JP5913690B2 - Silica glass generating delayed fluorescence - Google Patents
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims description 66
- 230000003111 delayed effect Effects 0.000 title claims description 42
- 238000002834 transmittance Methods 0.000 claims description 12
- 239000000460 chlorine Substances 0.000 claims description 8
- 206010021143 Hypoxia Diseases 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000000463 material Substances 0.000 description 11
- 230000005284 excitation Effects 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
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- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 3
- 229910003902 SiCl 4 Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
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- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
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- 239000005049 silicon tetrachloride Substances 0.000 description 3
- 239000013077 target material Substances 0.000 description 3
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- 150000003961 organosilicon compounds Chemical class 0.000 description 2
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- 241000668842 Lepidosaphes gloverii Species 0.000 description 1
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- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
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Description
本発明は、紫外線を照射したときにシリカガラスから発生する遅延蛍光を利用したシリカガラスで、特にシリカガラス光学冶具、シリカガラスファイバー、シリカガラスマイクロチップ、太陽光発電、波長変換レーザなど入射光の波長を変換する光学的な特徴を有効に利用するシリカガラス製紫外線センサーに使用されるシリカガラスに関する。 The present invention is a silica glass using delayed fluorescence generated from silica glass when irradiated with ultraviolet rays, and in particular, incident light such as silica glass optical jig, silica glass fiber, silica glass microchip, photovoltaic power generation, wavelength conversion laser, etc. The present invention relates to a silica glass used in an ultraviolet sensor made of silica glass that effectively uses an optical characteristic for converting a wavelength.
従来のシリカガラス製品は、紫外線照射によって可視光領域の蛍光を発生する蛍光シリカガラスが知られている（例えば、特許文献１）。しかしながら、可視光領域の蛍光は紫外線を照射したときにのみ観察されるものであり、紫外線の照射が止まってしまうと、可視光領域の蛍光の発生も止まってしまう。また、蛍光の強度は非常に弱く、入射された紫外線に対して、僅かな強度しか可視光領域の蛍光が発生しない状況であった。このため、シリカガラスは光の透過率は優れているものの、紫外線を可視光に変換する効率は非常に低く、有効な波長変換装置としては使用されていなかった。 As a conventional silica glass product, fluorescent silica glass that generates fluorescence in the visible light region by ultraviolet irradiation is known (for example, Patent Document 1). However, the fluorescence in the visible light region is observed only when irradiated with ultraviolet rays, and when the irradiation with ultraviolet rays stops, the generation of fluorescence in the visible light region also stops. Further, the intensity of the fluorescence is very weak, and the fluorescence in the visible light region is generated with a slight intensity with respect to the incident ultraviolet rays. For this reason, although silica glass has excellent light transmittance, the efficiency of converting ultraviolet light into visible light is very low and has not been used as an effective wavelength conversion device.
また、有機ＥＬ材料ではこうした遅延蛍光は観察される場合があるが、波長変換時に発熱するなどで効率が悪くなってしまう場合があり、問題があった。さらに、一般的なガラスでは燐光成分をガラス中にドープした発光性ガラスなども提案されている（特許文献２）。しかしながら、通常の光学ガラスでは紫外線の照射によってガラス自体が劣化する場合や、温度の変化などで燐光の発光効率が悪くなってしまう問題があった。 Further, such delayed fluorescence may be observed in the organic EL material, but the efficiency may deteriorate due to heat generation at the time of wavelength conversion. Further, as a general glass, a light-emitting glass in which a phosphorescent component is doped in a glass has been proposed (Patent Document 2). However, ordinary optical glass has a problem in that the glass itself deteriorates due to the irradiation of ultraviolet rays, or the phosphorescence efficiency decreases due to a change in temperature.
