WO2010041333A1 - Stripping fluid and process for cleaning objects - Google Patents

Stripping fluid and process for cleaning objects Download PDF

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Publication number
WO2010041333A1
WO2010041333A1 PCT/JP2008/068451 JP2008068451W WO2010041333A1 WO 2010041333 A1 WO2010041333 A1 WO 2010041333A1 JP 2008068451 W JP2008068451 W JP 2008068451W WO 2010041333 A1 WO2010041333 A1 WO 2010041333A1
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WO
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Prior art keywords
stripping solution
stripping
cleaning
liquid
water
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PCT/JP2008/068451
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French (fr)
Japanese (ja)
Inventor
充司 林田
映子 関
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アクアサイエンス株式会社
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Application filed by アクアサイエンス株式会社 filed Critical アクアサイエンス株式会社
Priority to KR1020117010534A priority Critical patent/KR20110079835A/en
Priority to JP2010532750A priority patent/JPWO2010041333A1/en
Priority to PCT/JP2008/068451 priority patent/WO2010041333A1/en
Publication of WO2010041333A1 publication Critical patent/WO2010041333A1/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
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table 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
    • 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
    • H01L21/0206—Cleaning during device manufacture during, before or after processing of insulating layers
    • H01L21/02063—Cleaning during device manufacture during, before or after processing of insulating layers the processing being the formation of vias or contact holes
    • 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
    • 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
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/0011—Working of insulating substrates or insulating layers
    • H05K3/0055—After-treatment, e.g. cleaning or desmearing of holes

Definitions

  • the present invention relates to foreign matters adhering to an object to be cleaned, more specifically, unnecessary substances such as polymer residues adhering to the surface of an object such as a semiconductor, a hard disk, a liquid crystal display, a printed board, and a flat panel display in a dry etching process.
  • the present invention relates to a stripping solution and a cleaning method used for stripping and removing.
  • Patent Documents 1 and 2 disclose a stripping solution containing an organic amine compound, an anticorrosive, and an organic solvent, and Patent Document 3
  • a stripping solution containing ammonium fluoride, an anticorrosive, and a water-soluble organic solvent has been proposed.
  • an object is to provide a stripping solution capable of processing an object under a low temperature condition.
  • the process is performed under high temperature conditions.
  • Patent Documents 4 and 5 it is possible to prevent the structure of the integrated circuit from being damaged or dissolved and to avoid dangers such as deleterious substances.
  • this method there is a problem that unnecessary objects such as polymer residues attached to the surface of the object in the dry etching process cannot be sufficiently removed.
  • none of the above-described conventional techniques is suitable for cleaning the polymer residue remaining on the side wall of the via hole. Since the via hole side wall is in a position that is difficult to clean, the use of strong chemicals or hard cleaning conditions (for example, spraying conditions) can damage the via holes, but do not use chemicals as in Patent Document 4 etc. If the conditions are mild, the adhering polymer residue will not be sufficiently cleaned. For example, in the method of Patent Document 4, since the sprayed material only flows along the surface of the polymer residue, it is difficult to remove the remaining polymer residue.
  • the present invention minimizes the influence on the environment without damaging or dissolving the structure of the integrated circuit, and in particular, the polymer residue attached to the side wall of the via hole without damaging the via hole of the object to be cleaned.
  • An object is to provide a means for reliably peeling and removing.
  • the present invention (1) is a stripping solution for stripping a polymer residue adhering to an object, comprising an aqueous solution containing a fluorine atom and substantially free of an organic solvent and an anticorrosive.
  • the present invention (2) is the stripping solution according to the invention (1), wherein the concentration of fluorine atoms in the aqueous solution is 5 to 450 ppm.
  • the present invention (3) is the stripping solution of the invention (1) or (2) having a pH of 2.0 to 6.0.
  • the present invention (4) is a method for cleaning an object, It is a method characterized by having a stripping solution jetting step of spraying a multiphase fluid containing the stripping solution and water vapor of any one of inventions (1) to (3) onto the surface of an object.
  • the present invention (5) is the method of the invention (4), wherein the temperature of the mixed phase fluid is 60 to 115 ° C.
  • the present invention (6) is the method of the invention (4) or (5), wherein the flow rate of the stripping solution in the mixed phase fluid is 0.05 to 0.4 dm 3 / min.
  • the present invention (7) is the method according to any one of the inventions (4) to (6), wherein an injection speed of the mixed phase fluid is 60 m / s or more.
  • the present invention (8) is the method according to any one of the inventions (4) to (7), wherein the treatment time of the stripping liquid spraying step is 25 to 180 seconds.
  • the present invention (9) is a method for cleaning an object, A stripping solution supplying step of heating the stripping solution of the invention (1) to (3) to 75 to 100 ° C. and feeding it to the surface of the object; An injection step of injecting a fluid consisting of water vapor and / or water onto the object after the stripping solution supplying step; It is the method characterized by having.
  • the present invention (10) is the method of the invention (9), wherein the stripping solution supplying step is a step of flowing down the stripping solution with respect to the object.
  • the present invention (11) is the method of the invention (10), wherein the flow-down time of the stripping solution supplying step is 25 to 240 seconds.
  • the present invention (12) is the method of the invention (9), wherein the stripping solution supplying step is a step of immersing the object in the stripping solution.
  • the present invention (13) is the method of the invention (12), wherein the immersion time in the stripping solution supplying step is 25 to 180 seconds.
  • the present invention (14) is the method according to any one of the inventions (9) to (13), wherein an ejection speed of the fluid in the ejecting step is 60 m / s or more.
  • the present invention is the method according to any one of the inventions (9) to (14), wherein a water flow rate in the fluid in the jetting step is 0.05 to 0.4 dm 3 / min.
  • the present invention (16) is the method according to any one of the inventions (9) to (15), wherein the temperature of the fluid in the jetting step is 75 to 115 ° C.
  • the present invention (17) is the method according to any one of the inventions (9) to (16), wherein the processing time of the injection step is 20 to 240 seconds.
  • the stripping solution used is neither strongly alkaline nor strongly acidic and does not substantially contain an organic solvent, it damages or dissolves the structure of the integrated circuit while ensuring operational safety and reducing environmental impact.
  • the polymer residue adhering to the via hole side wall of the object to be cleaned can be reliably peeled off and removed.
  • the stripping solution according to the present invention comprises an aqueous solution containing a fluorine atom and not containing an organic solvent and an anticorrosive agent.
  • a cleaning method using the stripping solution for example, a cleaning method including a stripping solution spraying step, a cleaning method including a stripping solution supplying step and a spraying step
  • the object can be sufficiently cleaned.
  • the “object” to be cleaned in the present invention is an object (for example, a semiconductor substrate, an electronic device such as a semiconductor, a hard disk, a liquid crystal display, a printed board, or a flat panel display) to which a polymer residue is adhered in a dry etching process. Parts).
  • the present invention is suitable for removing the polymer residue on the silicon oxide film.
  • the present invention is effective for an object in which a polymer residue adheres to a place that is difficult to remove, such as a side surface of a via hole, such as a semiconductor substrate after an etching process.
  • a polymer residue adheres to a place that is difficult to remove, such as a side surface of a via hole, such as a semiconductor substrate after an etching process.
  • the “polymer residue” is not particularly limited as long as it is a residue during dry etching, and is typically SiO 2 , Al 2 O 3 , TiO 2 and / or TiN.
  • the stripping solution according to the best mode comprises an aqueous solution containing a fluorine atom and substantially free of an organic solvent and an anticorrosive agent.
  • the existence form of the fluorine atom in the best mode is not particularly limited, and examples thereof include HF, F ⁇ , HF 2 —, etc. Among these, it is particularly preferable that HF 2 — is included. .
  • the fluoride which dissociates a fluorine ion in water is suitable, for example, hydrofluoric acid, Ammonium fluoride, acidic ammonium fluoride, methylamine hydrofluoride, ethylamine hydrofluoride, propylamine hydrofluoride, tetramethylammonium fluoride, tetraethylammonium fluoride, methanolamine hydrofluoride, N-methyl Methanolamine fluoride, N, N-dimethylmethanolamine fluoride, ethanolamine hydrofluoride, N-methylethanolamine hydrofluoride, N, N-dimethylethanolamine hydrofluoride, triethylenediamine hydrofluoride Etc.
  • a preferred fluorinated product is ammonium fluoride.
  • the fluorinated product may be added alone or in combination of two or more.
  • the concentration of fluorine atoms in the aqueous solution is preferably 5 to 450 ppm, more preferably 8 to 350 ppm, and even more preferably 10 to 100 ppm.
  • the fluorine atom concentration is the total weight (mg) of all fluorine atoms including fluorine ions (for example, F ⁇ , HF 2 ⁇ ) and non-dissociated fluoride contained in the aqueous solution. It means the value divided by the volume of water (L).
  • a substance for adjusting pH may be added.
  • carbon dioxide, sulfuric acid, nitric acid, citric acid, oxalic acid, acetic acid and the like can be cited as substances for adjusting the pH in the lower direction.
  • ammonia, 2-aminoethanol, choline and the like can be cited as substances for adjusting the pH in the higher direction.
  • the pH of the stripping solution is changed to an acidic region where the effect of stripping fluorine ions is enhanced.
  • the pH of the stripping solution is preferably 2.0 to 6.0, more preferably 3.0 to 4.5, and even more preferably 3.3 to 3.7.
  • the pH is measured by a method defined in JIS Z8802.
  • the speed at which SiO 2 is dissolved is remarkably increased with pH 3.5 as a peak.
  • HF 2 ⁇ which is a fluorine-based ion that dissolves SiO 2 the fastest, exists at the highest concentration at pH 3.5 under a constant ammonium fluoride concentration.
  • the concentration of the fluoride ion source is adjusted to a concentration range of the are dissolved SiO 2 is negligible and, peeling the polymeric residue without damaging or dissolve the structure of the integrated circuit Is possible.
  • the concentration is sufficiently low as long as the added amount is within the pH range. Will not hurt.
  • the stripping solution according to the best mode is substantially free of organic solvent and anticorrosive agent.
  • substantially not containing as used in the claims and the specification means that the content is not more than 0.1 wt%, for example, so that the influence on the environment is not a problem.
  • the organic solvent include amides such as N, N-dimethylformamide and dimethylacetamide, alcohols such as ethanol, isopropyl alcohol, glycerin, ethylene glycol and diethylene glycol, diethylene glycol monomethyl ether and dipropylene glycol monomethyl ether.
