WO2015075922A1 - Uv-transmitting-substrate cleaning device and cleaning method - Google Patents

Uv-transmitting-substrate cleaning device and cleaning method Download PDF

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Publication number
WO2015075922A1
WO2015075922A1 PCT/JP2014/005811 JP2014005811W WO2015075922A1 WO 2015075922 A1 WO2015075922 A1 WO 2015075922A1 JP 2014005811 W JP2014005811 W JP 2014005811W WO 2015075922 A1 WO2015075922 A1 WO 2015075922A1
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Prior art keywords
cleaning
substrate
ozone water
ultraviolet
wavelength
Prior art date
Application number
PCT/JP2014/005811
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French (fr)
Japanese (ja)
Inventor
隆行 自在丸
Original Assignee
野村マイクロ・サイエンス株式会社
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Filing date
Publication date
Application filed by 野村マイクロ・サイエンス株式会社 filed Critical 野村マイクロ・サイエンス株式会社
Priority to KR1020167006804A priority Critical patent/KR20160088283A/en
Priority to JP2015548988A priority patent/JPWO2015075922A1/en
Priority to CN201480056479.9A priority patent/CN105637619A/en
Publication of WO2015075922A1 publication Critical patent/WO2015075922A1/en

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    • 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
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041—Cleaning
    • H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
    • H01L21/02052—Wet cleaning only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
    • B08B3/04—Cleaning involving contact with liquid
    • B08B3/10—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • 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
    • 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
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
    • H01L21/02299—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment
    • H01L21/0231—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment treatment by exposure to electromagnetic radiation, e.g. UV light
    • 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
    • H01L21/6704—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like for wet cleaning or washing
    • H01L21/67051—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like for wet cleaning or washing using mainly spraying means, e.g. nozzles
    • 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
    • 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
    • C11D2111/22—

Definitions

  • the present invention relates to an ultraviolet transmissive substrate cleaning apparatus and cleaning method.
  • an RCA cleaning method or a wet cleaning method using a cleaning liquid such as an alkaline detergent has been performed as a method for cleaning a semiconductor silicon substrate or a liquid crystal glass substrate.
  • a concentrated chemical such as hydrogen peroxide, sulfuric acid, hydrochloric acid, or ammonia is used to remove an object to be removed from the substrate surface.
  • a method of combining brush cleaning, ultraviolet irradiation, ultrasonic cleaning, and the like with cleaning using an alkaline detergent or the like as a cleaning liquid is also performed. Since these methods use a large amount of concentrated chemicals and cleaning liquids, a cleaning method that uses as little concentrated chemicals and cleaning liquids as possible is required from the viewpoint of wastewater treatment work and environmental conservation.
  • the size of the glass substrate is much larger than that of the semiconductor wafer, and in recent years, the enlargement of the glass substrate is remarkable.
  • the amount of concentrated chemicals and cleaning liquid used and the amount of pure water used for rinsing them increase. Therefore, problems such as a rise in the manufacturing cost of the glass substrate and an increase in environmental load due to an increase in wastewater treatment load have arisen.
  • dry cleaning may be performed as pretreatment of wet cleaning.
  • surface treatment is performed by irradiating the substrate with ultraviolet rays, thereby decomposing organic substances on the substrate surface (see, for example, Patent Documents 1 and 2).
  • an inorganic material on the substrate surface is previously cleaned with an organic solvent or the like and rinsed with pure water.
  • the present invention has been made to solve the above-described problems, and is an ultraviolet transmissive substrate that can reduce wastewater treatment load and environmental load as compared with conventional cleaning methods using concentrated chemicals and cleaning liquids.
  • An object is to provide a cleaning apparatus and a cleaning method.
  • the cleaning device of the embodiment is a cleaning device for an ultraviolet transparent substrate, wherein the ozone water supply unit supplies ozone water to the cleaning surface of the substrate, and the ozone water is supplied to the cleaning surface of the substrate.
  • An ultraviolet irradiation unit that irradiates ultraviolet rays including a wavelength of 250 to 260 nm is provided on the surface opposite to the cleaning surface of the substrate.
  • the cleaning method of the embodiment is a method for cleaning an ultraviolet transmissive substrate, supplying ozone water to the cleaning surface of the substrate, and including an ultraviolet ray having a wavelength of 250 to 260 nm on the surface opposite to the cleaning surface of the substrate. It is characterized by irradiating.
  • the cleaning apparatus and the cleaning method of the ultraviolet transmissive substrate of the present invention it is possible to reduce the wastewater treatment load and the environmental load as compared with the conventional cleaning method using concentrated chemicals.
  • FIG. 1 is a diagram for explaining the cleaning method of this embodiment.
  • ultraviolet light is irradiated onto a surface (hereinafter referred to as an ultraviolet irradiation surface) 2b opposite to the cleaning surface 2a in a state where ozone water is supplied to the cleaning surface 2a of the substrate 2.
  • the object 3 to be removed in the present embodiment is, for example, an organic thin film such as a photoresist or an organic substance that adheres to the cleaning surface 2a in a clean room.
  • inorganic substances such as metal fine particles attached to the cleaning surface 2a can be removed.
  • the cleaning surface 2a is irradiated with ultraviolet light on the ultraviolet irradiation surface 2b while ozone water is supplied to the cleaning surface 2a, and the active surface is generated by irradiating the ozone water with ultraviolet rays. 2a to be removed 3 is removed.
  • the radical active species to be generated are mainly oxygen radicals generated by the reaction represented by the following formula (1) and hydroxy radicals generated by the reaction represented by the following formula (2).
  • oxygen radicals and hydroxy radicals are removed by oxidizing and decomposing organic substances on the cleaning surface 2a, and similarly, oxidizing inorganic substances to form oxides and removing them.
  • an ozone water film 4 having a predetermined thickness is present on the cleaning surface 2a.
  • Ozone molecules in the ozone water film 4 are decomposed by ultraviolet rays to generate radical active species.
  • the generated radical active species for example, oxidatively decompose and clean the organic matter to be removed 3. Since the object 3 to be removed adheres to the cleaning surface 2 a, among the radical active species generated in the ozone water film 4, radical active species mainly generated in the vicinity of the cleaning surface 2 a contribute to the decomposition and removal of the object 3 to be removed. .
  • the ultraviolet ray when the ultraviolet ray is irradiated from the cleaning surface 2a side, a part of the ultraviolet ray is scattered or refracted on the surface of the ozone water film 4, and the irradiated ultraviolet ray is attenuated before reaching the cleaning surface 2a. It is thought that. Further, a part of the ultraviolet rays are absorbed by ozone molecules present in the upper part of the ozone water film 4, and the amount of ultraviolet rays reaching the cleaning surface 2a with respect to the irradiated ultraviolet rays is reduced, so that in the vicinity of the cleaning surface 2a. There is also a possibility that the amount of oxygen radicals generated will be reduced.
  • a part of radical active species generated in the upper part of the ozone water film 4 causes a chain reaction of radical generation before reaching the removal target 3 on the cleaning surface 2a. Since water is drained from the substrate 2 to the outside in accordance with the flow of water, there is a possibility that the removal target 3 on the cleaning surface 2a may not be reached.
  • the surface 2b opposite to the cleaning surface 2a is irradiated with ultraviolet rays. Therefore, there is no attenuation of ultraviolet rays due to scattering, reflection, refraction, etc. of ultraviolet rays on the surface of the ozone water film 4. Further, there is no attenuation of ultraviolet rays when passing through the ozone water film 4. Further, radical active species generated in the ozone water film 4 are not drained from the substrate 2 to the outside according to the flow of ozone water. Therefore, the substrate can be cleaned more efficiently than when ultraviolet rays are irradiated from the cleaning surface 2a side.
  • FIG. 2 is a schematic side view showing the cleaning apparatus 1 of the present embodiment.
  • FIG. 3 is a schematic plan view showing the cleaning device 1 of the present embodiment.
  • the cleaning apparatus of this embodiment is a so-called flat-flow cleaning apparatus.
  • a cleaning apparatus 1 shown in FIG. 2 includes an ozone water supply unit 5 that supplies ozone water to a cleaning surface 2a of a substrate 2 to be cleaned, and a surface opposite to the cleaning surface 2a of the substrate 2 (hereinafter referred to as an ultraviolet irradiation surface).
  • 2b is provided with an ultraviolet irradiation unit 6 for irradiating ultraviolet rays.
  • an object to be removed 3 such as an organic substance or an inorganic substance adheres to the cleaning surface 2 a of the substrate 2.
  • Reference numeral 7 denotes a transport roller for transporting the substrate 2.
  • the transport roller 7 is disposed so as to transport the substrate 2 placed on the transport roller 7 below the ozone water supply unit 5.
  • the transport roller 7 transports the substrate 2 in the direction of the arrow A, and the cleaning device 1 installed in the middle of the transport path sequentially cleans the substrate 2.
  • the substrate 2 has an ultraviolet transmittance with an extinction coefficient with respect to ultraviolet rays having a wavelength of 254 nm, preferably 50% or less.
  • the substrate 2 preferably has an ultraviolet transmittance of the above-described wavelength (254 nm) of 50% or more, and more preferably 90% or more.
  • the substrate 2 is not particularly limited as long as it has the above-described extinction coefficient or ultraviolet transmittance.
