US20140045339A1 - Substrate treatment apparatus and substrate treatment method - Google Patents
Substrate treatment apparatus and substrate treatment method Download PDFInfo
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- US20140045339A1 US20140045339A1 US13/954,188 US201313954188A US2014045339A1 US 20140045339 A1 US20140045339 A1 US 20140045339A1 US 201313954188 A US201313954188 A US 201313954188A US 2014045339 A1 US2014045339 A1 US 2014045339A1
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- sulfuric acid
- ozone
- acid ozone
- water
- substrate
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- 239000000758 substrate Substances 0.000 title claims abstract description 125
- 238000000034 method Methods 0.000 title claims description 34
- VSHBTVRLYANFBK-UHFFFAOYSA-N ozone sulfuric acid Chemical compound [O-][O+]=O.OS(O)(=O)=O VSHBTVRLYANFBK-UHFFFAOYSA-N 0.000 claims abstract description 309
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 194
- 239000000203 mixture Substances 0.000 claims abstract description 92
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 74
- 238000002156 mixing Methods 0.000 claims abstract description 72
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000007788 liquid Substances 0.000 claims description 88
- 239000007789 gas Substances 0.000 description 41
- JRKICGRDRMAZLK-UHFFFAOYSA-N peroxydisulfuric acid Chemical compound OS(=O)(=O)OOS(O)(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-N 0.000 description 28
- 238000010586 diagram Methods 0.000 description 13
- 230000000717 retained effect Effects 0.000 description 13
- 230000001590 oxidative effect Effects 0.000 description 8
- 238000010276 construction Methods 0.000 description 7
- 230000002093 peripheral effect Effects 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- 238000004064 recycling Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000012895 dilution Substances 0.000 description 6
- 238000010790 dilution Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000005468 ion implantation Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000004380 ashing Methods 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- DAFQZPUISLXFBF-UHFFFAOYSA-N tetraoxathiolane 5,5-dioxide Chemical compound O=S1(=O)OOOO1 DAFQZPUISLXFBF-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
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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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30604—Chemical etching
-
- 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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31127—Etching organic layers
- H01L21/31133—Etching organic layers by chemical means
-
- 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
- B08B3/041—Cleaning travelling work
-
- 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
- B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/08—Acids
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/423—Stripping or agents therefor using liquids only containing mineral acids or salts thereof, containing mineral oxidizing substances, e.g. peroxy compounds
-
- 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
- H01L21/02057—Cleaning during device manufacture
-
- 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
- H01L21/67017—Apparatus for fluid treatment
- H01L21/67063—Apparatus for fluid treatment for etching
- H01L21/67075—Apparatus for fluid treatment for etching for wet etching
- H01L21/6708—Apparatus for fluid treatment for etching for wet etching using mainly spraying means, e.g. nozzles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B2203/00—Details of cleaning machines or methods involving the use or presence of liquid or steam
- B08B2203/005—Details of cleaning machines or methods involving the use or presence of liquid or steam the liquid being ozonated
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B2203/00—Details of cleaning machines or methods involving the use or presence of liquid or steam
- B08B2203/007—Heating the liquid
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- C11D2111/22—
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- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Computer Hardware Design (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Abstract
A substrate treatment apparatus is provided which is used for removing a resist from a front surface of a substrate. The apparatus includes a substrate holding unit which holds the substrate, and a sulfuric acid ozone/water mixture supplying unit which supplies a sulfuric acid ozone/water mixture to the front surface of the substrate held by the substrate holding unit, the sulfuric acid ozone/water mixture being a mixture which is prepared by mixing water with sulfuric acid ozone prepared by dissolving ozone gas in sulfuric acid.
Description
- 1. Field of the Invention
- The present invention relates to a substrate treatment apparatus and a substrate treatment method for removing a resist from a substrate such as a semiconductor wafer.
- 2. Description of Related Art
- In production processes for semiconductor devices, liquid crystal display devices and the like, a substrate treatment apparatus of a single substrate treatment type adapted to treat a single substrate at a time is often used for treating a substrate front surface with a treatment liquid. The substrate treatment apparatus of the single substrate treatment type includes a spin chuck which generally horizontally holds and rotates the substrate, and a nozzle which spouts the treatment liquid toward the front surface of the substrate rotated by the spin chuck.
- A semiconductor device production process, for example, includes the step of locally implanting an impurity such as phosphorus, arsenic or boron (ions) into a major surface (front surface) of a semiconductor wafer (hereinafter referred to simply as “wafer”). In order to prevent the ion implantation in an unnecessary portion of the wafer, a resist pattern of a photosensitive resin is formed on the front surface of the wafer to mask the unnecessary portion of the wafer with the resist in this step. After the ion implantation, the resist pattern formed on the front surface of the wafer becomes unnecessary and, therefore, a resist removing process is performed for removing the unnecessary resist.
- In a typical example of the resist removing process, the front surface of the wafer is irradiated with oxygen plasma to ash the resist on the front surface of the wafer. Then, a chemical liquid such as a sulfuric acid/hydrogen peroxide mixture is supplied to the front surface of the wafer to remove the ashed resist. Thus, the resist is removed from the front surface of the wafer. However, the irradiation with the oxygen plasma for the ashing of the resist damages a portion of the front surface of the wafer uncovered with the resist (e.g., an oxide film exposed from the resist pattern).
- In another example of the resist removing process, sulfuric acid ozone prepared by dissolving ozone gas in sulfuric acid (sulfuric acid solution) is supplied for lifting off the resist from the front surface of the wafer without the ashing. The resist lift-off process using the sulfuric acid ozone may be performed, for example, by means of a batch type apparatus disclosed in US2008/006295A1.
- In the apparatus disclosed in US2008/006295A1, sulfuric acid is retained in a treatment vessel, and ozone gas is fed into the sulfuric acid retained in the treatment vessel. Sulfuric acid ozone is prepared by mixing the sulfuric acid and the ozone gas together, and retained in the treatment vessel. Then, a substrate (wafer) having a resist pattern formed on a front surface thereof is immersed in the sulfuric acid ozone. Peroxodisulfuric acid contained in the sulfuric acid ozone has oxidative power. The resist is removed from the substrate by the oxidative power of the peroxodisulfuric acid.
- The peroxodisulfuric acid contained in the sulfuric acid ozone exhibits strong oxidative power at a higher temperature that is not lower than 140° C. Therefore, it is desirable to supply the sulfuric acid ozone at a higher temperature to the substrate for removing the resist with the use of the sulfuric acid ozone.
