JPH0323238A - Surface modifying method for glass base material - Google Patents
Surface modifying method for glass base materialInfo
- Publication number
- JPH0323238A JPH0323238A JP1156328A JP15632889A JPH0323238A JP H0323238 A JPH0323238 A JP H0323238A JP 1156328 A JP1156328 A JP 1156328A JP 15632889 A JP15632889 A JP 15632889A JP H0323238 A JPH0323238 A JP H0323238A
- Authority
- JP
- Japan
- Prior art keywords
- glass substrate
- glass
- ion
- laser
- implanted
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011521 glass Substances 0.000 title claims abstract description 78
- 239000000463 material Substances 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims description 11
- 239000000758 substrate Substances 0.000 claims abstract description 65
- 238000005468 ion implantation Methods 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000010409 thin film Substances 0.000 claims abstract description 7
- 238000012986 modification Methods 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000002715 modification method Methods 0.000 claims description 4
- -1 nitrogen ions Chemical class 0.000 abstract description 15
- 239000010408 film Substances 0.000 abstract description 11
- 150000002500 ions Chemical class 0.000 abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002585 base Substances 0.000 abstract description 7
- 239000003513 alkali Substances 0.000 abstract description 6
- 238000000137 annealing Methods 0.000 abstract description 5
- 239000004065 semiconductor Substances 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- 238000002513 implantation Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 33
- 229910052581 Si3N4 Inorganic materials 0.000 description 17
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 17
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 7
- 239000000470 constituent Substances 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000005360 phosphosilicate glass Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- HIVGXUNKSAJJDN-UHFFFAOYSA-N [Si].[P] Chemical compound [Si].[P] HIVGXUNKSAJJDN-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000002344 surface layer Substances 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
- C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
- C03C23/0005—Other surface treatment of glass not in the form of fibres or filaments by irradiation
- C03C23/0025—Other surface treatment of glass not in the form of fibres or filaments by irradiation by a laser beam
-
- 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
- C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
- C03C23/0005—Other surface treatment of glass not in the form of fibres or filaments by irradiation
- C03C23/0055—Other surface treatment of glass not in the form of fibres or filaments by irradiation by ion implantation
-
- 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
- C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
- C03C23/007—Other surface treatment of glass not in the form of fibres or filaments by thermal treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Optics & Photonics (AREA)
- Plasma & Fusion (AREA)
- Thermal Sciences (AREA)
- Surface Treatment Of Glass (AREA)
- Physical Vapour Deposition (AREA)
- Formation Of Insulating Films (AREA)
Abstract
Description
本発明は、イオン注入を用いたガラス基材の表面改質法
に間し、特に、良質な表面改質層を形成できる表面改貢
法に間する，The present invention relates to a method for surface modification of glass substrates using ion implantation, and in particular to a surface modification method that can form a high-quality surface modification layer.
従来から、イオン注入法を用いてガラス基板の表面を改
質する方法が知られている．
例えば、ナトリウムイオンを含んだガラス板にリンイオ
ンを約２５０ｋｅＶのエネルギーで注入し、その後６５
０℃でアニールして、注入したイオン種とガラス構成元
糞とを結合させて、ガラス板内部にリン珪酸ガラス層を
形成する方法、およびさらにその上に窒素イオンを約５
０ｋｅＶのエネルギーで注入し６６０℃でアニールして
、注入しｋ窒素イオンとガラス構成元素とを結合させて
窒化珪素層を形成する方法が知られている． 〈例えば
特間昭６３−２２２０４６）．A method of modifying the surface of a glass substrate using ion implantation has been known for some time. For example, phosphorus ions are implanted into a glass plate containing sodium ions at an energy of about 250 keV, and then 65
A method of forming a phosphosilicate glass layer inside the glass plate by annealing at 0°C to combine the implanted ionic species with the glass constituent material, and further adding nitrogen ions on top of the phosphosilicate glass layer.
A known method is to form a silicon nitride layer by implanting with an energy of 0 keV and annealing at 660° C. to combine the implanted nitrogen ions with glass constituent elements. (For example, Tokuma Showa 63-222046).
しかしながら、上記従来方法の表面改質法では、イオン
注入を行なった後のアニールをガラス基板の軟化温度以
下で行なう必要があり、注入イオン種とガラス構成元素
との反応が十分でないため、ｗ４待するほど良賞な表面
改質層が得られないという問題点があった．
これは、安価なガラス基板を表面改質して、より高品位
の基板として工業用に使用する際の問題点となっていた
．However, in the conventional surface modification method described above, it is necessary to perform annealing after ion implantation at a temperature below the softening temperature of the glass substrate, and the reaction between the implanted ion species and the glass constituent elements is not sufficient, so it is necessary to wait for w4. The problem was that it was not possible to obtain a surface-modified layer that was as good as it was. This has been a problem when surface-modifying an inexpensive glass substrate and using it as a higher-quality substrate for industrial use.
