%, SnO 2 crystals tend to precipitate, which is not preferable. A preferable range of SnO 2 is 0.05 to 0.3%. In addition, Ce, Ti, etc. exist as the thing which causes the valence change of Fe like Sn, However, Since these have absorption in an ultraviolet region, they are not preferable.
[0019]
Further, As 2 O 3 widely used as a fining agent has an absorption peak in the ultraviolet region. Furthermore, it functions to inhibit the valence change to Fe 2+ by SnO 2 . For this reason, the content of As 2 O 3 is limited to 0.1% or less. When the content of As 2 O 3 is more than 0.1%, the transmittance in the ultraviolet region is lowered, which is not preferable. Preferably it is 0.05% or less. In addition, in the alkali-free glass, when the content of As 2 O 3 used as a fining agent is reduced, it becomes difficult to obtain a glass free from bubbles, but SnO 2 added to increase the transmittance is reduced. Since it also acts as a fining agent, a glass free from bubbles can be obtained by appropriately combining Sb 2 O 3 and Cl. However, to have an absorption peak in the ultraviolet region as well as Sb 2 O 3 also As 2 O 3, the content thereof should be kept below 1.0%.
[0020]
Further, the addition of SnO 2, the Fe 2+ increases too much, because Fe 2+ is having an absorption peak around 1080 nm, the visible transmittance is reduced on the long wavelength side, the transmittance at a wavelength of 400 to 800 nm 89 There is a risk that it may not be possible to keep the ratio at more than%. In order to prevent this, it is necessary to adjust the total amount of Fe, and it is important to make it fall within the range of 0.005 to 0.03% in terms of Fe 2 O 3 . If the content of Fe 2 O 3 is more than 0.03%, the visible transmittance on the long wavelength side is lowered, which is not preferable. On the other hand, if the content is less than 0.005%, the cost becomes too high, which is not preferable. A preferable range of Fe 2 O 3 is 0.007 to 0.03%.
[0021]
The glass used in the present invention is alkali-free glass. The reason is that when an alkali metal oxide (Na 2 O, K 2 O, Li 2 O) is contained in the glass, the alkali components in the glass are characteristics of various films and TFT elements formed on the glass substrate. This is because the alkali component and various films react with each other to cause white turbidity and reduce the transmittance of the substrate.
[0022]
In addition, the specific composition of the glass substrate of the present invention may be appropriately determined depending on the application in consideration of chemical resistance, heat shrinkability, meltability, moldability, thermal expansion coefficient, and the like. Preferred compositions embodiment, by mass percentage, SiO 2 55~70%, Al 2 O 3 12~20%, B 2 O 3 5~15%, 0~5% MgO, CaO 0~12%, SrO 0~ Examples include alkali-free glass of 10%, BaO 0 to 10%, ZnO 0 to 5%, ZrO 2 0 to 5%, and Cl 0 to 0.5%.
[0023]
The reason for limiting the glass composition in this way is as follows.
[0024]
SiO 2 is a component that becomes a glass network former, and has the effect of improving the acid resistance of the glass and increasing the strain point of the glass to reduce the thermal shrinkage of the glass substrate. When the content is 55 to 70%, a glass substrate having high acid resistance and low thermal shrinkage can be obtained. A preferred range is 57-67%. In addition, when the content of SiO 2 increases, the high temperature viscosity of the glass increases, the meltability deteriorates, and the devitrification bristles of cristobalite tend to precipitate. Moreover, when the content decreases, the acid resistance and strain point of the glass tend to decrease.
[0025]
Al 2 O 3 is or increase the strain point of glass and is a component for suppressing the precipitation of cristobalite devitrification stones. When the content is 12 to 20%, a glass substrate having a low liquidus temperature can be obtained. A preferred range is 13-18%. In addition, when the content of Al 2 O 3 increases, the buffered hydrofluoric acid resistance of the glass tends to deteriorate, or the liquidus temperature tends to increase, making it difficult to form. Moreover, when the content decreases, the strain point of the glass tends to decrease.
[0026]
B 2 O 3 is a component that acts as a flux, lowers the viscosity of the glass, and improves the meltability. If content is 5 to 15%, the said effect can be acquired. A preferable range is 7 to 14%. In addition, when the content of B 2 O 3 increases, the strain point of the glass tends to decrease or the acid resistance tends to deteriorate. On the other hand, when the content is reduced, it does not sufficiently act as a flux and the meltability tends to decrease.
