JP2012246157A - Method for producing synthetic silica glass and the synthetic silica glass - Google Patents
Method for producing synthetic silica glass and the synthetic silica glass Download PDFInfo
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- JP2012246157A JP2012246157A JP2011117713A JP2011117713A JP2012246157A JP 2012246157 A JP2012246157 A JP 2012246157A JP 2011117713 A JP2011117713 A JP 2011117713A JP 2011117713 A JP2011117713 A JP 2011117713A JP 2012246157 A JP2012246157 A JP 2012246157A
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 181
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 55
- OMRRUNXAWXNVFW-UHFFFAOYSA-N fluoridochlorine Chemical compound ClF OMRRUNXAWXNVFW-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000000460 chlorine Substances 0.000 claims abstract description 30
- 239000011737 fluorine Substances 0.000 claims abstract description 24
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract 3
- 239000002994 raw material Substances 0.000 claims description 53
- 238000000034 method Methods 0.000 claims description 19
- 239000002019 doping agent Substances 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 description 44
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 19
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 13
- 229910052801 chlorine Inorganic materials 0.000 description 11
- 239000011521 glass Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229910020163 SiOCl Inorganic materials 0.000 description 2
- 229910020177 SiOF Inorganic materials 0.000 description 2
- 229910020175 SiOH Inorganic materials 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000013307 optical fiber Substances 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 238000004017 vitrification Methods 0.000 description 2
- 229910003902 SiCl 4 Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 229910008284 Si—F Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C13/00—Fibre or filament compositions
- C03C13/04—Fibre optics, e.g. core and clad fibre compositions
- C03C13/045—Silica-containing oxide glass compositions
-
- 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
- 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
- C03C2201/00—Glass compositions
- C03C2201/06—Doped silica-based glasses
- C03C2201/08—Doped silica-based glasses containing boron or halide
- C03C2201/11—Doped silica-based glasses containing boron or halide containing chlorine
-
- 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
- C03C2201/00—Glass compositions
- C03C2201/06—Doped silica-based glasses
- C03C2201/08—Doped silica-based glasses containing boron or halide
- C03C2201/12—Doped silica-based glasses containing boron or halide containing fluorine
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- 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)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Glass Melting And Manufacturing (AREA)
- Glass Compositions (AREA)
Abstract
Description
本発明は、合成シリカガラスの製造技術に関する。 The present invention relates to a technique for producing synthetic silica glass.
光ファイバ等の光学部材等の素材は、従来、以下のような方法で製造されている。まず、ＶＡＤ（Ｖａｐｏｒ ｐｈａｓｅ Ａｘｉａｌ Ｄｅｐｏｓｉｔｉｏｎ）法で合成した多孔質シリカ原料をガラス化装置で脱水及び透明化して合成シリカガラスを作製し、又はＣＶＤ（Ｃｈｅｍｉｃａｌ Ｖａｐｏｒ Ｄｅｐｏｓｉｔｉｏｎ）法で合成シリカガラスを作製し、次に、その合成シリカガラスを例えば酸水素火炎もしくは電気炉で加熱延伸することでガラスロッドを作製する。 A material such as an optical member such as an optical fiber is conventionally manufactured by the following method. First, a porous silica raw material synthesized by a VAD (Vapor Phase Axial Deposition) method is dehydrated and clarified by a vitrification apparatus to produce a synthetic silica glass, or a synthetic silica glass is produced by a CVD (Chemical Vapor Deposition) method, Next, the synthetic silica glass is heated and stretched with, for example, an oxyhydrogen flame or an electric furnace to produce a glass rod.
得られたガラスロッドに、さらにＶＡＤ法等によりシリカガラス粒子を堆積させて多孔質シリカ原料を形成し、ガラス化装置で脱水及び透明化を行うことで、プリフォームを作製する。 Silica glass particles are further deposited on the obtained glass rod by the VAD method or the like to form a porous silica raw material, and a preform is produced by dehydration and transparency using a vitrification apparatus.
多孔質シリカ原料を加熱処理する工程で、雰囲気中のフッ化塩素ガスの分圧を高くすると、プリフォームにドープされるフッ素の量が多くなり、負の比屈折率差を形成することができる。特許文献１〜４には、多孔質シリカ原料をＳＦ６、ＳｉＦ４、Ｓｉ２Ｆ６、Ｓｉ３Ｆ３等のフッ素ガス雰囲気に配置することで、フッ素をドープした具体例が開示されている。 If the partial pressure of chlorine fluoride gas in the atmosphere is increased in the step of heat-treating the porous silica raw material, the amount of fluorine doped into the preform increases and a negative relative refractive index difference can be formed. . Patent Documents 1 to 4 disclose specific examples in which fluorine is doped by disposing a porous silica raw material in a fluorine gas atmosphere such as SF 6 , SiF 4 , Si 2 F 6 , and Si 3 F 3 . .