  • sulfoxides such as dimethyl sulfoxide
  • organic nitriles such as acetonitrile, propionitrile, butyronitrile, isobutyronitrile, succinonitrile, benzonitrile, and adiponitrile.
  • the “anticorrosive” is not particularly limited as long as it is an anticorrosive used in a semiconductor process, and examples thereof include catechol, sorbitol, xylitol and the like.
  • the stripping solution has a problem of contamination of metals derived from raw materials (for example, Al, Cu, K, Mg, Na, Ti, Fe, Cr, Pt, Ni, Ca, Zn).
  • raw materials for example, Al, Cu, K, Mg, Na, Ti, Fe, Cr, Pt, Ni, Ca, Zn.
  • the raw materials are purified.
  • the amount of metal in the stripping solution has been reduced by contrivances such as. However, even with such a device, the amount of metal could be reduced only to the ppm order.
  • the concentration of fluorine ions can be reduced while using only water as a solvent, it is possible to achieve a desired amount of metal (for example, nano-order).
  • the amount of contamination metal derived from a fluoride can be reduced to 1/10 and 1/100 by setting the dilution amount with water to 10 times and 100 times.
  • the object cleaning system S1 includes a nozzle 101, operation valves 102a and 102b, water flow meters 103a and 103b, stop valves 104a and 104c, a water pressurization tank 105 (which can be replaced by a water pump), a steam generator 106, and a water supply pipe 107a.
  • a nitrogen supply pipe 108 a pressure reducing valve 109, pressure-resistant pipes 110 to 112, a stage 113, a chamber 114, a pressure gauge 115, a heater 116, a chemical liquid tank 117, and a CO 2 supply pipe 118.
  • a processing object (for example, a semiconductor wafer) W is set on the stage 113.
  • each element will be described in detail.
  • the nozzle 101 is disposed so as to face the object W, and generates a two-fluid jet of water vapor and stripping solution or pure water. Then, a mixed phase flow of pure water supplied from the water pressurization tank 105 or the peeling liquid supplied from the chemical liquid tank 117 and the water vapor supplied from the water vapor generator 106 to the object W through the nozzle 101. As a result of the spraying, the object is cleaned. At this time, if the supply of pure water and stripping solution is stopped, a jet of only water vapor is obtained. It is also possible to stop the supply of water vapor and simply allow the stripping solution to flow down to the object W.
  • the water pressurization tank 105 pressurizes pure water supplied from the water supply pipe 107b to a predetermined value A 1 (MP), and supplies a predetermined flow rate B 1 (l / min) of the pressurized pure water to the pressure pipe. 110 is sent to the nozzle 101 in a high-pressure state (however, depending on the nozzle shape, it is possible to send pure water to the nozzle without pressurization).
  • the water flow meter 103 a measures the flow rate of pure water supplied from the water pressure tank 105 to the nozzle 101. The operator can check the flow rate with the water flow meter 103a and adjust it to a desired value using the operation valve 102a. In addition, the supply of pure water can be stopped or restarted by opening and closing the stop valve 104a.
  • nitrogen is supplied from the nitrogen supply pipe 108 to the water pressurization tank 105.
  • pure water is mixed with nitrogen, but it is obvious that only pure water may be supplied to the nozzle 101.
  • it is not limited to nitrogen gas, It can substitute also with inert gas like Ar gas.
  • the chemical liquid tank 117 pressurized CO 2 that is supplied from the CO 2 supply pipe 118 to a predetermined value, to dissolve the CO 2 stripping solution in the chemical liquid tank.
  • a predetermined flow rate B 2 (l / min) of the pressurized stripping solution is sent to the nozzle 101 through the pressure tube 112.
  • the water flow meter 103b measures the flow rate of the stripping solution supplied from the chemical solution tank 117 to the nozzle 101.
  • the operator can check the flow rate with the water flow meter 103b and adjust it to a desired value using the operation valve 102b. Further, since the heater 116 is provided, the temperature of the stripping solution can be easily adjusted.
  • the supply of the stripping solution can be stopped or restarted by opening and closing the stop valve 104c.
  • CO 2 from the CO 2 supply pipe 118 is configured to be supplied to the chemical liquid tank 117.
  • the configuration may be such that carbon dioxide can be blown through a transport pipe from the tank to the nozzle, or may be mixed with a substance that adjusts the pH.
  • you may adjust pH at the time of stripping solution manufacture. For example, after dissolving carbon dioxide, the stripping solution may be supplied from a container sealed with carbon dioxide.
  • the water vapor generator 106 heats the pure water supplied from the water supply pipe 107 a to a predetermined temperature D 1 (° C.) or higher to generate water vapor, and is supplied to the nozzle 101 in a high pressure state via the pressure resistant pipe 111. Send it out.
  • the pressure gauge 115 measures the pressure of water vapor supplied from the water vapor generator 106 to the nozzle 101. An operator can check the pressure with the pressure gauge 115 and adjust it to a desired value using the pressure reducing valve 109. In addition, the supply of water vapor can be stopped or restarted by opening and closing the stop valve 104b.
  • FIG. 2 is a schematic block diagram of washing
  • this form is a system implemented in the place where a peeling liquid supply process and an injection process differ.
  • the cleaning system S ⁇ b> 2 includes an injection cleaning unit 100 and a stripping solution supply unit 200.
  • the stripping liquid supply unit 200 includes at least a casing 201 for storing liquid and a holding unit 202 for holding the object W in the space of the casing 201.
  • the stripping liquid supply unit 200 further includes a chemical liquid tank 203 that stores the stripping liquid, a CO 2 supply pipe 204 that introduces CO 2 into the chemical liquid tank, and a liquid for introducing the stripping liquid into the casing 201.
  • You may have the introduction means (for example, pump) 205, the heater 206 provided between the said liquid tank 203 and the liquid introduction means 205, and the liquid discharge means 207.
  • FIG. 3 is a schematic block diagram of the target-object cleaning system S3 which concerns on a 3rd form.
  • this embodiment is a system in which the stripping solution supply process and the spraying process are performed at different locations, and the object is automatically conveyed to the spraying process area after the stripping liquid supply process is completed.
  • many elements of the object cleaning system S3 have basically the same configuration as the object S2. Accordingly, the same reference numerals as those in FIG. Therefore, the description will focus on the differences from the second embodiment.
  • the transport unit 300 that moves the object W that has been subjected to the stripping liquid supply process from the object holding means 202 onto the stage 113 is provided. Further, the second embodiment is different from the second embodiment.
  • the transport unit 300 since the conveyance unit 300 is provided, all processes can be performed automatically and continuously.
  • the transport unit 300 includes an object holding unit 301, an operating unit 302 for operating the holding unit, and a support 303 that can adjust the holding unit 301 and the operating unit 302 to an appropriate height. Composed.
  • the object cleaning method according to the present invention includes (Method 1) a method of executing the stripping liquid treatment and the spraying process in one step, for example, a stripping liquid that sprays a multiphase flow composed of the stripping liquid and water vapor onto the surface of the object.
  • the method by the spraying step and (Method 2) the method of executing the stripping solution treatment and the spraying processing in separate steps, for example, the stripping solution supplying step for supplying the stripping liquid object surface and the fluid comprising water vapor and / or water
  • examples of the stripping solution supplying step in the latter method include a step of flowing the stripping solution on the surface of the object and a step of immersing the object in the stripping solution. Furthermore, according to the latter method, since the amount of the stripping solution used can be minimized, the influence on the environment is reduced. Hereinafter, each process in these methods is explained in full detail.
  • the stripping solution spraying step is a step of spraying a fluid, which is a mixture of the stripping solution according to the best mode and water vapor, onto an object.
  • the stripping solution according to the best mode is more effective in having a sufficient cleaning power even at the concentration and not damaging the semiconductor substrate by being sprayed onto the object by the method according to the spraying step. It demonstrates suitably. In particular, even polymer residues adhering to the side surface of a via hole after plasma etching, which has been conventionally considered difficult to peel off, have the ability to peel off suitably.
  • the method can be performed by, for example, the cleaning system S1 according to the best mode.
  • the temperature of the multiphase flow in the stripping solution jetting process is preferably 60 to 115 ° C, more preferably 80 to 113 ° C, and still more preferably 90 to 110 ° C. By setting the temperature at 60 ° C. or higher, the reaction rate is significantly increased.
  • the fluid temperature was defined as a steady-state temperature after a thermocouple was installed on the wafer and the fluid was ejected for 1 minute at a distance of 5 mm.
  • the injection speed of the multiphase flow is preferably 60 m / s or more, more preferably 140 m / s or more, and further preferably 260 m / s.
  • the ejection speed is a value obtained by dividing the volume flow rate of the fluid by the cross-sectional area of the nozzle opening.
  • Stripping solution the flow rate is suitably 0.05 ⁇ 0.4dm 3 / min, 0.1 ⁇ 0.3dm 3 / min is more preferred, 0.1 ⁇ 0.2dm 3 / min is more preferred is there.
  • the mixing ratio of water vapor and stripping solution is preferably 0.0003 to 0.01, more preferably 0.0004 to 0.05, and 0.0005 to 0.01 is more preferable.
  • the treatment time is preferably 25 to 180 seconds, more preferably 40 to 90 seconds, and even more preferably 50 to 70 seconds.
  • the numerical range is a value mainly indicating a limit value of a parameter that affects cleaning, and a combination of these can be easily selected and set according to the degree of required impact force.
  • the stripping solution supply step is a step of supplying the stripping solution to the object under a predetermined temperature condition for a predetermined time.
  • the stripping solution supply step is a step of supplying the stripping solution to the object under a predetermined temperature condition for a predetermined time.
  • the effect of removing the next injection step becomes remarkable. That is, even the concentration of the stripping solution according to the best mode contributes sufficiently to cleaning, and even a polymer residue adhered to the side surface of the via hole after plasma etching, which has been conventionally considered difficult to strip, does not damage the via hole. There is an effect that can be washed under such mild conditions.
  • As a peeling liquid supply process the process of flowing down peeling liquid on the target object surface, and the process of immersing a target object in peeling liquid are mentioned, for example.
  • the stripping solution supply step can be performed by, for example, the cleaning system S1 in the best mode.
  • the stripping solution supplied from the chemical tank 117 of the system S1 is supplied onto the surface of the object by the nozzle 101 while adjusting the temperature by the heater 116.
  • the temperature of the stripping solution is preferably 75 to 100 ° C., more preferably 80 to 95 ° C., and still more preferably 85 to 90 ° C. By performing the treatment in the temperature range, even if a stripping solution having a very low concentration of fluorine ions is used, a sufficient effect is exhibited.
