CN1495534A - Detergent for removing resist and method for making semiconductor - Google Patents

Detergent for removing resist and method for making semiconductor Download PDF

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Publication number
CN1495534A
CN1495534A CNA031464947A CN03146494A CN1495534A CN 1495534 A CN1495534 A CN 1495534A CN A031464947 A CNA031464947 A CN A031464947A CN 03146494 A CN03146494 A CN 03146494A CN 1495534 A CN1495534 A CN 1495534A
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China
Prior art keywords
composition
resist
film
detergent remover
remove
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CNA031464947A
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Chinese (zh)
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CN100370361C (en
Inventor
��Ұ���
菅野至
浅冈保宏
东雅彦
日高义晴
岸尾悦郎
青山哲男
¡
铃木智子
平贺敏隆
永井俊彦
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EKC Technology KK
Renesas Electronics Corp
Panasonic Holdings Corp
Original Assignee
Renesas Technology Corp
EKC Technology KK
Matsushita Electric Industrial Co Ltd
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Publication of CN1495534A publication Critical patent/CN1495534A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041—Cleaning
    • H01L21/02057—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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/08—Acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5004—Organic solvents
    • C11D7/5009—Organic solvents containing phosphorus, sulfur or silicon, e.g. dimethylsulfoxide
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5004—Organic solvents
    • C11D7/5013—Organic solvents containing nitrogen
    • 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
    • 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
    • G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/311—Etching the insulating layers by chemical or physical means
    • H01L21/31105—Etching inorganic layers
    • H01L21/31111—Etching inorganic layers by chemical means
    • H01L21/31116—Etching inorganic layers by chemical means by dry-etching
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/311—Etching the insulating layers by chemical or physical means
    • H01L21/31127—Etching organic layers
    • H01L21/31133—Etching organic layers by chemical means
    • 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
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76801—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing
    • H01L21/76802—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing by forming openings in dielectrics
    • H01L21/76814—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing by forming openings in dielectrics post-treatment or after-treatment, e.g. cleaning or removal of oxides on underlying conductors
    • C11D2111/22—
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/263—Ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3263—Amides or imides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/34—Organic compounds containing sulfur

Abstract

The cleaning composition for removing resists includes a salt of hydrofluoric acid and a base not containing a metal (A component), a water-soluble organic solvent (B1 component), at least one acid selected from a group consisting of organic acid and inorganic acid (C component), water (D component), and optionally an ammonium salt (E1 component), and its hydrogen ion concentration (pH) is 4-8. Thus, in the manufacturing process of a semiconductor device such as a copper interconnecting process, removing efficiency of resist residue and other etching residue after etching or ashing improves, and corrosion resistance of copper and insulating film also improves.

Description

Be used to remove the manufacture method of the detergent remover and the semiconductor devices of resist
Technical field
The present invention relates on Semiconductor substrate to form with copper is after the dry corrosion in the process of metal line of major component, peel off remove remaining resist film, resist residue and with the detergent remover that is used to remove resist of the residue (corrosion residue) of other etchant gases reactions, and use the manufacture method of its semiconductor devices.
Background technology
The manufacturing process of highly integrated semiconductor element, normally take following technology, promptly, constitute conduction with the wiring material of the metal film of wiring material etc. and the insulation between connecting up be to apply resist film on the layer insulation membrane material etc. of purpose, be shaped to the resist figure of setting by light etching process after, this resist film is carried out dry corrosion as mask, remove remaining resist film, as the technology of removing this resist film, generally be after carrying out plasma ashing, the resist residue that uses detergent remover will remain on wiring material and the interlayer dielectic is peeled off the wet processed of removing.
In the past, generally be to use the wiring material of AI system as wiring material, this moment as detergent remover be can enumerate detergent remover based on the fluorine based compound (spy open flat 7-201794 communique, spy are opened flat 8-202052 communique, the spy opens flat 11-271985 communique), contain azanol detergent remover (No. 5334332, United States Patent (USP)), contain the detergent remover (spy opens flat 7-247498 communique) of quaternary ammonium hydroxide etc.
; in recent years; miniaturization, high-speedization along with semiconductor element; production process of semiconductor device changes significantly; for example; for the requirement of the high speed of corresponding semiconductor element, wiring material is to having more low-resistance Cu or the conversion of Cu alloy than in the past Al or Al alloy, and interlayer dielectric is to the so-called Low-k film conversion that has lower specific inductive capacity than p-TEOS (Tetra EhylOrtho Silicate) film etc. in the past.As being considered to film that Low-k film likely can enumerate film that the inorganic material by porous matter monox etc. constitutes, polyamide, be made of the organic material of polyarylate etc., and the film that constitutes by the potpourri of above-mentioned inorganic material and organic material etc. now.
In addition, along with miniaturization, the resist that is used for light etching process also is to change to from the past i line resist to use KrF excimer laser resist and the such chemical amplifying type quasi-molecule resist of ArF excimer laser resist, high performance detergent remover that therefore need be corresponding with these.
Below narration in the past detergent remover and use the problem points of manufacture method of its semiconductor devices.
On the Semiconductor substrate that forms element (not shown)s such as transistor, use known mosaic technology that first bronze medal wiring 1 of baried type is formed on 2 of first dielectric films.In the above, with reference to Fig. 3 form silicon nitride film 3 in turn as the copper wiring protective film, as the Low-k film 4 of the interlayer dielectric of low-k, form the resist film 5 of regulation shape Butut thereon.As anticorrosive additive material, for example use the chemical amplifying type quasi-molecule resist of corresponding KrF excimer laser exposure or ArF quasi-molecule exposure.
Secondly, shown in Fig. 3 B, as after mask dry corrosion Low-k film 4 is till silicon nitride film 3 exposes, form through hole 21 with resist film 5.At this moment, be used for the gas of dry corrosion and the resultant of reaction of Low-k film and resist film and left behind, in pin hole 21, pile up resist residue 6.
Secondly, shown in Fig. 3 B and Fig. 3 C, use plasma ashing to remove resist film 5.At this moment, because heat and plasma reaction that ashing produces form metamorphic layer 7 on Low-k film surface 4.
Secondly, shown in Fig. 3 C and Fig. 3 D, use fluorine based compound in the past to handle, remove resist residue 6 as the detergent remover on basis.When this resist residue left behind, then can become reason with the later electric loose contact of upper wiring.Therefore, in order positively to remove the resist residue, used the detergent remover that dielectric film is also had corrosive attack in the past, and, made the internal diameter of through hole 21 enlarge so the metamorphic layer 7 on above-mentioned Low-k film surface and Low-k film 4 itself are corroded.
Then, shown in Fig. 3 E,, on Low-k film 4, be formed for the figure resist film 5 of shaping groove in order to form the wiring that is connected with through hole 21.
Secondly, shown in Fig. 3 F, with resist film 5 as mask dry corrosion Low-k film up to the centre position of Low-k film 4, form groove 22.At this moment, be used for the reaction of the gas of dry corrosion and Low-k film and resist and the resist residue 6 that generates is deposited in the inside of through hole 21 and groove 22.
Secondly, shown in Fig. 3 F and Fig. 3 G, use plasma ashing to remove resist film 5.At this moment, because heat and plasma reaction that ashing produces form metamorphic layer 7 on LOW-K film 4 surfaces.
Secondly, shown in Fig. 3 G and Fig. 3 H, use fluorine based compound in the past to handle, remove resist residue 6 as the detergent remover on basis.At this moment, for detergent remover in the past, when removing the resist residue, the metamorphic layer 7 on Low-k film surface also is corroded, and makes the internal diameter of through hole 21 enlarge and the expansion of groove 22 width.
Secondly, shown in Fig. 3 I, remove silicon nitride film 3, the copper wiring 1 of winning is exposed by dry corrosion.At this moment, corrosion residue 8 is deposited in the through hole 21.
Secondly, shown in Fig. 3 J,, use detergent remover to handle in order to wash copper wiring surface.In the detergent remover of fluorine based compound that uses in the past as the basis, in raising removing of resist, resist residue and other etching residue done the time spent, exist the problem of corrosion first bronze medal wiring 1.Therefore, in order to prevent the corrosion of first bronze medal wiring, to the agent that prevents copper corrosion (spy opens the 2001-83712 communique) of wherein adding benzotriazole (BTA) etc.,, exist further improving the resist residue and remove and do the time spent, prevent the problem that the copper corrosion effect descends for such washing agent.
Secondly, shown in Fig. 3 K, through hole 21 and groove 22 in, imbed copper by electroplating to wait, and then, connect up 10 by CMP (Chemical Mechanical Polishing) formation second bronze medal., first bronze medal wiring 1 is during by in the past detergent remover corrosion, because second bronze medal wiring 10 is not fully imbedded in the through hole 21, the joint resistance of first bronze medal wiring, 1 and second bronze medal wiring 10 raises or the problem of broken string so produce.