こうした現状に鑑み、本発明者等は、シリカガラスの遅延蛍光発生のメカニズムについて鋭意研究を重ねた結果、シリカガラス中に２００ｎｍ〜１８０ｎｍの波長域に最低励起三重項励起準位のＳｉＳｉＳｉ結合を効率的に形成させて３００ｎｍ以下の紫外線を吸収させれば、最低励起一重項励起準位への逆項間交差後に可視光領域に遅延蛍光が発生することを発見したのである。 In view of the present situation, the present inventors have conducted extensive research on the mechanism of delayed fluorescence generation of silica glass, and as a result, the SiSiSi bond having the lowest excited triplet excitation level in the silica glass in the wavelength region of 200 nm to 180 nm is efficiently obtained. It was discovered that delayed fluorescence is generated in the visible light region after crossing the inverse term to the lowest excited singlet excitation level if it is formed and absorbed at 300 nm or less.
本発明は、紫外線を照射することにより遅延蛍光を発生するシリカガラスであって、遅延蛍光を利用したシリカガラス製紫外線センサーに使用されるシリカガラスを提供することを目的とする。 An object of the present invention is to provide a silica glass that generates delayed fluorescence when irradiated with ultraviolet rays, and is used for an ultraviolet sensor made of silica glass using delayed fluorescence.
本発明のシリカガラスは、合成シリカガラスにおいて、ＯＨ基含有量が１ｐｐｍ以下であり、塩素の含有量が３０ｐｐｍ以下で、厚さ２ｍｍの波長１９０ｎｍでの透過率が５０％以下であり、１２８０℃での粘度（Ｌｏｇη）が１２．０poise以上であり、かつ酸素欠損を有し、低圧水銀ランプの２５４ｎｍの紫外線を照射した場合に４００ｎｍ〜６５０ｎｍの可視光領域に０．０１秒以上の遅延蛍光を発生することを特徴とする。 The silica glass of the present invention is a synthetic silica glass having an OH group content of 1 ppm or less, a chlorine content of 30 ppm or less, a transmittance of 2 mm in thickness at a wavelength of 190 nm of 50% or less, and 1280 ° C. When the viscosity (Log η) is 12.0 poise or more, oxygen deficiency is applied, and UV light of 254 nm of a low-pressure mercury lamp is irradiated, a delayed fluorescence of 0.01 seconds or more is observed in the visible light region of 400 nm to 650 nm. It is generated.
本発明のシリカガラスは、厚さ２ｍｍの波長２００ｎｍでの透過率が６０％以下であり、１２８０℃での粘度（Ｌｏｇη）が１２．３poise以上であり、かつ三重項励起電子準位と一重項励起準位を含有し、紫外線を照射することで可視光領域に１秒以上の遅延蛍光を発生することが好適である。 The silica glass of the present invention has a transmittance of 60% or less at a wavelength of 200 nm having a thickness of 2 mm, a viscosity (Log η) at 1280 ° C. of 12.3 poise or more, and a triplet excited electron level and a singlet. It is preferable to contain an excited level and generate delayed fluorescence of 1 second or more in the visible light region by irradiating with ultraviolet rays.
本発明のシリカガラス製紫外線センサーは、本発明のシリカガラスを用いたシリカガラス製紫外線センサーであって、３００ｎｍ以下の波長の紫外線の照射を遅延蛍光により可視光領域に変換し、感知することを特徴とする。 The silica glass ultraviolet sensor of the present invention is a silica glass ultraviolet sensor using the silica glass of the present invention, which converts the irradiation of ultraviolet light having a wavelength of 300 nm or less into a visible light region by delayed fluorescence and senses it. Features.
本発明によれば、紫外線を照射することにより遅延蛍光を発生するシリカガラス及び遅延蛍光を利用したシリカガラス製紫外線センサーを提供することができる。本発明のシリカガラスにより生じる遅延蛍光は、燐光物質をドープしていないために安定で、紫外線の照射による劣化もなく、また温度変化に対しても安定である。 ADVANTAGE OF THE INVENTION According to this invention, the silica glass ultraviolet sensor which utilizes delayed fluorescence and the silica glass which generate | occur | produces delayed fluorescence by irradiating an ultraviolet-ray can be provided. The delayed fluorescence produced by the silica glass of the present invention is stable because it is not doped with a phosphorescent substance, is not deteriorated by irradiation with ultraviolet rays, and is stable against temperature changes.