- In addition to the batch type apparatus, an apparatus of a single substrate treatment type adapted to treat a single substrate at a time is another type of the substrate treatment apparatus for treating the substrate with the treatment liquid. The substrate treatment apparatus of the single substrate treatment type includes a spin chuck which generally horizontally holds and rotates the substrate, and a treatment liquid nozzle which supplies the treatment liquid toward a front surface of the substrate held by the spin chuck.
- The inventors of the present invention contemplate that the sulfuric acid ozone is used as the treatment liquid to perform the resist removing process on the substrate by means of the substrate treatment apparatus of the single substrate treatment type. In particular, the inventors contemplate that the higher temperature sulfuric acid ozone is used for enhancing the resist removing capability in the resist removing process. In this case, more specifically, the sulfuric acid ozone is spouted from the treatment liquid nozzle toward the major surface (front surface) of the substrate held by the spin chuck.
- A conceivable arrangement for the substrate treatment apparatus of the single substrate treatment type is such that sulfuric acid heated up to a higher temperature equivalent to a treatment temperature (140° C.) is retained in a tank, and sulfuric acid ozone is prepared by dissolving ozone gas in the sulfuric acid retained in the tank and supplied as the treatment liquid to the treatment liquid nozzle.
- In this case, the ozone gas should be dissolved in the higher temperature sulfuric acid, so that a longer time may be required for the dissolution of the ozone gas. Further, the solubility of ozone in sulfuric acid is reduced as the liquid temperature of the sulfuric acid increases. Since the sulfuric acid retained in the tank has a higher temperature, the ozone in the sulfuric acid solution is liable to be gasified. Therefore, the sulfuric acid solution is liable to have a reduced ozone concentration. As a result, the sulfuric acid ozone supplied to the substrate is liable to contain only a small amount of peroxodisulfuric acid.
- As described above, it is necessary to supply the sulfuric acid ozone containing a greater amount of peroxodisulfuric acid in the substrate treatment apparatus of the single substrate treatment type.
- It is therefore an object of the present invention to provide a substrate treatment apparatus of a single substrate treatment type and a substrate treatment method, which are capable of advantageously removing a resist from a substrate by supplying sulfuric acid ozone containing a greater amount of peroxodisulfuric acid to the substrate.
- The present invention provides a substrate treatment apparatus to be used for removing a resist from a front surface of a substrate, the apparatus including: a substrate holding unit which holds the substrate; and a sulfuric acid ozone/water mixture supplying unit which supplies a sulfuric acid ozone/water mixture to the front surface of the substrate held by the substrate holding unit, the sulfuric acid ozone/water mixture being a mixture which is prepared by mixing water with sulfuric acid ozone prepared by dissolving ozone gas in sulfuric acid.
- With this arrangement, the sulfuric acid ozone/water mixture is supplied to the front surface of the substrate. The sulfuric acid ozone contains peroxodisulfuric acid (H2S2O8) which is a kind of persulfuric acid generated by the dissolution of the ozone gas. When the sulfuric acid ozone and the water are mixed together, dilution heat is generated by diluting the sulfuric acid ozone with the water, thereby increasing the temperature of the sulfuric acid ozone/water mixture to a predetermined higher temperature (e.g., not lower than 140° C.) that is not lower than the liquid temperature of the sulfuric acid ozone before the mixing.
- In this case, the sulfuric acid ozone/water mixture can be supplied at the higher temperature to the front surface of the substrate even if lower temperature sulfuric acid ozone (e.g., at lower than 100° C.) is used as the sulfuric acid ozone before the mixing. Further, where the sulfuric acid ozone is kept at a predetermined lower temperature before the mixing, the sulfuric acid ozone can contain a greater amount of ozone gas dissolved therein before the mixing.
- Therefore, the higher temperature sulfuric acid ozone containing a greater amount of ozone gas dissolved therein can be supplied to the front surface of the substrate. The sulfuric acid ozone in which a greater amount of ozone gas is dissolved contains a greater amount of peroxodisulfuric acid. In addition, the peroxodisulfuric acid exhibits stronger oxidative power at a higher temperature, so that the resist can be advantageously removed from the front surface of the substrate.
- The sulfuric acid ozone/water mixture supplying unit preferably includes a liquid mixture nozzle which spouts the sulfuric acid ozone/water mixture toward the front surface of the substrate held by the substrate holding unit.
- With this arrangement, the sulfuric acid ozone/water mixture containing a greater amount of ozone gas dissolved therein is spouted from the liquid mixture nozzle. Thus, the higher temperature sulfuric acid ozone containing a greater amount of peroxodisulfuric acid can be supplied to the front surface of the substrate by means of the simple arrangement.
- According to one embodiment of the present invention, the sulfuric acid ozone/water mixture supplying unit further includes a mixing portion which mixes the sulfuric acid ozone and the water together, a sulfuric acid ozone supplying portion which feeds the sulfuric acid ozone to the mixing portion, and a liquid mixture supply pipe which supplies the sulfuric acid ozone/water mixture prepared by the mixing in the mixing portion to the liquid mixture nozzle.
- With this arrangement, the sulfuric acid ozone and the water are mixed together in the mixing portion connected to the liquid mixture supply pipe. Therefore, the sulfuric acid ozone/water mixture is spouted from the liquid mixture nozzle substantially immediately after the mixing. Therefore, the sulfuric acid ozone/water mixture which is substantially free from reduction in peroxodisulfuric acid amount (concentration) can act on the resist present on the front surface of the substrate. Thus, the resist can be more advantageously removed from the front surface of the substrate.
- In this case, the sulfuric acid ozone supplying portion preferably includes a sulfuric acid ozone retaining portion which retains the sulfuric acid ozone, and a circulation passage connected to the sulfuric acid ozone retaining portion and the mixing portion to circulate the sulfuric acid ozone from the sulfuric acid ozone retaining portion back into the sulfuric acid ozone retaining portion therethrough.
- According to another embodiment of the present invention, the liquid mixture nozzle includes a mixing chamber in which the sulfuric acid ozone and the water are mixed together, a sulfuric acid ozone inlet port through which the sulfuric acid ozone is fed into the mixing chamber, a water inlet port through which the water is fed into the mixing chamber, and a liquid mixture outlet port from which the sulfuric acid ozone/water mixture prepared by the mixing in the mixing chamber is spouted.
