JPH06210287A - Treatment using dielectric barrier-electric discharge lamp - Google Patents

Abstract

PURPOSE:To make it possible to perform a variety of treatments maintaining high quality at high efficiency and adequate speed by ensuring that either of a material to be treated or a fluid for treatment receives an ultraviolet beam irradiation at least twice from a dielectric barrier-electric discharge lamp and a first chemical reaction is different from a second and following chemical reactions. CONSTITUTION:If air 1 for treatment is supplied to a reactor 5, ozone is generated from oxygen in the air 1 in a reaction space area 8 by irradiation of an ultraviolet beam from a first dielectric barrier-electric discharge lamp 6. Then the ozone moves to the reaction space area where it is subjected to the irradiation of an ultraviolet beam from a second dielectric barrier-electric discharge lamp 7, and is decomposed into active oxygen atom and oxygen molecule. Further, the active oxygen atom, the oxygen molecule and water 3 to be treated are mixed and this mixture is irradiation with an ultraviolet beam from the first and the second dielectric barrier-electric discharge lamp 7, 6. Consequently, impurities contained in the water are decomposed into harmless carbon dioxide and water, and the treated water is discharged from an outlet 12 with the air for treatment.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a treatment method utilizing a photochemical reaction, for example, treatment of CFC gas and various waste gases,
Alternatively, the present invention relates to a method for treating water such as clean water, sewage, and various industrial wastewater, or cleaning, or a film forming method for producing a hydrogenated amorphous silicon thin film used for a solar cell or the like.
In particular, it relates to improvements in processing methods using a dielectric barrier discharge lamp as a light source for photochemical reactions.

[0002]

2. Description of the Related Art As a technique related to the present invention, for example, Japanese Patent Laid-Open Publication No. Hei 3-211283 discloses a dielectric barrier discharge (also called ozonizer discharge. Revised new edition "Discharge Handbook" published by The Institute of Electrical Engineers, 1991. June Reprint, 7th issue, page 263), a thin film manufacturing apparatus by a CVD method using ultraviolet rays emitted from a lamp is described. In addition, Japanese Patent Laid-Open Publication No. 3-1
No. 22287 describes a method of metallizing a substrate using ultraviolet light emitted from a lamp using a dielectric barrier discharge. The treatment method using the dielectric barrier discharge lamp as described above can obtain a characteristic treatment because the dielectric barrier discharge lamp has various features that conventional low pressure mercury discharge lamps and high pressure arc discharge lamps do not have. Therefore, it is useful. For example, a method of manufacturing a thin film using a dielectric barrier discharge lamp is useful because a thin film for solar cells and various semiconductor elements can be formed with high quality.

The above-mentioned conventional treatment method employs a method of irradiating the treatment fluid, the object to be treated, or both of them with one kind of ultraviolet ray only once. For example, in a method of manufacturing a thin film using a dielectric barrier discharge lamp, a plurality of process gases that are processing fluids and a substrate that is an object to be processed are housed in one reaction chamber and one type of dielectric barrier discharge is used. The film was formed on the substrate by a method of irradiating the process gas with one type of ultraviolet light emitted from the lamp only once to decompose and activate the process gas. At this time, the substrate is also irradiated with ultraviolet rays that have not been absorbed by the process gas. In the above-mentioned conventional processing method, even if the irradiation of ultraviolet rays is repeated twice or more, the kind of chemical reaction generated on the process gas and the substrate is the same as that of the first irradiation of ultraviolet rays, and only the first time. It only corresponds to the longer irradiation time of the ultraviolet rays.

Generally, the optimum conditions for activating, decomposing, ionizing or synthesizing a substance by a photochemical reaction, that is, the wavelength and intensity of ultraviolet rays to be irradiated, the temperature of the substance, etc., differ depending on the type of substance. Therefore, in the method of treating an object to be treated by bringing the object to be treated into contact with the treating fluid, at least one of the object to be treated and the treating fluid is irradiated with one kind of ultraviolet ray from the dielectric barrier discharge lamp.
The method of irradiating only once has a problem that the treatment is incomplete, or the treatment speed or treatment efficiency is not always sufficient.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a processing method using a dielectric barrier discharge lamp capable of performing various kinds of processing with high quality and at high speed or with high efficiency. It is to be.

