JPH0446607B2 - - Google Patents
Info
- Publication number
- JPH0446607B2 JPH0446607B2 JP60213691A JP21369185A JPH0446607B2 JP H0446607 B2 JPH0446607 B2 JP H0446607B2 JP 60213691 A JP60213691 A JP 60213691A JP 21369185 A JP21369185 A JP 21369185A JP H0446607 B2 JPH0446607 B2 JP H0446607B2
- Authority
- JP
- Japan
- Prior art keywords
- gas
- zeolite
- impurities
- laser gas
- laser
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000012535 impurity Substances 0.000 claims description 38
- 239000010457 zeolite Substances 0.000 claims description 35
- 229910021536 Zeolite Inorganic materials 0.000 claims description 32
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 32
- 239000007787 solid Substances 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 18
- 238000009835 boiling Methods 0.000 claims description 13
- 150000004820 halides Chemical class 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 description 50
- 239000003513 alkali Substances 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 9
- 229910052724 xenon Inorganic materials 0.000 description 9
- 230000007423 decrease Effects 0.000 description 8
- 239000011575 calcium Substances 0.000 description 7
- 229910052734 helium Inorganic materials 0.000 description 7
- 229910052743 krypton Inorganic materials 0.000 description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- 239000013543 active substance Substances 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000002808 molecular sieve Substances 0.000 description 5
- 229910052754 neon Inorganic materials 0.000 description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000003203 everyday effect Effects 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 241000270281 Coluber constrictor Species 0.000 description 1
- -1 F 2 Substances 0.000 description 1
- 229910004014 SiF4 Inorganic materials 0.000 description 1
- OMOVVBIIQSXZSZ-UHFFFAOYSA-N [6-(4-acetyloxy-5,9a-dimethyl-2,7-dioxo-4,5a,6,9-tetrahydro-3h-pyrano[3,4-b]oxepin-5-yl)-5-formyloxy-3-(furan-3-yl)-3a-methyl-7-methylidene-1a,2,3,4,5,6-hexahydroindeno[1,7a-b]oxiren-4-yl] 2-hydroxy-3-methylpentanoate Chemical compound CC12C(OC(=O)C(O)C(C)CC)C(OC=O)C(C3(C)C(CC(=O)OC4(C)COC(=O)CC43)OC(C)=O)C(=C)C32OC3CC1C=1C=COC=1 OMOVVBIIQSXZSZ-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- 150000001674 calcium compounds Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- AFYPFACVUDMOHA-UHFFFAOYSA-N chlorotrifluoromethane Chemical compound FC(F)(F)Cl AFYPFACVUDMOHA-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000002354 daily effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- OQZCSNDVOWYALR-UHFFFAOYSA-N flurochloridone Chemical compound FC(F)(F)C1=CC=CC(N2C(C(Cl)C(CCl)C2)=O)=C1 OQZCSNDVOWYALR-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002366 halogen compounds Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- GVGCUCJTUSOZKP-UHFFFAOYSA-N nitrogen trifluoride Chemical compound FN(F)F GVGCUCJTUSOZKP-UHFFFAOYSA-N 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
- H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
- H01S3/14—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range characterised by the material used as the active medium
- H01S3/22—Gases
- H01S3/223—Gases the active gas being polyatomic, i.e. containing two or more atoms
- H01S3/225—Gases the active gas being polyatomic, i.e. containing two or more atoms comprising an excimer or exciplex
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
- H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
- H01S3/02—Constructional details
- H01S3/03—Constructional details of gas laser discharge tubes
- H01S3/036—Means for obtaining or maintaining the desired gas pressure within the tube, e.g. by gettering, replenishing; Means for circulating the gas, e.g. for equalising the pressure within the tube
Landscapes
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Engineering & Computer Science (AREA)
- Plasma & Fusion (AREA)
- Optics & Photonics (AREA)
- Lasers (AREA)
- Separation Of Gases By Adsorption (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、希ガスハライドエキシマーレーザー
ガスの固体アルカリ金属および／またはアルカリ
土類金属化合物とゼオライトとの組合せによる精
製に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to the purification of rare gas halide excimer laser gases by a combination of solid alkali metal and/or alkaline earth metal compounds and zeolites.