  • a compound semiconductor substrate such as a gallium arsenide (GaAs) substrate, a transparent resin substrate such as polyethylene phthalate (PET), polycarbonate (PC), or polyethylene naphthalate (PEN) can be used.
  • the ozone water supply unit 5 includes an ozone water nozzle 5 b that supplies ozone water to the cleaning surface 2 a of the substrate 2.
  • the ozone water supply unit 5 includes an ozone water production unit 5a that produces ozone water and supplies the ozone water to the ozone water nozzle 5b.
  • the ozone water production unit 5a produces ozone water by dissolving ozone in pure water.
  • a device that dissolves ozone gas in pure water through a gas permeable film or a device that dissolves ozone gas in pure water by making countercurrent contact between ozone gas and pure water in a packed tower is used. Can do.
  • the pure water may be pure water having a suitable purity according to the type and application of the substrate 2 and the purpose of cleaning.
  • the substrate 2 is a liquid crystal glass substrate
  • the resistivity in terms of 25 ° C.
  • Pure water of 10 M ⁇ ⁇ cm or more can be suitably used.
  • the concentration of ozone water produced by the ozone water production unit 5a is preferably 50 to 300 ppm, and more preferably 100 to 200 ppm.
  • carbon dioxide etc. to ozone water as a self-decomposition inhibitor.
  • the temperature of ozone water supplied by the ozone water supply unit 5 is not particularly limited, and may be about 15 ° C. to 25 ° C. (normal temperature). When ozone water is used at room temperature, it is possible to reduce the apparatus and energy for cleaning.
  • the ozone water may be heated.
  • the substrate surface is preferably 15 to 50 ° C., more preferably about room temperature (20 to 30 ° C.) to obtain a cleaner substrate surface in a short time. be able to.
  • a spray nozzle for injecting ozone water or a shower nozzle for spraying ozone water is used as the ozone water nozzle 5b.
  • the ozone water nozzle 5b is connected to the ozone water production unit 5a by a pipe.
  • the ozone water manufactured by the ozone water manufacturing unit 5a is supplied to the ozone water nozzle 5b through this pipe.
  • the supplied ozone water is supplied from the ozone water nozzle 5b to the cleaning surface 2a.
  • the ozone water nozzle 5b preferably includes a pressurizing device.
  • the pressurizing device can pressurize the ozone water and supply it to the cleaning surface 2a.
  • the flow rate of the ozone water supplied to the cleaning surface 2a is preferably about 0.5 to 5 m / s, whereby the cleaning efficiency can be improved.
  • the ozone water supply unit 5 preferably includes an ultrasonic application device.
  • the ultrasonic wave application device applies ultrasonic waves to the ozone water
  • the ozone water nozzle 5b supplies the ozone water to which the ultrasonic waves are applied to the cleaning surface 2a.
  • the frequency of the ultrasonic wave is preferably 30 kHz or more, more preferably 100 to 2,000 kHz, and still more preferably 700 to 1,500 kHz.
  • the ultraviolet irradiation unit 6 irradiates the surface 2b of the substrate 2 opposite to the cleaning surface 2a (hereinafter also referred to as an ultraviolet irradiation surface) 2b with ultraviolet rays having a wavelength of 250 to 260 nm.
  • the ultraviolet irradiation unit 6 preferably irradiates ultraviolet rays including at least a wavelength of 254 nm.
  • Ultraviolet rays having a wavelength of 250 to 260 nm, particularly ultraviolet rays having a wavelength of 254 nm have a higher absorption rate by ozone molecules in pure water than visible light or ultraviolet rays having other wavelengths. Therefore, the irradiation reaction of radical active species represented by the above formulas (1) and (2) is promoted by irradiating with ultraviolet rays including the above preferred wavelength range. As a result, the removal target 3 can be effectively removed.
  • the ultraviolet irradiation unit 6 may irradiate at least ultraviolet rays having a wavelength of 250 to 260 nm. Not only ultraviolet rays having the above wavelengths but also light having other wavelengths, for example, ultraviolet rays having a wavelength in the vicinity of 185 nm, 250 having a wavelength in the range of 220 to 400 nm. Irradiation with ultraviolet light having a wavelength other than ⁇ 260 nm, visible light other than ultraviolet light, or light having an infrared wavelength region may be performed. In this case, the region of the emission peak wavelength of the light irradiated by the ultraviolet irradiation unit 6 is not particularly limited, but preferably has the emission peak wavelength in a range of at least 250 to 260 nm.
  • the light source of the ultraviolet irradiation unit 6 is not limited as long as it generates ultraviolet light having the above-described wavelength.
  • a low pressure mercury lamp, a high pressure mercury lamp, a vacuum ultraviolet lamp, a xenon lamp, a light emitting diode (LED), or the like is used. Can do. Since the ultraviolet irradiation illuminance of the ultraviolet irradiation unit 6 greatly affects the generation concentration (generation amount) of radical active species, a light source that can irradiate ultraviolet rays with a stable illuminance and has a long emission lifetime and low running cost is preferable. As such a light source, a low-pressure mercury lamp is preferably used.
  • the substrate 2 when the substrate 2 is large, it is preferable to use an LED from the viewpoint of partial uniformity of the ultraviolet illuminance irradiated on the substrate 2 and miniaturization of the cleaning device. Since the LED has a long light emission life and excellent linearity of irradiated light, the running cost can be reduced by using the LED.
  • Ultraviolet illuminance of irradiating ultraviolet irradiation unit 6, in order to remove the matter to be removed 3 efficiently is preferably 2 ⁇ 20mW / m 2, more preferably 3 ⁇ 8mW / m 2.
  • the to-be-removed object 3 attached to the cleaning surface of the substrate 2 is decomposed by radical active species generated by irradiating ozone water with ultraviolet rays, and is removed by dissolving in ozone water.
  • the distance from the light source of the ultraviolet irradiation unit 6 to the ultraviolet irradiation surface 2b can be appropriately set depending on the absorption coefficient of the substrate 2, the concentration of ozone water, the type of light source used, and the like. Considering that the illuminance of ultraviolet rays is inversely proportional to the square of the distance from the light source in the air, it is set to several hundred mm or less, preferably 5 to 20 mm, for example. Thus, the ultraviolet light emitting intensity is, if 2 ⁇ 20mW / m 2 about ultraviolet light source, the ultraviolet intensity in the cleaning surface 2a can be a 3 mW / m 2 or more, thereby improving the cleaning efficiency .
  • the ultraviolet irradiation unit 6 is disposed between the plurality of transport rollers 7 by disposing the ultraviolet irradiation unit 6 on the surface 2 b side opposite to the cleaning surface 2 a of the substrate 2. be able to. Therefore, it is possible to reduce the size of the cleaning device 1. Furthermore, since the distance between the light source of the ultraviolet irradiation unit 6 and the glass substrate 2 can be reduced by providing the ultraviolet irradiation unit on the surface 2b side opposite to the cleaning surface 2a, the ultraviolet irradiation efficiency can be improved.
  • the ultraviolet irradiation unit 6 when the ultraviolet irradiation unit 6 is installed above the substrate 2, for example, there is a concern that an ozone water droplet splashes and touches the light source of the ultraviolet irradiation unit 6 and the light source of the ultraviolet irradiation unit 6 may be damaged. In some cases, the substrate 2 may be damaged. On the other hand, in the cleaning apparatus 1 of the present embodiment, since the ultraviolet irradiation unit 6 is installed below the substrate 2, waterproofing is easy.
  • the ultraviolet light source may be protected by a quartz glass tube, for example, in order to prevent the adhesion of ozone water droplets.
  • a quartz glass tube for example, in order to prevent the adhesion of ozone water droplets.
  • the cleaning apparatus 1 since the cleaning apparatus 1 according to the present embodiment includes the ultraviolet irradiation unit 6 below the substrate 2, the force for holding the ultraviolet irradiation unit 6 is also greater than when the ultraviolet irradiation unit 6 is provided above the substrate 2. Small is good. Therefore, the apparatus configuration can be simplified.
  • the step S100 for holding the substrate the step S200 for supplying ozone water to the cleaning surface of the held substrate, and the ozone water contacted the cleaning surface of the substrate.
  • the substrate is cleaned using the cleaning apparatus 1 of the present embodiment as follows. First, the substrate 2 to be cleaned is placed and held on the transport roller 7, and the transport roller 7 is operated to transport the substrate 2. Then, while supplying ozone from the ozone water nozzle 5b to the cleaning surface 2a of the substrate to be transported in step S200, the ultraviolet irradiation unit 6 irradiates ultraviolet rays from the ultraviolet irradiation surface 2b side in step S300.
  • the ozone water supply flow rate of the ozone water nozzle 5b is dependent on the area of the substrate 2 to be cleaned, in terms of cleaning performance, is preferably 1 m 2 per 40 ⁇ 400L / min, 1m 2 More preferably, it is 100 to 400 L / min.
  • the substrate 2 is placed and held on the transport roller 7, but the substrate 2 is in a state where ozone water is supplied to the cleaning surface 2a, and is opposite to the cleaning surface 2a.
  • the manner or method of holding the substrate 2 as long as the surface is held in such a manner that it can be irradiated with ultraviolet rays having the above-mentioned wavelength.
  • the cleaning of the substrate in the cleaning apparatus 1 may be performed batchwise or continuously. When cleaning a small substrate, it is preferable to use a batch method.