[0006]

The above object of the present invention is to provide a method of treating at least an object to be treated by bringing the object to be treated into contact with a treating fluid, wherein one of the object to be treated and the treating fluid is a dielectric barrier. It is characterized in that it receives UV irradiation from a discharge lamp at least twice, and at that time, a chemical reaction occurring in at least one of the first irradiation and the irradiation after the second irradiation is different in an object to be processed or a processing fluid. This is achieved by using a method of treating an object.

Particularly, in the treatment of a fluid, the first step of irradiating the object to be treated with the first ultraviolet ray emitted from the first dielectric barrier discharge lamp, and the object to be treated after the first step And a processing fluid are brought into contact with each other, and a second step of irradiating a second ultraviolet ray radiated from a second dielectric barrier discharge lamp is included, or the processing fluid has a first step. First step of irradiating a first ultraviolet ray radiated from the dielectric barrier discharge lamp of, and after the first step,
A treatment method comprising a second step of bringing the object to be treated into contact with a treatment fluid and irradiating a second ultraviolet ray emitted from a second dielectric barrier discharge lamp, or
A first step of bringing the object to be processed into contact with a processing fluid, and irradiating a first ultraviolet ray emitted from a first dielectric barrier discharge lamp; the object to be processed by the first step; The object of the present invention is further achieved by using a treatment method characterized in that it comprises a second step of irradiating the treatment fluid with a second ultraviolet light emitted from a second dielectric barrier discharge lamp. To be done.

Further, particularly in the treatment of solid or liquid, the first step of irradiating the object to be treated arranged in a predetermined atmosphere with the first ultraviolet ray emitted from the first dielectric barrier discharge lamp. After the first step, the method further comprises a second step of arranging the object to be treated under a processing fluid and irradiating a second ultraviolet ray emitted from a second dielectric barrier discharge lamp. Or a first step of irradiating an object to be processed placed under a predetermined processing fluid with a first ultraviolet ray emitted from a first dielectric barrier discharge lamp, after the first step And adopting a treatment method characterized by including a second step of arranging the object to be treated in a predetermined atmosphere and irradiating a second ultraviolet ray emitted from a second dielectric barrier discharge lamp. The object of the present invention is further achieved by .

[0009]

[Measures of the above means] In a method of treating an object to be treated by contacting the object to be treated with a processing fluid, at least using a photochemical reaction by ultraviolet rays, a dielectric barrier discharge lamp is used as a light source of ultraviolet rays. Then, the dielectric barrier discharge lamp is a nearly monochromatic light that can generate specific ultraviolet rays with high efficiency compared to the conventional low pressure mercury discharge lamp and high pressure arc discharge lamp, the temperature of the lamp is low, and the degree of freedom of shape is high. Because of its large size, high efficiency and high speed processing is possible with a small device. One of the object to be processed and the processing fluid receives ultraviolet irradiation from the dielectric barrier discharge lamp at least twice, and at that time, at least the first irradiation and the irradiation after the second irradiation in the object to be processed or the processing fluid. By adopting a method for treating an object to be treated characterized in that chemical reactions that occur at one time are different, it is possible to irradiate the object to be treated or the object to be treated with ultraviolet rays for the first time, and
The second irradiation of ultraviolet rays can be performed under optimum conditions, and thus activation, decomposition, ionization and synthesis are optimally performed, and as a result, high efficiency and high speed processing can be performed with a small device.

A first step of irradiating the object to be processed with a first ultraviolet ray emitted from a first dielectric barrier discharge lamp, and after the first step, bringing the object to be processed into contact with a processing fluid,
According to the treatment method including the second step of irradiating the second ultraviolet ray radiated from the second dielectric barrier discharge lamp, the wavelength and speed of the ultraviolet ray, the temperature of the object to be treated and the temperature of the treatment fluid are increased. Etc. can be optimally adjusted in the first step and the second step independently by selecting the type of the dielectric barrier discharge lamp, the temperature of the reaction chamber, etc. Therefore, high efficiency and high speed can be achieved. Processing becomes possible. By providing a means for adjusting the temperature of at least one of the object to be processed, the processing fluid and both, and adjusting the temperature, the chemical reaction in the first step and the second step can be optimally carried out. Therefore, highly efficient processing is possible.

Further, the first step of irradiating the object to be processed placed in a predetermined atmosphere with the first ultraviolet rays emitted from the first dielectric barrier discharge lamp, and after the first step, the object to be processed A second object for arranging an object to be processed under a processing fluid and irradiating a second ultraviolet ray emitted from a second dielectric barrier discharge lamp;
When the processing method is characterized by including the step of, for example, when the object to be processed is a solid and the atmosphere in the first step is a vacuum atmosphere, the gas generated from the object to be processed by the irradiation of the first ultraviolet light is rapidly generated. Since it is removed, the ultraviolet rays are not absorbed by the generated gas, so that highly efficient processing becomes possible.