[0027]
MgO is a component that improves the meltability of glass by lowering only the high temperature viscosity without lowering the strain point of the glass. If content is 5% or less, the meltability of glass can be improved. A preferable range is 0 to 3%. In addition, when the content of MgO increases, the devitrification bumps of enstatite are likely to precipitate. In addition, the resistance to buffered hydrofluoric acid is lowered, and in the photoetching process, the glass substrate surface is eroded, the reaction product adheres to the glass substrate surface, and the glass substrate is likely to become cloudy.
[0028]
CaO is a component that remarkably improves the meltability of the glass by reducing only the high temperature viscosity without reducing the strain point of the glass. If content is 12% or less, the meltability of glass can be improved. A preferred range is 3 to 10%. In addition, when content of CaO increases, there exists a tendency for buffered hydrofluoric acid resistance to deteriorate.
[0029]
SrO is a component that improves the chemical resistance and devitrification resistance of glass. If the content is 10% or less, the above effect can be obtained. A preferable range is 0 to 7%. In addition, when the SrO content increases, the density and thermal expansion coefficient of the glass tend to increase or the meltability tends to deteriorate.
[0030]
BaO, like SrO, is a component that improves the chemical resistance and devitrification resistance of glass. If the content is 10% or less, the above effect can be obtained. A preferable range is 0 to 5%. In addition, when the content of BaO increases, the density and thermal expansion coefficient of the glass tend to increase, and the meltability tends to deteriorate significantly.
[0031]
ZnO is a component that improves the buffered hydrofluoric acid resistance and meltability of glass. If the content is 3% or less, the above effect can be obtained. A preferable range is 0 to 2.5%. In addition, when content of ZnO increases, it exists in the tendency for the devitrification resistance and strain point of glass to fall.
[0032]
The alkaline earth metal oxides of MgO, CaO, SrO, and BaO can improve the meltability and devitrification resistance of the glass by mixing them, but the total amount of these components is large. Then, the density of the glass tends to increase, and it becomes difficult to reduce the weight of the glass substrate. Therefore, the total amount is preferably less than 11%.
[0033]
ZrO 2 is a component that improves the acid resistance of the glass. If content is 1% or less, the acid resistance of glass can be improved. A preferable range is 0 to 0.7%. In addition, when the content of ZrO 2 increases, the devitrification of zircon tends to precipitate.
[0034]
Cl is a component that acts as a glass refining agent. If the content increases, volatilization from the glass melt increases and striae are likely to occur. However, if the content is 0.5% or less, the above effect can be obtained without problems. A preferable range is 0 to 0.4%.
[0035]
Next, a method for producing the alkali-free glass substrate of the present invention will be described.
[0036]
First, while considering the amount of Fe contained as impurities, a non-alkali glass raw material is selected, and the raw material is used to prepare the glass composition range described above. Subsequently, the prepared raw materials are melted at a temperature of 1520 to 1680 ° C. in a continuous melting furnace. Thereafter, the alkali-free glass substrate can be obtained by forming the molten glass into a plate shape by a method such as a slot down draw method, an overflow down draw method, a float method, or a roll-out method and gradually cooling it.
[0037]
【Example】
Hereinafter, the present invention will be described in detail based on examples.
[0038]
Tables 1 to 4 show examples of the present invention (sample Nos. 1 to 20), and Table 5 shows comparative examples (samples No. 21 and 22), respectively.
[0039]
[Table 1]
[Table 2]
[Table 3]
[Table 4]
[Table 5]
Each sample in the table was prepared as follows.
[0045]
First, glass raw materials were prepared so as to have the composition shown in the table, melted in a platinum pot at 1600 ° C. for 24 hours, poured out on a carbon plate, and formed into a plate shape. Subsequently, both sides of these plate-like glasses were optically polished to produce a large and thin glass substrate having a longitudinal dimension of 300 mm, a transverse dimension of 300 mm, and a thickness of 0.7 mm.
[0046]
Various characteristics were evaluated for each sample thus prepared. The results are shown in the table.
[0047]
As can be seen from the table, the sample No. 1 to 20 all had a high transmittance of 55% or more at a wavelength of 300 nm, and a high transmittance of 90% or more at a wavelength of 400 to 800 nm. The density is as low as 2.43 g / cm 3 or less, and the weight of the substrate can be reduced. The thermal expansion coefficient was 30 to 34 × 10 −7 / ° C. Since the strain point is as high as 665 ° C. or higher, a glass substrate with small thermal shrinkage can be obtained. Further, since the temperature corresponding to 10 2.5 poise was 1610 ° C. or lower and the liquidus temperature was 1120 ° C. or lower, the meltability and moldability were also excellent. Furthermore, it was excellent in acid resistance and BHF resistance.
