WO2013051097A1 - 窒素添加レス・オゾン発生ユニット - Google Patents
窒素添加レス・オゾン発生ユニット Download PDFInfo
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- WO2013051097A1 WO2013051097A1 PCT/JP2011/072817 JP2011072817W WO2013051097A1 WO 2013051097 A1 WO2013051097 A1 WO 2013051097A1 JP 2011072817 W JP2011072817 W JP 2011072817W WO 2013051097 A1 WO2013051097 A1 WO 2013051097A1
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- ozone generator
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/087—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/10—Preparation of ozone
- C01B13/11—Preparation of ozone by electric discharge
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0803—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0873—Materials to be treated
- B01J2219/0892—Materials to be treated involving catalytically active material
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2201/00—Preparation of ozone by electrical discharge
- C01B2201/20—Electrodes used for obtaining electrical discharge
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2201/00—Preparation of ozone by electrical discharge
- C01B2201/30—Dielectrics used in the electrical dischargers
- C01B2201/32—Constructional details of the dielectrics
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2201/00—Preparation of ozone by electrical discharge
- C01B2201/70—Cooling of the discharger; Means for making cooling unnecessary
Definitions
- This invention relates to a nitrogen addition-less ozone generation unit equipped with a nitrogen addition-less ozone generator using high purity oxygen gas with a nitrogen addition amount of less than several thousand ppm as a raw material gas.
- a source gas in which nitrogen gas of several thousand ppm or more is added to oxygen gas is supplied to an ozone generator to generate high-concentration ozone gas.
- ozone oxide insulating film formation and ozone It is often used in ozone treatment processes such as cleaning.
- this semiconductor manufacturing field, etc. when supplying ozone gas to a multi-ozone processing apparatus composed of a plurality of ozone processing apparatuses, each corresponds to a plurality of ozone processing apparatuses, each of which includes an ozone generator, an ozone power source, and a flow rate.
- an ozone gas supply system unit
- each ozone generation mechanism independently supplies ozone gas to a corresponding ozone treatment apparatus.
- MFC controller
- a general oxygen gas In high-purity oxygen gas containing about 50 to several thousand ppm of nitrogen gas and having a low nitrogen content (less than 50 ppm), a trace amount (500 ppm or more) is contained in the ozone generator together with the high-purity oxygen gas. ) N 2 gas is added.
- the source oxygen gas contains 500 ppm or more of N 2 gas
- high concentration of ozone is generated by a catalytic reaction of a small amount of NO 2 generated by the discharge reaction shown in FIG.
- ozone is efficiently generated by a catalytic reaction of a small amount of nitrogen dioxide generated by discharge.
- the highest concentration of ozone is generated, and it has been experimentally verified that the raw material gas having a nitrogen addition amount in the range of 500 to 20000 ppm is the optimum condition for ozone generation performance.
- the discharge reaction shown in FIG. 10 generates high-concentration ozone by using photoelectric discharge light and a small amount of NO 2 catalyst gas as raw material oxygen O 2. Is realized.
- NO x by -product gases such as N 2 O 5 and N 2 O and nitric acid are also generated by silent discharge in the ozone generator.
- Specific chemical formulas for generating NO x by -product gas and nitric acid are as follows.
- nitric acid (HNO 3 ) clusters steam are generated by the reaction between the NO x gas component and the moisture contained in the raw material gas, and a small amount of NO together with oxygen and ozone gas.
- Ozonated gas is taken out with X gas and nitric acid clusters mixed. If this small amount of nitric acid cluster is contained in several hundred ppm or more, rust such as chromium oxide is precipitated by nitric acid on the inner surface of the stainless steel pipe that is the ozone gas outlet pipe, and metal impurities are mixed into the clean ozone gas.
- Metal impurities as gases adversely affect semiconductor manufacturing, and the small amount of generated nitric acid clusters can adversely affect semiconductor etching equipment's “etching of silicon oxide film with ozone” and “cleaning of wafers with ozone water” as reactive poisons. There was an interim topic to bring.
- the ozone gas supply system equipped with an ozone generator, ozone power supply, etc. is a raw material gas pipe that supplies the ozone generator via an ozone generator, ozone power supply, flow rate adjusting means such as MFC that controls the flow rate of ozone gas or raw material gas.
- the system has a pressure adjusting means such as APC for controlling the gas atmosphere pressure in the ozone generator, and has an ozone concentration detector and an ozone flow meter for detecting the concentration with respect to the ozone gas output from the ozone generator. It is generally conceivable to provide as many output gas piping systems as the number of systems of the multi-ozone treatment apparatus.
- Oxygen molecules which are the source gas, have a continuous light absorption spectrum (ultraviolet wavelength of 130 to 200 nm) at a wavelength of ultraviolet light of 245 nm or less, and the oxygen molecules dissociate into oxygen atoms by absorbing excimer light of ultraviolet light of 245 nm or less.
- the generation of ozone by the three-body collision of the dissociated oxygen atoms, oxygen molecules, and third substance is known for excimer lamps that emit ultraviolet rays.