以下に本発明の実施の形態を説明するが、これらは例示的に示されるもので、本発明の技術思想から逸脱しない限り種々の変形が可能なことはいうまでもない。 Embodiments of the present invention will be described below, but these are exemplarily shown, and it goes without saying that various modifications are possible without departing from the technical idea of the present invention.
本発明のシリカガラスは、合成シリカガラスにおいて、ＯＨ基含有量が１ｐｐｍ以下であり、塩素の含有量が３０ｐｐｍ以下で、厚さ２ｍｍの波長１９０ｎｍでの透過率が５０％以下であり、１２８０℃での粘度（Ｌｏｇη）が１２．０poise以上であり、かつ酸素欠損を有し、紫外線を照射することで可視光領域に０．０１秒以上の遅延蛍光を発生することを特徴とするシリカガラスである。 The silica glass of the present invention is a synthetic silica glass having an OH group content of 1 ppm or less, a chlorine content of 30 ppm or less, a transmittance of 2 mm in thickness at a wavelength of 190 nm of 50% or less, and 1280 ° C. A silica glass having a viscosity (Log η) of 12.0 poise or more, oxygen deficiency, and generation of delayed fluorescence of 0.01 seconds or more in the visible light region when irradiated with ultraviolet rays. is there.
本発明は、３００ｎｍ以下にＳｉＳｉＳｉ結合の吸収を有するシリカガラスに３００ｎｍ以下の紫外線を照射し、可視光領域に遅延蛍光を発生させ、この遅延蛍光を利用して紫外線の発生を感知したり、化学的な反応を活性化させるものである。 The present invention irradiates silica glass having absorption of SiSiSi bonds below 300 nm with ultraviolet rays of 300 nm or less, generates delayed fluorescence in the visible light region, and detects the generation of ultraviolet rays using this delayed fluorescence, It activates the general reaction.
シリカガラス中の最低励起三重項励起準位のＳｉＳｉＳｉの結合は、３００ｎｍ以下の１９０ｎｍ近傍に吸収を持つことが分かっている。また、最低励起一重項励起準位は３００ｎｍ以下の２４０ｎｍ近傍に吸収を持つことが分かっている。この最低励起一重項励起準位は、４６０ｎｍに蛍光を発生させることもわかっている。シリカガラス中に最低励起三重項励起準位、最低励起一重項励起準位の両方の準位を含有することで、遅延蛍光は発生する。 It has been found that the SiSiSi bond at the lowest excited triplet excited level in silica glass has an absorption near 190 nm of 300 nm or less. Further, it has been found that the lowest excitation singlet excitation level has absorption in the vicinity of 240 nm of 300 nm or less. This lowest singlet excitation level is also known to generate fluorescence at 460 nm. By including both the lowest excited triplet excited level and the lowest excited singlet excited level in the silica glass, delayed fluorescence is generated.
即ち、本発明のシリカガラスは、厚さ２ｍｍの波長１９０ｎｍでの透過率が５０％以下であり、３０％以下がより好ましい。また、本発明のシリカガラスは、厚さ２ｍｍの波長２００ｎｍでの透過率が６０％以下であることが好ましく、３０％以下であることがより好ましい。また、本発明のシリカガラスは、厚さ２ｍｍの波長２４０ｎｍでの透過率が８０％以下であることが好ましい。 That is, the silica glass of the present invention has a transmittance at a wavelength of 190 nm having a thickness of 2 mm of 50% or less, more preferably 30% or less. Further, the silica glass of the present invention preferably has a transmittance of 60% or less, more preferably 30% or less, at a wavelength of 200 nm having a thickness of 2 mm. The silica glass of the present invention preferably has a transmittance of 80% or less at a wavelength of 240 nm having a thickness of 2 mm.