Miniaturization along with element, interval 11 between wiring and the wiring is designed narrow and smallly, in above-mentioned technology, if use detergent remover in the past, then the metamorphic layer 7 on Low-k film surface and Low-k film 4 self also are corroded, and make that the interval 11 between wiring and the wiring is further narrow and small.For this reason,, produce the deterioration in characteristics of the actuating speed decline of so-called semiconductor element, perhaps cause the bad problem of the short circuit between wiring and the wiring because the electric capacity between wiring rises.In addition, for detergent remover in the past, the resist residue remove, prevent copper corrosion and prevent all can not obtain satisfied effect aspect the corrosion of Low-k film.
Summary of the invention
The object of the present invention is to provide the manufacture method that is used to remove the detergent remover of resist and uses its semiconductor devices, this method is in the copper Wiring technique, during to the removing of residue after the resist film after the dry corrosion and corrosion residue and the ashing and corrosion residue, have concurrently and good remove effect and for the anticorrosion effect of copper and interlayer dielectric, and, can under the condition of safety, gentleness, use.
In order to achieve the above object, the feature that is used for removing the detergent remover of resist of the present invention is the salt (A composition), the water-miscible organic solvent (B1 composition) that contain hydrofluorite and metal-free alkali, constitutes acid more than a kind (C composition) and the water (D composition) that the group selects by organic acid and mineral acid, and pH pH is 4～8.And then the detergent remover that is used to remove resist of the present invention except above-mentioned A composition, B composition, C composition, D composition, can also contain ammonium salt (E1 composition).
In addition, other the feature of detergent remover that is used to remove resist of the present invention is salt (A composition), water-miscible organic solvent (B2 composition), phosphonic acids (C1 composition), water (D composition) and the metal-free alkali (E composition) that contains hydrofluorite and metal-free alkali, and pH pH is 2～8.And then the detergent remover that is used to remove resist of the present invention except above-mentioned A composition, B2 composition, C1 composition, D composition and E composition, can also contain Cu corrosion inhibitor (f composition).
The feature of the manufacture method of semiconductor devices of the present invention be included in film forming on the Semiconductor substrate with copper be major component metal pattern operation and, form in the above dielectric film operation and, and then form thereon resist film operation and, by with this resist film be mask carry out dry corrosion in this dielectric film, be provided with hole or groove operation and, the operation of removing this resist with the plasma treatment or the heat treated of gas, and the resist residue operation that the reaction by etchant gas and resist film and Low-k film etc. produces when the detergent remover of removing resist with above-mentioned being used to after these operations is removed in dry corrosion.In addition, in etchant gas of the present invention, contain fluorocarbon, contain resist residue, carbon residue and these compound in the resist residue that the reaction by etchant gas and resist film and Low-k film etc. generates as major component.
In addition, the feature of another manufacture method of semiconductor devices of the present invention be included in film forming on the Semiconductor substrate with copper be major component metal film operation and, form in the above dielectric film operation and, and then form thereon resist film operation and, by being that mask carries out dry corrosion is provided with hole and groove in this dielectric film operation with this resist film, and the operation of the detergent remover of after these operations, the removing resist resist residue that the reaction of the insulating film by etchant gas and resist film and Low-k film etc. etc. generates when removing remaining resist film and dry corrosion with above-mentioned being used to.
Just, the detergent remover that is used to remove resist of the present invention has the high efficiency of removing the resist residue and for the high corrosion resistance of copper wiring film and dielectric film, so in above-mentioned semi-conductive manufacturing, can prevent that the interval between the copper wiring is narrow and small, deterioration in characteristics that the actuating speed of elimination semiconductor element descends or the bad phenomenon that between wiring and wiring, is short-circuited.
And then, the feature of other manufacture methods of semiconductor devices of the present invention be included in film forming on the Semiconductor substrate with copper be major component metal pattern operation and, in the above form dielectric film operation and, the operation of the corrosion residue of reaction generation by etchant gas and dielectric film when the detergent remover that the operation in the hole that reaches this metal film is set in this dielectric film and removes resist with above-mentioned being used to after these operations by dry corrosion is removed dry corrosion.
Because employed etchant gas is to be the gas of major component with the fluorocarbon among the present invention, and dry corrosion gas and dielectric film or with copper as the reaction of the metal film of major component and the major component of the corrosion residue that generates is the carbon residue, not only resist and resist residue can be removed so resist of the present invention is removed detergent remover, and the etching residue that does not contain resist and residue thereof can be removed.
Here, said is the metal of principal ingredient with copper, and the content that is meant the copper in this metal is more than the 90 quality %.
Above-mentioned and other purpose of the present invention, feature, mode and advantage are understood following detailed description of the present invention in conjunction with the drawings, will be clearer.
Description of drawings
Figure 1A～Fig. 1 K is to use the sectional drawing of each operation of an embodiment of the copper Wiring technique of detergent remover of the present invention.
Fig. 2 A～Fig. 2 I is to use the sectional drawing of each operation of another embodiment of the copper Wiring technique of detergent remover of the present invention.
Fig. 3 A～Fig. 3 K is to use the sectional drawing of each operation of the representational copper Wiring technique of detergent remover in the past.
Embodiment
Embodiment 1
Being used for of one of the application the detergent remover of removing resist contain hydrofluorite and metal-free alkali salt (A composition), water-miscible organic solvent (B1 composition), constitute acid more than a kind (C composition) and the water (D composition) that the group selects by organic acid and mineral acid, and pH pH is 4～8.
A composition of the present invention is the salt that contains hydrofluorite and metal-free alkali.As metal-free alkali, preferably use organic amine compound, ammonia, rudimentary quaternary ammonium base of the fatty amine, ester ring type amine, hetero ring type amine, aromatic amine etc. in hydroxyl amine, primary, the second month in a season or season etc.
As hydroxyl amine, can enumerate hydramine, N-methyl hydramine, N, N-dimethyl hydroxyl amine, N, N-diethyl hydramine etc.
As uncle's level fatty amine, can enumerate methylamine, ethamine, propylamine, butylamine, monoethanolamine, an isopropanolamine, 2-(2-aminoethylamino) ethanol etc.As secondary level fatty amine, can enumerate dimethylamine, diethylamine, di-n-propylamine, dibutylamine, diethanolamine, N-methylethanolamine, N-ehtylethanolamine etc.As season level fatty amine, can enumerate trimethylamine, triethylamine, tripropyl amine (TPA), tri-n-butylamine, N, N-dimethylethanolamine, N, N-diethyl ethanolamine, N methyldiethanol amine, N-ethyldiethanolamine, triethanolamine etc.
As ester ring type amine, can enumerate cyclo-hexylamine, dicyclohexyl amine etc.As hetero ring type amine, can enumerate pyrroles, pyrrolidine, pyridine, morpholine, pyrazine, piperidines, oxazole, thiazole etc.As aromatic amine, can enumerate benzyl amine, dibenzyl amine, N-methyl-benzyl amine, N-Ethylbenzyl amine etc.As rudimentary quaternary ammonium base, can enumerate tetramethyl-ammonium oxyhydroxide, (2-hydroxyethyl) trimethyl ammonium oxyhydroxide etc.
In above-mentioned alkali, preferably can enumerate ammonia, monoethanolamine, tetramethyl-ammonium oxyhydroxide etc.Wherein, particularly preferably be ammonia.
Above-mentioned A composition, removing property about the chemical amplifying type quasi-molecule resist after the dry corrosion, be by improving removing property with the reaction that is contained in the light oxygen generating agent in the chemical amplifying type quasi-molecule resist, for the resist residue after the ashing, improve removing property significantly by the disconnection that promotes the chemical bond in the resist residue.
In addition, the content of A composition is 0.01 quality %～1 quality %, 0.05 quality %～0.5 quality % preferably.During less than 0.01 quality %, reducing for the fissility of resist film, resist residue and other corrosion residue, when surpassing 1 quality %, for the corrosion fierceness of the interlayer dielectric of copper wiring and Low-k film etc., is unfavorable.
B1 composition of the present invention is a water-miscible organic solvent.So long as water-miscible organic solvent just is not particularly limited, but preferably use amide-type, polyvalent alcohol or derivatives thereof class etc.As amide-type, can enumerate formamide, N-NMF, N, dinethylformamide, N-ethyl-formamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethyl acetamide, N-ethyl acetamide, N, N-diethyl acetamide etc.
