JPH0672702A - Ozonizer - Google Patents
OzonizerInfo
- Publication number
- JPH0672702A JPH0672702A JP5162629A JP16262993A JPH0672702A JP H0672702 A JPH0672702 A JP H0672702A JP 5162629 A JP5162629 A JP 5162629A JP 16262993 A JP16262993 A JP 16262993A JP H0672702 A JPH0672702 A JP H0672702A
- Authority
- JP
- Japan
- Prior art keywords
- discharge
- ozone generator
- gas
- pressure
- dielectric
- 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.)
- Pending
Links
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 112
- 239000007789 gas Substances 0.000 claims abstract description 76
- 239000002994 raw material Substances 0.000 claims abstract description 24
- 239000000110 cooling liquid Substances 0.000 claims description 19
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 18
- 229910001882 dioxygen Inorganic materials 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 26
- 239000001301 oxygen Substances 0.000 abstract description 26
- 229910052760 oxygen Inorganic materials 0.000 abstract description 26
- 230000003247 decreasing effect Effects 0.000 abstract description 7
- 239000002826 coolant Substances 0.000 abstract description 4
- 239000004065 semiconductor Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000007423 decrease Effects 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000001307 helium Substances 0.000 description 6
- 229910052734 helium Inorganic materials 0.000 description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 6
- 239000000498 cooling water Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000002411 adverse Effects 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
Landscapes
- Oxygen, Ozone, And Oxides In General (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、放電方式のオゾン発生
装置に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a discharge type ozone generator.
【０００２】[0002]
【従来の技術】放電方式のオゾン発生装置は、その基本
構造としては、図３〜図７に概念的な断面図で示したも
のが実用化あるいは提案されている。図３〜図７におい
て、１３は高圧電極、１４はアース電極、１５は誘電
体、１６の部分が放電空間となる。また、１７は高圧交
流電源である。2. Description of the Related Art A discharge type ozone generator has been put to practical use or proposed as its basic structure, as shown in conceptual sectional views in FIGS. 3 to 7, 13 is a high-voltage electrode, 14 is a ground electrode, 15 is a dielectric, and 16 is a discharge space. Further, 17 is a high voltage AC power supply.
【０００３】図３に示すものはガラス管よりなる誘電体
１５と円筒形の電極１３、１４とを有するものであり、
図４、図５は共に平板状の誘電体１５と電極１３、１４
を有するもので、図４では誘電板７は電極の片側のみに
設置されているのに対し、図５では誘電板は電極の両面
に配置されている。図６は放電密度を上げるために電極
１３に突起を設けたもの、図７は沿面放電方式のもので
あり、放電は高圧電極１３の両端と誘電体１５の上面と
の間の放電空間１６で行われる。いずれの形式において
も高圧側と接地側を逆に接続しても使用可能であること
は自明である。The one shown in FIG. 3 has a dielectric 15 made of a glass tube and cylindrical electrodes 13 and 14,
4 and 5 both show a plate-shaped dielectric 15 and electrodes 13 and 14.
In FIG. 4, the dielectric plate 7 is installed only on one side of the electrode, whereas in FIG. 5, the dielectric plate 7 is arranged on both sides of the electrode. FIG. 6 shows a structure in which the electrodes 13 are provided with protrusions to increase the discharge density, and FIG. 7 shows a creeping discharge system in which discharge is performed in the discharge space 16 between both ends of the high voltage electrode 13 and the upper surface of the dielectric 15. Done. It is obvious that any type can be used even if the high-voltage side and the ground side are connected in reverse.
【０００４】近年、半導体製造産業ではオゾンの強力な
酸化作用、分解作用、反応促進作用とそのクリーンさに
着目し、急速に利用範囲が広がっている。半導体製造プ
ロセスに使用されるオゾン発生装置に対しては高濃度で
あると共に、発生したオゾン含有ガス中の汚染物を極限
にまで減少させることが要求される。従って、放電方式
のオゾン発生装置の原料である酸素ガスも純度９９．９
９％以上の高純度酸素の使用が望ましい。In recent years, in the semiconductor manufacturing industry, attention has been paid to ozone's strong oxidizing action, decomposing action, reaction accelerating action and its cleanliness, and its range of use is rapidly expanding. The ozone generator used in the semiconductor manufacturing process is required to have a high concentration and to reduce the pollutants in the generated ozone-containing gas to the utmost limit. Therefore, the purity of the oxygen gas, which is the raw material of the discharge type ozone generator, is 99.9.
It is desirable to use high purity oxygen of 9% or more.
【０００５】しかし、このような高純度の酸素を放電方
式のオゾン発生装置の原料として使用すると、経時的な
濃度低下が生じ高濃度のオゾンガスを安定して得ること
ができないという問題があった。この濃度低下現象は純
度９９．５％程度の工業用酸素ガスでは現れず、高純度
酸素ガスに特有の現象である。また、前記のように放電
方式のオゾン発生装置には種々の構造のものがあるが、
この経時的な濃度低下は程度の差はあっても全ての構造
のものに共通して起きる現象である。However, when such high-purity oxygen is used as a raw material for a discharge type ozone generator, there is a problem that the concentration decreases with time and a high-concentration ozone gas cannot be stably obtained. This phenomenon of concentration decrease does not appear in industrial oxygen gas having a purity of about 99.5%, and is a phenomenon peculiar to high-purity oxygen gas. Further, as described above, there are various types of discharge type ozone generators,
This decrease in concentration over time is a phenomenon that occurs in common to all structures, although to varying degrees.
