WO2010041333A1 - Fluide de décapage et procédé de nettoyage d'objets - Google Patents

Fluide de décapage et procédé de nettoyage d'objets 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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Prior art keywords
stripping solution
stripping
cleaning
liquid
water
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PCT/JP2008/068451
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English (en)
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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Priority to KR1020117010534A priority Critical patent/KR20110079835A/ko
Priority to JP2010532750A priority patent/JPWO2010041333A1/ja
Priority to PCT/JP2008/068451 priority patent/WO2010041333A1/fr
Publication of WO2010041333A1 publication Critical patent/WO2010041333A1/fr

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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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  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Cleaning Or Drying Semiconductors (AREA)
  • Drying Of Semiconductors (AREA)

Abstract

L'invention vise à procurer un moyen pour décaper de façon fiable et retirer un résidu polymère adhérant aux parois latérales de trous d'interconnexion d'un objet sans endommager ni dissoudre une structure de circuit intégré avec une influence minimisée sur l'environnement et en particulier sans endommager les trous d'interconnexion. A cet effet, l'invention porte sur un fluide de décapage pour décaper un résidu polymère adhérant à un objet, constitué d'une solution aqueuse qui est sensiblement exempte de solvants organiques contenant du fluor et d'agents anticorrosifs contenant du fluor.
PCT/JP2008/068451 2008-10-10 2008-10-10 Fluide de décapage et procédé de nettoyage d'objets WO2010041333A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020117010534A KR20110079835A (ko) 2008-10-10 2008-10-10 박리액 및 대상물 세정 방법
JP2010532750A JPWO2010041333A1 (ja) 2008-10-10 2008-10-10 剥離液及び対象物洗浄方法
PCT/JP2008/068451 WO2010041333A1 (fr) 2008-10-10 2008-10-10 Fluide de décapage et procédé de nettoyage d'objets

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2008/068451 WO2010041333A1 (fr) 2008-10-10 2008-10-10 Fluide de décapage et procédé de nettoyage d'objets

Publications (1)

Publication Number Publication Date
WO2010041333A1 true WO2010041333A1 (fr) 2010-04-15

Family

ID=42100298

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2008/068451 WO2010041333A1 (fr) 2008-10-10 2008-10-10 Fluide de décapage et procédé de nettoyage d'objets

Country Status (3)

Country Link
JP (1) JPWO2010041333A1 (fr)
KR (1) KR20110079835A (fr)
WO (1) WO2010041333A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003313594A (ja) * 2002-04-22 2003-11-06 Nec Corp 洗浄液および半導体装置の製造方法
JP2003332288A (ja) * 2002-05-10 2003-11-21 Lam Research Kk 水供給方法および水供給装置
JP2004317641A (ja) * 2003-04-14 2004-11-11 Nagase Chemtex Corp 非有機溶剤型レジスト剥離剤組成物
JP2004349577A (ja) * 2003-05-23 2004-12-09 Aqua Science Kk 対象物処理装置及び対象物処理方法
JP2006059906A (ja) * 2004-08-18 2006-03-02 Mitsubishi Gas Chem Co Inc 洗浄液および洗浄法。

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003313594A (ja) * 2002-04-22 2003-11-06 Nec Corp 洗浄液および半導体装置の製造方法
JP2003332288A (ja) * 2002-05-10 2003-11-21 Lam Research Kk 水供給方法および水供給装置
JP2004317641A (ja) * 2003-04-14 2004-11-11 Nagase Chemtex Corp 非有機溶剤型レジスト剥離剤組成物
JP2004349577A (ja) * 2003-05-23 2004-12-09 Aqua Science Kk 対象物処理装置及び対象物処理方法
JP2006059906A (ja) * 2004-08-18 2006-03-02 Mitsubishi Gas Chem Co Inc 洗浄液および洗浄法。

Also Published As

Publication number Publication date
JPWO2010041333A1 (ja) 2012-03-01
KR20110079835A (ko) 2011-07-08

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