In some cases, by adjusting the type of processing fluid and the temperature of the object to be processed and the processing fluid,
A treatment method is also possible in which the wavelengths of the first ultraviolet light and the second ultraviolet light are substantially the same. In this case, the first and second dielectric barrier discharge lamps can be of the same type, thus facilitating maintenance. When the wavelengths of the first ultraviolet light and the second ultraviolet light are substantially the same, the first dielectric barrier discharge lamp and the second dielectric barrier discharge lamp are combined into a single dielectric barrier. The discharge lamp can also serve as the dual-purpose, so that the size and efficiency of the device can be reduced.

When the dielectric barrier discharge lamp has an airtight discharge space and radiates ultraviolet rays through a light extraction window member that transmits ultraviolet rays, the wavelength ranges 180 to 200 and 165 to 190 are expressed in nm. , 240 to 2
55, 200 to 240, 120 to 190, and 3
By emitting ultraviolet rays in the wavelength range of 00 to 320, a highly efficient and high-quality treatment method can be achieved. Because, the ultraviolet rays in the above wavelength range, at least, by using a mixed gas of argon and fluorine, argon and chlorine, krypton and fluorine, krypton and chlorine, xenon and xenon and chlorine, respectively, as the main light emitting gas, respectively. This is because light can be emitted by the excimer molecules of the mixed gas of 1., but by using these gases, it is possible to realize a state in which the light emitting gas is less deteriorated and the light extraction window member is less deteriorated.

107 to 165 when the dielectric barrier discharge lamp does not have a solid lamp constituent material between the discharge space and the object to be processed or the processing fluid, that is, does not have a light extraction window member. By emitting ultraviolet rays in the wavelength range of 140 to 160, a highly efficient and high-quality processing method can be achieved. Because without the light extraction window member, the light emitting gas may contact the object to be processed and contaminate the object to be processed, but at least by using krypton and argon as the main light emitting gas. This is because the excimer molecules of each gas can emit ultraviolet rays in the above wavelength range, and these gases do not contaminate the object to be treated.

[0015]

EXAMPLE FIG. 1 shows a schematic view of a water treatment method which is a first example of the present invention. The box-shaped reaction vessel 5 has substantially two reaction space regions by two dielectric barrier discharge lamps 6 and 7 on a flat plate having a structure that radiates ultraviolet rays on both sides. A schematic diagram of a dielectric barrier discharge lamp is shown in FIG.
Flat dielectrics 20 and 21 and side plates 22 that transmit ultraviolet rays
The discharge space 23 is formed by the discharge space 2
Luminescent gas is filled in 3. When a voltage is applied to the transparent electrodes 24 and 25 made of a metal net provided on the surfaces of the dielectrics 20 and 21 by the AC power supply 26, the discharge space 23
A so-called dielectric barrier discharge, which is also called an ozonizer discharge or a silent discharge, is generated therein, and ultraviolet rays are radiated with high efficiency through the dielectrics 20 and 21 and the transparent electrodes 24 and 25.
Although not shown in the drawing, if necessary, the transparent electrode 24,
The surface of 25 is covered with an ultraviolet-transparent resin, glass or the like to be electrically insulated.

The first dielectric barrier discharge lamp 6 is filled with xenon gas as a main component of luminescent gas.
It emits UV light in the wavelength range of 120 to 190 nm, which has a maximum near 72 nm. Further, the second dielectric barrier discharge lamp 7 is filled with a mixed gas of krypton and chlorine as a main component of luminescent gas, and emits ultraviolet rays in the wavelength range of 200 to 240 nm having a maximum value near 222 nm. When air 1, which is a processing fluid, is supplied to the reaction vessel 5 from the processing fluid supply port 2, it has a maximum value near 172 nm emitted from the first dielectric barrier discharge lamp 6 and has a maximum value in the range of 120 to 190 nm. Ozone produces ozone in the reaction space region 8 from the oxygen in the air 1 by the ultraviolet rays. The ozone moves to the reaction space region 9,
222 emitted from the second dielectric barrier discharge lamp 7
It is decomposed into active oxygen atoms and oxygen molecules by being irradiated with ultraviolet rays in the wavelength range of 200 to 240 nm having a maximum value in the vicinity of nm. The active oxygen atoms and oxygen molecules are mixed with water 3, which is the object to be processed supplied from the object supply port 4 to the reaction vessel 5, and the mixed fluid in the reaction space regions 10 and 11 is mixed with the second and first fluids. Dielectric barrier discharge lamps 7 and 6 of
Is irradiated with ultraviolet rays from.