本発明は、上記問題点を解決するためになされたもので
あって、 イオン注入を用いたガラス基材の表面改質法
において、イオン注入の途中あるいは徨に、レーザー光
を用いてガラス基材のイオン注入した部分を加熱してい
る．
レーザー光の照射条件としては、イオンを注入したガラ
ス表面層が高温にできるものであれば何れでも使用でき
る．
例えば、Ｓ１を多量に含むイオン注入層では、Ｓｉによ
る吸収の高いエキシマレーザー及び八「レーザー等を用
いることにより、ガラス基材内部を直接加熱出来る．
また、イオン注入層で吸収の高いレーザー光を用いる他
に、ガラスでの吸収が高いＣＯ２レーザーを照射して、
ガラス層から間接的にイオン注入層を加熱することもで
きる．
また、該ｈａ熱はガラス基材上に設けたレーザー光を吸
収する材料の薄１１を介して行なっても良い．該薄膜の
種類とレーザー光の組合せは、該薄膜がイオン注入層を
含むガラス表面を高温に加熱できるものであれば何れで
も使用できる．例えば、Ｓｉをレーザー光を吸収する材
料の薄膜としてガラス表面に堆積する際には、レーザー
としてはＳＩＭでの吸収が良いエキシマレーザー及び八
「レーザー等が使用できる．
また、Ｓ１０２膜をガラス表面に堆積する際には、Ｓｉ
Ｏｚ膜での吸収が良いＣＯ２レーザーが使用できる．
該レーザー光を吸収する材料の薄膜として、Ｓ１等の半
導体膜を用いると、基板のアニール操作と、半導体膜の
結晶化操作とを同時に実施出来ることになり好ましい．
ガラス基材上に設けたレーザー光を吸収する材料のＷｉ
膜を介して加熱を行なう方法としては、［１］ガラス基
材の上に薄膜を堆積してイオン注入した後レーザー光を
ｗＩ射する．
［２コイオン注入したガラス基材の上にｉ膜を堆積しな
がらレーザー光を照射する．
［３］イオン注入したガラス基Ｉオの上にｉ１Ｍを堆積
した後レーザー光をＷｌｔＪ′４する．等の方法が例示
出来る．
該レーザー光の！１ｉ！利は任意の方向から実施でき、
例えば、ガラス基材の表面からであっても、あるいは裏
面からであってもかまわない．
該レーザー光の照射強度および照射時間は、イオン注入
したガラス基材の必要部分が、十分に加熱される範囲で
あって、ガラス基材の変形等の生じない範囲であれば、
任意の強度および時間で実施出来る．例えばレーザー光
を集光させてスポット的に基材に照射するのであれば、
短時間でガラス基材の必要部分の加熱は完了する．
本発明に使用するガラス基材としては、アルカＪ含有ガ
ラス基板，低アルカリガラス基板．無アルカリガラス基
板等任意のガラス基板が使用出来る．なかでも、アルカ
リ含有ガラス基板または低アルカリガラス基板が、本発
明の主目的である表面特性の改質効果が大きく表れるの
で好ましい．The present invention has been made in order to solve the above-mentioned problems, and in a method for surface modification of glass substrates using ion implantation, a laser beam is used to modify the surface of the glass substrate during or after ion implantation. The part where the ions were implanted is heated. Any laser beam irradiation conditions can be used as long as the glass surface layer into which ions are implanted can be heated to a high temperature. For example, in an ion-implanted layer containing a large amount of S1, the inside of the glass substrate can be directly heated by using an excimer laser, which is highly absorbed by Si, a laser, etc. In addition to using CO2 laser, which is highly absorbed by glass,
It is also possible to heat the ion implantation layer indirectly from the glass layer. Alternatively, the ha heating may be performed through a thin layer 11 of a material that absorbs laser light provided on the glass substrate. Any combination of the type of thin film and laser light can be used as long as the thin film can heat the glass surface including the ion-implanted layer to a high temperature. For example, when depositing Si as a thin film of a material that absorbs laser light on a glass surface, an excimer laser or a laser that has good absorption in SIM can be used as the laser. When depositing, Si
A CO2 laser with good absorption by the Oz film can be used. It is preferable to use a semiconductor film such as S1 as the thin film of the material that absorbs the laser light, since this allows the annealing operation of the substrate and the crystallization operation of the semiconductor film to be performed simultaneously. Wi, a material that absorbs laser light provided on a glass base material
As a method for heating through a film, [1] A thin film is deposited on a glass substrate, ions are implanted, and then a laser beam is irradiated. [Laser light is irradiated while depositing the i-film on the glass substrate into which 2 coin ions have been implanted. [3] After depositing i1M on the ion-implanted glass substrate Io, apply laser light WltJ'4. The following methods can be exemplified. The laser light! 1i! Interest can be implemented from any direction,
For example, it may be from the front side or the back side of the glass substrate. The irradiation intensity and irradiation time of the laser beam are within a range that sufficiently heats the necessary portion of the ion-implanted glass substrate and does not cause deformation of the glass substrate.