ArF、KrF、XeF、XeCl系に代表される希ガ
スハライドエキシマーレーザーは高出力の紫外光
源として半導体製造や光化学反応をはじめ種々の
分野への応用が急速に進展しているが、媒質とし
てF2、HClなどの極めて反応性の高い気体を用い
るので、レーザー容器等との反応によりその濃度
は減少し、不純物が発生する。このレーザーガス
の劣化はレーザー出力の著しい低下をもたらして
エキシマーレーザーの長期の連続運転を不可能と
するものであり、したがつてその改善が望まれて
いた。 Rare gas halide excimer lasers, represented by ArF, KrF, XeF, and XeCl systems, are being rapidly used as high-power ultraviolet light sources in various fields including semiconductor manufacturing and photochemical reactions . Since extremely reactive gases such as , HCl, etc. are used, their concentration decreases due to reactions with the laser container, etc., and impurities are generated. This deterioration of the laser gas causes a significant drop in laser output, making long-term continuous operation of the excimer laser impossible, and therefore, an improvement has been desired.
また、Kr、Xe、He、Ne等非常に高価なガス
を使用するため、劣化したガスを廃棄し新たにガ
スを導入、使用する方法は工業的には採用し難
い。 Furthermore, since very expensive gases such as Kr, Xe, He, and Ne are used, it is difficult to adopt a method of discarding degraded gas and introducing and using new gas industrially.
本発明はレーザーガス中の不純物を効率的に除
去し精製レーザーガスを循環使用し得るように
し、よつて長期にわたる安定した連続運転を可能
とするものである。 The present invention efficiently removes impurities in the laser gas, enables purified laser gas to be recycled, and thus enables stable continuous operation over a long period of time.
希ガスハライドエキシマーレーザーにおいて
は、F2、HCl等の活性物質と、それらと反応する
Ar、Kr、Xe等の希ガスが適宜目的に応じて選択
使用され、さらにこれらを希釈するHe、Ne等に
より主成分を形成する。一方、該エキシマーレー
ザーの運転中に発生する不純物は、使用するレー
ザーガスの組成によつて異なるが、CF4、C2F6、
SiF4、HF、NF3、SF6、CCl4、CClF3、CCl2F2、
CCl3F等のハロゲン化合物であり、従来、これら
の不純物を除去する目的で以下のような方法が提
案されている。すなわち、
比較的高い沸点の物質を低温下で凝縮させる
低温トラツプ法
金属カルシウムと反応し得る物質を金属カル
シウムと接触させカルシウム化合物とする金属
カルシウム反応法
活性炭やゲツター材（Ti−Zr合金）で被吸
着性物質を吸着する吸着法などがある。
In rare gas halide excimer lasers, active substances such as F 2 and HCl react with them.
Rare gases such as Ar, Kr, and Xe are selected and used depending on the purpose, and further diluted with He, Ne, and the like to form the main component. On the other hand, impurities generated during the operation of the excimer laser vary depending on the composition of the laser gas used, but include CF 4 , C 2 F 6 ,
SiF4 , HF, NF3 , SF6 , CCl4 , CClF3 , CCl2F2 ,
It is a halogen compound such as CCl 3 F, and the following methods have been proposed to remove these impurities. In other words, the low-temperature trap method in which substances with relatively high boiling points are condensed at low temperatures; the metal calcium reaction method in which a substance that can react with metallic calcium is brought into contact with metallic calcium to form a calcium compound; There are adsorption methods that adsorb adsorptive substances.
しかしながらの方法は、沸点の高い不純物に
ついては効率良く除去できるものの、CF4、NF3
等の低沸点の不純物は除去できず、さらに、レー
ザーガスの主成分である高沸点のKr、Xe等を同
時に凝縮してしまうため、限定的なレーザー系に
しか使用できない。の方法は650℃もの高温に
熱した金属カルシウムで不純物を除去しようとす
るもので、操作温度が高く、取扱い困難な金属カ
ルシウムを使用すること、さらに金属カルシウム
と反応し得るものしか除去できないため工業的に
有効な方法とは言い難い。またの方法は特定の
化学物質のみに有効な方法ではあるが、レーサー
ガスの不純物は非常に多種類に及ぶため、限定的
な不純物除去にしか使用し得ない。 However, although this method can efficiently remove impurities with high boiling points, it removes impurities such as CF 4 and NF 3
It cannot remove impurities with low boiling points such as Kr and Xe, which are the main components of laser gas, and condenses at the same time, so it can only be used in limited laser systems. This method attempts to remove impurities using metallic calcium heated to a high temperature of 650°C.The operating temperature is high and metallic calcium is difficult to handle.Furthermore, only substances that can react with metallic calcium can be removed, making it difficult to use industrially. It is difficult to say that this is an effective method. Although this method is effective only for specific chemical substances, since there are a wide variety of impurities in the racer gas, it can only be used for limited removal of impurities.