  • the treatment time is preferably 25 to 240 seconds, more preferably 40 to 90 seconds, and further preferably 50 to 70 seconds.
  • the cleaning system S2 when the object is immersed in the stripping solution, it can be performed, for example, by the cleaning system S2 or S3 according to the best mode.
  • the cleaning system S2 is used as a representative example, after the object W is mounted on the holding means 202 of the stripping solution supply unit 200, a predetermined fluorine ion concentration and a predetermined fluorine ion concentration are supplied from the liquid introduction means 205 into the housing 201.
  • a stripping solution adjusted to the carbon dioxide concentration is introduced, and the object W is immersed.
  • the temperature of the stripping solution is preferably 75 to 100 ° C., more preferably 80 to 95 ° C., and still more preferably 85 to 90 ° C.
  • the immersion time is preferably 25 to 180 seconds, more preferably 40 to 90 seconds, and further preferably 50 to 70 seconds.
  • Method 2 Injecting Step
  • the injecting step according to Method 2 is a step of removing the removal target by spraying water vapor and / or water onto the cleaning target that has been subjected to the above-described stripping liquid supply process.
  • This step can be performed by a known cleaning method (for example, the method described in Japanese Patent Application Laid-Open No. 2004-349577).
  • the object cleaning system S1 or the injection unit 100 of the system S2 or S3 can also be used. Is possible.
  • 60 m / s or more is suitable for the injection speed in an injection process, 120 m / s or more is more suitable, and 240 m / s or more is still more suitable.
  • Pure water flow rate is suitably 0.05 ⁇ 0.4dm 3 / min, is more preferably 0.1 ⁇ 0.3dm 3 / min, 0.1 ⁇ 0.2dm 3 / min is more preferred is there.
  • the fluid temperature is preferably 75 to 115 ° C, more preferably 80 to 95 ° C, and still more preferably 85 to 90 ° C.
  • the processing time is preferably 20 to 240 seconds, more preferably 40 to 90 seconds, and further preferably 50 to 70 seconds.
  • the treatment time is preferably 20 to 180 seconds, more preferably 40 to 90 seconds, and further preferably 50 to 70 seconds.
  • the numerical range in this step is a value indicating the limit value of the main parameter that affects cleaning, and these combinations can be easily selected and set according to the degree of required impact force. .
  • Object to be cleaned a TiN film having a thickness of 100 ⁇ m was formed on a silicon wafer having a thickness of 0.625 mm, and a silicon oxide film having a thickness of 1000 ⁇ m (hereinafter referred to as an oxide film) was further formed thereon. . Lithograph and dry etching were performed, and a hole with an opening diameter of 1 ⁇ m was opened to the depth of the interface between TiN and the oxide film. The object was cleaned by the object cleaning systems S1 and S2.
  • the conditions in the example are as follows.
  • the fluorine ion source used in this example is ammonium fluoride. Residual polymer and hole damage were observed with a scanning electron microscope.
  • the data of an Example and a comparative example are shown.
  • FIG. 1 is a schematic configuration diagram of a cleaning system S1 according to the first embodiment.
  • FIG. 2 is a schematic configuration diagram of the cleaning system S2 which is the second embodiment.
  • FIG. 3 is a schematic configuration diagram of a cleaning system S3 that is a third embodiment.

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Abstract

[PROBLEMS] To provide a means for reliably stripping and removing polymer residue adhering to the sidewalls of via holes of an object without damaging or dissolving integrated circuit structure with minimized influence on the environment, especially, without damaging the via holes. [MEANS FOR SOLVING PROBLEMS] A stripping fluid for stripping polymer residue adhering to an object, which consists of an aqueous solution which is substantially free from fluorine- containing organic solvents and fluorine-containing anticorrosives

Description

剥離液及び対象物洗浄方法Stripping solution and object cleaning method
　本発明は、洗浄対象物上に付着した異物、より詳細には、半導体・ハードディスク・液晶ディスプレイ・プリント基板・フラットパネルディスプレイ等の対象物表面にドライエッチング工程で付着したポリマ残渣等の不要物を剥離して除去するために使用される剥離液及び洗浄方法に関する。 The present invention relates to foreign matters adhering to an object to be cleaned, more specifically, unnecessary substances such as polymer residues adhering to the surface of an object such as a semiconductor, a hard disk, a liquid crystal display, a printed board, and a flat panel display in a dry etching process. The present invention relates to a stripping solution and a cleaning method used for stripping and removing.
　半導体、ハードディスク、液晶ディスプレイ、プリント基板又はフラットパネルディスプレイ等の対象物表面にエッチング工程で被着したポリマ残渣等の不要物は、当該工程後に剥離して除去される必要がある。ここで、レジスト膜の除去については、（１）プラズマ灰化、（２）化学薬品により除去する技術が用いられている。 Unnecessary substances such as polymer residues deposited on the surface of an object such as a semiconductor, a hard disk, a liquid crystal display, a printed board or a flat panel display in the etching process need to be peeled off and removed after the process. Here, with respect to the removal of the resist film, (1) plasma ashing and (2) a technique of removing with chemicals are used.
　しかしながら、（１）の技術では、僅かながらＳｉを損傷し、（２）の技術では、Ｓｉに加えて絶縁膜及び金属配線を溶解するという問題がある。近年の集積回路の高密度化に伴い、僅かでも集積回路の構造を損傷又は溶解することが許されなくなりつつある。 However, in the technique (1), Si is slightly damaged, and in the technique (2), there is a problem that the insulating film and the metal wiring are dissolved in addition to Si. With the recent increase in the density of integrated circuits, it is no longer allowed to damage or dissolve the structure of the integrated circuit.
　そこで、（２）の技術に関し、集積回路の構造を損傷又は溶解させない剥離液として、特許文献１及び２に、有機アミン系の化合物、防食剤及び有機溶剤を含有する剥離液や、特許文献３に、フッ化アンモニウム、防食剤及び水溶性有機溶剤を含有する剥離液が提案されている。また、これらの特許文献１～３においては、低温条件で対象物を処理可能な剥離液を提供することを目的としている。一方、高温条件での処理になるが、更に、集積回路の構造を損傷又は溶解させないようなマイルドな条件で対象物を洗浄する技術として、特許文献４や特許文献５に、水蒸気を対象物に噴射して当該対象物表面に付着した高分子膜等を剥離する手法が提案されている。
特開平７－６４２９７号公報 特開平８－３３４９０５号公報 特開平９－１９７６８１号公報 特開２００４－３４９５７７号公報 特開２００５－１７５１７２号公報 Therefore, regarding the technique of (2), as a stripping solution that does not damage or dissolve the structure of the integrated circuit, Patent Documents 1 and 2 disclose a stripping solution containing an organic amine compound, an anticorrosive, and an organic solvent, and Patent Document 3 In addition, a stripping solution containing ammonium fluoride, an anticorrosive, and a water-soluble organic solvent has been proposed. Further, in these Patent Documents 1 to 3, an object is to provide a stripping solution capable of processing an object under a low temperature condition. On the other hand, as a technique for cleaning an object under mild conditions that do not damage or dissolve the structure of the integrated circuit, the process is performed under high temperature conditions. There has been proposed a method of peeling off a polymer film or the like that has been sprayed and adhered to the surface of the object.
Japanese Unexamined Patent Publication No. 7-64297 JP-A-8-334905 JP-A-9-197681 JP 2004-349577 A JP 2005-175172 A
　ここで、特許文献１～３に記載された剥離剤は、強アルカリ性又は強酸性であったり有機溶剤を含有しているため、劇物又は消防法の危険物に該当する例が多い。従って、これら剥離剤は、洗浄作業及び廃液処理の従事者が危険に曝される、環境に重篤な影響を与える危険性がある、等の問題を有している。 Here, since the release agents described in Patent Documents 1 to 3 are strongly alkaline or strongly acidic, or contain an organic solvent, there are many examples that fall under the category of dangerous substances or dangerous substances of the Fire Service Act. Therefore, these stripping agents have problems such as the risk of seriously affecting the environment, and the workers engaged in cleaning operations and waste liquid treatment are exposed to danger.
　一方、特許文献４、５に開示された手法によると、集積回路の構造を損傷又は溶解させることの防止や、劇物等の危険回避はできる。しかし、当該手法では、対象物表面にドライエッチング工程で付着したポリマ残渣等の不要物を十分に剥離除去できないという問題がある。 On the other hand, according to the methods disclosed in Patent Documents 4 and 5, it is possible to prevent the structure of the integrated circuit from being damaged or dissolved and to avoid dangers such as deleterious substances. However, in this method, there is a problem that unnecessary objects such as polymer residues attached to the surface of the object in the dry etching process cannot be sufficiently removed.
　特に、前述したいずれの従来技術も、ビアホール側壁に残留したポリマ残渣の洗浄には不向きである。ビアホール側壁は特に洗浄し難い位置にあるため、強力な薬剤を使用したりハードな洗浄条件（例えば噴射条件）にするとビアホールが損傷してしまう一方、特許文献４等のように薬剤を使用しなかったり条件をマイルドにすると付着したポリマ残渣の洗浄が不十分となる。例えば、特許文献４の手法では、噴射物は当該ポリマ残渣表面に沿って流れるにすぎないため、残留したポリマ残渣を取り除くことが困難であった。 In particular, none of the above-described conventional techniques is suitable for cleaning the polymer residue remaining on the side wall of the via hole. Since the via hole side wall is in a position that is difficult to clean, the use of strong chemicals or hard cleaning conditions (for example, spraying conditions) can damage the via holes, but do not use chemicals as in Patent Document 4 etc. If the conditions are mild, the adhering polymer residue will not be sufficiently cleaned. For example, in the method of Patent Document 4, since the sprayed material only flows along the surface of the polymer residue, it is difficult to remove the remaining polymer residue.
　そこで、本発明は、集積回路の構造を損傷又は溶解すること無くかつ環境への影響を最小限にとどめると共に、特に、洗浄対象物のビアホールを損傷すること無く、ビアホール側壁に付着したポリマ残渣を確実に剥離して除去する手段を提供することを目的とする。 Therefore, the present invention minimizes the influence on the environment without damaging or dissolving the structure of the integrated circuit, and in particular, the polymer residue attached to the side wall of the via hole without damaging the via hole of the object to be cleaned. An object is to provide a means for reliably peeling and removing.
　本発明（１）は、フッ素原子を含む、有機溶剤及び防食剤を実質的に含有しない水溶液からなる、対象物に付着したポリマ残渣を剥離するための剥離液である。 The present invention (1) is a stripping solution for stripping a polymer residue adhering to an object, comprising an aqueous solution containing a fluorine atom and substantially free of an organic solvent and an anticorrosive.
