US20040045575A1 - Apparatus and method for processing a substrate - Google Patents
Apparatus and method for processing a substrate Download PDFInfo
- Publication number
- US20040045575A1 US20040045575A1 US10/658,422 US65842203A US2004045575A1 US 20040045575 A1 US20040045575 A1 US 20040045575A1 US 65842203 A US65842203 A US 65842203A US 2004045575 A1 US2004045575 A1 US 2004045575A1
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- inert gas
- substrate
- substrate surfaces
- lamp house
- moistened
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
- H01L21/67098—Apparatus for thermal treatment
- H01L21/67115—Apparatus for thermal treatment mainly by radiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B7/00—Cleaning by methods not provided for in a single other subclass or a single group in this subclass
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B7/00—Cleaning by methods not provided for in a single other subclass or a single group in this subclass
- B08B7/0035—Cleaning by methods not provided for in a single other subclass or a single group in this subclass by radiant energy, e.g. UV, laser, light beam or the like
- B08B7/0057—Cleaning by methods not provided for in a single other subclass or a single group in this subclass by radiant energy, e.g. UV, laser, light beam or the like by ultraviolet radiation
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
- C03C23/0075—Cleaning of glass
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
- H01L21/67017—Apparatus for fluid treatment
- H01L21/67028—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/1316—Methods for cleaning the liquid crystal cells, or components thereof, during manufacture: Materials therefor
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B23/00—Record carriers not specific to the method of recording or reproducing; Accessories, e.g. containers, specially adapted for co-operation with the recording or reproducing apparatus ; Intermediate mediums; Apparatus or processes specially adapted for their manufacture
- G11B23/50—Reconditioning of record carriers; Cleaning of record carriers ; Carrying-off electrostatic charges
- G11B23/505—Reconditioning of record carriers; Cleaning of record carriers ; Carrying-off electrostatic charges of disk carriers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S134/00—Cleaning and liquid contact with solids
- Y10S134/902—Semiconductor wafer
Definitions
- This invention relates to a method and an apparatus for treating surfaces of substrates such as of LCD panels, semiconductor wafers, magnetic storage disks and optical storage disks which are formed of glass, semiconductor, synthetic resin, ceramics, metals or a composite material of these materials, and more particularly to a method and an apparatus for treating substrate surfaces by irradiation of ultraviolet light in a washing or etching stage of a fabrication process.
- a circuit pattern including transparent electrodes is formed on a TFT substrate which constitutes a transparent substrate of an LCD panel by the use of a film-forming means.
- surfaces of substrates are processed by washing and etching treatments.
- so-call dry processes are introduced into this field, carrying out washing and etching treatments by irradiation of ultraviolet light.
- Japanese Laid-Open Patent Application H5-224167 discloses a method of washing glass substrates of LCD panel.
- substrates are irradiated with ultraviolet light prior to starting a wet process using a washing liquid.
- substrate surfaces are irradiated with ultraviolet light from a low-pressure mercury lamp in a preparatory stage leading to a washing stage.
- ultraviolet light from a low-pressure mercury lamp has peaks approximately at 185 nm and 254 nm in wavelength distribution. Ultraviolet light with such wavelength distribution characteristics can remove organic substances which have deposited on substrate surfaces.
- the mechanism of washing off organic substances by ultraviolet irradiation includes decomposition of organic substances into products of low molecular weights by severing chemical bonds, and activation of decomposed products.
- ozone is produced as a result of absorption of ultraviolet light by oxygen in the air, and ozone is converted into active oxygen. Therefore, through oxidative destructive reactions with active oxygen, activated organic contaminants are finally converted into volatile substances such as CO x , H 2 O, NO x are released into the air, that is, removed from substrate surfaces.
- ultraviolet light which is irradiated from a low-pressure mercury lamp has a wavelength of 185 nm on the shorter side. Therefore, of various organic compounds which have deposited on substrate surfaces, the ultraviolet light may not be able to decompose those compounds which have chemical bonds of strong energy like double bonds. This means that ultraviolet light of shorter wavelengths should be employed, in order to wash substrates more completely.
- the activated organic substances are converted into volatile substances such as CO x , H 2 O, NO x and so forth by oxidative reactions with active oxygen and ultimately released into the air.
- the treated substrate surfaces come to have a smaller contact angle in terms of wettability.
- an apparatus for treating substrate surfaces which comprises: a lamp house located over a substrate transfer path and face to face with a treating surface of a substrate being transferred along the transfer path by a conveyer means; a dielectric barrier discharge lamp fixedly mounted in the lamp house to irradiate ultravilot light toward the substrate; and a moistened inert gas generating means adapted to supply a water vapor-containing moistened inert gas to a space between the substrate and the dielectric barrier discharge lamp; producing a reducing active member [H.] and an oxidative active member [.OH] by irradiating said moistened inert gas with ultraviolet light from said dielectric barrier discharge lamp.
- the lamp house may be arranged to have an ultraviolet light transmitting window on the side which faces a substrate under treatment.
- the lamp house in a case where the lamp house is provided within a chamber, it may be opened to the chamber on the side which faces a substrate.
- an inert gas feed means is connected to the lamp house to put the latter in an inert gas atmosphere.
- the chamber is put in a moistened inert gas atmosphere which is substantially free of oxygen, between entrance and exit openings which are provided at upstream and downstream ends for substrates to be treated.
- the lamp house may left open on the side of the chamber, or may be fitted with such a partition member on the open side as will transmit ultraviolt light and contain a large number of passages to let the inert gas flow out.
- the lamp house is located in and opned to the chamber, and an inert gas feed means is connected to the lamp house.
- the moistened inert gas generating means may be arranged to include a moistened inert gas feed means which is connected to the chamber to supply a water vapor-containing moistened inert gas toward the surface of a substrate.
- the moistened inert gas generating means may be constituted by a pure water vessel which is located within the chamber with an upper open end face to face with the lamp house across the substrate transfer path, and an inert gas feed means which is provided with blow holes to blow an inert gas into the pure water vessel.
- a method for treating substrate surfaces which comprises the steps of: placing a substrate in a mixed atmosphere of an inert gas and water vapor under irradiation of ultraviolet light from a dielectric barrier discharge lamp, thereby splitting water vapor into a reducing active member [H.] and an oxidative active member [.OH]; and letting the reducing and oxidative active members [H.] and [.OH] contact with a surface of said substrate to be treated.
- the method for treating substrate surfaces comprises the steps of: horizontally transferring a substrate into a mixed atmosphere of an inert gas and water vapor under irradiation of ultraviolet light from a dielectric barrier discharge lamp, thereby decomposing organic substances deposited on a surface of the substrate and at the same time splitting water vapor into a reducing active member [H.] and an oxidative active member [.OH]; dry-washing and minimizing contact angle of a surface of the substrate by subjecting the reducing and oxidative active members [H.] and [.OH] to reactions with decomposition products of the organic substances; wet-washing the substrate by supplying a wash liquid thereto; and drying the substrate.
- FIG. 1 is a schematic view of a dielectric barrier discharge lamp assembly used on a substrate processing apparatus according to the present invention
- FIG. 2 is a fragmentary enlarged view of the dielectric barrier discharge lamp assembly shown in FIG. 1;
- FIG. 3 is a schematic sectional view of a substrate processing apparatus, adopted as a first embodiment of the present invention.
- FIG. 4 is a diagrammatic view of an inert gas moisturizer
- FIG. 5 is a schematic view of a substrate processing apparatus, adopted as a second embodiment of the present invention.
- FIG. 6 is a graph, showing results of wettability improving tests using various supply gases to substrates, which were irradiated with ultraviolet light in a standstill state;
- FIG. 7 is a schematic sectional view of a substrate processing apparatus, adopted as a third embodiment of the present invention.
- FIG. 8 is a schematic sectional view of a substrate processing apparatus, adopted as a fifth embodiment of the present invention.
- FIG. 9 is a schematic sectional view of a substrate processing apparatus, adopted as a sixth embodiment of the present invention.
- FIG. 10 is a schematic sectional view of a substrate processing apparatus, adopted as a seventh embodiment of the present invention.
- FIG. 11 is a schematic sectional view of a substrate processing apparatus, adopted as a eighth embodiment of the present invention.
- FIG. 12 is a schematic illustration of a substrate washing and drying line including a drying washing stage.
- FIGS. 1 and 2 schematically shown in FIGS. 1 and 2 is a dielectric barrier discharge lamp assembly (hereinafter referred to simply as ‘discharge lamp’ for brevity) which is employed on substrate processing apparatus according to the present invention.
- discharge lamp for brevity
- the discharge lamp 1 is constituted by a quartz glass tube 4 of an annular shape, having inner and outer tubes 2 and 3 which are both formed of quartz glass and integrally with each other.
- a hermetically closed discharge space 5 Provided internally of the quartz glass tube 4 is a hermetically closed discharge space 5 .
- a metal electrode 6 consisting of a cylindrical metal sheet.
- a metal mesh electrode 7 is provided on the outer periphery of the outer tube 3 .