It can be performed at any intensity and time. For example, if laser light is focused and irradiated onto the base material in spots,
Heating of the necessary parts of the glass substrate is completed in a short time. Glass substrates used in the present invention include alkali J-containing glass substrates, low-alkali glass substrates. Any glass substrate can be used, such as an alkali-free glass substrate. Among these, alkali-containing glass substrates or low-alkali glass substrates are preferred because they exhibit a large effect of modifying surface properties, which is the main objective of the present invention.
本発明によれば、レーザー光によりイオン注入層を瞬時
に加熱し、アニールできるので、必要部分をガラス基材
の軟化温度以上に加熱出来る．そのため、注入イオン種
とガラス構成元素との結合が十分に起こり、良質の表面
改質層が形成できる．According to the present invention, the ion-implanted layer can be instantaneously heated and annealed using a laser beam, so that the necessary portion can be heated to a temperature higher than the softening temperature of the glass substrate. Therefore, sufficient bonding occurs between the implanted ion species and the glass constituent elements, and a high-quality surface-modified layer can be formed.
実施例−１
ガラス基板の表面に、窒素イオンを３０ｋｅＶでＩＸＩ
ＯＩ７個／ｃｍ２注入し、ガラス＆板の表面から０．０
６μｍの深さに濃度ピークを持つイオン注入層を形成し
た．その後、ガラス基板の表面からＣＯ２レーザー（波
長１０．６μｍ）を照射した．Ｃ０２レーザーの？Ｍ射
条件は、ビーム径が２００１１ｍ、ビームパワーが４５
Ｗ、走査速度１． ５ｍ／ｍ ｉ ｎであった．
この後、試料をＸ線光電子分光法で測定したところ、Ｃ
Ｏ２レーザーを照刺した試料では、ＣＯ２レーザーを照
剥していない試料に比べて窒化珪素瀾度が５〜ｘＯ倍に
測定された．
また、イオン注入を行なった後、４００℃で熱処理した
ものと較べても、窒化珪素濃度は５〜１０倍と測定され
た．
上記窒化珪素の濶度は、ガラス基板に含まれるアルカリ
金属の拡散の防止能力に正の相間をすると考えられ、本
発明のレーザー光を用いた基板の加熱操作は、アルカリ
金属の拡散防止等のガラス基板表面特性の改良に効果が
あることがわかる．実施例−２
ガラス基板の表面に、リンイオンを１００ｋｅＶでＩＸ
ＩＯＩ７個／ｃｍ２注入し、ガラス基板の表面から０．
１μｍの深さに１度ピークを持つ第ｌのイオン注入
層を形成した後、窒素イオンを３０ｋｅＶでＩ Ｘ １
０Ｉ１／ｃｍ２注入してガラス基板の表面から０．０
６μｍの深さに濶度ビークを持つ第２のイオン注入層３
を形成した．
この後、上記実施例−１と同様の条件でＣＯ２レーザー
（波長１０．６μｍ）を照射した．この後、試料をＸ線
光電子分光法で測定したところ、ＣＯ２レーザーをｐ！
ｌ躬した試料では、ＣＯ２レーザーを照射していない試
料に比べて、第１のイオン注入層のリン珪酸濃度は２〜
３倍に、第２のイオン注入層の窒化珪素濃度は５〜１０
倍に測定された．
また、イオン注入を行なった後、４００℃で熱処理した
ものと較べても、リン珪酸濤度は２〜３倍に、窒化珪素
濶度は５〜ｌＯ倍に測定された．実施例−３
ガラス基板の表面に、珪素イオンを６０ｋｅＶでＩＸＩ
Ｏ１７ｌ／ｃｍ２注入してガラス基板の表面から０．０
６μｍの深さに瀾度ビークを持つイオン注入層を形成し
た後、窒素イオンを３０ｋｅＶでｌＸ１０１７個／ｃｍ
’注入して上記イオン注入層に重なる様に新たなイオン
注入層を形成した。
この後、該ガラス基板の表面あるいは裏面から、ＸｅＣ
Ｉのエキシマレーザー（波長３０８ｎｍ）を１００ｍＪ
／ｃｍ２のビーム強度で１パルスｐ！ＪｔＪ４した．
この試料をＸ線光電子分光法で測定したところ、エキシ
マレーザーを照射した試料では、エキシマレーザーを照
射していない試料に比べて、窒化珪素濃度が５〜ｌＯ倍