上述のように、これまで、レーザーガスの精製
法として決定的な手段は見出されていない。 As mentioned above, no definitive method for purifying laser gas has been found so far.
本発明は該希ガスハライドエキシマーレーザー
ガス中の不純物を効率的かつ効果的に除去する方
法、すなわち、レーザーガスをゼオライトに接触
させ不純物を吸着、除去するに際し、レーザーガ
スを固体アルカリ金属および／またはアルカリ土
類金属化合物（以下固体アルカリ化合物という）
と接触させゼオライトと反応し得る活性物質を反
応、除去する方法、およびレーザーガスを低温下
に導びき高沸点の不純物および一部の主成分物質
を凝縮分離し、該凝縮物質を固体アルカリ化合物
と接触させ活性な不純物を反応、除去した後、ゼ
オライトに接触させ残余の不純物を吸着、除去す
る方法を提供しようとするものである。
The present invention provides a method for efficiently and effectively removing impurities in the rare gas halide excimer laser gas, that is, when the laser gas is brought into contact with zeolite to adsorb and remove impurities, the laser gas is mixed with a solid alkali metal and/or Alkaline earth metal compounds (hereinafter referred to as solid alkali compounds)
A method for reacting and removing active substances capable of reacting with zeolite by contacting with zeolite; The object of the present invention is to provide a method of contacting with zeolite to adsorb and remove remaining impurities after reacting and removing active impurities.
ゼオライトは、一般式lM2／nO・
Al2O3mSiO2・yH2O（ただしＭはアルカリ金属ま
たはアルカリ土類金属を示し、ｎは価数を示し、
ｌ、ｍ、ｙは係数を示す）で表わされるガス吸着
性に富んだ多孔物質であり、しかも孔径の異なつ
た多孔質体を合成できるため“分子篩”と称さ
れ、多種類のガス化合物の吸着剤として使用され
ている。ゼオライトをガス吸着分離に使用する際
の工業上の利得は以下の通りである。 Zeolite has the general formula lM2/nO・
Al 2 O 3 mSiO 2 yH 2 O (where M represents an alkali metal or alkaline earth metal, n represents a valence,
It is a porous material with excellent gas adsorption properties (l, m, and y are coefficients), and it is called a "molecular sieve" because porous materials with different pore sizes can be synthesized, and it is capable of adsorbing many types of gas compounds. used as an agent. The industrial benefits of using zeolites for gas adsorption separations are as follows.
細孔径の選択によつてほとんどすべてのガス
物質を吸着除去することができる。 By selecting the pore size, almost all gaseous substances can be adsorbed and removed.
吸着ガスを脱気して再使用することができ
る。 Adsorbed gas can be degassed and reused.
しかし、このゼオライトをレーザーガスの精製
の目的で使用した場合、レーザーガス中の主成分
の活性物質であるF2、HCl等、および不純物であ
るHF等と化学的に反応し、ゼオライトを不活性
化し再生不能にするという事実が判明した。たと
えばF2が、0.01％程度存在してもゼオライトはそ
の吸着能を速やかに失うことが明らかとなつた。 However, when this zeolite is used for the purpose of purifying laser gas, it chemically reacts with the main active substances in the laser gas, such as F 2 and HCl, and impurities such as HF, rendering the zeolite inactive. It has been discovered that the data can be corrupted and become unplayable. For example, it has become clear that even if 0.01% of F 2 is present, zeolite quickly loses its adsorption ability.
このため、ゼオライトと反応し得る活性物質を
予め除去する方法について鋭意検討の結果、ソー
ダーライム、CaO、Ca（OH）2等の固体アルカリ
化合物を接触させることにより、活性なF2、
HF、HClのみならず比較的安定な酸性ガスSiF4、
CO2等も固体アルカリ化合物と反応し除去し得る
ことが明らかとなり、これらの物質を前以て除去
することで残余の不純物をゼオライトにより効率
的に除去し得るという事実を見出した。 For this reason, as a result of intensive study on a method to remove in advance active substances that can react with zeolite, we found that active F 2 ,
In addition to HF and HCl, relatively stable acid gas SiF 4 ,
It has become clear that CO 2 and the like can be removed by reacting with solid alkali compounds, and it has been discovered that by removing these substances in advance, remaining impurities can be efficiently removed using zeolite.
このようにして活性物質が固体アルカリ化合物
により除去された残余の不純物はゼオライトによ
り容易に吸着、除去される。またゼオライトが飽
和吸着量に達した時は、その加熱脱気によつて不
純物を容易に脱着でき、その吸着能を復元させる
ことができる。 The remaining impurities after the active substance is removed by the solid alkali compound are easily adsorbed and removed by the zeolite. Furthermore, when the zeolite reaches a saturated adsorption amount, impurities can be easily desorbed by heating and deaeration, and its adsorption capacity can be restored.