- An ac power source 7 is connected between the metal electrode 6 and metal mesh electrode 6 .
- a passage for a cooling fluid 11 e.g., cooling water
- a discharge gas is sealed in the quartz glass tube 4 , so that, upon applying an ac high voltage between the metal electrode 6 and the metal mesh electrode 7 , discharge plasma (dielectric barrier discharge) occurs across a dielectric between the inner and outer tubes 2 and 3 , and, by this discharge plasma, atoms of the discharge gas are excited into a plasma discharge state.
- Plasma discharge emission takes place as the discharge gas atoms in the plasma state return to a normal state. At this time, the emission spectrum varies depending upon the nature of the discharge gas which is sealed in the quartz glass tube 4 .
- Xe xenon
- the emission has a center wavelength of 126 nm which is shorter than that of a low-pressure mercury lamp.
- the metal electrode 6 functions as a reflector plate, while the metal mesh electrode 7 functions substantially as a transparent electrode. Therefore, ultraviolet light of short wavelength is irradiated from the side of the outer tube 3 .
- the charged pressure of xenon gas is approximately 350 torr.
- FIG. 3 Schematically illustrated in FIG. 3 is an apparatus for dry-washing transparent substrates of LCD panels by the use of the discharge lamp 1 as described above.
- the substrate 10 is a substrate plate under a dry-washing treatment.
- the substrate 10 consists of a thin plate of glass, semiconductor, synthetic resin, ceramics, metal and so forth, and of a rectangular or circular shape in plan view.
- the substrate 10 is supported on a transfer means, for example, on a roller conveyer 11 and thereby transferred in the direction indicated by an arrow in the same figure while receiving a dry-washing treatment on its surface or surfaces.
- a lamp house 12 of the washing apparatus is located in a predetermined position in the path of transfer by the roller conveyer 11 .
- the lamp house 12 is so positioned as to face the surface or surfaces of the substrate 10 which need a treatment.
- the lamp house 12 is in the form of an enclosure or a container which is open on the lower side, and is internally provided with one or a plural number of discharge lamps 1 (three discharge lamps in the case of the particular embodiment shown).
- the lower end of the lamp house 12 is positioned to face the upper surface of the substrate 10 in non-contacting state with the latter, more particularly, is maintained in small gap relation with the upper surface of the substrate 10 by adjusting a substrate transfer level by the roller conveyer 12 .
- a nitrogen gas feed pipe 13 which supplies the lamp house 12 with nitrogen gas (N 2 gas) as an inert gas in a dry state.
- the lamp house 12 is supplied with a dry nitrogen gas under a predetermined pressure to maintain the inside of the lamp house in an atmosphere free of oxygen.
- This arrangements prevent ultraviolet light from the discharge lamp 1 from attenuating before reaching a proximity of the treating surface of the substrate 10 .
- Indicated at 14 is a chamber for a dry-washing treatment, and the lower end of the lamp house 12 is opened to the chamber 14 , which contains the lower side of the roller conveyer 11 .
- a moistened inert gas feed pipe 15 which supplies the chamber 14 with a moistened inert gas, which is a mixed fluid of water vapor and nitrogen gas.
- the moistened inert gas is supplied under pressure which is slightly lower than the pressure of nitrogen gas which is supplied to the lamp house 12 . Therefore, although the lower end of the lamp house 12 is opened to the chamber 14 , the moistened inert gas would not go into the lamp house 12 .
- the chamber 14 is provided with an entrance opening 14 a at one end for admission of a substrate 10 and with an exit opening 14 b at the other end for a substrate leaving the chamber 14 .
- the chamber 14 is provided with pressure chambers 15 at its opposite ends, that is, on the outer side of the entrance and exit openings 14 a and 14 b , respectively.
- compressed air which is supplied through pipes 17 , the pressures in these pressure chambers 16 are maintained at a level which is slightly higher than the internal pressure of the chamber 14 .
- an exhaust pipe 18 is connected to the chamber 14 , forcibly discharge exhaust gases therethrough to maintain the inside of the chamber 14 constantly at a predetermined pressure level.
- the pressure chambers 16 may be maintained at a negative pressure level by applying suction force to the pipes 17 .
- the pressure chambers 16 are maintained at a negative pressure level, gases in the chamber 14 flow into the pressure chambers 16 through the entrance and exit openings 14 a and 14 b . Therefore, in this case, the pressure chambers 16 and pipes 17 function as an exhaust means, and it becomes unnecessary to connect the exhaust pipe 18 to the chamber 14 .
- the moistened inert gas feed pipe 15 which supplies a mixture of nitrogen gas and steam, is connected to an inert gas moisturizer, which is arranged, for example, as shown in FIG. 4.
- an inert gas moisturizer which is arranged, for example, as shown in FIG. 4.
- indicated at 20 is a nitrogen gas tank as a source of nitrogen gas.
- a feed pipe 21 from the nitrogen gas tank 20 is divided into two branch pipes 21 a and 21 b , of which the branch pipe 21 a is connecting to a mixing container 24 through a flow regulator valve 22 and a flow meter 23 .
- the branch pipe 21 b is connected to and submerged in a pure water tank 27 through a flow regulator valve 25 and a flow meter 26 .
- a submerged portion of the branch pipe 21 b in the pure water tank 27 is provided with a multitude of fine pores for blowing out nitrogen gas. Therefore, nitrogen gas, which is supplied into the pure water tank 27 through the branch pipe 21 b under a predetermined pressure, climbs up in the form of bubbles toward the water surface, generating water vapor on the way. As a result, nitrogen gas is moistened with water vapor, forming a moistened nitrogen gas which can serves as a moistened inert gas.
- the thus-formed moistened nitrogen gas is introduced into the mixing container 24 through a pipe 28 , and mixed with nitrogen gas from the branch pipe 21 a to adjust the water vapor concentration in the moistened inert gas.
- a pressure regulator valve 29 the moistened inert gas is supplied from the mixing container 24 to the moistened inert gas feed pipe 15 which is connected to the chamber 14 as described hereinbefore.
- the moistened nitrogen gas pressure in the chamber 14 can be adjusted by way of the pressure regulator valve 29 .
- the substrate surface with a smaller contact angle shows improved wettability in a subsequent wet washing treatment in a shower, permitting to wash away organic contaminants readily and completely from its surfaces. Accordingly, the substrate 10 can be washed into an extremely clean state.
- the above-described dry-washing treatment may be carried out for the purpose of improving surface conditions of substrates in a stage preparatory to application of a liquid developer or the like.
- the lamp house is connected to the lower chamber. However, for the sake of simplification in construction, it may be arranged, for example, as shown in FIG. 5.
- a lamp house 112 is arranged to completely cover or enshroud discharge lamps 1 .
- the lamp house 112 is provided on the side which faces a substrate 10 .
- the lamp house 112 is provided is with a window 112 a which is fitted with a pane of glass which is highly transmissive of ultraviolet light, such as synthetic quartz glass or the like.
- the inert gas is sealed in the lamp house 112 and not allowed to escape to the outside. Accordingly, in this case, there is no necessity for constantly feeding an inert gas to the lamp house 112 as long as a predetermined amount of inert gas is sealed therein.
- FIG. 6 Shown in FIG. 6 are results of wettability improving experiments using the apparatus of FIG. 5 and changing the nature of a feed gas to the substrate 10 .
- FIG. 6 plotted at a are results of experiments using dry air, at b are results of experiments using moistened air, at c are results of experiments using dry nitrogen gas, and at d are results of experiments using moistened nitrogen gas.
- the same gas can reduce the contact angle more quickly when it is moistened state. Comparing with air, nitrogen gas is more effecting in minimizing the contact angle quickly.
- the processing apparatus includes a lamp house 212 with discharge lamps 1 and a processing chamber 214 for dry-washing or other surface treatment, similarly to the foregoing first embodiment.
- a substrate 10 which is transferred on a roller conveyer 11 is admitted into the changer 214 through an entrance opening 214 a to receive a dry-washing treatment similarly under irradiation of ultraviolet light from the discharge lamps 1 before being further sent forward to a next treating stage through an exit opening 214 b .
- a nitrogen gas feed pipe 213 is connected to the lamp house 212 , while a moistened inert gas feed pipe 215 is connected to the chamber 214 .
- an exhaust pipe 218 is connected to the chamber 214 to forcibly discharge exhaust gases from the chamber 214 .
- a reflector plate 200 is provided within the lamp house 212 .
- the lamp house 212 is divided into a lower room 212 D with the discharge lamps 1 and an upper room 212 U in communication with the nitrogen gas feed pipe 213 .
- the reflector plate 200 itself is divided into a plural number of sections. Void portions in the reflector plate 200 provide dry nitrogen gas flow passages from the upper room 212 U to the lower room 212 D.
- gas flow passages of this sort can be formed by punching slits or holes therein.
- the efficiency of ultraviolet light irradiation can be improved all the more by coating a reflecting film on or mirror-finishing the entire inner wall surfaces of the lamp house 212 .