  • the cleaning method of the present invention is a cleaning method characterized by energy saving, cost reduction, and high cleaning ability, and exhibits a great effect particularly when applied to cleaning of a liquid crystal glass substrate having a large cleaning area. be able to.
  • the liquid crystal glass substrate has been remarkably increased in size in recent years, and flat-flow cleaning is becoming the mainstream for the purpose of cleaning uniformity and cleaning time.
  • the effect of the present invention is not limited only to the flat-flow cleaning method, the showering method in which the cleaning liquid is poured in the shower, the spin cleaning method for supplying the cleaning liquid onto the rotating substrate, and the batch type immersion bath in which the cleaning liquid is contained
  • any conventionally known cleaning method using a cleaning liquid such as an immersion cleaning method and a combination thereof
  • any cleaning method can improve the cleaning efficiency as in this embodiment.
  • the cleaning efficiency can be further improved by combining physical cleaning using a sponge or the like with each of the cleaning methods as described above.
  • the cleaning apparatus of the present embodiment it is possible to reduce the wastewater treatment load and the environmental burden compared to the conventional cleaning method using concentrated chemicals and cleaning liquids, and it is possible to simplify the apparatus configuration. . Therefore, the cleaning efficiency of the substrate with ozone water can be improved.
  • Example 1 As the object to be cleaned, a liquid crystal glass substrate having a size of 50 mm in length, 50 mm in width, and 0.7 mm in thickness and having a transmittance of 99% for ultraviolet rays having a wavelength of 254 nm was used. Ozone water having a concentration of 100 ppm is supplied to the cleaning surface of this substrate at a flow rate of 1 L / min (400 L / min per 1 m 2 ), and ultraviolet light having a wavelength near 254 nm is applied to the surface opposite to the cleaning surface from the glass substrate. Irradiation was performed at a UV illuminance of 3.8 mW / m 2 from below 10 mm. As the ultraviolet irradiation device, a low-pressure mercury lamp AY-11 (trade name, manufactured by Nippon Photo Science Co., Ltd.) was used.
  • the water contact angle on the surface of the liquid crystal glass substrate before cleaning and the water contact angle on the surface of the liquid crystal glass substrate after cleaning times of 0 seconds, 30 seconds, 60 seconds, 180 seconds, 300 seconds, and 600 seconds are measured with a contact angle meter PG-X ( (Trade name, manufactured by Matsubo Co., Ltd.).
  • the measurement results of the water contact angle are shown in Table 1. It shows that the smaller the water contact angle, the less organic matter adhered to the liquid crystal glass substrate and the better the cleaning is.
  • the wavelength characteristics of the low-pressure mercury lamp used are shown in FIG.
  • Example 1 the liquid crystal glass substrate was cleaned under the same conditions as in Example 1 except that ultraviolet rays were irradiated from the cleaning surface side, and the change with time of the water contact angle on the liquid crystal glass substrate surface was measured. The results are shown in Table 1.
  • Example 2 In Example 1, the liquid crystal glass substrate was cleaned under the same conditions as in Example 1 except that cleaning was performed without irradiating ultraviolet rays, and the change with time in the water contact angle on the liquid crystal glass substrate surface was measured. The results are also shown in Table 1.
  • Comparative Example 3 In Comparative Example 1, the liquid crystal glass substrate was cleaned under the same conditions as in Comparative Example 1 except that ultrasonic waves were applied to the ozone water supplied from the ozone water nozzle 5b using a fine jet (PT-010J50 (manufactured by Pretec)). And the change with time of the water contact angle on the surface of the liquid crystal glass substrate was measured. The results are shown in Table 1. In Comparative Example 3, only a cleaning effect substantially equivalent to that in Comparative Example 2 was shown. This indicates that the effect of ultraviolet irradiation did not appear because the ultraviolet water was reflected by the ozone water film due to the vibration applied to the ozone water film.
  • the cleaning efficiency is improved by irradiating ultraviolet rays having a wavelength of 250 to 260 nm.
  • the irradiation is performed from the cleaning surface side. It has been found that the contact angle decreases in a short time, that is, good cleaning is performed in a short time.

Abstract

A UV-transmitting-substrate cleaning device in an embodiment is provided with the following: an ozonated-water supply unit that supplies ozonated water to a cleaning surface of a substrate; and an ultraviolet-light irradiation unit that, with ozonated water supplied to said cleaning surface, irradiates the opposite surface of the substrate with ultraviolet light containing wavelengths in the 250-260 nm range.

Description

紫外線透過性基板の洗浄装置及び洗浄方法Cleaning apparatus and cleaning method for ultraviolet transmissive substrate
　本発明は、紫外線透過性基板の洗浄装置及び洗浄方法に関する。 The present invention relates to an ultraviolet transmissive substrate cleaning apparatus and cleaning method.
　従来、半導体用シリコン基板や液晶ガラス基板の洗浄方法としてＲＣＡ洗浄法や、アルカリ洗剤等の洗浄液を用いたウェット洗浄方法が行われている。ＲＣＡ洗浄法では、例えば、過酸化水素、硫酸、塩酸、アンモニア等の濃厚薬品を用い、基板表面の被除去物を除去する。また、洗浄液としてアルカリ洗剤等を用いる洗浄にブラシ洗浄、紫外線照射、超音波洗浄等を組み合わせる方法も行われている。これらの方法では、濃厚薬品や洗浄液を大量に用いるため、排水処理作業や環境保全の観点から、濃厚薬品や洗浄液をできるだけ使用しない洗浄方法が求められていた。また、ガラス基板は半導体ウェハと比べてサイズが非常に大きく、また、近年ガラス基板の大型化が顕著である。このような大型のガラス基板の洗浄においては、濃厚薬品や洗浄液の使用量や、これらをリンスする純水の使用量が増大する。そのため、ガラス基板の製造コストの高騰や、排水処理負荷の増大による環境負荷の増大等の問題が生じている。 Conventionally, an RCA cleaning method or a wet cleaning method using a cleaning liquid such as an alkaline detergent has been performed as a method for cleaning a semiconductor silicon substrate or a liquid crystal glass substrate. In the RCA cleaning method, for example, a concentrated chemical such as hydrogen peroxide, sulfuric acid, hydrochloric acid, or ammonia is used to remove an object to be removed from the substrate surface. In addition, a method of combining brush cleaning, ultraviolet irradiation, ultrasonic cleaning, and the like with cleaning using an alkaline detergent or the like as a cleaning liquid is also performed. Since these methods use a large amount of concentrated chemicals and cleaning liquids, a cleaning method that uses as little concentrated chemicals and cleaning liquids as possible is required from the viewpoint of wastewater treatment work and environmental conservation. In addition, the size of the glass substrate is much larger than that of the semiconductor wafer, and in recent years, the enlargement of the glass substrate is remarkable. In cleaning such a large glass substrate, the amount of concentrated chemicals and cleaning liquid used and the amount of pure water used for rinsing them increase. Therefore, problems such as a rise in the manufacturing cost of the glass substrate and an increase in environmental load due to an increase in wastewater treatment load have arisen.
　また、洗浄効率を向上させるために、ウェット洗浄の前処理として、ドライ洗浄が行われることもある。ドライ洗浄では、基板に紫外線を照射して表面処理を行い、これにより基板表面の有機物を分解する（例えば、特許文献１，２参照。）。また、前処理として、ドライ洗浄の代わりに、有機溶剤などであらかじめ基板表面の無機物を洗浄し、純水でリンスする方法も行われている。 Also, in order to improve the cleaning efficiency, dry cleaning may be performed as pretreatment of wet cleaning. In dry cleaning, surface treatment is performed by irradiating the substrate with ultraviolet rays, thereby decomposing organic substances on the substrate surface (see, for example, Patent Documents 1 and 2). In addition, as a pretreatment, instead of dry cleaning, an inorganic material on the substrate surface is previously cleaned with an organic solvent or the like and rinsed with pure water.
　しかしながら、従来のドライ洗浄では、無機物を除去することができないため、これを行った後、濃厚薬品や洗浄液を用いるウェット洗浄を行って、無機物を洗浄することが必要である。そのため、ウェット洗浄後に、多量の排水が生じ、この排水を処理する必要があった。また、前処理として有機溶剤を用いて洗浄する方法においても、有機溶剤洗浄後及びウェット洗浄後にそれぞれ純水でリンスするため、前記同様に多量の排水を処理する必要があった。 However, since the inorganic material cannot be removed by the conventional dry cleaning, it is necessary to clean the inorganic material by performing wet cleaning using a concentrated chemical or a cleaning liquid after performing this. For this reason, a large amount of wastewater is generated after wet cleaning, and this wastewater needs to be treated. Further, in the method of washing using an organic solvent as a pretreatment, since a rinse is performed with pure water after washing with an organic solvent and after wet washing, a large amount of waste water needs to be treated in the same manner as described above.
特開平５－１８２９４５号公報Japanese Patent Laid-Open No. 5-182945 特開平５－２２４１６７号公報Japanese Patent Laid-Open No. 5-224167
　本発明は上記した課題を解決するためになされたものであって、従来の濃厚薬品や洗浄液を用いた洗浄方法に比べて、排水処理負荷や環境負荷を軽減することのできる紫外線透過性基板の洗浄装置及び洗浄方法を提供することを目的とする。 The present invention has been made to solve the above-described problems, and is an ultraviolet transmissive substrate that can reduce wastewater treatment load and environmental load as compared with conventional cleaning methods using concentrated chemicals and cleaning liquids. An object is to provide a cleaning apparatus and a cleaning method.