本発明により、全ての成分系の希ガスハライド
系ガスにおけるKr、Xe、He、Ne等の高価な希
ガスは極く小量の損失に留めて精製回収され、ま
た不純物は完全に除去されるので、長期にわたる
安定した連続運転を可能とする。ただしレーザー
ガスの主成分であるF2、HCl等も除去されるた
め、レーザー装置の連続運転に際しては希ガス損
失分に相当する量と、F2、HCl等の主成分を添加
する必要がある。 According to the present invention, expensive rare gases such as Kr, Xe, He, and Ne in rare gas halide gases of all component systems can be purified and recovered with minimal loss, and impurities can be completely removed. This enables stable continuous operation over a long period of time. However, since the main components of the laser gas, such as F 2 and HCl, are also removed, it is necessary to add an amount equivalent to the rare gas loss and the main components, such as F 2 and HCl, during continuous operation of the laser device. .
上記F2、HClを回収、循環するには、固体アル
カリ化合物との反応、ゼオライトへの吸着に先立
ちレーザーガス中の不純物（殆どが高沸点であ
る）を低温下で凝縮分離する方法が採用でき、こ
れによりF2、HCl、Ar、Ne、He等の低沸点の主
成分物質はそのまま循環使用することが可能とな
る。 To recover and circulate the above F 2 and HCl, a method can be adopted in which impurities in the laser gas (most of which have a high boiling point) are condensed and separated at low temperatures prior to reaction with a solid alkali compound and adsorption onto zeolite. This makes it possible to recycle and use low-boiling main components such as F 2 , HCl, Ar, Ne, and He as they are.
本発明の高沸点の不純物とは、レーザーガスの
成分系、凝縮しようとする温度、ガス分圧等によ
るが、HF、C2F6、SiF4、SF6、CCl4、CClF3、
CCl2F2、CCl3F等の不純物であり、一方高沸点の
主成分物質はKr、Xe等である。凝縮分離された
上記不純物と主成分物質は、ゼオライトと接触に
先立ち、固体アルカリ化合物と接触させることに
より、ゼオライトと反応してゼオライトを再生不
能にするようなHF等の活性な不純物を反応、除
去し、さらにゼオライトとの接触により残余の不
純物を吸着、除去することにより、Kr、Xe等の
主成分物質を回収、循環させる。 The high boiling point impurities of the present invention include HF, C 2 F 6 , SiF 4 , SF 6 , CCl 4 , CClF 3 ,
These are impurities such as CCl 2 F 2 and CCl 3 F, while the main constituent substances with high boiling points are Kr, Xe, etc. Prior to contacting the condensed and separated impurities and main component substances with the zeolite, they are brought into contact with a solid alkaline compound to react and remove active impurities such as HF that would react with the zeolite and make the zeolite unrenewable. Then, by adsorbing and removing remaining impurities through contact with zeolite, main constituent substances such as Kr and Xe are recovered and recycled.
以下本発明を添付の図面に基いて説明する。 The present invention will be explained below based on the accompanying drawings.
例えば第１図における符号１はArF、XeCl系
等のレーザー発生装置であり、レーザーガスを固
体アルカリ充填管３に送入され、固体アルカリ化
合物との反応により活性物質Ｂ、たとえば主成分
であるF2、HCl、不純物であるHF、SiF4等が除
去され、さらにゼオライト充填管４に送入されゼ
オライトへの吸着により残余の不純物Ｃ、たとえ
ばC2F6、CCl2F2、CCl4、CClF3、CCl3F、CF4、
NF3等が除去される。しかしてHeやAr、Xe等の
希ガスはレーザー発生装置１に循環され、一方除
去された主成分のF2、HClや極微量の損失を生じ
たHeやAr、Xe等の希ガスＤは５において補充さ
れレーザー発生装置１に送入される。 For example, reference numeral 1 in FIG. 1 is an ArF, XeCl, etc. laser generator, in which laser gas is fed into a solid alkali-filled tube 3, and by reaction with a solid alkali compound, the active substance B, e.g. 2 , HCl, and impurities such as HF and SiF 4 are removed, and the remaining impurities C, such as C 2 F 6 , CCl 2 F 2 , CCl 4 , and CClF, are removed by adsorption to the zeolite tube 4. 3 , CCl3F , CF4 ,
NF 3 etc. are removed. Thus, the rare gases such as He, Ar, and Xe are circulated to the laser generator 1, while the main components of F 2 and HCl that have been removed and the rare gases D such as He, Ar, and Xe that have lost trace amounts are At step 5, it is replenished and sent to the laser generator 1.