- the lamp house 212 is partitioned into the upper room 212 U and the lower room 212 D. Accordingly, nitrogen gas which is supplied to the lamp house 212 through the nitrogen gas feed pipe 213 once dwells in the upper room 212 and then flows into the lower room 212 D through the void portions which are provided in a plural number of ditributed positions of the reflector plate 200 . As a consequence, the nitrogen gas flows into every part of the lower room 212 D uniformly in flow rate and pressure.
- the chamber 214 is provided with a partition plate 201 in assocation with the roller conveyer 11 .
- the partition plate 202 is provided with openings to receive top portions of the respective rollers of the roller conveyer 11 which abut against the lower side of the substrate 10 .
- the partition plate 303 itself is kept out of contact with the lower side of the substrate 10 .
- the partition plate 202 functions to suppress pressure fluctuations within the chamber 214 as well as disturbance in the moistened nitrogen gas flow which may otherwise occur as a substrate 10 is admitted into the chamber 214 or sent out of the chamber 214 through the exit opening 214 b.
- FIG. 8 Illustrated in FIG. 8 is a fourth embodiment of the present invention.
- a boundary is provided across an opening at the lower end of the lamp house 212 which is projected into the chamber 214 , drawing a border between a dry nitrogen gas atmosphere in the lamp house 212 and a moistened inert gas atmosphere in the chamber 214 .
- the boundary is formed by the use of a partition plate 202 of a predetermined thickness.
- the partition plate 202 is constituted, for example, by a plate of honeycomb or grid-like structure which contains a multitude of fine passages across its thickness and in its entire surface areas. Further, the partition plate is coated with a reflecting film, including inner surfaces of fine passages.
- the dry nitrogen gas in the lamp house 212 is maintained at a pressure level slightly higher than a gas pressure within the chamber 214 . Therefore, a border is defined between the dry nitrogen gas atmosphere in the lamp house 212 and the moistened inert gas atmosphere in the chamber 214 , and the moistened inert gas in the chamber 214 is prevented from flowing into the lamp house 212 .
- the partition plate 202 is provided with a multitude of fine passage and coated with a reflecting film substantially on its entire surfaces as described hereinbefore, the ultraviolet light rays from the discharge lamps can pass through the fine passages even if the thickness of the partition plate 202 is increased to some extent. The ultraviolt light rays are reflected on inner surfaces of the fine passages and thereby led into the chamber 214 .
- a window pane 202 of an ultraviolet light transmitting material such as quartz glass or the like may be fitted in the lower opening of the lamp house as in a fifth embodiment of the invention shown in FIG. 9.
- dry nitrogen gas is supplied to the lamp house 212 through a nitrogen gas feed pipe 213 , there is no necessity for keeping the supply of dry nitrogen gas because the lamp house 212 is substantially in a closed state.
- pressure chambers may be provided on the outer side of the entrance and exit openings 214 a and 214 b of the chamber 214 in the same manner as in the first embodiment.
- the exhaust pipe 218 is not required in case such pressure chambers are maintained at a negative pressure level.
- FIG. 10 Shown in FIG. 10 is a sixth embodiment of the present invention.
- the processing apparatus is arranged to generate moistened inert gas within a n upper chamber 30 .
- a lamp house 31 with one or a plural number of discharge lamps 1 is provided over the chamber 30 , and the lower end of the lamp house 31 opened to the latter.
- a nitrogen gas feed pipe 32 is connected to an upper portion of the lamp house 31 , supplying dry nitrogen gas under a predetermined pressure to maintain an oxygen-free atmosphere therein.
- the chamber 30 is arranged to circumvent the opening of the lamp house 31 and to extend to the lower side of a roller conveyer 33 which transfers a substrate 10 . Entrance and exit openings 31 a and 31 b for the substrate 10 are opened in upstream and downstream ends of the chamber 30 respectively.
- the chamber 30 is filled with pure water up to a predetermined level to provide a water vessel 34 under the roller conveyer 33 .
- the water vessel 34 is required to constantly supply fresh pure water, and, for this purpose, a water feed pipe 35 and a water discharge pipe 36 are connected to the water vessel 34 .
- the other end of the water feed pipe 35 is connected to a water supply tank 37 which is located at a higher position than the water vessel 34 .
- a nitrogen gas feed pipe which serves as an inert gas feed pipe.
- a fore end portion of this nitrogen gas feed pipe 38 is immersed in pure water in the water vessel 34 over a predetermined length.
- the nitrogen gas feed pipe 38 is provided with a large number of fine blow holes in its immersed fore end portion.
- nitrogen gas is supplied to the nitrogen gas feed pipe 38 under a predetermined pressure, bubbles of nitrogen gas are incessantly generated around the immersed fore end portion of the nitrogen gas feed pipe 38 , and water vapor is generated to moisten the nitrogen gas as the bubbles climb up toward the water surface within the vessel 34 .
- the inner space over the water surface level of the pure water vessel 34 is put in an atmosphere of moistened nitrogen gas which contains water vapor.
- the inside of the lamp house 31 is put in a dry nitrogen gas atmosphere, while the inside of the chamber 30 , except the lamp house 31 , is put in a moistened nitrogen gas atmosphere which conssits of nitrogen gas and water vapor and which is substantially free of oxygen.
- nitrogen gas which is supplied through the nitrogen gas feed pipe 38 , the inside of the lamp house 31 is maintained at a pressure level which is higher than the atomopheric pressure.
- an exhaust pipe 42 which is connected to the chamber 30 , the internal pressure of the chamber 30 is maintained at a level intermediate between the internal pressure of the lamp house 31 and the atmospheric pressure.
- the inside of the lamp house 31 is maintained in a dry state, precluding possibilities of water vapor entering the lamp house 31 .
- the chamber 30 is maintained at a higher pressure level than the atmospheric pressure, there is no possibility of air entering the chamber 30 from outside through entrance and exit openings 31 a and 31 b.
- the chamber 30 can be filled with moistened nitrogen gas which contains both nitrogen gas and water vapor. Accordingly, as the discharge lamps 1 are lit on and a substrate 10 on the roller conveyer 33 is advanced into the chamber 30 , the surface of the substrate 10 is dry-washed by irradiation of short wavelength ultraviolet light from the discharge lamps 1 , which strips and removes organic contaminants from the substrate surfaces, and at the same time treated to have a smaller contact angle.
- the moistened nitrogen gas forms a thin layer on the front surface of the substrate.
- the thickness of the nitrogen gas layer can be adjusted by way of a pressure differential between the lamp house 31 and the chamber 30 .
- the pressure differential can be maintained constantly at a predetermined value by adjusting the control level of the pressure control valve 43 in the nitrogen gas feed pipe 42 which is connected to the chamber 30 , while supplying nitrogen gas to the lamp house 31 through the nitrogen gas feed pipe 32 under a constant pressure.
- the thickness of a layer of the moistened nitrogen gas, i.e., a layer of a mixture of nitrogen gas and water vapor, between the discharge lamps 1 and the substrate 10 is increased to an excessive degree, the absorption of ultraviolet light by the moistened gas layer is increased correspondingly to lessen the effects on the substrate surface.
- the moistened nitrogen gas layer is too thin, the amount of decomposition products becomes smaller. Accordingly, the effciency of dry-washing of substrate surfaces can be enhanced by setting an appropriate control value for the pressure control valve 43 . Similar effects can be attained by controlling the flow rate of nitrogen gas through the nitrogen gas feed pipe 32 along with the flow rate of water vapor-containing nitrogen gas through the exhaust pipe 42 .
- a pane of quartz glass or other ultraviolet light transmitting glass may be fitted in the lower open side of the lamp house 31 thereby to hold an inert gas in the lamp house 31 a sealed state and to prevent its leaks to the outside.
- the lamp house 31 it is desirable for the lamp house 31 to include a function of reflecting back upward components of ultraviolet light toward the substrate. More particularly, a reflector plate 45 is located above the discharge lamps 1 in the case of the embodiment of FIG. 10, while a reflecting film 46 is coated on entire inner surfaces of the lamp house 31 in the case of the embodiment of FIG. 11.
- FIG. 12 indicated at 50 is the above-described dry-washing stage, which in this particular case is followed by a wet-washing stage 51 and a drying stage 52 to clean up the surface of each substrate 10 completely.
- a drying system suitable for use in the drying stage 52 there may be employed, for example, a spin-drier or an air knife drier which is provided with an air knife nozzle 52 a as shown in the drawing for drying substrates by air knife effects.
- a spin-drier or an air knife drier which is provided with an air knife nozzle 52 a as shown in the drawing for drying substrates by air knife effects.
- the dry-washing may be carried out in a stage subsequent to the wet-washing and drying stages.
- the dry-washing is carried out as a pretreatment prior to application of a liquid developer, firstly contaminant substances are removed from surface of a substrate 10 by wet-washing and then once dried before sending the substrate to dry-washing to improve its surface conditions, particularly, to improve its contact angle.
- the dry-washing treatment makes it possible to apply a liquid developer or the like uniformly on the substrate surface in a subsequent stage.