As polyvalent alcohol or derivatives thereof class, can enumerate ethylene glycol, the glycol monomethyl methyl ether, ethylene glycol monomethyl ether, the glycol monomethyl propyl ether, ethylene glycol monobutyl ether, the ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, glycol monomethyl propyl ether acetic acid esters, the ethylene glycol monobutyl ether acetic acid esters, diglycol, the diglycol monotertiary methyl ether, carbiphene, the diglycol monotertiary propyl ether, the diglycol monotertiary butyl ether, the diglycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diglycol monotertiary propyl ether acetic acid esters, diglycol monotertiary butyl ether acetic acid esters, the triethylene glycol monomethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol list ethylether, propylene glycol list propyl ether, the propylene glycol single-butyl ether, the dipropylene glycol monomethyl ether, dipropylene glycol list ethylether, dipropylene glycol list propyl ether, the dipropylene glycol single-butyl ether, the dipropylene glycol monomethyl ether acetate, dipropylene glycol list ethylether acetic acid esters, dipropylene glycol list propyl ether acetic acid esters, dipropylene glycol single-butyl ether acetic acid esters, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, the diglycol dipropyl ether, the diglycol dibutyl ethers, the dipropylene glycol dimethyl ether, the dipropylene glycol Anaesthetie Ether, the dipropylene glycol dipropyl ether, dipropylene glycol dibutyl ethers etc.
In addition, as B1 composition of the present invention, preferably use the potpourri of above-mentioned amide-type and polyvalent alcohol or derivatives thereof class.Mixing quality ratio for amide-type and polyvalent alcohol or derivatives thereof class is not particularly limited, but if the viewpoint of the removing property of the chemical amplifying type quasi-molecule resist after the dry corrosion, when removing KrF with resist (the krF resisit) (krF excimer laser resist), because its main framing is the polycarboxylated styrene of phenol skeleton, thus use ratio to the high polyvalent alcohol or derivatives thereof class of its dissolubility high for well.In addition, for the resist residue after dry corrosion and the ashing tendency same as described above is arranged also.That is, corresponding to employed resist kind before the dry corrosion as long as the mixing quality of decision amide-type and polyvalent alcohol or derivatives thereof class is more passable than just.
Particularly, in the manufacturing of a semiconductor devices, and when use resist with resist and KrF, be useful as the potpourri of B1 composition use amide-type and polyvalent alcohol or its derivant class with ArF.At this moment, the mixing quality of the amide-type in B1 composition ratio is 0.3～0.5, from the dissolubility of two resists is seen it is particularly preferred.
The content of above-mentioned B1 composition, preferably 50 quality %～98 quality %, 60 quality %～95 quality % more preferably.When less than 50 quality %, in the time of for the removing property reduction of resist film, resist residue, for the corrosion fierceness of copper wiring.On the other hand, when surpassing 98 quality %, to the removing property reduction of resist film, resist residue, so be unfavorable.
As C composition of the present invention, use more than one the acid of forming that mass selection goes out from organic acid and mineral acid.As organic acid, can enumerate the aromatic acid etc. of the aliphatic acid, benzoic acid, toluic acid, phthalic acid etc. of formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, glycolic acid, tartrate, citric acid etc.As mineral acid, can enumerate sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid etc.Such C composition is the pH (pH) that is used to regulate the detergent remover that is used to remove resist, is not particularly limited for addition.
The pH that is used to remove the detergent remover of resist of the present invention is 4～8, preferably 5.5～7.5, more preferably 6.5～7.5.In the present invention, the pH of detergent remover has epochmaking influence.During pH less than 4, be the corrosion fierceness of metal film for copper, pH surpasses at 8 o'clock, for the removing property reduction of resist film, resist residue and other corrosion residue, in addition, is that the corrosion of metal film and Low-k film becomes big to copper, so be unfavorable.
As D composition of the present invention, make water.Glassware for drinking water has following effect, that is, will be as the salt ionization of hydrofluorite and metal-free alkali of A composition, improve for resist residue and other corrosion residue remove performance the time, the ignition point with detergent remover improves easily.
Embodiment 2
The detergent remover that another kind of the present invention is used for removing resist is the salt (A composition), the water-miscible organic solvent (B1 composition) that comprise hydrofluorite and metal-free alkali, constitutes the acid more than a kind (C composition), water (D composition) and the ammonium salt (E1 composition) that the group selects by organic acid and mineral acid, and pH pH is 4～8.That is, present embodiment is the basis of A composition, B1 composition, C composition and D composition of detergent remover that is used to remove resist at above-mentioned embodiment 1, adds the E1 composition, and pH is made 4～8.
At this, ammonium salt (E1 composition) has the corrosive attack of inhibition to dielectric film, its content, preferably 0.01 quality %～5 quality %, 0.05 quality %～3 quality % more preferably.During less than 0.01 quality %, for TEOS, SiN, SiON, SiO 2The corrosion fierceness of the dielectric film of class is when surpassing 5 quality %, for the removing property reduction of resist film and resist residue etc.
As E1 composition of the present invention, so long as ammonium salt just is not particularly limited.For example, can enumerate the aminophosphonic acid ammonium salt etc. of the hydroxycarboxylic acid ammonium salt, Amcide Ammate etc. of the aliphatics polybasic carboxylic acid ammonium salt, ammonium lactate, ammonium gluconate, ammonium tartrate, malic acid ammonium, ammonium citrate etc. of the aliphatic monocarboxylic acid ammonium salt, glycol acid ammonium, ammonium oxalate, malonic acid, succinic acid, maleic acid ammonium, glutaric acid ammonium, ammonium adipate etc. of ammonium formate, ammonium acetate, propionic acid ammonium, butyric acid ammonium etc.
Embodiment 3
Another detergent remover that is used to remove resist of the present invention is salt (A composition), water-miscible organic solvent (B2 composition), phosphonic acids (C1 composition), water (D composition) and the metal-free alkali (E composition) that comprises hydrofluorite and metal-free alkali, and pH pH is 2～8.By adding phosphonic acids (C1 composition) and metal-free alkali (E composition), having improved copper is the anticorrosive property of metal film, so, can use wide being used to of pH scope to remove the detergent remover of resist.
A composition of the present invention is hydrofluorite and the salt that does not contain the alkali of metal, and its details is as explanation in the enforcement mode 1.
B2 composition of the present invention is a water-miscible organic solvent.So long as water-miscible organic solvent just is not particularly limited, but preferably use acyl ammonium class, pyrrolidinone compounds, alkyl urea class, sulfoxide class, sulfone class, imidazolidine ketone, polyvalent alcohol or derivatives thereof class, lactone, carboxylic acid derivates class etc.
As amide-type, can enumerate formamide, N-NMF, N, dinethylformamide, N-ethyl-formamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethyl acetamide, N-ethyl acetamide, N, N-diethyl acetamide etc.As pyrrolidinone compounds, can enumerate N-N-methyl-2-2-pyrrolidone N-, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-Pyrrolidone, N-hydroxyethyl-2-Pyrrolidone etc.As alkyl urea class, can enumerate 4-methyl urea, tetraethyl urea etc.As the sulfoxide class, can enumerate dimethyl sulfoxide (DMSO), diethyl sulfoxide etc.As the sulfone class, can enumerate dimethyl sulfone, diethyl sulfone, two (2-hydroxyethyl) sulfone, tetramethylene sulfone etc.As the imidazolidine ketone, can enumerate 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone etc.
As polyvalent alcohol or derivatives thereof class, can enumerate ethylene glycol, the glycol monomethyl methyl ether, ethylene glycol monomethyl ether, the glycol monomethyl propyl ether, ethylene glycol monobutyl ether, the ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, glycol monomethyl propyl ether acetic acid esters, the ethylene glycol monobutyl ether acetic acid esters, diglycol, the diglycol monotertiary methyl ether, carbiphene, the diglycol monotertiary propyl ether, the diglycol monotertiary butyl ether, the diglycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diglycol monotertiary propyl ether acetic acid esters, diglycol monotertiary butyl ether acetic acid esters, the triethylene glycol monomethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol list ethylether, propylene glycol list propyl ether, the propylene glycol single-butyl ether, the dipropylene glycol monomethyl ether, dipropylene glycol list ethylether, dipropylene glycol list propyl ether, the dipropylene glycol single-butyl ether, the dipropylene glycol monomethyl ether acetate, dipropylene glycol list ethylether acetic acid esters, dipropylene glycol list propyl ether acetic acid esters, dipropylene glycol single-butyl ether acetic acid esters, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, the diglycol dipropyl ether, the diglycol dibutyl ethers, the dipropylene glycol dimethyl ether, the dipropylene glycol Anaesthetie Ether, the dipropylene glycol dipropyl ether, dipropylene glycol dibutyl ethers etc.
As lactone, can enumerate gamma-butyrolacton, σ-valerolactone etc.As carboxylic acid derivates, can enumerate methyl acetate, ethyl acetate, methyl lactate, ethyl lactate etc.
In addition, B2 composition of the present invention preferably uses the sulfocompound of above-mentioned sulfoxide class or sulfonic acid class etc. and the potpourri of polyvalent alcohol or derivatives thereof.The mixture quality ratio of sulfocompound and polyvalent alcohol or derivatives thereof, be not particularly limited, but if the viewpoint of the removing property of the chemical amplifying type quasi-molecule resist after the dry corrosion, when removing KrF and use resist, because its main framing is the polycarboxylated styrene of phenol skeleton, thus use ratio to the high sulfocompound of its dissolubility high for well.When removing ArF and use resist because its main framing is an acrylic acid series, so use ratio to the high polyvalent alcohol or derivatives thereof of its dissolubility also high for well.In addition, for the resist residue after dry corrosion and the ashing tendency same as described above is arranged also.That is, corresponding to the resist kind of using before the dry corrosion as long as the mixture quality of decision sulfocompound and polyvalent alcohol or derivatives thereof is more passable than just.