　実施形態の洗浄装置は、紫外線透過性基板の洗浄装置であって、前記基板の洗浄面にオゾン水を供給するオゾン水供給部と、前記基板の洗浄面にオゾン水が供給された状態で前記基板の洗浄面と反対側の面に２５０～２６０ｎｍの波長を含む紫外線を照射する紫外線照射部とを備えることを特徴とする。 The cleaning device of the embodiment is a cleaning device for an ultraviolet transparent substrate, wherein the ozone water supply unit supplies ozone water to the cleaning surface of the substrate, and the ozone water is supplied to the cleaning surface of the substrate. An ultraviolet irradiation unit that irradiates ultraviolet rays including a wavelength of 250 to 260 nm is provided on the surface opposite to the cleaning surface of the substrate.
　実施形態の洗浄方法は、紫外線透過性基板の洗浄方法であって、前記基板の洗浄面にオゾン水を供給するとともに、前記基板の洗浄面の反対側の面に２５０～２６０ｎｍの波長を含む紫外線を照射することを特徴とする。 The cleaning method of the embodiment is a method for cleaning an ultraviolet transmissive substrate, supplying ozone water to the cleaning surface of the substrate, and including an ultraviolet ray having a wavelength of 250 to 260 nm on the surface opposite to the cleaning surface of the substrate. It is characterized by irradiating.
　本発明の紫外線透過性基板の洗浄装置及び洗浄方法によれば、従来の濃厚薬品を用いた洗浄方法に比べて排水処理負荷や環境負荷を軽減することができる。 According to the cleaning apparatus and the cleaning method of the ultraviolet transmissive substrate of the present invention, it is possible to reduce the wastewater treatment load and the environmental load as compared with the conventional cleaning method using concentrated chemicals.
実施形態の洗浄方法を説明する図である。It is a figure explaining the washing | cleaning method of embodiment. 実施形態の洗浄装置を概略的に示す側面図である。It is a side view which shows roughly the washing | cleaning apparatus of embodiment. 実施形態の洗浄装置を概略的に示す平面図である。It is a top view which shows roughly the washing | cleaning apparatus of embodiment. 実施形態の洗浄方法を示すフロー図である。It is a flowchart which shows the washing | cleaning method of embodiment. 実施例で用いた低圧水銀ランプの波長特性を示す図である。It is a figure which shows the wavelength characteristic of the low pressure mercury lamp used in the Example.
　以下、本発明の実施の形態を、図面を用いて説明する。各図において同一の機能を有する構成には同一の符号を付して重複する説明を省略する。本発明は以下の実施形態に限定されるものではない。 Hereinafter, embodiments of the present invention will be described with reference to the drawings. In the drawings, components having the same function are denoted by the same reference numerals, and redundant description is omitted. The present invention is not limited to the following embodiments.
　図１は本実施形態の洗浄方法を説明する図である。本実施形態の洗浄方法は、基板２の洗浄面２ａにオゾン水を供給した状態で、洗浄面２ａと反対側の面（以下、紫外線照射面という。）２ｂに紫外線を照射する。本実施形態における被除去物３は例えば、フォトレジスト等の有機薄膜やクリーンルーム内で洗浄面２ａに付着する有機物である。また、本実施形態の洗浄方法では、洗浄面２ａに付着した金属微粒子等の無機物を除去することもできる。 FIG. 1 is a diagram for explaining the cleaning method of this embodiment. In the cleaning method of the present embodiment, ultraviolet light is irradiated onto a surface (hereinafter referred to as an ultraviolet irradiation surface) 2b opposite to the cleaning surface 2a in a state where ozone water is supplied to the cleaning surface 2a of the substrate 2. The object 3 to be removed in the present embodiment is, for example, an organic thin film such as a photoresist or an organic substance that adheres to the cleaning surface 2a in a clean room. In the cleaning method of the present embodiment, inorganic substances such as metal fine particles attached to the cleaning surface 2a can be removed.
　本実施形態の洗浄方法においては、洗浄面２ａにオゾン水を供給した状態で紫外線照射面２ｂに紫外線を照射し、オゾン水に紫外線を照射することで発生するラジカル活性種を利用して洗浄面２ａの被除去物３を除去する。発生するラジカル活性種は、主に下記（１）式で示す反応で生じる酸素ラジカルや、下記(２)式で示す反応で生じるヒドロキシラジカルである。 In the cleaning method of the present embodiment, the cleaning surface 2a is irradiated with ultraviolet light on the ultraviolet irradiation surface 2b while ozone water is supplied to the cleaning surface 2a, and the active surface is generated by irradiating the ozone water with ultraviolet rays. 2a to be removed 3 is removed. The radical active species to be generated are mainly oxygen radicals generated by the reaction represented by the following formula (1) and hydroxy radicals generated by the reaction represented by the following formula (2).
　Ｏ３＋ｈν　→　Ｏ２＋Ｏ・　　　　…（１） O 3 + hν → O 2 + O · (1)
　Ｏ・＋Ｈ２Ｏ　→　２ＯＨ・　　　　…（２） O · + H 2 O → 2OH · (2)
　これら酸素ラジカルやヒドロキシラジカルは、洗浄面２ａの有機物を酸化分解して除去し、同様に、無機物を酸化して酸化物を生成し、除去する。 These oxygen radicals and hydroxy radicals are removed by oxidizing and decomposing organic substances on the cleaning surface 2a, and similarly, oxidizing inorganic substances to form oxides and removing them.
　洗浄面２ａにオゾン水を供給している状態において、洗浄面２ａ上には、所定の厚さを有するオゾン水膜４がある。このオゾン水膜４中のオゾン分子が紫外線によって分解してラジカル活性種が発生する。発生したラジカル活性種が例えば有機物の被除去物３を酸化分解して洗浄する。被除去物３は洗浄面２ａに付着しているので、オゾン水膜４中で生じるラジカル活性種のうち、主として洗浄面２ａ近傍で生じるラジカル活性種がこの被除去物３の分解除去に寄与する。 In a state where ozone water is supplied to the cleaning surface 2a, an ozone water film 4 having a predetermined thickness is present on the cleaning surface 2a. Ozone molecules in the ozone water film 4 are decomposed by ultraviolet rays to generate radical active species. The generated radical active species, for example, oxidatively decompose and clean the organic matter to be removed 3. Since the object 3 to be removed adheres to the cleaning surface 2 a, among the radical active species generated in the ozone water film 4, radical active species mainly generated in the vicinity of the cleaning surface 2 a contribute to the decomposition and removal of the object 3 to be removed. .
　ここで、洗浄面２ａ側から紫外線を照射した場合には、オゾン水膜４表面で紫外線の一部が散乱や屈折して、照射した紫外線が、洗浄面２ａに到達するまでの間に減衰してしまうと考えられる。また、紫外線の一部がオゾン水膜４内上方部分に存在するオゾン分子に吸収され、照射した紫外線に対して洗浄面２ａに到達する紫外線量が減少してしまうことで、洗浄面２ａ近傍での酸素ラジカルの発生量が少なくなる可能性もある。さらに、オゾン水膜４内の上方部分で発生したラジカル活性種の一部が、洗浄面２ａ上の被除去物３に到達する前にラジカル生成の連鎖反応を起こしたり、ラジカル活性種が、オゾン水の流れにしたがって基板２上から外部に排水されるため、洗浄面２ａ上の被除去物３に到達しない可能性もある。 Here, when the ultraviolet ray is irradiated from the cleaning surface 2a side, a part of the ultraviolet ray is scattered or refracted on the surface of the ozone water film 4, and the irradiated ultraviolet ray is attenuated before reaching the cleaning surface 2a. It is thought that. Further, a part of the ultraviolet rays are absorbed by ozone molecules present in the upper part of the ozone water film 4, and the amount of ultraviolet rays reaching the cleaning surface 2a with respect to the irradiated ultraviolet rays is reduced, so that in the vicinity of the cleaning surface 2a. There is also a possibility that the amount of oxygen radicals generated will be reduced. Further, a part of radical active species generated in the upper part of the ozone water film 4 causes a chain reaction of radical generation before reaching the removal target 3 on the cleaning surface 2a. Since water is drained from the substrate 2 to the outside in accordance with the flow of water, there is a possibility that the removal target 3 on the cleaning surface 2a may not be reached.
　これに対し、本実施形態の洗浄方法では、洗浄面２ａと反対側の面２ｂに紫外線を照射する。そのため、オゾン水膜４表面での紫外線の散乱、反射、屈折等による紫外線の減衰がない。また、オゾン水膜４中を通過する際の紫外線の減衰もない。また、オゾン水膜４中で発生したラジカル活性種がオゾン水の流れにしたがって基板２上から外部へ排水されることもない。そのため、紫外線を洗浄面２ａ側から照射した場合に比べて、効率よく基板洗浄を行うことができる。 In contrast, in the cleaning method of the present embodiment, the surface 2b opposite to the cleaning surface 2a is irradiated with ultraviolet rays. Therefore, there is no attenuation of ultraviolet rays due to scattering, reflection, refraction, etc. of ultraviolet rays on the surface of the ozone water film 4. Further, there is no attenuation of ultraviolet rays when passing through the ozone water film 4. Further, radical active species generated in the ozone water film 4 are not drained from the substrate 2 to the outside according to the flow of ozone water. Therefore, the substrate can be cleaned more efficiently than when ultraviolet rays are irradiated from the cleaning surface 2a side.