固体アルカリ化合物としては、ソーダライム
CaO、Ca（OH）2、NaOH、KOH等が使用される
が、ガスと良好に接触し、ガス流速によつて飛散
しない程度の粉粒体であれば使用できる。操作温
度は室温〜500℃の範囲であるが、好ましくは固
体アルカリ化合物との反応性、操作の容易さを考
慮して80℃〜200℃の範囲がよい。 As a solid alkali compound, soda lime
CaO, Ca(OH) 2 , NaOH, KOH, etc. are used, but any powder or granular material that makes good contact with the gas and does not scatter due to the gas flow rate can be used. The operating temperature is in the range of room temperature to 500°C, preferably in the range of 80°C to 200°C in consideration of reactivity with the solid alkali compound and ease of operation.
ゼオライトは除去すべきガス成分によつてその
細孔径を選択しなければならないが、モレキユラ
ーシーブ5A（米国Linde社製）は希ガスハライド
エキシマーレーザーガスの精製に最も適してい
る。必要に応じて、さらに細孔径の異なる複数の
種類のゼオライトを組合せて使用することも勿論
可能である。ゼオライト充填管４の操作において
は低温高圧ほど吸着量が多くなるが、−180〜＋
100℃程度の温度範囲、装置が耐えうる程度の圧
力範囲でよい。 The pore size of the zeolite must be selected depending on the gas component to be removed, and Molecular Sieve 5A (manufactured by Linde, USA) is most suitable for purifying rare gas halide excimer laser gas. Of course, it is also possible to use a combination of multiple types of zeolites with different pore diameters, if necessary. In the operation of the zeolite-filled tube 4, the adsorption amount increases as the temperature and pressure increase, but from −180 to +
A temperature range of about 100°C and a pressure range that the device can withstand are sufficient.
また、例えば第２図における符号１，３，４は
第１図に示した符号と同様にそれぞれレーザー発
生装置、固体アルカリ充填管、ゼオライト充填管
を示す。２はレーザーガス中の高沸点物質を低温
下で凝縮する低温トラツプであり、液体窒素、ア
ルゴン、酸素、空気等の冷媒を用いて冷却するこ
とにより低沸点のF2、HCl、He、Ne等の主成分
物質Ａはそのままレーザー発生装置１に循環され
るが、高沸点の主成分物質であるKr、Xe等、不
純物であるHF、C2F6、SiF4、SF6、CCl4、
CClF3、CCl3F等が凝縮分離される。これら凝縮
物質のうち活性な不純物B1、たとえばHFSiF4は
固体アルカリ充填管３により除去され、残余の不
純物Ｃ、たとえばC2F6、SF6、CCl4、CClF3等が
ゼオライト充填管４において除去される。また主
成分物質の微量の損失分相当量Ｄが補充されレー
ザー装置１に送入される。 Further, for example, numerals 1, 3, and 4 in FIG. 2, like the numerals shown in FIG. 1, respectively indicate a laser generator, a solid alkali-filled tube, and a zeolite-filled tube. 2 is a low-temperature trap that condenses high-boiling point substances in laser gas at low temperatures, and by cooling with a refrigerant such as liquid nitrogen, argon, oxygen, or air, it can condense low-boiling point substances such as F 2 , HCl, He, Ne, etc. The main component substance A is circulated as it is to the laser generator 1, but the main component substances with high boiling points such as Kr and Xe, and impurities such as HF, C 2 F 6 , SiF 4 , SF 6 , CCl 4 ,
CClF 3 , CCl 3 F, etc. are condensed and separated. Among these condensed substances, active impurities B 1 , such as HFSiF 4 , are removed in a solid alkali-filled tube 3 , and remaining impurities C, such as C 2 F 6 , SF 6 , CCl 4 , CClF 3 , etc., are removed in a zeolite-filled tube 4 . removed. In addition, an amount D corresponding to the slight loss of the main component substance is replenished and sent to the laser device 1.
なお、比較的低沸点の不純物のCF4、NF3が主
成分物質Ａとともに循環し蓄積される可能性があ
るが、それによりレーザー出力の低下を生じた際
には、予めバイパス６を設け、一たん第１図に示
す方法と同様な操作を行うことによりそれら不純
物を除去できる。 Note that there is a possibility that relatively low boiling point impurities such as CF 4 and NF 3 circulate and accumulate together with the main component substance A, but if this causes a decrease in laser output, a bypass 6 is provided in advance. These impurities can be removed once by performing the same operation as shown in FIG.