【０００６】上記したように、放電方式のオゾン発生装
置に高純度酸素ガスを通してオゾンを発生させた場合
に、経時的に濃度低下がおこる現象を防止するために、
原料の高純度酸素ガス中に窒素、アルゴン、ヘリウム、
二酸化炭素などの添加ガスを混入する方法が提案されて
いる。As described above, in order to prevent a phenomenon in which the concentration decreases with time when ozone is generated through high-purity oxygen gas in the discharge type ozone generator,
Nitrogen, argon, helium, etc. in the high-purity oxygen gas of the raw material
A method of mixing an additive gas such as carbon dioxide has been proposed.
【０００７】すなわち、例えば特開平１−２９８００３
号公報には半導体装置の製造工程などで使用される高純
度酸素を原料としたオゾン発生方法において、特に半導
体装置の製造工程で汎用されている、電極の表面にグレ
ーズコート層、アルミナまたは石英などの被覆からなる
誘電体を形成したオゾン発生装置において、オゾン発生
装置に高純度酸素ガスを通してオゾンガスを発生させる
場合経時的に発生オゾンガス濃度が低下する。該特許公
報の明細書ではこの経時的な発生オゾンガス濃度の低下
を防止するために高純度の窒素ガスを混入させる方法を
提案している。なお、この公報の明細書によれば、高純
度のアルゴンやヘリウムを混入させた場合では高純度の
窒素ガスを混入させた場合のように有効な経時的発生オ
ゾンガス濃度低下防止作用は得られないと記載されてい
る。That is, for example, Japanese Patent Laid-Open No. 1-298003.
In the publication, in a method for generating ozone using high-purity oxygen as a raw material used in the manufacturing process of semiconductor devices, etc., it is commonly used in the manufacturing process of semiconductor devices. In an ozone generator having a dielectric formed of the above coating, when generating high-purity oxygen gas to generate ozone gas in the ozone generator, the generated ozone gas concentration decreases with time. The specification of the patent publication proposes a method of mixing high-purity nitrogen gas in order to prevent the concentration of generated ozone gas from decreasing with time. According to the specification of this publication, when the high-purity argon or helium is mixed, the effective effect of preventing the decrease in the concentration of ozone gas generated over time as in the case of mixing the high-purity nitrogen gas cannot be obtained. Is described.
【０００８】特開平３−２１８９０５号公報には半導体
ウエハ上に絶縁膜を形成するのに用いる高濃度のオゾン
ガスを発生させるために、オゾン発生装置に通す高純度
酸素ガスに０．０２〜２％の窒素ガスを混入させる方法
を提案している。JP-A-3-218905 discloses that in order to generate a high-concentration ozone gas used to form an insulating film on a semiconductor wafer, 0.02 to 2% of high-purity oxygen gas is passed through an ozone generator. It proposes the method of mixing the nitrogen gas.
【０００９】また、特開平１−２８２１０４号公報に
は、シリコンウエハ上に存在する有機性汚れやフォトレ
ジストのアッシングの目的で使用するオゾンガスを得る
ために、オゾンガス発生装置に高純度の酸素ガスを使用
するが、上記の諸事例と同様経時的な発生オゾンガス濃
度の低下を防止する対策として、オゾン発生装置に通す
高純度酸素ガスに１．０〜１０．０ｖｏｌ％の窒素、ア
ルゴン、ヘリウムや炭酸ガスのような不活性ガスを混入
させる方法を提案している。Further, in Japanese Patent Application Laid-Open No. 1-282104, in order to obtain ozone gas used for the purpose of ashing organic stains and photoresist existing on a silicon wafer, a high-purity oxygen gas is supplied to an ozone gas generator. Although used, as a measure to prevent the concentration of generated ozone gas from decreasing with time as in the above-mentioned cases, 1.0 to 10.0 vol% of nitrogen, argon, helium or carbon dioxide is added to high purity oxygen gas passed through the ozone generator. A method of mixing an inert gas such as gas is proposed.
【００１０】しかしながら、上記した諸種の事例で行わ
れたように、経時的発生オゾンガス濃度の低下防止対策
として、高純度酸素ガスに他の種類のガスを添加する
と、発生オゾンガス中に添加ガスが混在することになり
半導体製造プロセスに使用する上で悪影響を及ぼす。However, as was done in the above-mentioned various cases, when another type of gas is added to the high-purity oxygen gas as a measure to prevent the concentration of generated ozone gas from decreasing over time, the added gas is mixed in the generated ozone gas. This will adversely affect the use in the semiconductor manufacturing process.
【００１１】またそれと共に、原料ガスとして予め混合
ガスを混入させたガスボンベを用意するか、または高純
度酸素ガスと添加ガスの混入手段を設ける必要があると
いう問題点があった。At the same time, there is a problem that it is necessary to prepare a gas cylinder in which a mixed gas is mixed as a raw material gas in advance, or to provide a mixing means for mixing the high-purity oxygen gas and the additional gas.