As a result, methanol, isopropyl alcohol, methyl ethyl ketone, trichloroethylene, dodecylbenzene sulfonic acid, polyoxyethylene octyl phenyl ether, which are contained in water as impurities,
Trimethylamine, tetramethylammonium hydroxide, etc. are decomposed and converted into harmless carbon dioxide gas, water, etc. Treated water, together with the treating air, exit 1
Emitted from 2.

As an advantage of this embodiment, firstly, since the lamps for ozone generation and ozone decomposition are constructed in different types, the wavelength and intensity of ultraviolet rays are adjusted so that each chemical reaction is optimized. Second, a highly efficient treatment is possible, and secondly, in addition to the ultraviolet rays from the second dielectric barrier discharge lamp, the first dielectric is added to the mixture of the object to be treated and the pretreated processing fluid. With the barrier discharge lamp, it is possible to irradiate highly efficient short wavelength ultraviolet rays that cannot be generated by conventional low pressure mercury discharge lamps and high pressure arc lamps.
Trimethylamine, which was difficult to decompose by conventional methods,
Tetramethylammonium hydroxide, etc. can be decomposed, and thirdly, the light output characteristics of the first and second dielectric barrier discharge lamps do not change with the ambient temperature. Stable treatment of water, which requires a lot of energy,
Fourthly, since there is a great degree of freedom in changing the shapes of the first and second dielectric barrier discharge lamps, it becomes possible to perform the first step, the second step and the subsequent steps in the immediate vicinity, Therefore, high efficiency processing can be performed.

The second embodiment of the present invention is the same as the first embodiment except that the object supply port 4 is closed and the object 3 is processed.
And a processing fluid 1 is mixed and supplied from the processing fluid supply port 2. This method has the advantage of simplifying the device.

In the third embodiment of the present invention, the first dielectric material of the second dielectric barrier discharge lamp in the first embodiment is used.
Of the dielectric barrier discharge lamp, or the discharge spaces of the first and second dielectric barrier discharge lamps are the same, that is, one dielectric barrier discharge lamp. In this embodiment, the reaction space regions 8, 9
In this case, ozone is mainly generated and the mixed gas of the object to be processed and ozone is irradiated with ultraviolet rays in the reaction space regions 10 and 11 to process the object to be processed. The method of this embodiment has the advantage that the device is simple.

The fourth embodiment of the present invention uses hydrogen peroxide as the processing fluid in the first or second embodiment. Hydrogen peroxide is supplied as hydrogen peroxide solution. The supplied hydrogen peroxide water produces hydroxy radicals in the reaction space regions 8 and 9 by irradiation with ultraviolet rays. The mixture of the object to be treated and the pretreated hydrogen peroxide solution is irradiated with ultraviolet rays in the reaction space regions 10 and 11 to treat the object to be treated.

The fifth embodiment of the present invention is the same as the first to third embodiments, except that the material to be treated is industrial wastewater or sewage. In this embodiment as well, a pretreatment step such as separation of solid matter contained in the object to be treated may be required, but the object to be treated is treated by the same mechanism as in the first to third embodiments. To be done. In the first to fifth examples, the object to be processed was a liquid, but in the sixth example, the object to be processed in the first to fifth examples was replaced with gas. For example, CFC-1 that destroys the ozone layer in the stratosphere
1, CFC-12, CFC-114 and CFC-11
When CFCs such as 2 are used and oxygen is used as a treatment fluid, CFCs, which are compounds of carbon, chlorine, and fluorine, can be converted into harmless lower fluororesin, carbon dioxide, or hydrogen chloride by the treatment method. Become. The hydrogen chloride gas is treated as a sodium compound or the like in a separate process. Various waste gases such as industrial waste gases containing carbon tetrachloride and methyl chloroform can be treated by the method of the sixth embodiment.