　図２は、本実施形態の洗浄装置１を示す概略側面図である。図３は、本実施形態の洗浄装置１を示す概略平面図である。本実施形態の洗浄装置は、いわゆる平流し洗浄装置である。図２に示す洗浄装置１は、洗浄対象である基板２の洗浄面２ａにオゾン水を供給するオゾン水供給部５と、基板２の洗浄面２ａと反対側の面(以下、紫外線照射面ともいう。)２ｂに紫外線を照射する紫外線照射部６とを備えている。基板２の洗浄面２ａには例えば有機物や無機物等の被除去物３が付着している。 FIG. 2 is a schematic side view showing the cleaning apparatus 1 of the present embodiment. FIG. 3 is a schematic plan view showing the cleaning device 1 of the present embodiment. The cleaning apparatus of this embodiment is a so-called flat-flow cleaning apparatus. A cleaning apparatus 1 shown in FIG. 2 includes an ozone water supply unit 5 that supplies ozone water to a cleaning surface 2a of a substrate 2 to be cleaned, and a surface opposite to the cleaning surface 2a of the substrate 2 (hereinafter referred to as an ultraviolet irradiation surface). 2b is provided with an ultraviolet irradiation unit 6 for irradiating ultraviolet rays. For example, an object to be removed 3 such as an organic substance or an inorganic substance adheres to the cleaning surface 2 a of the substrate 2.
　符号７は基板２を搬送する搬送ローラを示している。搬送ローラ７は、搬送ローラ７上に載置された基板２を、オゾン水供給部５の下方に搬送するように配設されている。搬送ローラ７は矢印Ａの方向に基板２を搬送し、搬送経路の途中に設置された洗浄装置１が基板２を順次洗浄する。 Reference numeral 7 denotes a transport roller for transporting the substrate 2. The transport roller 7 is disposed so as to transport the substrate 2 placed on the transport roller 7 below the ozone water supply unit 5. The transport roller 7 transports the substrate 2 in the direction of the arrow A, and the cleaning device 1 installed in the middle of the transport path sequentially cleans the substrate 2.
　基板２は、２５４ｎｍの波長の紫外線に対する吸光係数が好ましくは５０％以下の紫外性透過性を有している。基板２は、上記した波長（２５４ｎｍ）の紫外線の透過率が５０％以上であることが好ましく、９０％以上であることがより好ましい。 The substrate 2 has an ultraviolet transmittance with an extinction coefficient with respect to ultraviolet rays having a wavelength of 254 nm, preferably 50% or less. The substrate 2 preferably has an ultraviolet transmittance of the above-described wavelength (254 nm) of 50% or more, and more preferably 90% or more.
　基板２としては、上記した吸光係数又は紫外線透過率を有する基板であれば特に限定されず、具体的には、石英ガラス基板、有機ＥＬ用ガラス基板、液晶ガラス基板、炭化ケイ素（ＳｉＣ）基板やガリウムヒ素（ＧａＡｓ）基板等の化合物半導体基板、ポリエチレンフタラート（ＰＥＴ）、ポリカーボネート（ＰＣ）、ポリエチレンナフタレート（ＰＥＮ）等の透明樹脂基板などを用いることができる。 The substrate 2 is not particularly limited as long as it has the above-described extinction coefficient or ultraviolet transmittance. Specifically, a quartz glass substrate, a glass substrate for organic EL, a liquid crystal glass substrate, a silicon carbide (SiC) substrate, A compound semiconductor substrate such as a gallium arsenide (GaAs) substrate, a transparent resin substrate such as polyethylene phthalate (PET), polycarbonate (PC), or polyethylene naphthalate (PEN) can be used.
　本実施形態の洗浄装置１において、オゾン水供給部５は、基板２の洗浄面２ａにオゾン水を供給するオゾン水ノズル５ｂを備えている。また、オゾン水供給部５は、オゾン水を製造してオゾン水ノズル５ｂに供給するオゾン水製造部５ａを備えている。オゾン水製造部５ａは、純水にオゾンを溶解させてオゾン水を製造する。オゾン水製造部５ａとしては、ガス透過膜を介してオゾンガスを純水に溶解させる装置や、オゾンガスと純水とを充填塔内で向流接触させてオゾンガスを純水に溶解させる装置を用いることができる。純水は、基板２の種類や用途及び洗浄目的に応じて、適した純度の純水を使用すればよいが、例えば基板２が液晶ガラス基板である場合には、２５℃換算の抵抗率が１０ＭΩ・ｃｍ以上の純水を好適に用いることができる。
　オゾン水製造部５ａが製造するオゾン水の濃度は、５０～３００ｐｐｍであることが好ましく、１００～２００ｐｐｍであることがより好ましい。また、オゾンの自己分解を抑制してオゾンを効率的に利用するために、オゾン水には、自己分解抑制剤として二酸化炭素等を添加することが好ましい。 In the cleaning apparatus 1 of the present embodiment, the ozone water supply unit 5 includes an ozone water nozzle 5 b that supplies ozone water to the cleaning surface 2 a of the substrate 2. The ozone water supply unit 5 includes an ozone water production unit 5a that produces ozone water and supplies the ozone water to the ozone water nozzle 5b. The ozone water production unit 5a produces ozone water by dissolving ozone in pure water. As the ozone water production unit 5a, a device that dissolves ozone gas in pure water through a gas permeable film or a device that dissolves ozone gas in pure water by making countercurrent contact between ozone gas and pure water in a packed tower is used. Can do. The pure water may be pure water having a suitable purity according to the type and application of the substrate 2 and the purpose of cleaning. For example, when the substrate 2 is a liquid crystal glass substrate, the resistivity in terms of 25 ° C. Pure water of 10 MΩ · cm or more can be suitably used.
The concentration of ozone water produced by the ozone water production unit 5a is preferably 50 to 300 ppm, and more preferably 100 to 200 ppm. Moreover, in order to suppress the self-decomposition of ozone and use ozone efficiently, it is preferable to add carbon dioxide etc. to ozone water as a self-decomposition inhibitor.
　オゾン水供給部５が供給するオゾン水の温度は、特に限定されず、１５℃～２５℃程度（常温）であってよい。オゾン水を常温で用いる場合には、洗浄のための装置やエネルギーを削減することが可能である。また、オゾン水は、加熱してもよく、この場合には好ましくは１５～５０℃、より好ましくは常温（２０～３０℃）程度とすることで、短時間でより清浄化した基板表面を得ることができる。 The temperature of ozone water supplied by the ozone water supply unit 5 is not particularly limited, and may be about 15 ° C. to 25 ° C. (normal temperature). When ozone water is used at room temperature, it is possible to reduce the apparatus and energy for cleaning. The ozone water may be heated. In this case, the substrate surface is preferably 15 to 50 ° C., more preferably about room temperature (20 to 30 ° C.) to obtain a cleaner substrate surface in a short time. be able to.
　オゾン水ノズル５ｂとしては、オゾン水を噴射するスプレーノズルや、オゾン水を噴霧するシャワーノズルが用いられる。オゾン水ノズル５ｂは、配管によってオゾン水製造部５ａに接続されている。この配管を介してオゾン水製造部５ａで製造されたオゾン水がオゾン水ノズル５ｂに供給される。供給されたオゾン水は、オゾン水ノズル５ｂから洗浄面２ａに供給される。オゾン水ノズル５ｂは、加圧装置を備えることが好ましく、この場合、加圧装置がオゾン水を加圧して洗浄面２ａに供給することができる。洗浄面２ａに供給されるオゾン水の流速は０．５～５ｍ／ｓ程度であることが好ましく、これにより、洗浄効率を向上させることができる。 As the ozone water nozzle 5b, a spray nozzle for injecting ozone water or a shower nozzle for spraying ozone water is used. The ozone water nozzle 5b is connected to the ozone water production unit 5a by a pipe. The ozone water manufactured by the ozone water manufacturing unit 5a is supplied to the ozone water nozzle 5b through this pipe. The supplied ozone water is supplied from the ozone water nozzle 5b to the cleaning surface 2a. The ozone water nozzle 5b preferably includes a pressurizing device. In this case, the pressurizing device can pressurize the ozone water and supply it to the cleaning surface 2a. The flow rate of the ozone water supplied to the cleaning surface 2a is preferably about 0.5 to 5 m / s, whereby the cleaning efficiency can be improved.
　また、オゾン水供給部５は、超音波印加装置を備えることが好ましい。この場合、超音波印加装置がオゾン水に超音波を印加して、オゾン水ノズル５ｂが超音波の印加されたオゾン水を洗浄面２ａに供給する。超音波の周波数は、好ましくは３０ｋＨｚ以上、より好ましくは１００～２，０００ｋＨｚ、さらに好ましくは７００～１，５００ｋＨｚである。オゾン水に超音波印加する場合には、ラジカル活性種の発生を促進し、洗浄効果を高めることができる。 The ozone water supply unit 5 preferably includes an ultrasonic application device. In this case, the ultrasonic wave application device applies ultrasonic waves to the ozone water, and the ozone water nozzle 5b supplies the ozone water to which the ultrasonic waves are applied to the cleaning surface 2a. The frequency of the ultrasonic wave is preferably 30 kHz or more, more preferably 100 to 2,000 kHz, and still more preferably 700 to 1,500 kHz. When ultrasonic waves are applied to ozone water, generation of radical active species can be promoted, and the cleaning effect can be enhanced.
