JP2007176778A - Radiation-resistant optical glass and method for producing the same - Google Patents
Radiation-resistant optical glass and method for producing the same Download PDFInfo
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- 239000005304 optical glass Substances 0.000 title claims abstract description 24
- 230000005855 radiation Effects 0.000 title abstract description 27
- 238000004519 manufacturing process Methods 0.000 title abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 21
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000460 chlorine Substances 0.000 claims abstract description 20
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 20
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 20
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 19
- 239000011737 fluorine Substances 0.000 claims abstract description 19
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 7
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 7
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 7
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 7
- 150000003624 transition metals Chemical class 0.000 claims abstract description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 18
- 238000002834 transmittance Methods 0.000 claims description 9
- 230000006866 deterioration Effects 0.000 abstract description 3
- 230000007774 longterm Effects 0.000 abstract description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- 239000012535 impurity Substances 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 230000007547 defect Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000002950 deficient Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000004071 soot Substances 0.000 description 3
- 229910008284 Si—F Inorganic materials 0.000 description 2
- 238000001015 X-ray lithography Methods 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000013307 optical fiber Substances 0.000 description 2
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 229910008045 Si-Si Inorganic materials 0.000 description 1
- 229910003902 SiCl 4 Inorganic materials 0.000 description 1
- 229910004014 SiF4 Inorganic materials 0.000 description 1
- 229910006411 Si—Si Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/14—Other methods of shaping glass by gas- or vapour- phase reaction processes
- C03B19/1453—Thermal after-treatment of the shaped article, e.g. dehydrating, consolidating, sintering
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/14—Other methods of shaping glass by gas- or vapour- phase reaction processes
- C03B19/1453—Thermal after-treatment of the shaped article, e.g. dehydrating, consolidating, sintering
- C03B19/1461—Thermal after-treatment of the shaped article, e.g. dehydrating, consolidating, sintering for doping the shaped article with flourine
-
- 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
- C03C3/06—Glass compositions containing silica with more than 90% silica by weight, e.g. quartz
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2201/00—Type of glass produced
- C03B2201/06—Doped silica-based glasses
- C03B2201/07—Impurity concentration specified
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2201/00—Type of glass produced
- C03B2201/06—Doped silica-based glasses
- C03B2201/08—Doped silica-based glasses doped with boron or fluorine or other refractive index decreasing dopant
- C03B2201/12—Doped silica-based glasses doped with boron or fluorine or other refractive index decreasing dopant doped with fluorine
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2201/00—Type of glass produced
- C03B2201/06—Doped silica-based glasses
- C03B2201/20—Doped silica-based glasses doped with non-metals other than boron or fluorine
- C03B2201/23—Doped silica-based glasses doped with non-metals other than boron or fluorine doped with hydroxyl groups
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
- Glass Melting And Manufacturing (AREA)
- Glass Compositions (AREA)
Abstract
Description
本発明は、放射線特にＸ線を照射しても、可視光の光量減少が少なく、放射線照射に対しての劣化が少ない長期信頼性の高い光学ガラスの製造方法に関する。 The present invention relates to a method for producing optical glass with high long-term reliability, which has little decrease in the amount of visible light even when irradiated with radiation, particularly X-rays, and little deterioration with respect to radiation irradiation.
近年放射線照射を用いるＸ線リソグラフィー、非破壊検査、医療画像等に、光ファイバ、レンズおよびプリズムの利用が拡大している。これらは特に放射線被曝内で使用することが多い。 In recent years, the use of optical fibers, lenses, and prisms is expanding for X-ray lithography using radiation irradiation, non-destructive inspection, medical images, and the like. These are particularly often used within radiation exposure.
しかしながら、長期にわたって放射線を照射すると、ガラス材料が劣化してしまい、光の透過率が低下してしまう。更に放射線を照射すると、ほとんど光が通さなくなり、不透明になっていった。 However, irradiation with radiation over a long period of time degrades the glass material and reduces the light transmittance. Furthermore, when radiation was irradiated, almost no light passed through and it became opaque.