しかし、特許文献２の方法では、塩素処理(脱水目的)後にフッ素処理を行うため、フッ素処理時に塩素がフッ素に置換され、塩素が屈折率分布に寄与しない。特許文献１、３及び４の方法では、原料に塩素を含むＳｉＣｌ４等を使用しても多孔質シリカ原料に含有される塩素は少なく、フッ素処理時に塩素がフッ素に置換され、塩素は屈折率分布に寄与しない。また、ＳｉＦ４等を使用するために高温処理が必要であり、これにより多孔質シリカ原料の収縮、つまり嵩密度の増加が発生し、均一なドープが困難になる。このため、多孔質シリカ原料の長軸方向においては加熱処理を制御することにより長軸方向の屈折率分布が均一となるが、断面方向においてはシリカガラスの比屈折率差が合成シリカガラスの断面内において不均一であるため、得られる合成シリカガラスロッド内の断面方向の屈折率が不均等になりやすいという問題がある。 However, in the method of Patent Document 2, since the fluorine treatment is performed after the chlorine treatment (for the purpose of dehydration), chlorine is replaced with fluorine during the fluorine treatment, and chlorine does not contribute to the refractive index distribution. In the methods of Patent Documents 1, 3 and 4, even if SiCl 4 containing chlorine is used as a raw material, the amount of chlorine contained in the porous silica raw material is small, and chlorine is replaced with fluorine during the fluorine treatment. Does not contribute to the distribution. Further, since high-temperature treatment is required in order to use SiF 4 or the like, shrinkage of the porous silica raw material, that is, increase in bulk density occurs, and uniform dope becomes difficult. For this reason, the refractive index distribution in the major axis direction becomes uniform by controlling the heat treatment in the major axis direction of the porous silica raw material, but the relative refractive index difference of the silica glass in the sectional direction is a cross section of the synthetic silica glass. Since the inside is non-uniform, there is a problem that the refractive index in the cross-sectional direction in the resulting synthetic silica glass rod tends to be non-uniform.
本発明は、以上の実情に鑑みてなされたものであり、合成シリカガラス内の屈折率を均等化できる合成シリカガラスの製造方法及び合成シリカガラスを提供することを目的とする。 This invention is made | formed in view of the above situation, and it aims at providing the manufacturing method of synthetic silica glass and synthetic silica glass which can equalize the refractive index in synthetic silica glass.
本発明者らは、多孔質シリカ原料を、フッ化塩素ガスを含む雰囲気に配置することで、形成される比屈折率差の大きさがシリカガラス内において均等化することを見出し、本発明を完成するに至った。具体的に、本発明は以下のものを提供する。 The present inventors have found that by arranging the porous silica raw material in an atmosphere containing chlorine fluoride gas, the magnitude of the relative refractive index difference formed is equalized in the silica glass. It came to be completed. Specifically, the present invention provides the following.
（１） １００ｐｐｍ以上のＦ元素と、１ｐｐｍ以上でありかつＦ元素の含有量の−β／α（式中、αはＣｌ元素１ｐｐｍあたり変化する屈折率の値、βはＦ元素１ｐｐｍあたり変化する屈折率の値）倍以下であるＣｌ元素とを含み、屈折率（ｎｄ）１．４５８５０をリファレンスとしたときの断面内の比屈折率差が０．０１％以下である合成シリカガラス。 (1) 100 ppm or more of the F element and 1 ppm or more and the content of the F element -β / α (where α is a refractive index value that changes per 1 ppm of the Cl element, and β changes per 1 ppm of the F element. Synthetic silica glass containing a Cl element that is less than or equal to (refractive index value) and having a relative refractive index difference in the cross section of 0.01% or less when the refractive index (nd) of 145850 is used as a reference.
（２） 多孔質シリカ原料にフッ素をドープし、透明化されてなり、
前記ドープは、前記多孔質シリカ原料を、フッ化塩素ガスを含む所定温度の雰囲気に配置することで行う（１）記載の合成シリカガラス。
(2) The porous silica raw material is doped with fluorine and made transparent,
The said dope is a synthetic silica glass as described in (1) performed by arrange | positioning the said porous silica raw material in the atmosphere of the predetermined temperature containing chlorine fluoride gas.
（３） 前記所定温度は８００℃未満である（２）記載の合成シリカガラス。 (3) The synthetic silica glass according to (2), wherein the predetermined temperature is less than 800 ° C.
（４） 前記所定温度は前記フッ化塩素の沸点以上である（２）又は（３）記載の合成シリカガラス。 (4) The synthetic silica glass according to (2) or (3), wherein the predetermined temperature is equal to or higher than a boiling point of the chlorine fluoride.
（５） 前記多孔質シリカ原料は、０．２ｇ／ｃｍ３以上１．２ｇ／ｃｍ３以下の密度を有する（２）から（４）いずれか記載の合成シリカガラス。 (5) The synthetic silica glass according to any one of (2) to (4), wherein the porous silica raw material has a density of 0.2 g / cm 3 or more and 1.2 g / cm 3 or less.
（６） 前記フッ化塩素ガスの分圧が１．０気圧以下で製造される（２）から（５）いずれか記載の合成シリカガラス。 (6) The synthetic silica glass according to any one of (2) to (5), which is produced at a partial pressure of the chlorine fluoride gas of 1.0 atm or less.
（７） 前記フッ化塩素ガスの分圧を１．０気圧超４．０気圧以下の圧力へと加圧してなる（２）から（５）いずれか記載の合成シリカガラス。 (7) The synthetic silica glass according to any one of (2) to (5), wherein the partial pressure of the chlorine fluoride gas is increased to a pressure of more than 1.0 atm and 4.0 atm or less.