　本実施形態の洗浄装置１において、紫外線照射部６は、基板２の洗浄面２ａと反対側の面(以下、紫外線照射面ともいう。)２ｂに２５０～２６０ｎｍの波長を含む紫外線を照射する。紫外線照射部６は、少なくとも波長２５４ｎｍを含む紫外線を照射することが好ましい。波長２５０～２６０ｎｍの紫外線、特に、波長２５４ｎｍの紫外線は、その他の波長の可視光線ないし紫外線よりも純水中のオゾン分子による吸収率が高い。そのため、上記好ましい波長範囲を含む紫外線を照射することで、上記式（１），（２）に示すラジカル活性種の生成反応が促進される。その結果、被除去物３を効果的に除去することができる。 In the cleaning apparatus 1 of the present embodiment, the ultraviolet irradiation unit 6 irradiates the surface 2b of the substrate 2 opposite to the cleaning surface 2a (hereinafter also referred to as an ultraviolet irradiation surface) 2b with ultraviolet rays having a wavelength of 250 to 260 nm. The ultraviolet irradiation unit 6 preferably irradiates ultraviolet rays including at least a wavelength of 254 nm. Ultraviolet rays having a wavelength of 250 to 260 nm, particularly ultraviolet rays having a wavelength of 254 nm, have a higher absorption rate by ozone molecules in pure water than visible light or ultraviolet rays having other wavelengths. Therefore, the irradiation reaction of radical active species represented by the above formulas (1) and (2) is promoted by irradiating with ultraviolet rays including the above preferred wavelength range. As a result, the removal target 3 can be effectively removed.
　紫外線照射部６は、少なくとも波長２５０～２６０ｎｍの紫外線を照射すればよく、上記した波長の紫外線のみでなく、これ以外の波長の光、例えば波長１８５ｎｍ付近の紫外線、波長２２０～４００ｎｍの範囲の２５０～２６０ｎｍ以外の波長の紫外線、紫外線以外の可視光線や赤外線の波長の領域の光を照射してもよい。この場合、紫外線照射部６の照射する光の発光ピーク波長の領域は特に限定されないが、少なくとも２５０～２６０ｎｍの範囲に発光ピーク波長を有していることが好ましい。 The ultraviolet irradiation unit 6 may irradiate at least ultraviolet rays having a wavelength of 250 to 260 nm. Not only ultraviolet rays having the above wavelengths but also light having other wavelengths, for example, ultraviolet rays having a wavelength in the vicinity of 185 nm, 250 having a wavelength in the range of 220 to 400 nm. Irradiation with ultraviolet light having a wavelength other than ˜260 nm, visible light other than ultraviolet light, or light having an infrared wavelength region may be performed. In this case, the region of the emission peak wavelength of the light irradiated by the ultraviolet irradiation unit 6 is not particularly limited, but preferably has the emission peak wavelength in a range of at least 250 to 260 nm.
　紫外線照射部６の光源としては、上記した波長の紫外線を発生するものであれば限定されず、例えば低圧水銀ランプ、高圧水銀ランプ、真空紫外ランプ、キセノンランプ、発光ダイオード（ＬＥＤ）等を用いることができる。紫外線照射部６の紫外線照射照度はラジカル活性種の生成濃度（生成量）に大きく影響を与えるため、安定した照度で紫外線を照射でき、発光寿命が長いことでランニングコストが低い光源が好ましい。このような光源としては、低圧水銀ランプを用いることが好ましい。また、例えば基板２が大型のものである場合は、基板２に対して照射される紫外線照度の部分的均一性や洗浄装置の小型化の点から、ＬＥＤを用いることが好ましい。ＬＥＤは発光寿命が長く照射光の直進性にも優れるため、ＬＥＤを用いることでランニングコストを低減することもできる。 The light source of the ultraviolet irradiation unit 6 is not limited as long as it generates ultraviolet light having the above-described wavelength. For example, a low pressure mercury lamp, a high pressure mercury lamp, a vacuum ultraviolet lamp, a xenon lamp, a light emitting diode (LED), or the like is used. Can do. Since the ultraviolet irradiation illuminance of the ultraviolet irradiation unit 6 greatly affects the generation concentration (generation amount) of radical active species, a light source that can irradiate ultraviolet rays with a stable illuminance and has a long emission lifetime and low running cost is preferable. As such a light source, a low-pressure mercury lamp is preferably used. Further, for example, when the substrate 2 is large, it is preferable to use an LED from the viewpoint of partial uniformity of the ultraviolet illuminance irradiated on the substrate 2 and miniaturization of the cleaning device. Since the LED has a long light emission life and excellent linearity of irradiated light, the running cost can be reduced by using the LED.
　紫外線照射部６が照射する紫外線照度は、被除去物３を効率よく除去するために、２～２０ｍＷ／ｍ２であることが好ましく、３～８ｍＷ／ｍ２であることがより好ましい。基板２の洗浄面に付着した被除去物３は、オゾン水に紫外線を照射することで生じたラジカル活性種により分解され、オゾン水中に溶解することで除去される。 Ultraviolet illuminance of irradiating ultraviolet irradiation unit 6, in order to remove the matter to be removed 3 efficiently, is preferably 2 ~ 20mW / m 2, more preferably 3 ~ 8mW / m 2. The to-be-removed object 3 attached to the cleaning surface of the substrate 2 is decomposed by radical active species generated by irradiating ozone water with ultraviolet rays, and is removed by dissolving in ozone water.
　紫外線照射部６の光源から紫外線照射面２ｂまでの距離は、基板２の吸光係数やオゾン水の濃度、使用する光源の種類等により適宜設定することができる。空気中において、紫外線照度が光源からの距離の２乗に反比例することを考慮して、例えば、数百ｍｍ以下、好ましくは５～２０ｍｍとする。これにより、紫外線発光照度が、２～２０ｍＷ／ｍ２程度の紫外線光源であれば、洗浄面２ａにおける紫外線照度を３ｍＷ／ｍ２以上とすることができ、これにより洗浄効率を向上させることができる。 The distance from the light source of the ultraviolet irradiation unit 6 to the ultraviolet irradiation surface 2b can be appropriately set depending on the absorption coefficient of the substrate 2, the concentration of ozone water, the type of light source used, and the like. Considering that the illuminance of ultraviolet rays is inversely proportional to the square of the distance from the light source in the air, it is set to several hundred mm or less, preferably 5 to 20 mm, for example. Thus, the ultraviolet light emitting intensity is, if 2 ~ 20mW / m 2 about ultraviolet light source, the ultraviolet intensity in the cleaning surface 2a can be a 3 mW / m 2 or more, thereby improving the cleaning efficiency .
　本実施形態の洗浄装置１によれば、紫外線照射部６を基板２の洗浄面２ａと反対側の面２ｂ側に配置することで、紫外線照射部６を複数の搬送ローラ７の間に設置することができる。そのため、洗浄装置１を小型化することが可能である。さらに、紫外線照射部を洗浄面２ａと反対側の面２ｂ側に設けることで、紫外線照射部６の光源とガラス基板２の距離を小さくできるため、紫外線照射効率を向上させることができる。また、紫外線照射部６を基板２の上方に設置する場合には、例えばオゾン水滴がはねて紫外線照射部６光源に触れ、紫外線照射部６の光源が破損する事故が起こる懸念があり、この場合には、基板２を破損するおそれがある。これに対し、本実施形態の洗浄装置１では、紫外線照射部６を基板２の下方に設置するため、防水措置をし易い。 According to the cleaning apparatus 1 of the present embodiment, the ultraviolet irradiation unit 6 is disposed between the plurality of transport rollers 7 by disposing the ultraviolet irradiation unit 6 on the surface 2 b side opposite to the cleaning surface 2 a of the substrate 2. be able to. Therefore, it is possible to reduce the size of the cleaning device 1. Furthermore, since the distance between the light source of the ultraviolet irradiation unit 6 and the glass substrate 2 can be reduced by providing the ultraviolet irradiation unit on the surface 2b side opposite to the cleaning surface 2a, the ultraviolet irradiation efficiency can be improved. Further, when the ultraviolet irradiation unit 6 is installed above the substrate 2, for example, there is a concern that an ozone water droplet splashes and touches the light source of the ultraviolet irradiation unit 6 and the light source of the ultraviolet irradiation unit 6 may be damaged. In some cases, the substrate 2 may be damaged. On the other hand, in the cleaning apparatus 1 of the present embodiment, since the ultraviolet irradiation unit 6 is installed below the substrate 2, waterproofing is easy.
　また、紫外線照射部６を洗浄面２ａの上方に備える場合には、オゾン水滴の付着を防ぐために、紫外線の光源を例えば石英ガラス管で保護することがある。石英ガラス管と基板２の距離が近いときには、洗浄時、洗浄された有機物を含んだ水滴が飛散して、石英ガラス管に付着し、その付着した水滴が再び基板２に落下し、基板２を再汚染するおそれがある。これに対し、本実施形態の洗浄装置１では、紫外線照射部６を基板２の下方に備えるため、このようなおそれがない。さらに、本実施形態の洗浄装置１では、紫外線照射部６を基板２の下方に備えるため、紫外線照射部６を基板２の上方に備える場合に比べて、紫外線照射部６を保持するための力も小さくて良い。したがって、装置構成を簡易にできる。 In the case where the ultraviolet irradiation unit 6 is provided above the cleaning surface 2a, the ultraviolet light source may be protected by a quartz glass tube, for example, in order to prevent the adhesion of ozone water droplets. When the distance between the quartz glass tube and the substrate 2 is short, at the time of cleaning, water droplets containing the washed organic matter are scattered and adhere to the quartz glass tube, and the adhered water droplets fall again on the substrate 2, There is a risk of recontamination. On the other hand, in the cleaning apparatus 1 of the present embodiment, since the ultraviolet irradiation unit 6 is provided below the substrate 2, there is no such fear. Furthermore, since the cleaning apparatus 1 according to the present embodiment includes the ultraviolet irradiation unit 6 below the substrate 2, the force for holding the ultraviolet irradiation unit 6 is also greater than when the ultraviolet irradiation unit 6 is provided above the substrate 2. Small is good. Therefore, the apparatus configuration can be simplified.
　次に、本実施形態の洗浄装置を用いた洗浄方法について図４を参照して説明する。図４に示す本実施形態の洗浄方法は、前記基板を保持する工程Ｓ１００と、保持された前記基板の洗浄面にオゾン水を供給する工程Ｓ２００と、前記基板の洗浄面にオゾン水の接触した状態で前記基板の洗浄面２ａの反対側の面に２５０～２６０ｎｍの波長を含む紫外線を照射する工程Ｓ３００とを備えている。 Next, a cleaning method using the cleaning apparatus of this embodiment will be described with reference to FIG. In the cleaning method of this embodiment shown in FIG. 4, the step S100 for holding the substrate, the step S200 for supplying ozone water to the cleaning surface of the held substrate, and the ozone water contacted the cleaning surface of the substrate. And a step S300 of irradiating the surface of the substrate opposite to the cleaning surface 2a with ultraviolet light having a wavelength of 250 to 260 nm.
　本実施形態の洗浄装置１を用いた基板の洗浄は次のように行う。先ず、搬送ローラ７上に洗浄対象である基板２を載置して保持し、搬送ローラ７を作動させて基板２を搬送する。そして、搬送される基板の洗浄面２ａに、工程Ｓ２００でオゾン水ノズル５ｂからオゾンを供給しながら、工程Ｓ３００で紫外線照射面２ｂ側から紫外線照射部６により紫外線を照射する。このときの、オゾン水ノズル５ｂのオゾン水供給流量は、洗浄対象となる基板２の面積に依存するが、洗浄性能の点から、１ｍ２あたり４０～４００Ｌ／ｍｉｎであることが好ましく、１ｍ２あたり１００～４００Ｌ／ｍｉｎであることがより好ましい。 The substrate is cleaned using the cleaning apparatus 1 of the present embodiment as follows. First, the substrate 2 to be cleaned is placed and held on the transport roller 7, and the transport roller 7 is operated to transport the substrate 2. Then, while supplying ozone from the ozone water nozzle 5b to the cleaning surface 2a of the substrate to be transported in step S200, the ultraviolet irradiation unit 6 irradiates ultraviolet rays from the ultraviolet irradiation surface 2b side in step S300. In this case, the ozone water supply flow rate of the ozone water nozzle 5b is dependent on the area of the substrate 2 to be cleaned, in terms of cleaning performance, is preferably 1 m 2 per 40 ~ 400L / min, 1m 2 More preferably, it is 100 to 400 L / min.
　なお、上記実施形態では、搬送ローラ７上に基板２を載置して保持しているが、基板２が、洗浄面２ａにオゾン水を供給している状態で、洗浄面２ａと反対側の面に上記波長の紫外線を照射可能な態様で保持されていれば、基板２の保持の態様や方法は特に限定されない。 In the above embodiment, the substrate 2 is placed and held on the transport roller 7, but the substrate 2 is in a state where ozone water is supplied to the cleaning surface 2a, and is opposite to the cleaning surface 2a. There are no particular limitations on the manner or method of holding the substrate 2 as long as the surface is held in such a manner that it can be irradiated with ultraviolet rays having the above-mentioned wavelength.
　洗浄装置１における基板の洗浄は、バッチ式で行ってもよく、連続式で行ってもよい。小型の基板を洗浄する場合にはバッチ式で行うことが好ましい。 The cleaning of the substrate in the cleaning apparatus 1 may be performed batchwise or continuously. When cleaning a small substrate, it is preferable to use a batch method.
　本発明の洗浄方法は、省エネルギー化、低コスト化、高洗浄能を有することを特徴とする洗浄方法であり、特に、洗浄面積の大きい液晶ガラス基板の洗浄に適用することで大きな効果を発揮することができる。特に、液晶ガラス基板は近年その大型化が顕著であり、洗浄の均一性及び洗浄時間の短縮を目的として平流し洗浄が主流となりつつある。本発明の効果は平流し洗浄方法のみに限定されず、洗浄液をシャワー等で掛け流すシャワリング法や、回転する基板上に洗浄液を供給するスピン洗浄法、基板を洗浄液の入ったバッチ式浸漬槽に浸漬する浸漬洗浄法及びそれらの組み合わせ等の、洗浄液を用いる従来公知のあらゆる洗浄方法に適用することが可能であり、いずれの洗浄方法についても本実施形態と同様に、洗浄効率の向上効果を得ることができる。また、上述したような各洗浄方法にスポンジなどを使用した物理的洗浄を併用することにより、洗浄効率を一層高めることもできる。 The cleaning method of the present invention is a cleaning method characterized by energy saving, cost reduction, and high cleaning ability, and exhibits a great effect particularly when applied to cleaning of a liquid crystal glass substrate having a large cleaning area. be able to. In particular, the liquid crystal glass substrate has been remarkably increased in size in recent years, and flat-flow cleaning is becoming the mainstream for the purpose of cleaning uniformity and cleaning time. The effect of the present invention is not limited only to the flat-flow cleaning method, the showering method in which the cleaning liquid is poured in the shower, the spin cleaning method for supplying the cleaning liquid onto the rotating substrate, and the batch type immersion bath in which the cleaning liquid is contained It is possible to apply to any conventionally known cleaning method using a cleaning liquid, such as an immersion cleaning method and a combination thereof, and any cleaning method can improve the cleaning efficiency as in this embodiment. Obtainable. In addition, the cleaning efficiency can be further improved by combining physical cleaning using a sponge or the like with each of the cleaning methods as described above.
　以上、本実施形態の洗浄装置によれば、従来の濃厚薬品や洗浄液を用いた洗浄方法に比べて排水処理負荷や環境負荷を軽減することができ、装置構成も簡素化することが可能である。したがって、オゾン水による基板の洗浄効率を向上させることができる。 As described above, according to the cleaning apparatus of the present embodiment, it is possible to reduce the wastewater treatment load and the environmental burden compared to the conventional cleaning method using concentrated chemicals and cleaning liquids, and it is possible to simplify the apparatus configuration. . Therefore, the cleaning efficiency of the substrate with ozone water can be improved.
　次に、実施例を説明する。
(実施例１)
　被洗浄物として、大きさが縦５０ｍｍ×横５０ｍｍ×厚み０．７ｍｍであって、２５４ｎｍの波長の紫外線に対する透過率が９９％の液晶ガラス基板を用いた。この基板の洗浄面に、濃度１００ｐｐｍのオゾン水を流量１Ｌ／ｍｉｎ（１ｍ２あたりで４００Ｌ／ｍｉｎ）で供給するとともに、洗浄面の反対側の面に２５４ｎｍ付近の波長の紫外線を、ガラス基板より１０ｍｍ下方から紫外線照度３．８ｍＷ／ｍ２で照射した。紫外線照射装置としては、低圧水銀ランプＡＹ－１１(商品名、日本フォトサイエンス(株)社製)を用いた。 Next, examples will be described.
(Example 1)
As the object to be cleaned, a liquid crystal glass substrate having a size of 50 mm in length, 50 mm in width, and 0.7 mm in thickness and having a transmittance of 99% for ultraviolet rays having a wavelength of 254 nm was used. Ozone water having a concentration of 100 ppm is supplied to the cleaning surface of this substrate at a flow rate of 1 L / min (400 L / min per 1 m 2 ), and ultraviolet light having a wavelength near 254 nm is applied to the surface opposite to the cleaning surface from the glass substrate. Irradiation was performed at a UV illuminance of 3.8 mW / m 2 from below 10 mm. As the ultraviolet irradiation device, a low-pressure mercury lamp AY-11 (trade name, manufactured by Nippon Photo Science Co., Ltd.) was used.
　洗浄前の液晶ガラス基板表面における水接触角と、洗浄時間０秒、３０秒、６０秒、１８０秒、３００秒、６００秒後の液晶ガラス基板表面における水接触角を接触角計ＰＧ－Ｘ(商品名、（株）マツボー社製)により測定した。水接触角の測定結果を表１に示す。水接触角が小さいほど、液晶ガラス基板に付着した有機物が少なく、より良好に洗浄されていることを示す。また、用いた低圧水銀ランプの波長特性を図５に示す。 The water contact angle on the surface of the liquid crystal glass substrate before cleaning and the water contact angle on the surface of the liquid crystal glass substrate after cleaning times of 0 seconds, 30 seconds, 60 seconds, 180 seconds, 300 seconds, and 600 seconds are measured with a contact angle meter PG-X ( (Trade name, manufactured by Matsubo Co., Ltd.). The measurement results of the water contact angle are shown in Table 1. It shows that the smaller the water contact angle, the less organic matter adhered to the liquid crystal glass substrate and the better the cleaning is. The wavelength characteristics of the low-pressure mercury lamp used are shown in FIG.