【００１２】さらに、特に添加ガスとして窒素を使用し
た場合には、放電により発生するＮＯx ガス（各種の酸
化窒素ガス）がそのまま半導体製造プロセスに注入され
て悪影響を及ぼすという問題点もあった。Further, especially when nitrogen is used as an additive gas, there is a problem that NO x gas (various nitric oxide gases) generated by discharge is directly injected into the semiconductor manufacturing process and has a bad influence.
【００１３】[0013]
【発明が解決しようとする課題】本発明は上記従来技術
の欠点を解決し、高純度酸素ガスのみを用いて、経時的
に濃度低下を起こすことなく安定して高濃度にオゾンガ
スを発生する放電方式のオゾン発生装置を提供すること
にある。DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned drawbacks of the prior art and uses only high-purity oxygen gas to stably generate ozone gas at a high concentration without causing a concentration decrease over time. The purpose is to provide a system-type ozone generator.
【００１４】[0014]
【課題を解決するための手段】上記課題は本発明のオゾ
ン発生装置によって達成される。The above object can be achieved by the ozone generator of the present invention.
【００１５】すなわち、原料ガスに純度９９．９９％以
上の高純度酸素ガスを使用する放電方式のオゾン発生装
置において、（１）該オゾン発生装置の放電体の放電部
の気体の圧力を大気圧に対して少なくとも１．１ｋｇｆ
／ｃｍ2 以上高くしたことを特徴とするオゾン発生装
置。That is, in a discharge type ozone generator using high purity oxygen gas having a purity of 99.99% or more as a source gas, (1) the gas pressure in the discharge part of the discharge body of the ozone generator is atmospheric pressure. Against at least 1.1 kgf
/ Cm ozone generator according to claim 2 or higher was possible.
【００１６】および（２）オゾン発生装置の放電体を液
冷却方式とし、該冷却液の液温を１５℃以上としたオゾ
ン発生装置である。And (2) An ozone generator in which the discharge body of the ozone generator is of a liquid cooling type and the liquid temperature of the cooling liquid is 15 ° C. or higher.
【００１７】ここで、上記放電体の放電部の気体の圧力
および冷却液の液温は一定の圧力および温度に制御され
ることが望ましい。Here, it is desirable that the pressure of the gas and the temperature of the cooling liquid in the discharge part of the discharge body are controlled to be constant pressure and temperature.
【００１８】また、本発明のオゾン発生装置は放電体内
の圧力をゲージ圧で１．１ｋｇｆ／ｃｍ2 以上にすると
同時に放電体を冷却する冷却液の温度を１５℃以上とし
ても構わない。Further, in the ozone generator of the present invention, the pressure inside the discharge body may be set to 1.1 kgf / cm 2 or higher in gauge pressure, and at the same time, the temperature of the cooling liquid for cooling the discharge body may be set to 15 ° C. or higher.
【００１９】本発明のオゾン発生装置の好ましい構成
は、放電体の構造として誘電体を挟む電極の一方は誘電
体側の面に複数の土手状突起が設けてあり、該突起の先
端は誘電体に接するかあるいは極めて接近するようにし
た構造とし、該突起間の凹部と前記誘電体との間に形成
されるトンネル状空間を原料および生成物が通過し、ま
たこの空間で放電が行われる構成とすることである。In a preferred construction of the ozone generator of the present invention, one of the electrodes sandwiching the dielectric is provided with a plurality of bank-like projections on the surface of the dielectric as the structure of the discharge body, and the tip of the projection is formed on the dielectric. A structure in which the raw materials and products pass through a tunnel-like space formed between the recesses between the protrusions and the dielectric and discharge is performed in this space. It is to be.
【００２０】本発明において、高純度酸素とは純度９
９．９９％以上の酸素を意味する。In the present invention, high purity oxygen means a purity of 9
It means 9.99% or more oxygen.
【００２１】従来、放電方式のオゾン発生装置に純度９
９．５％の酸素を通して使用する場合では、放電体の温
度は低温であるほど高濃度のオゾンガスが得られるとさ
れている。Conventionally, a discharge type ozone generator has a purity of 9
When used with 9.5% oxygen, it is said that the lower the temperature of the discharge body, the higher the concentration of ozone gas obtained.
【００２２】本発明のオゾン発生装置でも、純度９９．
５％の工業用酸素を原料に使用した場合には冷却温度が
低い方が高濃度が得られ、かつその濃度は経時的に安定
したものであったが、高純度酸素を原料にしたとき、発
生オゾンガス濃度の経時的安定性に関して冷却温度が高
い方が安定するという結果が得られた。Even in the ozone generator of the present invention, the purity is 99.
When 5% of industrial oxygen was used as the raw material, the higher the cooling temperature, the higher the concentration obtained, and the concentration was stable over time. It was found that the higher the cooling temperature, the more stable the generated ozone gas concentration was.
【００２３】また、放電体の冷却液温を比較的低温の４
℃とした時、放電体内圧力を１．１ｋｇｆ／ｃｍ2 （ゲ
ージ圧）としたところ、冷却液温を上げたときと同様
に、発生オゾンガス濃度は当初若干低下するものの１０
０ｍｇ／ノーマルリットル以上の高濃度で安定した。Further, the cooling liquid temperature of the discharge body is set to a relatively low temperature of 4
When the internal pressure of the discharge was set to 1.1 kgf / cm 2 (gauge pressure) when the temperature was set to 0 ° C, the generated ozone gas concentration initially slightly decreased, as in the case where the cooling liquid temperature was raised.