FIG. 3 shows a schematic view of a wet cleaning method according to the seventh embodiment. In the box-shaped cleaning tank 30, two flat plate-shaped dielectric barrier discharge lamps 6 and 7 having a structure that radiates ultraviolet rays on both sides are installed. The structure of the dielectric barrier discharge lamp is substantially the same as that shown in FIG. The first dielectric barrier discharge lamp 6 is filled with xenon gas as a main component of luminescent gas and emits ultraviolet rays in a wavelength range of 120 to 190 nm having a maximum value near 172 nm. Further, the second dielectric barrier discharge lamp 7 is filled with a mixed gas of krypton and fluorine as a main component of luminescent gas and has a maximum value near 249 nm.
It emits ultraviolet light in the wavelength range of 0 to 255 nm. When air 1, which is a processing fluid, is supplied from the processing fluid supply port 2, the maximum value around 172 nm emitted from the first dielectric barrier discharge lamp 6 is 120 to 190 nm.
Ozone in the reaction space region 8 is generated from oxygen in the air 1 by the ultraviolet rays in the range. The ozone moves to the reaction space region 9 and the second dielectric barrier discharge lamp 7
Emitted from 240 with a maximum near 249 nm
Is irradiated with ultraviolet rays in the wavelength range of ˜255 nm to decompose into active oxygen atoms and oxygen molecules. The active oxygen atoms and oxygen molecules are mixed into the water 32 in the cleaning tank 30 through the whisk 31 provided at the bottom of the cleaning tank 30.

An object to be processed, for example, a plastic bottle 33
Is submerged in the ozone-mixed water 32 by the support 34, and the outer surface is cleaned by irradiation with ultraviolet rays from the first and second dielectric barrier discharge lamps. By the cleaning, printing on the outer surface of the bottle 33 can be performed with high quality. A method of rotating the plastic bottle 33 that is the object to be processed by rotating the support tool 34, or a method of rotating the support tool 34 facing the first and second dielectric barrier discharge lamps.
The processing speed can be increased by disposing the dielectric barrier discharge lamp (1) so as to sandwich the bottle 33.

FIG. 4 shows a schematic view of the ashing method of the photoresist which is the eighth embodiment. The processing fluid oxygen 1 injected into the ashing duct 40 is converted into ozone by the ultraviolet rays emitted from the first dielectric barrier discharge lamp group 41 provided in the ashing duct 40. The first dielectric barrier discharge lamp group 41 is formed by bundling a plurality of hollow coaxial cylindrical dielectric barrier discharge lamps 41a as shown in FIG. 5 on a pedestal 44. The structure of each dielectric barrier discharge lamp 41a is as follows. Inside the inner dielectric 51, there is provided an aluminum foil 52 which also serves as an ultraviolet reflector and an electrode.
1 has a structure in which an electrode 54 that transmits ultraviolet rays is provided outside the outer dielectric 53 that is provided coaxially with 1. The hollow cylindrical portion 55 formed by the inner dielectric 51 and the outer dielectric 53 is filled with a gas for light emission. Electrode 52,
When a voltage is applied between 54 by the power supply 26, ozonizer discharge is generated in the hollow cylindrical portion 55, and ultraviolet rays are emitted from the outer dielectric 54.

Ozone generated by the ultraviolet rays emitted from the first dielectric barrier discharge lamp group 41 is converted into activated oxygen atoms by the ultraviolet rays emitted from the second dielectric barrier discharge lamp. The photoresist applied to the semiconductor substrate 43, which is the object to be processed, reacts with the activated oxygen atoms under the irradiation of the ultraviolet rays from the second dielectric barrier discharge lamp group 42 to be ashed. The structure of each discharge lamp 42a is the same as that of the discharge lamp 41a, and is attached to the pedestal 44. The distance between the lamp group 41 and the lamp group 42 can be adjusted by adjusting the positions of the two pedestals 44.

The second dielectric barrier discharge lamp group 42 is
Relatively long wavelength 240 to 255 nm, 200 to 2
When the luminescent material is selected so as to emit ultraviolet rays in the range of 40 nm and 300 to 320 nm, the substrate 43 is less likely to be damaged because the energy of photons with which the substrate 43 is irradiated is small. In addition, the second dielectric barrier discharge lamp group 42 has a relatively short wavelength range of 180 to 200 nm, 16
When a luminescent substance is selected so as to emit ultraviolet rays in the range of 0 to 190 nm and 120 to 190 nm, the ultraviolet rays have a large absorption cross-section of oxygen molecules, so that the density of highly active oxygen atoms near the substrate surface is extremely high. Since the photons that can be generated and the energy of the photons with which the substrate 43 is irradiated are large, it is possible to ash the photoresist that is hard to be ashed by the ion implantation.