に測定された．
また、イオン注入を行なった後、４００℃で熱処理した
ものと較べても、窒化珪素濶度は５〜１０倍と測定され
た．
以上説明した様に、本発明はｌ稽のイオンを注入した単
層の改質層の他に、複数のイオン種を注入した積層型の
改質層にも適用できることは明かである．
実施例−４
ガラス基板の表面に、窒素イオンを３０ｋｅＶでＩＸＩ
Ｏ”個／ｃｍ２注入し、ガラス基板の表爾から０．０６
μｍの深さに瀾度ビークを持つイオン注入層を形成した
後、該ガラス基板の表面に厚さ１０ｎｍの非晶質Ｓｉ膜
を堆積し、該ガラス基板の表面からＸｅＣｌのエキシマ
レーザー（波長３０８ｎｍ）を１００ｍＪ／ｃｍ’のビ
ーム強度で１パルス照刺した．
この後、試料をＸ線光電子分光法で測定したところ、非
晶質ＳｉＭを堆積してエキシマレーザーをＮＩＩ４Ｌｒ
た試料では、イオン注入後の試料に比べて窒化珪Ｉｌａ
度が５〜１０倍に測定された．また、イオン注入を行な
った後、４００℃で熱処理したものと較べても、窒化珪
素瀾度は５〜１０倍と測定された．
実施Ｗ４−５
ガラス基板の表面に、リンイオンを１ ０ ０ ｋ ｅ
ＶでＩＸＩＯｌ７個／ｃｍ２注入し、ガラス基板の表面
から０． １μｍの深さに濃度ピークを持つ第１のイ
オン注入層を形成した後、窒素イオンを３ｏｋｅＶでＩ
Ｘ １ ０１７１Ｍ／ ｃｍ２注入してガラス基板の
表面から０．０６μｍの深さに濃度ピークを持つ第２の
イオン注入層を形成した．この後、該ガラス基板の表面
に厚さ１０ｎｍの非晶１（Ｓｉ膜を堆積し、該ガラス基
板の表面から、上記実施例１と同様の条件でＸｅＣ＋の
エキシマレーザーを照射した．
この後、試料をＸ線光電子分光法で測定したところ、非
晶１ｆｓｉＭを堆積してエキシマレーザ−を照射した試
料では、イオン注入後の試料に比べて、第１のイオン注
入層のリン珪酸濃度が２〜３倍に、第２のイオン注入層
の窒化珪素濃度が５〜１０倍に測定された．
また、イオン注入を行なった後、４００℃で熱処理した
ものと較べても、リン珪ｔｉｎ度が２〜３ｆ５に、窒化
珪素濃度が５〜ＩＯ倍に測定された．実施例−５
ガラス基板の表面に、珪素イオンを６０ｋｅＶでＩ Ｘ
１ ０”Ｏｆｆ／ ｃｍ”注入してガラス基板の表面
から０．０６μｍの深さに濃度ピークを持つイオン注入
層を形成した後、窒素イオンを３０ｋｅＶでＩ ＸＩ
Ｏ”ｕ／ｃｍ２注入して上記イオン注入層に重なる様に
新たなイオン注入層を形成した．この後、該ガラス基板
の表面に厚ざ１０ｎｍの非晶質ＳＩ膜を堆積し、該ガラ
ス基板の表面から、上記実施例−４と同様の条件でＸｅ
Ｃｌのエキシマレーザーを照躬した．
この試料をＸ線光電子分光法で測定したところ、非品質
Ｓｉｌｌを堆積してエキシマレーザーを照射した試料で
は、イオン注入後の試料に比べて、室化珪素濃度が５〜
ＩＯ倍に測定された．また、イオン注入を行なった後、
４００℃で熱処理したものと較べても、窒化珪素濃度は
５〜ｌＯ＠とｉｌｌ１定された．
実施例−７
ガラス基板の表面に、窒素イオンを３ ０ ｋ ｃ Ｖ
でＩＸＩＯＩ７個／ｃｍ’注入し、ガラス基板の表面か
ら０．０６μｍの深さに濃度ピークを持つイオン注入層
を形成した後、該ガラス基板の表面にＩグさ＋７ｚｍの
ＳｉＯ２Ｍを堆積し、ＣＯ２レーザー（波長１０．６μ
ｍ）を照射した．ＣＯ２レーザーのＩ Ｉｔ条件は、ビ
ーム径が２ ０ ０ Ｉｔ ｍ、ビームバワーが４５Ｗ
、走査速度１．５ｍ／ｍｉｎであった。
この後、試料をＸ線光電子分光法で測定したところ、Ｓ
ｉＯ２膜を堆積してＣＯ２レーザーを照利した試料では
、イオン注入後の試料に比べて窒化珪ｇ濃度が５〜１０
倍と瀾定された．
また、イオン注入を行なった後、４００℃で熱処理した
ものと較べても、窒化珪素ａ度は５〜１０倍と測定され
た．
上記実施例においては、レーザー光の照射をガラス基板
の表面から行なっているが、該照躬はガラス基板表面か
らに限らず裏面等任意の方向であってかまわない．
また、ガラス基材の形状も、基板に限らず任意の形状で
あって良い・Example-1 IXI nitrogen ions at 30 keV on the surface of a glass substrate
Inject 7 OI/cm2, 0.0 from the surface of glass & plate
An ion implantation layer with a concentration peak at a depth of 6 μm was formed. Thereafter, a CO2 laser (wavelength: 10.6 μm) was irradiated from the surface of the glass substrate. C02 laser? The M shooting conditions are a beam diameter of 20011 m and a beam power of 45 m.
W, scanning speed 1. It was 5m/min. After this, when the sample was measured by X-ray photoelectron spectroscopy, it was found that C