- silent discharge such as an ozone generator in high pressure of 1 atm or higher mainly composed of oxygen gas does not emit excimer light with ultraviolet light of 245 nm or less. Therefore, the reaction constant of the reaction process of oxygen atom dissociation and ozone generation by silent discharge light is very small, and it cannot be considered as a reaction capable of generating high concentration ozone gas of several percent or more.
- a raw material gas containing nitrogen gas of several thousand ppm or more or a raw material oxygen as disclosed in Patent Document 1 a raw material gas containing nitrogen gas of several thousand ppm or more or a raw material oxygen as disclosed in Patent Document 1
- One set of ozone is used to supply raw material gas with nitrogen gas forcibly added to the gas to the ozone generator, generate high-concentration ozone, and supply ozone gas to multiple ozone treatment devices.
- An ozone gas supply system is adopted that increases the capacity of the generator, separates the piping system that outputs ozone gas into multiple piping, and outputs ozone gas at a predetermined flow rate and concentration to each multi-ozone treatment device in a stepwise manner. It was coming.
- the conventional ozone gas supply system for supplying ozone to the multi-ozone treatment apparatus disclosed in Patent Document 1 is configured as described above, and supplies a raw material oxygen gas containing nitrogen and moisture to provide one ozone generator 71.
- Ozone gas is output from the pipe, and the output piping system is distributed. Therefore, the ozone gas to be output is supplied with an active gas containing nitrogen oxidation by-products, nitric acid clusters, and OH radicals, and the output piping material, nitrogen oxidation by-products, nitric acid clusters, and OH radicals are supplied.
- ozone gas containing a large amount of metal contamination due to abnormal heating or corrosion is supplied by chemical decomposition or oxidation reaction with a substance.
- the present invention has been made to solve the above-described problems, and it is possible to produce a high-purity and high-concentration ozone gas using only high-purity oxygen gas that does not add nitrogen gas to the raw material gas.
- an ozone generator cooling the ozone generator to a low temperature, and covering the ozone generator with a heat insulating material so that the discharge part of the generator can be efficiently cooled, the nitrogen addition less ozone
- An object of the present invention is to obtain a nitrogen addition-less ozone generation unit capable of outputting a larger amount of ozone gas output from a generator.
- the nitrogen addition-less ozone generation unit has a photocatalytic substance for generating ozone on a discharge surface, and generates a nitrogen addition-less ozone generator that generates ozone gas, and the nitrogen addition-less ozone generator.
- a mass flow controller MFC that includes an ozone power source for supplying a high voltage and a control unit related to the ozone generator, and the control unit controls the flow rate of the raw material gas supplied to the ozone generator without nitrogen addition.
- a pressure detection / pressure adjustment means including an auto pressure controller (APC) for automatically controlling an internal pressure which is a pressure in the ozone generator.
- APC auto pressure controller
- Addition-less ozone generation unit is an integrated structure integrating the nitrogen addition-less ozone generator, the ozone power supply, and the control means.
- the nitrogen addition-less ozone generator is formed with a high voltage terminal for receiving the high voltage from the ozone power source and a cooling medium input for supplying and discharging a low temperature cooling medium of 15 ° C. or less obtained from the outside.
- a storage portion for storing the photocatalyst layer and the cooling path therein, and the cooling medium inlet / outlet is formed on a predetermined configuration surface constituting a part of the outer peripheral portion of the storage portion, and the outer periphery of the storage portion Pierce
- the high-voltage terminal is provided, is formed over at least said predetermined configuration surface in the housing part, further comprising an insulating layer made of heat insulating material.
- the nitrogen addition-less ozone generator in the nitrogen addition-less ozone generation unit according to the present invention is provided with a cooling medium inlet / outlet that is a supply and discharge port of a low-temperature cooling medium at 15 ° C. or lower, and there is a concern about the occurrence of condensation. Since a heat insulating layer made of a heat insulating material is formed so as to cover a predetermined component surface, condensation is generated on the predetermined component surface by cooling the ozone generator itself to a low temperature without being affected by the atmospheric temperature by the heat insulating layer. Can be reliably prevented. As a result, the ozone generator, ozone power supply, and control means can reliably avoid problems caused by intrusion of moisture in the ozone power supply and control means existing outside the storage section of the nitrogen addition-less ozone generator. Can be integrated.
- the photocatalytic effect by the photocatalytic layer is improved, and as a result, the ozone generation efficiency and the ozone decomposition effect are enhanced. This produces the effect that more high quality ozone can be generated.
- FIG. 1 is a block diagram showing the configuration of a gas system centered on an ozone generator that does not contain nitrogen.
- an ozone generator using a high-purity oxygen source gas with a nitrogen addition amount of 10 ppm or more and 1000 ppm or less is called a “nitrogen addition suppression / ozone generator”, and a high-purity oxygen source gas with a nitrogen addition amount of less than 10 ppm is called The ozone generator used is called “nitrogen addition-less ozone generator”.
- an ozone generator using a high-purity oxygen source gas of 1000 ppm or less is collectively referred to as “nitrogen addition-less ozone generator”.