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Abstract
A lamp house is located face to face with a substrate which is transferred by a conveyer means. A dielectric barrier discharge lamp is provided in the lamp house to irradiate the substrate with ultraviolet light, while a moistened inert gas, consisting of an inert gas and water vapor, is supplied to a space between the substrate and the dielectric barrier discharge lamp from a moistened inert gas generating means. Under irradiation of ultraviolet light from the dielectric barrier discharge lamp, water vapor in the moistened inert gas is split into a reducing active member [H.] and an oxidative active member [.OH].
Description
- 1. Field of the Art
- This invention relates to a method and an apparatus for treating surfaces of substrates such as of LCD panels, semiconductor wafers, magnetic storage disks and optical storage disks which are formed of glass, semiconductor, synthetic resin, ceramics, metals or a composite material of these materials, and more particularly to a method and an apparatus for treating substrate surfaces by irradiation of ultraviolet light in a washing or etching stage of a fabrication process.
- 2. Prior Art
- For instance, a circuit pattern including transparent electrodes is formed on a TFT substrate which constitutes a transparent substrate of an LCD panel by the use of a film-forming means. In suc a substrate fabrication process, surfaces of substrates are processed by washing and etching treatments. In a processing of this sort, it has been the general practice to employ a wet process in which treating liquids are applied or injected on substrate surfaces. However, recently the so-call dry processes are introduced into this field, carrying out washing and etching treatments by irradiation of ultraviolet light.
- For example, Japanese Laid-Open Patent Application H5-224167 discloses a method of washing glass substrates of LCD panel. In this case, substrates are irradiated with ultraviolet light prior to starting a wet process using a washing liquid. In this known washing method, substrate surfaces are irradiated with ultraviolet light from a low-pressure mercury lamp in a preparatory stage leading to a washing stage. By irradiation of ultraviolet light, organic substances on the substrate surfaces are chemically removed, and at the same time wettability of substrate surfaces is improved to have a smaller contact angle for removing inorganic contaminants efficiently when subsequently washed in a shower or the like. In this regard, ultraviolet light from a low-pressure mercury lamp has peaks approximately at 185 nm and 254 nm in wavelength distribution. Ultraviolet light with such wavelength distribution characteristics can remove organic substances which have deposited on substrate surfaces.
- The mechanism of washing off organic substances by ultraviolet irradiation includes decomposition of organic substances into products of low molecular weights by severing chemical bonds, and activation of decomposed products. In addition, simultaneously ozone is produced as a result of absorption of ultraviolet light by oxygen in the air, and ozone is converted into active oxygen. Therefore, through oxidative destructive reactions with active oxygen, activated organic contaminants are finally converted into volatile substances such as COx, H2O, NOx are released into the air, that is, removed from substrate surfaces.
- As mentioned hereinbefore, ultraviolet light which is irradiated from a low-pressure mercury lamp has a wavelength of 185 nm on the shorter side. Therefore, of various organic compounds which have deposited on substrate surfaces, the ultraviolet light may not be able to decompose those compounds which have chemical bonds of strong energy like double bonds. This means that ultraviolet light of shorter wavelengths should be employed, in order to wash substrates more completely.
- In an attempt to solve this problem, proposed in Japanese Laid-Open Patent Specification H7-196303 is a method of dry-washing work, irradiating substrate surfaces with vacuum ultraviolet light from a dielectric barrier discharge lamp.
- In the case of this washing method according to Japanese Laid-Open Patent Specification H7-196303, in removing organic contaminants which have deposited on substrate surfaces, active oxidative decomposition products are produced by chemical reaction with ultraviolet light rays in vacuum. Namely, in this case, ultraviolet light rays of 172 nm which are irradiated from a dielectric barrier discharge lamp decompose organic substances into products of low molecular weight by destructing chemical bonds in the organic substances, while at the same time activating the decomposition products. At the same time, oxygen in the air is decomposed and activated by the action of the ultraviolet light. Therefore, the activated organic substances are converted into volatile substances such as COx, H2O, NOx and so forth by oxidative reactions with active oxygen and ultimately released into the air. As a result, the treated substrate surfaces come to have a smaller contact angle in terms of wettability.
- However, since ultraviolet light is consumed for cracking oxygen in the air, an air layer between the discharge lamp and a substrate is increased in thickness to cause an exponential attenuation to the amount of ultraviolet light rays which can reach a substrate surface. Consequently, there occur conspicuous degradations in the capacities of activating organic substances on substrate surfaces and producing active oxygen in the vicinity of substrate surfaces, that is, in the capacity of removing contaminant organic substances by ultraviolet light. Besides, it is only active oxidative decomposition products that are produced by irradiation of an oxygen-containing fluid with ultraviolet light in vacuum. Therefore, depending upon the kinds of organic substances which have deposited on substrate surfaces, it is often found difficult to remove deposited organic contaminants from substrate surfaces simply by oxidative reactions.
- In view of the foregoing situations, it is an object of the present invention to enhance the accuracy and efficiency in washing or treating substrate surfaces with ultraviolet light rays. It is a more specific object of the present invention to enhance decomposing effects on organic contaminant substances on substrate surfaces while at the same time minimizing the contact angle of substrate surfaces by irradiating same with ultraviolet light in an atmosphere substantially free of oxygen.
- It is another object of the present invention to provide a method and an apparatus for producing an oxidative active member and a reducing active member by irradiating substrate surfaces with ultraviolet light rays in a mixed atmosphere of an inert gas and, thereby ensuring reactions with decomposition products of organic substances to proceed efficiently in an assured manner.
- In accordance with the present invention, for achieving the above-stated objectives, there is provided an apparatus for treating substrate surfaces, which comprises: a lamp house located over a substrate transfer path and face to face with a treating surface of a substrate being transferred along the transfer path by a conveyer means; a dielectric barrier discharge lamp fixedly mounted in the lamp house to irradiate ultravilot light toward the substrate; and a moistened inert gas generating means adapted to supply a water vapor-containing moistened inert gas to a space between the substrate and the dielectric barrier discharge lamp; producing a reducing active member [H.] and an oxidative active member [.OH] by irradiating said moistened inert gas with ultraviolet light from said dielectric barrier discharge lamp.
- The lamp house may be arranged to have an ultraviolet light transmitting window on the side which faces a substrate under treatment. Alternatively, in a case where the lamp house is provided within a chamber, it may be opened to the chamber on the side which faces a substrate. In such a case, an inert gas feed means is connected to the lamp house to put the latter in an inert gas atmosphere. The chamber is put in a moistened inert gas atmosphere which is substantially free of oxygen, between entrance and exit openings which are provided at upstream and downstream ends for substrates to be treated. Alternatively, the lamp house may left open on the side of the chamber, or may be fitted with such a partition member on the open side as will transmit ultraviolt light and contain a large number of passages to let the inert gas flow out.
- In another form of the present invention, the lamp house is located in and opned to the chamber, and an inert gas feed means is connected to the lamp house. Further, the moistened inert gas generating means may be arranged to include a moistened inert gas feed means which is connected to the chamber to supply a water vapor-containing moistened inert gas toward the surface of a substrate.
- Alternatively, the moistened inert gas generating means may be constituted by a pure water vessel which is located within the chamber with an upper open end face to face with the lamp house across the substrate transfer path, and an inert gas feed means which is provided with blow holes to blow an inert gas into the pure water vessel.
- On the other hand, according to the present invention, there is also provided a method for treating substrate surfaces, which comprises the steps of: placing a substrate in a mixed atmosphere of an inert gas and water vapor under irradiation of ultraviolet light from a dielectric barrier discharge lamp, thereby splitting water vapor into a reducing active member [H.] and an oxidative active member [.OH]; and letting the reducing and oxidative active members [H.] and [.OH] contact with a surface of said substrate to be treated.
- According to a more specific form of the present invention, the method for treating substrate surfaces comprises the steps of: horizontally transferring a substrate into a mixed atmosphere of an inert gas and water vapor under irradiation of ultraviolet light from a dielectric barrier discharge lamp, thereby decomposing organic substances deposited on a surface of the substrate and at the same time splitting water vapor into a reducing active member [H.] and an oxidative active member [.OH]; dry-washing and minimizing contact angle of a surface of the substrate by subjecting the reducing and oxidative active members [H.] and [.OH] to reactions with decomposition products of the organic substances; wet-washing the substrate by supplying a wash liquid thereto; and drying the substrate.
- The above and other objects, features and advantages of the present invention will become apparent from the following particular description of the invention, taken in conjunction with the accompanying drawings. Needless to say, the accompanying drawings show by way of example some preferred embodiments of the present invention for illustrative purposes only, and should not be construed as being limitative of the invention in any way whatsoever.
- In the accompanying drawings:
- FIG. 1 is a schematic view of a dielectric barrier discharge lamp assembly used on a substrate processing apparatus according to the present invention;
- FIG. 2 is a fragmentary enlarged view of the dielectric barrier discharge lamp assembly shown in FIG. 1;
- FIG. 3 is a schematic sectional view of a substrate processing apparatus, adopted as a first embodiment of the present invention;
- FIG. 4 is a diagrammatic view of an inert gas moisturizer;
- FIG. 5 is a schematic view of a substrate processing apparatus, adopted as a second embodiment of the present invention;
- FIG. 6 is a graph, showing results of wettability improving tests using various supply gases to substrates, which were irradiated with ultraviolet light in a standstill state;
- FIG. 7 is a schematic sectional view of a substrate processing apparatus, adopted as a third embodiment of the present invention;
- FIG. 8 is a schematic sectional view of a substrate processing apparatus, adopted as a fifth embodiment of the present invention;
- FIG. 9 is a schematic sectional view of a substrate processing apparatus, adopted as a sixth embodiment of the present invention;
- FIG. 10 is a schematic sectional view of a substrate processing apparatus, adopted as a seventh embodiment of the present invention;
- FIG. 11 is a schematic sectional view of a substrate processing apparatus, adopted as a eighth embodiment of the present invention; and
- FIG. 12 is a schematic illustration of a substrate washing and drying line including a drying washing stage.
- Hereafter, the present invention is described more particularly by way of its preferred embodiments shown in the drawings. Firstly, schematically shown in FIGS. 1 and 2 is a dielectric barrier discharge lamp assembly (hereinafter referred to simply as ‘discharge lamp’ for brevity) which is employed on substrate processing apparatus according to the present invention.
- In these figures, indicated at1 is the discharge lamp. The
discharge lamp 1 is constituted by aquartz glass tube 4 of an annular shape, having inner andouter tubes quartz glass tube 4 is a hermetically closeddischarge space 5. Securely fixed to the inner side of theinner tube 2 is ametal electrode 6 consisting of a cylindrical metal sheet. On the other hand, provided on the outer periphery of theouter tube 3 is ametal mesh electrode 7. Anac power source 7 is connected between themetal electrode 6 andmetal mesh electrode 6. Further, a passage for a cooling fluid 11 (e.g., cooling water) is provided on the inner side of theinner tube 2 for cooling themetal electrode 6. - A discharge gas is sealed in the
quartz glass tube 4, so that, upon applying an ac high voltage between themetal electrode 6 and themetal mesh electrode 7, discharge plasma (dielectric barrier discharge) occurs across a dielectric between the inner andouter tubes quartz glass tube 4. In the case of a xenon (Xe) gas, for example, monochrome light having a center wavelength at 172 nm is emitted. In a case where argon (Ar) gas is used as a discharge gas, the emission has a center wavelength of 126 nm which is shorter than that of a low-pressure mercury lamp. Themetal electrode 6 functions as a reflector plate, while themetal mesh electrode 7 functions substantially as a transparent electrode. Therefore, ultraviolet light of short wavelength is irradiated from the side of theouter tube 3. In this instance, for example, the charged pressure of xenon gas is approximately 350 torr. - Schematically illustrated in FIG. 3 is an apparatus for dry-washing transparent substrates of LCD panels by the use of the
discharge lamp 1 as described above. In this figure, indicated at 10 is a substrate plate under a dry-washing treatment. For example, thesubstrate 10 consists of a thin plate of glass, semiconductor, synthetic resin, ceramics, metal and so forth, and of a rectangular or circular shape in plan view. Thesubstrate 10 is supported on a transfer means, for example, on aroller conveyer 11 and thereby transferred in the direction indicated by an arrow in the same figure while receiving a dry-washing treatment on its surface or surfaces. For this purpose, alamp house 12 of the washing apparatus is located in a predetermined position in the path of transfer by theroller conveyer 11. Thelamp house 12 is so positioned as to face the surface or surfaces of thesubstrate 10 which need a treatment. - The
lamp house 12 is in the form of an enclosure or a container which is open on the lower side, and is internally provided with one or a plural number of discharge lamps 1 (three discharge lamps in the case of the particular embodiment shown). In this instance, the lower end of thelamp house 12 is positioned to face the upper surface of thesubstrate 10 in non-contacting state with the latter, more particularly, is maintained in small gap relation with the upper surface of thesubstrate 10 by adjusting a substrate transfer level by theroller conveyer 12. Connected to thelamp house 12 is a nitrogengas feed pipe 13 which supplies thelamp house 12 with nitrogen gas (N2 gas) as an inert gas in a dry state. Namely, thelamp house 12 is supplied with a dry nitrogen gas under a predetermined pressure to maintain the inside of the lamp house in an atmosphere free of oxygen. This arrangements prevent ultraviolet light from thedischarge lamp 1 from attenuating before reaching a proximity of the treating surface of thesubstrate 10. - Indicated at14 is a chamber for a dry-washing treatment, and the lower end of the
lamp house 12 is opened to thechamber 14, which contains the lower side of theroller conveyer 11. Connected to thechamber 14 is a moistened inertgas feed pipe 15 which supplies thechamber 14 with a moistened inert gas, which is a mixed fluid of water vapor and nitrogen gas. The moistened inert gas is supplied under pressure which is slightly lower than the pressure of nitrogen gas which is supplied to thelamp house 12. Therefore, although the lower end of thelamp house 12 is opened to thechamber 14, the moistened inert gas would not go into thelamp house 12. - Further, the
chamber 14 is provided with an entrance opening 14 a at one end for admission of asubstrate 10 and with anexit opening 14 b at the other end for a substrate leaving thechamber 14. In order to prevent the nitrogen gas and the moistened inert gas from escaping through the entrance andexit openings chamber 14 is provided withpressure chambers 15 at its opposite ends, that is, on the outer side of the entrance andexit openings pipes 17, the pressures in thesepressure chambers 16 are maintained at a level which is slightly higher than the internal pressure of thechamber 14. Further, anexhaust pipe 18 is connected to thechamber 14, forcibly discharge exhaust gases therethrough to maintain the inside of thechamber 14 constantly at a predetermined pressure level. - Alternatively, instead of supplying compressed air, the
pressure chambers 16 may be maintained at a negative pressure level by applying suction force to thepipes 17. In case thepressure chambers 16 are maintained at a negative pressure level, gases in thechamber 14 flow into thepressure chambers 16 through the entrance andexit openings pressure chambers 16 andpipes 17 function as an exhaust means, and it becomes unnecessary to connect theexhaust pipe 18 to thechamber 14. - The moistened inert
gas feed pipe 15, which supplies a mixture of nitrogen gas and steam, is connected to an inert gas moisturizer, which is arranged, for example, as shown in FIG. 4. In this figure, indicated at 20 is a nitrogen gas tank as a source of nitrogen gas. Afeed pipe 21 from thenitrogen gas tank 20 is divided into twobranch pipes branch pipe 21 a is connecting to a mixingcontainer 24 through aflow regulator valve 22 and aflow meter 23. - On the other hand, the
branch pipe 21 b is connected to and submerged in apure water tank 27 through aflow regulator valve 25 and aflow meter 26. A submerged portion of thebranch pipe 21 b in thepure water tank 27 is provided with a multitude of fine pores for blowing out nitrogen gas. Therefore, nitrogen gas, which is supplied into thepure water tank 27 through thebranch pipe 21 b under a predetermined pressure, climbs up in the form of bubbles toward the water surface, generating water vapor on the way. As a result, nitrogen gas is moistened with water vapor, forming a moistened nitrogen gas which can serves as a moistened inert gas. The thus-formed moistened nitrogen gas is introduced into the mixingcontainer 24 through apipe 28, and mixed with nitrogen gas from thebranch pipe 21 a to adjust the water vapor concentration in the moistened inert gas. Through apressure regulator valve 29, the moistened inert gas is supplied from the mixingcontainer 24 to the moistened inertgas feed pipe 15 which is connected to thechamber 14 as described hereinbefore. Thus, the moistened nitrogen gas pressure in thechamber 14 can be adjusted by way of thepressure regulator valve 29. - With the arrangements arranged as described above, dry nitrogen gas is fed to the
lamp house 12 of the processing apparatus having thedischarge lamp 1 lit on, while moistened nitrogen gas filled in thechamber 14 to provide an atmosphere substantially free of oxygen. In this state, asubstrate 10 on the roller conveyer 11 (having a plural number of rollers mounted on rotational shafts at predetermined intervals in the substrate transfer direction) is fed into thechamber 14 through the entrance opening 14 a and passed through thechamber 14 under thelamp house 12 at a predetermined speed. While passing through thechamber 14, the surface of thesubstrate 10 is irradiated with short wavelength ultraviolet light from thedischarge lamp 1 for dry-washing and improving wettability of the substrate surface. - At this time, a mixed fluid of nitrogen gas and water exists on or in the vicinity of the substrate surface, and water is cracked under irradiation of ultraviolet light from the