（８） 前記透明化を、ドーパントが実質的に存在しない雰囲気で行ってなる（２）から（７）いずれか記載の合成シリカガラス。 (8) The synthetic silica glass according to any one of (2) to (7), wherein the transparency is performed in an atmosphere substantially free of dopant.
（９） 多孔質シリカ原料にフッ素をドープし、透明化する合成シリカガラスの製造方法であって、
前記ドープは、前記多孔質シリカ原料を、フッ化塩素ガスを含む所定温度の雰囲気に配置することで行う製造方法。
(9) A method for producing a synthetic silica glass in which a porous silica raw material is doped with fluorine to be transparent,
The said dope is a manufacturing method performed by arrange | positioning the said porous silica raw material in the atmosphere of the predetermined temperature containing a chlorine fluoride gas.
（１０） 前記所定温度は８００℃未満である（９）記載の製造方法。 (10) The manufacturing method according to (9), wherein the predetermined temperature is less than 800 ° C.
（１１） 前記所定温度は前記フッ化塩素の沸点以上である（９）又は（１０）記載の製造方法。 (11) The manufacturing method according to (9) or (10), wherein the predetermined temperature is equal to or higher than a boiling point of the chlorine fluoride.
（１２） 前記多孔質シリカ原料は、０．２ｇ／ｃｍ３以上１．２ｇ／ｃｍ３以下の密度を有する（９）から（１１）いずれか記載の製造方法。 (12) The method according to any one of (9) to (11), wherein the porous silica raw material has a density of 0.2 g / cm 3 or more and 1.2 g / cm 3 or less.
（１３） 前記フッ化塩素ガスの分圧を１．０気圧以下とする（９）から（１２）いずれか記載の製造方法。 (13) The production method according to any one of (9) to (12), wherein a partial pressure of the chlorine fluoride gas is 1.0 atm or less.
（１４） 前記フッ化塩素ガスの分圧を１．０気圧超４．０気圧以下の圧力へと加圧する工程をさらに有する（９）から（１２）いずれか記載の製造方法。 (14) The production method according to any one of (9) to (12), further including a step of pressurizing the partial pressure of the chlorine fluoride gas to a pressure higher than 1.0 atm and lower than 4.0 atm.
（１５） 前記透明化は、ドーパントが実質的に存在しない雰囲気で行う（９）から（１４）いずれか記載の製造方法。 (15) The method according to any one of (9) to (14), wherein the transparency is performed in an atmosphere in which a dopant is not substantially present.
本発明によれば、多孔質シリカ原料を、フッ化塩素ガスを含む雰囲気に配置することで、形成される比屈折率差の大きさが断面内において均等化する。このようにして、１ｐｐｍ以上でありかつＦ元素の含有量の−β／α（式中、αはＣｌ元素１ｐｐｍあたり変化する屈折率の値、βはＦ元素１ｐｐｍあたり変化する屈折率の値）倍以下であるＣｌ元素とを含み、屈折率（ｎｄ）１．４５８５０をリファレンスとしたときの断面内の比屈折率差が０．０１％以下である合成シリカガラスが得られ、断面内の屈折率の均等化を実現できる。 According to this invention, the magnitude | size of the relative refractive index difference formed is equalized in a cross section by arrange | positioning the porous silica raw material in the atmosphere containing chlorine fluoride gas. In this way, -β / α of 1 ppm or more and the content of F element (where α is a refractive index value that changes per 1 ppm of Cl element and β is a refractive index value that changes per 1 ppm of F element) And a synthetic silica glass having a relative refractive index difference in the cross section of 0.01% or less when a refractive index (nd) of 145850 is used as a reference. Rate equalization can be realized.
以下、本発明の実施形態を説明するが、これが本発明を限定するものではない。 Hereinafter, although embodiment of this invention is described, this does not limit this invention.
本発明に係る合成シリカガラスの製造方法は、多孔質シリカ原料にフッ素をドープし、透明化する工程を有する。フッ素がドープされることで負の比屈折率差が形成されるため、屈折率が小さい合成シリカガラスを得ることができる。ここでＳＦ６、ＳｉＦ４、Ｓｉ２Ｆ６、Ｓｉ３Ｆ３等の従来のフッ素含有ガスを用いると、形成される比屈折率差の大きさが合成シリカガラスの断面内において不均一であるため、得られる合成シリカガラスの断面内の屈折率が不均等になりやすい。 The method for producing a synthetic silica glass according to the present invention includes a step of doping a porous silica raw material with fluorine to make it transparent. Since a negative relative refractive index difference is formed by doping with fluorine, a synthetic silica glass having a small refractive index can be obtained. Here, when a conventional fluorine-containing gas such as SF 6 , SiF 4 , Si 2 F 6 , or Si 3 F 3 is used, the magnitude of the relative refractive index difference formed is not uniform in the cross section of the synthetic silica glass. Therefore, the refractive index in the cross section of the synthetic silica glass obtained tends to be uneven.