In the sample that was irradiated with the O2 laser, the silicon nitride hardness was measured to be 5 to xO times higher than that of the sample that was not irradiated with the CO2 laser. Furthermore, the silicon nitride concentration was measured to be 5 to 10 times higher than that of a sample that was heat-treated at 400° C. after ion implantation. The above-mentioned degree of silicon nitride is considered to have a positive correlation with the ability to prevent the diffusion of alkali metals contained in the glass substrate, and the heating operation of the substrate using the laser beam of the present invention is effective in preventing the diffusion of alkali metals. It can be seen that this method is effective in improving the surface characteristics of glass substrates. Example-2 IX phosphorus ions at 100 keV on the surface of a glass substrate
7 IOI/cm2 was injected, and 0.0% was injected from the surface of the glass substrate.
After forming the first ion-implanted layer having a peak of 1 degree at a depth of 1 μm, nitrogen ions were injected at I×1 at 30 keV.
0I1/cm2 injection from the surface of the glass substrate to 0.0
Second ion implantation layer 3 having a degree peak at a depth of 6 μm
was formed. Thereafter, CO2 laser (wavelength: 10.6 μm) was irradiated under the same conditions as in Example-1 above. After this, the sample was measured by X-ray photoelectron spectroscopy, and the CO2 laser was used at p!
The phosphosilicate concentration of the first ion-implanted layer was 2 to 2 in the sample that had been irradiated with CO2 laser compared to the sample that had not been irradiated with the CO2 laser.
3 times, the silicon nitride concentration of the second ion-implanted layer is 5-10
It was measured twice as much. Furthermore, even when compared with those heat-treated at 400° C. after ion implantation, the phosphosilicate degree was measured to be 2 to 3 times higher, and the silicon nitride degree was measured to be 5 to 10 times higher. Example-3 IXI silicon ions were applied to the surface of a glass substrate at 60 keV.
0.0 from the surface of the glass substrate by injecting O17l/cm2
After forming an ion implantation layer with a heat peak at a depth of 6 μm, nitrogen ions were injected at 30 keV at 1×1017 ions/cm.