It was stable at a high concentration of 0 mg / normal liter or more.
【００２４】従来通常、放電方式のオゾン発生装置で
は、放電体内圧力は大気圧から０．５ｋｇｆ／ｃｍ2
（ゲージ圧）程度の低圧で使用される。これは低圧の方
がガスのインピーダンスが小さいので、電力が入り易
く、オゾン発生量が増えるという理由によるものである
が、高純度酸素を原料にしたときの発生オゾンガス濃度
の経時的安定性に関しては、圧力が高い方が安定すると
いう結果が得られた。Conventionally, in the discharge type ozone generator, the internal pressure of the discharge is from atmospheric pressure to 0.5 kgf / cm 2.
Used at low pressure (gauge pressure). This is because the low-pressure gas has a smaller impedance of gas, so that it is easy to input power and increase the ozone generation amount.However, regarding the stability of the generated ozone gas concentration with time when high-purity oxygen is used as a raw material, The result is that the higher the pressure is, the more stable it is.
【００２５】本発明のオゾン発生装置では最高３．０ｋ
ｇｆ／ｃｍ2 （ゲージ圧）まで上げることができる。放
電体の強度をあげればより高圧に耐えるものも製作でき
るが大型でかつ高価なものとなり実用的でない。The ozone generator of the present invention has a maximum of 3.0 k.
It can be increased to gf / cm 2 (gauge pressure). If the strength of the discharge body is increased, it is possible to manufacture one that can withstand higher pressure, but it is large and expensive, which is not practical.
【００２６】また放電体の冷却液温の上限は特に冷却液
が気化するまで制限されない。実際、冷却液の温度を４
０℃に保って９９．９９％の高純度酸素を用いてより高
濃度のオゾンを安定に発生させることができるが、冷却
液の温度は２０℃にすることで９９．９９％の高純度酸
素を用いて２００ｍｇ／ノーマルリットルの高濃度のオ
ゾンを安定に発生させることができるので実用的には十
分である。The upper limit of the cooling liquid temperature of the discharge body is not particularly limited until the cooling liquid vaporizes. In fact, the temperature of the coolant is 4
It is possible to stably generate a higher concentration of ozone by using 99.99% high-purity oxygen by keeping it at 0 ° C, but by setting the cooling liquid temperature to 20 ° C, 99.99% high-purity oxygen can be obtained. Since it is possible to stably generate high concentration ozone of 200 mg / normal liter, it is practically sufficient.
【００２７】上記したような、放電方式のオゾン発生装
置において放電体の冷却液温が高い方が高濃度のオゾン
ガスが経時的に安定して得られ、また放電体内圧力につ
いても圧力が高い方が高濃度のオゾンガスが経時的に安
定して得られるという知見は従来認められていない結果
であり、高純度酸素を原料にしてオゾンガスを発生させ
て初めて得られた結果であり驚くべき現象である。なぜ
高純度酸素を原料にしてオゾンガスを発生させた場合に
かかる現象が起こるのか、その原因は不明である。In the discharge type ozone generator as described above, the higher the temperature of the cooling liquid of the discharge body, the higher the concentration of ozone gas can be stably obtained over time, and the higher the pressure in the discharge body is. The finding that a high-concentration ozone gas can be stably obtained over time is a result that has not been previously recognized, and it is a result obtained only when ozone gas is generated using high-purity oxygen as a raw material, which is a surprising phenomenon. The reason why such a phenomenon occurs when high-purity oxygen is used as a raw material to generate ozone gas is unknown.
【００２８】放電方式のオゾン発生装置において放電体
内圧力を高くして放電したり、放電体の冷却液温を高く
して放電するためには、オゾン発生装置の放電体の構造
をこれらの条件に適するものとする必要がある。In the discharge type ozone generator, the structure of the discharge body of the ozone generator is set to these conditions in order to discharge by increasing the pressure in the discharge body or by raising the cooling liquid temperature of the discharge body. It has to be suitable.
【００２９】本発明のオゾン発生装置では、上記した通
り放電体の放電部内圧力を１．１ｋｇｆ／ｃｍ2 とする
か、又は冷却温度を１５℃とすれば９９．９９％の高純
度酸素を用いて１００ｍｇ／ノーマルリットル以上の高
濃度のオゾンを安定に発生させることができる。In the ozone generator of the present invention, 99.99% high-purity oxygen is used if the pressure inside the discharge part of the discharge body is 1.1 kgf / cm 2 as described above, or if the cooling temperature is 15 ° C. It is possible to stably generate a high concentration of ozone of 100 mg / normal liter or more.
【００３０】もし、従来のオゾン発生装置を用いて放電
部内圧力を０．５ｋｇｆ／ｃｍ2 とし、冷却温度を４℃
で９９．９９５％の高純度酸素を用いてオゾンを発生さ
せたとするとたとえ運転開始時に１００ｍｇ／ノーマル
リットルの高濃度のオゾンが得られたとしても、経時的
にオゾン濃度は低下する。上記した先行技術によれば
０．５％程度の高純度窒素ガスを添加すれば高濃度のオ
ゾンガスの発生を維持できるけれども、ヘリウムガスを
同程度添加しても高濃度のオゾンガスの発生を維持でき
ない。しかしながら本発明に従って放電部内圧力を１．
１ｋｇｆ／ｃｍ2とすれば他のガスを添加せずとも高濃
度のオゾンガスの発生を維持できる。If a conventional ozone generator is used, the pressure inside the discharge section is set to 0.5 kgf / cm 2 , and the cooling temperature is 4 ° C.