- With this arrangement, the sulfuric acid ozone and the water are mixed together within the liquid mixture nozzle. Therefore, the sulfuric acid ozone/water mixture is supplied to the front surface of the substrate immediately after the mixing. Accordingly, the sulfuric acid ozone/water mixture which is substantially free from reduction in peroxodisulfuric acid amount (concentration) can act on the resist present on the front surface of the substrate. Thus, the resist can be more advantageously removed from the front surface of the substrate.
- The sulfuric acid ozone/water mixture supplying unit may include a sulfuric acid ozone nozzle which spouts the sulfuric acid ozone toward the front surface of the substrate held by the substrate holding unit, and a water nozzle which spouts the water toward the front surface of the substrate held by the substrate holding unit.
- With this arrangement, the sulfuric acid ozone spouted from the sulfuric acid ozone nozzle and the water spouted from the water nozzle are mixed together on the front surface of the substrate, so that the sulfuric acid ozone/water mixture which is substantially free from reduction in peroxodisulfuric acid amount (concentration) can act on the resist present on the front surface of the substrate. Thus, the resist can be more advantageously removed from the front surface of the substrate.
- The present invention further provides a substrate treatment method to be used for removing a resist from a substrate front surface, the method comprising a sulfuric acid ozone/water mixture supplying step of supplying a sulfuric acid ozone/water mixture to a front surface of a substrate held by a substrate holding unit, the sulfuric acid ozone/water mixture being a mixture which is prepared by mixing water with sulfuric acid ozone prepared by dissolving ozone gas in sulfuric acid.
- In this method, the sulfuric acid ozone/water mixture is supplied to the front surface of the substrate. The sulfuric acid ozone contains peroxodisulfuric acid (H2S2O8) which is a kind of persulfuric acid generated by the dissolution of the ozone gas. When the sulfuric acid ozone and the water are mixed together, dilution heat is generated by diluting the sulfuric acid ozone with the water, thereby increasing the temperature of the sulfuric acid ozone/water mixture to a predetermined higher temperature (e.g., not lower than 140° C.) that is not lower than the liquid temperature of the sulfuric acid ozone before the mixing.
- In this case, the sulfuric acid ozone/water mixture can be supplied at the higher temperature to the front surface of the substrate even if lower temperature sulfuric acid ozone (e.g., at lower than 100° C.) is used as the sulfuric acid ozone before the mixing. Further, where the sulfuric acid ozone is kept at a predetermined lower temperature before the mixing, the sulfuric acid ozone can contain a greater amount of ozone gas dissolved therein before the mixing.
- Thus, the higher temperature sulfuric acid ozone containing a greater amount of ozone gas dissolved therein can be supplied to the front surface of the substrate. The sulfuric acid ozone in which a greater amount of ozone gas is dissolved contains a greater amount of peroxodisulfuric acid. In addition, the peroxodisulfuric acid exhibits stronger oxidative power at a higher temperature, so that the resist can be advantageously removed from the front surface of the substrate.
- The foregoing and other objects, features and effects of the present invention will become more apparent from the following detailed description of the preferred embodiments with reference to the attached drawings.
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FIG. 1 is a diagram schematically showing the construction of a substrate treatment apparatus according to one embodiment of the present invention. -
FIG. 2 is a block diagram showing the electrical construction of the substrate treatment apparatus shown inFIG. 1 . -
FIG. 3 is a process diagram showing an exemplary resist removing process to be performed by the substrate treatment apparatus shown inFIG. 1 . -
FIG. 4 is a diagram showing a relationship between the liquid temperature of sulfuric acid and the ozone saturated concentration of sulfuric acid. -
FIG. 5 is a diagram showing the results of resist removing test. -
FIG. 6 is a diagram schematically showing the construction of a substrate treatment apparatus according to another embodiment of the present invention. -
FIG. 7 is a diagram schematically showing the construction of a substrate treatment apparatus according to further another embodiment of the present invention. -
FIG. 8 is a diagram schematically showing the construction of a substrate treatment apparatus according to still another embodiment of the present invention. -
FIG. 1 is a diagram schematically showing the construction of asubstrate treatment apparatus 1 according to one embodiment of the present invention. Thesubstrate treatment apparatus 1 is an apparatus of a single wafer treatment type adapted to treat a single round wafer W (an example of the substrate) at a time. Thesubstrate treatment apparatus 1 includes atreatment chamber 2 in which a resist removing process is performed to remove an unnecessary resist from a front surface (major surface) of a wafer W after an ion implantation process is performed to implant an impurity into the front surface of the wafer W or after a dry etching process is performed on the front surface of the wafer W, and a sulfuric acidozone supplying portion 3 provided separately from thetreatment chamber 2 for supplying sulfuric acid ozone (a liquid prepare by dissolving ozone gas in sulfuric acid) to thetreatment chamber 2. - The
treatment chamber 2 is defined by a partition wall, and accommodates therein a spin chuck (substrate holding unit) 4 which generally horizontally holds the wafer W and rotates the wafer W about a rotation axis (vertical axis) A1 vertically extending through the center thereof, a sulfuric acid ozone/water nozzle (liquid mixture nozzle) 5 which spouts a sulfuric acid ozone/water mixture (a mixture of sulfuric acid ozone and water) toward the front surface of the wafer W held by thespin chuck 4, and a container-like cup 6 which surrounds thespin chuck 4 to receive the sulfuric acid ozone/water mixture, a rinse liquid and SC1 (ammonia/hydrogen peroxide mixture) flowing down or splashed from the wafer W. - The
spin chuck 4 is, for example, of a clamping type. More specifically, thespin chuck 4 includes aspin motor 8, aspin shaft 9 unitary with a drive shaft of thespin motor 8, a disk-shapedspin base 10 generally horizontally attached to an upper end of thespin shaft 9, and a plurality of clampingmembers 11 which are arranged generally equidistantly on a peripheral edge portion of thespin base 10. Thus, thespin chuck 4 is capable of rotating the horizontally held wafer W together with thespin base 10 about the rotation axis A1 by rotating thespin base 10 by a rotative drive force of thespin motor 8 with the wafer W clamped by the clampingmembers 11. - The
spin chuck 4 is not limited to the clamping type, but may be of a vacuum suction type (vacuum chuck) capable of horizontally holding the wafer W by sucking a back surface of the wafer W by vacuum and rotating about the vertical rotation axis in this state to rotate the wafer W held by thespin chuck 4. - The
cup 6 includes a hollow cylindricalfirst cup 41 which collects the rinse liquid and the SC1, a hollow cylindricalsecond cup 42 which collects the sulfuric acid ozone/water mixture, a hollow cylindricalfirst guard 43 which is movable up and down with respect to thefirst cup 41, a hollow cylindricalsecond guard 44 which is movable up and down with respect to thesecond cup 42, and a guard lift mechanism 45 (seeFIG. 2 ) which independently moves up and down thefirst guard 43 and thesecond guard 44. Awaste liquid line 50 is connected to a bottom of thefirst cup 41. Thewaste liquid line 50 is connected to a waste liquid treatment facility (not shown) provided outside thesubstrate treatment apparatus 1. Arecovery line 7 for recovering the sulfuric acid ozone/water mixture is connected to a bottom of thesecond cup 42. Theguard lift mechanism 45 moves up and down therespective guards guard guard - The sulfuric acid ozone/water nozzle 5 is attached to a distal end of an
arm 12 generally horizontally extending above thespin chuck 4. Thearm 12 is supported by an arm support shaft (not shown) generally vertically extending on a lateral side of thespin chuck 4. Anozzle drive mechanism 14 is connected to thearm 12 so that thearm 12 can be pivoted about the arm support shaft by a drive force of thenozzle drive mechanism 14. A sulfuric acid ozone/water supply pipe (liquid mixture supply pipe) 16 extending from a water mixing portion (mixing portion) 15 is connected at its distal end to the sulfuric acid ozone/water nozzle 5. - A sulfuric acid
ozone supply pipe 17 to which sulfuric acid ozone (prepared, for example, by dissolving ozone gas at a higher ozone concentration on the order of 55 to 65 ppm in 96 to 98 wt % concentrated sulfuric acid) is supplied from the sulfuric acidozone supply portion 3 and awater supply pipe 18 to which water is supplied are connected to thewater mixing portion 15. The water is supplied from a water supply source to thewater supply pipe 18. Awater valve 20 which opens and closes thewater supply pipe 18 is provided in thewater supply pipe 18. Examples to the water to be supplied to thewater supply pipe 18 include DIW (deionized water), carbonated water, electrolytic ion water, ozone water, reduced water (hydrogen water) and magnetic water. - The sulfuric acid ozone to be supplied to the sulfuric acid
ozone supply pipe 17 is maintained at a predetermined lower temperature (lower than 100° C., e.g., about 80° C.) in the sulfuric acidozone supplying portion 3. The water to be supplied to thewater supply pipe 18 has a liquid temperature equal to an ordinary temperature (about 25° C.). The flow rate ratio (weight ratio) between the sulfuric acid ozone supplied to the sulfuric acidozone supply pipe 17 and the water supplied to thewater supply pipe 18 is, for example, 1: not less than 0.1 and less than 0.4, for example, 1:0.3. - A stirring
flow pipe 21 is provided in the sulfuric acid ozone/water supply pipe 16. The stirringflow pipe 21 includes a pipe member, and a plurality of stirring fins of rectangular plates which are each twisted approximately 180 degrees about an axis extending in a liquid flow direction and arranged along a pipe center axis extending in the liquid flow direction in the pipe member with their twist angular positions alternately offset by 90 degrees about the pipe center axis. It is noted that the stirringflow pipe 21 is not necessarily required. - The sulfuric acid
ozone supplying portion 3 is defined by a partition wall, and includes a sulfuric acid ozone tank (sulfuric acid ozone retaining portion) 22 which retains the sulfuric acid ozone to be supplied to thewater mixing portion 15, and the sulfuric acidozone supply pipe 17 described above. In the sulfuric acid ozone retained in the sulfuricacid ozone tank 22, sulfate ions (SO4 2−) present in sulfuric acid are oxidized through an oxidation reaction to generate peroxodisulfuric acid (H2S2O8) that has stronger oxidative power than peroxomonosulfuric acid. - The sulfuric acid
ozone supply pipe 17 is connected at its one end to thewater mixing portion 15, and connected at its other end to the sulfuricacid ozone tank 22. Apump 24, aheater 23, an ozone gas mixing portion 25, afilter 26 and a three-way valve 27 are provided in this order from the sulfuricacid ozone tank 22 in the sulfuric acidozone supply pipe 17. Theheater 23 is capable of controlling the temperature of the sulfuric acid ozone flowing through the sulfuric acidozone supply pipe 17. Thepump 24 is capable of pumping the sulfuric acid ozone from the sulfuricacid ozone tank 22 into the sulfuric acidozone supply pipe 17. Thepump 24 is constantly driven to constantly pump up the sulfuric acid ozone from the sulfuricacid ozone tank 22. Thefilter 26 is capable of removing foreign matter from the sulfuric acid ozone flowing through the sulfuric acidozone supply pipe 17. - A
return pipe 28 through which the sulfuric acid ozone flowing through the sulfuric acidozone supply pipe 17 is returned into the sulfuricacid ozone tank 22 is connected to the three-way valve 27 to be branched from the sulfuric acidozone supply pipe 17. Thus, acirculation passage 30 is formed which extends from the sulfuricacid ozone tank 22 to the three-way valve 27 through the sulfuric acidozone supply pipe 17 and back to the sulfuricacid ozone tank 22 through thereturn pipe 28. The three-way valve 27 feeds the sulfuric acid ozone flowing through the sulfuric acidozone supply pipe 17 selectively to thewater mixing portion 15 or to thereturn pipe 28. - An ozone
gas supply pipe 31 which supplies ozone gas from an ozone gas generation source is connected to the ozone gas mixing portion 25 to be branched from the sulfuric acidozone supply pipe 17. Anozone gas valve 32 which opens and closes the ozonegas supply pipe 31 is provided in the ozonegas supply pipe 31. The ozone gas mixing portion 25 is adapted to mix the ozone gas with the sulfuric acid ozone flowing through the sulfuric acidozone supply pipe 17. - A sulfuric
acid replenishment pipe 33 through which fresh sulfuric acid (e.g., fresh concentrated sulfuric acid having a concentration of 96 to 98 wt %) is supplied to the sulfuricacid ozone tank 22 for replenishment is connected to the sulfuricacid ozone tank 22. Areplenishment valve 34 which opens and closes the sulfuricacid replenishment pipe 33 is provided in the sulfuricacid replenishment pipe 33. By opening and closing thereplenishment valve 34, the supply of the fresh sulfuric acid to the sulfuricacid ozone tank 22 is switched on and off. The supply of the fresh sulfuric acid to the sulfuricacid ozone tank 22 for the replenishment is carried out when the sulfuricacid ozone tank 22 is empty or when the amount of the sulfuric acid ozone retained in the sulfuricacid ozone tank 22 is reduced to less than a predetermined amount. - On the other hand, the
recovery line 7 is connected at its one end to a bottom of the cup 6 (second cup 42), and connected at its other end to a recycling device (not shown) provided outside thesubstrate treatment apparatus 1. The sulfuric acid ozone received by the cup 6 (second cup 42) is fed into the recycling device through therecovery line 7, then subjected to a predetermined treatment in the recycling device, and supplied to the sulfuricacid supplying portion 3. - When the three-
way valve 27 is controlled to feed the sulfuric acid ozone from the sulfuric acidozone supply pipe 17 to thereturn pipe 28 with thepump 24 driven, the sulfuric acid ozone pumped up from the sulfuricacid ozone tank 22 flows through theheater 23, thefilter 26, the three-way valve 27 and thereturn pipe 28 back into the sulfuricacid ozone tank 22. Thus, the sulfuric acid ozone is circulated from the sulfuricacid ozone tank 22 through thecirculation passage 30. The sulfuric acid ozone circulated from the sulfuricacid ozone tank 22 through thecirculation passage 30 is temperature-controlled by theheater 23 to be maintained at the predetermined lower temperature (e.g., about 80° C.). The concentration of the sulfuric acid ozone in the sulfuric acid ozone tank 22 (the ozone concentration of the sulfuric acid ozone) is constantly controlled by opening and closing thereplenishment valve 34 and theozone gas valve 32. The sulfuric acid ozone circulated from the sulfuricacid ozone tank 22 through thecirculation passage 30 is filtered by thefilter 26, whereby particles and other foreign matter are removed from the sulfuric acid ozone. This substantially prevents sulfuric acid ozone containing foreign matter from being supplied to the sulfuric acid ozone/water nozzle 5. - When the three-
way valve 27 is controlled to feed the sulfuric acid ozone from the sulfuric acidozone supply pipe 17 to thewater mixing portion 15 with thepump 24 driven, the sulfuric acid ozone pumped up from the sulfuricacid ozone tank 22 flows through theheater 23, thefilter 26 and the three-way valve 27 into thewater mixing portion 15. At the same time, thewater valve 20 is opened, whereby the water flows into thewater mixing portion 15. Thus, the sulfuric acid ozone and the water flow from thewater mixing portion 15 toward the sulfuric acid ozone/water nozzle 5 through the sulfuric acid ozone/water supply pipe 16. The sulfuric acid ozone and the water pass through the stirringflow pipe 21 to be thereby sufficiently stirred, when flowing through the sulfuric acid ozone/water supply pipe 16. The stirring causes the sulfuric acid ozone to sufficiently react with the water, and dilution heat generated when the sulfuric acid ozone is diluted with the water increases the temperature of the sulfuric acid ozone to a temperature not lower than the liquid temperature (e.g., about 80° C.) of the sulfuric acid ozone before the mixing. Thus, the sulfuric acid ozone/water mixture is spouted from an outlet port of the sulfuric acid ozone/water nozzle 5 at a predetermined higher temperature (not lower than 140° C., e.g., about 150° C.) that is optimum for the resist removing process. - The
substrate treatment apparatus 1 further includes a rinseliquid nozzle 46 which supplies a rinse liquid to the front surface of the wafer W held by thespin chuck 4, and anSC1 nozzle 49 which supplies SC1 as a cleaning chemical liquid to the front surface of the wafer W held by thespin chuck 4. The rinseliquid nozzle 46 is, for example, a straight nozzle which spouts the rinse liquid in the form of a continuous stream, and is fixedly provided above thespin chuck 4 with its outlet port directing toward around the rotation center of the wafer W. A rinseliquid supply pipe 47 to which the rinse liquid is supplied from a rinse liquid supply source is connected to the rinseliquid nozzle 46. Examples of the rinse liquid include DIW, carbonated water, electrolytic ion water, ozone water, reduced water (hydrogen water) and magnetic water. A rinseliquid valve 48 which switches on and off the supply of the rinse liquid from the rinseliquid nozzle 46 is provided in the rinseliquid supply pipe 47. - The
SC1 nozzle 49 is, for example, a straight nozzle which spouts the SC1 in the form of a continuous stream, and is fixedly provided above thespin chuck 4 with its outlet port directing toward around the rotation center of the wafer W. AnSC1 supply pipe 50 to which the SC1 is supplied from an SC1 supply source is connected to theSC1 nozzle 49. AnSC1 valve 51 which switches on and off the supply of the SC1 from theSC1 nozzle 49 is provided in theSC1 supply pipe 50. -
FIG. 2 is a block diagram showing the electrical construction of thesubstrate treatment apparatus 1. - The
substrate treatment apparatus 1 includes acontroller 40 configured to include a microcomputer. Thecontroller 40 controls the operations of thespin motor 8, thenozzle movement mechanism 14, thepump 24, theguard lift mechanism 45 and the like. Thecontroller 40 switches on and off energization of theheater 23. Further, thecontroller 40 controls the switching operation of the three-way valve 27 and the opening and closing operations of theozone gas valve 32, thereplenishment valve 34 and the like. -
FIG. 3 is a process diagram showing an exemplary resist removing process to be performed by thesubstrate treatment apparatus 1. Referring toFIGS. 1 to 3 , the exemplary process to be performed by thesubstrate treatment apparatus 1 will hereinafter be described. - In the resist removing process, a transport robot (not shown) is controlled to load a wafer W subjected to the ion implantation process into the treatment chamber 2 (Step S1: wafer loading step). It is herein assumed that the wafer W is not subjected to a resist ashing process. The wafer W is transferred to the
spin chuck 4 with its front surface facing up. During the loading of the wafer W, the sulfuric acid ozone/water nozzle 5 is retracted to a lateral side of thespin chuck 4, and the first andsecond guards guards - In turn, a sulfuric acid ozone treatment step (sulfuric acid ozone/water mixture supplying step) is performed in which the sulfuric acid ozone is supplied to the wafer W (Step S2). More specifically, the
controller 40 controls thenozzle movement mechanism 14 to move the sulfuric acid ozone/water nozzle 5 to above the rotation center of the wafer W held by thespin chuck 4. Thecontroller 40 controls theguard lift mechanism 45 to move down thefirst guard 43 to the lower position and move up thesecond guard 44 to the upper position. Further, thecontroller 40 controls thespin motor 8 to rotate the wafer W held by thespin chuck 4. Then, thecontroller 40 spouts the sulfuric acid ozone/water mixture from the sulfuric acid ozone/water nozzle 5 toward the rotation center of the front surface of the wafer W, while causing thespin chuck 4 to rotate the wafer W. Thus, the sulfuric acid ozone/water mixture is supplied to the entire front surface of the wafer W, whereby the front surface of the wafer W is treated with the sulfuric acid ozone/water mixture (sulfuric acid ozone treatment). - The sulfuric acid ozone/water mixture containing a greater amount of ozone gas dissolved therein, is spouted at the higher temperature (e.g., about 150° C.) from the sulfuric acid ozone/water nozzle 5. Since a greater amount of ozone gas is dissolved in the sulfuric acid ozone, the sulfuric acid ozone contains a greater amount of peroxodisulfuric acid. In addition, the sulfuric acid ozone has a higher temperature (e.g., about 150° C.) at which the peroxodisulfuric acid exhibits stronger oxidative power. Therefore, the resist can be advantageously removed from the front surface of the wafer W. The sulfuric acid ozone/water mixture is splashed from the peripheral edge portion of the front surface of the wafer W, and received by the interior wall of the
second guard 44 to be, retained in a bottom portion of thesecond cup 42 and recovered through therecovery line 7. - After the sulfuric acid ozone treatment is performed for a predetermined period, the
controller 40 stops spouting the sulfuric acid ozone/water mixture from the sulfuric acid ozone/water nozzle 5. Thereafter, thecontroller 40 controls thenozzle drive mechanism 14 to retract the sulfuric acid ozone/water nozzle 5 to the lateral side of thespin chuck 4. Thecontroller 40 controls theguard lift mechanism 45 to move up the first andsecond guards - In the sulfuric acid ozone treatment step, the
nozzle drive mechanism 14 may be controlled so that a supplying position at which the sulfuric acid ozone/water mixture is supplied from the sulfuric acid ozone/water nozzle 5 on the front surface of the wafer W is reciprocally moved along an arcuate path crossing a wafer rotating direction within a region extending from the rotation center of the wafer W to the peripheral edge portion of the wafer W. - Subsequently, a rinsing step is performed in which the rinse liquid is supplied to the wafer W (Step S3). More specifically, the
controller 40 opens the rinseliquid valve 48 to spout the rinse liquid from the rinseliquid nozzle 46 toward the center portion of the front surface of the wafer W, while causing thespin chuck 4 to rotate the wafer W. Thus, the rinse liquid is supplied to the entire front surface of the wafer W, whereby the sulfuric acid ozone adhering to the wafer W is rinsed away with the rinse liquid (rinsing process). The rinse liquid (rinse liquid containing the sulfuric acid ozone) is splashed from the peripheral edge portion of the front surface of the wafer W, and received by the interior wall of thefirst guard 43 to be retained in a bottom portion of thefirst cup 41 and drained through thewaste liquid line 50. After the rinsing process is performed for a predetermined period, thecontroller 40 closes the rinseliquid valve 48 to stop spouting the rinse liquid from the rinseliquid nozzle 46. - In turn, an SC1 treatment step is performed in which the SC1 is supplied to the wafer W (Step S4). More specifically, the
controller 40 opens theSC1 valve 51 to spout the SC1 from theSC1 nozzle 49 toward the center portion of the front surface of the wafer W, while causing thespin chuck 4 to rotate the wafer W. Thus, the SC1 is supplied to the entire front surface of the wafer W, whereby the sulfuric acid adhering to the wafer W is washed away with the SC1 (SC1 treatment). The SC1 is splashed from the peripheral edge portion of the front surface of the wafer W, and received by the interior wall of thefirst guard 43 to be retained in the bottom portion of thefirst cup 41 and drained through thewaste liquid line 50. After the SC1 treatment is performed for a predetermined period, thecontroller 40 closes theSC1 valve 51 to stop spouting the SC1 from theSC1 nozzle 49. - Where the
SC1 nozzle 49 is a movable nozzle like the sulfuric acid ozone/water nozzle 5, a supplying position at which the SC1 is supplied from theSC1 nozzle 49 on the front surface of the wafer W is reciprocally moved along an arcuate path crossing the wafer rotating direction within the region extending from the rotation center of the wafer W to the peripheral edge portion of the wafer W in the SC1 treatment step. - In turn, a rinsing step is performed in which the rinse liquid is supplied to the wafer W (Step S5). More specifically, the
controller 40 opens the rinseliquid valve 48 to spout the rinse liquid from the rinseliquid nozzle 46 toward the center portion of the front surface of the wafer W, while causing thespin chuck 4 to rotate the wafer W. Thus, the rinse liquid is supplied to the entire front surface of the wafer W, whereby the SC1 adhering to the wafer W is rinsed away with the rinse liquid (rinsing process). The rinse liquid (rinse liquid containing the SC1) is splashed from the peripheral edge portion of the front surface of the wafer W, and received by the interior wall of thefirst guard 43 to be retained in the bottom portion of thefirst cup 43 and drained through thewaste liquid line 50. After the rinsing process is performed for a predetermined period, thecontroller 40 closes the rinseliquid valve 48 to stop spouting the rinse liquid from the rinseliquid nozzle 46. - Subsequently, a spin drying step is performed to spin-dry the wafer W (Step S6). More specifically, the
controller 40 controls thespin motor 8 to rotate the wafer W at a higher rotation speed (e.g., not lower than 2500 rpm). Thus, the rinse liquid adhering to the front surface of the wafer W is spun off around the wafer W. Thus, the rinse liquid is removed from the wafer W to dry the wafer W (spin drying process). After the spin drying process is performed for a predetermined period, thecontroller 40 controls thespin motor 8 to cause thespin chuck 4 to stop rotating the wafer W, and controls theguard lift mechanism 45 to move down thefirst guard 43 and thesecond guard 44 to the lower position. Thus, the resist removing process on the single wafer W is completed. The transport robot (not shown) unloads the treated wafer W from the treatment chamber 2 (Step S7). -
FIG. 4 is a diagram showing a relationship between the liquid temperature of sulfuric acid and the ozone saturated concentration of sulfuric acid. -
FIG. 4 indicates that the ozone saturated concentration of sulfuric acid is reduced as the liquid temperature of sulfuric acid increases. - Since the sulfuric acid ozone is circulated at the predetermined lower temperature (e.g., about 80° C.) through the
circulation passage 30 in the sulfuric acidozone supplying portion 3, the circulated sulfuric acid ozone can have a higher ozone concentration (55 to 65 ppm). - According to this embodiment, as described above, the sulfuric acid ozone/water mixture prepared by mixing the sulfuric acid ozone and the water together is supplied to the front surface of the wafer W from the sulfuric acid ozone/water nozzle 5. The sulfuric acid ozone contains peroxodisulfuric acid (H2S2O8) which is a kind of persulfuric acid generated by the dissolution of the ozone gas. When the sulfuric acid ozone and the water are mixed together, dilution heat is generated by diluting the sulfuric acid ozone with the water, thereby increasing the temperature of the sulfuric acid ozone/water mixture to a temperature not lower than the liquid temperature of the sulfuric acid ozone before the mixing.
- Further, the sulfuric acid ozone having the predetermined lower temperature (e.g., about 80° C.) is used as the sulfuric acid ozone before the mixing. Since the sulfuric acid ozone has the lower temperature before the mixing, a greater amount of ozone gas can be dissolved in the sulfuric acid ozone before the mixing. That is, the sulfuric acid ozone has a higher ozone concentration before the mixing.
- Therefore, the sulfuric acid ozone containing a greater amount of ozone gas can be supplied at the higher temperature (e.g., about 150° C.) to the front surface of the wafer W. Since a greater amount of ozone gas is dissolved in the sulfuric acid ozone, a greater amount of peroxodisulfuric acid is contained in the sulfuric acid ozone. In addition, the peroxodisulfuric acid exhibits stronger oxidative power at a higher temperature, so that the resist can be advantageously removed from the front surface of the wafer W.
- The sulfuric acid ozone and the water are mixed together in the
water mixing portion 15 connected to the sulfuric acid ozone/water supply pipe 16. Therefore, the sulfuric acid ozone/water mixture is spouted from the sulfuric acid ozone/water nozzle 5 substantially immediately after the mixing. Accordingly, the sulfuric acid ozone/water mixture which is substantially free from reduction in peroxodisulfuric acid amount (concentration) can act on the resist present on the front surface of the wafer W. Thus, the resist can be more advantageously removed from the front surface of the wafer W. - Next, a resist removing test will be described.
- A resist removing test was performed by the
substrate treatment apparatus 1 to remove (lift off) an unashed resist from a front surface of a wafer W. The front surface of the wafer W to be subjected to the resist removing test was entirely covered with the resist. After the resist removing test, the front surface of the wafer W was checked for resist lift-off state. More specifically, the area percentage of a region (lift-off region) of the front surface of the wafer W from which the resist is removed (lifted off) was determined with respect to the entire front surface of the wafer W through visual inspection. In the resist removing test, the exemplary process shown inFIG. 3 was performed, and the treatment period was 160 seconds. DIW was used as the water to be mixed with the sulfuric acid ozone. In the resist removing test, the threshold of the percentage of the lift-off region was defined to be 80% by way of example. If the percentage of the lift-off region is not less than 80%, the standard requirements are satisfied. If the percentage of the lift-off region is less than 80%, the standard requirements are not satisfied. - The flow rate ratio (weight ratio) between the sulfuric acid ozone (SOM) and the DIW in the sulfuric acid ozone/water mixture was 1:0.15 by way of example.
- The liquid temperature (treatment temperature) of the sulfuric acid ozone/water mixture spouted from the sulfuric acid ozone/water nozzle 5 after the mixing was 134° C.
- The flow rate ratio (weight ratio) between the sulfuric acid ozone and the DIW in the sulfuric acid ozone/water mixture was 1:0.3 by way of example. The liquid temperature (treatment temperature) of the sulfuric acid ozone/water mixture spouted from the sulfuric acid ozone/water nozzle 5 after the mixing was 151° C.
- The water was not mixed with the sulfuric acid ozone, but only the sulfuric acid ozone was spouted at 80° C. (treatment temperature) from the sulfuric acid ozone/water nozzle 5.
-
FIG. 5 is a diagram showing the results of the resist removing test. - In Examples 1 and 2, as shown in
FIG. 5 , the percentage of the lift-off region was not less than 80%. In Example 1, particularly, the percentage of the lift-off region was not less than 90%, indicating a very high lift-off capability. - While one embodiment of the present invention has thus been described, the invention may be embodied in other ways.
- As shown in
FIG. 6 , the sulfuric acid ozone and the water may be mixed together within the sulfuric acid ozone/water nozzle. In this case, thewater mixing portion 15 is obviated, and a sulfuric acid ozone/water nozzle (liquid mixture nozzle) 100 is provided at a distal end of the sulfuric acidozone supply pipe 17. The sulfuric acid ozone/water nozzle 100 has, for example, a so-called straight nozzle structure, and includes acasing 100A. Thecasing 100A includes a hollowcylindrical flow pipe 101 and awater inlet pipe 105 connected at its one end to an upstream end portion of theflow pipe 101. Thewater inlet pipe 105 has awater inlet port 106 at its other end which is connected to thewater supply pipe 18. Theflow pipe 101 has an outlet port (liquid mixture outlet port) 102 at its distal end for spouting the sulfuric acid ozone/water mixture toward the outside. Theflow pipe 101 has a sulfuric acidozone inlet port 103 at its proximal end for feeding the sulfuric acid ozone therein. The sulfuric acidozone inlet port 103 is connected to the distal end of the sulfuric acidozone supply pipe 17. Theflow pipe 101 includes a mixingchamber 104 defined therein. The mixingchamber 104 has an open distal end which serves as theoutlet port 102. The sulfuric acid ozone supplied from the sulfuric acidozone inlet port 103 and the water supplied from the water inlet port 106 (for the dilution) are fed into the mixingchamber 104, and mixed together. The sulfuric acid ozone/water mixture prepared by the mixing in the mixingchamber 104 is spouted downward from theoutlet port 102. - In this case, the sulfuric acid ozone and the water are mixed together within the sulfuric acid ozone/
water nozzle 100. Therefore, the sulfuric acid ozone/water mixture is supplied to the front surface of the wafer W immediately after the mixing. Accordingly, the sulfuric acid ozone/water mixture which is substantially free from reduction in peroxodisulfuric acid amount (concentration) can act on the resist present on the front surface of the wafer W. Thus, the resist can be more advantageously removed from the front surface of the wafer W. - Further, as shown in
FIGS. 7 and 8 , the substrate treatment apparatus may be configured so that the water is mixed with sulfuric acid ozone just spouted from a sulfuricacid ozone nozzle 200. In this case, thewater mixing portion 15 is obviated, and the sulfuricacid ozone nozzle 200 is provided at the distal end of the sulfuric acidozone supply pipe 17. The sulfuricacid ozone nozzle 200 is a straight nozzle adapted to spout the sulfuric acid ozone toward the front surface of the wafer W. - As shown in
FIG. 7 , for example, the substrate treatment apparatus may be configured so that the water is spouted (sprayed) from awater nozzle 201 toward the sulfuric acid ozone spouted from the sulfuricacid ozone nozzle 200 before reaching the wafer W. In this case, the sulfuric acid ozone and the water are mixed together above the wafer W, and the resulting sulfuric acid ozone/water mixture is supplied to the front surface of the wafer W. Thus, the sulfuric acid ozone having a higher ozone concentration can act on the resist present on the front surface of the wafer W. - Further, as shown in
FIG. 8 , the substrate treatment apparatus may be configured so that the water (for the dilution) is spouted (sprayed) from thewater nozzle 201 toward the front surface of the wafer W. In this case, the sulfuric acid ozone spouted from the sulfuricacid ozone nozzle 200 and the water spouted from thewater nozzle 201 are mixed together on the front surface of the wafer W. Thus, the sulfuric acid ozone having a higher ozone concentration can act on the resist present on the front surface of the wafer W. It is needless to say that the mixing of the sulfuric acid ozone and the water on the front surface of the wafer W as shown inFIG. 8 is one exemplary method of supplying the sulfuric acid ozone/water mixture to the front surface of the wafer W. - In the embodiment shown in
FIGS. 1 to 3 , the substrate treatment apparatus is adapted to prepare the sulfuric acid ozone by the mixing of the ozone gas in the ozone gas mixing portion 25 by way of example but, instead, may be arranged so that a bubbler (not shown) is provided on the bottom of the sulfuricacid ozone tank 22 and the sulfuric acid retained in the sulfuricacid ozone tank 22 is bubbled with the ozone gas supplied to the bubbler through an ozone gas supply valve (not shown) to prepare the sulfuric acid ozone. - The recycling device (not shown) may be provided within the
substrate treatment apparatus 1. In other words, a mechanism for the recovery and the recycling of the sulfuric acid ozone (recovery/recycling mechanism) may be provided within thesubstrate treatment apparatus 1. In this case, a treatment process for the recovery and the reuse (recycling) of the sulfuric acid ozone can be performed in thesubstrate treatment apparatus 1 without the use of any device provided outside thesubstrate treatment apparatus 1. - While the present invention has been described in detail by way of the embodiments thereof, it should be understood that these embodiments are merely illustrative of the technical principles of the present invention but not limitative of the invention. The spirit and scope of the present invention are to be limited only by the appended claims.
- This application corresponds to Japanese Patent Application No. 2012-176233 filed in the Japan Patent Office on Aug. 8, 2012, the disclosure of which is incorporated herein by reference in its entirety.
Claims (7)
1. A substrate treatment apparatus to be used for removing a resist from a front surface of a substrate, the apparatus comprising:
a substrate holding unit which holds the substrate; and
a sulfuric acid ozone/water mixture supplying unit which supplies a sulfuric acid ozone/water mixture to the front surface of the substrate held by the substrate holding unit, the sulfuric acid ozone/water mixture being a mixture which is prepared by mixing water with sulfuric acid ozone prepared by dissolving ozone gas in sulfuric acid.
2. The substrate treatment apparatus according to claim 1 , wherein the sulfuric acid ozone/water mixture supplying unit includes a liquid mixture nozzle which spouts the sulfuric acid ozone/water mixture toward the front surface of the substrate held by the substrate holding unit.
3. The substrate treatment apparatus according to claim 2 , wherein the sulfuric acid ozone/water mixture supplying unit further includes:
a mixing portion which mixes the sulfuric acid ozone and the water together;
a sulfuric acid ozone supplying portion which feeds the sulfuric acid ozone to the mixing portion; and
a liquid mixture supply pipe which supplies the sulfuric acid ozone/water mixture prepared by the mixing in the mixing portion to the liquid mixture nozzle.
4. The substrate treatment apparatus according to claim 3 , wherein the sulfuric acid ozone supplying portion includes a sulfuric acid ozone retaining portion which retains the sulfuric acid ozone, and a circulation passage connected to the sulfuric acid ozone retaining portion and the mixing portion to circulate the sulfuric acid ozone from the sulfuric acid ozone retaining portion back into the sulfuric acid ozone retaining portion therethrough.
5. The substrate treatment apparatus according to claim 2 , wherein the liquid mixture nozzle includes:
a mixing chamber in which the sulfuric acid ozone and the water are mixed together;
a sulfuric acid ozone inlet port through which the sulfuric acid ozone is fed into the mixing chamber;
a water inlet port through which the water is fed into the mixing chamber; and
a liquid mixture outlet port from which the sulfuric acid ozone/water mixture prepared by the mixing in the mixing chamber is spouted.
6. The substrate treatment apparatus according to claim 1 , wherein the sulfuric acid ozone/water mixture supplying unit includes a sulfuric acid ozone nozzle which spouts the sulfuric acid ozone toward the front surface of the substrate held by the substrate holding unit, and a water nozzle which spouts the water toward the front surface of the substrate held by the substrate holding unit.
7. A substrate treatment method to be used for removing a resist from a substrate front surface, the method comprising a sulfuric acid ozone/water mixture supplying step of supplying a sulfuric acid ozone/water mixture to a front surface of a substrate held by a substrate holding unit, the sulfuric acid ozone/water mixture being a mixture which is prepared by mixing water with sulfuric acid ozone prepared by dissolving ozone gas in sulfuric acid.
Priority Applications (1)
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US15/433,538 US10290511B2 (en) | 2012-08-08 | 2017-02-15 | Substrate treatment apparatus and substrate treatment method |
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JP2012-176233 | 2012-08-08 | ||
JP2012176233A JP6168271B2 (en) | 2012-08-08 | 2012-08-08 | Substrate processing apparatus and substrate processing method |
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US20170162400A1 (en) | 2017-06-08 |
US10290511B2 (en) | 2019-05-14 |
JP6168271B2 (en) | 2017-07-26 |
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