' A new ion implantation layer was formed so as to overlap the above ion implantation layer. After that, from the front or back surface of the glass substrate,
I excimer laser (wavelength 308 nm) at 100 mJ
1 pulse p with a beam intensity of /cm2! I did JtJ4. When this sample was measured by X-ray photoelectron spectroscopy, the silicon nitride concentration was measured to be 5 to 10 times higher in the sample irradiated with excimer laser than in the sample not irradiated with excimer laser. Furthermore, the silicon nitride yield was measured to be 5 to 10 times higher than that of a sample that was heat-treated at 400°C after ion implantation. As explained above, it is clear that the present invention can be applied not only to a single-layer modified layer in which one or more ions are implanted, but also to a laminated modified layer in which multiple ion species are implanted. Example-4 IXI nitrogen ions at 30 keV on the surface of a glass substrate
O" pieces/cm2 were injected, and 0.06 from the surface of the glass substrate.
After forming an ion implantation layer with a heat peak at a depth of μm, an amorphous Si film with a thickness of 10 nm is deposited on the surface of the glass substrate, and a XeCl excimer laser (wavelength 308 nm) is applied to the surface of the glass substrate. ) was irradiated with one pulse at a beam intensity of 100 mJ/cm'. After this, when the sample was measured by X-ray photoelectron spectroscopy, it was found that amorphous SiM was deposited and the excimer laser was applied to NII4Lr.
Compared to the sample after ion implantation, the silicon nitride Ila
The intensity was measured to be 5 to 10 times higher. Furthermore, the degree of silicon nitride hardness was measured to be 5 to 10 times higher than that obtained by heat treatment at 400° C. after ion implantation. Implementation W4-5 Phosphorus ions were applied to the surface of the glass substrate at 100 ke.
7 IXIOl/cm2 were injected at V and 0.0 V from the surface of the glass substrate. After forming the first ion-implanted layer with a concentration peak at a depth of 1 μm, nitrogen ions were injected into the I
A second ion-implanted layer having a concentration peak at a depth of 0.06 μm from the surface of the glass substrate was formed by implanting X 1 0171 M/cm2. After this, an amorphous 1 (Si film) with a thickness of 10 nm was deposited on the surface of the glass substrate, and a XeC+ excimer laser was irradiated from the surface of the glass substrate under the same conditions as in Example 1. After this, When the sample was measured by X-ray photoelectron spectroscopy, it was found that the phosphosilicate concentration of the first ion-implanted layer was 2 to 2, compared to the sample after ion implantation in the sample in which amorphous 1fsiM was deposited and irradiated with excimer laser. The silicon nitride concentration in the second ion-implanted layer was measured to be 3 times higher and the silicon nitride concentration in the second ion-implanted layer was measured to be 5 to 10 times higher.Also, even when compared with the case where the silicon nitride concentration in the second ion-implanted layer was heat-treated at 400°C, the phosphorus silicon concentration was 2 times higher. At ~3f5, the silicon nitride concentration was measured to be 5~IO times higher.Example-5 Silicon ions were irradiated with IX at 60 keV onto the surface of a glass substrate.
1 After implanting 0"Off/cm" to form an ion implantation layer having a concentration peak at a depth of 0.06 μm from the surface of the glass substrate, nitrogen ions were implanted at 30 keV.
A new ion-implanted layer was formed by implanting O"u/cm2 so as to overlap the above ion-implanted layer. After this, an amorphous SI film with a thickness of 10 nm was deposited on the surface of the glass substrate. from the surface of Xe under the same conditions as in Example-4 above.
Illuminated a Cl excimer laser. When this sample was measured by X-ray photoelectron spectroscopy, it was found that the silicon chamber concentration in the sample deposited with non-quality Sill and irradiated with excimer laser was 5 to 5% higher than that in the sample after ion implantation.
Measured IO times. In addition, after performing ion implantation,
Even when compared with that heat treated at 400°C, the silicon nitride concentration was determined to be 5~1O@. Example-7 Nitrogen ions were applied to the surface of a glass substrate at 30 k c V
After injecting 7 IXIOI/cm' to form an ion-implanted layer with a concentration peak at a depth of 0.06 μm from the surface of the glass substrate, SiO2M of I×+7zm was deposited on the surface of the glass substrate, and CO2 Laser (wavelength 10.6μ
m) was irradiated. The CO2 laser I It conditions are a beam diameter of 200 It m and a beam power of 45 W.
, and the scanning speed was 1.5 m/min. After this, when the sample was measured by X-ray photoelectron spectroscopy, S
In the sample deposited with iO2 film and illuminated with CO2 laser, the silicon nitride concentration was 5 to 10% higher than in the sample after ion implantation.