今までのシリカガラスでは最低励起一重項励起準位のみが形成されていただけで、遅延蛍光現象は確認されておらず、通常の蛍光のみが検出されていた。しかしながら、シリカガラス中のＳｉＳｉＳｉ結合をさらに増加させると、紫外線を照射させることにより励起された電子が、最低励起三重項励起準位のＳｉＳｉＳｉ結合に一次トラップされた後に、再度最低励起一重項励起準位に戻り、その後蛍光を発生するために蛍光発生までの時間が遅延されることになる。このため、遅延蛍光の寿命は０．０１秒以上、好ましくは１秒〜１０数秒程度と非常に長く、遅延蛍光の発生を目視で観察することが可能である。 In conventional silica glass, only the lowest excited singlet excited level has been formed, the delayed fluorescence phenomenon has not been confirmed, and only normal fluorescence has been detected. However, when the SiSiSi bond in the silica glass is further increased, electrons excited by irradiation with ultraviolet light are first trapped in the SiSiSi bond of the lowest excited triplet excited level, and then again the lowest excited singlet excited level. In order to generate fluorescence after that, the time until fluorescence generation is delayed. For this reason, the lifetime of delayed fluorescence is as long as 0.01 seconds or more, preferably about 1 to 10 seconds, and the occurrence of delayed fluorescence can be visually observed.
遅延蛍光は、通常の蛍光と違い、エネルギーの変換が非常に優れているので、入射した３００ｎｍ以下の紫外線のパワーに見合った遅延蛍光が発生することになる。このため、３００ｎｍ以下の紫外線をシリカガラスによって効率よく波長を可視光に領域に変換することが可能となる。また、３００ｎｍ以下の紫外線はシリカガラスで吸収されてしまうので、完全に紫外線を可視光に変換できるメリットがある。 Unlike normal fluorescence, delayed fluorescence is very excellent in energy conversion. Therefore, delayed fluorescence corresponding to the power of incident ultraviolet rays of 300 nm or less is generated. For this reason, it becomes possible to efficiently convert the wavelength of ultraviolet light of 300 nm or less into a visible light region by silica glass. Further, since ultraviolet rays of 300 nm or less are absorbed by silica glass, there is an advantage that ultraviolet rays can be completely converted into visible light.
本発明のシリカガラスは、可視光領域、好ましくは４００〜６５０ｎｍの可視光領域に遅延蛍光を発生するものであり、例えば、低圧水銀ランプの２５４ｎｍを照射した場合、蛍光の波長は４６０ｎｍにピークをもつ波長であり、数秒間も継続することが可能である。ただし、蛍光の波長はそれぞれの電位準位の吸収の波長によっても変わることがあり、３６０ｎｍ〜７８０ｎｍの可視光領域に変化させることは可能である。 The silica glass of the present invention generates delayed fluorescence in the visible light region, preferably in the visible light region of 400 to 650 nm. For example, when 254 nm of a low-pressure mercury lamp is irradiated, the fluorescence wavelength has a peak at 460 nm. It can be continued for several seconds. However, the fluorescence wavelength may vary depending on the absorption wavelength of each potential level, and can be changed to a visible light region of 360 nm to 780 nm.