discharge lamp 1 into a reducing active member [H.] and an oxidative active member [.OH]. Accordingly, by irradiation of short wavelength ultraviolet light, organic contaminants which have deposited on the surface of thesubstrate 10 are decomposed into products of lower molecular weights. Further, the low molecular weight products resulting from the decomposition of organic contaminants are subjected to reducing and oxidative reactions with the cracked active members of water. More specifically, not only oxidative reactions with the oxidative active member [.OH] but also reducing reactions with reducing active member [H.] take place on or in the vicinity of the surface of thesubstrate 10 to convert decomposed organic substances into volatile substances quickly in a more assured manner, and the resulting volatile substances are released to the outside through theexhaust pipe 18. As a result of this dry washing treatment, organic contaminants are removed from the surface of thesubstrate 10. Besides, the substrate surface becomes to have a smaller contact angle as a result of irradiation of short wavelength ultraviolet light in the presence of water vapor. - In this manner, the substrate surface with a smaller contact angle shows improved wettability in a subsequent wet washing treatment in a shower, permitting to wash away organic contaminants readily and completely from its surfaces. Accordingly, the
substrate 10 can be washed into an extremely clean state. The above-described dry-washing treatment may be carried out for the purpose of improving surface conditions of substrates in a stage preparatory to application of a liquid developer or the like. - In the case of the first embodiment described above, the lamp house is connected to the lower chamber. However, for the sake of simplification in construction, it may be arranged, for example, as shown in FIG. 5. In the embodiment of FIG. 5, a
lamp house 112 is arranged to completely cover or enshrouddischarge lamps 1. In this case, on the side which faces asubstrate 10, thelamp house 112 is provided is with awindow 112 a which is fitted with a pane of glass which is highly transmissive of ultraviolet light, such as synthetic quartz glass or the like. With thelamp house 112 of this construction, the inert gas is sealed in thelamp house 112 and not allowed to escape to the outside. Accordingly, in this case, there is no necessity for constantly feeding an inert gas to thelamp house 112 as long as a predetermined amount of inert gas is sealed therein. - Shown in FIG. 6 are results of wettability improving experiments using the apparatus of FIG. 5 and changing the nature of a feed gas to the
substrate 10. - In the experiments, dry air, moistened air containing water vapor, dry nitrogen gas and moistened nitrogen gas containing water vapor were used as a feed gas. The apparatus of FIG. 4 was used for moistened air and for moistened nitrogen gas, preparing a moistened gas by connecting to a pure water tank a pipe of 5 mm in inside diameter having 10 pores of 1 mm in diameter in its submerged fore end portions. Produced moistened gas was mixed with a dry gas in a ratio of 1:1. When a
substrate 10 came to a position under thelamp house 12, theroller conveyer 11 was stopped for a treatment. The results of experiments are shown in FIG. 6. - In FIG. 6, plotted at a are results of experiments using dry air, at b are results of experiments using moistened air, at c are results of experiments using dry nitrogen gas, and at d are results of experiments using moistened nitrogen gas. As seen in this figure, as compared with effects in a dry state, the same gas can reduce the contact angle more quickly when it is moistened state. Comparing with air, nitrogen gas is more effecting in minimizing the contact angle quickly. When actually washing
substrates 10, the transfer speed of thesubstrates 10 by theroller conveyer 11 is determined depending upon the size of thelamp house 12. For example, in a process using moistened nitrogen gas and alamp house 12 measuring 450 mm in length in the substrate transfer direction, it suffices to transfer substrates at a speed of 30 mm/sec and to irradiate same with ultraviolet light for a time duration of approximately 15 seconds to attain an initial objective of the treatment. - The results of experiments show that the wettability can be improved more quickly and in an assured manner particularly when moistened nitrogen gas is feed to a
substrate 10. In addition, organic contaminants on substrate surfaces can be decomposed smoothly and reliably into volatile forms not only through oxidative reactions but also through reducing reactions. Accordingly, it is most advantageous in a case wheresubstrates 10 need to be processed on an industrial scale. Whilesubstrates 10 are sent into thechamber 14 successively at a predetermined speed, the water vapor in the moistened nitrogen gas is constantly maintained in a floating state within the entire inner space of thechamber 14. Threfore, the substrates as a whole can be wahsed clean and improved in wettability effciently in an assured manner. - Now, turning to FIG. 7, there is shown a third embodiment of the present invention. In this particularly embodiment, the processing apparatus includes a
lamp house 212 withdischarge lamps 1 and aprocessing chamber 214 for dry-washing or other surface treatment, similarly to the foregoing first embodiment. Asubstrate 10 which is transferred on aroller conveyer 11 is admitted into thechanger 214 through an entrance opening 214 a to receive a dry-washing treatment similarly under irradiation of ultraviolet light from thedischarge lamps 1 before being further sent forward to a next treating stage through anexit opening 214 b. A nitrogengas feed pipe 213 is connected to thelamp house 212, while a moistened inertgas feed pipe 215 is connected to thechamber 214. Further, anexhaust pipe 218 is connected to thechamber 214 to forcibly discharge exhaust gases from thechamber 214. These arrangements are substantially same as in the foregoing first embodiment. - In this case, however, a
reflector plate 200 is provided within thelamp house 212. By thereflector plates 200, thelamp house 212 is divided into alower room 212D with thedischarge lamps 1 and anupper room 212U in communication with the nitrogengas feed pipe 213. Thereflector plate 200 itself is divided into a plural number of sections. Void portions in thereflector plate 200 provide dry nitrogen gas flow passages from theupper room 212U to thelower room 212D. In case thereflector plate 200 is constituted by a single undivided body, gas flow passages of this sort can be formed by punching slits or holes therein. - The lower side of the
reflector plate 200 on the side of thelower room 212D is mirror-finished or coated with a reflecting film to provide a total reflection surface. Therefore, of the ultraviolet light which is emitted from thedischarge lamps 1, upward components are substantially totally reflected off thereflector plate 200 in downward directions to irradiate thesubstrate 10. The void portions in thereflector plate 200, that is, the dry nitrogen gas flow passages are located substantially immediately above thedischarge lamps 1. Naemly, thereflector plate 200 does not exist immediately above thedischarge lamps 1 because reflected ultraviolet light from these positions would be blocked by thedischarge lamps 1 without reaching thesubstrate 10. It follows that almost all of the ultraviolet light, which is irradiated by thedischarge lamps 1, contributes to the dry-washing of thesubstrate 10 without losses. In this regard, if desired, the efficiency of ultraviolet light irradiation can be improved all the more by coating a reflecting film on or mirror-finishing the entire inner wall surfaces of thelamp house 212. - Further, by the
reflector plate 200, thelamp house 212 is partitioned into theupper room 212U and thelower room 212D. Accordingly, nitrogen gas which is supplied to thelamp house 212 through the nitrogengas feed pipe 213 once dwells in theupper room 212 and then flows into thelower room 212D through the void portions which are provided in a plural number of ditributed positions of thereflector plate 200. As a consequence, the nitrogen gas flows into every part of thelower room 212D uniformly in flow rate and pressure. Especially, since a reflector plate portion which contains no void gap is located beneath the inlet opening of the nitrogengas feed pipe 213, nitrogen gas from a single feed pipe is distributed uniformly to the entire space of thelower room 212D of thelamp house 212. - Further, the
chamber 214 is provided with apartition plate 201 in assocation with theroller conveyer 11. Thepartition plate 202 is provided with openings to receive top portions of the respective rollers of theroller conveyer 11 which abut against the lower side of thesubstrate 10. However, the partition plate 303 itself is kept out of contact with the lower side of thesubstrate 10. Thepartition plate 202 functions to suppress pressure fluctuations within thechamber 214 as well as disturbance in the moistened nitrogen gas flow which may otherwise occur as asubstrate 10 is admitted into thechamber 214 or sent out of thechamber 214 through theexit opening 214 b. - In this instance, the
partition plate 202 can be arranged to function also as a plate heater. If so arranged, eachsubstrate 10 which is transferred by theroller conveyer 11 can be heated in thechamber 214 for the purpose of enhancing the efficiency and capacity of the dry-washing treatment all the more. - Illustrated in FIG. 8 is a fourth embodiment of the present invention. In this embodiment, a boundary is provided across an opening at the lower end of the
lamp house 212 which is projected into thechamber 214, drawing a border between a dry nitrogen gas atmosphere in thelamp house 212 and a moistened inert gas atmosphere in thechamber 214. The boundary is formed by the use of apartition plate 202 of a predetermined thickness. Thepartition plate 202 is constituted, for example, by a plate of honeycomb or grid-like structure which contains a multitude of fine passages across its thickness and in its entire surface areas. Further, the partition plate is coated with a reflecting film, including inner surfaces of fine passages. - In this case, the dry nitrogen gas in the
lamp house 212 is maintained at a pressure level slightly higher than a gas pressure within thechamber 214. Therefore, a border is defined between the dry nitrogen gas atmosphere in thelamp house 212 and the moistened inert gas atmosphere in thechamber 214, and the moistened inert gas in thechamber 214 is prevented from flowing into thelamp house 212. Besides, thepartition plate 202 is provided with a multitude of fine passage and coated with a reflecting film substantially on its entire surfaces as described hereinbefore, the ultraviolet light rays from the discharge lamps can pass through the fine passages even if the thickness of thepartition plate 202 is increased to some extent. The ultraviolt light rays are reflected on inner surfaces of the fine passages and thereby led into thechamber 214. - Furthermore, in place of the above-described partition plate, a