（比較例１）
　実施例１において、紫外線を洗浄面側から照射した以外は実施例１と同様の条件で液晶ガラス基板の洗浄を行い、液晶ガラス基板表面における水接触角の経時変化を測定した。結果を表１に示す。 (Comparative Example 1)
In Example 1, the liquid crystal glass substrate was cleaned under the same conditions as in Example 1 except that ultraviolet rays were irradiated from the cleaning surface side, and the change with time of the water contact angle on the liquid crystal glass substrate surface was measured. The results are shown in Table 1.
（比較例２）
　実施例１において、紫外線を照射しないで洗浄を行った以外は実施例１と同様の条件で液晶ガラス基板の洗浄を行い、液晶ガラス基板表面における水接触角の経時変化を測定した。結果を表１に併せて示す。 (Comparative Example 2)
In Example 1, the liquid crystal glass substrate was cleaned under the same conditions as in Example 1 except that cleaning was performed without irradiating ultraviolet rays, and the change with time in the water contact angle on the liquid crystal glass substrate surface was measured. The results are also shown in Table 1.
(比較例３)
　比較例１において、ファインジェット（ＰＴ－０１０Ｊ５０（プレテック社製)）を用いてオゾン水ノズル５ｂから供給するオゾン水に超音波を印加した以外は比較例１と同様の条件で液晶ガラス基板の洗浄を行い、液晶ガラス基板表面における水接触角の経時変化を測定した。結果を表１に示す。比較例３では、比較例２とほぼ同等の洗浄効果しか示さなった。これは、オゾン水膜に振動が与えられたことで、紫外線がオゾン水膜によって反射されるため、紫外線照射の効果が表れなかったことを示す。 (Comparative Example 3)
In Comparative Example 1, the liquid crystal glass substrate was cleaned under the same conditions as in Comparative Example 1 except that ultrasonic waves were applied to the ozone water supplied from the ozone water nozzle 5b using a fine jet (PT-010J50 (manufactured by Pretec)). And the change with time of the water contact angle on the surface of the liquid crystal glass substrate was measured. The results are shown in Table 1. In Comparative Example 3, only a cleaning effect substantially equivalent to that in Comparative Example 2 was shown. This indicates that the effect of ultraviolet irradiation did not appear because the ultraviolet water was reflected by the ozone water film due to the vibration applied to the ozone water film.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　以上より、波長２５０～２６０ｎｍの紫外線を照射することで洗浄効率が向上し、特に液晶ガラス基板の洗浄面と反対側の面から紫外線を照射した場合には、洗浄面側から照射した場合に比べ、短時間で接触角が小さくなる、すなわち、短時間で良好な洗浄が行われることが判明した。 As described above, the cleaning efficiency is improved by irradiating ultraviolet rays having a wavelength of 250 to 260 nm. In particular, when irradiating ultraviolet rays from the surface opposite to the cleaning surface of the liquid crystal glass substrate, the irradiation is performed from the cleaning surface side. It has been found that the contact angle decreases in a short time, that is, good cleaning is performed in a short time.
　１…洗浄装置、２…基板、２ａ…洗浄面、２ｂ…紫外線照射面、３…被洗浄物
４…オゾン水膜、５…オゾン水供給部、５ａ…オゾン水製造部、５ｂ…オゾン水ノズル、６…紫外線照射部、７…搬送ローラ。 DESCRIPTION OF SYMBOLS 1 ... Cleaning apparatus, 2 ... Board | substrate, 2a ... Cleaning surface, 2b ... Ultraviolet irradiation surface, 3 ... Object to be cleaned 4 ... Ozone water film, 5 ... Ozone water supply part, 5a ... Ozone water production part, 5b ... Ozone water nozzle , 6... UV irradiation unit, 7.

Claims (12)

  1. 　紫外線透過性の基板の洗浄装置であって、
    　前記基板の洗浄面にオゾン水を供給するオゾン水供給部と、
    　前記基板の洗浄面にオゾン水が供給された状態で前記基板の洗浄面と反対側の面に２５０～２６０ｎｍの波長を含む紫外線を照射する紫外線照射部と、
    を備えることを特徴とする紫外線透過性基板の洗浄装置。     An ultraviolet transmissive substrate cleaning apparatus,
    An ozone water supply unit for supplying ozone water to the cleaning surface of the substrate;
    An ultraviolet irradiation unit that irradiates ultraviolet light having a wavelength of 250 to 260 nm on a surface opposite to the cleaning surface of the substrate in a state where ozone water is supplied to the cleaning surface of the substrate;
    An ultraviolet transmissive substrate cleaning apparatus comprising:
  2. 　前記オゾン水供給部は、前記洗浄面に、前記オゾン水を供給するオゾン水ノズルを備えることを特徴とする請求項１記載の紫外線透過性基板の洗浄装置。 The apparatus for cleaning an ultraviolet transmissive substrate according to claim 1, wherein the ozone water supply unit includes an ozone water nozzle for supplying the ozone water on the cleaning surface.
  3. 　オゾン水を製造して前記オゾン水供給部に供給するオゾン水製造部を備えることを特徴とする請求項１又は２記載の紫外線透過性基板の洗浄装置。 3. The ultraviolet transmissive substrate cleaning apparatus according to claim 1, further comprising an ozone water production unit that produces ozone water and supplies the ozone water to the ozone water supply unit.
  4. 　前記紫外線照射部の光源から前記基板の洗浄面と反対側の面までの距離は、５～２０ｍｍであることを特徴とする請求項１又は２記載の紫外線透過性基板の洗浄装置。 3. The ultraviolet transmissive substrate cleaning apparatus according to claim 1, wherein the distance from the light source of the ultraviolet irradiation unit to the surface opposite to the cleaning surface of the substrate is 5 to 20 mm.
  5. 　前記紫外線照射部は、低圧水銀ランプ、エキシマランプ及び発光ダイオード（ＬＥＤ）から選ばれる１種以上を備えることを特徴とする請求項１又は２記載の紫外線透過性基板の洗浄装置。 3. The ultraviolet transmissive substrate cleaning apparatus according to claim 1, wherein the ultraviolet irradiation unit includes at least one selected from a low pressure mercury lamp, an excimer lamp, and a light emitting diode (LED).
  6. 　前記基板は、２５４ｎｍの波長の紫外線に対する吸光係数が５０％以下であることを特徴とする請求項１又は２記載の紫外線透過性基板の洗浄装置。 3. The ultraviolet transmissive substrate cleaning apparatus according to claim 1, wherein the substrate has an absorption coefficient of 50% or less with respect to ultraviolet rays having a wavelength of 254 nm.
  7. 　前記基板は、液晶ガラス基板であることを特徴とする請求項１又は２記載の紫外線透過性基板の洗浄装置。 3. The ultraviolet transmissive substrate cleaning apparatus according to claim 1, wherein the substrate is a liquid crystal glass substrate.
  8. 　紫外線透過性の基板の洗浄方法であって、
    　前記基板を保持する工程と、
    　保持された前記基板の洗浄面にオゾン水を供給する工程と、
    　前記基板の洗浄面にオゾン水の接触した状態で前記基板の洗浄面の反対側の面に２５０～２６０ｎｍの波長を含む紫外線を照射する工程と
    　を備えることを特徴とする紫外線透過性基板の洗浄方法。     A method for cleaning an ultraviolet transparent substrate,
    Holding the substrate;
    Supplying ozone water to the cleaning surface of the held substrate;
    Irradiating the surface opposite to the cleaning surface of the substrate with ultraviolet light having a wavelength of 250 to 260 nm in a state where the cleaning surface of the substrate is in contact with ozone water. Method.
  9. 　前記オゾン水は、オゾン濃度が５０ｐｐｍ以上であることを特徴とする請求項８記載の紫外線透過性基板の洗浄方法。 The method for cleaning an ultraviolet transmissive substrate according to claim 8, wherein the ozone water has an ozone concentration of 50 ppm or more.
  10. 　前記オゾン水の温度は、１５℃～５０℃であることを特徴とする請求項８又は９記載の紫外線透過性基板の洗浄方法。 10. The method for cleaning an ultraviolet transmissive substrate according to claim 8, wherein the temperature of the ozone water is 15 ° C. to 50 ° C.
  11. 　前記基板は、２５４ｎｍの波長の紫外線に対する吸光係数が５０％以下であることを特徴とする請求項８又は９記載の紫外線透過性基板の洗浄方法。 10. The ultraviolet transmissive substrate cleaning method according to claim 8 or 9, wherein the substrate has an absorption coefficient of 50% or less with respect to ultraviolet rays having a wavelength of 254 nm.
  12. 　前記基板は、液晶ガラス基板であることを特徴とする請求項８又は９記載の紫外線透過性基板の洗浄方法。 10. The ultraviolet transmissive substrate cleaning method according to claim 8, wherein the substrate is a liquid crystal glass substrate.
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