The content of above-mentioned B2 composition, preferably 50 quality %～95 quality %, 55 quality %～90 quality % more preferably.When less than 50 quality %, in the time of for the removing property reduction of resist film, resist residue, for the corrosion fierceness of copper wiring.On the other hand, when surpassing 95 quality %, for the removing property reduction of resist film, resist residue, so be unfavorable.
CI composition among the present invention is a phosphonic acids.Can enumerate diethylene triamine five (methylene phosphonic acid) as phosphonic acids used in the present invention, phenyl-phosphonic acid, methylenediphosphonate, ethylidene diphosphonic acid, 1-hydroxy ethylene-1, the 1-di 2 ethylhexyl phosphonic acid, 1-hydroxy propylidene-1, the 1-di 2 ethylhexyl phosphonic acid, 1-hydroxy butylidene-1, the 1-di 2 ethylhexyl phosphonic acid, ethylamino two (methylene phosphonic acid), dodecyl amino two (methylene phosphonic acid), ethylenediamine two (methylene phosphonic acid), ethylenediamine tetraacetic (methylene phosphonic acid), hexane diamine four (methylene phosphonic acid), different propane diamine two (methylene phosphonic acid), different propane diamine four (methylene phosphonic acid), cyano group three (methylene phosphonic acid) etc.
Employed phosphonic acids among the present invention (CI composition) by with the alkali that does not contain metal (E composition) and usefulness, be the dielectric film of metal film or Low-k film etc. when having corrosion proof function for copper as wiring material, also have the function of pH regulator agent.Here, the content of CI composition is 0.1 quality %～20 quality % preferably, more preferably 0.5 quality %～15 quality %.When the content of CI composition is lower than 0.1 quality %, being the corrosion resistance reduction of metal pattern or Low-k film for copper, when surpassing 20 quality %, to the removal reduction of resist residue or corrosion residue, also is bad.
Be to use water as D composition of the present invention, described in its details such as the enforcement mode 1.
E composition among the present invention is the alkali that does not contain metal.As the employed alkali that does not contain metal among the present invention, have no particular limits, can use organic amine compound, ammonium, rudimentary quaternary ammonium base of hydroxyl amine, primary, the second month in a season or uncle's fatty amine, ester ring type amine, hetero ring type amine, aromatic amine etc. etc.
As hydramine, can enumerate hydramine, N-methyl hydramine, N, N-dimethyl hydroxyl amine, N, N-dimethyl hydroxyl amine etc.
Can enumerate methylamine, ethamine, propylamine, butylamine, monoethanolamine, an isopropanolamine, 2-(2-amino ethyl amine) ethanol etc. as uncle's fatty amine.Can enumerate dimethylamine, diethylamine, di-n-propylamine, dibutylamine, diethanolamine, N-methylethanolamine, N-ehtylethanolamine etc. as secondary fatty amine.Can enumerate trimethylamine, triethylamine, tripropyl amine (TPA), tri-n-butylamine, N as uncle's fatty amine, N one dimethylethanolamine, N, N one diethyl ethanolamine, N monomethyl diethanolamine, N one ethyldiethanolamine, triethanolamine etc.
Can enumerate cyclohexylamine, dicyclohexyl amine etc. as ester ring type amine.Can enumerate pyrroles, pyrrolidine, pyridine, morpholine, pyrazine, piperidines, oxazole, thiazole etc. as hetero ring type amine.Can enumerate benzylamine, dibenzyl amine, N-methyl-benzyl amine, N-Ethylbenzyl amine etc. as aromatic amine.Can enumerate tetramethyl-ammonium oxyhydroxide, (2-hydroxyethyl) trimethyl ammonium oxyhydroxide etc. as rudimentary quaternary ammonium base.
Among the present invention the employed alkali (E composition) that does not contain metal by with phosphoric acid (CI composition) and usefulness, be the dielectric film of metal film or Low-k film etc. when having corrosion proof function for copper as wiring material, also have the function of pH regulator agent.Here, the content of E composition is 0.1 quality %～20 quality % preferably, more preferably 0.5 quality %～15 quality %.When the content of E composition is lower than 0.1 quality %, being the corrosion resistance increasing of metal pattern or Low-k film for copper, when surpassing 20 quality %, to the removal reduction of resist residue or corrosion residue, also is bad.
The pH that being used in the embodiment of the present invention removed the detergent remover of resist is 2～8, preferably 2.5～7.5.PH is less than 2 o'clock, is that the corrosivity of metal pattern increases to copper, and pH is greater than 8 o'clock, to the removal reduction of resist residue and other corrosion residue, is that the corrosion of metal pattern and Low-k film becomes big to copper in addition, so be unfavorable.In the present embodiment, by adding phosphonic acids (CI composition) and not containing the alkali (E composition) of metal, can improve corrosion resistivity to metal pattern, compare so remove the pH scope (pH4～8) of the detergent remover of resist with being used in embodiment 1 and the embodiment 2, can be used to remove the detergent remover use of resist in pH scope (pH2～8) conduct widely.
Embodiment 4
Of the present invention another be used to remove the detergent remover of resist, contain hydrofluorite and do not contain salt (A composition), water-miscible organic solvent (B2 composition), phosphonic acids (C1 composition), water (D composition), the alkali (E composition) that does not contain metal and the Cu resist (F composition) of the alkali of metal, and pH pH is 2～8.Just, present embodiment is to add the F composition on the basis of A composition, B2 composition, C1 composition, D composition and the E composition of being used in above-mentioned embodiment 3 removing the detergent remover of resist, and pH is made 2～8.
Here, it is the corrosive attack of metal film to copper that Cu resist (F composition) has inhibition, its amount is 0.01 quality %～5 quality % preferably, 0.05 quality %～3 quality % more preferably, be that the corrosion of metal pattern increases the weight of to copper when being lower than 0.01 quality %, when surpassing 5 quality %, for the removing property decline of resist film and resist residue etc.
Can use triazole type, aliphatic carboxylic acid class, aromatic carboxylic acid class or aminocarboxylic acids as F composition of the present invention.In addition, also can be also with more than 2 kinds of these F compositions.Can enumerate benzotriazole, o-tolyl triazole, a tolyl-triazole, p-methylphenyl triazole, carboxyl benzotriazole, I-hydroxybenzotriazole, nitrobenzene and triazolam, dihydroxypropyl benzotriazole etc. as triazole type.Can enumerate oxalic acid, malonic acid, acrylic acid, methacrylic acid, maleic acid, fumaric acid, succinic acid, itaconic acid, glutaric acid, hexane diacid, lactic acid, malic acid, citric acid, tartrate etc. as aliphatic carboxylic acid.Can enumerate benzoic acid, phthalic acid, trimellitic acid, trimesic acid, 5-sulfosalicylic acid, 2,4-dihydroxy-benzoic acid etc. as aromatic carboxylic acid.Can enumerate glycocoll, dihydroxyethylglycin, alanine, valine, leucine, asparagine, glutamine, aspartic acid, glutamine, lysine, arginine, imino-diacetic acetic acid, cyano group three acetic acid, ethylene dinitrilotetra-acetic acid, 1 as amino carboxylic acid, 2-cyclohexanediamine four acetic acid, diethylene triamine five acetic acid etc.
Below, be example with the copper Wiring technique, for the detergent remover that is used to remove resist that uses the present application, be that the embodiment of manufacture method of the semiconductor devices of feature describes to remove resist film, resist residue and other corrosion residue.
Embodiment 5
Use an embodiment of the copper Wiring technique of detergent remover of the present invention with reference to Figure 1A～Fig. 1 K explanation.Figure 1A～Fig. 1 C is identical with the situation of Fig. 3 A～Fig. 3 C of operation in the past.Here shown in Fig. 1 C and Fig. 1 D, use detergent remover of the present invention, remove the resist residue 6 that when forming through hole 21, is produced.Detergent remover of the present invention is minimum for the etching extent of Low-k film 4 and rotten film 7, so the internal diameter of through hole 21 can not produce expansion.
Fig. 1 E～1G be with operation in the past in 3E～3G be identical.Below shown in Fig. 1 G and Fig. 1 H, use detergent remover of the present invention to remove the resist residue 6 that when forming groove 21, is produced.Detergent remover of the present invention is minimum for the etching extent of Low-k film 4 and rotten film 7, so the internal diameter of through hole and groove width can not produce expansion.