以下に本発明の具体的実施例を比較例と対比し
て詳述する。
Below, specific examples of the present invention will be described in detail in comparison with comparative examples.
比較例 １
Kr−Ｆ系放電励起型エキシマーレーザーを５
パルス／秒でレーザー発振させたところ、２時間
の運転で出力が70％に低下した。Comparative example 1 Kr-F discharge excited excimer laser
When the laser was oscillated at pulses per second, the output decreased to 70% after 2 hours of operation.
最初に導入したガスはKr5Nl（５％）、F20.3Nl
（0.3％）、He94.7Nl（94.7％）であつたが、２時間
後にはF2濃度は0.2％に低下し、不純物として
SiF4、HF、CF4、H2O、CO2、O2、N2が確認さ
れた。 The first gas introduced was Kr5Nl (5%), F 2 0.3Nl
(0.3%) and He94.7Nl (94.7%), but after 2 hours, the F2 concentration decreased to 0.2%, and as an impurity.
SiF 4 , HF, CF 4 , H 2 O, CO 2 , O 2 and N 2 were confirmed.
実施例 １
第１図に示す精製システムにおいて、固体アル
カリ充填管（1000mm×50mmφSuS304製）にソー
ダライムペツト（５mm×２mmφ）１Kgを充填
し、さらにゼオライト充填管（1000ml×12mmφ）
にモレキユラーシーブ5Aを20ｇ充填した設備
（あらかじめHeを充填）を使用し、比較例１にお
いて２時間運転したガスの精製を行なつた。固体
アルカリ充填管、ゼオライト充填管の操作温度は
それぞれ100℃および室温であつた。精製損失と
して、Kr0.1Nが生じたので、0.1NのKrと、
新たにF20.3Nを精製ガスに混合し、再びレー
ザーを運転したところ出力は100％に回復してい
た。Example 1 In the purification system shown in Figure 1, a solid alkali-filled tube (1000 mm x 50 mmφ made of SuS304) was filled with 1 kg of soda lime pet (5 mm x 2 mmφ), and a zeolite-filled tube (1000 ml x 12 mmφ) was filled.
The gas that had been operated for 2 hours in Comparative Example 1 was purified using equipment (previously filled with He) filled with 20 g of Molecular Sieve 5A. The operating temperatures of the solid alkali-filled tube and the zeolite-filled tube were 100°C and room temperature, respectively. Since 0.1N of Kr was generated as a refining loss, 0.1N of Kr,
When F 2 0.3N was newly mixed with the purified gas and the laser was operated again, the output was restored to 100%.
実施例 ２
実施例１と同様な装置で2.5／minの循環量
でレーザーガスを精製循環させ、Krを0.0025
／min、F2を0.01／minづつ連続的に供給さ
せつつレーザーを１日５時間の連続運転を毎日継
続したところ30日経てもレーザー出力の低下は生
じなかつた。なお、ゼオライト充填管は毎日300
℃、真空下で脱着して使用した。Example 2 Laser gas was purified and circulated at a circulation rate of 2.5/min using the same device as in Example 1, and Kr was reduced to 0.0025.
When the laser was operated continuously for 5 hours a day while continuously supplying F2 at a rate of 0.01/min and F2 at a rate of 0.01/min, no decrease in laser output occurred even after 30 days. In addition, 300 zeolite-filled tubes are used every day.
℃, and was used after desorption under vacuum.
ソーダライムを交替し、さらに連続運転を継続
したところ、さらに30日間同様に出力の低下は認
められなかつた。 After replacing the soda lime and continuing continuous operation, no decrease in output was observed for another 30 days.
実施例 ３
実施例１の装置に容積１のSUS304製低温ト
ラツプを付設し冷媒として液体窒素を用いて第２
図に示すシステムについて実施例２と同様の連続
運転を行なつた。Example 3 A SUS304 low-temperature trap with a volume of 1 was attached to the apparatus of Example 1, and a second trap was installed using liquid nitrogen as the refrigerant.
The system shown in the figure was operated continuously in the same manner as in Example 2.
レーザーを連続運転しつつ2.5／minでガス
を抜き出し、Krを0.025／minおよび精製時に
損失するF2を0.001／min連続的に導入したと
ころ、実施例２と同様30日経てもレーザー出力の
低下は認められなかつた。 While the laser was operated continuously, gas was extracted at a rate of 2.5/min, and Kr was continuously introduced at 0.025/min and F2 , which was lost during purification, was continuously introduced at 0.001/min. As in Example 2, the laser output decreased even after 30 days. was not recognized.