- FIG. 2 is a characteristic diagram showing the ozone concentration characteristics by the nitrogen addition-less ozone generator 1 shown in FIG.
- FIG. 3 is a schematic diagram for explaining the dissociation mechanism of oxygen molecules into oxygen atoms by oxygen molecules and a photocatalyst.
- FIG. 4 is a schematic diagram for explaining the generation mechanism of ozone by the triple collision of oxygen atoms and oxygen molecules generated by the nitrogen addition-less ozone generator 1.
- symbol shows the same or an equivalent part.
- the nitrogen addition-less ozone generator in this invention is a high-quality product that eliminates by-products such as high-concentration ozone gas of 200 g / m 3 or more, clean ozone gas such as semiconductor manufacturing equipment and cleaning equipment, NO x and OH radical substances. This is effective in the case where a nitrogen-less ozone gas or a device with high ozone generation efficiency is required.
- a raw material supply system 99 for supplying oxygen (raw material gas) with a purity of 99.99% or more is composed of a high-purity oxygen cylinder 991, a pressure reducing valve 992, and an on-off valve 993, and supplies oxygen gas 994 to the outside. To do. Then, oxygen gas 994 is supplied to the nitrogen addition-less ozone generator 1 as raw material gas 995 through MFC 3.
- the nitrogen addition-less ozone generator 1 includes electrodes 1a and 1b, a dielectric 1c, and a photocatalyst (layer) 1d. The two electrodes 1a and 1b are opposed to each other, and a dielectric 1c is provided on a surface (discharge surface) of the electrode 1a facing the electrode 1b. And it is the structure which apply
- a moisture removal gas filter for reducing the amount of water contained in the high-purity oxygen supplied from the cylinder to 0.1 ppm or less is provided, and nitrogen, a moisture-free raw material that suppresses the amount of moisture as much as possible.
- An oxygen gas 994 is supplied to the nitrogen addition-less ozone generator 1 as a raw material gas 995 through a flow rate regulator (MFC) 3 that regulates the amount of gas.
- MFC flow rate regulator
- N 2 is contained in 151 ⁇ 10 2 ppb (ie, 15 ppm). Thus, inevitable N 2 is mixed, but in order to obtain high-purity ozone gas, it is desirable to use raw material oxygen gas with less N 2 mixing.
- FIG. 3 schematically shows the electron coordination structure in solid and the dissociation mechanism of oxygen molecules in the solid electron theory (bandgap theory) of the photocatalyst during silent discharge.
- bandgap theory solid electron theory
- Holes are formed in the valence band where the electrons have moved.
- the lifetime of the electrons that have moved to the conduction band ends depending on whether they move to the surroundings or emit electrons to the discharge region. That is, the electrons that have moved to the conduction band have a very short lifetime and several tens of psec. Since holes in the valence band continue to exist unless electrons moved to the conduction band return by recombination, the lifetime of the holes is as long as 200 to 300 nsec.
- the light absorption wavelength is visible light having a wavelength of 428 nm to 620 nm.
- Silent discharge is generated in this visible light regardless of whether oxygen does not contain nitrogen or oxygen and argon gas. It has the ability to emit light wavelengths in the region (discharge). Therefore, when a photocatalyst with a band gap of 2.0 eV to 2.9 eV is applied to the electrode surface (wall surface) of the ozone generator, the discharge light emitted by the silent discharge in the case of oxygen not containing nitrogen or in oxygen and argon gas.
- the photocatalyst is absorbed to excite the photocatalyst, and oxygen can be dissociated by the adsorption dissociation action of the excited photocatalyst and oxygen gas. Further, as shown in the schematic diagram of FIG. 4, the coupling action is caused on the photocatalyst 1 d (wall M) by the three-body collision between the dissociated oxygen atom, the supplied oxygen molecule (raw material oxygen gas), and the third substance. Ozone can be generated by the promoted work.
- silent discharge with nitrogen gas in an ozone generator has the ability to emit (discharge) light wavelengths in the ultraviolet region (ultraviolet light of 413 nm to 344 nm).
- the photocatalyst having a band gap of 3.0 eV to 3.6 eV can be photoexcited. Can produce high quality ozone gas by its ability to dissociate oxygen molecules.
- a photocatalyst with a band gap of 3.0 eV to 3.6 eV can be photoexcited
- a photocatalyst with a bandgap of 2.0 eV to 2.9 eV can be photoexcited
- the allowable band gap range of the photocatalyst provided on the dielectric or electrode in the discharge region can be from 2.0 eV to 3.6 eV.
- the ozone generation reaction can be promoted by using not only oxygen but also nitrogen discharge light (ultraviolet light). That is, when N 2 gas is included, the ozone generation function by the invention effect of the present application is enhanced.
- the photocatalytic substance applied to the discharge surface of the ozone generator is a kind of semiconductor and has a band gap peculiar to a semiconductor, and shows a value larger than the band gap of a normal semiconductor substance.