If 99.995% of high-purity oxygen is used to generate ozone, even if a high concentration of 100 mg / normal liter of ozone is obtained at the start of operation, the ozone concentration will decrease with time. According to the above-mentioned prior art, generation of high-concentration ozone gas can be maintained by adding high-purity nitrogen gas of about 0.5%, but generation of high-concentration ozone gas cannot be maintained even if helium gas is added in the same amount. . However, according to the present invention, the pressure in the discharge section is set to 1.
When the pressure is 1 kgf / cm 2 , generation of high-concentration ozone gas can be maintained without adding other gas.
【００３１】さらにヘリウムガスを添加して原料酸素の
純度を９９．０％にし、放電部内圧力を１．１ｋｇｆ／
ｃｍ2 に維持したとき、オゾン濃度は前記１００ｍｇ／
ノーマルリットルよりは低下するが、時間が経過しても
その濃度を維持することはできる。Further, helium gas was added to make the raw material oxygen have a purity of 99.0%, and the internal pressure of the discharge part was 1.1 kgf /.
When maintained at cm 2 , the ozone concentration is 100 mg /
Although it is lower than the normal liter, its concentration can be maintained over time.
【００３２】このことは、本発明に使用する原料酸素の
純度を９９．９９％以上と制限したが、例えばヘリウム
ガスのように全く不活性なガスの添加によって原料酸素
の純度をこの制限純度以下にしても本発明と同様な現象
が生ずることを示す。This limits the purity of the raw material oxygen used in the present invention to 99.99% or more. However, the purity of the raw material oxygen is set to be less than the limited purity by adding a completely inert gas such as helium gas. However, it is shown that the same phenomenon as in the present invention occurs.
【００３３】なお、本発明において原料の酸素の含む不
純物の成分は平均的な大気の空気に含まれる成分からな
るものである。しかし、それらの組成は変わり得る。In the present invention, the component of impurities containing oxygen as a raw material is a component contained in average atmospheric air. However, their composition can vary.
【００３４】[0034]
【実施例】次に実施例により、本発明の構成と作用をよ
り具体的に説明するが、本発明はこの実施例に限定され
るものではない。EXAMPLES Next, the structure and operation of the present invention will be described more specifically by way of examples, but the present invention is not limited to these examples.
【００３５】（実施例１）本発明の１実施態様を図１お
よび図２を参照しつつ説明する。(Embodiment 1) One embodiment of the present invention will be described with reference to FIGS. 1 and 2.
【００３６】図１に示した本発明のオゾン発生装置２は
その放電体の電極を冷却媒体供給装置３で冷却しつつ、
その電極に交流電源からエネルギー、ガスボンベ１から
高純度酸素を供給してオゾンガスを発生する。In the ozone generator 2 of the present invention shown in FIG. 1, while the electrodes of the discharge body are being cooled by the cooling medium supply device 3,
Energy is supplied to the electrode from an AC power source, and high-purity oxygen is supplied from the gas cylinder 1 to generate ozone gas.
【００３７】本実施例１においてオゾン発生装置２に設
置した放電体４は図２に示したものである。The discharge body 4 installed in the ozone generator 2 in the first embodiment is the one shown in FIG.
【００３８】図２において放電体４は、誘電板７を挟ん
で突起を有する対極６と電極５が設けられ、該電極５と
対極６とはガスの流路を兼ねた適当な放電空間８を保つ
ようにスペーサ１２をおいて電極押さえ枠１１で固定さ
れて構成されている。In FIG. 2, the discharge body 4 is provided with a counter electrode 6 and an electrode 5 having a projection sandwiching a dielectric plate 7, and the electrode 5 and the counter electrode 6 form an appropriate discharge space 8 which also serves as a gas flow path. A spacer 12 is provided so as to keep it and is fixed by an electrode pressing frame 11.
【００３９】この放電体４に交流電源１０から電極５と
対極６との間に交番電圧をかけ、放電空間８にガスボン
ベ１から高純度酸素を供給しオゾン発生させる。An alternating voltage is applied to the discharge body 4 from the AC power source 10 between the electrode 5 and the counter electrode 6, and high purity oxygen is supplied from the gas cylinder 1 to the discharge space 8 to generate ozone.
【００４０】オゾン発生装置２の放電体として図２に示
した放電体４を使用し、純度９９．５％の工業用酸素を
原料として、放電体内圧力を大気圧に、放電体冷却水温
度を４℃として運転したところ、１ノーマルリットル／
分の流量でオゾンガス濃度２００ｍｇ／ノーマルリット
ル以上の超高濃度が得られた。しかしながら、発生した
オゾンガスを半導体製品の加工に使用するような場合純
度９９．５％の工業用酸素では含まれる不純物により半
導体製品に悪影響を与えることがあり使用できない。The discharge body 4 shown in FIG. 2 was used as the discharge body of the ozone generator 2, and the internal pressure of the discharge body was set to the atmospheric pressure and the cooling water temperature of the discharge body was adjusted by using industrial oxygen having a purity of 99.5% as a raw material. When operated at 4 ° C, 1 normal liter /
An ultra-high concentration of 200 mg / normal liter or more was obtained at a flow rate of minutes. However, when the generated ozone gas is used for processing semiconductor products, industrial oxygen having a purity of 99.5% cannot be used because it may adversely affect the semiconductor products due to impurities contained therein.