FIG. 6 shows a schematic view of the surface modification method of the ninth embodiment. The plastic 60 as the object to be processed is installed in the first processing duct 61 filled with the atmosphere of nitrogen 62 supplied from above, and the wavelength range of 120 to 190 nm from the first dielectric barrier discharge lamp group 63. Is exposed to the ultraviolet rays of, the bonds of molecules existing on the surface are broken. Then, the plastic 60 is transferred to the carrier device 6
4 is carried to the second processing duct 65 and is irradiated with ultraviolet rays from the second dielectric barrier discharge lamp group 66 in the atmosphere of oxygen or air 1 supplied from the processing fluid supply port 2, and its surface is exposed. A -C00H group and a -OH group are generated. By the above-mentioned treatment, printing and adhesion to the plastic surface can be performed with high quality. In this embodiment, since the object to be processed is in the atmosphere of atmospheric pressure or higher, there is an advantage that the object to be processed can be easily moved. Further, an argon gas is used instead of the nitrogen 62, and a windowless lamp is used as the first dielectric barrier discharge lamp group 63 (Japanese Patent Application Laid-Open No. Hei 3 (1999) -58).
No. 2-11283), the first
From the dielectric barrier discharge lamp group 63, the ultraviolet rays in the wavelength range of 107 to 165 nm emitted from the excimer molecules of argon are radiated, and the surface of a very stable resin such as a fluororesin can be modified. Like

FIG. 7 shows a schematic view of the film forming method of the tenth embodiment. A first dielectric barrier discharge lamp group 63 having no window member is provided in the vicinity of the light emission gas supply port 75 provided on the upper part of the reaction vessel 70. When the emission gas argon 74 is supplied from the emission gas supply port 75, ultraviolet rays in the wavelength range of 107 to 165 nm emitted from the excimer molecules of argon are emitted from the first dielectric barrier discharge lamp group 63. The mixed gas 1 of the processing fluid monosilane gas and methane gas supplied from the processing fluid supply port 2 is decomposed and activated by the ultraviolet rays in the wavelength range of 107 to 165 nm emitted from the first dielectric barrier discharge lamp group 63, A thin film of hydrogenated amorphous silicon carbide is formed on the surface of the substrate 71, which is the object to be processed, by being reactivated by the ultraviolet rays from the second dielectric barrier discharge lamp group 66. When a lamp that emits an ultraviolet ray having a relatively long wavelength is adopted as the second dielectric barrier discharge lamp group 66, the energy of photons applied to the film is small, so that the film is not damaged and a high quality film is obtained. can get. By decomposing and activating the processing fluid with the ultraviolet rays of the first dielectric barrier discharge lamp and irradiating it with the second ultraviolet rays during the film formation, it becomes possible to form a high-quality film. A mechanism for adjusting the temperature of the object to be processed is installed in the object support device 72 to adjust the temperature of the object to be processed, and the distance between the object to be processed and the first dielectric barrier discharge lamp group 63 is increased by the support tool 73. By adjusting, it becomes possible to form a film of higher quality. Reference numeral 76 is a discharge port for the discharge gas and the processing gas.

FIG. 8 shows a schematic view of the sterilization method of the 11th embodiment. As shown in FIG. 8, the dielectric barrier discharge lamp is formed by coaxially arranging three tubular dielectrics, and includes an inner dielectric 51, an intermediate dielectric 88 and an outer dielectric 53. Inner discharge chamber 87 arranged coaxially and independently
And an outer discharge chamber 86, and an intermediate electrode 89 embedded in the intermediate dielectric 88, a transparent electrode 82 provided on the inner surface of the inner dielectric 51, and a transparent outer electrode 54 provided on the outer surface of the outer dielectric 53. In this lamp, a voltage is applied by the AC power supplies 26a and 26b, respectively, to perform dielectric barrier discharge in the inner discharge chamber 87 and the outer discharge chamber 86. Xenon gas is used as the light emitting gas in the inner discharge chamber 87 to radiate ultraviolet rays in the wavelength range of 120 to 190 nm, and a mixed gas of krypton and fluorine is used as the light emitting gas in the outer discharge chamber 86.
It emits ultraviolet rays in the wavelength range of.