It was determined that it was double. Furthermore, the silicon nitride a degree was measured to be 5 to 10 times higher than that of a material that was heat-treated at 400° C. after ion implantation. In the above embodiment, the laser beam is irradiated from the front surface of the glass substrate, but the irradiation is not limited to the front surface of the glass substrate, but may be from any direction such as the back surface. Furthermore, the shape of the glass base material is not limited to the substrate, and may be any shape.
Claims (3)
いて、イオン注入の途中あるいは後に、レーザー光を用
いて、ガラス基材のイオン注入した部分を加熱すること
を特徴とするガラス基材の表面改質法。(1) A glass substrate surface modification method using ion implantation, in which the ion-implanted portion of the glass substrate is heated using laser light during or after ion implantation. surface modification method.
収する材料の薄膜を介して行なう請求項１記載のガラス
基材の表面改質法。(2) The method for surface modification of a glass substrate according to claim 1, wherein the heating is performed via a thin film of a material that absorbs laser light provided on the glass substrate.
ある請求項１または２項記載のガラス基材の表面改質法
。(3) The method for surface modification of a glass substrate according to claim 1 or 2, wherein the heating temperature is higher than the softening temperature of the glass substrate.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1156328A JPH0323238A (en) | 1989-06-19 | 1989-06-19 | Surface modifying method for glass base material |
| DE4018804A DE4018804A1 (en) | 1989-06-19 | 1990-06-12 | METHOD FOR MODIFYING THE SURFACE OF GLASS SUBSTRATES |
| CA002018781A CA2018781A1 (en) | 1989-06-19 | 1990-06-12 | Method of modifying the surface of glass substrate |
| GB9013187A GB2234968B (en) | 1989-06-19 | 1990-06-13 | Method of modifying the surface of a glass substrate |
| IT02065990A IT1248863B (en) | 1989-06-19 | 1990-06-15 | METHOD OF MODIFICATION OF THE SURFACE OF A GLASS SUBSTRATE |
| FR9007678A FR2648454B1 (en) | 1989-06-19 | 1990-06-19 | METHOD FOR MODIFYING THE SURFACE OF A GLASS SUBSTRATE |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1156328A JPH0323238A (en) | 1989-06-19 | 1989-06-19 | Surface modifying method for glass base material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0323238A true JPH0323238A (en) | 1991-01-31 |
Family
ID=15625384
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1156328A Pending JPH0323238A (en) | 1989-06-19 | 1989-06-19 | Surface modifying method for glass base material |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPH0323238A (en) |
| CA (1) | CA2018781A1 (en) |
| DE (1) | DE4018804A1 (en) |
| FR (1) | FR2648454B1 (en) |
| GB (1) | GB2234968B (en) |
| IT (1) | IT1248863B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007238378A (en) * | 2006-03-09 | 2007-09-20 | Central Glass Co Ltd | Glass plate having high fracture toughness and method of manufacturing the same |
| JP2019513672A (en) * | 2016-04-12 | 2019-05-30 | エージーシー グラス ユーロップＡｇｃ Ｇｌａｓｓ Ｅｕｒｏｐｅ | Antireflection, scratch resistant glass substrate and method of manufacturing the same |
| JP2019513676A (en) * | 2016-04-12 | 2019-05-30 | エージーシー グラス ユーロップＡｇｃ Ｇｌａｓｓ Ｅｕｒｏｐｅ | Intermediate color antireflective glass substrate and method of manufacturing the same |
| JP2019513674A (en) * | 2016-04-12 | 2019-05-30 | エージーシー グラス ユーロップＡｇｃ Ｇｌａｓｓ Ｅｕｒｏｐｅ | Glass substrate with reduced internal reflectance and method of making same |
| JP2019513671A (en) * | 2016-04-12 | 2019-05-30 | エージーシー グラス ユーロップＡｇｃ Ｇｌａｓｓ Ｅｕｒｏｐｅ | Heat-treatable antireflective glass substrate and method of manufacturing the same |
| JP2019513675A (en) * | 2016-04-12 | 2019-05-30 | エージーシー グラス ユーロップＡｇｃ Ｇｌａｓｓ Ｅｕｒｏｐｅ | Anti-reflection glass substrate and method of manufacturing the same |