これは、ガラス構造そのものが損傷を受け、各種の欠陥が起こることによって、新たな吸収帯の発生及び屈折率や均質性の変化による透過特性の変化から生じる。 This occurs because the glass structure itself is damaged and various defects occur, resulting in the generation of new absorption bands and changes in transmission characteristics due to changes in refractive index and homogeneity.
これらの問題に対処するために、酸化珪素内組成内のＯＨ基を高める方法がとられていた。しかし、このＯＨ基含有量が多すぎると、水の吸収によって放射線の損傷を受けることが発生した。それゆえにＯＨ基含有量を制限される。 In order to cope with these problems, a method of increasing the OH group in the composition in silicon oxide has been taken. However, if the OH group content is too high, radiation damage may occur due to water absorption. Therefore, the OH group content is limited.
別の対処方法として、フッ素をわずかにドープする方法がある。このことによって、放射線の耐久性は向上する。しかしながら、この方法では酸化珪素内にフッ素が多すぎる場合には、８００℃以上の温度をかけると（Ｓｉ−Ｆ）＋（Ｓｉ−Ｆ）→（Ｓｉ−Ｓｉ）＋Ｆ２の反応によって酸素欠乏型欠陥が生じるために、光透過率が劣化する。放射線に対する耐久性を上げるためには加熱処理することが必要なために酸素欠乏型欠陥の生成を避けるのが困難である。そのためにフッ素のドープも制限される。As another countermeasure, there is a method of slightly doping fluorine. This improves the durability of radiation. However, in this method, when there is too much fluorine in silicon oxide, when a temperature of 800 ° C. or higher is applied, an oxygen-deficient type is caused by a reaction of (Si—F) + (Si—F) → (Si—Si) + F 2. Since the defect is generated, the light transmittance is deteriorated. It is difficult to avoid the generation of oxygen-deficient defects because heat treatment is required to increase durability against radiation. Therefore, fluorine doping is also limited.
また、遷移金属類、アルカリ土類金属、アルカリ金属が放射線照射による劣化による光透過率が減少するためにそれぞれの含有量は２０ｐｐｍ未満にしなければならなかった。 In addition, since the light transmittance of transition metals, alkaline earth metals, and alkali metals due to deterioration by radiation irradiation is reduced, the respective contents must be less than 20 ppm.
更に塩素は酸化珪素内で≡Ｓｉ−Ｃｌ結合を生じる。この≡Ｓｉ−Ｃ結合は放射線により容易に解離して、欠陥の要因になるために、塩素の含有量はできるだけ少ない方が望ましい。この含有量は１ｐｐｍ未満にしなければならなかった。 In addition, chlorine produces ≡Si-Cl bonds in silicon oxide. Since this ≡Si—C bond is easily dissociated by radiation and causes defects, it is desirable that the chlorine content is as small as possible. This content had to be less than 1 ppm.
本発明の課題は、上記したようなことに対して、その目的とするところは、水の吸収や酸素欠乏型欠陥を防止して、放射線による劣化する遷移金属類、アルカリ土類金属、アルカリ金属および塩素を除去することによって、放射線を照射しても光透過率の減少を防ぎ、耐用寿命を延ばし、耐放射線優れた光学ガラスを得ることである。 The object of the present invention is to prevent the absorption of water and oxygen-deficient defects and to deteriorate by radiation, transition metals, alkaline earth metals, alkali metals. By removing chlorine and chlorine, a reduction in light transmittance is prevented even when irradiated with radiation, the service life is extended, and an optical glass excellent in radiation resistance is obtained.