これに対し、本発明では、ドープを、フッ化塩素ガスを含む所定温度の雰囲気に多孔質シリカ原料を配置することで行う。これにより、形成される比屈折率差の大きさが断面内において均等化するため、断面内の屈折率を均等化できる合成シリカガラスを製造することができる。なお、本発明における「断面」とは、棒状である多孔質シリカ原料の長軸に略垂直な断面を指し、かかる断面内の全箇所は製造過程において互いに略同じ処理履歴を経る。 On the other hand, in this invention, dope is performed by arrange | positioning a porous silica raw material in the atmosphere of the predetermined temperature containing chlorine fluoride gas. Thereby, since the magnitude | size of the relative refractive index difference formed equalizes in a cross section, the synthetic silica glass which can equalize the refractive index in a cross section can be manufactured. The “cross section” in the present invention refers to a cross section that is substantially perpendicular to the long axis of the rod-shaped porous silica raw material, and all points in the cross section undergo substantially the same processing history in the manufacturing process.
その作用を、フッ化塩素ガスの一例であるＣｌＦ３を用いた場合を例示して説明する。雰囲気中のＣｌＦ３が多孔質シリカ原料表面のＳｉＯＨに接触すると、そのＳｉＯＨがＳｉＯＦ３、ＳｉＦもしくはＳｉＣｌ、ＳｉＯＣｌへと変化し、表面にフッ素もしくは塩素がドープされる。このとき、副産物としてＨＦ及びＨＣｌが生成する。ＨＦは多孔質シリカ原料内部のＳｉ−Ｏ−Ｓｉ結合を破壊し、そこへＣｌＦ３ガスが供給されることによりＳｉＦ、ＳｉＯＦの形でフッ素がドープされる。同様にＣｌガスが供給されることによりＳｉＣｌやＳｉＯＣｌの形で塩素がドープされる。多孔質シリカ原料の処理ガス接触はフッ素及び塩素に限らず同程度であり、特定量のフッ素がドープされる箇所には、特定量の塩素もドープされる。これにより、フッ素による負の比屈折率差の一部が、塩素による正の比屈折率差により相殺されるため、比屈折率差の大きさが断面内において均等化する。 The operation will be described by exemplifying a case where ClF 3 which is an example of chlorine fluoride gas is used. When ClF 3 in the atmosphere comes into contact with SiOH on the surface of the porous silica raw material, the SiOH changes to SiOF 3 , SiF or SiCl, and SiOCl, and the surface is doped with fluorine or chlorine. At this time, HF and HCl are generated as by-products. HF breaks Si—O—Si bonds in the porous silica raw material, and ClF 3 gas is supplied thereto, so that fluorine is doped in the form of SiF and SiOF. Similarly, chlorine is doped in the form of SiCl or SiOCl by supplying Cl gas. The treatment gas contact of the porous silica raw material is not limited to fluorine and chlorine, but is the same level, and a specific amount of chlorine is also doped at a location where a specific amount of fluorine is doped. Thereby, a part of the negative relative refractive index difference due to fluorine is offset by the positive relative refractive index difference due to chlorine, so that the magnitude of the relative refractive index difference is equalized in the cross section.
フッ化塩素ガスは、ＣｌＦ３に限らず、上記のような作用を呈するものであれば、特に限定されず、例えば、ＣｌＦ、ＣｌＦ５等であってよく、１種又は２種以上を組み合わせて使用してよい。また、ドープ時の雰囲気は、フッ化塩素ガスに限らず他のガスを含んでよい。 The chlorine fluoride gas is not limited to ClF 3 and is not particularly limited as long as it exhibits the above-described action. For example, ClF, ClF 5 and the like may be used, and one or two or more kinds may be combined. May be used. Moreover, the atmosphere at the time of dope is not limited to chlorine fluoride gas, and may include other gases.
多孔質シリカ原料は、従来公知の方法、例えばＶＡＤ（Ｖａｐｏｒ ｐｈａｓｅ Ａｘｉａｌ Ｄｅｐｏｓｉｔｉｏｎ）法で合成したものであってよい。 The porous silica raw material may be synthesized by a conventionally known method, for example, a VAD (Vapor Phase Axial Deposition) method.
フッ化塩素ガスを含む雰囲気の所定温度は、過大であると、多孔質シリカ原料の密度が大きく増加し、多孔質シリカ原料内部へのドープが不充分になりやすい一方、過小であると、フッ化塩素の気体での供給量が少なくなり、ドープ効率が低下する。そこで、所定温度は、８００℃未満であることが好ましく、より好ましくは５００℃以下であり、フッ化塩素の沸点（例えば、ＣｌＦ３であれば１１．７５℃）以上であることが好ましい。フッ化塩素ガスは、ＳｉＦ４等の従来の処理ガスと比較して低温処理が可能であるため、多孔質シリカ原料の収縮が抑制される。これにより、嵩密度の増加を抑制され、均一ドープ、高濃度ドープが可能となる。また、ＨＦ及びＨＣｌがイオン化して多孔質シリカ原料内部へと侵入しやすい点で、雰囲気の所定温度は１００℃以上であることが好ましく、より好ましくは２００℃以上である。 If the predetermined temperature of the atmosphere containing chlorine fluoride gas is excessive, the density of the porous silica raw material increases greatly, and the dope into the porous silica raw material tends to be insufficient. The supply amount of chlorine chloride gas decreases, and the dope efficiency decreases. Therefore, the predetermined temperature is preferably less than 800 ° C., more preferably 500 ° C. or less, and preferably not less than the boiling point of chlorine fluoride (for example, 11.75 ° C. for ClF 3 ). Since chlorine fluoride gas can be processed at a lower temperature than conventional processing gases such as SiF 4 , shrinkage of the porous silica raw material is suppressed. Thereby, an increase in bulk density is suppressed, and uniform doping and high concentration doping are possible. In addition, the predetermined temperature of the atmosphere is preferably 100 ° C. or higher, more preferably 200 ° C. or higher, in that HF and HCl are easily ionized and penetrate into the porous silica raw material.
多孔質シリカ原料の密度は、過大であると、多孔質シリカ原料内部へのドープが不充分になりやすい点を考慮し、適宜設定されてよい。ただし、前述のように、本発明では、従来のガス（１０００〜１２００℃）に比べて低温でフッ素ドープが可能であるため、従来許容されるよりも高い密度の多孔質シリカ原料を使用することもできる。具体的に、多孔質シリカ原料の密度の下限は、０．２ｇ／ｃｍ３であることが好ましく、より好ましくは０．３ｇ／ｃｍ３であり、最も好ましくは０．４ｇ／ｃｍ３である。多孔質シリカ原料の密度の上限は、１．２ｇ／ｃｍ３であることが好ましく、より好ましくは１．１ｇ／ｃｍ３であり、最も好ましくは１．０ｇ／ｃｍ３である。なお、本明細書における多孔質シリカ原料の密度は、非接触式の形状測定装置を用いて多孔質シリカ原料の体積を測定し、その体積と重量から嵩密度を算出することで得られる。 If the density of the porous silica raw material is excessive, it may be appropriately set in consideration of the point that the dope into the porous silica raw material tends to be insufficient. However, as described above, in the present invention, it is possible to dope fluorine at a low temperature as compared with the conventional gas (1000 to 1200 ° C.). You can also. Specifically, the lower limit of the density of the porous silica raw material is preferably 0.2 g / cm 3 , more preferably 0.3 g / cm 3 , and most preferably 0.4 g / cm 3 . The upper limit of the density of the porous silica raw material is preferably 1.2 g / cm 3 , more preferably 1.1 g / cm 3 , and most preferably 1.0 g / cm 3 . In addition, the density of the porous silica raw material in this specification is obtained by measuring the volume of the porous silica raw material using a non-contact type shape measuring device and calculating the bulk density from the volume and weight.
ドープ時のフッ化塩素ガスの分圧は、高くなるにつれ、多孔質シリカ原料内部へのドープが促進される一方、過大であると、設備及びコストの観点で不利である。前述のように、本発明では、フッ化塩素ガスを用いることで多孔質シリカ原料内部へのドープが既に容易であるため、雰囲気を加圧する工程を行わなくてもよい。即ち、フッ化塩素ガスの分圧は１．０気圧以下であってよい。かかる態様では、加圧のための設備及びコストを削減することができる。ただし、フッ化塩素ガスの分圧を１．０気圧超４．０気圧以下の圧力へと加圧することは、簡便な加圧設備及び低コストで多孔質シリカ原料内部へのドープをより促進できる点で好ましい。かかる加圧時のフッ化塩素ガスの分圧の下限は、より好ましくは１．１気圧、最も好ましくは２．０気圧であり、上限は、より好ましくは４．０気圧、最も好ましくは３．０気圧である。 As the partial pressure of the chlorine fluoride gas at the time of doping increases, the doping into the porous silica raw material is promoted. On the other hand, if the partial pressure is excessive, it is disadvantageous in terms of equipment and cost. As described above, in the present invention, it is not necessary to perform the step of pressurizing the atmosphere because doping into the porous silica raw material is already easy by using chlorine fluoride gas. That is, the partial pressure of chlorine fluoride gas may be 1.0 atm or less. In this aspect, the equipment and cost for pressurization can be reduced. However, pressurizing the partial pressure of the chlorine fluoride gas to a pressure higher than 1.0 atm and lower than 4.0 atm can further promote the dope into the porous silica raw material with simple pressurization equipment and low cost. This is preferable. The lower limit of the partial pressure of the chlorine fluoride gas during pressurization is more preferably 1.1 atm, most preferably 2.0 atm, and the upper limit is more preferably 4.0 atm, most preferably 3. 0 atm.
次に、フッ素がドープされた多孔質シリカ原料を透明化する。これにより、屈折率が低下した透明な合成シリカガラスが得られる。透明化は、従来公知の条件に従ってよく、特に限定されないが、例えば、多孔質シリカ原料を約１０００〜約１３００℃で約１〜約２０時間に亘り加熱し、さらに約１３５０〜約１６００℃で加熱してよい。透明化の間、加圧をしてもよく、減圧をしてもよい。 Next, the porous silica raw material doped with fluorine is made transparent. Thereby, a transparent synthetic silica glass having a reduced refractive index is obtained. The transparency may be according to conventionally known conditions, and is not particularly limited. For example, the porous silica raw material is heated at about 1000 to about 1300 ° C. for about 1 to about 20 hours, and further heated at about 1350 to about 1600 ° C. You can do it. During the clarification, pressure may be applied or reduced pressure.
透明化は、ドープと同一雰囲気で行ってもよく、あるいは異なる雰囲気で行ってもよい。後者は、フッ素がドープされた多孔質シリカ原料を、予め形成しておいた雰囲気に移すだけで、透明化を開始できるので、製造時間を短縮できる点で好ましい。後者の場合、透明化時の雰囲気にはドーパントが実質的に存在しないことが一般的である。なお、ここでいう「実質的に存在しない」とは、全く存在しないのみならず、不可避的に存在する量（例えば、多孔質シリカ原料の表面から僅少量のドーパントが雰囲気へと逃避する）程度で存在することも包含する。 The transparency may be performed in the same atmosphere as the dope or in a different atmosphere. The latter is preferable in that the production time can be shortened because the transparent silica raw material doped with fluorine can be started by simply transferring it to a previously formed atmosphere. In the latter case, it is general that the dopant is not substantially present in the atmosphere at the time of transparency. Here, “substantially non-existing” is not only completely absent but also unavoidably present (for example, a small amount of dopant escapes from the surface of the porous silica raw material to the atmosphere). It is also included.
なお、ドープ及び透明化に用い得る装置は、従来周知であるため、その説明を省略する。 In addition, since the apparatus which can be used for dope and transparency is conventionally known, the description is abbreviate | omitted.
このようにして製造される合成シリカガラスは、光ファイバ、光学系装置のレンズ、ミラー、プリズム、窓部材等の光学部材として有用である。 The synthetic silica glass thus produced is useful as an optical member such as an optical fiber, a lens of an optical system device, a mirror, a prism, or a window member.
本発明の方法で製造される合成シリカガラスは、１００ｐｐｍ以上のＦ元素と、１ｐｐｍ以上でありかつＦ元素の含有量の−β／α（式中、αはＣｌ元素１ｐｐｍあたり変化する屈折率の値、βはＦ元素１ｐｐｍあたり変化する屈折率の値）倍以下であるＣｌ元素とを含み、屈折率（ｎｄ）１．４５８５０をリファレンスとしたときの断面内の比屈折率差が０．０１％以下である。なお、Ｆ元素及びＣｌ元素の量はイオンクロマトグラフ分析により測定され、合成シリカガラスの断面における平均値である。 The synthetic silica glass produced by the method of the present invention has an F element of 100 ppm or more, and a content of F element -β / α of 1 ppm or more (where α is a refractive index that changes per 1 ppm of Cl element). And β is a Cl element that is less than or equal to twice the value of the refractive index that changes per 1 ppm of the F element, and the relative refractive index difference in the cross section when the refractive index (nd) of 145850 is used as a reference is 0.01. % Or less. The amounts of the F element and the Cl element are measured by ion chromatographic analysis, and are average values in the cross section of the synthetic silica glass.
また、断面内の比屈折率差は、合成シリカガラスの断面における重心と、外周より内側に１０ｍｍの任意の１箇所とにおける比屈折率の差である。比屈折率は、次の式に基づいて算出される。
屈折率Ａ ＝ α×Ｃｌ元素量(ｐｐｍ) ＋ β×Ｆ元素量(ｐｐｍ) ＋ 1.45850
（式中、αはＣｌ元素含有量１ｐｐｍの変化による屈折率変化量の値であり、Ｃｌ元素濃度と屈折率との関数を近似曲線とし、その曲線における傾き、即ちＳｉ−Ｃｌの場合１．３×１０−７であり、
βは、Ｆ元素含有量１ｐｐｍの変化による屈折率変化量の値、Ｆ元素濃度と屈折率との関数を近似曲線とし、その曲線における傾き、即ちＳｉ−Ｆの場合−３．８×１０−７である。）
比屈折率 ＝（1.45850−屈折率Ａ） ／ 1.45850 × 100
Moreover, the relative refractive index difference in the cross section is a difference in relative refractive index between the center of gravity in the cross section of the synthetic silica glass and any one place 10 mm inward from the outer periphery. The relative refractive index is calculated based on the following formula.
Refractive index A = α × Cl element amount (ppm) + β × F element amount (ppm) +1.45850
(Where α is the value of the refractive index change due to the change in the Cl element content of 1 ppm, and the function of the Cl element concentration and the refractive index is used as an approximate curve. 3 × 10 −7 ,
β is the refractive index variation in the values due to changes in the F element content 1 ppm, and the approximate curve function of the F element concentration and the refractive index, the slope of the curve, that is, when the Si-F -3.8 × 10 - 7 . )
Specific refractive index = (1.45850-Refractive index A) / 1.45850 x 100
Ｆ元素の含有量は１００ｐｐｍ以上、より好ましくは１０００ｐｐｍ以上、最も好ましくは２０００ｐｐｍ以上であり、所望の屈折率変化の程度、Ｃｌ元素の量等に依存して適宜選択される。一方、Ｃｌ元素の含有量は検出限界である１ｐｐｍ以上、より好ましくは１０ｐｐｍ以上、最も好ましくは２０ｐｐｍ以上であり、Ｆ元素の含有量に対して−β／α倍以下である。 The content of F element is 100 ppm or more, more preferably 1000 ppm or more, and most preferably 2000 ppm or more, and is appropriately selected depending on the desired degree of refractive index change, the amount of Cl element, and the like. On the other hand, the Cl element content is 1 ppm or more, more preferably 10 ppm or more, and most preferably 20 ppm or more, which is the detection limit, and is −β / α times or less than the F element content.
断面内の比屈折率差は、合成シリカガラスの屈折率（ｎｄ）１．４５８５０に対し０．０１％以下であることが好ましく、より好ましくは０．００５％以下である。 The relative refractive index difference in the cross section is preferably 0.01% or less, more preferably 0.005% or less with respect to the refractive index (nd) of 145850 of the synthetic silica glass.
＜実施例１＞
ＶＡＤ法で合成した密度０．５ｇ／ｃｍ３の多孔質シリカ原料の棒状体を公知のドープ装置のシリカガラス炉内に挿入した。シリカガラス炉内にはＡｒガスを満たしておき、このシリカガラス炉内に、５００℃に保ったＣｌＦ３ガスを５００ｓｃｃｍ、５６０秒で供給し、０．３気圧（ＣｌＦ３ガスの分圧）へと昇圧した。その後、シリカガラス炉内の条件を保ち４時間保持させた。その後、多孔質シリカ原料を１１００〜１２００℃に設定した別の炉内に挿入し、減圧下３〜１０時間に亘って加熱し、その後１２００〜１４００℃に昇温し減圧下で１０〜２０時間に亘って加熱することで、透明化を行い、合成シリカガラスを得た。
<Example 1>
A rod-shaped body of porous silica raw material having a density of 0.5 g / cm 3 synthesized by the VAD method was inserted into a silica glass furnace of a known doping apparatus. The silica glass furnace is filled with Ar gas, and the ClF 3 gas maintained at 500 ° C. is supplied into the silica glass furnace at 500 sccm for 560 seconds to 0.3 atm (ClF 3 gas partial pressure). And boosted. Thereafter, the conditions in the silica glass furnace were maintained and held for 4 hours. Thereafter, the porous silica raw material was inserted into another furnace set at 1100 to 1200 ° C., heated under reduced pressure for 3 to 10 hours, then heated to 1200 to 1400 ° C. and then heated under reduced pressure for 10 to 20 hours. It was made transparent by heating over a period of time to obtain a synthetic silica glass.
＜実施例２＞
ドープ時の温度を５００℃ではなく１５０℃にし、ＣｌＦ３ガス分圧を０．３気圧ではなく０．２５気圧にした点を除き、実施例１と同様の手順で合成シリカガラスを得た。
<Example 2>
A synthetic silica glass was obtained in the same procedure as in Example 1 except that the temperature at the time of dope was changed to 150 ° C. instead of 500 ° C., and the ClF 3 gas partial pressure was changed to 0.25 atm.
＜実施例３＞
ドープ時の温度を５００℃ではなく８００℃にし、ＣｌＦ３ガス分圧を０．３気圧ではなく０．１気圧にした点を除き、実施例１と同様の手順で合成シリカガラスを得た。
<Example 3>
A synthetic silica glass was obtained in the same procedure as in Example 1 except that the temperature at the time of dope was changed to 800 ° C. instead of 500 ° C. and the ClF 3 gas partial pressure was changed to 0.1 atm instead of 0.3 atm.
＜実施例４＞
ＶＡＤ法で合成した密度０．５ｇ／ｃｍ３の多孔質シリカ原料を公知のドープ装置のシリカガラス炉内に挿入した。シリカガラス炉内にはＡｒガスを満たしておき、このシリカガラス炉内を２０℃に保った状態で、Ａｒガスと置換しながらＣｌＦ３ガスを５００ｓｃｃｍ、５５０秒流して０．９気圧（ＣｌＦ３ガスの分圧）まで昇圧した。その後、シリカガラス炉内の条件を保ち３３０時間保持させた。その後、多孔質シリカ原料を１１００〜１２００℃に設定した別の炉内に挿入し、減圧下３〜１０時間に亘って加熱し、その後１２００〜１４００℃に昇温し減圧下で１０〜２０時間に亘って加熱することで透明化を行い、合成シリカガラスを得た。
<Example 4>
A porous silica raw material having a density of 0.5 g / cm 3 synthesized by the VAD method was inserted into a silica glass furnace of a known doping apparatus. The silica glass furnace was filled with Ar gas, and while the inside of the silica glass furnace was kept at 20 ° C., ClF 3 gas was flowed at 500 sccm for 550 seconds while being replaced with Ar gas, and 0.9 atm (ClF 3 (Partial pressure of gas). Thereafter, the conditions in the silica glass furnace were maintained and held for 330 hours. Thereafter, the porous silica raw material was inserted into another furnace set at 1100 to 1200 ° C., heated under reduced pressure for 3 to 10 hours, then heated to 1200 to 1400 ° C. and then heated under reduced pressure for 10 to 20 hours. The glass was made transparent by heating to obtain a synthetic silica glass.