【００４１】次に他の条件はそのままとし、放電体内圧
力を０．５ｋｇｆ／ｃｍ2 （ゲージ圧）とし、原料を９
９．９９５％の高純度酸素に変更したところ、図８に示
すように発生オゾンガス濃度は経時的に低下し安定した
高濃度は得られなかった。Next, the other conditions were left unchanged, the internal pressure of the discharge was 0.5 kgf / cm 2 (gauge pressure), and the raw material was 9
When the purity was changed to 9.995% high purity oxygen, the generated ozone gas concentration decreased with time as shown in FIG. 8, and a stable high concentration could not be obtained.
【００４２】これに対し、他の条件はそのままとし、冷
却水温度のみ１５℃に変更したところ、発生オゾンガス
濃度は当初若干低下するものの、１００ｍｇ／ノーマル
リットル以上の高濃度で安定した。（図８） なお、この実施例では、冷却のための熱媒体として水を
使用したが、水以外のものを熱媒体としても同様の効果
が得られた。On the other hand, when the other conditions were left unchanged and only the temperature of the cooling water was changed to 15 ° C., the ozone gas concentration generated was slightly lowered at the beginning, but stabilized at a high concentration of 100 mg / normal liter or more. (FIG. 8) Although water was used as the heat medium for cooling in this example, the same effect was obtained by using a medium other than water as the heat medium.
【００４３】（実施例２）他の条件は実施例１の通りと
し、冷却水温を４℃に戻し、放電体内圧力を１．１ｋｇ
ｆ／ｃｍ2 （ゲージ圧）としたところ、冷却水温を上げ
たときと同様に、発生オゾンガス濃度は当初若干低下す
るものの１００ｍｇ／ノーマルリットル以上の高濃度で
安定した。(Example 2) Other conditions were as in Example 1, the cooling water temperature was returned to 4 ° C, and the internal pressure of the discharge was 1.1 kg.
When f / cm 2 (gauge pressure) was set, similarly to when the temperature of the cooling water was raised, the concentration of generated ozone gas initially slightly decreased, but was stable at a high concentration of 100 mg / normal liter or higher.
【００４４】（実施例３）冷却水温を２０℃とし、放電
体内圧力を２．０ｋｇｆ／ｃｍ2 （ゲージ圧）としたと
ころ、発生オゾンガス濃度は当初から２００ｍｇ／ノー
マルリットル以上の高濃度で安定し、経時的な濃度低下
は全くみられなくなった。（図８） これらの実施例の結果より、放電体の放電空間の気体圧
力が大気圧に対して少くとも１．１ｋｇｆ／ｃｍ2 以上
高いか、又はオゾン発生装置が液冷却方式の放電体を含
み、その冷却液温を１５℃以上としたとき、高濃度のオ
ゾンガスが経時的な濃度低下を生ずることなく安定して
得られることがわかる。Example 3 When the cooling water temperature was 20 ° C. and the pressure in the discharge body was 2.0 kgf / cm 2 (gauge pressure), the generated ozone gas concentration was stable at a high concentration of 200 mg / normal liter or more from the beginning. , The concentration did not decrease with time. (FIG. 8) From the results of these examples, it is confirmed that the gas pressure in the discharge space of the discharge body is higher than the atmospheric pressure by at least 1.1 kgf / cm 2 or more, or the ozone generator uses a liquid cooling type discharge body. It can be seen that when the temperature of the cooling liquid is set to 15 ° C. or higher, a high concentration ozone gas can be stably obtained without causing a concentration decrease over time.
【００４５】[0045]
【発明の効果】このように、本発明によれば冷却液温や
放電体内圧力を上げるという極めて簡便な方法で、高純
度酸素を原料としたときの発生オゾンガス濃度を、高濃
度で安定させることができ、高純度のオゾンガスを半導
体プロセスへ供給することが可能となり、予め混合ガス
を用意したり、ガスの混合装置を設けたりする必要が無
くなると共に、半導体プロセスに悪影響を与える恐れの
あるＮ2 やＣＯ2 などの添加ガスや添加ガスから生じる
副生ガスの注入を防ぐことが可能となり大きな効果を挙
げることができる。As described above, according to the present invention, the ozone gas concentration generated when high-purity oxygen is used as a raw material is stabilized at a high concentration by a very simple method of increasing the temperature of the cooling liquid and the pressure in the discharge body. Therefore, it becomes possible to supply high-purity ozone gas to the semiconductor process, it becomes unnecessary to prepare a mixed gas in advance or to install a gas mixing device, and N 2 which may adversely affect the semiconductor process. It is possible to prevent injection of an additive gas such as CO 2 and CO 2 and a by-product gas generated from the additive gas, and a great effect can be achieved.
【００４６】なお、半導体プロセスでは、オゾンガス濃
度を安定させること以外の目的で、オゾン発生装置の高
純度酸素原料に他の種類のガスを混合させることがある
が、この場合でも本発明の装置を使用することによる効
果が有効であることはいうまでもない。In the semiconductor process, other types of gas may be mixed with the high-purity oxygen raw material of the ozone generator for the purpose other than stabilizing the ozone gas concentration. Even in this case, the apparatus of the present invention is used. It goes without saying that the effect of using it is effective.