- the photocatalytic substance is a metal oxide substance in which a metal and an oxygen atom are usually bonded, and the crystal of the metal oxide substance is not a complete bond between the metal atom and the oxygen atom, but an oxide having a crystal structure having an oxygen deficiency.
- a metal material is said to have a semiconductor effect or a photocatalytic effect.
- the photocatalytic materials such as iron oxide and tungsten oxide are Fe 2 O x and WO x , and oxygen bonds
- X ⁇ 3 the number of oxygen atoms
- up to three oxygen atoms can be bonded, but in order to be a photocatalytic substance, it has a crystal structure that leaves an oxygen deficient portion in the oxygen bond. .
- the photocatalytic substance is applied to the discharge surface to increase the photocatalytic effect and generate high-concentration ozone. In order to greatly increase the surface area of the applied photocatalytic substance on the discharge surface.
- FIG. 5 is an explanatory diagram showing the configuration of the nitrogen addition-less ozone generation unit and its periphery according to the embodiment of the present invention. In the figure, the same components as those shown in FIG.
- the nitrogen addition-less ozone generation unit 7 of the present embodiment has a nitrogen addition-less ozone generator 1 having means for generating ozone gas, and means for supplying predetermined power to the ozone gas.
- the MFC 3 having means for controlling the raw material gas flow rate Q supplied to the ozone generator 2 and the nitrogen addition-less ozone generator 1 to a constant value, and the pressure value in the nitrogen addition-less ozone generator 1 to a constant value It has APC4 which has a means to do.
- the nitrogen addition-less ozone generator 1 has a high voltage terminal housing portion 20 for guiding the high voltage HV from the ozone power source 2 into the ozone generator outer frame 1x outside the ozone generator outer frame 1x. ing.
- the nitrogen addition-less ozone generator 1x is a housing that serves as a housing for the nitrogen addition-less ozone generator 1, and includes a high-voltage electrode 1a, a ground electrode 1b, a dielectric 1c, a photocatalyst 1d, and a connection block 498 (FIG.
- the high-pressure cooling plate 45 (not shown in FIG. 5) is housed inside.
- adiabatic cooling water pipes 31 for supplying / discharging low-temperature cooling water 33 (cooling medium) to / from the ozone generator outer frame 1x are supplied with ozone. It is provided outside the generator outer frame 1x. A high voltage terminal PH and a ground terminal PL in the high voltage terminal storage unit 20 are provided so as to penetrate the ozone generator outer frame 1x.
- the nitrogen addition-less ozone generator 1 includes a raw material inlet 38 for supplying the raw material gas 995 obtained through the MFC 3 and an ozone gas outlet 39 for outputting the generated ozone gas 996 to the external APC 4. It is provided on the outer frame 1x.
- the nitrogen addition-less ozone generator 1 is further used for input of low-temperature cooling water 33 (cooling medium) from the adiabatic cooling water input pipe 31I and output of low-temperature cooling water 33 to the adiabatic cooling water output pipe 31O.
- the cooling water inlet / outlet 34 is provided in the ozone generator outer frame 1x.
- the nitrogen addition-less ozone generation unit 7 includes the above-described nitrogen addition-less ozone generator 1 (including the high-voltage terminal storage unit 20), the ozone power source 2, the MFC 3, the APC 4, and the adiabatic cooling.
- a plurality of functional means such as the water pipe 31 (31I + 31O) are integrated to form a unit package unit.
- the heat insulating layer 8 is made of a heat insulating material such as an insulator, and is formed to cover substantially the entire surface of the ozone generator outer frame 1x. In other words, it is formed so as to cover the outer periphery of the ozone generator outer frame 1x while ensuring a flow path to the cooling water inlet / outlet 34, the raw material inlet 38 and the ozone gas outlet 39. However, the heat insulating layer 8 is not formed on the outer periphery of the high-voltage terminal storage unit 20.
- a high voltage HV is applied from the ozone power source 2 to the high-voltage electrode 1a through the high-voltage terminal PH in the high-voltage terminal storage section 20, and a ground voltage LV is applied to the ground electrode 1b through the ground terminal PL. Is done.
- the high-voltage terminal storage unit 20 is configured to store the high-voltage terminal PH in a predetermined space capable of air insulation and supply the purge gas 23 from the purge gas system 21 via a purge gas input pipe described later. ing.
- the adiabatic cooling water input pipe 31I is provided to input the low-temperature cooling water 33 obtained from the cooling water system 30 into the nitrogen addition-less ozone generator 1, and the adiabatic cooling water output pipe 31O does not contain nitrogen addition / ozone generation. It is provided to return the low-temperature cooling water 33 discharged from the vessel 1 to the cooling water system 30.
- the cooling water system 30 sets the temperature of the low-temperature cooling water 33 to 15 ° C. or less.
- the nitrogen addition-less / ozone generation unit 7 includes a nitrogen addition-less / ozone generator 1 (including the high-voltage terminal storage unit 20), an ozone power source 2 and control devices (MFC3, APC4, etc.) Are aggregated and unitized.