上記課題を解決するため、酸化珪素の諸物性と耐放射線性との関係を鋭意検討した結果、酸化珪素のＯＨ基、酸素欠乏型欠陥、金属不純物及び塩素の濃度が、放射線耐性に対して特に重要であり、それぞれの値を特定の範囲内にする事にとって、耐放射線に優れた光学ガラスを得られることを見出した。 In order to solve the above problems, as a result of intensive studies on the relationship between various physical properties of silicon oxide and radiation resistance, the concentration of OH groups, oxygen-deficient defects, metal impurities, and chlorine in silicon oxide is particularly high against radiation resistance. It was important, and it was found that an optical glass excellent in radiation resistance can be obtained by setting each value within a specific range.
すなわち、本発明は酸化珪素を主成分として、フッ素ドープ量を１〜９ｐｐｍ、ＯＨ基濃度は８００〜１２００ｐｐｍにする。遷移金属類、アルカリ土類金属、アルカリ金属をそれぞれ２０ｐｐｍ未満にする。更に塩素含有量を１ｐｐｍ未満にしたものである。 That is, in the present invention, silicon oxide is the main component, the fluorine doping amount is 1 to 9 ppm, and the OH group concentration is 800 to 1200 ppm. The transition metal, alkaline earth metal, and alkali metal are each made less than 20 ppm. Further, the chlorine content is less than 1 ppm.
本発明の方法により、放射線照射による耐久性に優れた光学ガラスの提供が可能になった。本発明の方法では、ＯＨ基、酸素欠乏型欠陥、金属不純物及び塩素の各含有量を制限することで構造を安定化し、光透過率の変化量を減少しており、放射線照射による耐久性を高めている。その際、特殊な製造方法によることなく、安価で、優れた耐放射線光学ガラスの提供が可能である。 According to the method of the present invention, it is possible to provide an optical glass excellent in durability by radiation irradiation. In the method of the present invention, the structure is stabilized by limiting the contents of OH groups, oxygen-deficient defects, metal impurities, and chlorine, and the amount of change in light transmittance is reduced. It is increasing. At that time, it is possible to provide an inexpensive radiation-resistant optical glass without using a special manufacturing method.
従って、本発明の光学ガラスは半導体素子の高密度化に伴う、超細密化回路パターンのためのＸ線リソグラフィーを用いる装置内の光学ガラスに効果的に用いられる。また、非破壊検査、医療画像の放射線環境下での画像・信号伝送等の光ファイバ、レンズおよびプリズムとして、安定した状態で適用できる効果を得る。 Therefore, the optical glass of the present invention can be effectively used as an optical glass in an apparatus using X-ray lithography for an ultra-fine circuit pattern as the density of semiconductor elements increases. Further, it is possible to obtain an effect that can be applied in a stable state as an optical fiber, a lens, and a prism for nondestructive inspection and image / signal transmission in a radiation environment for medical images.
上記した本発明は光学ガラスは、以下のような製造方法により、製造される。
ＶＡＤ法により、ＳｉＣｌ４を原料として、酸水素バーナーを用いて、石英棒表面上に酸化珪素を主成分としたガラススートを形成する。次いで、このガラススートを加熱炉に投入して、水素Ｈ２の供給量を適宜調整して、ＯＨ基の含有量を調整し、４フッ化珪素ＳｉＦ４の供給量を適宜調整して、フッ素ドープ量を調整する。この該ガス雰囲気下で５００〜７００℃の温度で加熱して、ガラススートを透明化して、所定のＯＨ基及びフッ素ドープ量を有する光学ガラスを得るものである。In the present invention described above, the optical glass is manufactured by the following manufacturing method.
A glass soot containing silicon oxide as a main component is formed on the surface of the quartz rod by the VAD method using SiCl 4 as a raw material and using an oxyhydrogen burner. Next, the glass soot is put into a heating furnace, the supply amount of hydrogen H2 is adjusted as appropriate, the OH group content is adjusted, the supply amount of silicon tetrafluoride SiF4 is adjusted as appropriate, and the fluorine doping amount Adjust. In this gas atmosphere, the glass soot is made transparent by heating at a temperature of 500 to 700 ° C. to obtain an optical glass having a predetermined OH group and fluorine doping amount.
以下の実施例により本発明を具体的に説明するが、本発明はこれら実施例に限定されるものではない。放射線耐性については以下の通りである。 The present invention will be specifically described by the following examples, but the present invention is not limited to these examples. The radiation resistance is as follows.
〔放射線耐性〕
Ｘ線を照射線量２．５×１０４Ｃ／ｋｇ・ｈ（照射条件、Ｒｈ管球、管電圧５０ｋＶ、管電流５０ｍＡ）で３時間照射し、照射前後の光透過率を確認して、放射線耐性を評価した。その際の測定試料の厚みは５０ｍｍとした。[Radiation resistance]
X-rays were irradiated for 3 hours at an irradiation dose of 2.5 × 10 4 C / kg · h (irradiation conditions, Rh tube, tube voltage 50 kV, tube current 50 mA), and the light transmittance before and after irradiation was confirmed. Resistance was evaluated. The thickness of the measurement sample at that time was 50 mm.
実施例１
上記した製造方法により、酸化珪素を主成分として、ＯＨ基１０００ｐｐｍ、フッ素ドープ量５ｐｐｍ、遷移金属類、アルカリ土類金属、アルカリ金属（以下、金属不純物という）２０ｐｐｍ未満、塩素含有量１ｐｐｍ未満である光学ガラスを製造した。Example 1
By the manufacturing method described above, silicon oxide as a main component, OH group 1000 ppm, fluorine doping amount 5 ppm, transition metal, alkaline earth metal, alkali metal (hereinafter referred to as metal impurity) less than 20 ppm, and chlorine content less than 1 ppm. Optical glass was manufactured.
実施例２
上記した製造方法により、酸化珪素を主成分として、ＯＨ基８００ｐｐｍ、フッ素ドープ量５ｐｐｍ、金属不純物を２０ｐｐｍ未満、塩素含有量１ｐｐｍ末満である光学ガラスを製造した。Example 2
By the manufacturing method described above, an optical glass containing silicon oxide as a main component, OH group 800 ppm, fluorine doping amount 5 ppm, metal impurities less than 20 ppm, and chlorine content less than 1 ppm was manufactured.
実施例３
上記した製造方法により、酸化珪素を主成分として、ＯＨ基１２００ｐｐｍ、フッ素ドープ量５ｐｐｍ、金属不純物を２０ｐｐｍ未満、塩素含有量１ｐｐｍ未満である光学ガラスを製造した。Example 3
By the manufacturing method described above, an optical glass containing silicon oxide as a main component and having an OH group of 1200 ppm, a fluorine doping amount of 5 ppm, a metal impurity of less than 20 ppm, and a chlorine content of less than 1 ppm was produced.
実施例４
上記した製造方法により、酸化珪素を主成分として、ＯＨ基１０００ｐｐｍ、フッ素ドープ量１ｐｐｍ、金属不純物を２０ｐｐｍ未満、塩素含有量１ｐｐｍ未満である光学ガラスを製造した。Example 4
By the manufacturing method described above, an optical glass having silicon oxide as a main component, OH group 1000 ppm, fluorine doping amount 1 ppm, metal impurities less than 20 ppm, and chlorine content less than 1 ppm was manufactured.
実施例５
上記した製造方法により、酸化珪素を主成分として、ＯＨ基１０００ｐｐｍ、フッ素ドープ量９ｐｐｍ、金属不純物を２０ｐｐｍ未満、塩素含有量１ｐｐｍ未満である光学ガラスを製造した。Example 5
By the manufacturing method described above, an optical glass containing silicon oxide as a main component and having an OH group of 1000 ppm, a fluorine doping amount of 9 ppm, a metal impurity of less than 20 ppm, and a chlorine content of less than 1 ppm was produced.
比較例１
上記した製造方法により、酸化珪素を主成分として、ＯＨ基５００ｐｐｍ、フッ素ドープ量５ｐｐｍ、金属不純物を２０ｐｐｍ未満、塩素含有量１ｐｐｍ未満である光学ガラスを製造した。Comparative Example 1
By the manufacturing method described above, an optical glass containing silicon oxide as a main component and having an OH group of 500 ppm, a fluorine doping amount of 5 ppm, a metal impurity of less than 20 ppm, and a chlorine content of less than 1 ppm was produced.
比較例２
上記した製造方法により、酸化珪素を主成分として、ＯＨ基１５００ｐｐｍ、フッ素ドープ量５ｐｐｍ、金属不純物を２０ｐｐｍ未満、塩素含有量１ｐｐｍ未満である光学ガラスを製造した。Comparative Example 2
By the manufacturing method described above, an optical glass having silicon oxide as a main component, OH group 1500 ppm, fluorine doping amount 5 ppm, metal impurities less than 20 ppm, and chlorine content less than 1 ppm was manufactured.
比較例３
上記した製造方法により、酸化珪素を主成分として、ＯＨ基１０００ｐｐｍ、フッ素ドープ量２０ｐｐｍ、遷移金属類、アルカリ土類金属、アルカリ金属をそれぞれ２０ｐｐｍ未満、塩素含有量１ｐｐｍ末満である光学ガラスを製造した。Comparative Example 3
By the manufacturing method described above, an optical glass having silicon oxide as a main component, OH group 1000 ppm, fluorine doping amount 20 ppm, transition metals, alkaline earth metals and alkali metals each less than 20 ppm and chlorine content less than 1 ppm is manufactured. did.
比較例４
上記した製造方法により、酸化珪素を主成分として、ＯＨ基１０００ｐｐｍ、フッ素ドープ量１ｐｐｍ未満、金属不純物を５０ｐｐｍ、塩素含有量１ｐｐｍ未満である光学ガラスを製造した。Comparative Example 4
By the manufacturing method described above, an optical glass containing silicon oxide as a main component and having an OH group of 1000 ppm, a fluorine doping amount of less than 1 ppm, a metal impurity of 50 ppm, and a chlorine content of less than 1 ppm was manufactured.
比較例５
上記した製造方法により、酸化珪素を主成分として、ＯＨ基１０００ｐｐｍ、フッ素ドープ量９ｐｐｍ、金属不純物を５０ｐｐｍ、塩素含有量１ｐｐｍ未満である光学ガラスを製造した。Comparative Example 5
By the manufacturing method described above, an optical glass containing silicon oxide as a main component and having an OH group of 1000 ppm, a fluorine doping amount of 9 ppm, a metal impurity of 50 ppm, and a chlorine content of less than 1 ppm was manufactured.
比較例６
上記した製造方法により、酸化珪素を主成分として、ＯＨ基１０００ｐｐｍ、フッ素ドープ量９ｐｐｍ、金属不純物を２０ｐｐｍ未満、塩素含有量５ｐｐｍである光学ガラスを製造した。Comparative Example 6
By the manufacturing method described above, an optical glass containing silicon oxide as a main component, OH group 1000 ppm, fluorine doping amount 9 ppm, metal impurities less than 20 ppm, and chlorine content 5 ppm was manufactured.
以下の表１に実施例１〜５及び比較例１〜５の試料の各物性値示す。 Table 1 below shows the physical property values of the samples of Examples 1 to 5 and Comparative Examples 1 to 5.
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| JP2005381274A JP2007176778A (en) | 2005-12-28 | 2005-12-28 | Radiation-resistant optical glass and method for producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2013174867A (en) * | 2012-01-23 | 2013-09-05 | Sumitomo Electric Ind Ltd | Optical fiber and optical fiber base material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2013174867A (en) * | 2012-01-23 | 2013-09-05 | Sumitomo Electric Ind Ltd | Optical fiber and optical fiber base material |
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