【００４７】又、上記実施例は特定構造の放電体に関連
して述べたが、本発明のオゾン発生装置には他の構造の
放電体を使用できることは明らかである。Although the above embodiments have been described with reference to a discharge body having a specific structure, it is obvious that a discharge body having another structure can be used in the ozone generator of the present invention.
【図１】本発明の放電方式オゾン発生装置の概要構成
図。FIG. 1 is a schematic configuration diagram of a discharge-type ozone generator of the present invention.
【図２】本発明の放電方式オゾン発生装置の放電体の一
例を示す断面図。FIG. 2 is a cross-sectional view showing an example of a discharge body of the discharge type ozone generator of the present invention.
【図３】従来のガラス管式の放電方式オゾン発生装置の
放電体断面図。FIG. 3 is a cross-sectional view of a discharge body of a conventional glass tube type discharge ozone generator.
【図４】従来の片側のみに誘電板を有する平板構造の放
電方式オゾン発生装置の放電体断面図。FIG. 4 is a cross-sectional view of a conventional discharge type ozone generator having a flat plate structure having a dielectric plate only on one side.
【図５】従来の両側に誘電板を有する平板構造の放電方
式オゾン発生装置の放電体断面図。FIG. 5 is a cross-sectional view of a conventional discharge type ozone generator having a flat plate structure having dielectric plates on both sides.
【図６】従来の電極に突起を設けた平板構造の放電方式
オゾン発生装置の放電体断面図。FIG. 6 is a sectional view of a discharge body of a conventional discharge type ozone generator having a flat plate structure in which protrusions are provided on electrodes.
【図７】従来の沿面放電方式オゾン発生装置の放電体断
面図。FIG. 7 is a sectional view of a discharge body of a conventional creeping discharge ozone generator.
【図８】本発明の放電方式オゾン発生装置の発生オゾン
ガス濃度の経時的変化を示す図。FIG. 8 is a diagram showing changes over time in the generated ozone gas concentration of the discharge-type ozone generator of the present invention.
１ 高純度酸素ガスボンベ ２ オゾン発生装置 ３ 冷却媒体供給装置 ４ 放電体 ５ 電極 ６ 対極 ７ 誘電板 ８ 流路兼放電空間 ９ 冷却液流路 １０ 交流電源 １１ 電極押さえ枠 １２ スペーサ兼シール材 １３ 高圧電極 １４ アース電極 １５ 誘電体 １６ 放電空間 １７ 高圧交流電源 1 High-purity oxygen gas cylinder 2 Ozone generator 3 Cooling medium supply device 4 Discharge body 5 Electrode 6 Counter electrode 7 Dielectric plate 8 Flow passage / discharge space 9 Cooling liquid flow passage 10 AC power supply 11 Electrode holding frame 12 Spacer / sealant 13 High voltage electrode 14 ground electrode 15 dielectric 16 discharge space 17 high-voltage AC power supply
───────────────────────────────────────────────────── フロントページの続き (72)発明者 西岡 由紀子 神奈川県藤沢市本藤沢４丁目２番１号 株 式会社荏原総合研究所内 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Yukiko Nishioka 4-2-1 Motofujisawa, Fujisawa City, Kanagawa Prefecture EBARA Research Institute
Claims (8)
度酸素ガスを使用する放電方式のオゾン発生装置におい
て、該オゾン発生装置の放電体の放電部の気体の圧力を
大気圧に対して少なくとも１．１ｋｇｆ／ｃｍ2 以上高
くしたことを特徴とするオゾン発生装置。1. A discharge-type ozone generator using high-purity oxygen gas having a purity of 99.99% or more as a raw material gas, wherein the pressure of the gas in the discharge part of the discharge body of the ozone generator is set to atmospheric pressure. An ozone generator characterized by having a height of at least 1.1 kgf / cm 2 or higher.
気体の圧力を大気圧に対して少なくとも１．１ｋｇｆ／
ｃｍ2 以上高い圧力に一定に制御したことを特徴とする
請求項１記載のオゾン発生装置。2. The pressure of the gas in the discharge part of the discharge body of the ozone generator is at least 1.1 kgf / atmospheric pressure.
The ozone generator according to claim 1, wherein the pressure is constantly controlled to a pressure higher than cm 2 .
度酸素ガスを使用する放電方式のオゾン発生装置におい
て、該オゾン発生装置の放電体を液冷却方式とし、該冷
却液の液温を１５℃以上としたことを特徴とするオゾン
発生装置。3. In a discharge type ozone generator using a high purity oxygen gas having a purity of 99.99% or more as a source gas, the discharge body of the ozone generator is of a liquid cooling type, and the liquid temperature of the cooling liquid is changed. An ozone generator characterized in that the temperature is 15 ° C. or higher.
式とし、該冷却液の液温を１５℃以上に一定に制御した
ことを特徴とする請求項３記載のオゾン発生装置。4. The ozone generator according to claim 3, wherein the discharge body of the ozone generator is of a liquid cooling type, and the liquid temperature of the cooling liquid is controlled to be constant at 15 ° C. or higher.