[0048]
On the other hand, sample No. which is a comparative example. 21 and 22 had a low transmittance of 40% or less at a wavelength of 300 nm.
[0049]
About the transmittance | permeability, the transmittance | permeability of the sample in wavelength 300nm, 400nm, 600nm, 800nm was measured with the spectrophotometer.
[0050]
The density was measured by the well-known Archimedes method.
[0051]
The thermal expansion coefficient is obtained by measuring an average thermal expansion coefficient at 30 to 380 ° C. using a dilatometer.
[0052]
The strain point is measured based on the method of ASTM C336-71, and the higher this value, the smaller the thermal shrinkage of the glass. log [eta at 10 2.5 is indicative of a temperature corresponding to a viscosity of 10 2.5 poise at a high temperature viscosity, the higher the temperature is lower, so that excellent in meltability.
[0053]
About liquid phase temperature, it carried out in the following ways. First, each sample was pulverized and washed to a size of 300 to 500 μm, put into a platinum boat, transferred to a temperature gradient furnace at 1000 to 1300 ° C. and held for 24 hours. I took out the boat. Thereafter, the glass was taken out from the platinum boat. The sample thus obtained was observed with a polarizing microscope, the crystal precipitation point was measured, and this was taken as the liquidus temperature.
[0054]
The HCl resistance was evaluated by immersing each sample in a 10% by mass hydrochloric acid aqueous solution maintained at 80 ° C. for 3 hours and then visually observing the surface state thereof. Buffered hydrofluoric acid resistance is determined by immersing each sample in buffered hydrofluoric acid composed of 30% by mass ammonium fluoride and 6% by mass hydrofluoric acid maintained at 20 ° C. for 30 minutes, and then visually checking the surface condition of each sample. Evaluation was made by observation. The case where there was no change on the surface of the glass substrate was indicated by ○, and the case where the color changed was indicated by ×.
[0055]
【The invention's effect】
As described above, the alkali-free glass substrate of the present invention has a high transmittance over the entire visible range, and thus is suitable as a glass substrate used for substrates such as flat panel displays and sensors, and cover glasses for solid-state imaging devices. . Moreover, since the transmittance in the ultraviolet region is high, it is particularly suitable as a non-alkali glass substrate used for a TFT type active matrix liquid crystal display in which a TFT element is produced by back exposure.
Claims (7)
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| JP2002359046A JP4305817B2 (en) | 2002-12-11 | 2002-12-11 | Alkali-free glass substrate |
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| JP2002359046A JP4305817B2 (en) | 2002-12-11 | 2002-12-11 | Alkali-free glass substrate |
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| JP5201519B2 (en) * | 2004-10-01 | 2013-06-05 | 日本電気硝子株式会社 | Display board |
| JP5013308B2 (en) * | 2005-06-27 | 2012-08-29 | 日本電気硝子株式会社 | Glass substrate for display |
| CN102603183B (en) * | 2005-06-28 | 2015-04-15 | 康宁股份有限公司 | Alkali-free glass and its manufacture method |
| DE102005039377A1 (en) * | 2005-08-19 | 2007-02-22 | Schott Ag | Production of aluminosilicate float glass for flat display screens, especially TFT displays, involves purifying the melt before floating, using a combination of arsenic-III oxide and tin-IV oxide |
| DE102005039378A1 (en) * | 2005-08-19 | 2007-02-22 | Schott Ag | Method for avoiding surface defects in floated flat glass |
| EP1996525B1 (en) * | 2006-02-10 | 2019-05-22 | Corning Incorporated | Glass compositions having high thermal and chemical stability and methods of making thereof |
| JP5703535B2 (en) * | 2006-05-23 | 2015-04-22 | 日本電気硝子株式会社 | Alkali-free glass substrate |