　本発明（２）は、前記水溶液中のフッ素原子濃度が、５～４５０ｐｐｍである、発明（１）の剥離液である。 The present invention (2) is the stripping solution according to the invention (1), wherein the concentration of fluorine atoms in the aqueous solution is 5 to 450 ppm.
　本発明（３）は、ｐＨが２.０～６.０である、発明（１）又は（２）の剥離液である。 The present invention (3) is the stripping solution of the invention (1) or (2) having a pH of 2.0 to 6.0.
　本発明（４）は、対象物を洗浄する方法において、
　発明（１）～（３）のいずれか一つの剥離液と水蒸気とを含む混相流体を対象物表面に対して噴射する、剥離液噴射工程を有することを特徴とする方法である。 The present invention (4) is a method for cleaning an object,
It is a method characterized by having a stripping solution jetting step of spraying a multiphase fluid containing the stripping solution and water vapor of any one of inventions (1) to (3) onto the surface of an object.
　本発明（５）は、前記混相流体の温度が、６０～１１５℃である、発明（４）の方法である。 The present invention (5) is the method of the invention (4), wherein the temperature of the mixed phase fluid is 60 to 115 ° C.
　本発明（６）は、前記混相流体中の前記剥離液の流量が、０．０５～０．４ｄｍ３／ｍｉｎである、発明（４）又は（５）の方法である。 The present invention (6) is the method of the invention (4) or (5), wherein the flow rate of the stripping solution in the mixed phase fluid is 0.05 to 0.4 dm 3 / min.
　本発明（７）は、前記混相流体の噴射速度が、６０ｍ／ｓ以上である、発明（４）～（６）のいずれか一項記載の方法である。 The present invention (7) is the method according to any one of the inventions (4) to (6), wherein an injection speed of the mixed phase fluid is 60 m / s or more.
　本発明（８）は、前記剥離液噴射工程の処理時間が、２５～１８０秒である、発明（４）～（７）のいずれか一つの方法である。 The present invention (8) is the method according to any one of the inventions (4) to (7), wherein the treatment time of the stripping liquid spraying step is 25 to 180 seconds.
　本発明（９）は、対象物を洗浄する方法において、
　発明（１）～（３）の剥離液を７５～１００℃に加熱して、対象物表面に供給する剥離液供給工程と、
　前記剥離液供給工程後、水蒸気及び／又は水からなる流体を前記対象物に噴射する噴射工程と、
を有することを特徴とする方法である。 The present invention (9) is a method for cleaning an object,
A stripping solution supplying step of heating the stripping solution of the invention (1) to (3) to 75 to 100 ° C. and feeding it to the surface of the object;
An injection step of injecting a fluid consisting of water vapor and / or water onto the object after the stripping solution supplying step;
It is the method characterized by having.
　本発明（１０）は、前記剥離液供給工程が、前記対象物に対して前記剥離液を流下する工程である、発明（９）の方法である。 The present invention (10) is the method of the invention (9), wherein the stripping solution supplying step is a step of flowing down the stripping solution with respect to the object.
　本発明（１１）は、前記剥離液供給工程の流下時間が、２５～２４０秒である、発明（１０）の方法である。 The present invention (11) is the method of the invention (10), wherein the flow-down time of the stripping solution supplying step is 25 to 240 seconds.
　本発明（１２）は、前記剥離液供給工程が、前記対象物を前記剥離液に浸漬する工程である、発明（９）の方法である。 The present invention (12) is the method of the invention (9), wherein the stripping solution supplying step is a step of immersing the object in the stripping solution.
　本発明（１３）は、前記剥離液供給工程の浸漬時間が、２５～１８０秒である、発明（１２）の方法である。 The present invention (13) is the method of the invention (12), wherein the immersion time in the stripping solution supplying step is 25 to 180 seconds.
　本発明（１４）は、前記噴射工程における前記流体の噴射速度が、６０ｍ／ｓ以上である、発明（９）～（１３）のいずれか一つの方法である。 The present invention (14) is the method according to any one of the inventions (9) to (13), wherein an ejection speed of the fluid in the ejecting step is 60 m / s or more.
　本発明（１５）は、前記噴射工程における前記流体中の水流量が、０．０５～０．４ｄｍ３／ｍｉｎである、発明（９）～（１４）のいずれか一つの方法である。 The present invention (15) is the method according to any one of the inventions (9) to (14), wherein a water flow rate in the fluid in the jetting step is 0.05 to 0.4 dm 3 / min.
　本発明（１６）は、前記噴射工程における前記流体の温度が、７５～１１５℃である、発明（９）～（１５）のいずれか一つの方法である。 The present invention (16) is the method according to any one of the inventions (9) to (15), wherein the temperature of the fluid in the jetting step is 75 to 115 ° C.
　本発明（１７）は、前記噴射工程の処理時間が、２０～２４０秒である、発明（９）～（１６）のいずれか一つの方法である。 The present invention (17) is the method according to any one of the inventions (9) to (16), wherein the processing time of the injection step is 20 to 240 seconds.
　本発明によれば、フッ素イオンによりポリマ残渣の一部が溶解すると同時に、溶解により生じたポリマ残渣上の段差や亀裂に流体の物理力がポリマ残渣の除去する力として効果的に伝わることに加え、使用する剥離液が強アルカリ性や強酸性でなくかつ有機溶剤を実質的に含有するものでもないため、操業の安全確保及び環境負荷の低減を担保しつつ、集積回路の構造を損傷又は溶解すること無く、特に、洗浄対象物のビアホール側壁に付着したポリマ残渣を確実に剥離して除去することが可能となるという効果を奏する。 According to the present invention, a part of the polymer residue is dissolved by the fluorine ions, and at the same time, the physical force of the fluid is effectively transmitted as a force for removing the polymer residue to the steps and cracks on the polymer residue caused by the dissolution. Since the stripping solution used is neither strongly alkaline nor strongly acidic and does not substantially contain an organic solvent, it damages or dissolves the structure of the integrated circuit while ensuring operational safety and reducing environmental impact. In particular, the polymer residue adhering to the via hole side wall of the object to be cleaned can be reliably peeled off and removed.
発明を実施するための最良形態BEST MODE FOR CARRYING OUT THE INVENTION
　本発明に係る剥離液は、フッ素原子を含む、有機溶剤及び防食剤を含有しない水溶液からなる。このようなフッ素溶液であっても、本発明に係る、当該剥離液を用いた洗浄方法（例えば、剥離液噴射工程からなる洗浄方法や、剥離液供給工程及び噴射工程からなる洗浄方法）により、対象物を十分に洗浄することが可能となる。ここで、本発明において洗浄対象となる「対象物」は、ドライエッチング工程でポリマ残渣が付着した対象物（例えば、半導体、ハードディスク、液晶ディスプレイ、プリント基板又はフラットパネルディスプレイ等の、半導体基板や電子部品）である。本発明は、シリコン酸化膜上のポリマ残渣を剥離するのに好適である。特に、本発明は、エッチング工程後の半導体基板のように、ビアホール側面といった除去しにくい場所にポリマ残渣が付着した対象物に対して有効である。以下、まず本発明に係る剥離液の構成と、当該剥離液を用いた洗浄方法を実施可能な装置構成を説明し、続いて洗浄方法について詳述することとする。また、「ポリマ残渣」は、ドライエッチング時の残渣であれば特に限定されず、典型的には、ＳｉＯ２、Ａｌ２Ｏ３、ＴｉＯ２及び／又はＴｉＮである。 The stripping solution according to the present invention comprises an aqueous solution containing a fluorine atom and not containing an organic solvent and an anticorrosive agent. Even with such a fluorine solution, according to the present invention, a cleaning method using the stripping solution (for example, a cleaning method including a stripping solution spraying step, a cleaning method including a stripping solution supplying step and a spraying step), The object can be sufficiently cleaned. Here, the “object” to be cleaned in the present invention is an object (for example, a semiconductor substrate, an electronic device such as a semiconductor, a hard disk, a liquid crystal display, a printed board, or a flat panel display) to which a polymer residue is adhered in a dry etching process. Parts). The present invention is suitable for removing the polymer residue on the silicon oxide film. In particular, the present invention is effective for an object in which a polymer residue adheres to a place that is difficult to remove, such as a side surface of a via hole, such as a semiconductor substrate after an etching process. Hereinafter, first, the configuration of the stripping solution according to the present invention and the configuration of an apparatus capable of performing the cleaning method using the stripping solution will be described, and then the cleaning method will be described in detail. The “polymer residue” is not particularly limited as long as it is a residue during dry etching, and is typically SiO 2 , Al 2 O 3 , TiO 2 and / or TiN.
《剥離液》
　まずは、本最良形態に係る剥離液の構成から説明する。本最良形態に係る剥離液は、フッ素原子を含む、有機溶剤及び防食剤を実質的に含有しない水溶液からなる。ここで、本最良形態におけるフッ素原子の存在形態としては、特に限定されないが、例えば、ＨＦ、Ｆ－、ＨＦ２ －等が挙げられ、これらの中でもＨＦ２ －が含まれることが特に好適である。本発明の剥離液に用いるフッ素原子のもととなるフッ素化物としては、特に限定されないが、水溶性であり、水中でフッ素イオンを解離するフッ素化物が好適であり、例えば、フッ化水素酸、フッ化アンモニウム、酸性フッ化アンモニウム、メチルアミンフッ化水素塩、エチルアミンフッ化水素塩、プロピルアミンフッ化水素塩、フッ化テトラメチルアンモニウム、フッ化テトラエチルアンモニウム、メタノールアミンフッ化水素塩、Ｎ－メチルメタノールアミンフッ化物、Ｎ，Ｎ－ジメチルメタノールアミンフッ化物、エタノールアミンフッ化水素塩、Ｎ－メチルエタノールアミンフッ化水素塩、Ｎ，Ｎ－ジメチルエタノールアミンフッ化水素塩、トリエチレンジアミンフッ化水素塩等が挙げられる。これらの中でも好適なフッ素化物は、フッ化アンモニウムである。尚、フッ素化物は、単独で添加しても二以上を組合せて添加してもよい。水溶液中のフッ素原子濃度は、５～４５０ｐｐｍが好適であり、８～３５０ｐｐｍがより好適であり、１０～１００ｐｐｍが更に好適である。ここで、フッ素原子濃度とは、水溶液中に含まれる、フッ素イオン（例えば、Ｆ－、ＨＦ２－）や、解離していないフッ素化物を含めた全てのフッ素原子の重量の総和（ｍｇ）を水の容積（Ｌ）で割った値を意味する。このような濃度範囲に設定することにより、絶縁膜の溶解を抑制しつつ十分な洗浄（ポリマ残渣剥離）効果を顕著に発揮できる。更に、バリアメタルの溶解が抑制される。 <Release liquid>
First, the configuration of the stripping solution according to the best mode will be described. The stripping solution according to the best mode comprises an aqueous solution containing a fluorine atom and substantially free of an organic solvent and an anticorrosive agent. Here, the existence form of the fluorine atom in the best mode is not particularly limited, and examples thereof include HF, F − , HF 2 —, etc. Among these, it is particularly preferable that HF 2 — is included. . Although it does not specifically limit as a fluoride used as the origin of the fluorine atom used for the peeling liquid of this invention, The fluoride which dissociates a fluorine ion in water is suitable, for example, hydrofluoric acid, Ammonium fluoride, acidic ammonium fluoride, methylamine hydrofluoride, ethylamine hydrofluoride, propylamine hydrofluoride, tetramethylammonium fluoride, tetraethylammonium fluoride, methanolamine hydrofluoride, N-methyl Methanolamine fluoride, N, N-dimethylmethanolamine fluoride, ethanolamine hydrofluoride, N-methylethanolamine hydrofluoride, N, N-dimethylethanolamine hydrofluoride, triethylenediamine hydrofluoride Etc. Among these, a preferred fluorinated product is ammonium fluoride. The fluorinated product may be added alone or in combination of two or more. The concentration of fluorine atoms in the aqueous solution is preferably 5 to 450 ppm, more preferably 8 to 350 ppm, and even more preferably 10 to 100 ppm. Here, the fluorine atom concentration is the total weight (mg) of all fluorine atoms including fluorine ions (for example, F − , HF 2− ) and non-dissociated fluoride contained in the aqueous solution. It means the value divided by the volume of water (L). By setting to such a concentration range, a sufficient cleaning (polymer residue peeling) effect can be remarkably exhibited while suppressing dissolution of the insulating film. Furthermore, dissolution of the barrier metal is suppressed.
　本最良形態に係る剥離液の性能を向上させるために、ｐＨを調整する物質を加えてもよい。ここで、ｐＨを低い方向へ調整するための物質として、二酸化炭素、硫酸、硝酸、クエン酸、シュウ酸、酢酸等が挙げられる。また、ｐＨを高い方向へ調整するための物質として、アンモニア、２－アミノエタノール、コリン等が挙げられる。ｐＨ調整成分を剥離液中に導入することにより、剥離液のｐＨが、フッ素イオンの剥離効果が高まる酸性域に変化する。ここで、剥離液のｐＨは、２.０～６.０が好適であり、３.０～４.５がより好適であり、３.３～３.７が更に好適である。ここで、ｐＨは、ＪＩＳ　Ｚ８８０２に既定されている方法により測定する。このような範囲のｐＨとすることにより、ｐＨ３．５をピークとして、ＳｉＯ２を溶かす速度が顕著に高くなる。ＳｉＯ２を溶かす速度が最も早いフッ素系のイオンであるＨＦ２ －が、フッ化アンモニウム濃度が一定の条件では、ｐＨ３．５において、最も高濃度で存在するためである。但し、ＳｉＯ２を溶かすものの、フッ素イオン源の濃度が前記の濃度範囲に調節されているため、溶かすＳｉＯ２は、極僅かであり、集積回路の構造を損傷又は溶解させることなくポリマ残渣を剥離することが可能である。また、前記のような一般的に腐食性を有するとされる物質をｐＨ調整成分として加えても、当該ｐＨの範囲内となるような添加量であれば、十分に濃度が低いため、半導体基板を傷つけることもない。 In order to improve the performance of the stripping solution according to the best mode, a substance for adjusting pH may be added. Here, carbon dioxide, sulfuric acid, nitric acid, citric acid, oxalic acid, acetic acid and the like can be cited as substances for adjusting the pH in the lower direction. In addition, ammonia, 2-aminoethanol, choline and the like can be cited as substances for adjusting the pH in the higher direction. By introducing the pH adjusting component into the stripping solution, the pH of the stripping solution is changed to an acidic region where the effect of stripping fluorine ions is enhanced. Here, the pH of the stripping solution is preferably 2.0 to 6.0, more preferably 3.0 to 4.5, and even more preferably 3.3 to 3.7. Here, the pH is measured by a method defined in JIS Z8802. By setting the pH within such a range, the speed at which SiO 2 is dissolved is remarkably increased with pH 3.5 as a peak. This is because HF 2 −, which is a fluorine-based ion that dissolves SiO 2 the fastest, exists at the highest concentration at pH 3.5 under a constant ammonium fluoride concentration. However, although the dissolved SiO 2, since the concentration of the fluoride ion source is adjusted to a concentration range of the are dissolved SiO 2 is negligible and, peeling the polymeric residue without damaging or dissolve the structure of the integrated circuit Is possible. Further, even if a substance generally considered to be corrosive as described above is added as a pH adjusting component, the concentration is sufficiently low as long as the added amount is within the pH range. Will not hurt.
　本最良形態に係る剥離液は、有機溶剤及び防食剤を実質的に含有しない。ここで、本特許請求の範囲及び本明細書にいう「実質的に含有しない」とは、環境への影響が問題にならない程度の、例えば、０.１ｗｔ％以下の含有量であることを意味する。尚、有機溶剤としては、例えば、Ｎ，Ｎ－ジメチルホルムアミド、ジメチルアセトアミド等のアミド類や、エタノール、イソプロピルアルコール、グリセリン、エチレングリコール、ジエチレングリコール等のアルコール類や、ジエチレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル等のグリコールエーテル類や、ジメチルスルホキシド等のスルホキシド類や、アセトニトリル、プロピオニトリル、ブチロニトリル、イソブチロニトリル、スクシノニトリル、ベンゾニトリル、アジポニトリル等の有機ニトリル類等、が挙げられる。「防食剤」としては、半導体プロセスにおいて使用される防食剤であれば特に限定されず、例えば、カテコール、ソルビトール、キシリトール等が挙げられる。 The stripping solution according to the best mode is substantially free of organic solvent and anticorrosive agent. Here, “substantially not containing” as used in the claims and the specification means that the content is not more than 0.1 wt%, for example, so that the influence on the environment is not a problem. To do. Examples of the organic solvent include amides such as N, N-dimethylformamide and dimethylacetamide, alcohols such as ethanol, isopropyl alcohol, glycerin, ethylene glycol and diethylene glycol, diethylene glycol monomethyl ether and dipropylene glycol monomethyl ether. And the like, sulfoxides such as dimethyl sulfoxide, and organic nitriles such as acetonitrile, propionitrile, butyronitrile, isobutyronitrile, succinonitrile, benzonitrile, and adiponitrile. The “anticorrosive” is not particularly limited as long as it is an anticorrosive used in a semiconductor process, and examples thereof include catechol, sorbitol, xylitol and the like.
　以上のような剥離液構成とすることで、本発明の主効果である、ビアホールに付着したポリマ残渣の剥離効果に加え、以下で述べるような副次的効果をも奏することが可能となる。剥離液には原料由来の金属（例えば、Ａｌ、Ｃｕ、Ｋ、Ｍｇ、Ｎａ、Ｔｉ、Ｆｅ、Ｃｒ、Ｐｔ、Ｎｉ、Ｃａ、Ｚｎ）汚染の問題があり、従来技術においては、原料を精製する等といった工夫をして剥離液中の金属量の低減を図ってきた。しかしながら、そのような工夫によってもせいぜいｐｐｍオーダーまでしか金属量を低減することができなかった。他方、本発明では、溶媒を水のみとした上でのフッ素イオン量の低濃度化を実現できたため、所望オーダーの金属量（例えばナノオーダー）とすることが可能となる。具体的には、水での希釈量を１０倍、１００倍とすることで、フッ素化物由来の汚染金属量を１／１０、１／１００とすることが可能となる。 By adopting the stripping solution configuration as described above, in addition to the stripping effect of the polymer residue adhering to the via hole, which is the main effect of the present invention, the following secondary effects can be achieved. The stripping solution has a problem of contamination of metals derived from raw materials (for example, Al, Cu, K, Mg, Na, Ti, Fe, Cr, Pt, Ni, Ca, Zn). In the prior art, the raw materials are purified. The amount of metal in the stripping solution has been reduced by contrivances such as. However, even with such a device, the amount of metal could be reduced only to the ppm order. On the other hand, in the present invention, since the concentration of fluorine ions can be reduced while using only water as a solvent, it is possible to achieve a desired amount of metal (for example, nano-order). Specifically, the amount of contamination metal derived from a fluoride can be reduced to 1/10 and 1/100 by setting the dilution amount with water to 10 times and 100 times.
《装置構成》
第一形態
　続いて、本発明に係る洗浄方法に用いる装置について説明する。図１を参照しながら、第一形態に係る対象物洗浄システムＳ１について詳述する。洗浄システムＳ１は、ノズル１０１、操作バルブ１０２ａ～ｂ、水流量計１０３ａ～ｂ、ストップバルブ１０４ａ～ｃ、水加圧タンク１０５（水圧送ポンプでも代替できる）、水蒸気発生器１０６、水供給管１０７ａ～ｂ、窒素供給管１０８、減圧弁１０９、耐圧管１１０～１１２、ステージ１１３、チャンバ１１４、圧力計１１５、ヒータ１１６、薬液タンク１１７、ＣＯ２供給管１１８で構成されている。ステージ１１３上には処理対象物（例えば半導体ウエハ）Ｗがセットされている。以下、各要素について詳述する。 "Device configuration"
First Embodiment Next, an apparatus used in the cleaning method according to the present invention will be described. The object cleaning system S1 according to the first embodiment will be described in detail with reference to FIG. The cleaning system S1 includes a nozzle 101, operation valves 102a and 102b, water flow meters 103a and 103b, stop valves 104a and 104c, a water pressurization tank 105 (which can be replaced by a water pump), a steam generator 106, and a water supply pipe 107a. And b, a nitrogen supply pipe 108, a pressure reducing valve 109, pressure-resistant pipes 110 to 112, a stage 113, a chamber 114, a pressure gauge 115, a heater 116, a chemical liquid tank 117, and a CO 2 supply pipe 118. A processing object (for example, a semiconductor wafer) W is set on the stage 113. Hereinafter, each element will be described in detail.
　まず、ノズル１０１は、対象物Ｗに対向するように配置されており、水蒸気と、剥離液又は純水の２流体噴流を発生する。そして、当該ノズル１０１を介して、水加圧タンク１０５から供給された純水又は薬液タンク１１７から供給された剥離液と、水蒸気発生器１０６から供給された水蒸気との混相流が対象物Ｗに吹き付けられる結果、対象物の洗浄処理が行われる。この際、純水及び剥離液の供給を止めれば水蒸気のみの噴流となる。また、水蒸気の供給を止めて、剥離液を対象物Ｗに対して単に流下することも可能である。 First, the nozzle 101 is disposed so as to face the object W, and generates a two-fluid jet of water vapor and stripping solution or pure water. Then, a mixed phase flow of pure water supplied from the water pressurization tank 105 or the peeling liquid supplied from the chemical liquid tank 117 and the water vapor supplied from the water vapor generator 106 to the object W through the nozzle 101. As a result of the spraying, the object is cleaned. At this time, if the supply of pure water and stripping solution is stopped, a jet of only water vapor is obtained. It is also possible to stop the supply of water vapor and simply allow the stripping solution to flow down to the object W.
　水加圧タンク１０５は、水供給管１０７ｂから供給される純水を所定値Ａ１（ＭＰ）に加圧し、加圧した純水のうち所定の流量Ｂ１（ｌ／ｍｉｎ）を、耐圧管１１０を介して高圧状態でノズル１０１に送り出す（但し、ノズル形状によっては、加圧しないで純水をノズルに送り出すことが可能）。水流量計１０３ａは、水加圧タンク１０５からノズル１０１に供給される純水の流量を計測する。作業員は、水流量計１０３ａで当該流量を確認し、操作バルブ１０２ａを用いて所望の値に調整することができる。また、ストップバルブ１０４ａを開閉することにより、純水の供給を停止したり、再開したりすることもできる。 The water pressurization tank 105 pressurizes pure water supplied from the water supply pipe 107b to a predetermined value A 1 (MP), and supplies a predetermined flow rate B 1 (l / min) of the pressurized pure water to the pressure pipe. 110 is sent to the nozzle 101 in a high-pressure state (however, depending on the nozzle shape, it is possible to send pure water to the nozzle without pressurization). The water flow meter 103 a measures the flow rate of pure water supplied from the water pressure tank 105 to the nozzle 101. The operator can check the flow rate with the water flow meter 103a and adjust it to a desired value using the operation valve 102a. In addition, the supply of pure water can be stopped or restarted by opening and closing the stop valve 104a.
　尚、本形態においては、窒素供給管１０８から窒素が水加圧タンク１０５に供給されるように構成されている。本最良形態では純水に窒素を混合したが、純水のみをノズル１０１に供給してもよいことは明らかである。また、窒素ガスに限定されず、Ａｒガスのような不活性ガスでも代替可能である。 In this embodiment, nitrogen is supplied from the nitrogen supply pipe 108 to the water pressurization tank 105. In this best mode, pure water is mixed with nitrogen, but it is obvious that only pure water may be supplied to the nozzle 101. Moreover, it is not limited to nitrogen gas, It can substitute also with inert gas like Ar gas.
　続いて、薬液タンク１１７は、ＣＯ２供給管１１８から供給されるＣＯ２を所定値に加圧し、薬液タンク内の剥離液にＣＯ２を溶解させる。次に、加圧した剥離液のうち所定の流量Ｂ２（ｌ／ｍｉｎ）を、耐圧管１１２を介してノズル１０１に送り出す。水流量計１０３ｂは、薬液タンク１１７からノズル１０１に供給される剥離液の流量を計測する。作業員は、水流量計１０３ｂで当該流量を確認し、操作バルブ１０２ｂを用いて所望の値に調整することができる。更に、ヒータ１１６が設けられているため、剥離液の温度を容易に調節できる。また、ストップバルブ１０４ｃを開閉することにより、剥離液の供給を停止したり、再開したりすることもできる。 Subsequently, the chemical liquid tank 117, pressurized CO 2 that is supplied from the CO 2 supply pipe 118 to a predetermined value, to dissolve the CO 2 stripping solution in the chemical liquid tank. Next, a predetermined flow rate B 2 (l / min) of the pressurized stripping solution is sent to the nozzle 101 through the pressure tube 112. The water flow meter 103b measures the flow rate of the stripping solution supplied from the chemical solution tank 117 to the nozzle 101. The operator can check the flow rate with the water flow meter 103b and adjust it to a desired value using the operation valve 102b. Further, since the heater 116 is provided, the temperature of the stripping solution can be easily adjusted. In addition, the supply of the stripping solution can be stopped or restarted by opening and closing the stop valve 104c.
　尚、本形態においては、ＣＯ２供給管１１８からＣＯ２が薬液タンク１１７に供給されるように構成されている。このように、薬液タンク中の剥離液にＣＯ２を供給可能に構成することにより、対象物に供給する剥離液中に含まれるＣＯ２の濃度を適宜調整することが可能となる。また、当該構成でなくとも、タンクからノズルまでの輸送管で二酸化炭素を吹き込み可能なように構成したり、ｐＨを調整する物質と混合可能に構成してもよい。その他、当該混合手段を有していなくとも、剥離液製造時にｐＨを調整してもよい。例えば、二酸化炭素を溶解させた後、二酸化炭素で封入した容器から剥離液を供給してもよい。 In the present embodiment, CO 2 from the CO 2 supply pipe 118 is configured to be supplied to the chemical liquid tank 117. In this manner, by configuring so that CO 2 can be supplied to the stripping solution in the chemical tank, it is possible to appropriately adjust the concentration of CO 2 contained in the stripping solution supplied to the object. In addition, the configuration may be such that carbon dioxide can be blown through a transport pipe from the tank to the nozzle, or may be mixed with a substance that adjusts the pH. In addition, even if it does not have the said mixing means, you may adjust pH at the time of stripping solution manufacture. For example, after dissolving carbon dioxide, the stripping solution may be supplied from a container sealed with carbon dioxide.
　次に、水蒸気発生器１０６は、水供給管１０７ａから供給される純水を所定温度Ｄ１（℃）以上に加温して水蒸気を発生し、耐圧管１１１を介して高圧状態でノズル１０１に送り出す。圧力計１１５は、水蒸気発生器１０６からノズル１０１に供給される水蒸気の圧力を計測する。作業員は、圧力計１１５で当該圧力を確認し、減圧弁１０９を用いて所望の値に調整することができる。また、ストップバルブ１０４ｂを開閉することにより、水蒸気の供給を停止したり、再開したりすることもできる。 Next, the water vapor generator 106 heats the pure water supplied from the water supply pipe 107 a to a predetermined temperature D 1 (° C.) or higher to generate water vapor, and is supplied to the nozzle 101 in a high pressure state via the pressure resistant pipe 111. Send it out. The pressure gauge 115 measures the pressure of water vapor supplied from the water vapor generator 106 to the nozzle 101. An operator can check the pressure with the pressure gauge 115 and adjust it to a desired value using the pressure reducing valve 109. In addition, the supply of water vapor can be stopped or restarted by opening and closing the stop valve 104b.
第二形態
　図２は、本最良形態に係る第二形態である洗浄システムＳ２の概略構成図である。ここで、本形態は、剥離液供給工程と噴射工程とが異なる場所で実施されるシステムである。洗浄システムＳ２は、噴射洗浄部１００と剥離液供給部２００とから構成される。 2nd form FIG. 2 is a schematic block diagram of washing | cleaning system S2 which is the 2nd form which concerns on this best form. Here, this form is a system implemented in the place where a peeling liquid supply process and an injection process differ. The cleaning system S <b> 2 includes an injection cleaning unit 100 and a stripping solution supply unit 200.
　まずは、噴射部１００の構造を説明する。対象物洗浄システムＳ２の噴射部１００の多くの要素は、対象物Ｓ１と基本的に同様の構成を有している。従って、これら要素については図１と同一の符号を付すことにより説明を省略する。相違点について説明すれば、薬液タンク等の剥離液をノズルに供給するための手段が省かれていることである。 First, the structure of the injection unit 100 will be described. Many elements of the injection unit 100 of the object cleaning system S2 have basically the same configuration as the object S1. Accordingly, the same reference numerals as those in FIG. To explain the difference, a means for supplying a stripping solution such as a chemical tank to the nozzle is omitted.
　次に、本形態の剥離液供給部２００について説明する。剥離液供給部２００は、液体を貯蓄するための筐体２０１と、当該筐体２０１空間内で対象物Ｗを保持するための保持手段２０２と、を少なくとも有する。剥離液供給部２００は、更に、剥離液を貯蓄する薬液タンク２０３と、薬液タンク内へとＣＯ２を導入するＣＯ２供給管２０４と、当該筐体２０１内へ剥離液を導入するための液体導入手段（例えばポンプ）２０５と、当該液体タンク２０３と液体導入手段２０５の間に設けられたヒータ２０６と、液体排出手段２０７と、を有していてもよい。 Next, the stripping solution supply unit 200 of this embodiment will be described. The stripping liquid supply unit 200 includes at least a casing 201 for storing liquid and a holding unit 202 for holding the object W in the space of the casing 201. The stripping liquid supply unit 200 further includes a chemical liquid tank 203 that stores the stripping liquid, a CO 2 supply pipe 204 that introduces CO 2 into the chemical liquid tank, and a liquid for introducing the stripping liquid into the casing 201. You may have the introduction means (for example, pump) 205, the heater 206 provided between the said liquid tank 203 and the liquid introduction means 205, and the liquid discharge means 207.
第三形態
　図３は、第三形態に係る対象物洗浄システムＳ３の概略構成図である。ここで、本形態は、剥離液供給工程と噴射工程とが異なる場所で実施され、かつ、剥離液供給工程終了後に対象物が自動的に噴射工程エリアに搬送されるシステムである。尚、対象物洗浄システムＳ３の多くの要素は、対象物Ｓ２と基本的に同様の構成を有している。従って、これら要素については図２と同一の符号を付すことにより説明を省略する。そこで、第二形態との相違点を中心に説明すると、本形態は、剥離液供給処理を施された対象物Ｗを対象物保持手段２０２からステージ１１３の上へと移動させる、搬送部３００を更に有する点で第二形態と相違する。このように、本形態では搬送部３００を有するため、自動的かつ連続的に全工程を行うことが可能となる。ここで、搬送部３００は、対象物保持手段３０１と、前記保持手段を動作させるための作動手段３０２と、当該保持手段３０１及び作動手段３０２を適切な高さに調節可能な支持体３０３とから構成される。 3rd form FIG. 3: is a schematic block diagram of the target-object cleaning system S3 which concerns on a 3rd form. Here, this embodiment is a system in which the stripping solution supply process and the spraying process are performed at different locations, and the object is automatically conveyed to the spraying process area after the stripping liquid supply process is completed. It should be noted that many elements of the object cleaning system S3 have basically the same configuration as the object S2. Accordingly, the same reference numerals as those in FIG. Therefore, the description will focus on the differences from the second embodiment. In this embodiment, the transport unit 300 that moves the object W that has been subjected to the stripping liquid supply process from the object holding means 202 onto the stage 113 is provided. Further, the second embodiment is different from the second embodiment. Thus, in this embodiment, since the conveyance unit 300 is provided, all processes can be performed automatically and continuously. Here, the transport unit 300 includes an object holding unit 301, an operating unit 302 for operating the holding unit, and a support 303 that can adjust the holding unit 301 and the operating unit 302 to an appropriate height. Composed.
《洗浄方法》
　本発明に係る対象物洗浄方法は、（方法１）剥離液処理と噴射処理を一工程で実行する方法、例えば、剥離液と水蒸気とからなる混相流を対象物表面に対して噴射する剥離液噴射工程による方法と、（方法２）剥離液処理と噴射処理とを別工程で実行する方法、例えば、剥離液対象物表面に供給する剥離液供給工程と水蒸気及び／又は水からなる流体を前記対象物に噴射する噴射工程との少なくとも二工程を含む方法が挙げられる。ここで、後者の方法における剥離液供給工程としては、例えば、対象物表面に剥離液を流下する工程と、剥離液中に対象物を浸漬する工程が挙げられる。更に後者の方法によれば、剥離液の使用量を最小限にとどめることができるため、環境への影響が少なくなる。以下、これらの方法における各工程を詳述する。 《Cleaning method》
The object cleaning method according to the present invention includes (Method 1) a method of executing the stripping liquid treatment and the spraying process in one step, for example, a stripping liquid that sprays a multiphase flow composed of the stripping liquid and water vapor onto the surface of the object. The method by the spraying step and (Method 2) the method of executing the stripping solution treatment and the spraying processing in separate steps, for example, the stripping solution supplying step for supplying the stripping liquid object surface and the fluid comprising water vapor and / or water There is a method including at least two steps of an injection step of injecting the object. Here, examples of the stripping solution supplying step in the latter method include a step of flowing the stripping solution on the surface of the object and a step of immersing the object in the stripping solution. Furthermore, according to the latter method, since the amount of the stripping solution used can be minimized, the influence on the environment is reduced. Hereinafter, each process in these methods is explained in full detail.
（方法１）剥離液噴射工程
　まずは、方法１に係る剥離液噴射工程について説明する。剥離液噴射工程は、本最良形態に係る剥離液と水蒸気とを混合した流体を対象物に噴射する工程である。本最良形態に係る剥離液は、当該噴射工程に係る方法で対象物に噴射されることにより、当該濃度であっても十分な洗浄力を有し、且つ、半導体基板を損傷しないという効果をより好適に発揮する。特に、従来、剥離し難いとされていたプラズマエッチング後のビアホール側面に付着したポリマ残渣であっても、好適に剥離する能力を有する。当該方法は、例えば、本最良形態に係る洗浄システムＳ１により、実施可能である。当該方法を用いることにより、より迅速に洗浄を行うことが可能となる。ここで、剥離液噴射工程の各種条件について説明する。剥離液噴射工程における混相流の温度は、６０～１１５℃が好適であり、８０～１１３℃がより好適であり、９０～１１０℃が更に好適である。６０℃以上とすることにより、著しく反応速度が上がる。流体温度は、熱電対をウエハに設置し、５ｍｍ離して１分間流体を噴射した後の定常状態の温度を流体温度とした。混相流の噴射速度は、６０ｍ／ｓ以上が好適であり、１４０ｍ／ｓ以上がより好適であり、２６０ｍ／ｓが更に好適である。上限は特に限定されないが、６００ｍ／ｓ以下である。噴射速度は、流体の体積流量をノズル口の断面積で除した値とする。剥離液流量は、０．０５～０．４ｄｍ３／ｍｉｎが好適であり、０．１～０．３ｄｍ３／ｍｉｎがより好適であり、０．１～０．２ｄｍ３／ｍｉｎが更に好適である。水蒸気と剥離液の混合比（［剥離液体積］／［水蒸気体積］）は、０．０００３～０．０１が好適であり、０．０００４～０．０５がより好適であり、０．０００５～０．０１が更に好適である。処理時間は、２５～１８０秒が好適であり、４０～９０秒がより好適であり、５０～７０秒が更に好適である。尚、当該数値範囲は主に洗浄に影響するパラメータの限界値を示した値であり、これらの組合せは必要となる衝撃力の度合いに応じて容易に選択し設定することが可能である。 (Method 1) Stripping solution spraying step First, the stripping solution spraying step according to Method 1 will be described. The stripping solution spraying step is a step of spraying a fluid, which is a mixture of the stripping solution according to the best mode and water vapor, onto an object. The stripping solution according to the best mode is more effective in having a sufficient cleaning power even at the concentration and not damaging the semiconductor substrate by being sprayed onto the object by the method according to the spraying step. It demonstrates suitably. In particular, even polymer residues adhering to the side surface of a via hole after plasma etching, which has been conventionally considered difficult to peel off, have the ability to peel off suitably. The method can be performed by, for example, the cleaning system S1 according to the best mode. By using this method, it becomes possible to perform cleaning more rapidly. Here, the various conditions of a peeling liquid injection process are demonstrated. The temperature of the multiphase flow in the stripping solution jetting process is preferably 60 to 115 ° C, more preferably 80 to 113 ° C, and still more preferably 90 to 110 ° C. By setting the temperature at 60 ° C. or higher, the reaction rate is significantly increased. The fluid temperature was defined as a steady-state temperature after a thermocouple was installed on the wafer and the fluid was ejected for 1 minute at a distance of 5 mm. The injection speed of the multiphase flow is preferably 60 m / s or more, more preferably 140 m / s or more, and further preferably 260 m / s. Although an upper limit is not specifically limited, It is 600 m / s or less. The ejection speed is a value obtained by dividing the volume flow rate of the fluid by the cross-sectional area of the nozzle opening. Stripping solution the flow rate is suitably 0.05 ~ 0.4dm 3 / min, 0.1 ~ 0.3dm 3 / min is more preferred, 0.1 ~ 0.2dm 3 / min is more preferred is there. The mixing ratio of water vapor and stripping solution ([stripping solution volume] / [water vapor volume]) is preferably 0.0003 to 0.01, more preferably 0.0004 to 0.05, and 0.0005 to 0.01 is more preferable. The treatment time is preferably 25 to 180 seconds, more preferably 40 to 90 seconds, and even more preferably 50 to 70 seconds. Note that the numerical range is a value mainly indicating a limit value of a parameter that affects cleaning, and a combination of these can be easily selected and set according to the degree of required impact force.
（方法２）剥離液供給工程
　次に、方法２の第一工程に係る剥離液供給工程について説明する。剥離液供給工程は、対象物に対して、所定温度条件のもと、所定時間剥離液を供給する工程である。本工程により、次に行われる噴射工程の除去効果が顕著となる。即ち、最良形態に係る剥離液の濃度であっても十分に洗浄に寄与し、従来、剥離し難いとされていたプラズマエッチング後のビアホール側面に付着したポリマ残渣であっても、ビアホールを損傷しないようなマイルドな条件で洗浄可能とする効果を奏する。剥離液供給工程としては、例えば、対象物表面に剥離液を流下する工程と、剥離液中に対象物を浸漬する工程が挙げられる。 (Method 2) Stripping Solution Supply Step Next, the stripping solution supply step according to the first step of Method 2 will be described. The stripping solution supply step is a step of supplying the stripping solution to the object under a predetermined temperature condition for a predetermined time. By this step, the effect of removing the next injection step becomes remarkable. That is, even the concentration of the stripping solution according to the best mode contributes sufficiently to cleaning, and even a polymer residue adhered to the side surface of the via hole after plasma etching, which has been conventionally considered difficult to strip, does not damage the via hole. There is an effect that can be washed under such mild conditions. As a peeling liquid supply process, the process of flowing down peeling liquid on the target object surface, and the process of immersing a target object in peeling liquid are mentioned, for example.
　まず、対象物表面に剥離液を流下する場合、剥離液供給工程は、例えば、本最良形態における洗浄システムＳ１によって行うことが可能である。本工程においては、システムＳ１の薬液タンク１１７から供給される剥離液をヒータ１１６により温度を調節しながら、ノズル１０１により対象物表面上に供給する。ここで、剥離液供給工程における各種条件について説明する。剥離液の温度は、７５～１００℃が好適であり、８０～９５℃がより好適であり、８５～９０℃が更に好適である。当該温度範囲で処理を行うことにより、フッ素イオンが極めて低濃度の剥離液を用いたとしても、十分な効果を発揮する。処理時間は、２５～２４０秒が好適であり、４０～９０秒がより好適であり、５０～７０秒が更に好適である。 First, when the stripping solution flows down on the surface of the object, the stripping solution supply step can be performed by, for example, the cleaning system S1 in the best mode. In this step, the stripping solution supplied from the chemical tank 117 of the system S1 is supplied onto the surface of the object by the nozzle 101 while adjusting the temperature by the heater 116. Here, various conditions in the stripping solution supply step will be described. The temperature of the stripping solution is preferably 75 to 100 ° C., more preferably 80 to 95 ° C., and still more preferably 85 to 90 ° C. By performing the treatment in the temperature range, even if a stripping solution having a very low concentration of fluorine ions is used, a sufficient effect is exhibited. The treatment time is preferably 25 to 240 seconds, more preferably 40 to 90 seconds, and further preferably 50 to 70 seconds.