Oxygen gas 1 which is a processing fluid is poured from one end 81 of the tubular inner dielectric 51, and the first reaction space 8
120 to 190 radiated from the inner discharge chamber 87 in
Ozone generated by ultraviolet rays in the wavelength range of nm is ejected from the other end 84 of the inner dielectric body 51. The ozone was emitted from the outer discharge chamber 86 in the reaction space 85 240
Is decomposed by UV light in the wavelength range from
Active oxygen atoms are generated, and the active oxygen atoms sterilize the inner surface of the food cup 90 that is the object to be treated. Further, the ultraviolet rays in the wavelength range of 240 to 255 nm radiated from the outer discharge chamber 86 that irradiates the inner surface of the food cup 90 directly contact the inner surface of the food cup 90 because the ultraviolet light in this wavelength range has the optimum bactericidal action. Sterilization, and therefore, sterilization and disinfection can be performed in a short time.

FIG. 9 shows a schematic view of the etching method of the twelfth embodiment. The chlorine gas 1, which is the processing fluid injected into the processing duct 40, passes between the lamps of the dielectric barrier discharge lamp group 41 provided in the processing duct 40 while the dielectric barrier discharge lamp group 41 is provided. It is converted into active chlorine atoms by the ultraviolet rays emitted from the. The active chlorine atoms are sprayed onto the silicon substrate 92 masked with silicon oxide 91, react with the silicon substrate under the irradiation of ultraviolet rays from the dielectric barrier discharge lamp group 41 to generate silicon chloride, and the silicon substrate To etch. If the dielectric barrier discharge lamp group 41 selects a light-emitting substance so as to emit ultraviolet rays having relatively long wavelengths in the range of 240 to 255 nm and 300 to 320 nm, the photon energy with which the substrate 92 is irradiated is small. Less likely to damage 92.

FIG. 10 shows a schematic diagram of the dry cleaning method of the thirteenth embodiment. Figure 5 shows the dielectric barrier discharge lamp.
Although it is a hollow coaxial double tube type as shown in FIG.
2 is a transparent electrode unlike the case of FIG. That is,
Ultraviolet rays are also emitted inside. Xenon gas is used as the luminescent gas to emit ultraviolet rays in the wavelength range of 120 to 190 nm, and oxygen is used as the processing fluid 1. In the reaction space 83, the oxygen 1 is converted into ozone,
It is injected from the outlet 84. The ozone is further decomposed into active oxygen by irradiation of the ultraviolet rays in the second reaction space 85 formed by the bottle 101 as the object to be treated and the dielectric barrier discharge lamp. This active oxygen can decompose and remove the organic substances attached to the inner surface of the bottle in a short time.

[0034]

As described above, according to the present invention, it is possible to provide a processing method capable of performing various kinds of processing with high quality, high efficiency and at a sufficient speed.

[Brief description of drawings]

FIG. 1 is an explanatory diagram of a water treatment method using the present invention.

FIG. 2 is a schematic diagram of a dielectric barrier discharge lamp.

FIG. 3 is an explanatory diagram of a wet cleaning method using the present invention.

FIG. 4 is an explanatory diagram of a method for ashing a photoresist using the present invention.

FIG. 5 is a schematic view of a dielectric barrier discharge lamp having another structure.

FIG. 6 is an explanatory diagram of a plastic surface modification method using the present invention.

FIG. 7 is an explanatory diagram of a film forming method using the present invention.

FIG. 8 is an explanatory diagram of a sterilization method using the present invention.

FIG. 9 is an explanatory diagram of a silicon substrate etching method using the present invention.

FIG. 10 is an explanatory diagram of a dry cleaning method using the present invention.

[Explanation of symbols]

1 Processing Fluid 3 Processing Object 6,7 Dielectric Barrier Discharge Lamp 8, 9, 10, 11 Reaction Space Area 20,21 Dielectric 23 Discharge Space 24,25 Transparent Electrode 26 AC Power Supply

Claims (22)