また、一般的な有機ＥＬ材料では遅延蛍光を発生するときに、熱が放出されてしまうためにエネルギーがロスし、変換効率が悪くなってしまう。このため交換効率を良くするためには、材料を液体窒素などで冷却するなどの処理が必要であったが、本発明のシリカガラスでは熱を放出することがないので、室温でも十分な変換効率を得ることが可能である。 Further, in general organic EL materials, when delayed fluorescence is generated, heat is released, so that energy is lost and conversion efficiency is deteriorated. For this reason, in order to improve the exchange efficiency, a treatment such as cooling the material with liquid nitrogen or the like was necessary. However, since the silica glass of the present invention does not release heat, sufficient conversion efficiency can be obtained even at room temperature. It is possible to obtain
蛍光とは、（１）エネルギーを受けた電子が一重項励起電子のもっともエネルギーレベルの高いところへ移る。（２）次に一重項励起電子でエネルギーレベルの高いところから低いところへ移り、一気に基底状態まで戻る。（３）このときに発生する可視光が蛍光で、一連の過程はナノ秒以下という非常に短い時間でおこる。
遅延蛍光とは、（１）エネルギーを受けた電子が一重項励起電子のもっともエネルギーレベルの高いところへ移る。（２）一重項励起電子が直接基底状態に戻るのではなく、いったんエネルギーレベルの低い三重項励起電子に移る。（３）さらに三重項励起電子から再び一重項励起電子にあがり、そこから一気に基底状態に戻る。（４）このとき発生するのが可視光の蛍光であるが、三重項励起電子から基底への転移が一重項励起を経由するので蛍光の発生が遅延され、秒といった長いスケールで蛍光が継続するのが特徴である。
Fluorescence is (1) an electron receiving energy moves to a place where the energy level of singlet excited electrons is highest. (2) Next, the singlet excited electrons move from a high energy level to a low energy level and return to the ground state all at once. (3) The visible light generated at this time is fluorescence, and the series of processes takes place in a very short time of nanoseconds or less.
With delayed fluorescence, (1) electrons that have received energy move to a place where the singlet excited electrons have the highest energy level. (2) Singlet excited electrons do not directly return to the ground state, but once move to triplet excited electrons having a low energy level. (3) Further, triplet excited electrons rise again to singlet excited electrons, and then return to the ground state all at once. (4) Visible light fluorescence is generated at this time, but since the transition from triplet excited electrons to the base passes through singlet excitation, the generation of fluorescence is delayed, and the fluorescence continues on a long scale such as seconds. Is the feature.
本発明においては、シリカガラス中に三重項励起電子準位のＳｉＳｉＳｉ結合を多く形成させることにより、また併せて一重項励起電子準位の吸収を２４０ｎｍに形成させることで、常温でも遅延蛍光を観察することが可能となった。よって、今まで有機ＬＥＤ材料では常温ではなしえなかった波長変換を、この遅延蛍光現象を用いることによって可能となったのである。 In the present invention, delayed fluorescence is observed even at room temperature by forming a lot of triplet excited electron level SiSiSi bonds in silica glass and also forming singlet excited electron level absorption at 240 nm. It became possible to do. Therefore, wavelength conversion, which could not be achieved at room temperature with organic LED materials until now, has become possible by using this delayed fluorescence phenomenon.
本発明のシリカガラスにおいて、ＯＨ基含有量は１ｐｐｍ以下であり、０．５ｐｐｍ以下がより好ましい。また、塩素の含有量は３０ｐｐｍ以下であり、１０ｐｐｍ以下がより好ましい。 In the silica glass of the present invention, the OH group content is 1 ppm or less, and more preferably 0.5 ppm or less. The chlorine content is 30 ppm or less, and more preferably 10 ppm or less.
本発明のシリカガラスは高耐熱性合成シリカガラスであって、１２８０℃での粘度（Ｌｏｇη）は１２．０poise以上であり、１２．３poise以上が好ましく、１２．４poise以上がより好ましい。 The silica glass of the present invention is a high heat-resistant synthetic silica glass, and the viscosity (Log η) at 1280 ° C. is 12.0 poise or higher, preferably 12.3 poise or higher, more preferably 12.4 poise or higher.
本発明では、特に、シリカガラス中には燐光発生する物質を含有させておらず、またシリカガラスそのものであることから、いろいろな形状にすることが可能である。例えば、ファイバー状に延伸したり、研磨して薄膜にしたり、１ｍ角以上の大きな基板も作成することが可能である。さらに、プリズムやレンズ形状、または球状の遅延蛍光を発生する製品を提供することが可能となる。従って、レーザ光を照射することが容易で、これによって効率よく波長を変換した４６０ｎｍにピークをもつ可視光を得ることが可能である。 In the present invention, in particular, the silica glass does not contain a phosphorescent substance, and since it is the silica glass itself, various shapes are possible. For example, it is possible to draw in a fiber shape, or to make a thin film by polishing, or to create a large substrate of 1 m square or more. Furthermore, it is possible to provide a product that generates a delayed fluorescent light having a prism or lens shape or a spherical shape. Therefore, it is easy to irradiate a laser beam, and thereby, it is possible to obtain visible light having a peak at 460 nm that has been efficiently converted in wavelength.
こうした可視光の遅延蛍光により、燐光物質を含有しないシリカガラスでも可視光を発生することができるので、液晶テレビのバックライトや照明装置への応用が考えられる。また、紫外線レーザを照射することで、可視光に波長を変化したレーザ光を発生させることも可能となる。 By virtue of such delayed fluorescence of visible light, visible light can be generated even in silica glass that does not contain a phosphorescent substance. Therefore, it can be applied to backlights of liquid crystal televisions and lighting devices. Further, by irradiating with an ultraviolet laser, it becomes possible to generate laser light having a wavelength changed to visible light.
最低励起三重項励起準位のＳｉＳｉＳｉ結合を効率的に形成する方法は特に規定はしないが、例えば合成シリカガラススート母材にＣｌを含有する化合物を反応させＳｉ−Ｃｌ結合を形成した後に、このＳｉ−Ｃｌ結合からＣｌを還元雰囲気で引き抜くことで達成することができる。 The method for efficiently forming the SiSiSi bond of the lowest excited triplet excited level is not particularly defined. For example, after forming a Si-Cl bond by reacting a compound containing Cl with a synthetic silica glass soot base material, This can be achieved by extracting Cl from the Si-Cl bond in a reducing atmosphere.
紫外線を照射すると蛍光を発生する光学ガラスを利用した紫外線センサーは実用化されているが、シリカガラスを利用した紫外線センサーは実用化されてはいない。通常の紫外線センサー（（株）住田光学ガラス製ルミラスＢ）では、ガラス内部に多量の発光イオン（元素）を分散している。このため、高温下で使用すると劣化して長期間使用することができない場合や、薬液やガス雰囲気との反応性によってはガラス表面があれてしまい、センサーとしての感度が低下して使用することができなくなる可能性がある。シリカガラスの場合には、高温でも安定であり、しかもガスや薬液との反応性もなく非常に安定しているので、過酷な雰囲気下でも長時間使用することが可能である。また、シリカガラスでも場合によっては、紫外線が照射されているときだけ蛍光が発生する場合があるが、本発明のシリカガラスを用いることにより、紫外線が照射されているかを直接確認できない場合、紫外線発生の大元を遮断後、数秒の時間を経過したのちでも遅延蛍光が発生している為、紫外線発生の有無を確認することが可能となる。 Ultraviolet sensors using optical glass that emits fluorescence when irradiated with ultraviolet rays have been put into practical use, but ultraviolet sensors using silica glass have not been put into practical use. In a normal ultraviolet sensor (Lumillas B manufactured by Sumita Optical Glass Co., Ltd.), a large amount of luminescent ions (elements) are dispersed inside the glass. For this reason, if it is deteriorated when used at high temperatures and cannot be used for a long time, or depending on the reactivity with the chemical solution or gas atmosphere, the glass surface may be lost, and the sensitivity as a sensor may be reduced. It may not be possible. In the case of silica glass, it is stable even at high temperatures and is very stable without reacting with gases and chemicals, so that it can be used for a long time even in a harsh atmosphere. Also, in some cases, silica glass may generate fluorescence only when irradiated with ultraviolet rays. However, if silica glass of the present invention cannot be used to directly confirm whether ultraviolet rays are being irradiated, ultraviolet rays are generated. Since the delayed fluorescence is generated even after several seconds have elapsed after blocking the main element, it is possible to confirm the presence or absence of ultraviolet rays.
以下に実施例をあげて本発明をさらに具体的に説明するが、これらの実施例は例示的に示されるもので限定的に解釈されるべきでないことはいうまでもない。 The present invention will be described more specifically with reference to the following examples. However, it is needless to say that these examples are shown by way of illustration and should not be construed in a limited manner.