| JP2013173670A (en) * | 2006-05-23 | 2013-09-05 | Nippon Electric Glass Co Ltd | Alkali-free glass and alkali-free glass substrate |
| JP5071878B2 (en) * | 2006-09-12 | 2012-11-14 | 日本電気硝子株式会社 | Alkali-free glass and alkali-free glass substrate using the same |
| US7534734B2 (en) | 2006-11-13 | 2009-05-19 | Corning Incorporated | Alkali-free glasses containing iron and tin as fining agents |
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| JP5234387B2 (en) * | 2007-06-12 | 2013-07-10 | 日本電気硝子株式会社 | Alkali-free glass, alkali-free glass substrate and method for producing the same |
| US7709406B2 (en) * | 2007-07-31 | 2010-05-04 | Corning Incorporation | Glass compositions compatible with downdraw processing and methods of making and using thereof |
| DE102008005857A1 (en) * | 2008-01-17 | 2009-07-23 | Schott Ag | Alkali-free glass |
| TWI494286B (en) | 2009-03-19 | 2015-08-01 | Nippon Electric Glass Co | Alkali-free glass |
| JP5874304B2 (en) * | 2010-11-02 | 2016-03-02 | 日本電気硝子株式会社 | Alkali-free glass |
| WO2012132449A1 (en) * | 2011-03-31 | 2012-10-04 | ＡｖａｎＳｔｒａｔｅ株式会社 | Method for producing glass substrate |
| KR101528396B1 (en) * | 2011-07-01 | 2015-06-11 | 아반스트레이트 가부시키가이샤 | Glass substrate for flat pannel display |
| JP5201542B2 (en) * | 2011-08-24 | 2013-06-05 | 日本電気硝子株式会社 | Display board |
| EP3444229A1 (en) | 2012-12-21 | 2019-02-20 | Corning Incorporated | Glass with improved total pitch stability |
| US20140309099A1 (en) * | 2013-04-15 | 2014-10-16 | Ppg Industries Ohio, Inc. | Low iron, high redox ratio, and high iron, high redox ratio, soda-lime-silica glasses and methods of making same |
| CN113060935A (en) | 2013-08-15 | 2021-07-02 | 康宁股份有限公司 | Alkali-doped and alkali-free boroaluminosilicate glasses |
| JP6584013B2 (en) | 2013-08-15 | 2019-10-02 | コーニング インコーポレイテッド | Glass with medium to high CTE and glass article provided with the same |
| WO2016115685A1 (en) * | 2015-01-20 | 2016-07-28 | Schott Glass Technologies (Suzhou) Co. Ltd. | Low cte glass with high uv-transmittance and solarization resistance |
| CN106746601B (en) | 2016-12-30 | 2019-06-04 | 东旭集团有限公司 | It is used to prepare the composition, glassware and purposes of glass |
| TWI809029B (en) | 2018-01-15 | 2023-07-21 | 美商康寧公司 | Dimensionally stable fast etching glasses |
| TWI814817B (en) | 2018-05-01 | 2023-09-11 | 美商康寧公司 | Low alkali high transmission glasses |
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| JP3897194B2 (en) * | 1997-07-24 | 2007-03-22 | 日本電気硝子株式会社 | Alkali-free glass and method for producing the same |
| WO1999033759A1 (en) * | 1997-12-26 | 1999-07-08 | Nippon Sheet Glass Co., Ltd. | Ultraviolet/infrared absorbent glass, ultraviolet/infrared absorbent glass plate, ultraviolet/infrared absorbent glass plate coated with colored film, and window glass for vehicle |
| JP2000103625A (en) * | 1998-07-31 | 2000-04-11 | Hoya Corp | Production of glass material and production of glass fiber |
| DE19934072C2 (en) * | 1999-07-23 | 2001-06-13 | Schott Glas | Alkali-free aluminoborosilicate glass, its uses and processes for its manufacture |
| JP2001151534A (en) * | 1999-11-25 | 2001-06-05 | Nippon Electric Glass Co Ltd | Glass substrate for liquid crystal display |
| JP2001261366A (en) * | 2000-03-22 | 2001-09-26 | Nippon Electric Glass Co Ltd | Glass substrate for liquid crystal display, and liquid crystal display |
| DE10034985C1 (en) * | 2000-07-19 | 2001-09-06 | Schott Glas | Production of an alkali-free aluminosilicate glass used as a substrate glass for displays comprises adding tin oxide as refining agent to the starting materials, melting the glass and hot molding the glass |
| JP2002308643A (en) * | 2001-02-01 | 2002-10-23 | Nippon Electric Glass Co Ltd | Alkali-free glass and glass substrate for display |
| JP2002293571A (en) * | 2001-03-30 | 2002-10-09 | Nippon Electric Glass Co Ltd | Glass for illumination |
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