Secondly, as shown in figure 11, remove silicon nitride film 3, expose the 1st bronze medal wiring 1 by dry corrosion.At this moment, on the surface of the 1st bronze medal wiring, piling up the corrosion residue 8 that the reaction owing to etchant gas and silicon nitride generates.Then shown in Fig. 1 I and Fig. 1 J, use detergent remover of the present invention to wash the surface of first bronze medal wiring 1.At this moment, detergent remover of the present invention is different with detergent remover in the past, and the surface of connecting up for first bronze medal does not produce corrosion.Then, shown in Fig. 1 J and Fig. 1 K, use electrochemical plating, reflow sputter method or use MOCVD (the Metal Organic ChemicalVapor Deposition) method etc. of the CVD (Chemical Vapor Deposition) of organometallics that copper is imbedded in through hole 21 and the groove 22, remove part not by CMP, form second bronze medal wiring 10.Detergent remover of the present invention so the joint of first bronze medal wiring, 1 and second bronze medal wiring 10 is good, can not produce the problem that engages resistance height or broken string owing to the surface of not corroding first bronze medal wiring 1 like this.Detergent remover of the present invention in addition is minimum for the corrosion of Low-k film 4 and metamorphic layer 7, so that the interval 11 between copper wiring and the copper wiring can not become is narrow, can not produce that property of semiconductor element descends or wiring between the problem that is short-circuited etc.
Embodiment 6
Use other embodiments of the copper Wiring technique of detergent remover of the present invention with reference to Fig. 2 A～Fig. 2 I explanation.Fig. 2 A and Fig. 2 B were with Fig. 3 A and Fig. 3 B of operation were identical in the past.Shown in Fig. 2 B and Fig. 2 C, after through hole 21 dry corrosion,, use detergent remover of the present invention to remove resist film 5 and resist residue 6 not carrying out the plasma ashing processing or carrying out under the state of insufficient and residual resist film 5.Present embodiment is not owing to forming metamorphic layer on Low-k film 4 surfaces, so be preferred embodiment.
Fig. 2 D and Fig. 2 E were with Fig. 3 E and Fig. 3 F of operation were identical in the past.Shown in Fig. 2 E and Fig. 2 F, after the dry corrosion of groove, handle or carry out using detergent remover of the present invention to remove resist film 5 and resist residue 6 under the state of residual resist film 5 when insufficient not carrying out plasma ashing.Present embodiment is not owing to forming metamorphic layer on Low-k film 4 surfaces, so be preferred embodiment.
Then shown in Fig. 2 G, remove silicon nitride film 3, expose first bronze medal wiring 1 with dry corrosion.Piling up because the corrosion residue 8 that etchant gas and silicon nitride reaction generate on the surface of first bronze medal wiring this moment 1.Then shown in Fig. 2 G and Fig. 2 H, use detergent remover of the present invention to wash the surface of first bronze medal wiring 1.Detergent remover of the present invention is different with detergent remover in the past, and it does not corrode the surface of first bronze medal wiring 1.Then, same as described above, shown in Fig. 2 H and Fig. 2 I, in through hole 21 and groove 22, imbed copper, remove part not after, form second bronze medal wiring 10.Detergent remover of the present invention so the joint of first bronze medal wiring, 1 and second bronze medal wiring 10 is good, can not produce the problem that engages resistance height or broken string owing to the surface of not corroding first bronze medal wiring 1 like this.Detergent remover of the present invention in addition is minimum for the corrosion of Low-k film 4, so that the interval 11 between copper wiring and the copper wiring can not become is narrow, can not produce that property of semiconductor element descends or wiring between the problem that is short-circuited.
Below further specify the present invention particularly.The removing property to the resist residue of dry corrosion of the detergent remover that is used to remove resist of the present invention, the removing property of the corrosion residue that the reaction of dry corrosion gas and inorganic plasma membrane is generated, to the corrosion resistance of copper film or Low-k film, estimate according to following.
(1) is used to remove the preparation of the detergent remover of resist
Remove the embodiment of the detergent remover of resist as being used in the embodiment 1, the detergent remover that is used to remove resist of preparation embodiment 1～embodiment 21, remove the embodiment of the detergent remover of resist as being used in the embodiment 2, the detergent remover that is used to remove resist of preparation embodiment 22～embodiment 25, remove the embodiment of the detergent remover of resist as being used in the embodiment 3, the detergent remover that is used to remove resist of preparation embodiment 26～embodiment 56, remove the embodiment of the detergent remover of resist, the detergent remover that is used to remove resist of preparation embodiment 57～embodiment 61 as being used in the embodiment 4.
Being used in the embodiment 1 removed the detergent remover of resist, be the definite quality % of expression in the mixture table 1～table 3 A composition, B1 composition and, necessary D composition (water) makes component amount to 95 quality %, add a spot of nitric acid and propionic acid as the C composition, be adjusted to the pH value of setting, and then adding D composition is prepared the feasible 100 quality % that reach.In addition, being used in the embodiment 2 removed the detergent remover of resist, be the definite quality % of expression in the mixture table 4 A composition, B1 composition, E1 composition and, necessary D composition (water) makes component amount to 95 quality %, add a spot of nitric acid and propionic acid as the C composition, be adjusted to the pH value of setting, and then adding D composition is prepared the feasible 100 quality % that reach.The amount of the C composition that should add is to change according to the pH that should regulate, and is 0.3 quality %～3 quality %.
Being used in the embodiment 3 removed the detergent remover of resist, be to add D composition (water) in A composition, B2 composition, C1 composition and the E composition of definite quality % of expression in table 5～table 8 to make it reach 100 quality %, Yi Bian confirm pH, Yi Bian prepare.In addition, being used in the embodiment 4 removed the detergent remover of resist, is the D composition that adds in A composition, B2 composition, C1 composition, E composition and the F composition of the definite quality % of expression in table 9, makes it reach 100 quality %, confirm pH on one side, Yi Bian prepare.
(2) the removing property of resist residue
With reference to Figure 1A; use common mosaic technology; form first bronze medal wiring 1 of baried type between as the silicon oxide film of first dielectric film 2; in turn form thickness as the first bronze medal wiring protective film in the above and be the silicon nitride film 3 of 60nm and be the CVD-SiON film (specific inductive capacity 2.8) of 600nm as the thickness of Low-k film 4, form Butut in the above thickness be the eurymeric resist film 5 of 400nm.Here, be to use the PAR-101 (Sumitomo Chemical society system) of the chemical amplifying type ArF quasi-molecule resist that contains acryl resin as ArF with resist, be to use the SEPR-430 (chemistry society of SHIN-ETSU HANTOTAI system) of the chemical amplifying type KrF quasi-molecule resist that contains phenolic resin as KrF with resist.
Then, shown in Figure 1B, use parallel-plate RIE arranged side by side, with processing pressure 10Pa, RF electric power 300W, with the combination gas of fluorocarbon and Ar the CVD-SiON film as Low-k film 4 is carried out dry corrosion, formation through hole 21 exposes silicon nitride film 3.At this moment, in through hole, seen resist residue 6.
Then shown in Fig. 1 C, at room temperature, the resist figure of the plasma by using oxygen after to dry corrosion carries out 90 seconds ashing treatment.At this moment, form metamorphic layer 7, in this surface and through hole 21, seen resist residue 6 simultaneously on the surface of Low-k film.
Then, under 24 ℃, with above-mentioned chip that residue is arranged (the big or small 20mm * that pays 20mm) at the 200cm that forms shown in table 1, table 2, table 4, table 5, table 6, table 8 and the table 9 3The detergent remover dipping that is used for removing resist is after 30 minutes, and the washing back is dry.Use in the embodiment 1 be used to remove the detergent remover of resist the time, ArF is illustrated in table 1, KrF is illustrated in table 2 with the removing property of resist and residue thereof with the removing property of resist and residue thereof.In addition, use in the embodiment 2 be used to remove the detergent remover of resist the time, ArF is illustrated in table 4 with the removing property of resist and residue thereof.In addition, when using being used in the embodiment 3 to remove the detergent remover of resist ArF is illustrated in table 5 and table 8 with the removing property of resist and residue thereof, KrF is illustrated in table 6 and table 8 with the removing property of resist and residue thereof.And then, when using being used in the embodiment 4 to remove the detergent remover of resist ArF is illustrated in table 9 with the removing property of resist and residue thereof and to KrF with the removing property of resist and residue thereof.In the above-mentioned table, 00 and zero is to represent not see resist residue (0 zero to zero surface state is good), and * expression confirms to have the resist residue.
Then, shown in Fig. 1 E～Fig. 1 G,, form groove 22, shown in Fig. 1 G～Fig. 1 H, remove residual resist residue with step same as described above in Low-k film 4 parts with step same as described above.The removing property of resist is with identical at table 1, table 2, table 4, table 5, table 6, table 8 and table 9 at this moment.
(3) the removing property of the reaction residue of etchant gas and inorganic plasma membrane
Then, shown in Fig. 1 I, use parallel-plate RIE arranged side by side, with processing pressure 10Pa, RF electric power 300W, combination gas with fluorocarbon and Ar, silicon nitride film is carried out exposing after the dry corrosion first bronze medal wiring 1, at this moment, on first bronze medal connects up 1 surface, piled up the resist residue 8 that the etchant gas that produces owing to above-mentioned dry corrosion and silicon nitride film react.
Then, shown in Fig. 1 I and Fig. 1 J, use the method identical to remove above-mentioned corrosion residue 8 with the detergent remover that is used to remove resist of composition with table 3, table 7 and table 8 or table 9 with (2).Its result is illustrated in the corresponding table.Table 3, table 7 and table 8 or table 900, zero, * use and identical canonical representations such as table 1.
Below, with reference to Fig. 1 K, in through hole 21 and groove 22, imbed copper with electrochemical plating, removing unwanted part by CMP, form second bronze medal wiring 10.
(4) corrosion resistance that connects up for copper
Corrosion resistance for the copper wiring is to measure by following method, be about to copper coin chip (thickness 500nm, 20mm * 20mm) in detergent remover with the composition shown in table 1～table 9, carry out washing and drying at dipping under 24 ℃ after 30 minutes, use the etching extent (minimizing of thickness) of 4probe (Four Dimension society system) the mensuration copper coin of the determining film thickness device of fluorescent x-ray afterwards.With the not enough 1nm of etching extent as 00, not enough 2nm as zero, more than the 2nm as * be illustrated in table 1～table 9.
(5) corrosion resistance of Low-k film
The corrosion resistance of Low-k film is to measure by following method, be about to CVD-SiON film chip (thickness 500nm, 20mm * 20mm) the detergent remover that is used for removing resist with the composition shown in table 1～table 9 24 ℃ down dipping carry out washing and drying after 30 minutes, use the NanoSpec (Nanometrics society system) of light diffraction-type determining film thickness device to measure the etching extent (minimizing of thickness) of CVD-SiON film chip afterwards.With the not enough 1nm of etching extent as 00, not enough 2nm as zero, more than the 2nm as * be illustrated in table 1～table 9.
In addition, in table 1～table 9, NH 4F is meant that ammonium fluoride, DMAC are meant N, N-dimethyl acetamide, DGBE are meant that diethylene glycol monobutyl ether, DMSO are meant that dimethyl sulfoxide (DMSO), DGME are meant that diethylene glycol monomethyl ether, MDP are meant that methylenediphosphonate, DEEA are meant N, N-diethyl ethanolamine, DMAC are meant that N,N-dimethylacetamide, PGME are meant that propylene glycol monomethyl ether, PGBE are meant that propylene glycol monobutyl ether, MEA are meant that monoethanolamine, BTA are meant benzotriazole.
[table 1]
Comparative example 1 Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Comparative example 2 Comparative example 3
A composition: NH 4F (quality %) ????0.0 ????0.1 ????0.1 ????0.1 ????0.5 ????0.1 ????0.1
The B1 composition DMAC+DGBE (quality %) ????80 ????80 ????80 ????80 ????80 ????80 ????80
DMAC mixing quality ratio ????0.3 ????0.3 ????0.3 ????0.3 ????0.3 ????0.3 ????0.3
DGBE mixing quality ratio ????0.7 ????0.7 ????0.7 ????0.7 ????0.7 ????0.7 ????0.7
pH ????6.5 ????5.5 ????6.5 ????7.5 ????6.5 ????3.5 ????8.5
ArF is with removing property of resist ????× ????○ ????○ ????○○ ????○○ ????× ????○○
Cu film corrosion resistance ????○ ????○ ????○ ????○ ????○ ????× ????×
Low-k film corrosion resistance ????○ ????○ ????○ ????○ ????○ ????○ ????×
Embodiment 5 Embodiment 3 Embodiment 6 Embodiment 7 Embodiment 8
A composition: NH 4F (quality %) ????0.1 ????0.1 ????0.1 ????0.1 ????0.1
The B1 composition DMAG+DGBE (quality %) ????80 ????80 ????80 ????80 ????80
DMAG mixing quality ratio ????0 ????0.3 ????0.5 ????0.7 ????1
DGBE mixing quality ratio ????1 ????0.7 ????0.5 ????0.3 ????0
pH ????7.5 ????7.5 ????7.5 ????7.5 ????7.5
ArF is with removing property of resist ????○○ ????○○ ????○○ ????○ ????○
Cu film corrosion resistance ????○ ????○ ????○ ????○ ????○
Low-k film corrosion resistance ????○ ????○ ????○ ????○ ????○
Being used to of embodiment 1～embodiment 8, the detergent remover of removing resist comprised all the components of A composition, B1 composition, C composition and D composition, and its pH is in 4～8 scope, so ArF is big with removing property of resist, Cu film corrosion resistance and Low-k erosion.In contrast, because comparative example 1 does not contain the A composition, so ArF diminishes with removing property of resist.Because the pH of comparative example 2 is littler than 4, so ArF reduces with removing property of resist and Cu film corrosion resistance.Because the pH of comparative example 3 is bigger than 8, so Cu film corrosion resistance and Low-k film corrosion resistance reduce.
In addition, show many more ArF resist and the residues thereof that are rich in acryl resin of removing more of the diethylene glycol monobutyl ether content in the B1 composition from embodiment 3 and embodiment 5～embodiment 8.
[table 2]
Comparative example 4 Embodiment 9 Embodiment 10 Embodiment 11 Embodiment 12 Comparative example 5 Comparative example 6
A composition: NH 4F (quality %) ????0.0 ????0.1 ????0.1 ????0.1 ????0.5 ????0.1 ????0.1
The B1 composition DMAC+DGBE (quality %) ????80 ????80 ????80 ????80 ????80 ????80 ????80
DMAC mixing quality ratio ????0.7 ????0.7 ????0.7 ????0.7 ????0.7 ????0.7 ????0.7
DGBE mixing quality ratio ????0.3 ????0.3 ????0.3 ????0.3 ????0.3 ????0.3 ????0.3
pH ????7.0 ????5.5 ????6.5 ????7.5 ????7.0 ????3.5 ????8.5
KrF is with removing property of resist ????× ????○○ ????○○ ????○○ ????○○ ????○○ ????×
Cu film corrosion resistance ????○ ????○ ????○ ????○ ????○ ????× ????×
Low-k film corrosion resistance ????○ ????○ ????○ ????○ ????○ ????○ ????×
Embodiment 13 Embodiment 10 Embodiment 14 Embodiment 15 Embodiment 16
A composition: NH 4F (quality %) ????0.1 ????0.1 ????0.1 ????0.1 ????0.1
The B1 composition DMAC+DGBE (quality %) ????80 ????80 ????80 ????80 ????80
DMAC mixing quality ratio ????1 ????0.7 ????0.5 ????0.3 ????0
DGBE mixing quality ratio ????0 ????0.3 ????0.5 ????0.7 ????1
pH ????6.5 ????6.5 ????6.5 ????6.5 ????6.5
KrF is with removing property of resist ????○○ ????○○ ????○○ ????○○ ????○
Cu film corrosion resistance ????○ ????○ ????○ ????○ ????○
Low-k film corrosion resistance ????○ ????○ ????○ ????○ ????○
Being used to of embodiment 9～embodiment 16, the detergent remover of removing resist comprised all the components of A composition, B1 composition, C composition and D composition, its pH is in 4～8 scope, so KrF reaches big to Low-k film corrosion resistance with removing property of resist, Cu film corrosion resistance.In contrast, because comparative example 4 does not contain the A composition, so ArF diminishes with removing property of resist.Because the pH of comparative example 5 is littler than 4, so Cu film corrosion resistance reduces.Because the pH of comparative example 6 is bigger than 8, so KrF reduces with removing property of resist, Cu film corrosion resistance and Low-k film corrosion resistance.
In addition, show many more KrF resist and the residues thereof that are rich in phenolic resin of removing more of the N,N-dimethylacetamide content in the B1 composition from embodiment 10 and embodiment 13～embodiment 16.
[table 3]
Comparative example 7 Embodiment 17 Embodiment 18 Embodiment 19 Embodiment 20 Embodiment 21 Comparative example 8 Comparative example 9
A composition: NH 4F (quality %) ????0.0 ????0.1 ????0.1 ????0.1 ????0.1 ????0.5 ????0.1 ????0.1
The B1 composition DMAC+DGBE (quality %) ???80 ????80 ????80 ????80 ????80 ????80 ????80 ????80
DMAC mixing quality ratio ????0.3 ????0.3 ????0.3 ????0.3 ????0.7 ????0.3 ????0.3 ????0.3
DGBE mixing quality ratio ????0.7 ????0.7 ????0.7 ????0.7 ????0.3 ????0.7 ????0.7 ????0.7
pH ????6.5 ????5.5 ????6.5 ????7.5 ????7.5 ????6.5 ????3.5 ????8.5
Removing property of corrosion residue ????× ????○ ????○ ????○ ????○ ????○○ ????○ ????○
Cu film corrosion resistance ????○ ????○ ????○ ????○ ????○ ????○ ????× ????×
Low-k film corrosion resistance ????○ ????○ ????○ ????○ ????○ ????○ ????○ ????×
Being used to of embodiment 17～embodiment 21, the detergent remover of removing resist comprised all the components of A composition, B1 composition, C composition and D composition, its pH is in 4～8 scope, so big with removing property, Cu film corrosion resistance and the Low-k film corrosion resistance of resist to ArF.Though this corrosion residue does not contain above-mentioned resist and resist residue, contains the carbon residue from etchant gas in a large number, so the detergent remover that is used to remove resist of the present invention is applicable.
In contrast, because comparative example 7 does not contain the A composition, so removing property of corrosion residue diminishes.Because the pH of comparative example 8 is littler than 4, so Cu film corrosion resistance reduces.Because the pH of comparative example 9 is bigger than 8, so Cu film corrosion resistance and Low-k film corrosion resistance reduce.
[table 4]
Embodiment 22 Embodiment 23 Embodiment 24 Embodiment 25
A composition: NH 4F (quality %) ????0.1 ????0.1 ????0.1 ????0.1
The B1 composition DMAC+DGBE (quality %) ????80 ????80 ????80 ????80
DMAC mixing quality ratio ????0.3 ????0.5 ????0.3 ????0.5
DGBE mixing quality ratio ????0.7 ????0.5 ????0.7 ????0.5
The E1 composition Ammonium acetate (quality %) ????1.5 ????1.5 ????- ????-
Amcide Ammate (quality %) ????- ????- ????1.5 ????1.5
pH ????7.5 ????7.5 ????7.5 ????7.5
ArF is with removing property of resist ????○○ ????○○ ????○○ ????○○
Cu film corrosion resistance ????○ ????○ ????○ ????○
Low-k film corrosion resistance ????○ ????○ ????○ ????○
Being used to of embodiment 22～embodiment 25, the detergent remover of removing resist comprised all the components of A composition, B1 composition, C composition, D composition and E1 composition, its pH is in 4～8 scope, so ArF is big with removing property of resist, Cu film corrosion resistance and Low-k film corrosion resistance.In addition, during with the embodiment 3 that does not contain the E1 composition, embodiment 6 contrasts,, can see that Low-k film corrosion resistance has the trend of further raising although the symbol in the table all is 0.Such trend not only can see in resist and removing property of resist residue thereof for ArF, and also can see in resist and removing property of resist residue thereof for KrF.
[table 5]
Comparative example 10 Embodiment 26 Embodiment 27 Embodiment 28 Embodiment 29 Comparative example 11 Comparative example 12
A composition: NH 4F (quality %) ????0.0 ????0.1 ????0.1 ????0.1 ????0.1 ????0.1 ????0.1
The B2 composition DMSO+DGME (quality %) ????70 ????70 ????70 ????70 ????70 ????70 ????70
DMSO mixing quality ratio ????0.3 ????0.3 ????0.3 ????0.3 ????0.3 ????0.3 ????0.3
DGME mixing quality ratio ????0.7 ????0.7 ????0.7 ????0.7 ????0.7 ????0.7 ????0.7
C1 composition: MDP (quality %) ????5 ????5 ????5 ????5 ????6 ????7 ????5
E composition: DEEA (quality %) ????3 ????1.5 ????3 ????5 ????5 ????1 ????7
pH ????6.0 ????3.0 ????6.0 ????7.5 ????6.0 ????1.5 ????8.5
ArF is with removing property of resist ????× ????○ ????○○ ????○○ ????○○ ????○ ????○
Cu film corrosion resistance ????○ ????○ ????○ ????○ ????○ ????× ????×
Low-k film corrosion resistance ????○○ ????○○ ????○○ ????○○ ????○○ ????○○ ????×
Embodiment 30 Embodiment 27 Embodiment 31 Embodiment 32 Embodiment 33 Embodiment 34 Embodiment 35
A composition: NH 4F (quality %) ????0.1 ????0.1 ????0.1 ????0.1 ????0.1 ????0.1 ????0.1
The B2 composition DMSO+DGME (quality %) ????70 ????70 ????70 ????70 ????70 ????80 ????60
DMSO mixing quality ratio ????0.0 ????0.3 ????0.5 ????0.7 ????1.0 ????0.3 ????0.3
DGME mixing quality ratio ????1.0 ????0.7 ????0.5 ????0.3 ????0.0 ????0.7 ????0.7
C1 composition: MDP (quality %) ????5 ????5 ????5 ????5 ????5 ????5 ????10
E composition: DEEA (quality %) ????3 ????3 ????3 ????3 ????3 ????3 ????7
pH ????6.0 ????6.0 ????6.0 ????6.0 ????6.0 ????6.0 ????6.0
ArF is with removing property of resist ????○○ ????○○ ????○○ ????○○ ????○ ????○○ ????○○
Cu film corrosion resistance ????○ ????○ ????○ ????○ ????○ ????○ ????○
Low-k film corrosion resistance ????○○ ????○○ ????○○ ????○○ ????○○ ????○○ ????○○
Being used to of embodiment 26～embodiment 35, the detergent remover of removing resist comprised all the components of A composition, B2 composition, C1 composition, D composition and E composition, its pH is in 2～8 scope, so ArF is big with removing property of resist, Cu film corrosion resistance and Low-k film corrosion resistance.In contrast, because comparative example 10 does not contain the A composition, so ArF diminishes with removing property of resist.Because the pH of comparative example 11 is littler than 2, so Cu film corrosion resistance reduces.Because the pH of comparative example 12 is bigger than 8, so Cu film corrosion resistance and Low-k film corrosion resistance reduce.
In addition, show many more ArF resist and the residues thereof that are rich in acryl resin of removing more of the diethylene glycol monomethyl ether content in the B2 composition from embodiment 27 and embodiment 30～embodiment 33.
[table 6]
Comparative example 13 Embodiment 36 Embodiment 37 Embodiment 38 Embodiment 39 Comparative example 14 Comparative example 15
A composition: NH 4F (quality %) ????0.0 ????0.1 ????0.1 ????0.1 ????0.5 ????0.1 ????0.1
The B2 composition DMS0+DGME (quality %) ????70 ????70 ????70 ????70 ????70 ????70 ????70
DMSO mixing quality ratio ????0.7 ????0.7 ????0.7 ????0.7 ????0.7 ????0.7 ????0.7
DGME mixing quality ratio ????0.3 ????0.3 ????0.3 ????0.3 ????0.3 ????0.3 ????0.3
C1 composition: MOP (quality %) ????5 ????5 ????5 ????5 ????6 ????7 ????5
E composition: DEEA (quality %) ????3 ????1.5 ????3 ????5 ????5 ????1 ????7
pH ????6.0 ????3.0 ????6.0 ????7.5 ????6.0 ????1.5 ????8.5
KrF is with removing property of resist ????× ????○○ ????○○ ????○ ????○○ ????○○ ????×
Cu film corrosion resistance ????○ ????○ ????○ ????○ ????○ ????× ????×
Low-k film corrosion resistance ????○○ ????○○ ????○○ ????○○ ????○○ ????○○ ????×
Embodiment 40 Embodiment 41 Embodiment 42 Embodiment 37 Embodiment 43 Embodiment 44 Embodiment 45
A composition: NH 4F (quality %) ????0.1 ????0.1 ????0.1 ????0.1 ????0.1 ????0.1 ????0.1
The B2 composition DMSO+DGME (quality %) ????70 ????70 ????70 ????70 ????70 ????80 ????60
DMSO mixing quality ratio ????0.0 ????0.3 ????0.5 ????0.7 ????1.0 ????0.7 ????0.7
DGME mixing quality ratio ????1.0 ????0.7 ????0.5 ????0.3 ????0.0 ????0.3 ????0.3
C1 composition: MPP (quality %) ????5 ????5 ????5 ????5 ????5 ????5 ????10
E composition: DEEA (quality %) ????3 ????3 ????3 ????3 ????3 ????3 ????7
pH ????6.0 ????6.0 ????6.0 ????6.0 ????6.0 ????6.0 ????6.0
KrF is with removing property of resist ????○ ????○○ ????○○ ????○○ ????○○ ????○○ ????○○
Cu film corrosion resistance ????○ ????○ ????○ ????○ ????○ ????○ ????○
Low-k film corrosion resistance ????○○ ????○○ ????○○ ????○○ ????○○ ????○ ????○○
Being used to of embodiment 36～embodiment 45, the detergent remover of removing resist comprised all the components of A composition, B2 composition, C1 composition, D composition and E composition, its pH is in 2～8 scope, so KrF is big with removing property of resist, Cu film corrosion resistance and Low-k film corrosion resistance.In contrast, because comparative example 13 does not contain the A composition, so KrF diminishes with removing property of resist.Because the pH of comparative example 14 is littler than 2, so Cu film corrosion resistance reduces.Because the pH of comparative example 15 is bigger than 8, so KrF reduces with removing property of resist, Cu film corrosion resistance and Low-k film corrosion resistance.