- a nitrogen addition-less ozone generation unit 7 is cooled to a low temperature by the low-temperature cooling water 33, the surface of the ozone generator outer frame 1x of the nitrogen addition-less ozone generator 1 is cooled.
- the nitrogen addition-less / ozone generation unit 7 of the present embodiment covers substantially the entire outer periphery of the nitrogen addition-less / ozone generator 1, and is a heat insulating layer made of a heat insulating material that does not pass moisture and has low thermal conductivity. Therefore, the surface of the ozone generator outer frame 1x of the ozone generator 1 is not in direct contact with the atmosphere, so that dew generation on the surface of the ozone generator outer frame 1x is ensured. It can be avoided.
- the nitrogen addition-less ozone generator 1 has an effect of increasing the ozone generation efficiency and decreasing the effect of decomposing the generated ozone as the temperature is lowered to a low temperature, and increasing the amount of ozone to be extracted. For this reason, means (such as the low-temperature cooling water system 30 and the adiabatic cooling water pipe 31) for cooling the nitrogen addition-less ozone generator 1 itself to a low temperature is provided.
- the low-temperature refrigerant cooling water 33
- step S1 The cold heat that is cooled in step S1 is taken to the atmosphere side, and the discharge electrode cell itself composed of the high-voltage electrode 1a and the ground electrode 1b of the nitrogen addition-less ozone generator 1 cannot be sufficiently cooled. As a result, the ozone generation efficiency is lowered and the ozone performance is lowered.
- the nitrogen addition-less ozone generation unit 7 of the present embodiment covers the substantially entire outer periphery of the nitrogen addition-less ozone generator 1 and forms a heat insulating layer 8 made of a heat insulating material having a low thermal conductivity. Therefore, the phenomenon in which the cold heat in the nitrogen addition-less ozone generator 1 is taken to the atmosphere side can be reliably prevented.
- the cooling effect of the nitrogen addition-less ozone generator 1 is not hindered by the atmospheric temperature. Therefore, by sufficiently cooling the nitrogen addition-less ozone generator 1 (ozone generator outer frame 1x), There is an effect that the ozone generation efficiency can be sufficiently increased.
- the heat insulation layer 8 is formed so as to cover substantially the entire outer peripheral portion of the ozone generator outer frame 1x which is a storage portion. It is possible to reliably avoid problems caused by the intrusion of moisture into the ozone power source 2 and the control means (MFC3, APC4) existing outside the generator 1.
- the cooling water 33 is used as the low-temperature cooling medium, but the following cooling medium may be used instead of the cooling water 33.
- an ethylene glycol aqueous solution (PRTR) having a refrigerant temperature of ⁇ 20 ° C. to 65 ° C. and a hydrofluoropolyether (HFPE) having a refrigerant temperature of ⁇ 40 ° C. to 60 ° C. can be considered.
- the temperature at the time of supplying the cooling water 33 to the nitrogen addition-less ozone generator 1 is set to 5 ° C. or less. The reason for this will be described. Conventionally, it has been common to generate ozone by flowing water at a temperature of 20 ° C. into the ozone generator 1 and cooling it with ozone.
- the nitrogen addition-less ozone generator 1 when the inside of the nitrogen addition-less ozone generator 1 is cooled using 20 ° C. water, which is substantially the same as the atmospheric temperature, and the discharge cell is discharged to generate ozone, the nitrogen addition-less ozone generator is generated.
- the instantaneous micro discharge gas temperature in the micro discharge space of the dielectric barrier discharge is 37 ° C. when compared with the conventional discharge input power. To 22 ° C. or lower.
- the dielectric barrier discharge sustain voltage V * spark voltage
- V * spark voltage
- the photocatalytic effect of the photocatalyst (substance) 1d applied to the surfaces of the electrodes 1a and 1b is greatly increased, and the ability to dissociate oxygen gas into oxygen atoms is further promoted and dissociated.
- the concentration of ozone inevitably generated can be increased.
- the amount of ozone decomposition due to the gas temperature is slightly reduced when the average gas temperature is low, and the ozone concentration that can be output is also increased.
- FIG. 6 is a graph showing the ozone concentration characteristic of the ozone gas concentration with respect to the raw material gas flow rate Q, which is the flow rate of the raw material gas 995.
- the ozone concentration characteristic LA has a set temperature of the cooling water 33 of 20 ° C.
- the ozone concentration characteristic LB has a set temperature of the cooling water 33 of 20 ° C. in the case of the conventional configuration in which the heat insulating layer 8 is not provided.
- the ozone concentration characteristic LC indicates the ozone concentration characteristic when the temperature of the cooling water 33 is 5 ° C. and the heat insulating layer 8 is provided.
- the ozone concentration characteristics are improved in the order of the ozone concentration characteristic LA, the ozone concentration characteristic LB, and the ozone concentration characteristic LC. That is, from FIG. 6, setting the temperature of the cooling water 33 to 5 ° C. or less and providing the heat insulating layer 8 have the effect of improving the ozone concentration characteristics related to the ozone generated by the nitrogen addition-less ozone generator 1. I understand that.