[Claims] 1. A method for treating an object to be treated by contacting the object to be treated with a treating fluid, wherein one of the object to be treated and the treating fluid is irradiated with ultraviolet rays from a dielectric barrier discharge lamp at least twice or more. A method for treating an object to be treated, characterized in that, at that time, a chemical reaction occurring in at least one of the first irradiation and the second and subsequent irradiation in the object or the processing fluid is different. 2. A first step of irradiating an object to be processed with a first ultraviolet ray emitted from a first dielectric barrier discharge lamp,
After the first step, the object to be processed and the processing fluid are brought into contact with each other, and the second dielectric barrier discharge lamp emits a second beam.
2. The method for treating using a dielectric barrier discharge lamp according to claim 1, further comprising a second step of irradiating the ultraviolet ray. 3. A first step of irradiating the processing fluid with a first ultraviolet ray emitted from a first dielectric barrier discharge lamp, and after the first step, contacting the object to be processed with the processing fluid. 4. The method of treating a dielectric barrier discharge lamp according to claim 1, further comprising a second step of irradiating a second ultraviolet ray emitted from the second dielectric barrier discharge lamp. 4. A first step of bringing an object to be processed into contact with a processing fluid and irradiating a first ultraviolet ray radiated from a first dielectric barrier discharge lamp, and the step treated by the first step. The dielectric barrier discharge lamp according to claim 1, further comprising a second step of irradiating the object to be processed and the processing fluid with a second ultraviolet ray emitted from the second dielectric barrier discharge lamp. Processing method using. 5. A first step of irradiating an object to be processed arranged in a predetermined atmosphere with a first ultraviolet ray emitted from a first dielectric barrier discharge lamp, and after the first step, the object to be processed is irradiated. 2. The dielectric barrier according to claim 1, further comprising a second step of arranging the object to be processed under a processing fluid and irradiating a second ultraviolet ray emitted from a second dielectric barrier discharge lamp. Treatment method using a discharge lamp. 6. A first dielectric barrier discharge lamp radiating from a first dielectric barrier discharge lamp to an object to be processed arranged under a predetermined processing fluid.
The first step of irradiating the second ultraviolet ray, and the second step of irradiating the second ultraviolet ray emitted from the second dielectric barrier discharge lamp after arranging the object to be treated in a predetermined atmosphere after the first step. Two
The processing method using a dielectric barrier discharge lamp according to claim 1, further comprising: 7. The treatment method using a dielectric barrier discharge lamp according to claim 1, wherein the wavelengths of the first ultraviolet ray and the second ultraviolet ray are substantially the same. . 8. The dielectric according to claim 7, wherein one dielectric barrier discharge lamp also serves as the first dielectric barrier discharge lamp and the second dielectric barrier discharge lamp. Treatment method using body barrier discharge lamp. 9. At least one dielectric barrier discharge lamp of the first dielectric barrier discharge lamp and the second dielectric barrier discharge lamp is a solid between the discharge space and the object to be processed or the processing fluid. 9. The processing method using the dielectric barrier discharge lamp according to claim 1, wherein the lamp constituent material is not included. 10. The dielectric barrier discharge lamp has a wavelength range of 180 to 200, 165 to 19 in nm units.
9. The dielectric barrier discharge lamp according to claim 1, wherein the dielectric barrier discharge lamp has radiated light in at least one wavelength range of 0, 240 to 255, 200 to 240, 120 to 190, and 300 to 320. The processing method used. 11. The dielectric barrier discharge lamp of claim 9, wherein the dielectric barrier discharge lamp has radiation in at least one of wavelength ranges 107 to 165 and 140 to 160 expressed in nm. Treatment method using a dielectric barrier discharge lamp. 12. The processing method using a dielectric barrier discharge lamp according to claim 1, further comprising means for varying the temperature of the object to be processed or the processing fluid. 13. A water treatment method using the treatment method using the dielectric barrier discharge lamp according to any one of claims 1 to 8, claim 10, and claim 12. 14. A waste liquid treatment method using the treatment method using the dielectric barrier discharge lamp according to any one of claims 1 to 8, claim 10, and claim 12. 15. A waste gas treatment method using the treatment method using the dielectric barrier discharge lamp according to claim 1. Description: 16. A wet cleaning method characterized by using the processing method using the dielectric barrier discharge lamp according to any one of claims 1 to 8, claim 10 and claim 12. 17. A dry cleaning method using the processing method using the dielectric barrier discharge lamp according to claim 1. Description: 18. An ashing method characterized by using the processing method using the dielectric barrier discharge lamp according to claim 1. Description: 19. A surface reforming method, characterized by using the treatment method using the dielectric barrier discharge lamp according to claim 1. Description: 20. A film forming method using the processing method using the dielectric barrier discharge lamp according to claim 1. Description: 21. A sterilization method using the processing method using the dielectric barrier discharge lamp according to any one of claims 1 to 8, claim 10 and claim 12. 22. An etching method using the processing method using the dielectric barrier discharge lamp according to claim 1. Description: