JP2010018481A - Ultraviolet ray- and infrared ray-absorbing synthetic silica glass and method for producing the same - Google Patents
Ultraviolet ray- and infrared ray-absorbing synthetic silica glass and method for producing the same Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 238000002834 transmittance Methods 0.000 claims abstract description 35
- 238000010521 absorption reaction Methods 0.000 claims abstract description 18
- 230000007547 defect Effects 0.000 claims abstract description 17
- 239000012535 impurity Substances 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 230000002950 deficient Effects 0.000 claims abstract description 6
- 239000012298 atmosphere Substances 0.000 claims description 29
- 238000010438 heat treatment Methods 0.000 claims description 14
- 230000001603 reducing effect Effects 0.000 claims description 12
- 230000009467 reduction Effects 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 238000010304 firing Methods 0.000 claims description 5
- 230000005298 paramagnetic effect Effects 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 3
- 239000011521 glass Substances 0.000 abstract description 4
- 238000010348 incorporation Methods 0.000 abstract 1
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 15
- 239000004065 semiconductor Substances 0.000 description 15
- 238000006722 reduction reaction Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 206010021143 Hypoxia Diseases 0.000 description 5
- 229910018557 Si O Inorganic materials 0.000 description 5
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000004071 soot Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 229910003902 SiCl 4 Inorganic materials 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 2
- 238000002798 spectrophotometry method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DWAWYEUJUWLESO-UHFFFAOYSA-N trichloromethylsilane Chemical compound [SiH3]C(Cl)(Cl)Cl DWAWYEUJUWLESO-UHFFFAOYSA-N 0.000 description 2
- 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 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910008045 Si-Si Inorganic materials 0.000 description 1
- 229910006411 Si—Si Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000000804 electron spin resonance spectroscopy Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000005375 photometry Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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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
- C03B2201/00—Type of glass produced
- C03B2201/02—Pure silica glass, e.g. pure fused quartz
- C03B2201/03—Impurity concentration specified
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Melting And Manufacturing (AREA)
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Abstract
Description
本発明は、紫外線赤外線吸収合成シリカガラス及びその製造方法に関する。 The present invention relates to an ultraviolet and infrared absorbing synthetic silica glass and a method for producing the same.
シリカガラスは、赤外線から真空紫外線までの広い波長範囲において透明であるばかりでなく、耐熱性、耐薬品性にも優れ、様々な製造装置、実験装置において、多用されてきた。反面、透明性が高いことによって、例えば発光源からの紫外線を遮断したり、高温発光源からの赤外線を遮蔽して保熱する用途には、不適であった。 Silica glass is not only transparent in a wide wavelength range from infrared rays to vacuum ultraviolet rays, but also excellent in heat resistance and chemical resistance, and has been widely used in various production apparatuses and experimental apparatuses. On the other hand, the high transparency makes it unsuitable for applications such as blocking ultraviolet rays from a light-emitting source or shielding infrared rays from a high-temperature light-emitting source to retain heat.
これらの問題を解決する為に、特許文献１においては、金属不純物を高濃度に含有させて紫外と赤外域の光線を吸収する紫外線赤外線吸収ガラスを提案している。但し、このようにして作られた紫外線赤外線吸収ガラスは、１０００℃を超えるような高温用途では耐熱性が不足し、また、金属不純物による汚染が問題視される用途には、使用することができなかった。 In order to solve these problems, Patent Document 1 proposes an ultraviolet-infrared absorbing glass that contains a metal impurity at a high concentration and absorbs light in the ultraviolet and infrared regions. However, the ultraviolet and infrared absorbing glass made in this way can be used for applications where heat resistance is insufficient for high temperature applications exceeding 1000 ° C. and contamination by metal impurities is considered a problem. There wasn't.
例えば、半導体製造工程で使用されるシリカガラス部材に要求される金属不純物の純度レベルは、極めて高い。天然シリカガラス中に含まれる金属不純物は、ｐｐｍレベルであるにも関わらず、近年の半導体製造工程では、許容されず、より高純度である合成シリカガラスの必要性が高まっている。但し、シリカガラスは、紫外から赤外まで光透過率が極めて高く、特に、紫外線の遮蔽や、赤外線を遮蔽しての保熱しが必要な半導体製造装置用途には適さず、製造される半導体素子の収率が大幅に低下する問題があった。
こうした現状を踏まえて、本発明者等は鋭意研究した結果、金属不純物を含有させることなく、紫外域と赤外域の光線透過率を低下させた、合成シリカガラスを作成することに成功した。
本発明は、金属不純物を含有させることなく、紫外域と赤外域の光線透過率を低下させ、且つ可視域の透過率が高い紫外線赤外線吸収合成シリカガラス及びその製造方法を提供することを目的とする。
In light of these circumstances, the present inventors have conducted extensive research and have succeeded in producing a synthetic silica glass in which the light transmittance in the ultraviolet region and the infrared region is reduced without containing metal impurities.
It is an object of the present invention to provide an ultraviolet-infrared-absorbing synthetic silica glass having a low transmittance in the ultraviolet region and an infrared region and having a high transmittance in the visible region and a method for producing the same without containing metal impurities. To do.
上記課題を達成するために、本発明の紫外線赤外線吸収合成シリカガラスは、金属不純物濃度の総和が１ｐｐｍ以下であり、波長２５０ｎｍにおける酸素欠損型欠陥量が吸収係数で０．１〜２／ｃｍであり、波長２５０ｎｍ以下の光線の内部透過率が０％／ｃｍ以上８０％／ｃｍ以下であり、波長５００ｎｍから１１００ｎｍまでの光線の内部透過率が５０％／ｃｍ以上９２％／ｃｍ以下であり、波長１５００ｎｍ以上の光線の内部透過率が０％／ｃｍ以上８５％／ｃｍ以下であることを特徴とする。 In order to achieve the above-mentioned problems, the ultraviolet-infrared-absorbing synthetic silica glass of the present invention has a total metal impurity concentration of 1 ppm or less, and an oxygen-deficient defect amount at a wavelength of 250 nm is 0.1 to 2 / cm as an absorption coefficient. Yes, the internal transmittance of light having a wavelength of 250 nm or less is 0% / cm or more and 80% / cm or less, and the internal transmittance of light having a wavelength of 500 nm to 1100 nm is 50% / cm or more and 92% / cm or less, The internal transmittance of light having a wavelength of 1500 nm or more is 0% / cm or more and 85% / cm or less.
この紫外線赤外線吸収合成シリカガラス中に、常磁性欠陥が、１×１０１３spins／ｇ以上１×１０２０spins／ｇ以下存在することが好適である。 It is preferable that paramagnetic defects are present in the ultraviolet-infrared-absorbing synthetic silica glass in an amount of 1 × 10 13 spins / g to 1 × 10 20 spins / g.
本発明の紫外線赤外線吸収合成シリカガラスの製造方法は、本発明の合成シリカガラスの製造方法であって、多孔質合成シリカガラス体を還元性を有する雰囲気中で加熱する還元処理を行った後、水素を含む雰囲気中で加熱処理し、その後焼成して緻密なシリカガラス体とすることを特徴とする。 The method for producing the ultraviolet-infrared-absorbing synthetic silica glass of the present invention is a method for producing the synthetic silica glass of the present invention, and after performing a reduction treatment in which the porous synthetic silica glass body is heated in a reducing atmosphere, The heat treatment is performed in an atmosphere containing hydrogen, followed by firing to form a dense silica glass body.
前記還元性を有する雰囲気が揮発性有機珪素化合物を含む還元性雰囲気であることが好ましい。前記焼成処理を加圧雰囲気で行うことが好適である。 The reducing atmosphere is preferably a reducing atmosphere containing a volatile organosilicon compound. It is preferable to perform the baking treatment in a pressurized atmosphere.
本発明の合成シリカガラスは、紫外域と赤外域の光線透過率が低く、一方で可視域の透過率は高く保持されるので、紫外線を遮蔽しつつ、保熱しながら、可視光線による光透過確認が可能である。また、金属不純物が含有されない合成シリカガラス素材であるため、半導体製造工程で適用されるには、最も適した素材である。 The synthetic silica glass of the present invention has a low light transmittance in the ultraviolet region and the infrared region, while the transmittance in the visible region is kept high, so that light transmission confirmation by visible light is performed while shielding ultraviolet rays and keeping heat. Is possible. Further, since it is a synthetic silica glass material that does not contain metal impurities, it is the most suitable material to be applied in the semiconductor manufacturing process.
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.
本発明の紫外線赤外線吸収合成シリカガラスは、金属不純物濃度の総和が１ｐｐｍ以下であり、且つ波長２５０ｎｍでの酸素欠損型欠陥量が吸収係数で０．１〜２／ｃｍであり、波長２５０ｎｍ以下の光線の内部透過率が０％／ｃｍ以上８０％／ｃｍ以下であり、波長５００ｎｍから１１００ｎｍまでの光線の内部透過率が５０％／ｃｍ以上９２％／ｃｍ以下であり、波長１５００ｎｍ以上の光線の内部透過率が０％／ｃｍ以上８５％／ｃｍ以下であることを特徴とする。 The ultraviolet-infrared-absorbing synthetic silica glass of the present invention has a total metal impurity concentration of 1 ppm or less, an oxygen-deficient defect amount at a wavelength of 250 nm is an absorption coefficient of 0.1 to 2 / cm, and a wavelength of 250 nm or less. The internal transmittance of light is 0% / cm or more and 80% / cm or less, the internal transmittance of light from a wavelength of 500 nm to 1100 nm is 50% / cm or more and 92% / cm or less, and the light having a wavelength of 1500 nm or more The internal transmittance is 0% / cm or more and 85% / cm or less.
シリカガラス中の金属不純物濃度の総和が１ｐｐｍを越えると、シリカガラス表面から含有金属不純物が微量に放出され、放出された金属不純物は、半導体素材あるいは半導体素子上に飛散して、特性劣化の原因となる。この金属不純物としては、特にアルカリ金属元素、アルカリ土類金属元素、遷移元素が挙げられ、具体的には、Ｌｉ、Ｎａ、Ｋ、Ｃａ、Ｍｇ、Ａｌ、Ｔｉなどが挙げられる。 If the total concentration of metal impurities in the silica glass exceeds 1 ppm, a small amount of metal impurities are released from the silica glass surface, and the released metal impurities are scattered on the semiconductor material or semiconductor element, causing deterioration in characteristics. It becomes. Examples of the metal impurities include alkali metal elements, alkaline earth metal elements, and transition elements, and specifically include Li, Na, K, Ca, Mg, Al, Ti, and the like.
本発明の紫外線赤外線吸収合成シリカガラスの製造方法としては、多孔質シリカガラス体を、還元性を有する雰囲気中で加熱する還元処理した後、水素を含む雰囲気中で加熱処理し、その後焼成して緻密なシリカガラス体とする方法が挙げられる。 As a method for producing the ultraviolet-infrared-absorbing synthetic silica glass of the present invention, the porous silica glass body is subjected to a reduction treatment in which the porous silica glass body is heated in a reducing atmosphere, followed by a heat treatment in an atmosphere containing hydrogen, followed by firing. A method for forming a dense silica glass body is exemplified.
前記多孔質シリカガラス体の製造方法は特に制限はなく、スート法やゾルゲル法等の公知の方法により得ることができるが、スート法が好適である。例えば、多重管構造の石英ガラス製バーナーの中心からＳｉＣｌ４などの原料ガスを供給し、その外側の管から水素やメタン及び酸素を供給し、前記原料を火炎加水分解してシリカ粒子を得、それをターゲット上に堆積させて、多孔質合成シリカガラス体（スート体）を得ることが好ましい。 The method for producing the porous silica glass body is not particularly limited and can be obtained by a known method such as a soot method or a sol-gel method, but the soot method is preferable. For example, a raw material gas such as SiCl 4 is supplied from the center of a quartz glass burner having a multi-tube structure, hydrogen, methane and oxygen are supplied from the outer tube, and the raw material is subjected to flame hydrolysis to obtain silica particles. It is preferable to deposit it on the target to obtain a porous synthetic silica glass body (soot body).
前記多孔質合成石英ガラス体は、水酸基を多く含んでいるものが好ましい。水酸基を含むことで還元処理におけるガス反応が促進される。還元反応にはＯＨ基を約５０から１０００ｐｐｍ含有することが必要で、好ましくは１００から５００ｐｐｍ含有するとよい。これ以下では、反応種の量が少なく、効果が見られず、これ以上では、反応が追いつかず、ゲル化する。 The porous synthetic quartz glass body preferably contains many hydroxyl groups. The gas reaction in the reduction treatment is promoted by including a hydroxyl group. The reduction reaction needs to contain about 50 to 1000 ppm of OH groups, preferably 100 to 500 ppm. Below this, the amount of reactive species is small and no effect is seen, and above this, the reaction cannot catch up and gelation occurs.
多孔質合成シリカガラス体を、還元性を有する雰囲気中、好ましくは揮発性有機珪素化合物を含む還元性雰囲気中で加熱する還元処理を行うことによって、合成シリカガラスの中に、約２５０ｎｍ（５．０ｅＶ）の酸素欠損型欠陥量を、その吸収係数で０．１〜２／ｃｍの範囲に作成して、２５０ｎｍ以下の光線の内部透過率が８０％／ｃｍ以下とする。 The porous synthetic silica glass body is subjected to a reduction treatment by heating in a reducing atmosphere, preferably in a reducing atmosphere containing a volatile organosilicon compound, whereby about 250 nm (5. The oxygen deficiency defect amount of 0 eV) is created in the range of 0.1 to 2 / cm in terms of its absorption coefficient, and the internal transmittance of light having a wavelength of 250 nm or less is 80% / cm or less.
前記還元処理において、還元性を有する雰囲気に含まれる気体としては、ヘキサメチルジシラザン（［（ＣＨ３）３Ｓｉ］２ＮＨ）、トリクロロメチルシラン（（ＣＨ２Ｃｌ）３ＳｉＨ）、ヘキサメチルジシロキサン［（ＣＨ３）３Ｓｉ］２Ｏ等の揮発性有機珪素化合物や、アンモニア（ＮＨ３）、ヒドラジン（Ｎ２Ｈ４）、エタノール（Ｃ２Ｈ５ＯＨ）、一酸化炭素（ＣＯ）、塩素（Ｃｌ２）、四塩化ケイ素（ＳｉＣｌ４）が挙げられ、揮発性有機珪素化合物がより好ましい。 In the reduction treatment, the gases contained in the reducing atmosphere include hexamethyldisilazane ([(CH 3 ) 3 Si] 2 NH), trichloromethylsilane ((CH 2 Cl) 3 SiH), hexamethyldi Volatile organic silicon compounds such as siloxane [(CH 3 ) 3 Si] 2 O, ammonia (NH 3 ), hydrazine (N 2 H 4 ), ethanol (C 2 H 5 OH), carbon monoxide (CO), Examples include chlorine (Cl 2 ) and silicon tetrachloride (SiCl 4 ), and volatile organic silicon compounds are more preferable.
前記還元処理における加熱温度は、１００〜１３００℃が好ましく、より好ましくは４００〜１０００℃である。処理時間は加熱温度に応じて適宜選択すればよいが、１０時間〜１００時間が好ましい。 The heating temperature in the reduction treatment is preferably 100 to 1300 ° C, more preferably 400 to 1000 ° C. The treatment time may be appropriately selected according to the heating temperature, but is preferably 10 hours to 100 hours.
本発明で規定する酸素欠損型欠陥は、シリカガラスの構造欠陥の１つである酸素原子の欠損に基づく欠陥であるが、この酸素欠損型欠陥が存在すると、Ｓｉ−Ｓｉ結合が増大し、その吸収性により波長２５０ｎｍ以下の光線の透過率が低下する。
前記酸素欠損型欠陥量はその吸収係数で０．１〜２／ｃｍの範囲が良い。吸収係数が０．１／ｃｍ未満では、酸素欠損型欠陥による波長２５０ｎｍ以下の光線の透過率の低減効果がなく、また、２／ｃｍを越えると可視光線の透過率が必要以上に低下する。
The oxygen deficiency type defect defined in the present invention is a defect based on the deficiency of an oxygen atom, which is one of the structural defects of silica glass. If this oxygen deficiency type defect exists, the Si-Si bond increases, The transmittance of light having a wavelength of 250 nm or less is reduced due to absorption.
The oxygen deficiency type defect amount is preferably in the range of 0.1 to 2 / cm in terms of its absorption coefficient. When the absorption coefficient is less than 0.1 / cm, there is no effect of reducing the transmittance of light having a wavelength of 250 nm or less due to oxygen deficiency defects, and when it exceeds 2 / cm, the transmittance of visible light is unnecessarily lowered.
酸素欠損型欠陥の吸収係数は、酸素欠損型欠陥が約２５０ｎｍ（５．０ｅＶ）の吸収帯としてあらわれる（H. Imai et at. (1988) Two types of oxygen-deficient centers in synthetic silica glass. physical Review B. Vol. 38, No.17, pp12772~12775）。この２５０ｎｍの吸収係数を測定し、下記式（１）に当て嵌めることにより内部透過率が算出できる。
Ｔ＝１０−ｋｄ ・・・（１）
（前記式（１）において、Ｔは内部透過率（％）、ｄは測定試料の厚さ（ｃｍ）、ｋは物質固有の吸収係数である。）
The absorption coefficient of oxygen-deficient defects appears as an absorption band of about 250 nm (5.0 eV) (H. Imai et at. (1988) Two types of oxygen-deficient centers in synthetic silica glass. Physical Review B. Vol. 38, No. 17, pp12772-12775). The internal transmittance can be calculated by measuring the absorption coefficient of 250 nm and fitting it to the following formula (1).
T = 10 −kd (1)
(In the above formula (1), T is the internal transmittance (%), d is the thickness of the measurement sample (cm), and k is the absorption coefficient specific to the substance.)
前記還元処理後、さらに、上記水素を含む雰囲気中で加熱処理することによって、合成シリカガラスの中に、赤外線を吸収するＳｉ−Ｏ結合を所望量作成して、該波長１５００ｎｍ以上の光線の内部透過率を８５％／ｃｍ以下とする。 After the reduction treatment, further heat treatment is performed in an atmosphere containing hydrogen to create a desired amount of Si—O bonds that absorb infrared rays in the synthetic silica glass, and the inside of the light having a wavelength of 1500 nm or more. The transmittance is set to 85% / cm or less.
前記水素を含む雰囲気中での加熱処理の温度条件は、３００〜１９００℃が好ましく、より好ましくは５００〜１５００℃である。処理時間は加熱温度に応じて適宜選択すればよいが、１時間〜５００時間が好ましく、３０時間〜５００時間がより好ましい。圧力条件は、０．１Ｐａから加圧雰囲気、好ましくは大気圧又は加圧雰囲気、より好ましくは加圧雰囲気の圧力範囲が好適である。前記水素を含む雰囲気での加熱処理を加圧雰囲気で行うことにより、シリカガラス中のＳｉ−Ｏの生成量を増大させることができる。上記加圧雰囲気における加圧範囲としては、０を超える圧力以上０．９ＭＰａ以下であることが好ましい。 As for the temperature conditions of the heat processing in the atmosphere containing the said hydrogen, 300-1900 degreeC is preferable, More preferably, it is 500-1500 degreeC. The treatment time may be appropriately selected according to the heating temperature, but is preferably 1 hour to 500 hours, more preferably 30 hours to 500 hours. The pressure condition is from 0.1 Pa to a pressurized atmosphere, preferably atmospheric pressure or a pressurized atmosphere, more preferably a pressure range of a pressurized atmosphere. By performing the heat treatment in an atmosphere containing hydrogen in a pressurized atmosphere, the amount of Si—O generated in the silica glass can be increased. The pressurizing range in the pressurizing atmosphere is preferably a pressure exceeding 0 to 0.9 MPa.
Ｓｉ−Ｏ結合は、３３００〜３４００ガウスの磁場を掛けたときに観察される、常磁性欠陥の一種で、スピン密度の総量が、１×１０１３spins／ｇ以上１×１０２０spins／ｇ以下の範囲にあることが好ましく、２×１０１３spins／ｇ以上１×１０１９spins／ｇ以下の範囲がより好ましい。常磁性欠陥が１×１０１３spins／ｇ未満では、赤外線吸収が小さくなりすぎ、効果がなく、１×１０２０spins／ｇを超える場合では、余分なＳｉ−Ｏ結合が気泡発生原因となって、使用に適さなくなる。 The Si—O bond is a kind of paramagnetic defect observed when a magnetic field of 3300 to 3400 gauss is applied, and the total amount of spin density is 1 × 10 13 spins / g or more and 1 × 10 20 spins / g or less. The range is preferably 2 × 10 13 spins / g or more and 1 × 10 19 spins / g or less. If the paramagnetic defect is less than 1 × 10 13 spins / g, the infrared absorption is too small and has no effect. If the paramagnetic defect exceeds 1 × 10 20 spins / g, excess Si—O bonds cause bubbles. , Not suitable for use.
上記２つの吸収要因によって、波長５００ｎｍから１１００ｎｍまでの光線の内部透過率は、上記２つの光吸収因子の影響を受けて若干低下するが、５０％／ｃｍ以上に保持される。 Due to the above two absorption factors, the internal transmittance of light having a wavelength of 500 nm to 1100 nm is slightly reduced by the influence of the two light absorption factors, but is maintained at 50% / cm or more.
前記焼成処理としては特に制限はないが、０．１Ｐａから加圧雰囲気、好ましくは大気圧又は加圧雰囲気、より好ましくは加圧雰囲気の圧力範囲において、１１００〜１９００℃、好ましくは１２００〜１８００℃の温度で焼成して緻密化シリカガラス体を作ることが好適である。上記加圧雰囲気における加圧範囲としては、０を超える圧力以上０．９ＭＰａ以下であることが好ましい。前記焼成処理を加圧雰囲気で行うことにより、特に赤外線の吸収因子であるＳｉ−Ｏをガラス体内に保持し、大きな赤外線吸収を発生させることができる。
前記焼成処理の雰囲気としては、不活性ガスが好ましく、Ｎ２、Ａｒ、Ｈｅがより好ましい。処理時間は加熱温度に応じて適宜選択すればよいが、１０分〜５００時間が好ましく、１時間〜１００時間がより好ましい。
Although there is no restriction | limiting in particular as said baking process, It is 1100-1900 degreeC in the pressure range of 0.1 Pa to pressurization atmosphere, Preferably atmospheric pressure or pressurization atmosphere, More preferably, pressurization atmosphere, Preferably it is 1200-1800 degreeC. It is preferable to make a densified silica glass body by firing at the temperature of The pressurizing range in the pressurizing atmosphere is preferably a pressure exceeding 0 to 0.9 MPa. By performing the baking treatment in a pressurized atmosphere, particularly Si—O, which is an infrared absorption factor, can be held in the glass body and large infrared absorption can be generated.
As the atmosphere for the baking treatment, an inert gas is preferable, and N 2 , Ar, and He are more preferable. The treatment time may be appropriately selected according to the heating temperature, but is preferably 10 minutes to 500 hours, and more preferably 1 hour to 100 hours.
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.
各物性値の測定方法は下記の通りである。
（１）アルミニウム，アルカリ金属、およびアルカリ土類金属元素各含有量の測定；原子吸光光度法。
（２）吸収係数の測定；紫外線分光光度法。
（３）内部透過率（２面鏡面１０ｔ）の測定；紫外線分光光度法。
（４）常時性欠陥の測定：ＥＳＲ分光測定法。
The measuring method of each physical property value is as follows.
(1) Measurement of each content of aluminum, alkali metal, and alkaline earth metal element; atomic absorption photometry.
(2) Measurement of absorption coefficient; ultraviolet spectrophotometry.
(3) Measurement of internal transmittance (dihedral mirror surface 10t); ultraviolet spectrophotometry.
(4) Measurement of permanent defects: ESR spectroscopy.
（実施例１）
テトラクロロシランの火炎加水分解によって得た、外径１００ｍｍ×内径６０ｍｍ×長さ３００ｍｍの円筒状で密度が０．７ｇ／ｃｍ３の多孔質合成シリカガラス体（ＯＨ基約３００ｐｐｍ含有）約１ｋｇを電気炉内に装着されたシリカガラス製の炉心管（直径２００ｍｍ）内にセットし、次いで、炉心管内を排気した後、５００℃に加熱し、この温度で約６０分間予熱した。
Example 1
About 1 kg of porous synthetic silica glass body (containing about 300 ppm of OH group) obtained by flame hydrolysis of tetrachlorosilane and having a cylindrical shape with an outer diameter of 100 mm, an inner diameter of 60 mm and a length of 300 mm and a density of 0.7 g / cm 3 It was set in a silica glass core tube (diameter 200 mm) mounted in the furnace, and then the inside of the core tube was evacuated and then heated to 500 ° C. and preheated at this temperature for about 60 minutes.
その後、ヘキサメチルジシラザン蒸気を大気圧で、Ｎ２ガスで希釈しながら供給し、ヘキサメチルジシラザンと多孔質合成シリカガラス体中のＯＨ基とを反応させた。前記ヘキサメチルジシラザンによる還元処理の条件を表１に示す。なお、ヘキサメチルジシラザン蒸気及びＮ２ガスの流量はそれぞれ１ｍｏｌ／ｈｒである。
還元処理終了後、多孔質合成シリカガラス体を加熱炉内に移し、炉内温度を８００℃に昇温し、Ｈ２ガスを１ｍｏｌ／ｈｒ掛け流しながら、０．１ＭＰａ加圧した圧力条件で１時間保持した。
次いで、炉内をＮ２雰囲気中にて０．４ＭＰａとし、１５００℃に昇温し、１時間保持した。それを室温まで冷却して緻密化された外径１００ｍｍ×内径９０ｍｍ×長さ３００ｍｍの透明なシリンダー状シリカガラスを得た。水素処理及び焼成処理の条件を表２に示す。
Thereafter, hexamethyldisilazane vapor was supplied at atmospheric pressure while diluting with N 2 gas to react hexamethyldisilazane with OH groups in the porous synthetic silica glass body. The conditions for the reduction treatment with hexamethyldisilazane are shown in Table 1. The flow rates of hexamethyldisilazane vapor and N 2 gas are 1 mol / hr, respectively.
After completion of the reduction treatment, the porous synthetic silica glass body is transferred into a heating furnace, the furnace temperature is raised to 800 ° C., and H 2 gas is applied at a pressure of 0.1 MPa while flowing 1 mol / hr. Held for hours.
Next, the inside of the furnace was set to 0.4 MPa in an N 2 atmosphere, and the temperature was raised to 1500 ° C. and held for 1 hour. It was cooled to room temperature to obtain a transparent cylindrical silica glass having an outer diameter of 100 mm, an inner diameter of 90 mm, and a length of 300 mm. Table 2 shows the conditions for the hydrogen treatment and the firing treatment.
得られたシリンダー状シリカガラスについてその物性値を測定し、それを表３に示した。また、このシリンダー状シリカガラスについて波長２００ｎｍから２５００ｎｍの光線の内部透過率を調べた。その結果を図１に示す。
作成されたシリカガラスを用い、半導体製造装置の赤外線保温板を作成し、装置に取り付けて、半導体素子の製造を行った。半導体素子製造エリア各部の保温状況が一定、且つ、安定化し、その結果、半導体素子の製造収率も向上した。結果を表３に示す。なお、半導体製造装置内保温性の測定は、装置内反応エリアの加熱処理中の温度均一性が１０％以内の場合をＯＫ、１０％を超える場合をＮ．Ｇ．として評価した。
The physical properties of the obtained cylindrical silica glass were measured and are shown in Table 3. Further, the internal transmittance of light having a wavelength of 200 nm to 2500 nm was examined for this cylindrical silica glass. The result is shown in FIG.
Using the prepared silica glass, an infrared heat insulating plate of a semiconductor manufacturing apparatus was prepared and attached to the apparatus to manufacture a semiconductor element. The heat insulation state in each part of the semiconductor element manufacturing area was constant and stabilized, and as a result, the manufacturing yield of the semiconductor element was also improved. The results are shown in Table 3. The measurement of the heat retention in the semiconductor manufacturing apparatus is OK when the temperature uniformity during the heat treatment in the reaction area within the apparatus is within 10%, and when the temperature uniformity exceeds 10%. G. As evaluated.
（実施例２）
表１及び表２に示した如く、ヘキサメチルジシラザンの代わりにトリクロロメチルシラン（（ＣＨ２Ｃｌ）３ＳｉＨ）を用いた以外、実施例１と同様にしてシリンダー状シリカガラスを得た。得られたシリンダー状シリカガラスについてその物性値を測定し、それを表３に示した。また、このシリカガラスについても波長２００ｎｍから２５００ｎｍの光線の透過率を調べた。その結果を図１に示す。半導体素子試作結果を表３に示す。
(Example 2)
As shown in Tables 1 and 2, a cylindrical silica glass was obtained in the same manner as in Example 1 except that trichloromethylsilane ((CH 2 Cl) 3 SiH) was used instead of hexamethyldisilazane. The physical properties of the obtained cylindrical silica glass were measured and are shown in Table 3. Further, the transmittance of light having a wavelength of 200 nm to 2500 nm was also examined for this silica glass. The result is shown in FIG. Table 3 shows the results of semiconductor device trial manufacture.
（実施例３）
表１及び表２に示した如く、ヘキサメチルジシラザンの代わりにヘキサメチルジシロキサン［（ＣＨ３）３Ｓｉ］２を用いた以外、実施例１と同様にしてシリンダー状シリカガラスを得た。得られたシリンダー状シリカガラスについてその物性値を測定し、それを表２に示した。また、このシリカガラスについて波長２００ｎｍから２５００ｎｍの光線の透過率を調べた。その結果を図１に示す。半導体素子試作結果を表３に示す。
Example 3
As shown in Tables 1 and 2, a cylindrical silica glass was obtained in the same manner as in Example 1 except that hexamethyldisiloxane [(CH 3 ) 3 Si] 2 was used instead of hexamethyldisilazane. The physical properties of the obtained cylindrical silica glass were measured and are shown in Table 2. Further, the transmittance of light having a wavelength of 200 nm to 2500 nm was examined for this silica glass. The result is shown in FIG. Table 3 shows the results of semiconductor device trial manufacture.
（比較例１）
テトラクロロシランの火炎加水分解によって得た、外径１００ｍｍ×内径６０ｍｍ×長さ３００ｍｍの円筒状で密度が０．７ｇ／ｃｍ３の多孔質合成シリカガラス体（ＯＨ基約３００ｐｐｍ含有）約１ｋｇを電気炉内に装着されたシリカガラス製の炉心管（直径２００ｍｍ）内にセットした。次いで、炉心管内を排気した後、５００℃に加熱し、この温度で６０分間予熱した。その後、Ｎ２ガスを供給し、表１の条件で加熱処理を行った。
(Comparative Example 1)
About 1 kg of porous synthetic silica glass body (containing about 300 ppm of OH group) obtained by flame hydrolysis of tetrachlorosilane and having a cylindrical shape with an outer diameter of 100 mm, an inner diameter of 60 mm and a length of 300 mm and a density of 0.7 g / cm 3 It was set in a furnace core tube (diameter 200 mm) made of silica glass mounted in the furnace. Next, after exhausting the inside of the furnace tube, it was heated to 500 ° C. and preheated at this temperature for 60 minutes. Then, the N 2 gas is supplied, a heat treatment was performed under the conditions of Table 1.
その後、多孔質合成シリカガラス体を加熱炉内に移し、炉内温度を８００℃に昇温し、Ｎ２ガスを１ｍｏｌ／ｈｒ掛け流しながら、１時間保持した。炉内を０．１Ｐａに減圧するとともに、１５００℃に昇温し、１時間保持した。室温まで冷却し、緻密化され外径１００ｍｍ×内径９０ｍｍ×長さ３００ｍｍの透明なシリンダー状シリカガラスを得た。 Thereafter, the porous synthetic silica glass body was transferred into a heating furnace, the furnace temperature was raised to 800 ° C., and maintained for 1 hour while flowing N 2 gas at 1 mol / hr. While reducing the pressure in the furnace to 0.1 Pa, the temperature was raised to 1500 ° C. and held for 1 hour. After cooling to room temperature, a transparent cylindrical silica glass having an outer diameter of 100 mm, an inner diameter of 90 mm, and a length of 300 mm was obtained.
得られたシリンダー状シリカガラスについて物性値を測定し、それを表３に示した。また、このシリンダー状シリカガラスについて波長２００ｎｍから２５００ｎｍの光線の内部透過率を調べた。その結果を図１に示す。半導体素子試作結果を表３に示す。 The physical properties of the obtained cylindrical silica glass were measured and are shown in Table 3. Further, the internal transmittance of light having a wavelength of 200 nm to 2500 nm was examined for this cylindrical silica glass. The result is shown in FIG. Table 3 shows the results of semiconductor device trial manufacture.
（比較例２）
天然シリカガラスについて物性値を測定し、それを表３に示した。また、天然シリカガラスについて波長２００ｎｍから２５００ｎｍの光線の内部透過率を調べた。その結果を図１に示す。半導体素子試作結果を表３に示す。
(Comparative Example 2)
The physical properties of natural silica glass were measured and are shown in Table 3. Moreover, the internal transmittance of light having a wavelength of 200 nm to 2500 nm was examined for natural silica glass. The result is shown in FIG. Table 3 shows the results of semiconductor device trial manufacture.
Claims (5)
多孔質合成シリカガラス体を還元性を有する雰囲気中で加熱する還元処理を行った後、水素を含む雰囲気中で加熱処理し、その後焼成して緻密なシリカガラス体とすることを特徴とする紫外線赤外線吸収合成シリカガラスの製造方法。 A method for producing the ultraviolet and infrared absorbing synthetic silica glass according to claim 1 or 2,
An ultraviolet ray characterized by performing a reduction treatment in which a porous synthetic silica glass body is heated in an atmosphere having a reducing property, followed by a heat treatment in an atmosphere containing hydrogen and then firing to form a dense silica glass body. A method for producing infrared-absorbing synthetic silica glass.
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| WO2004050570A1 (en) * | 2002-11-29 | 2004-06-17 | Shin-Etsu Quartz Products Co., Ltd. | Method for producing synthetic quartz glass and synthetic quartz glass article |
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| JP2009298686A (en) * | 2008-05-12 | 2009-12-24 | Shinetsu Quartz Prod Co Ltd | Synthetic silica glass, method for producing the same, and device provided with lamp for electric-discharge lamp or synthetic silica soot firing furnace core tube using the synthetic silica glass |
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| WO2004050570A1 (en) * | 2002-11-29 | 2004-06-17 | Shin-Etsu Quartz Products Co., Ltd. | Method for producing synthetic quartz glass and synthetic quartz glass article |
| JP2005067914A (en) * | 2003-08-26 | 2005-03-17 | Tosoh Corp | Quartz glass and manufacturing method therefor |
| JP2009298686A (en) * | 2008-05-12 | 2009-12-24 | Shinetsu Quartz Prod Co Ltd | Synthetic silica glass, method for producing the same, and device provided with lamp for electric-discharge lamp or synthetic silica soot firing furnace core tube using the synthetic silica glass |
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