度酸素ガスを使用する放電方式のオゾン発生装置におい
て、該オゾン発生装置の放電体を液冷却方式とし、該冷
却液の液温を１５℃以上とした上に、該放電体の放電部
の気体の圧力を大気圧に対して少なくとも１．１ｋｇｆ
／ｃｍ2 以上高くしたことを特徴とするオゾン発生装
置。5. A discharge type ozone generator using a high purity oxygen gas having a purity of 99.99% or more as a raw material gas, wherein the discharge body of the ozone generator is of a liquid cooling type, and the liquid temperature of the cooling liquid is adjusted. The temperature of the gas in the discharge part of the discharge body is at least 1.1 kgf with respect to the atmospheric pressure.
/ Cm ozone generator according to claim 2 or higher was possible.
式とし、該冷却液の液温を１５℃以上に一定に制御した
上に、前記放電体の放電部の気体の圧力を大気圧に対し
て少なくとも１．１ｋｇｆ／ｃｍ2 以上に高い圧力に一
定に制御したことを特徴とする請求項５記載のオゾン発
生装置。6. The discharge body of the ozone generator is of a liquid cooling type, the liquid temperature of the cooling liquid is controlled to be constant at 15 ° C. or higher, and the gas pressure in the discharge part of the discharge body is set to atmospheric pressure. On the other hand, the ozone generator according to claim 5, wherein the pressure is constantly controlled to a high pressure of at least 1.1 kgf / cm 2 or more.
度酸素ガスを使用する放電方式のオゾン発生装置におい
て、該オゾン発生装置の放電体を液冷却方式とし、該冷
却液の液温を１５℃以上とした上に、前記放電体の放電
部の気体の圧力を大気圧に対して少なくとも１．１ｋｇ
ｆ／ｃｍ2 以上高くし、かつ、放電体の構造として誘電
体を挟む電極の一方は誘電体側の面に複数の土手状突起
が設けてあり、該突起の先端は誘電体に接するかあるい
は極めて接近し、該突起間の凹部と前記誘電体との間に
形成されるトンネル状空間を原料および生成物流路兼放
電空間としたことを特徴とするオゾン発生装置。7. A discharge type ozone generator using a high purity oxygen gas having a purity of 99.99% or more as a raw material gas, wherein the discharge body of the ozone generator is a liquid cooling system, and the liquid temperature of the cooling liquid is The pressure of the gas in the discharge part of the discharge body is at least 1.1 kg with respect to the atmospheric pressure, in addition to 15 ° C. or higher.
f / cm 2 or more, and one of the electrodes sandwiching the dielectric as the structure of the discharge body is provided with a plurality of bank-shaped projections on the surface on the dielectric side, and the tips of the projections are in contact with the dielectric or extremely An ozone generator characterized in that a tunnel-like space formed between the recesses between the projections and the dielectric is close to serve as a discharge space for the raw material and product.
式とし、該冷却液の液温を１５℃以上に一定に制御した
上に、前記放電体の放電部の気体の圧力を大気圧に対し
て少なくとも１．１ｋｇｆ／ｃｍ2 以上に高い圧力に一
定に制御し、かつ、放電体の構造として誘電体を挟む電
極の一方は誘電体側の面に複数の土手状突起が設けてあ
り、該突起の先端は誘電体に接するかあるいは極めて接
近し、該突起間の凹部と前記誘電体との間に形成される
トンネル状空間を原料および生成物流路兼放電空間とし
たことを特徴とする請求項７記載のオゾン発生装置。8. The discharge body of the ozone generator is of a liquid cooling type, the liquid temperature of the cooling liquid is controlled to a constant value of 15 ° C. or higher, and the gas pressure in the discharge part of the discharge body is set to atmospheric pressure. On the other hand, one of the electrodes, which is controlled to a constant high pressure of at least 1.1 kgf / cm 2 or more, and has one of the electrodes sandwiching the dielectric as the structure of the discharge body, is provided with a plurality of bank-like protrusions on the surface of the dielectric The tips of the protrusions are in contact with or extremely close to the dielectric, and the tunnel-like space formed between the recesses between the protrusions and the dielectric is used as the raw material and product flow paths and discharge space. Item 8. The ozone generator according to item 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5162629A JPH0672702A (en) | 1992-07-03 | 1993-06-30 | Ozonizer |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19900692 | 1992-07-03 | ||
| JP4-199006 | 1992-07-03 | ||
| JP5162629A JPH0672702A (en) | 1992-07-03 | 1993-06-30 | Ozonizer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0672702A true JPH0672702A (en) | 1994-03-15 |
Family
ID=26488350
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5162629A Pending JPH0672702A (en) | 1992-07-03 | 1993-06-30 | Ozonizer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0672702A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0901983A1 (en) * | 1996-03-04 | 1999-03-17 | KABUSHIKI KAISHA KOBE SEIKO SHO also known as Kobe Steel Ltd. | Ozonizer |
| JP2008285408A (en) * | 2008-07-03 | 2008-11-27 | Sumitomo Precision Prod Co Ltd | Ozone generation method |
-
1993
- 1993-06-30 JP JP5162629A patent/JPH0672702A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0901983A1 (en) * | 1996-03-04 | 1999-03-17 | KABUSHIKI KAISHA KOBE SEIKO SHO also known as Kobe Steel Ltd. | Ozonizer |
| JP2008285408A (en) * | 2008-07-03 | 2008-11-27 | Sumitomo Precision Prod Co Ltd | Ozone generation method |
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