しかし30日経過以降徐々にレーザー出力の低下
が認められ、40日目においては当初の85％に低下
した。これは低沸点の不純物であるCF4、NF3が
循環、畜積したことによるものであるが、レーザ
ーガスをバイパス６を介して直接固体アルカリ充
填管３、さらにゼオライト充填管４に導びくシス
テムに変換し、実施例２と同様な操作を３時間実
施したところ、前記不純物は完全に除去されて出
力は100％に回復し、引続き本実施例前段で述べ
たシステムでさらに30日実施してもレーザー出力
の低下は認められなかつた。 However, after 30 days, a gradual decrease in laser output was observed, and by the 40th day, it had decreased to 85% of the initial level. This is due to the circulation and accumulation of low boiling point impurities such as CF 4 and NF 3 , but the system guides the laser gas directly through the bypass 6 to the solid alkali filling tube 3 and then to the zeolite filling tube 4. When the same operation as in Example 2 was carried out for 3 hours, the impurities were completely removed and the output recovered to 100%, and the operation was continued for another 30 days using the system described in the first part of this example. However, no decrease in laser output was observed.
実施例 ４
XeCl系レーザーで実施例１と同様な装置を使
用した。本実施例においてはゼオライト充填管
に、モレキユラーシーブ5A10ｇとモレキユラー
シーブ10X10ｇを２層に充填した。Example 4 The same equipment as in Example 1 was used with a XeCl-based laser. In this example, a zeolite-filled tube was filled with 10 g of molecular sieve 5A and 10 g of molecular sieve in two layers.
レーザーガスの循環量は１／minで、Xeを
0.002／min、HClを0.01／minづつ連続的に
供給し、レーザー発振１日５時間の連続運転を毎
日継続したところ、30日経てもレーザー出力の低
下は生じなかつた。なおゼオライト充填管は毎日
300℃、真空下で脱着して使用した。 The circulation rate of laser gas is 1/min, and Xe is
When 0.002/min and HCl were continuously supplied at a rate of 0.01/min and laser oscillation was continued for 5 hours a day every day, no decrease in laser output occurred even after 30 days. The zeolite-filled tube is filled daily.
It was used after desorption at 300℃ under vacuum.
以上のように本発明はあらゆる成分系の希ガス
ハライドエキシマーレーザーに適用でき有害な不
純物を除去することにより長期にわたる連続運転
においてもレーザー出力を低下することがなく、
一方主成分物質を効率よく回収、循環使用できる
のでランニングコストが低廉ですむという著しい
効果を奏するものである。
As described above, the present invention can be applied to rare gas halide excimer lasers of all component systems, and by removing harmful impurities, the laser output does not decrease even during long-term continuous operation.
On the other hand, since the main component substances can be efficiently recovered and recycled, running costs can be kept low, which is a remarkable effect.
第１図、第２図は本発明の実施の態様を示し、
１はレーザー発生装置、２は低温トラツプ、３は
固体アルカリ充填管、４はゼオライト充填管を示
す。
1 and 2 show embodiments of the present invention,
1 is a laser generator, 2 is a low-temperature trap, 3 is a solid alkali-filled tube, and 4 is a zeolite-filled tube.