| JP2019515863A (en) * | 2016-04-12 | 2019-06-13 | エージーシー グラス ユーロップ エスエーＡｇｃ Ｇｌａｓｓ Ｅｕｒｏｐｅ Ｓａ | Blue reflective glass substrate and method of manufacturing the same |
| JP2019524613A (en) * | 2016-06-28 | 2019-09-05 | コーニング インコーポレイテッド | Thin glass-based article with high resistance to contact damage |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4467597B2 (en) | 2007-04-06 | 2010-05-26 | 株式会社オハラ | Inorganic composition article |
| DE102012213787A1 (en) * | 2012-08-03 | 2014-02-06 | Robert Bosch Gmbh | Surface structuring for cell biological and / or medical applications |
| FR3002240B1 (en) | 2013-02-15 | 2015-07-10 | Quertech Ingenierie | METHOD FOR TREATING AN ION BEAM TO PRODUCE SUSTAINABLE GLAND-FREE GLASS MATERIALS |
| EP3181533A1 (en) * | 2015-12-18 | 2017-06-21 | AGC Glass Europe | Glass substrate for chemical strengthening and method for chemically strengthening with controlled curvature |
| US10731403B2 (en) * | 2017-10-06 | 2020-08-04 | Vkr Holding A/S | Vacuum insulated glazing unit |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4281030A (en) * | 1980-05-12 | 1981-07-28 | Bell Telephone Laboratories, Incorporated | Implantation of vaporized material on melted substrates |
| JPS5999713A (en) * | 1982-11-30 | 1984-06-08 | Agency Of Ind Science & Technol | Manufacture of substrate for thin-film transistor |
| DE3539047C2 (en) * | 1984-12-27 | 1994-06-01 | Bayer Ag | Process for decorating or marking objects with enamelled surfaces using a laser beam |
-
1989
- 1989-06-19 JP JP1156328A patent/JPH0323238A/en active Pending
-
1990
- 1990-06-12 DE DE4018804A patent/DE4018804A1/en not_active Withdrawn
- 1990-06-12 CA CA002018781A patent/CA2018781A1/en not_active Abandoned
- 1990-06-13 GB GB9013187A patent/GB2234968B/en not_active Expired - Fee Related
- 1990-06-15 IT IT02065990A patent/IT1248863B/en active IP Right Grant
- 1990-06-19 FR FR9007678A patent/FR2648454B1/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007238378A (en) * | 2006-03-09 | 2007-09-20 | Central Glass Co Ltd | Glass plate having high fracture toughness and method of manufacturing the same |
| JP2019513672A (en) * | 2016-04-12 | 2019-05-30 | エージーシー グラス ユーロップＡｇｃ Ｇｌａｓｓ Ｅｕｒｏｐｅ | Antireflection, scratch resistant glass substrate and method of manufacturing the same |
| JP2019513676A (en) * | 2016-04-12 | 2019-05-30 | エージーシー グラス ユーロップＡｇｃ Ｇｌａｓｓ Ｅｕｒｏｐｅ | Intermediate color antireflective glass substrate and method of manufacturing the same |
| JP2019513674A (en) * | 2016-04-12 | 2019-05-30 | エージーシー グラス ユーロップＡｇｃ Ｇｌａｓｓ Ｅｕｒｏｐｅ | Glass substrate with reduced internal reflectance and method of making same |
| JP2019513671A (en) * | 2016-04-12 | 2019-05-30 | エージーシー グラス ユーロップＡｇｃ Ｇｌａｓｓ Ｅｕｒｏｐｅ | Heat-treatable antireflective glass substrate and method of manufacturing the same |
| JP2019513675A (en) * | 2016-04-12 | 2019-05-30 | エージーシー グラス ユーロップＡｇｃ Ｇｌａｓｓ Ｅｕｒｏｐｅ | Anti-reflection glass substrate and method of manufacturing the same |
| JP2019515863A (en) * | 2016-04-12 | 2019-06-13 | エージーシー グラス ユーロップ エスエーＡｇｃ Ｇｌａｓｓ Ｅｕｒｏｐｅ Ｓａ | Blue reflective glass substrate and method of manufacturing the same |
| JP2019524613A (en) * | 2016-06-28 | 2019-09-05 | コーニング インコーポレイテッド | Thin glass-based article with high resistance to contact damage |
Also Published As
| Publication number | Publication date |
|---|---|
| IT9020659A1 (en) | 1991-12-15 |
| FR2648454B1 (en) | 1993-07-09 |
| DE4018804A1 (en) | 1990-12-20 |
| GB2234968A (en) | 1991-02-20 |
| CA2018781A1 (en) | 1990-12-19 |
| IT1248863B (en) | 1995-01-30 |
| GB9013187D0 (en) | 1990-08-01 |
| IT9020659A0 (en) | 1990-06-15 |
| FR2648454A1 (en) | 1990-12-21 |
| GB2234968B (en) | 1993-02-17 |
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