- the cooling water 33 serving as a low-temperature cooling medium is set to a temperature of 5 ° C. or less when supplied into the nitrogen addition-less / ozone generator 1. Therefore, it is possible to further improve the concentration of generated ozone by further enhancing the photocatalytic effect in the photocatalyst (layer) 1d.
- Heat insulation material used for the heat insulation layer 8 As the heat insulating material used for the heat insulation layer 8, a material that does not allow water or moisture to pass through and has a very small thermal conductivity compared to metal is effective. For example, there are carbon fibers, ceramic fibers, Teflon (registered trademark) fibers, which are heat-resistant inorganic fibers. A heat insulating board made of hard urethane or the like whose heat insulating material is shaped into a board shape may be used as the heat insulating layer 8.
- FIG. 7 is an explanatory view showing details of the high-voltage terminal storage section 20.
- the high voltage terminal PH provided in the high voltage terminal accommodating portion 20 includes a high voltage insulator 24, an electrode rod 25, and nuts 26 (26a, 26b).
- the high voltage insulator 24 made of an insulating material is provided from the inside of the ozone generator 1 through the ozone generator outer frame 1x to the inside of the housing 22 of the high voltage terminal storage unit 20 from the inside of the ozone generator 1. That is, the high-voltage insulator 24 that forms the high-voltage terminal PH1 is formed through the ozone generator outer frame 1x that separates the inside and outside of the nitrogen addition-less ozone generator 1.
- the high voltage HV is applied to the high-voltage electrode 1a of the discharge electrode cell via the electrode rod 25 in the high-voltage insulator 24 constituting the high-voltage terminal PH and the electric wires 27a and 27b.
- the high voltage insulator 24 touches the atmosphere and the nitrogen addition-less ozone generator 1 is cooled to a temperature lower than the atmospheric temperature, the high voltage insulator 24 also becomes low temperature, so that the surface of the high voltage insulator 24 is condensed. There is a concern that the insulation property of the high-voltage insulator 24 deteriorates.
- the high voltage insulator 24 of the high voltage terminal PH is arranged in the high voltage terminal accommodating portion 20, and the purge gas 23 (nitrogen, inert gas) generated from the purge gas system 21 from the purge gas input pipe 28 is provided. Therefore, the purge gas 23 can reliably prevent the surface of the high-voltage insulator 24 from condensing at a low temperature. As a result, in the present embodiment, by reducing the temperature of the ozone generator, even if the high voltage insulator 24 in the nitrogen addition-less ozone generator 1 becomes low temperature, the surface of the high voltage insulator 24 is condensed. However, the high voltage insulator 24 has an effect of maintaining good insulation.
- the purge gas 23, which is a dry gas, is constantly supplied to a predetermined space in the housing 22, so that the purge gas 23 exists around the high voltage insulator 24, and the surface of the high voltage insulator 24. Condensation is prevented.
- the high-voltage terminal storage unit that can supply the purge gas 23 from the purge gas system 21 to the predetermined space in the housing 22 from the purge gas input pipe 28.
- the dew point purge gas 23 having a relatively low dew point can be present around the high voltage insulator 24. For this reason, it is possible to reliably avoid the occurrence of condensation on the surface of the high voltage insulator 24 without deteriorating the application capability of the high voltage HV by the high voltage terminal PH.
- FIG. 8 is an explanatory diagram showing details of the configuration of the nitrogen addition-less ozone generator 1. As shown in the figure, in a form in which two high-voltage electrodes 1a share one ground electrode 1b, a plurality of electrode cells each made up of a pair of high-voltage electrodes 1a and ground electrodes 1b are formed.
- the dielectric 1c is formed on both surfaces thereof, and the photocatalyst (layer) 1d is formed on the surface (discharge surface) of the dielectric 1c on the ground electrode 1b side of the two dielectrics 1c formed on both surfaces. Is applied, and a high-pressure cooling plate 45 serving as a cooling path is provided on the surface of the dielectric 1c opposite to the ground electrode 1b.
- the ozone generator outer frame 1x, the high-pressure cooling plate 45, and a connecting block 49 described later are made of a metal material.
- Each ground electrode 1b is coated with a photocatalyst (layer) 1d on both sides, and a space between the photocatalyst 1d coated on the dielectric 1c of the high-voltage electrode 1a and the photocatalyst 1d of the ground electrode 1b is a discharge space 46.
- ozone gas 996 is generated by the photocatalytic effect of the photocatalyst 1d in the discharge space 46 using the raw material gas 995 supplied from the MFC 3 through the raw material inlet 38 provided in the ozone generator outer frame 1x.
- connection block 49 is provided so as to connect the end regions of the high-pressure cooling plate 45 and the ground electrode 1b.
- connection block 49, the high-pressure cooling plate 45, and the ground electrode 1b are provided with cooling water passages through which the low-temperature cooling water 33 can circulate, so that they can be obtained from the outside of the nitrogen addition-less ozone generator 1.
- the low-temperature cooling water 33 to be generated is connected to the connecting block 49, the high-pressure cooling plate 45, and the ground electrode 1b that constitute the cooling path portion via the cooling water inlet / outlet 34 (cooling medium inlet / outlet) provided in the ozone generator outer frame 1x. It can be circulated in the cooling water flow path.
- the high-voltage electrode 1a and the ground electrode 1b themselves existing in the vicinity of the high-pressure cooling plate 45 can be effectively cooled.
- a cooling water inlet / outlet 34, a raw material inlet 38, and an ozone gas outlet are provided on the upper surface 1xu (predetermined constituent surface) of the ozone generator outer frame 1x. 39 and the high-voltage terminal storage portion 20 (high-voltage terminal PH) are provided collectively.
- the heat insulating layer formation shown in FIG. 8 that covers only the upper surface portion 1 xu, not the aspect in which the heat insulating layer 8 is formed so as to cover substantially the entire surface of the ozone generator outer frame 1 x.
- Other modes in which the heat insulating layer is selectively formed only in the region 48 may be adopted.
- the inside of the ozone generator outer frame 1x is effectively exhibited by the heat-insulating function of the cooling water inlet / outlet 34 serving as the inlet / outlet of the cooling water supplied from the low-temperature cooling water system 30 and the vicinity thereof.
- the temperature low there is an effect that a lot of ozone can be generated.
- the temperature difference between the inside and outside of the ozone generator outer frame 1x is larger than that of other portions, and the cooling water inlet / outlet 34, the raw material inlet 38, the ozone gas outlet 39, and the high voltage terminal storage unit 20 (high voltage terminal PH) ) And its vicinity region can effectively exhibit a heat insulating action to prevent condensation.
- another aspect of the present embodiment has the effect of generating a large amount of ozone without generating condensation while minimizing the formation volume of the heat insulating layer 8.
- a high-quality oxide insulating film can be formed in a relatively short time by utilizing the nitrogen addition-less ozone generation unit 7 according to this embodiment (including other aspects) for semiconductor manufacturing technology. .
Abstract
Description
・窒素分子のイオン化反応
N2+e⇒2N+
・NO2の生成反応
2N++O2+M⇒NO2
(数ppm~数十ppmのNO2ガス生成)
(2) NO2の放電光による触媒効果での酸素原子Oの生成
・NO2の光解離反応
NO2+hν⇒NO+O
・NOの酸化反応
NO+O2(原料酸素)⇒NO2+O
*上記2つの反応でNO2が触媒になって酸素原子が生成
(2)の反応で生成した多量の酸素原子Oと酸素ガス分子O2との反応でオゾンO3が生成される。
R2;O+O2+M→O3+M
上記(1)~(3)によって、高濃度なオゾンを発生させている。
N2*;窒素の励起
窒素ガスによる紫外光
H2O+e⇒H+OH+e (水蒸気の電離)
N2+e⇒2N-+e (窒素分子の電離)
NO2+hν(295~400nm)⇒NO+O(3P)
H+O2+M⇒HO2+M
HO2+NO⇒OH+NO2
N2O5+H2O⇒2HNO3
OH+NO2+M⇒HNO3+M
このように、オゾンガス以外にNOX副生ガスや硝酸も生成される。
この発明の実施の形態で述べるオゾンガス供給システムで用いる窒素添加レス・オゾン発生器を図1ないし図4について説明する。図1は窒素添加レス・オゾン発生器を中心としたガス系統の構成を示すブロック図である。
図5はこの発明の実施の形態である窒素添加レス・オゾン発生ユニット及びその周辺の構成を示す説明図である。なお、同図において、図1で示した構成と同様な構成は同一符号を付して説明を適宜省略し特徴部分を中心に説明する。
図5に示すように、窒素添加レス・オゾン発生ユニット7として、窒素添加レス・オゾン発生器1(高電圧用端子収納部20を含む)、オゾン電源2及び制御機器(MFC3、APC4等)とが集約してユニット化されている。このような窒素添加レス・オゾン発生ユニット7に対し、低温冷却水33によって窒素添加レス・オゾン発生器1を低温に冷やすと、窒素添加レス・オゾン発生器1のオゾン発生器外枠1xの表面が大気との温度差で結露して、結露した水滴が、オゾン電源2やMFC3,APC4等の制御機器に付着することにより、電気絶縁性が悪くなり、オゾン電源2及び上記制御機器の故障原因になる。
本実施の形態では、低温の冷却媒体として冷却水33を用いたが、冷却水33に代えて以下の冷却媒体を用いても良い。例えば、冷媒温度-20℃~65℃のエチレングリコール水溶液(PRTR)や冷媒温度-40℃~60℃のハイドロフルオロポリエーテル(HFPE)等が考えられる。
本実施の形態では冷却水33の窒素添加レス・オゾン発生器1への供給時の温度を5℃以下に設定した。この理由について説明する。従来は、水温20℃の水を窒素添加レス・オゾン発生器1内に流して冷却してオゾンを発生させるのが一般的であった。
断熱層8に用いる断熱材としては、水や湿気を通さず、金属に比べ、熱伝導が非常に小さいものが有効である。例えば、耐熱性無機繊維である炭素繊維やセラミック繊維やテフロン(登録商標)繊維等がある。断熱材がボード状に整形された硬質ウレタン等を素材にした断熱ボードを断熱層8として用いても良い。
図7は高電圧用端子収納部20の詳細を示す説明図である。同図に示すように、高電圧用端子収納部20内に設けられる高電圧用端子PHは、高電圧碍子24、電極棒25、ナット26(26a,26b)から構成される。
図8は窒素添加レス・オゾン発生器1の構成の詳細を示す説明図である。同図に示すように、2つの高圧電極1aが一つの接地電極1bを共有する態様で、一対の高圧電極1a、接地電極1bよりなる電極セルが複数個積層して形成される。
また、半導体分野では、窒素を含まない酸素とオゾンガスのみの高純度なオゾンガスを用いて、半導体の高品質な酸化膜を形成した絶縁成膜をすることが特に望まれている。そのため、窒素レスとしたオゾン発生装置は必須の条件であって、かつ、オゾン発生器から供給される窒素レスオゾンガスは、より高濃度化されたオゾンガスが求められており、酸化絶縁成膜の成膜速度をより高めることや成膜厚みを増すことで、絶縁性能アップさせることが望まれている。
Claims (5)
- 窒素添加レス・オゾン発生ユニット(7)であって、
放電面にオゾンを生成するための光触媒物質を有し、オゾンガスを発生する窒素添加レス・オゾン発生器(1)と、
前記窒素添加レス・オゾン発生器に高電圧(HV)を供給するオゾン電源(2)と、
前記オゾン発生器に関連した制御手段(3,4)とを備え、
前記制御手段は、
前記窒素添加レス・オゾン発生器に供給される原料ガス流量(Q)を制御するマスフローコントローラ(MFC)(3)を含む流量検出・流量調整手段と、
前記窒素添加レス・オゾン発生器内の圧力である内部圧力を自動制御するオートプレッシャコントローラ(APC)(4)を含む圧力検出・圧力調整手段とを有し、
前記窒素添加レス・オゾン発生ユニットは、前記窒素添加レス・オゾン発生器、前記オゾン電源、及び前記制御手段を集約して一体化構造で形成され、
窒素添加レス・オゾン発生器は、
前記オゾン電源からの前記高電圧を受ける高電圧用端子(PH)と、
外部から得られる15℃以下の低温の冷却媒体を供給及び排出するための冷却媒体入出口(34)と、
前記高電圧用端子を介して前記高電圧が付与される高圧電極(1a)とを含み、前記高圧電極の少なくとも一つの主面が前記放電面として規定され、
前記高圧電極の前記放電面側に設けられた前記光触媒物質からなる光触媒層(1d)と、
前記高圧電極の近傍に設けられ、前記冷却媒体入出口を介して供給される前記冷却媒体が内部を流通可能な冷却経路部(45)と、
前記高圧電極、前記光触媒層及び前記冷却経路を内部に収納する収納部(1x)とを含み、前記収納部の外周部の一部を構成する所定の構成面に前記冷却媒体入出口が形成され、前記収納部の前記外周部を貫通して前記高電圧用端子が設けられ、
前記収納部における前記所定の構成面を少なくとも覆って形成される、断熱材からなる断熱層(8)をさらに含む、
窒素添加レス・オゾン発生ユニット。 - 請求項1記載の窒素添加レス・オゾン発生ユニットであって、
前記窒素添加レス・オゾン発生器は、
外部から原料ガス(995)を前記流量検出・流量調整手段を介して供給するための原料ガス入口部(38)と、
生成したオゾンガスを前記圧力検出・圧力調整手段を介して外部に出力するためのオゾンガス出口部(39)とをさらに含み、
前記所定の構成面に前記原料ガス入口部、前記オゾンガス出口部が形成されるとともに、前記高電圧用端子は前記所定の構成面を貫通して形成され、
前記断熱層は前記所定の構成面のみを選択的に覆って形成される、
窒素添加レス・オゾン発生ユニット。 - 請求項1記載の窒素添加レス・オゾン発生ユニットであって、
前記断熱層は前記収納部の外周部の略全面を覆って形成される、
窒素添加レス・オゾン発生ユニット。 - 請求項1記載の窒素添加レス・オゾン発生ユニットであって、
前記冷却媒体は前記窒素添加レス・オゾン発生器の前記収納部内への供給時の温度を5℃以下に設定可能な低温冷却媒体を含み、前記窒素添加レス・オゾン発生器自身を低温にして構成する、
窒素添加レス・オゾン発生ユニット。 - 請求項1ないし請求項4のうち、いずれか1項に記載の窒素添加レス・オゾン発生ユニットであって、
前記高電圧用端子(PH)の主要部を所定の空間内に配置するように収納する高電圧用端子収納部(20)をさらに備え、
前記高電圧用端子収納部は、所定の空間に露点が比較的低い結露防止用のパージガス(23)を外部から供給可能なパージガス供給口(28)を有する、
窒素添加レス・オゾン発生ユニット。
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