（比較例１）
ＶＡＤ法で合成した密度０．５ｇ／ｃｍ３の多孔質シリカ原料を公知のドープ装置のシリカガラス炉内に挿入した。シリカガラス炉内にはＡｒガスを満たしておき、このシリカガラス炉内を５００℃に保った状態で、Ａｒガスと置換しながらＳｉＦ４ガスを５００ｓｃｃｍ、７００秒流して０．３気圧（ＳｉＦ４ガスの分圧）まで昇圧した。その後、シリカガラス炉内の条件を保ち４時間保持させた。その後、多孔質シリカ原料を１１００〜１２００℃に設定した別の炉内に挿入し、減圧下３〜１０時間に亘って加熱し、その後１２００〜１４００℃に昇温し減圧下で１０〜２０時間に亘って加熱することで透明化を行い、合成シリカガラスを得た。
(Comparative Example 1)
A porous silica raw material having a density of 0.5 g / cm 3 synthesized by the VAD method was inserted into a silica glass furnace of a known doping apparatus. The silica glass furnace was filled with Ar gas, and while the silica glass furnace was maintained at 500 ° C., SiF 4 gas was allowed to flow at 500 sccm for 700 seconds while being replaced with Ar gas, and 0.3 atm (SiF 4 (Partial pressure of gas). Thereafter, the conditions in the silica glass furnace were maintained and held for 4 hours. Thereafter, the porous silica raw material was inserted into another furnace set at 1100 to 1200 ° C., heated under reduced pressure for 3 to 10 hours, then heated to 1200 to 1400 ° C. and then heated under reduced pressure for 10 to 20 hours. The glass was made transparent by heating to obtain a synthetic silica glass.
（比較例２）
ＶＡＤ法で合成した密度０．３ｇ／ｃｍ３の多孔質シリカ原料を公知のドープ装置のシリカガラス炉内に挿入した。シリカガラス炉内には窒素ガスを満たしておき、このシリカガラス炉内を１２００℃に保った状態で、窒素ガス雰囲気にＣｌ２ガスを７００ｓｃｃｍ流し、８時間保持した。その後、シリカガラス炉内を１０００℃に保った状態で、窒素ガス及び塩素ガス雰囲気に、ＳｉＦ４ガスを５００ｓｃｃｍ流し、４時間保持した。その後、多孔質シリカ原料を１１００〜１２００℃に設定した別の炉内に挿入し、減圧下３〜１０時間に亘って加熱し、その後１２００〜１４００℃に昇温し減圧下で１０〜２０時間に亘って加熱することで透明化を行い、合成シリカガラスを得た。
(Comparative Example 2)
A porous silica raw material having a density of 0.3 g / cm 3 synthesized by the VAD method was inserted into a silica glass furnace of a known doping apparatus. The silica glass furnace was filled with nitrogen gas, and while the silica glass furnace was maintained at 1200 ° C., 700 sccm of Cl 2 gas was allowed to flow in a nitrogen gas atmosphere and held for 8 hours. Thereafter, with the inside of the silica glass furnace maintained at 1000 ° C., 500 sccm of SiF 4 gas was allowed to flow in a nitrogen gas and chlorine gas atmosphere and held for 4 hours. Thereafter, the porous silica raw material was inserted into another furnace set at 1100 to 1200 ° C., heated under reduced pressure for 3 to 10 hours, then heated to 1200 to 1400 ° C. and then heated under reduced pressure for 10 to 20 hours. The glass was made transparent by heating to obtain a synthetic silica glass.
［評価］
実施例１〜４及び比較例１〜２で得た合成シリカガラスについて、屈折率（ｎｄ）１．４５８５０をリファレンスとしたときの断面の比屈折率差をデジタル精密屈折計によって測定した。また、Ｆ元素及びＣｌ元素の含有量をイオンクロマトグラフ分析によって測定した。この結果を表１に示す。
[Evaluation]
About the synthetic silica glass obtained in Examples 1-4 and Comparative Examples 1-2, the relative refractive index difference of the cross section when using refractive index (nd) 1.45850 as a reference was measured with a digital precision refractometer. Further, the contents of F element and Cl element were measured by ion chromatography analysis. The results are shown in Table 1.
Claims (15)
前記ドープは、前記多孔質シリカ原料を、フッ化塩素ガスを含む所定温度の雰囲気に配置することで行う請求項１記載の合成シリカガラス。 Porous silica raw material is doped with fluorine and made transparent,
The synthetic silica glass according to claim 1, wherein the dope is performed by placing the porous silica raw material in an atmosphere having a predetermined temperature containing chlorine fluoride gas.
前記ドープは、前記多孔質シリカ原料を、フッ化塩素ガスを含む所定温度の雰囲気に配置することで行う製造方法。 A method for producing synthetic silica glass in which a porous silica raw material is doped with fluorine to be transparent,
The said dope is a manufacturing method performed by arrange | positioning the said porous silica raw material in the atmosphere of the predetermined temperature containing a chlorine fluoride gas.
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| JP2022031249A (en) * | 2020-08-06 | 2022-02-18 | ヘレウス・クアルツグラース・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング・ウント・コンパニー・コマンディット・ゲゼルシャフト | Alternative fluorination agent for manufacturing fluorinated quartz glass |
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