window pane 202 of an ultraviolet light transmitting material such as quartz glass or the like may be fitted in the lower opening of the lamp house as in a fifth embodiment of the invention shown in FIG. 9. In this case, although dry nitrogen gas is supplied to thelamp house 212 through a nitrogengas feed pipe 213, there is no necessity for keeping the supply of dry nitrogen gas because thelamp house 212 is substantially in a closed state. - Any way, in the foregoing second to fifth embodiments, pressure chambers may be provided on the outer side of the entrance and
exit openings chamber 214 in the same manner as in the first embodiment. Theexhaust pipe 218 is not required in case such pressure chambers are maintained at a negative pressure level. - Shown in FIG. 10 is a sixth embodiment of the present invention. In this embodiment, the processing apparatus is arranged to generate moistened inert gas within a n
upper chamber 30. In a manner similar to the foregoing first embodiment, alamp house 31 with one or a plural number ofdischarge lamps 1 is provided over thechamber 30, and the lower end of thelamp house 31 opened to the latter. Further, a nitrogengas feed pipe 32 is connected to an upper portion of thelamp house 31, supplying dry nitrogen gas under a predetermined pressure to maintain an oxygen-free atmosphere therein. - The
chamber 30 is arranged to circumvent the opening of thelamp house 31 and to extend to the lower side of aroller conveyer 33 which transfers asubstrate 10. Entrance andexit openings 31 a and 31 b for thesubstrate 10 are opened in upstream and downstream ends of thechamber 30 respectively. Thechamber 30 is filled with pure water up to a predetermined level to provide awater vessel 34 under theroller conveyer 33. In addition to simply holding water, thewater vessel 34 is required to constantly supply fresh pure water, and, for this purpose, awater feed pipe 35 and awater discharge pipe 36 are connected to thewater vessel 34. The other end of thewater feed pipe 35 is connected to awater supply tank 37 which is located at a higher position than thewater vessel 34. Accordingly, pure water is supplied to thewater vessel 34 under pressure of water head. Thewater discharge pipe 36 is opened into thetank 34 at a position of a predetermined level, so that water in thevessel 34 is allowed to overflow into thewater discharge pipe 36 as soon as the water level rises up to the position of thewater discharge pipe 36. Accordingly, the water surface level in thevessel 34 is maintained constantly at a predetermined height. - In the drawing, indicated at38 is a nitrogen gas feed pipe which serves as an inert gas feed pipe. A fore end portion of this nitrogen
gas feed pipe 38 is immersed in pure water in thewater vessel 34 over a predetermined length. The nitrogengas feed pipe 38 is provided with a large number of fine blow holes in its immersed fore end portion. As nitrogen gas is supplied to the nitrogengas feed pipe 38 under a predetermined pressure, bubbles of nitrogen gas are incessantly generated around the immersed fore end portion of the nitrogengas feed pipe 38, and water vapor is generated to moisten the nitrogen gas as the bubbles climb up toward the water surface within thevessel 34. As a result, the inner space over the water surface level of thepure water vessel 34 is put in an atmosphere of moistened nitrogen gas which contains water vapor. - Nitrogen gas may be supplied to the nitrogen
gas feed pipe 38 from a bomb or steel bottle. However, in the case of the embodiment shown in FIG. 10, nitrogen gas is supplied from inside of thechamber 30. For this purpose, a circulatingpipe 40 is connected to a wall portion of thechamber 30. The other end of the circulatingpipe 40 is connected to apump 41 the delivering side of which is connected to the nitrogengas feed pipe 38. Accordingly, upon actuating thepump 41, nitrogen gas in thechamber 30 is taken up into the circulatingpipe 40 and supplied to the nitrogengas feed pipe 38. Further, connected to thechamber 30 is anexhaust pipe 42 which is provided with apressure control valve 43 within its length. Therefore, as soon as the internal pressure of thechamber 30 exceeds a preset value, excessive nitrogen gas in thechamber 30 is discharged through theexhaust pipe 42 to maintain thechamber 30 constantly at a predetermined pressure level. - With these arrangements, the inside of the
lamp house 31 is put in a dry nitrogen gas atmosphere, while the inside of thechamber 30, except thelamp house 31, is put in a moistened nitrogen gas atmosphere which conssits of nitrogen gas and water vapor and which is substantially free of oxygen. By nitrogen gas which is supplied through the nitrogengas feed pipe 38, the inside of thelamp house 31 is maintained at a pressure level which is higher than the atomopheric pressure. However, by way of anexhaust pipe 42 which is connected to thechamber 30, the internal pressure of thechamber 30 is maintained at a level intermediate between the internal pressure of thelamp house 31 and the atmospheric pressure. As a consequence, due to constant gas flows from thelamp house 31 into thechamber 30, the inside of thelamp house 31 is maintained in a dry state, precluding possibilities of water vapor entering thelamp house 31. On the other hand, thechamber 30 is maintained at a higher pressure level than the atmospheric pressure, there is no possibility of air entering thechamber 30 from outside through entrance andexit openings 31 a and 31 b. - With the arrangements just described, the
chamber 30 can be filled with moistened nitrogen gas which contains both nitrogen gas and water vapor. Accordingly, as thedischarge lamps 1 are lit on and asubstrate 10 on theroller conveyer 33 is advanced into thechamber 30, the surface of thesubstrate 10 is dry-washed by irradiation of short wavelength ultraviolet light from thedischarge lamps 1, which strips and removes organic contaminants from the substrate surfaces, and at the same time treated to have a smaller contact angle. - In this instance, when the
substrate 10 comes face to face with thelamp house 31, the moistened nitrogen gas forms a thin layer on the front surface of the substrate. The thickness of the nitrogen gas layer can be adjusted by way of a pressure differential between thelamp house 31 and thechamber 30. In this regard, the pressure differential can be maintained constantly at a predetermined value by adjusting the control level of thepressure control valve 43 in the nitrogengas feed pipe 42 which is connected to thechamber 30, while supplying nitrogen gas to thelamp house 31 through the nitrogengas feed pipe 32 under a constant pressure. - If the thickness of a layer of the moistened nitrogen gas, i.e., a layer of a mixture of nitrogen gas and water vapor, between the
discharge lamps 1 and thesubstrate 10 is increased to an excessive degree, the absorption of ultraviolet light by the moistened gas layer is increased correspondingly to lessen the effects on the substrate surface. On the contrary, in case the moistened nitrogen gas layer is too thin, the amount of decomposition products becomes smaller. Accordingly, the effciency of dry-washing of substrate surfaces can be enhanced by setting an appropriate control value for thepressure control valve 43. Similar effects can be attained by controlling the flow rate of nitrogen gas through the nitrogengas feed pipe 32 along with the flow rate of water vapor-containing nitrogen gas through theexhaust pipe 42. - In this instance, as shown in FIG. 11, a pane of quartz glass or other ultraviolet light transmitting glass may be fitted in the lower open side of the
lamp house 31 thereby to hold an inert gas in the lamp house 31 a sealed state and to prevent its leaks to the outside. - Further, also in the case of the sixth embodiment shown in FIG. 10 and the seventh embodiment shown in FIG. 11, it is desirable for the
lamp house 31 to include a function of reflecting back upward components of ultraviolet light toward the substrate. More particularly, areflector plate 45 is located above thedischarge lamps 1 in the case of the embodiment of FIG. 10, while a reflectingfilm 46 is coated on entire inner surfaces of thelamp house 31 in the case of the embodiment of FIG. 11. - As described hereinbefore, no matter whether moistened inert gas is supplied to the lamp house or it is generated within the lamp house, organic contaminants are removed from an irradiated surface of a
substrate 10 and at the same time the contact angle of the substrate surface is minimized by a dry-washing treatment in the apparatus shown in the first to seventh embodiments of the invention. After a dry-washing treatment, thesubstrate 10 is further processed as schematically shown in FIG. 12. - In FIG. 12, indicated at50 is the above-described dry-washing stage, which in this particular case is followed by a wet-
washing stage 51 and a dryingstage 52 to clean up the surface of eachsubstrate 10 completely. - In the wet-
washing stage 51, inorganic contaminants on the surface of asubstrate 10 are removed by a shower of ultrasonically vibrated pure water which is spurted out from ashower unit 51 a. In this regard, the wet-dryingstage 51 may be arranged to include a wet-washing treatment other than wet-washing in a pure water shower, for example, a treatment such as scrubbing by the use of brushes or dipping in an ultrasound water bath singly or in combination. By the end of the wet-washing operation, organic as well as inorganic contaminants are almost completely removed from the surface of thesubstrate 10 to bring the latter to an extremely clean state. Further, as for a drying system suitable for use in the dryingstage 52, there may be employed, for example, a spin-drier or an air knife drier which is provided with anair knife nozzle 52 a as shown in the drawing for drying substrates by air knife effects. Thus,substrates 10 are washed and dried completely through the processing line as described above. - Alternatively, the dry-washing may be carried out in a stage subsequent to the wet-washing and drying stages. For instance, in a case where the dry-washing is carried out as a pretreatment prior to application of a liquid developer, firstly contaminant substances are removed from surface of a
substrate 10 by wet-washing and then once dried before sending the substrate to dry-washing to improve its surface conditions, particularly, to improve its contact angle. The dry-washing treatment makes it possible to apply a liquid developer or the like uniformly on the substrate surface in a subsequent stage.