Claims (1)
を吸着、除去するに際し、あらかじめレーザーガ
スを固体アルカリ金属および／またはアルカリ土
類金属化合物と接触させるようにしたことを特徴
とする希ガスハライドエキシマーレーザーガスの
精製法。 ２ レーザーガスを低温下に導びき高沸点の不純
物および一部の主成分物質を凝縮分離し、該凝縮
物質を固体アルカリ金属および／またはアルカリ
土類金属化合物と接触させ次いでゼオライトと接
触させるようにしたことを特徴とする希ガスハラ
イドエキシマーレーザーガスの精製法。 ３ 定時的にレーザーガスを低温下に導びく工程
を省略し、レーザーガスを直接固体アルカリ金属
および／またはアルカリ土類金属化合物と接触さ
せ、次いでゼオライトと接触させるようにしたこ
とを特許とする特許請求の範囲第２項記載の希ガ
スハライドエキシマーレーザーガスの精製法。[Claims] 1. A rare gas characterized in that the laser gas is brought into contact with a solid alkali metal and/or alkaline earth metal compound in advance when bringing the laser gas into contact with zeolite to adsorb and remove impurities. Purification method for halide excimer laser gas. 2. Laser gas is led to a low temperature to condense and separate high-boiling point impurities and some main component substances, and the condensed substance is brought into contact with a solid alkali metal and/or alkaline earth metal compound, and then brought into contact with a zeolite. A method for purifying rare gas halide excimer laser gas, which is characterized by: 3. A patent for omitting the step of periodically introducing the laser gas to a low temperature and bringing the laser gas into direct contact with a solid alkali metal and/or alkaline earth metal compound and then with zeolite. A method for purifying rare gas halide excimer laser gas according to claim 2.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60213691A JPS6274430A (en) | 1985-09-28 | 1985-09-28 | Method of purifying rare gas halide excimer laser gas |
| CA000518663A CA1298959C (en) | 1985-09-28 | 1986-09-19 | Method of refining rare gas halide excimer laser gas |
| US06/909,702 US4740982A (en) | 1985-09-28 | 1986-09-22 | Method of refining rare gas halide excimer laser gas |
| GB8622799A GB2182484B (en) | 1985-09-28 | 1986-09-22 | Method of refining rare gas halide excimer laser gas |
| FR868613476A FR2587914B1 (en) | 1985-09-28 | 1986-09-26 | PROCESS FOR PURIFYING GAS FROM A RARE GAS HALIDE EXCESSOR LASER |
| DE19863632995 DE3632995A1 (en) | 1985-09-28 | 1986-09-29 | METHOD FOR PURIFYING GASES FOR EDELGAS HALOGENIDE EXCIMER LASERS |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60213691A JPS6274430A (en) | 1985-09-28 | 1985-09-28 | Method of purifying rare gas halide excimer laser gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6274430A JPS6274430A (en) | 1987-04-06 |
| JPH0446607B2 true JPH0446607B2 (en) | 1992-07-30 |
Family
ID=16643387
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60213691A Granted JPS6274430A (en) | 1985-09-28 | 1985-09-28 | Method of purifying rare gas halide excimer laser gas |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6274430A (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6379665U (en) * | 1986-11-13 | 1988-05-26 | ||
| JPH0760914B2 (en) * | 1989-01-30 | 1995-06-28 | セントラル硝子株式会社 | Eximer laser gas purification method and apparatus |
| JPH03256831A (en) * | 1990-02-23 | 1991-11-15 | Toyo Kanetsu Kk | Cutting of corrugated cardboard case |
| JP3891834B2 (en) * | 2001-12-04 | 2007-03-14 | 大陽日酸株式会社 | Gas supply method and apparatus |
| JP5216220B2 (en) * | 2007-01-09 | 2013-06-19 | 岩谷産業株式会社 | Neon recovery method |
| JP5011013B2 (en) * | 2007-07-24 | 2012-08-29 | 大陽日酸株式会社 | Xenon difluoride gas supply device |
| JP4891969B2 (en) * | 2008-10-03 | 2012-03-07 | 株式会社荏原製作所 | Impurity removing apparatus for removing impurities and operation method thereof |
-
1985
- 1985-09-28 JP JP60213691A patent/JPS6274430A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6274430A (en) | 1987-04-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1298959C (en) | Method of refining rare gas halide excimer laser gas | |
| RU2206499C1 (en) | Gaseous nitrogen trifluoride purification method | |
| WO2008060544A2 (en) | Method and apparatus for the recovery and re-use of process gases | |
| US5087778A (en) | Regeneration of zeolites used for purifying 1,1,1,2-tetrafluoroethane | |
| CA2008294C (en) | Method of refining rare gas fluoride excimer laser gas | |
| JPH0553725B2 (en) | ||
| KR20160018645A (en) | Device and method for recovering low concentration sulfur hexafluoride gas | |
| JPH0446607B2 (en) | ||
| US7384618B2 (en) | Purification of nitrogen trifluoride | |
| JPH0379288B2 (en) | ||
| JP3516716B2 (en) | Purification method of trifluoromethane | |
| JPS62279824A (en) | Refining method for rare gas halide excimer laser gas | |
| JP2000015056A (en) | How to collect fluoride | |
| JP3650588B2 (en) | Perfluoro compound recycling method | |
| EP1153885B1 (en) | A process for concentrating fluorine compounds | |
| JP2000005561A (en) | Fluoride treatment method | |
| JP3908819B2 (en) | CFC recovery method | |
| JP3463873B2 (en) | How to recycle perfluoro compounds | |
| JPH07106675A (en) | Method and equipment for refining laser medium of excimer laser | |
| JPH04925B2 (en) | ||
| JPH02281786A (en) | Refining method for fluorine eximer laser gas and its device | |
| JPS63201007A (en) | Purification of nitrogen trifluoride |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |