CN102031203B - Cleaning liquid, cleaning method, cleaning system, and method for manufacturing microstructure - Google Patents
Cleaning liquid, cleaning method, cleaning system, and method for manufacturing microstructure Download PDFInfo
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- CN102031203B CN102031203B CN2010102876290A CN201010287629A CN102031203B CN 102031203 B CN102031203 B CN 102031203B CN 2010102876290 A CN2010102876290 A CN 2010102876290A CN 201010287629 A CN201010287629 A CN 201010287629A CN 102031203 B CN102031203 B CN 102031203B
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- hydrofluoric acid
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- 238000000034 method Methods 0.000 title claims abstract description 59
- 238000004140 cleaning Methods 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000007788 liquid Substances 0.000 title abstract description 18
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 260
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 244
- 230000001590 oxidative effect Effects 0.000 claims abstract description 110
- 239000007800 oxidant agent Substances 0.000 claims abstract description 74
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 238000005868 electrolysis reaction Methods 0.000 claims description 72
- 239000001117 sulphuric acid Substances 0.000 claims description 53
- 235000011149 sulphuric acid Nutrition 0.000 claims description 53
- 230000002000 scavenging effect Effects 0.000 claims description 30
- 238000002360 preparation method Methods 0.000 claims description 27
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- 239000000463 material Substances 0.000 claims description 19
- 238000010926 purge Methods 0.000 claims description 17
- 150000002978 peroxides Chemical class 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 14
- 229910003460 diamond Inorganic materials 0.000 claims description 10
- 239000010432 diamond Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 125000005385 peroxodisulfate group Chemical group 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 14
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 158
- 229960002050 hydrofluoric acid Drugs 0.000 description 108
- 239000000126 substance Substances 0.000 description 42
- 238000003860 storage Methods 0.000 description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 23
- 230000008859 change Effects 0.000 description 18
- 229910052581 Si3N4 Inorganic materials 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 14
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 14
- 239000000758 substrate Substances 0.000 description 14
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- 238000010790 dilution Methods 0.000 description 10
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- 238000010586 diagram Methods 0.000 description 9
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- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 7
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- 239000002184 metal Substances 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000001312 dry etching Methods 0.000 description 6
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- 239000010703 silicon Substances 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 230000002349 favourable effect Effects 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000003014 ion exchange membrane Substances 0.000 description 4
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- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 238000004380 ashing Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- -1 dry etching remnants Substances 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
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- 230000009183 running Effects 0.000 description 3
- 229960001866 silicon dioxide Drugs 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
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- 229910021397 glassy carbon Inorganic materials 0.000 description 2
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- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- 238000000059 patterning Methods 0.000 description 2
- 230000010363 phase shift Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229920003935 Flemion® Polymers 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
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- 230000007797 corrosion Effects 0.000 description 1
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- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XEMZLVDIUVCKGL-UHFFFAOYSA-N hydrogen peroxide;sulfuric acid Chemical compound OO.OS(O)(=O)=O XEMZLVDIUVCKGL-UHFFFAOYSA-N 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000011900 installation process Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 230000004304 visual acuity Effects 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—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
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31127—Etching organic layers
- H01L21/31133—Etching organic layers by chemical means
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/423—Stripping or agents therefor using liquids only containing mineral acids or salts thereof, containing mineral oxidizing substances, e.g. peroxy compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—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
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- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
According to embodiments, a cleaning liquid includes an oxidizing substance and hydrofluoric acid and exhibiting acidity. A cleaning method is disclosed. The method includes producing an oxidizing solution including an oxidizing substance by one selected from electrolyzing a sulfuric acid solution, electrolyzing hydrofluoric acid added to a sulfuric acid solution, and mixing a sulfuric acid solution with aqueous hydrogen peroxide. The method includes supplying the oxidizing solution and hydrofluoric acid to a surface of an object to be cleaned.
Description
The cross reference relevant with application
The No.2009-219890 of Japanese patent application formerly that the application submitted based on September 25th, 2009, and require its right of priority; Its all the elements are here cited adding.
Technical field
Embodiment described herein is usually directed to the method for scavenging solution, purging method, cleaning system and manufacturing microstructure.
Background technology
Microstructure with meticulous wall body utilizes lithography technique to make from the teeth outwards, for example in semiconducter device and MEMS field (MEMS).The resist that in manufacturing processed, forms is needs no longer, use SPM solution (sulfuric acid hydrogen peroxide mixture) to peel off and remove, for example, and the mixing liquid of concentrated sulfuric acid solution and aqueous hydrogen peroxide solution (for example :) referring to JP-A2007-123330 (kokai).
Oxidizing substance (for example, peroxide one sulfuric acid) through mixing the preparation of the vitriol oil and aqueous hydrogen peroxide solution is included in the SPM solution.
In addition, proposed to utilize oxidizing substance (for example peroxide one sulfuric acid) to remove the technology (referring to JP-A 2006-111943 (kokai)) that sticks to the resist on wafer and the analogue through the preparation of the electrolysis vitriolic aqueous solution.
The technology that resist is an organic substance of removing of decomposing has been discussed in JP-A2007-123330 (kokai) and JP-A2006-111943 (kokai), and it utilizes the oxidizing substance with high oxidation resolving power of preparation.
Here, when the semiconducter device of high speed operation is made, introduce a large amount of impurity, a large amount of impurity of introducing have formed the layer that changes on the resist surface.The resist with change layer that forms there can not be removed easily; And very misfortune only can not obtain the required edge of removing through the oxidative decomposition capacity of top described oxidizing substance.
Description of drawings
Accompanying drawing 1 is the synoptic diagram according to the cleaning system of embodiment;
Accompanying drawing 2A and 2B are the synoptic diagram of oxidizing substance preparating mechanism;
Accompanying drawing 3 is that concentration and the vitriolic concentration of oxidizing substance is with respect to the figure that peels off chronergy;
Accompanying drawing 4 is schemas of purging method;
Accompanying drawing 5 is the schemas according to the purging method of another embodiment;
Accompanying drawing 6 is synoptic diagram of cleaning system, and the sulphuric acid soln that wherein is added with hydrofluoric acid has also carried out electrolysis; With
Accompanying drawing 7 is synoptic diagram of a kind of cleaning system, and it does not have the structure of solution circulated.
Embodiment
Generally speaking, according to an embodiment, a kind of scavenging solution comprises oxidizing substance and hydrofluoric acid, and shows acid.
In another embodiment, a kind of purging method is disclosed.This method comprises a kind of oxidizing solution that comprises oxidizing substance of preparation, joins the hydrofluoric acid in the sulphuric acid soln and makes sulphuric acid soln and the aqueous hydrogen peroxide solution blended is a kind of prepares through being selected from electrolysis sulphuric acid soln, electrolysis.This method comprises to body surface to be cleaned provides oxidizing solution and hydrofluoric acid.
In another embodiment, cleaning system comprises the sulfuric acid electrolysis cells, sulfuric acid feed unit, clean unit, the first hydrofluoric acid feed unit and oxidizing solution feed unit.The sulfuric acid electrolysis cells comprises: anode, and negative electrode, the barrier film between anode and negative electrode, the cathode compartment between anolyte compartment between anode and the barrier film and negative electrode and the barrier film, the electrolysis sulphuric acid soln is with the sulfuric acid electrolysis cells of preparation oxidizing substance in the anolyte compartment.Sulfuric acid feed unit anode chamber and cathode compartment are supplied with sulphuric acid soln.The clean process of agitation object is carried out in the clean unit.The first hydrofluoric acid feed unit is supplied with hydrofluoric acid to the clean unit.In addition, the oxidizing solution feed unit is supplied with the oxidizing solution that comprises oxidizing substance to the clean unit.
In another embodiment, cleaning system comprises the sulfuric acid electrolysis cells, sulfuric acid feed unit, clean unit, the second hydrofluoric acid feed unit and oxidizing solution feed unit.The sulfuric acid electrolysis cells comprises: anode, and negative electrode, the barrier film between anode and negative electrode, the cathode compartment between anolyte compartment between anode and the barrier film and negative electrode and the barrier film, the electrolysis sulphuric acid soln is with the sulfuric acid electrolysis cells of preparation oxidizing substance in the anolyte compartment.Sulfuric acid feed unit anode chamber and cathode compartment are supplied with sulphuric acid soln.The clean process of agitation object is carried out in the clean unit.Hydrofluoric acid is supplied with in the second hydrofluoric acid feed unit anode chamber.In addition, the oxidizing solution feed unit is supplied with the oxidizing solution that comprises oxidizing substance to the clean unit.
A kind of method of manufacture of microstructure is disclosed in another embodiment.This method comprises uses above-mentioned purging method agitation object to clean and form microstructure.
With reference to accompanying drawing embodiment is described.Assembly similar in the accompanying drawing uses identical Reference numeral, and has omitted detailed explanation according to circumstances.
Accompanying drawing 1 is the synoptic diagram according to the cleaning system of this embodiment;
Shown in accompanying drawing 1, cleaning system 5 comprises: sulfuric acid electrolysis cells 10, hydrofluoric acid feed unit 50, clean unit 12, solution circulated unit 14 and sulfuric acid feed unit 15.
Sulfuric acid electrolysis cells 10 has electrolysis sulphuric acid soln and the function for preparing oxidizing substance in anolyte compartment 30.Though (for example go out pollutent that object to be cleaned is stained with when using the solution comprise oxidizing substance; Settling such as resist, metallic impurity, particle, dry etching remnants, silicon-dioxide, halogenide etc.) time; The ability of oxidation that comprises the solution of oxidizing substance weakens, but sulfuric acid electrolysis cells 10 has the function of the oxidation capacity of recovering to weaken.
Sulfuric acid electrolysis cells 10 comprises: anode 32, negative electrode 42, the barrier film 20 between anode 32 and negative electrode 42, the cathode compartment 40 between anolyte compartment 30 between anode 32 and the barrier film 20 and negative electrode 42 and the barrier film 20.
Upper end sealing unit 22 is provided in the upper end of barrier film 20, anolyte compartment 30 and cathode compartment 40; Lower end at barrier film 20, anolyte compartment 30 and cathode compartment 40 provides lower end sealing unit 23.Anode 32 is relative with negative electrode 42, between it, is inserted with barrier film 20.Anode 32 is supported through anode carrier body 33; Negative electrode 42 is supported through cathode branch support body 43.Between anode 32 and negative electrode 42, be connected with direct supply 26.
Anode 32 is made up of with anode conducting film 35 the anode substrate element 34 of conduction, and anode conducting film 35 forms on the surface of anode substrate element 34.Anode substrate element 34 is by the inner face support of anode carrier body 33; Anode conducting film 35 is towards the anolyte compartment 30.
Lower end, 30 side is formed with anode inlet 19 in the anolyte compartment; And be formed with anode export 17 in side upper end.Anode inlet 19 is communicated with anolyte compartment 30 with anode export 17.Be formed with cathode inlet 18 in lower end, cathode compartment 40 side; And be formed with cathode outlet 16 in side upper end.Cathode inlet 18 is communicated with cathode compartment 40 with cathode outlet 16.
Hydrofluoric acid feed unit 50 comprises that preserving hydrogen fluoride (HF) aqueous solution is the storage tank 51 of hydrofluoric acid, pump 52 and open/closed valve 71.Storage tank 51, pump 52 links to each other with allocation units 61 with piping 74 through piping (piping line) 53 with open/closed valve 71.Hydrofluoric acid is kept in the storage tank 51, can supply to allocation units 61 through piping 53 and piping 74 by pump 52 runnings.In other words, hydrofluoric acid feed unit 50 has and supplies to the function of the allocation units 61 in the clean unit 12 with being stored in hydrofluoric acid in the storage tank 51; And the hydrofluoric acid that will supply to allocation units 61 can supply to the surface of wanting cleaning object W.Through provide with piping 74 and allocation units opened in 61 minutes non-illustrated piping and allocation units, hydrofluoric acid also can supply to object W to be cleaned through the tubing system of separating with the tubing system of the solution that comprises oxidizing substance (oxidizing solution).
Solution that comprises oxidizing substance (oxidizing solution) that use obtains in sulfuric acid electrolysis cells 10 and the hydrofluoric acid of being supplied with by hydrofluoric acid feed unit 50, clean unit 12 has the function of cleaning object to be cleaned.
The oxidizing solution that in sulfuric acid electrolysis cells 10, obtains supplies to the allocation units 61 that in clean unit 12, provide through solution circulated unit 14.Hydrofluoric acid is supplied to the allocation units 61 that in clean unit 12, provide by hydrofluoric acid feed unit 50.Oxidizing solution and hydrofluoric acid can be supplied with in order; And oxidizing solution and hydrofluoric acid can be supplied with basically simultaneously.
Oxidizing solution and hydrofluoric acid may be combined in together; And can supply with mixing liquid (scavenging solution).Basically supplied to simultaneously under the situation of piping 74 by the hydrofluoric acid of hydrofluoric acid feed unit 50 supplies and the oxidizing solution of being supplied with by sulfuric acid electrolysis cells 10, piping 74 has formed the mixed cell that mixes two kinds of solution.
Moreover, can provide a kind of non-illustrated storage tank to be used for mixed oxidization solution and hydrofluoric acid.In this case, non-illustrated storage tank has formed mixed cell.Through non-diagram storage tank is provided, the flow velocity fluctuation (scavenging solution) of mixing liquid can obtain buffering, mixing rate can obtain adjustment etc.Moreover the character of mixing liquid mixing rate (scavenging solution) will be more even also.
Though in the clean unit 12 shown in the accompanying drawing 1, used so-called single-chip cleaning, also can use batch treatment.
The oxidizing solution of in sulfuric acid electrolysis cells 10, making supplies to clean unit 12 through solution circulated unit 14 by anode export 17.Keep the unit as solution, anode export 17 is connected with storage tank 28 through piping 73, and open/closed valve 73a is provided in piping.Storage tank 28 is connected with allocation units 61 through piping 74.Oxidizing solution is kept in the storage tank 28, can be supplied with through piping 74 by the running of pump 81 and give allocation units 61.Distribution side at pump 81 provides open/closed valve 74a in piping 74.In this embodiment, storage tank 28, pump 81 etc. have formed the oxidizing solution feed unit, supply with the oxidizing solution that comprises oxidizing substance to the clean unit.In this case, the fluctuation of the flow velocity of the oxidizing solution of preparation can cushion through oxidizing solution is preserved and maintained in the storage tank 28 in sulfuric acid electrolysis cells 10.The temperature control of oxidizing solution can be through providing well heater to carry out to storage tank 28.
The oxidizing solution of 12 dischargings can reclaim and supply to again clean unit 12 through solution circulated unit 14 from the clean unit.For example: through the return tank 63 of flowing through in order, strainer 64, pump 82 and open/closed valve 76, the oxidizing solution that gives off from clean unit 12 can supply to the anode inlet 19 of sulfuric acid electrolysis cells 10.In other words, oxidizing solution can circulate between sulfuric acid electrolysis cells 10 and clean unit 12.In this case, as required, the oxidizing solution that in clean, uses can supply to sulfuric acid electrolysis cells 10; Then, carry out the oxidizing solution that comprises oxidizing substance that electrolysis the obtain storage tank 28 etc. of can flowing through at sulfuric acid electrolysis cells 10; And oxidizing solution can supply to clean unit 12.
Here, as required, can supply with used oxidizing solution to sulfuric acid electrolysis cells 10 and to sulfuric acid electrolysis cells 10, carry out electrolysis then and prepare oxidizing solution through supply with dilute sulphuric acid from sulfuric acid feed unit 15.Here the oxidizing solution that obtains storage tank 28 grades of can flowing through supply to clean unit 12 then.Repeat such oxidizing solution that utilizes again as much as possible, can reduce the amount of the preparation necessary raw material of oxidizing solution (chemical solution etc.), and the amount that reduces waste liquid in the process of cleaning object W to be cleaned.
Perhaps, the oxidizing solution that gives off from clean unit 12 can supply to storage tank 28, and return tank 63, strainer 64, pump 82 and open/closed valve 91 through flowing through in order that is to say, the sulfuric acid electrolysis cells 10 of not flowing through.Here, continue, the clean of agitation object is through providing oxidizing solution to carry out to clean unit 12 from storage tank 28.In this case, the oxidizing solution after the use can utilize again in clean.Repeat such oxidizing solution that utilizes again as much as possible, can reduce the amount of the preparation necessary raw material of oxidizing solution (chemical solution etc.), and the amount of waste liquid.
The mixing liquid (scavenging solution) of the hydrofluoric acid of discharging and oxidizing solution and hydrofluoric acid also can likewise circulate and utilize from clean unit 12.Non-illustrated return tank, open/closed valve etc. can be connected to clean unit 12, be used for the separation of hydrogen fluoric acid with reclaim hydrofluoric acid and oxidizing solution.In this case, supply with hydrofluoric acid and oxidizing solution in order, separating and reclaim can execution during supplying with separately.Utilize through separating to handle again etc. can to separate again.
Sulfuric acid feed unit 15 has the function that dilution heat of sulfuric acid is supplied to sulfuric acid electrolysis cells 10 (anolyte compartment 30 and cathode compartment 40).Sulfuric acid feed unit 15 comprise supply with dilution heat of sulfuric acid to the anolyte compartment 30 with the pump 80 of cathode compartment 40, storage tank 60 and open/closed valve 70 and 72 of preservation dilute sulphuric acid.
Dilution heat of sulfuric acid has the sulfuric acid concentration that for example is not less than 30 weight % and is not higher than 70 weight %, is kept in the storage tank 60.Driving pump 80, make sulphuric acid soln in the storage tank 60 flow through open/closed valve 70, supply in the anolyte compartment 30 through the piping and the anode inlet 19 in open/closed valve 76 downstream sides.Equally, driving pump 80, make sulphuric acid soln in the storage tank 60 flow through open/closed valve 72, supply in the cathode compartment 40 through the piping 86 and the cathode inlet 18 in open/closed valve 72 downstream sides.
In this embodiment, the damage of the barrier film 20 that causes owing to the vitriolic electrolysis is suppressible, and this is to be low because supply to the concentration of the sulphuric acid soln of cathode side.In other words, during the vitriolic electrolytic reaction, moved to anode side at the water of cathode side; The concentration of cathode side sulphuric acid soln increases; And barrier film 20 damages easily.In addition, be used as at ion-exchange membrane under the situation of barrier film 20, the resistance of ion-exchange membrane increases when the water ratio of the vitriol oil descends; And bath voltage does not desirably increase.Therefore, in order to alleviate such problem, can be through supplying with dilute sulphuric acid suppresses resistance for the ion-exchange membrane that feeds water to cathode side increase.
Supply to the sulfuric acid concentration of sulfuric acid electrolysis cells 10 through minimizing, the productive rate that is included in the oxidizing substance (for example peroxide one sulfuric acid and peroxo disulfate acid) in the oxidizing solution will be improved.The productive rate that improves oxidizing substance is described below.
Above described open/closed valve 70,71,72,73a, 74a, 75a, 76 and 91 have the function of the multiple solution flow rate of control.Pump 80,81 and 82 also has the function of the multiple flow of solution speed of control.
From the chemical resistant properties aspect; The material of the lid 29 of anode carrier body 33, cathode branch support body 43, cathode outlet 16, anode export 17, cathode inlet 18, anode inlet 19 and clean unit 12 can advantageously for example comprise fluorocarbon resin, like tetrafluoroethylene.
The mixing liquid (scavenging solution) of supplying with oxidizing solution, hydrofluoric acid and oxidizing solution and hydrofluoric acid can comprise the fluorocarbon resin pipe to the piping of clean unit 12, and coiling is with insulation layer etc.Such piping also can have the online well heater of being processed by fluorocarbon resin.Pump is taken out the pump of the mixing liquid (scavenging solution) of oxidizing solution, hydrofluoric acid and oxidizing solution and hydrofluoric acid, can comprise by having the surge pump that thermotolerance and chemical-resistant fluorocarbon resin are processed.
The material of preserving the storage tank of sulphuric acid soln can comprise for example quartzy.The material of each storage tank of the mixing liquid (scavenging solution) of preservation hydrofluoric acid and oxidizing solution and hydrofluoric acid can comprise for example fluorocarbon resin.Each storage tank also can depend on the circumstances and comprise and overflow gear, temperature-control device etc.
Here, through temperature-control device is provided for storage tank, for piping provides online well heater etc., to improve with the reactivity of resist etc., can shorten the treatment time through improving solution temperature (treatment temp).Yet,, maybe or cause the allowable temperature that the assembly (for example piping, open/closed valve, pump, each unitary storage tank, the unitary lid of clean etc.) of cleaning system is relevant and the problem of intensity if the temperature that increases is too high.Element is formed by for example fluorocarbon resin etc. usually, with the chemical resistant properties of raising and hydrofluoric acid, sulfuric acid and oxidizing solution contact part.In this case, the words that temperature is too high can't obtain needed intensity.
Therefore, consider and shorten treatment time and cleaning system allowable temperature, intensity etc. that the temperature of hydrofluoric acid, sulfuric acid and oxidizing solution is favourable is not less than 100 ℃ and be not more than 110 ℃.
The material of the base members 34 of anodic conduction can comprise that for example p-type silicon and valve metal are such as niobium.Here " valve metal " is meant, a kind of metal is coated with the sull that anodic oxidation forms uniformly on the surface, and has superior corrosion resistance.The base members 44 of negative electrode conduction can comprise, for example n-type silicon.
The material of anode conducting film 35 and negative electrode conductive film 45 can comprise, for example vitreous carbon.From the persistence aspect, have higher sulfuric acid concentration and in solution, added under the situation of hydrofluoric acid the suitable diamond thin that uses conduction at solution.
For anode and negative electrode, conductive film and base members can be formed by identical materials.For example, be used as under the situation of cathode substrate element at vitreous carbon and the diamond self-supporting film of conduction is used as under the situation of anode substrate element, base members self has formed the conductive film with electrolysis character and can contribute for electrolytic reaction.
Though diamond has stable chemistry, machinery and thermal property, thereby in electrochemical systems, be difficult to use diamond owing to its relatively poor electric conductivity.Yet, when the diamond thin that provides boron gas and nitrogen to utilize hot-wire chemical gas-phase deposition (HF-CVD) to obtain to conduct electricity.The diamond thin of conduction has wide potential window, for example 3 to 5 volts and such as the resistance of 5 to 100 milli-ohm-cms.
Here, potential window is that minimum current potential (being not less than 1.2 volts) is that brine electrolysis is necessary.The potential window quality of materials is different.Have the material of broad potential window and the current potential in potential window carries out having the electrolytic reaction of the redox potential in potential window under the electrolytic situation in use, can have precedence over the electrolysis of water; And the material electrolysis that is not easy to experience oxidizing reaction or reduction reaction can preferentially be carried out.Therefore, it is possible utilizing the diamond decomposition and the synthetic of conduction, and these materials can't experience the Traditional electrochemical reaction.
In HF-CVD, decomposition is carried out through under the condition of high temperature, supplying with source-material gas to tungsten filament.Formed the necessary group of film.Then, group is diffused into the surface of substrate, is reflected on the substrate of requirement with other reactive gas and forms film.
To be described in the mechanism of preparation oxidizing substance in the sulfuric acid electrolysis cells 10 now.
Accompanying drawing 2A and 2B are the synoptic diagram of oxidizing substance preparating mechanism; Accompanying drawing 2A is the side cross sectional representation of sulfuric acid electrolysis cells.Accompanying drawing 2B is the synoptic diagram of accompanying drawing 2A along the cross section of A-A line.
Shown in accompanying drawing 2A and 2B, anode 32 is provided with negative electrode 42 toward each other, and barrier film 20 inserts therebetween.Anode 32 by anode carrier body 33 support, the anode conducting film 35 of anode 32 is towards the anolyte compartment 30.Negative electrode 42 by cathode branch support body 43 support, the negative electrode conductive film 45 of negative electrode 42 is towards cathode compartment 40.Provide the electrolysis cells case 24 shells in each end of barrier film 20, anode carrier body 33 and cathode branch support body 43.
Sulphuric acid soln (dilution heat of sulfuric acid) with 70 weight % is for example supplied with from storage tank anode chambers 30 60 through anode inlet 19.Sulphuric acid soln (dilution heat of sulfuric acid) with 70 weight % is for example also supplied with to cathode compartment 40 from storage tank 60 through cathode inlet 18.
Apply positive voltage and negative voltage is provided through anode 32, with cathode compartment 40 electrolytic reaction takes place in each anolyte compartment 30 to negative electrode 42.The reaction of Chemical formula 1, Chemical formula 2 and chemical formula 3 occurs in the anolyte compartment.
Chemical formula 1
2HSO
4 -→S
2O
8 2-+2H
++2e
-
Chemical formula 2
HSO
4 -+H
2O→HSO
5 -+2H
++2e
-
2H
2O→4H
++4e
-+O
2↑
Here, the water (H in Chemical formula 2 and chemical formula 3
2O) be included in the sulphuric acid soln of 70 weight % with 30 weight %.In the anolyte compartment 30, the prepared in reaction of Chemical formula 2 peroxide one sulfate ion (HSO
5 -).The total reaction of chemical formula 4 is carried out through the primitive reaction of Chemical formula 1 and chemical formula 3, has prepared peroxide one sulfate ion (HSO
5 -) and sulfuric acid.Peroxide one sulfuric acid has higher cleaning capacity than sulfuric acid.
Chemical formula 4
S
2O
8 2-+H
++H
2O→HSO
5-+H
2SO
4
Perhaps, sometimes at preparation hydrogen peroxide (H
2O
2) the back peroxide one sulfate ion (HSO for preparing chemical formula 4
5 -), by chemical formula 5 explanations that come from the primitive reaction of Chemical formula 1 and chemical formula 3.Sometimes, peroxo disulfate acid (H
2S
2O
8) prepare by the reaction of Chemical formula 1.Chemical formula 4 is second order reactions of Chemical formula 1 with chemical formula 5.
S
2O
8 2-+H
++H
2O→H
2O
2+H
2SO
4
Prepared hydrogen shown in chemical formula 6 at cathode compartment 40.This is because of the hydrogen ion (H in anode preparation
+) pass barrier film 20 and moved to negative electrode, and electrolysis has taken place.From zone 40, give off hydrogen through cathode outlet 16.
Chemical formula 6
2H
++2e-→H
2↑
In the embodiment shown in chemical formula 7, can obtain for example peroxide one sulfuric acid (H of oxidizing substance through the electrolysis sulphuric acid soln
2SO
5), peroxo disulfate acid (H
2S
2O
8) etc.; And the oxidizing solution that can obtain to comprise these oxidizing substances.Though hydrogen prepares as sub product, hydrogen does not influence the removal of resist etc.
Chemical formula 7
H
2SO
4+ H
2O → oxidizing substance+H
2
Using under the peroxide one vitriolic situation, for example the speed of reaction of resist is very fast with organic substance.Therefore, even the bigger resist of the amount that will remove removes, and also can in short time span, accomplish.Equally, using under the peroxide one vitriolic situation, removing is possible at a lower temperature.Therefore, it is unnecessary waiting for accurate adjustment such as temperature risings.In addition, peroxide one sulfuric acid can stably prepare in a large number.Therefore, with the speed of reaction of the object that will remove even also can increase at low temperatures.
Here, improve productive rate in order to shorten the treatment time, the oxidizing substance that increases q.s is enough.In this case, the size that the preparation amount of oxidizing substance can be through increasing equipment, the amount that apply power, increase dilution heat of sulfuric acid that increases wait and increase.Yet work will cause higher production cost and environment will be impacted like this.Therefore, be necessary to prepare effectively oxidizing substance through improving electrolytic efficiency.
According to the knowledge that the contriver obtained, under constant electrolytic parameter (the for example value of electric current, flow velocity, temperature etc.) situation, can prepare more oxidizing substance through vitriolic concentration during reducing electrolysis.Therefore, be included in the productive rate of oxidizing substance in the oxidizing solution (for example, peroxide one sulfuric acid and peroxo disulfate acid), can increase through the sulfuric acid concentration that minimizing supplies to sulfuric acid electrolysis cells 10.
Accompanying drawing 3 illustrates concentration and the vitriolic concentration of the oxidizing substance effect for the time of peeling off (removing the time).The concentration of oxidizing substance is the transverse axis of figure.Peel off the time longitudinal axis that (removing the time) is figure.In accompanying drawing 3, B1 is that sulfuric acid concentration is the situation of 70 weight %; B2 is that sulfuric acid concentration is the situation of 80 weight %; B3 is that sulfuric acid concentration is the situation of 85 weight %; B4 is that sulfuric acid concentration is the situation of 90 weight %; B5 is that sulfuric acid concentration is the situation of 95 weight %.
Can find out that from accompanying drawing 3 when sulfuric acid got the concentration minimizing, therefore the concentration that has prepared more oxidizing substance and oxidizing substance increased.Equally, the sulfuric acid concentration for identical peels off the time (removing the time) and shortens along with the raising (when the amount of oxidizing substance increases) of oxidizing substance concentration.
In other words, at the preparatory phase of oxidizing substance,, vitriolic concentration can prepare more oxidizing substance along with reducing.Thereby the time of peeling off can be shortened (removing the time).
Therefore, in this embodiment, supply to the dilution heat of sulfuric acid of sulfuric acid electrolysis cells 10, have the sulfuric acid concentration that is not less than 30 weight % and is not higher than 70 weight %.
Therefore, the electrolytic efficiency of raising sulfuric acid electrolysis cells 10 can prepare more oxidizing substance.Therefore, can supply with the oxidizing solution that comprises a large amount of oxidizing substances to the surface of object W to be cleaned.Thereby shortened the treatment time.
, when the semiconducter device that runs up is made, introduce a large amount of impurity here, formed the change layer on the resist surface owing to introduce a large amount of impurity.Having the resist that changes layer enough is not removed easily; And only the oxidative decomposition capacity through top described oxidizing substance can not obtain the required edge of removing unfortunately.
In this case, conceivable arriving, use have than oxidizing substance more the material of high de-agglomeration ability and the ability of removal remove and be formed with the resist that changes layer from the teeth outwards.For example, hydrofluoric acid is used to remove sull and original sull, has high de-agglomeration ability and high removal ability.Therefore, conceivable arriving uses hydrofluoric acid to remove the resist that is formed with the change layer on the surface.
Yet, have the ability of decomposing and removing oxide compound (for example silica membrane etc.) and nitride (for example silicon nitride film etc.) with the hydrofluoric acid that removes sull and original sull.Therefore, sull that on wafer, forms and nitride film possibly undesirably be removed; Therefore perhaps be called film reductive phenomenon.Particularly, be exposed at sull, nitride film etc. under the situation of the part that is not coated with resist, such part might desirably not be removed.
Therefore, hydrofluoric acid has been considered to can't be used in the application with the object that removes organic substance such as resist.
As contriver's result of study, obtained such understanding, hydrofluoric acid will be inhibited to the removal ability of oxide compound (for example silica membrane etc.) and nitride (for example silicon nitride film etc.) in comprising the acidic solution of oxidizing substance.Also obtain such understanding in this case,, but obtained enhancing through the ability that comprises hydrofluoric acid removal resist even the ability of oxide compound and nitride of removing is inhibited.
Form 1 has compared to be removed sull, nitride film and has the ability that wherein forms the resist that changes layer.
Silica membrane (SiO
2) be that use thermal oxide film method forms sull and forms on silicon substrate.Silicon nitride film (SiN) is on silicon substrate, to form nitride film through the LP-CVD method to form.Have the resist that changes layer in order to form there, with resist-coated to silicon substrate, exposure, development and patterning; And used 10
16Atom/cm
2Arsenic changed the surface of resist.
SPM solution is that (sulphuric acid soln: aqueous hydrogen peroxide solution=3: 1) mixed sulphuric acid soln and aqueous hydrogen peroxide solution were prepared from, and vitriolic concentration is 98 weight %, and the concentration of hydrogen peroxide is 35 weight % in 3: 1 according to volume ratio.In this case, mix sulphur acid solution and aqueous hydrogen peroxide solution have prepared oxidizing substance (peroxide one sulfuric acid (H for example
2SO
5), peroxo disulfate acid (H
2S
2O
8) etc.).Therefore, SPM solution also is a kind of oxidizing solution that comprises oxidizing substance.
Comprise that the oxidizing solution of oxidizing substance has the dilution heat of sulfuric acid preparation of 70 weight % sulfuric acid concentrations through electrolysis.
The aqueous solution of hydrofluoric acid is through adding the hydrofluoric acid preparation to water, forming hydrofluoric acid concentration is the aqueous solution of 1000ppm.
Adding hydrofluoric acid to prepared adding hydrofluoric acid in the sulphuric acid soln that sulfuric acid concentration is 98 weight % sulphuric acid soln, is 1000ppm thereby hydrofluoric acid concentration is provided.
Adding to hydrofluoric acid through the electrolysis sulfuric acid concentration is in the solution for preparing of the dilution heat of sulfuric acid of 70 weight %, prepared the oxidizing solution that adds hydrofluoric acid, thereby the hydrofluoric acid concentration that obtains is 1000ppm.
Estimate sull (silicon oxide film, i.e. SiO through erosive velocity
2) and the removal of nitride film (silicon nitride film, i.e. SiN); And under 60 ℃ treatment temp, the etch quantity in 3 minute treatment time is measured.
Estimated removal with the resist that changes layer through naked-eye observation.Removal has the treatment temp of the resist that changes layer, under the situation of using hydrofluoric acid aqueous solution, is 80 ℃, under the situation of using other solution, is 130 ℃.
Form 1
Shown in form 1, silicon oxide film (SiO
2) and silicon nitride film (SiN) only using SPM solution (through the oxidizing solution that comprises oxidizing substance of mix sulphur acid solution and aqueous hydrogen peroxide solution preparation) and only using under the situation of the oxidizing solution that comprises oxidizing substance through the preparation of electrolysis dilution heat of sulfuric acid and can not remove.In other words, silicon oxide film (SiO
2) and silicon nitride film (SiN) for example can not sustain damage under the situation of resist only using the oxidizing solution comprise oxidizing substance to remove organic substance.Yet when removal had the resist of the change layer that forms in the surface, resist can not fully be removed, and stayed the so-called remnants of peeling off (remnants).
Have such risk here, such peel off remnants (remnants) through the situation of next art breading under yield will descend significantly.Though, conceivablely can solve such problem to the chemical solution technology of in above-mentioned technology, utilizing more accurately dry etching situation and implementing other, cost will increase and produce new problem for example the oxidation of wafer might take place.
Under the situation of using hydrofluoric acid concentration as the aqueous solution of 1000ppm, silicon oxide film (SiO
2) and silicon nitride film (SiN) is etched and not desirably removal.In other words, only using hydrofluoric acid aqueous solution to remove organic substance for example under the situation of resist, exist to make silicon oxide film (SiO
2) and the impaired danger of silicon nitride film (SiN).
The experiment performed according to the contriver confirms that the resist with the change layer that in the surface, forms can't be removed under the situation of the aqueous solution that uses hydrofluoric acid.In other words, the aqueous solution of confirming hydrofluoric acid is not suitable for removing resist.
Hydrofluoric acid be added in the sulphuric acid soln and in the sulphuric acid soln concentration of hydrofluoric acid be under the situation of 1000ppm, silicon oxide film (SiO
2) and not desirably etching and the removal of silicon nitride film (SiN) quilt.In other words, only using the sulphuric acid soln added hydrofluoric acid to remove organic substance for example under the situation of resist, exist to make silicon oxide film (SiO
2) and the impaired danger of silicon nitride film (SiN).
Equally, the experiment performed according to the contriver confirmed to be added with under the situation of sulphuric acid soln of hydrofluoric acid in use, can't remove the resist with the change layer that in its surface, forms.In other words, confirm that the aqueous sulfuric acid that is added with hydrofluoric acid is not suitable for removing resist.
On the contrary, under the situation of using the sulphuric acid soln (concentration of the hydrofluoric acid that oxidizing solution has in this experiment is 1000ppm) that is added with hydrofluoric acid, silicon nitride film (SiN) is etched a little and is removed, but to silicon oxide film (SiO
2) etching but received inhibition with removing.Further, the resist with the change layer that in its surface, forms is removed, and does not peel off remnants (remnants).
Therefore; The oxidizing solution that is added with hydrofluoric acid when use is during as scavenging solution; According to the resist that routine is difficult to remove, can not stay and peel off remnants (remnants) and be removed, and not damage that silicon oxide film (SiO with the change layer that in its surface, forms
2) and silicon nitride film (SiN).
Routinely, essential change layer through dry etching ashing (ashing) removal resist surface uses SPM solution to carry out then and handles to remove remaining resist.Therefore, will cause more treatment process, more eurypalynous treatment facility, long treatment time etc.On the contrary, the oxidizing solution that is added with hydrofluoric acid during as scavenging solution, can be removed the resist with the change layer that in its surface, forms through one type technology.Therefore, can boost productivity, reduce production cost etc.
Though in the described situation of this embodiment, in oxidizing solution, added hydrofluoric acid in advance, removing resist etc. also can be through for example side by side supplying with oxidizing solution and hydrofluoric acid is implemented to the surface of object W to be cleaned according to priority or basically.Not only can implement and remove, but also can in the surface, implement on the resist of change layer resist with the change layer that in its surface, forms.Yet the resist that has the change layer that in its surface, forms in its surface is particularly useful for removing, and it is difficult to be removed usually.
Purging method according to this embodiment will be described now.
Accompanying drawing 4 is schemas of purging method.
At first, the oxidizing solution that comprises oxidizing substance (for example peroxide one sulfuric acid and peroxo disulfate acid) prepares through electrolysis sulphuric acid soln (step S1-1).In this case, be not less than 30 weight % and be not more than 70 weight % through the sulfuric acid concentration that makes sulphuric acid soln and can prepare oxidizing substance effectively.
Then, adjust the temperature (step S1-2) of prepared oxidizing solution.Temperature regulation although it is so is always unessential, considers the temperature that shortens treatment time and cleaning system permission and intensity etc., the temperature of oxidizing solution is adjusted into is not less than 100 ℃ and to be not more than 110 ℃ be favourable.Can be during the oxidizing solution that has prepared, preparation the oxidizing solution of (during electrolysis) and any one the adjusted temperature that is used for electrolytic sulphuric acid soln to supply.
Regulate the temperature (step S2) of hydrofluoric acid.Temperature regulation although it is so is always unessential, considers the temperature that shortens treatment time and cleaning system permission and intensity etc., the temperature of hydrofluoric acid is adjusted into is not less than 100 ℃ and to be not more than 110 ℃ be favourable.
Then, can side by side supply with hydrofluoric acid and oxidizing solution (step S3) according to priority or basically to the surface of object W to be cleaned.Each the object W that cleans for needs can pass through supplies such as allocation units, and is immersed in according to priority in hydrofluoric acid and the oxidizing solution.Equally, for example can side by side supply with hydrofluoric acid and oxidizing solution according to priority or basically from the separator tube wire system.Can use so-called single wafer processing, batch treatment etc.
Accompanying drawing 5 is the schemas according to the purging method of another embodiment;
Oxidizing solution and hydrofluoric acid mix in this embodiment; And mixture supplied with the surface to object W to be cleaned.
At first, the oxidizing solution that comprises oxidizing substance (for example peroxide one sulfuric acid and peroxo disulfate acid) prepares through electrolysis sulphuric acid soln (step S10).In this case, be not less than 30 weight % and be not more than 70 weight % through the sulfuric acid concentration that makes sulphuric acid soln and come to prepare effectively oxidizing substance.
Then, oxidizing solution and hydrofluoric acid are mixed preparation scavenging solution (step S11).During this time, suitably adjust the amount of oxidizing substance in concentration and the scavenging solution of hydrofluoric acid.
Then, adjust the temperature (step S12) of prepared scavenging solution.Temperature regulation although it is so is always unessential, considers the temperature that shortens treatment time and cleaning system permission and intensity etc., the temperature of scavenging solution is adjusted into is not less than 100 ℃ and to be not more than 110 ℃ be favourable.Can before mixing, carry out temperature regulation to oxidizing solution and hydrofluoric acid.
Then, can supply with scavenging solution (mixing liquid of hydrofluoric acid and oxidizing solution) (step S13) to the surface of object W to be cleaned.Each the object W that cleans for needs can pass through supplies such as allocation units, and is immersed in the scavenging solution.Can use so-called single wafer processing, batch treatment etc.
Though situation shown in accompanying drawing 5 after the oxidizing solution preparation, has joined hydrofluoric acid in the oxidizing solution that comprises oxidizing substance, can hydrofluoric acid be joined in the starting materials sulphuric acid soln of oxidizing solution; Then this electrolysis of solutions is prepared the scavenging solution that comprises oxidizing substance and in it, adds hydrofluoric acid (referring to accompanying drawing 6).
Moreover, through mix sulphur acid solution and aqueous hydrogen peroxide solution and add hydrofluoric acid preparation and comprise the oxidizing solution (SPM solution) of oxidizing substance, thereby can comprise that the oxidizing solution (SPM solution) of oxidizing substance prepares scavenging solution through preparation.In addition, comprise the scavenging solution of oxidizing substance and the hydrofluoric acid that adds in addition, can prepare through mix sulphur acid solution, aqueous hydrogen peroxide solution and hydrofluoric acid.
In other words, for scavenging solution, demonstrate acidity and comprise that the solution of oxidizing substance hydrofluoric acid is enough.Its method of manufacture can be included in preparation and comprise that the acidic solution (oxidizing solution) of oxidizing substance adds hydrofluoric acid afterwards, or prepares oxidizing substance from the sulphuric acid soln with the hydrofluoric acid that wherein adds.
Accompanying drawing 6 is synoptic diagram of a kind of cleaning system, wherein the sulphuric acid soln with the hydrofluoric acid that wherein adds is carried out electrolysis.
Shown in accompanying drawing 6, hydrofluoric acid feed unit 50 comprises storage tank 51, pump 52 and the open/closed valve 71 of preserving hydrofluoric acid.Storage tank 51, pump 52 and open/closed valve 71 link to each other with the piping of sulfuric acid feed unit 15 sides through piping 53a.In other words, piping 53a is communicated on the piping in open/closed valve 70 downstream.Hydrofluoric acid is kept in the storage tank 51, can be supplied to the anolyte compartment 30 of sulfuric acid electrolysis cells 10 by the running of pump 52 through piping 53a.In other words, hydrofluoric acid feed unit 50 has being kept at the function that hydrofluoric acid in the storage tank 51 supplies to the anolyte compartment 30 in the sulfuric acid electrolysis cells 10; And comprise oxidizing substance and the scavenging solution of the hydrofluoric acid that wherein adds, can have the sulphuric acid soln that wherein adds hydrofluoric acid through electrolysis and prepare.
Consider the adding of hydrofluoric acid, to process be favourable to anode conducting film 35 by the diamond thin of conduction at least.
The method of making microstructure according to this embodiment will be described now.
The instance of making the method for microstructure comprises, for example makes the method for semiconducter device.Here; The manufacturing process of semiconducter device comprises so-called front-end process; Such as form, apply resist, exposure, development, etching, removal resist etc. through film; Go up the technology that forms pattern, checkout procedure, cleaning process, heat treatment process, introducing impurity process, diffusion process, formation process etc. at substrate (wafer).So-called backend process comprises the installation process, accumulation of scribing, bonding, sealing etc., the checkout procedure of function and safety etc.
In this case, remove utilization for example above-described scavenging solution, purging method and cleaning system in the processing at resist, the removable property of resist can obtain increasing.Particularly,, can be removed and do not stay and peel off remnants (remnants) according to the resist that in its surface, form to change layer that routine is difficult to remove, and (the SiO that do not damage silicon oxide film
2) and silicon nitride film (SiN).
Usually, the essential dry etching that uses is removed the change layer on resist surface through ashing, uses SPM solution to carry out then and handles to remove remaining resist.Therefore, will cause more treatment process, more eurypalynous treatment facility, long treatment time etc.On the contrary, when utilizing above-described scavenging solution, purging method and cleaning system, can remove through a kind of type process and in its surface, form the resist that changes layer.Therefore, can boost productivity and reduce production cost etc.
Above basis, the purging method and cleaning system of described embodiment, can also with known technical application in processing, will omit its detailed description.
Only explain that as example of method of making microstructure the method for making microstructure is not limited thereto though make the method for semiconducter device.For example, can be applicable to micromotor, precison optical component etc. in field such as liquid-crystal display, phase shift screen (phase shift masks), the MEMS field.
In the cleaning system of describing, provide the structure of solution circulated always not necessary in the above.Shown in accompanying drawing 7, the solution that is used for clean unit 12 can be recovered in the return tank 63 with pollutent etc., is discharged into outside the system through discharging piping 75 then.
Such technology not only can be used for removing the resist of being processed by organic substance, can also same being used for remove metallic impurity, particle and dry etching remnants etc.
For example, during having the pattern of metal interconnect lines case of large aspect ratio, oxide compound and halogenide, the obstruction metal etc. of many interconnection line metals, interconnection line metal have been deposited.Equally, during having the silicon system patterning case of big aspect ratio, many silicon-dioxide and halogenide have been deposited.As a rule, these materials are can not be removed in the oxidation capacity of the oxidizing substance through SPM solution only.
Yet many such depositions can be used hydrofluoric acid to decompose and remove.Described scavenging solution, purging method and cleaning system above the utilization, such removal can not damage silicon oxide film (SiO
2) and silicon nitride film (SiN).
In other words, remove the pollutent that sticks on the microstructure a lot of methods are arranged.In this case, when having oxide compound and nitride on the surface, be useful especially, this is because can under the situation that suppresses removal oxide compound and nitride, remove the depollution thing.
Can use robot to transmit object to be cleaned.In the storage tank 51 of the storage tank 60 of preservation sulphuric acid soln and preservation hydrofluoric acid each can be connected to the pipeline of factory and automatically refill full solution.After removing pollutent, the object that rinse bath comes rinsing to clean can be set.This rinse bath can comprise the temperature-control device that overflows gear and the online well heater of use.Be fit to use quartzy material as rinse bath.
Hereinbefore, embodiment has been described.Yet the present invention is not limited to its description.
The Change In Design that those skilled in the art do top described embodiment is also included within the scope of the invention that characteristic of the present invention contains.
For example, the structure of cleaning system element, size, material quality, configuration etc. be not limited to described herein those, but can suitably change.
Further, the composition of described embodiment can make up within the bounds of possibility above; Yet in the scope of the invention that combination is included in characteristic of the present invention too and is contained like this.
Described some embodiments, but these embodiments only being to be used for illustrating, is not restriction scope of the present invention.In fact, new liquid, purging method, cleaning system and working method described herein can be with other embodied; The change of multiple omission, displacement and the form of in addition, liquid described herein, purging method, cleaning system and working method being done does not all deviate from connotation of the present invention.Claim subsequently and their equivalent are used for covering such form or modification, also will fall in scope of the present invention and the spirit.
Claims (17)
1. scavenging solution, it contains oxidizing substance, water, sulfuric acid and hydrofluoric acid, and show acid,
Through being selected from a kind of oxidizing substance for preparing in the sulphuric acid soln that electrolysis sulphuric acid soln and electrolysis also comprise hydrofluoric acid, the concentration of said sulphuric acid soln is for being not less than 30 weight % and being not more than 70 weight %.
2. purging method, it comprises:
Comprise oxidizing substance, water and vitriolic oxidizing solution a kind of preparation the through being selected from the sulphuric acid soln that electrolysis sulphuric acid soln and electrolysis also comprise hydrofluoric acid, the concentration of said sulphuric acid soln for be not less than 30 weight % and be not more than 70 weight % and
To body surface to be cleaned this oxidizing solution and hydrofluoric acid are provided.
3. method according to claim 2, wherein oxidizing substance comprises and is selected from least a in peroxide one sulfuric acid and the peroxo disulfate acid.
4. method according to claim 2 wherein is selected from and is not less than one of at least 100 ℃ and be not more than 110 ℃ in the temperature of temperature and hydrofluoric acid of oxidizing solution.
5. method according to claim 2, wherein oxidizing solution supplies to body surface to be cleaned with hydrofluoric acid in order or side by side.
6. method according to claim 2, wherein
Oxidizing solution and hydrofluoric acid are mixed, and
Mixing solutions is supplied to body surface to be cleaned.
7. method according to claim 6, wherein the temperature of mixing solutions is not less than 100 ℃ and be not more than 110 ℃.
8. cleaning system, it comprises:
The sulfuric acid electrolysis cells; This sulfuric acid electrolysis cells comprises anode, negative electrode, the cathode compartment between the anolyte compartment between the barrier film that provides between anode and the negative electrode, anode and the barrier film and negative electrode and barrier film, this sulfuric acid electrolysis cells in the anolyte compartment electrolysis sulphuric acid soln with the preparation oxidizing substance;
Anode chamber and cathode compartment are supplied with the sulfuric acid feed unit of sulphuric acid soln;
The agitation object carries out the clean unit of clean;
Supply with the first hydrofluoric acid feed unit of hydrofluoric acid to the clean unit; With
Supply with the oxidizing solution feed unit of the oxidizing solution that comprises oxidizing substance to the clean unit.
9. system according to claim 8, wherein the first hydrofluoric acid feed unit carries out to clean unit supply hydrofluoric acid and oxidizing solution feed unit supply oxidizing solution in order or side by side.
10. system according to claim 8, it comprises mixed cell further, is used for mixing hydrofluoric acid that the first hydrofluoric acid feed unit provides and the oxidizing solution that is provided by the oxidizing solution feed unit.
11. system according to claim 8; It comprises the solution circulated unit further; This solution circulated unit reclaims and is selected from the oxidizing solution and at least a material in the hydrofluoric acid that from the clean unit, discharges, and resupplies this at least a material and arrives the clean unit.
12. system according to claim 11, wherein the solution circulated unit comprises well heater, and this well heater is carried out the temperature control of oxidizing solution.
13. system according to claim 8 wherein is selected from the diamond thin of the conduction that forms on the surface of the base members that is included in one of at least conduction in anode and the negative electrode.
14. a cleaning system, it comprises:
The sulfuric acid electrolysis cells; This sulfuric acid electrolysis cells comprises anode, negative electrode, the cathode compartment that between the anolyte compartment that provides between the barrier film that provides between anode and the negative electrode, anode and the barrier film and negative electrode and barrier film, provides, the sulfuric acid electrolysis cells in the anolyte compartment electrolysis sulphuric acid soln with the preparation oxidizing substance;
Anode chamber and cathode compartment are supplied with the sulfuric acid feed unit of sulphuric acid soln;
The agitation object carries out the clean unit of clean;
The second hydrofluoric acid feed unit of hydrofluoric acid is supplied with in the anode chamber; With
Supply with the oxidizing solution oxidizing solution feed unit that comprises oxidizing substance to the clean unit.
15. system according to claim 14; It comprises the solution circulated unit further; This solution circulated unit reclaims and is selected from the oxidizing solution and at least a material in the hydrofluoric acid that from the clean unit, discharges, and resupplies this at least a material and arrives the clean unit.
16. system according to claim 14 wherein is selected from the diamond thin of the conduction that forms on the surface of the base members that is included in one of at least conduction in anode and the negative electrode.
17. a method of making microstructure, it comprises through purging method and cleans object to be cleaned and form microstructure,
Said washing out method comprises:
Comprise oxidizing substance, water and vitriolic oxidizing solution a kind of preparation the through being selected from the sulphuric acid soln that electrolysis sulphuric acid soln and electrolysis also comprise hydrofluoric acid, the concentration of said sulphuric acid soln for be not less than 30 weight % and be not more than 70 weight % and
To object surfaces to be cleaned oxidizing solution and hydrofluoric acid are provided.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP219890/2009 | 2009-09-25 | ||
| JP2009219890A JP5066152B2 (en) | 2009-09-25 | 2009-09-25 | Cleaning system |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102031203A CN102031203A (en) | 2011-04-27 |
| CN102031203B true CN102031203B (en) | 2012-10-17 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2010102876290A Active CN102031203B (en) | 2009-09-25 | 2010-09-20 | Cleaning liquid, cleaning method, cleaning system, and method for manufacturing microstructure |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20110073489A1 (en) |
| JP (1) | JP5066152B2 (en) |
| KR (1) | KR101252347B1 (en) |
| CN (1) | CN102031203B (en) |
| TW (1) | TWI443190B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140116464A1 (en) * | 2011-07-11 | 2014-05-01 | Kurita Water Industries Ltd. | Method for cleaning metal gate semiconductor |
| JP6493839B2 (en) | 2015-03-24 | 2019-04-03 | 株式会社Ｓｃｒｅｅｎホールディングス | Substrate processing method and substrate processing apparatus |
| WO2016152371A1 (en) * | 2015-03-24 | 2016-09-29 | 株式会社Ｓｃｒｅｅｎホールディングス | Substrate processing method and substrate processing device |
| US10780461B2 (en) * | 2015-05-15 | 2020-09-22 | Taiwan Semiconductor Manufacturing Co., Ltd | Methods for processing substrate in semiconductor fabrication |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101009206A (en) * | 2006-01-18 | 2007-08-01 | 芝浦机械电子株式会社 | Apparatus for treating substrates and method of treating substrates |
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| CA1059943A (en) * | 1976-07-20 | 1979-08-07 | Pierre L. Claessens | Electrolytically forming peroxosulfuric acid to oxidize organic material in sulfuric acid |
| JP2787788B2 (en) * | 1990-09-26 | 1998-08-20 | インターナショナル・ビジネス・マシーンズ・コーポレーション | Residue removal method |
| JPH0750281A (en) * | 1993-08-05 | 1995-02-21 | Sumitomo Chem Co Ltd | Cleaning method for silicon wafer |
| US6827814B2 (en) * | 2000-05-08 | 2004-12-07 | Tokyo Electron Limited | Processing apparatus, processing system and processing method |
| KR100684064B1 (en) * | 2002-04-02 | 2007-02-16 | 페르메렉덴꾜꾸가부시끼가이샤 | Functional water, and the process and the apparatus for preparing the same |
| JP2004247416A (en) * | 2003-02-12 | 2004-09-02 | Toshiba Corp | Cleaning liquid and method for manufacturing electronic device |
| US20050139487A1 (en) * | 2003-05-02 | 2005-06-30 | Fraunhofer-Gesellschaft Zur Forderung Der Angewandten Forschung E.V. | Method for the oxidative treatment of components comprised of or containing elementary silicon and/or substantially inorganic silicon compounds |
| JP4462146B2 (en) * | 2004-09-17 | 2010-05-12 | 栗田工業株式会社 | Sulfuric acid recycling type cleaning system and sulfuric acid recycling type persulfuric acid supply device |
| KR100685738B1 (en) * | 2005-08-08 | 2007-02-26 | 삼성전자주식회사 | Removing composition for an insulation material, method of removing an insulation layer and method of recycling a substrate using the same |
| JP4816888B2 (en) * | 2005-08-18 | 2011-11-16 | 栗田工業株式会社 | Sulfuric acid recycling cleaning system |
| JP2007266497A (en) * | 2006-03-29 | 2007-10-11 | Kurita Water Ind Ltd | Semiconductor substrate cleaning system |
| US8303797B2 (en) * | 2006-06-16 | 2012-11-06 | Kabushiki Kaisha Toshiba | Cleaning system and cleaning method |
| JP5087325B2 (en) * | 2006-06-16 | 2012-12-05 | 株式会社東芝 | Cleaning system and cleaning method |
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| KR101532224B1 (en) * | 2007-05-18 | 2015-06-30 | 티이엘 에프에스아이, 인코포레이티드 | Process for treatment of substrates with water vapor or steam |
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2009
- 2009-09-25 JP JP2009219890A patent/JP5066152B2/en active Active
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2010
- 2010-09-13 US US12/880,450 patent/US20110073489A1/en not_active Abandoned
- 2010-09-13 TW TW099130900A patent/TWI443190B/en active
- 2010-09-20 KR KR1020100092471A patent/KR101252347B1/en active IP Right Grant
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| CN101009206A (en) * | 2006-01-18 | 2007-08-01 | 芝浦机械电子株式会社 | Apparatus for treating substrates and method of treating substrates |
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| Publication number | Publication date |
|---|---|
| KR20110033797A (en) | 2011-03-31 |
| TW201127950A (en) | 2011-08-16 |
| US20110073489A1 (en) | 2011-03-31 |
| JP2011068937A (en) | 2011-04-07 |
| TWI443190B (en) | 2014-07-01 |
| CN102031203A (en) | 2011-04-27 |
| JP5066152B2 (en) | 2012-11-07 |
| KR101252347B1 (en) | 2013-04-08 |
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Address after: Tokyo, Japan, Japan Patentee after: Toshiba Corp Patentee after: Shibaura Mechantronics Corp. Patentee after: DE NORA PERMELEC LTD Address before: Tokyo, Japan, Japan Patentee before: Toshiba Corp Patentee before: Shibaura Mechantronics Corp. Patentee before: Permelec Electrode Ltd. |