Claims (30)
1. An apparatus for treating substrate surfaces, comprising:
a lamp house located over a substrate transfer path and face to face with a treating surface of a substrate being transferred along said transfer path by a conveyer means;
a dielectric barrier discharge lamp fixedly mounted in said lamp house to irradiate ultravilot light toward said substrate; and
a moistened inert gas generating means adapted to supply a water vapor-containing moistened inert gas to a space between said substrate and said dielectric barrier discharge lamp;
producing a reducing active member [H.] and an oxidative active member [.OH] by irradiating said moistened inert gas with ultraviolet light from said dielectric barrier discharge lamp.
2. An apparatus for treating substrate surfaces as defined in claim 1 , wherein said substrate is a plate of glass, synthetic resin, ceramics or metal, or a composite plate of such materials.
3. An apparatus for treating substrate surfaces as defined in claim 1 , wherein said moistened inert gas is a mixed fluid of pure water vapor and nitrogen gas.
4. An apparatus for treating substrate surfaces as defined in claim 1 , wherein said lamp house is provided within a chamber holding a moistened inert gas atmosphere therein, and provided with entrance and exit openings at upstream and downstream ends thereof for said substrate.
5. An apparatus for treating substrate surfaces as defined in claim 4 , wherein said chamber is adapted to hold a substantially oxygen-free atmosphere therein.
6. An apparatus for treating substrate surfaces as defined in claim 4 , wherein said conveyer means is constituted by a roller conveyer extending into and across said chamber.
7. An apparatus for treating substrate surfaces as defined in claim 6 , wherein said chamber includes a partition plate located beneath a substrate transfer surface of said roller conveyer and out of contact with said substrate, said partition plate being provided with slots to receive top portions of rollers of said roller conveyer to be brought into abutting engagement with said substrate.
8. An apparatus for treating substrate surfaces as defined in claim 7 , wherein said partition plate is constituted by a heater plate.
9. An apparatus for treating substrate surfaces as defined in claim 4 , wherein said lamp house is opened into said chamber, and an inert gas feed means is connected to said lamp house.
10. An apparatus for treating substrate surfaces as defined in claim 9 , wherein said inert gas feed means is constituted by an inert gas feed pipe connected to a top side of said lamp house, and a reflector plate is provided over said dielectric barrier discharge lamp in said lamp house to reflect upward components of said ultraviolet light, said reflector plate being so located as to divide said lamp house into an upper room in communication with said inert gas feed pipe and a lower room accommodating said dielectric barrier discharge lamp, said reflector plate containing void portions to circulate said inert gas from said upper room to said lower room.
11. An apparatus for treating substrate surfaces as defined in claim 9 , wherein said moistened inert gas generating means includes a moistened inert gas feed means connected to said chamber and adapted to supply a water vapor-containing moistened inert gas toward said treating surface of said substrate.
12. An apparatus for treating substrate surfaces as defined in claim 11 , wherein said moistened inert gas feed means is adapted to supply said moistened inert gas toward a position forward of said substrate advancing toward the said lamp house.
13. An apparatus for treating substrate surfaces as defined in claim 10 , wherein said inert gas feed means is adapted to supply said inert gas to said lamp house under a higher pressure than said moistened inert gas supplied by said moistened inert gas feed means.
14. An apparatus for treating substrate surfaces as defined in claim 10 , wherein said moistened inert gas feed means is constituted by a pure water tank, and a nitrogen gas feed pipe having a multitude of fine gas blow holes in a fore end portion which is submerged in said pure water tank to generate a moistened inert gas.
15. An apparatus for treating substrate surfaces as defined in claim 14 , further comprising a moistened inert gas induction pipe connecting said pure water tank to a mixing container to adjust concentration of water vapor in said moistened inert gas from said pure water tank, said mixing container being connected to said chamber through said moistened inert gas feed pipe.
16. An apparatus for treating substrate surfaces as defined in claim 15 , further comprising an exhaust pipe connected to said chamber.
17. An apparatus for treating substrate surfaces as defined in claim 4 , wherein said moistened inert gas generating means is constituted by a pure water vessel, which pure water vessel being open at a top end located face to face with said lamp house and adapted to hold pure water therein, and an inert gas feed means located in said pure water vessel and provided with a multitude of inert gas blow holes.
18. An apparatus for treating substrate surfaces as defined in claim 17 , wherein a roller conveyer of said substrate conveyer means is located acrosss said chamber, and said pure water vessel is located on the lower side of said roller conveyer.
19. An apparatus for treating substrate surfaces as defined in claim 17 , wherein said lamp house is opened toward a front surface of said substrate being transferred along said path of transfer, and said inert gas feed means is connected to said lamp house.
20. An apparatus for treating substrate surfaces as defined in claim 17 , wherein said inert gas feed means includes an inert gas feed pipe immersed in pure water in said pure water vessel and provided with a multitude of gas blow holes.
21. An apparatus for treating substrate surfaces as defined in claim 17 , further comprising a water feed pipe connected to said pure water vessel at one end thereof, and an overflow type water discharge pipe opened at a predetermined height of said pure water vessel.
22. An apparatus for treating substrate surfaces as defined in claim 21 , wherein the other end of said water feed pipe is connected to a water tank located in a higher position than said pure water vessel.
23. An apparatus for treating substrate surfaces as defined in claim 17 , further comprising an exhaust pipe connected at one end to said chamber and at the other end to a suction side of a pump, the delivery side of which pump being connected to said inert gas feed means.
24. An apparatus for treating substrate surfaces as defined in claim 4 , wherein said lamp house is hermetically closed by an ultraviolet light transmitting window provided on a side facing toward said substrate.
25. An apparatus for treating substrate surfaces as defined in claim 24 , wherein said window is paned with quartz glass.
26. An apparatus for treating substrate surfaces as defined in claim 9 , wherein said lamp house is provided with a partition member of a predetermined thickness on a side facing toward said substrate, said partition member being provided with a multitude of fine holes across said thickness, and a reflecting film coated on entire surfaces of said partition member including inner surfaces of said fine holes.
27. An apparatus for treating substrate surfaces as defined in claim 1 , wherein inner surfaces of said lamp house is coated with a reflecting film to reflect off ultraviolt light.
28. A method for treating substrate surfaces, comprising the steps of:
placing a substrate in a mixed atmosphere of an inert gas and water vapor under irradiation of ultraviolet light from a dielectric barrier discharge lamp, thereby splitting water vapor into a reducing active member [H.] and an oxidative active member [.OH]; and
letting said reducing and oxidative active members [H.] and [.OH] contact with a surface of said substrate to be treated.
29. A method for treating substrate surfaces, comprising the steps of:
horizontally transferring a substrate into a mixed atmosphere of an inert gas and water vapor under irradiation of ultraviolet light from a dielectric barrier discharge lamp, thereby decomposing organic substances deposited on a surface of said substrate and at the same time splitting water vapor into a reducing active member [H.] and an oxidative active member [.OH]; and
subjecting said reducing and oxidative active members [H.] and [.OH] to reactions with decomposition products of said organic substances.
30. A method for treating substrate surfaces, comprising the steps of:
horizontally transferring a substrate into a mixed atmosphere of an inert gas and water vapor under irradiation of ultraviolet light from a dielectric barrier discharge lamp, thereby decomposing organic substances deposited on a surface of said substrate and at the same time splitting water vapor into a reducing active member [H.] and an oxidative active member [.OH];
dry-washing and minimizing contact angle of a surface of said substrate by subjecting said reducing and oxidative active members [H.] and [.OH] to reactions with decomposition products of said organic substances;
wet-washing siad substrate by supplying a wash liquid thereto; and
drying said substrate.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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US10/658,422 US20040045575A1 (en) | 1999-08-05 | 2003-09-10 | Apparatus and method for processing a substrate |
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JP2000-165839 | 2000-06-02 | ||
JP2000165839A JP4318011B2 (en) | 2000-06-02 | 2000-06-02 | Substrate processing apparatus and processing method |
US09/631,619 US6631726B1 (en) | 1999-08-05 | 2000-08-04 | Apparatus and method for processing a substrate |
US10/658,422 US20040045575A1 (en) | 1999-08-05 | 2003-09-10 | Apparatus and method for processing a substrate |
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US09/631,619 Division US6631726B1 (en) | 1999-08-05 | 2000-08-04 | Apparatus and method for processing a substrate |
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US10/658,422 Abandoned US20040045575A1 (en) | 1999-08-05 | 2003-09-10 | Apparatus and method for processing a substrate |
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