　次に、剥離液中に対象物を浸漬する場合、例えば、本最良形態に係る洗浄システムＳ２又はＳ３により、実施可能である。洗浄システムＳ２を用いた場合を代表例として説明すれば、剥離液供給部２００の保持手段２０２に対象物Ｗを搭載した後、筐体２０１内に液体導入手段２０５から、所定のフッ素イオン濃度及び二酸化炭素濃度に調整された剥離液を導入し、対象物Ｗが浸漬する状態とする。ここで、剥離液の温度は、７５～１００℃が好適であり、８０～９５℃がより好適であり、８５～９０℃が更に好適である。当該温度範囲で処理を行うことにより、フッ素イオンが極めて低濃度の剥離液を用いたとしても、十分な効果を発揮する。浸漬時間は、２５～１８０秒が好適であり、４０～９０秒がより好適であり、５０～７０秒が更に好適である。浸漬後、筐体２０１内の剥離液を液体排出手段２０７によって排出し、筐体２０１内の対象物を噴射部１００のステージ１１３上に移動して噴射工程へと移行する。 Next, when the object is immersed in the stripping solution, it can be performed, for example, by the cleaning system S2 or S3 according to the best mode. If the cleaning system S2 is used as a representative example, after the object W is mounted on the holding means 202 of the stripping solution supply unit 200, a predetermined fluorine ion concentration and a predetermined fluorine ion concentration are supplied from the liquid introduction means 205 into the housing 201. A stripping solution adjusted to the carbon dioxide concentration is introduced, and the object W is immersed. Here, the temperature of the stripping solution is preferably 75 to 100 ° C., more preferably 80 to 95 ° C., and still more preferably 85 to 90 ° C. By performing the treatment in the temperature range, even if a stripping solution having a very low concentration of fluorine ions is used, a sufficient effect is exhibited. The immersion time is preferably 25 to 180 seconds, more preferably 40 to 90 seconds, and further preferably 50 to 70 seconds. After the immersion, the stripping liquid in the housing 201 is discharged by the liquid discharging means 207, and the object in the housing 201 is moved onto the stage 113 of the spraying unit 100 to shift to the spraying process.
（方法２）噴射工程
　方法２に係る噴射工程は、先述の剥離液供給処理を施した洗浄対象物に対して、水蒸気及び／又は水を噴射することにより、除去対象物を取り除く工程である。本工程は、公知の洗浄方法（例えば、特開２００４－３４９５７７号公報記載の方法）により行うことが可能であるが、例えば、対象物洗浄システムＳ１又は、システムＳ２若しくはＳ３の噴射部１００によっても行うことが可能である。 (Method 2) Injecting Step The injecting step according to Method 2 is a step of removing the removal target by spraying water vapor and / or water onto the cleaning target that has been subjected to the above-described stripping liquid supply process. This step can be performed by a known cleaning method (for example, the method described in Japanese Patent Application Laid-Open No. 2004-349577). For example, the object cleaning system S1 or the injection unit 100 of the system S2 or S3 can also be used. Is possible.
　ここで、本最良形態における噴射工程の各種条件について説明する。噴射工程における噴射速度は、６０ｍ／ｓ以上が好適であり、１２０ｍ／ｓ以上がより好適であり、２４０ｍ／ｓ以上が更に好適である。純水流量は、０．０５～０．４ｄｍ３／ｍｉｎが好適であり、０.１～０.３ｄｍ３／ｍｉｎがより好適であり、０.１～０.２ｄｍ３／ｍｉｎが更に好適である。流体温度は、７５～１１５℃が好適であり、８０～９５℃がより好適であり、８５～９０℃が更に好適である。剥離液供給工程が流下である場合、処理時間は、２０～２４０秒が好適であり、４０～９０秒がより好適であり、５０～７０秒が更に好適である。剥離液供給工程が浸漬である場合、処理時間は、２０～１８０秒が好適であり、４０～９０秒がより好適であり、５０～７０秒が更に好適である。尚、本工程における数値範囲は洗浄に影響する主なパラメータの限界値を示した値であり、これらの組合せは必要となる衝撃力の度合いに応じて容易に選択し設定することが可能である。 Here, various conditions of the injection process in the best mode will be described. 60 m / s or more is suitable for the injection speed in an injection process, 120 m / s or more is more suitable, and 240 m / s or more is still more suitable. Pure water flow rate is suitably 0.05 ~ 0.4dm 3 / min, is more preferably 0.1 ~ 0.3dm 3 / min, 0.1 ~ 0.2dm 3 / min is more preferred is there. The fluid temperature is preferably 75 to 115 ° C, more preferably 80 to 95 ° C, and still more preferably 85 to 90 ° C. When the stripping solution supplying step is flowing down, the processing time is preferably 20 to 240 seconds, more preferably 40 to 90 seconds, and further preferably 50 to 70 seconds. When the stripping solution supplying step is immersion, the treatment time is preferably 20 to 180 seconds, more preferably 40 to 90 seconds, and further preferably 50 to 70 seconds. The numerical range in this step is a value indicating the limit value of the main parameter that affects cleaning, and these combinations can be easily selected and set according to the degree of required impact force. .
　洗浄対象の対象物：厚さ０.６２５ｍｍのシリコンウエハ上に、厚さ１００μｍのＴｉＮの膜を形成し、さらにその上に厚さ１０００μｍのシリコン酸化膜（以後、酸化膜と記述）を形成した。リソグラフ、ドライエッチングを行い、開口径１μｍの穴を、ＴｉＮと酸化膜の界面の深さまで開けた。
　対象物洗浄システムＳ１、Ｓ２により、対象物を洗浄した。当該実施例における条件は以下のとおりである。尚、本実施例で用いたフッ素イオン源は、フッ化アンモニウムである。ポリマの残存及びホールの損傷は走査型電子顕微鏡により観察した。以下、実施例及び比較例のデータを示す。 Object to be cleaned: a TiN film having a thickness of 100 μm was formed on a silicon wafer having a thickness of 0.625 mm, and a silicon oxide film having a thickness of 1000 μm (hereinafter referred to as an oxide film) was further formed thereon. . Lithograph and dry etching were performed, and a hole with an opening diameter of 1 μm was opened to the depth of the interface between TiN and the oxide film.
The object was cleaned by the object cleaning systems S1 and S2. The conditions in the example are as follows. The fluorine ion source used in this example is ammonium fluoride. Residual polymer and hole damage were observed with a scanning electron microscope. Hereafter, the data of an Example and a comparative example are shown.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
図１は、第一形態である洗浄システムＳ１の概略構成図である。FIG. 1 is a schematic configuration diagram of a cleaning system S1 according to the first embodiment. 図２は、第二形態である洗浄システムＳ２の概略構成図である。FIG. 2 is a schematic configuration diagram of the cleaning system S2 which is the second embodiment. 図３は、第三形態である洗浄システムＳ３の概略構成図である。FIG. 3 is a schematic configuration diagram of a cleaning system S3 that is a third embodiment.
符号の説明Explanation of symbols
Ｓ１～３：対象物洗浄システム
Ｗ：対象物
１００：噴射洗浄部
１０１：ノズル
１０２ａ～ｂ：操作バルブ
１０３ａ～ｂ：水流量計
１０４ａ～ｃ：ストップバルブ
１０５：水加圧タンク
１０６：水蒸気発生器
１０７ａ～ｂ：水供給管
１０８：窒素供給管
１０９：減圧弁
１１０～１１２：耐圧管
１１３：ステージ
１１４：チャンバ
１１５：圧力計
１１６：ヒータ
１１７：薬液タンク
１１８：ＣＯ２供給管
２００：剥離液供給部
２０１：筐体
２０２：保持手段
２０３：薬液タンク
２０４：ＣＯ２供給管
２０５：液体導入手段
２０６：ヒータ
２０７：液体排出手段
３００：搬送部
３０１：対象物保持手段
３０２：作動手段
３０３：支持体 S1-3: Object cleaning system W: Object 100: Jet cleaning unit 101: Nozzle 102a-b: Operation valve 103a-b: Water flow meter 104a-c: Stop valve 105: Water pressurization tank 106: Steam generator 107a-b: water supply pipe 108: nitrogen supply pipe 109: pressure reducing valve 110-112: pressure-resistant pipe 113: stage 114: chamber 115: pressure gauge 116: heater 117: chemical tank 118: CO 2 supply pipe 200: stripping liquid supply part 201: housing 202: holding means 203: liquid tank 204: CO 2 supply pipe 205: liquid introducing means 206: heater 207: liquid discharge means 300: the transport unit 301: the object holding means 302: operation unit 303: support

Claims (4)

  1. 　フッ素原子を含む、有機溶剤及び防食剤を実質的に含有しない水溶液からなる、対象物に付着したポリマ残渣を剥離するための剥離液。 A stripping solution for stripping a polymer residue adhering to an object, comprising an aqueous solution containing a fluorine atom and substantially free of an organic solvent and an anticorrosive.
  2. 　前記水溶液中のフッ素原子濃度が、５～４５０ｐｐｍである、請求項１記載の剥離液。 The stripping solution according to claim 1, wherein the concentration of fluorine atoms in the aqueous solution is 5 to 450 ppm.
  3. 　ｐＨが２.０～６.０である、請求項１又は２記載の剥離液。 3. The stripping solution according to claim 1 or 2, wherein the pH is 2.0 to 6.0.
  4. 　対象物を洗浄する方法において、
    　請求項１～３のいずれか一項記載の剥離液と水蒸気とを含む混相流体を対象物表面に対して噴射する、剥離液噴射工程を有することを特徴とする方法。     In a method for cleaning an object,
    4. A method comprising a stripping liquid ejecting step of spraying a mixed phase fluid containing the stripping liquid according to claim 1 and water vapor onto a surface of an object.
PCT/JP2008/068451 2008-10-10 2008-10-10 Stripping fluid and process for cleaning objects WO2010041333A1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003313594A (en) * 2002-04-22 2003-11-06 Nec Corp Detergent solution and method for producing semiconductor device
JP2003332288A (en) * 2002-05-10 2003-11-21 Lam Research Kk Water feeding method and water feeding apparatus
JP2004317641A (en) * 2003-04-14 2004-11-11 Nagase Chemtex Corp Non-organic solvent type resist stripper composition
JP2004349577A (en) * 2003-05-23 2004-12-09 Aqua Science Kk Object processing device and object processing method
JP2006059906A (en) * 2004-08-18 2006-03-02 Mitsubishi Gas Chem Co Inc Cleaning liquid and cleaning method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003313594A (en) * 2002-04-22 2003-11-06 Nec Corp Detergent solution and method for producing semiconductor device
JP2003332288A (en) * 2002-05-10 2003-11-21 Lam Research Kk Water feeding method and water feeding apparatus
JP2004317641A (en) * 2003-04-14 2004-11-11 Nagase Chemtex Corp Non-organic solvent type resist stripper composition
JP2004349577A (en) * 2003-05-23 2004-12-09 Aqua Science Kk Object processing device and object processing method
JP2006059906A (en) * 2004-08-18 2006-03-02 Mitsubishi Gas Chem Co Inc Cleaning liquid and cleaning method

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