（実施例１）
シリカガラススート母材を、四塩化ケイ素（ＳｉＣｌ４）ガスを水素と酸素の火炎の中で加水分解を起こして、ターゲット材に堆積させて作成した。次いで、このスート母材を有機ケイ素化合物のガス中で脱水し、還元性雰囲気中で加熱後、真空炉中で１５５０℃でガラス化して、酸素欠損を有する合成シリカガラスを作成した。
Example 1
A silica glass soot base material was prepared by hydrolyzing silicon tetrachloride (SiCl 4 ) gas in a flame of hydrogen and oxygen and depositing it on the target material. Next, this soot base material was dehydrated in an organosilicon compound gas, heated in a reducing atmosphere, and then vitrified in a vacuum furnace at 1550 ° C. to produce a synthetic silica glass having oxygen deficiency.
得られた合成シリカガラスの１８０〜２２０ｎｍの透過率及び吸光度を測定し、その結果を図１及び表１に示した。また、ＯＨ基含有量、Ｃｌ含有量及び粘度を測定し、その結果を表１に示した。金属不純物含有量を測定し、その結果を表３に示した。ＯＨ基含有量については、赤外分光光度計にて、２．７μｍの赤外線の吸収スペクトルから測定を行った。Ｃｌ含有量については、蛍光Ｘ線分析にて測定を行った。粘度に関しては、ビームベンディング法によって測定を行った。金属不純物含有量については、四重極型誘導結合プラズマ質量分析にて測定を行った。 The transmittance and absorbance of the obtained synthetic silica glass at 180 to 220 nm were measured, and the results are shown in FIG. Further, the OH group content, Cl content and viscosity were measured, and the results are shown in Table 1. The metal impurity content was measured and the results are shown in Table 3. The OH group content was measured from an infrared absorption spectrum of 2.7 μm with an infrared spectrophotometer. The Cl content was measured by fluorescent X-ray analysis. The viscosity was measured by a beam bending method. The metal impurity content was measured by quadrupole inductively coupled plasma mass spectrometry.
また、得られた合成シリカガラスに２５４ｎｍの紫外線（低圧水銀ランプ）を照射した場合の蛍光及び遅延蛍光の状態を測定し、その結果を表２及び図２に示した。遅延蛍光の発生は分光蛍光光度計を用いて測定を行った。励起波長２５４ｎｍでＵＶ３１フィルターにより励起光をカット、また入射側スリット幅、出射側スリット幅は５ｍｍで、フォトマルの電圧は９５０Ｖとした。励起光をカット後、０．０１秒、１秒、３秒、５秒後の遅延蛍光の強度を図２に示した。 The obtained synthetic silica glass was measured for the state of fluorescence and delayed fluorescence when irradiated with 254 nm ultraviolet light (low pressure mercury lamp), and the results are shown in Table 2 and FIG. The generation of delayed fluorescence was measured using a spectrofluorometer. The excitation light was cut by a UV31 filter at an excitation wavelength of 254 nm, the incident side slit width and the output side slit width were 5 mm, and the photomultiplier voltage was 950V. FIG. 2 shows the intensity of delayed fluorescence after 0.01 seconds, 1 second, 3 seconds, and 5 seconds after the excitation light was cut.
（実施例２）
シリカガラススート母材を、四塩化ケイ素（ＳｉＣｌ４）ガスを水素と酸素の火炎の中で加水分解を起こして、ターゲット材に堆積させて作成した。次いで、このスート母材を有機ケイ素化合物のガス中で脱水し、水素雰囲気中で焼成した後、還元性雰囲気中で加熱後、真空炉中で１５５０℃でガラス化して、酸素欠損を有する合成シリカガラスを作成した。得られた合成シリカガラスに対して、実施例１と同様に測定を行った。結果を表１，２，３及び図１，２に示した。
(Example 2)
A silica glass soot base material was prepared by hydrolyzing silicon tetrachloride (SiCl 4 ) gas in a flame of hydrogen and oxygen and depositing it on the target material. Next, this soot base material is dehydrated in an organosilicon compound gas, baked in a hydrogen atmosphere, heated in a reducing atmosphere, and then vitrified at 1550 ° C. in a vacuum furnace to produce synthetic silica having oxygen deficiency. Glass was created. The obtained synthetic silica glass was measured in the same manner as in Example 1. The results are shown in Tables 1, 2, 3 and FIGS.
（比較例１）
シリカガラススート母材を、四塩化ケイ素（ＳｉＣｌ４）ガスを水素と酸素の火炎の中で加水分解を起こして、ターゲット材に堆積させて作成した。次いで、このスート母材を真空炉中で１５５０℃加熱して、酸素欠損を有しない合成シリカガラスを作成した。得られた合成シリカガラスに対して、実施例１と同様に測定を行った。結果を表１，２，３及び図１，２に示した。
(Comparative Example 1)
A silica glass soot base material was prepared by hydrolyzing silicon tetrachloride (SiCl 4 ) gas in a flame of hydrogen and oxygen and depositing it on the target material. Subsequently, this soot base material was heated at 1550 ° C. in a vacuum furnace to produce a synthetic silica glass having no oxygen deficiency. The obtained synthetic silica glass was measured in the same manner as in Example 1. The results are shown in Tables 1, 2, 3 and FIGS.
表１，２及び図１，２に示した如く、三重項励起電子準位と一重項励起電子準位を含有する実施例１及び２では、４００〜６００ｎｍに遅延蛍光が確認された。特に、実施例２では、１０秒レベルの４６０ｎｍの遅延蛍光が認められた。一方、比較例１は、紫外線照射中も紫外線照射後も蛍光は一切認められなかった。また、実施例１及び実施例２、比較例１で得られた合成シリカガラスの金属不純物を分析したところ、表３に示したとおりであった。 As shown in Tables 1 and 2 and FIGS. 1 and 2, delayed fluorescence was confirmed at 400 to 600 nm in Examples 1 and 2 containing triplet excited electron levels and singlet excited electron levels. In particular, in Example 2, 460 nm delayed fluorescence at a 10-second level was observed. On the other hand, in Comparative Example 1, no fluorescence was observed during or after UV irradiation. Moreover, when the metal impurity of the synthetic silica glass obtained in Example 1, Example 2, and Comparative Example 1 was analyzed, it was as shown in Table 3.
Claims (2)
２５４ｎｍの照射された紫外線を０．０１秒以上で４００ｎｍ〜６５０ｎｍの可視光領域の遅延蛍光に波長変換することを特徴とする遅延蛍光を発生しかつ紫外線センサーに使用されるシリカガラス。 In the synthetic silica glass, the OH group content is 1 ppm or less, the chlorine content is 30 ppm or less, the transmittance at a wavelength of 190 nm with a thickness of 2 mm is 50% or less, and the viscosity (Log η) at 1280 ° C. is 12.0 poise or more and oxygen deficiency,
Silica glass that generates delayed fluorescence and is used for an ultraviolet sensor, which converts wavelength of irradiated ultraviolet light of 254 nm into delayed fluorescence in the visible light region of 400 nm to 650 nm in 0.01 seconds or more.
照射された紫外線を１秒以上の可視光領域の遅延蛍光に波長変換することを特徴とする請求項１記載の遅延蛍光を発生しかつ紫外線センサーに使用されるシリカガラス。 The transmittance at a wavelength of 200 nm with a thickness of 2 mm is 60% or less, the viscosity (Log η) at 1280 ° C. is 12.3 poise or more, and contains triplet and singlet excited electron levels. ,
2. The silica glass for generating delayed fluorescence and used in an ultraviolet sensor according to claim 1, wherein the wavelength of the irradiated ultraviolet light is converted into delayed fluorescence in the visible light region of 1 second or longer.
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