In addition, show many more KrF resist and the residues thereof that are rich in phenolic resin of removing more of the dimethyl sulfoxide (DMSO) content in the B2 composition from embodiment 37 and embodiment 40～embodiment 43.
[table 7]
Comparative example 16 Embodiment 46 Embodiment 47 Embodiment 48 Embodiment 49 Embodiment 50 Comparative example 17 Comparative example 18
A composition: NH 4F (quality %) ????0.0 ????0.1 ????0.1 ????0.1 ????0.1 ????0.5 ????0.1 ????0.1
The B2 composition DMSO+DGME (quality %) ????70 ????70 ????70 ????70 ????70 ????70 ????70 ????70
DMS0 mixing quality ratio ????0.3 ????0.3 ????0.3 ????0.7 ????0.7 ????0.3 ????0.3 ????0.3
DGME mixing quality ratio ????0.7 ????0.7 ????0.7 ????0.3 ????0.3 ????0.7 ????0.7 ????0.7
C1 composition: MDP (quality %) ????5 ????5 ????5 ????5 ????10 ????5 ????7 ????5
E composition: DEEA (quality %) ????3 ????1.5 ????3 ????3 ????7 ????3.5 ????1 ????7
pH ????6.0 ????3.0 ????6.0 ????6.0 ????6.0 ????6.5 ????1.5 ????8.5
Removing property of corrosion residue ????× ????○○ ????○○ ????○○ ????○○ ????○○ ????× ????○
Cu film corrosion resistance ????○ ????○ ????○ ????○ ????○ ????○ ????× ????×
Low-k film corrosion resistance ????○○ ????○○ ????○○ ????○○ ????○○ ????○○ ????○ ????×
Being used to of embodiment 46～embodiment 50, the detergent remover of removing resist comprised all the components of A composition, B2 composition, C1 composition, D composition and E composition, its pH is in 2～8 scope, so removing property of corrosion residue, Cu film corrosion resistance and Low-k film corrosion resistance are all big.This corrosion residue does not contain above-mentioned resist and resist residue, but is rich in the carbon residue from etchant gas, so the applicable detergent remover that is used to remove resist of the present invention.
In contrast, because comparative example 16 does not contain the A composition, so removing property of corrosion residue diminishes.Because the pH of comparative example 17 is littler than 2, so corrosion removing property of residue and Cu film corrosion resistance reduce.Because the pH of comparative example 18 is bigger than 8, so Cu film corrosion resistance and Low-k film corrosion resistance reduce.
[table 8]
Embodiment 51 Embodiment 52 Embodiment 53 Embodiment 54 Embodiment 55 Embodiment 56 Comparative example 19 Comparative example 20
A composition: NH 4F (quality %) ????0.1 ????0.1 ????0.1 ????0.1 ????0.1 ????0.1 ????0.1 ????0.1
B 2 compositions B2 composition (quality %) ????70 ????70 ????70 ????70 ????70 ????70 ????70 ????70
DMSO mixing quality ratio ????0.3 ????0.3 ????0.3 ????0.3 ????0.3 ????0.3 ????0.3
DMAC mixing quality ratio ????0.3
DGME mixing quality ratio ????0.7 ????0.7 ????0.7 ????0.7 ????0.7
DGBE mixing quality ratio ????0.7
PGME mixing quality ratio ????0.7
PGBE mixing quality ratio ????0.7
C1 composition: MDP (quality %) ????5 ????5 ????5 ????5 ????5 ????5 ????7 ????5
E composition: compound name (quality %) ????DEEA ????3 ????DEEA ????3 ????DEEA ????3 ????DEEA ????3 ????DEEA ????3 ????MEA ????2.5 ????DEEA ????1 ????DEEEA ????7
pH ????6.0 ????6.0 ????6.0 ????6.0 ????6.0 ????6.0 ????1.5 ????8.5
ArF is with removing property of resist ????○○ ????○○ ????○○ ????○○ ????○○ ????○○ ????○ ????○○
KrF is with removing property of resist ????○○ ????○○ ????○○ ????○○ ????○○ ????○○ ????○○ ????×
Removing property of corrosion residue ????○○ ????○○ ????○○ ????○○ ????○○ ????○○ ????○○ ????○○
Cu film corrosion resistance ????○ ????○ ????○ ????○ ????○ ????○ ????× ????×
Low-k film corrosion resistance ????○○ ????○○ ????○○ ????○○ ????○○ ????○○ ????○○ ????×
Being used to of embodiment 51～embodiment 56, the detergent remover of removing resist comprised all the components of A composition, B2 composition, C1 composition, D composition and E composition, its pH is in 2～8 scope, so ArF is big with removing property of resist, removing property of corrosion residue, Cu film corrosion resistance and Low-k film corrosion resistance with removing property of resist, KrF.In addition, the foregoing description shows, as the B2 composition, and the potpourri of sulfocompound (for example dimethyl sulfoxide (DMSO)) or amine (for example N,N-dimethylacetamide) and polyvalent alcohol or derivatives thereof (for example diethylene glycol monomethyl ether, diethylene glycol monobutyl ether etc.) preferably.
[table 9]
Comparative example 21 Embodiment 57 Embodiment 58 Embodiment 59 Embodiment 60 Embodiment 61 Comparative example 22 Comparative example 23
A composition: NH 4F (quality %) ????0.0 ????0.1 ????0.1 ????0.1 ????0.1 ????0.1 ????0.1 ????0.1
The B2 composition DMSO+DGME (quality %) ????70 ????70 ????70 ????70 ????70 ????70 ????70 ????70
DMSO mixing quality ratio ????0.3 ????0.3 ????0.3 ????0.3 ????0.3 ????0.3 ????0.3 ????0.3
DGME mixing quality ratio ????0.7 ????0.7 ????0.7 ????0.7 ????0.7 ????0.7 ????0.7 ????0.7
C1 composition: MDP (quality %) ????5 ????5 ????5 ????5 ????5 ????5 ????7 ????5
E composition: DEEA (quality %) ????3 ????1.5 ????3 ????3 ????3 ????3 ????1 ????7
F composition: compound name (quality %) ????BTA ????1 ????BTA ????1 ????BTA ????1 Oxalic acid 1 Benzoic acid 1 Glycocoll 1 ????BTA ????1 ????BTA ????1
pH ????6.0 ????3.0 ????6.0 ????6.0 ????6.0 ????6.0 ????1.5 ????8.5
ArF is with removing property of resist ????× ????○ ????○○ ????○○ ????○○ ????○○ ????○ ????○
KrF is with removing property of resist ????× ????○○ ????○○ ????○○ ????○○ ????○○ ????○○ ????×
Removing property of corrosion residue ????× ????○○ ????○○ ????○○ ????○○ ????○○ ????× ????○
Cu film corrosion resistance ????○○ ????○○ ????○○ ????○○ ????○○ ????○○ ????× ????×
Low-k film corrosion resistance ????○○ ????○○ ????○○ ????○○ ????○○ ????○○ ????○○ ????×
Being used to of embodiment 57～embodiment 61, the detergent remover of removing resist comprised all the components of A composition, B2 composition, C1 composition, D composition, E composition and F composition, its pH is in 2～8 scope, so ArF is big with removing property of resist, removing property of corrosion residue, Cu film corrosion resistance and Low-k film corrosion resistance with removing property of resist, KrF.This corrosion residue does not contain above-mentioned resist and resist residue, but is rich in the carbon residue from etchant gas, so the applicable detergent remover that is used to remove resist of the present invention.
In contrast, because comparative example 21 does not contain the A composition, so ArF diminishes with removing property of resist and removing property of corrosion residue with removing property of resist, KrF.Because the pH of comparative example 22 is littler than 2, so corrosion removing property of residue and Cu film corrosion resistance reduce.Because the pH of comparative example 23 is bigger than 8, so KrF reduces with removing property of resist, Cu film corrosion resistance and Low-k film corrosion resistance.
Though understand the present invention in detail, these only are examples, the present invention is not limited by these, should be clear, and the spirit and scope of invention are only limited by additional claim scope.

Claims (13)

1. detergent remover that is used to remove resist, it is characterized in that containing hydrofluorite and metal-free alkali salt (A composition), water-miscible organic solvent (B1 composition), constitute acid more than a kind (C composition) and the water of selecting among the group (D composition) by organic acid and mineral acid, and pH pH is 4～8.
2. detergent remover that is used to remove resist, it is characterized in that containing hydrofluorite and metal-free alkali salt (A composition), water-miscible organic solvent (B1 composition), constitute the acid more than a kind (C composition), water (D composition) and the ammonium salt of selecting among the group (EI composition) by organic acid and mineral acid, and pH pH is 4～8.
3. the detergent remover that is used to remove resist according to claim 1 is characterized in that water-miscible organic solvent (B1 composition) is the potpourri of amide-type and polyvalent alcohol or its derivant.
4. the detergent remover that is used to remove resist according to claim 1, the metal-free alkali that it is characterized in that being used to form the salt (A composition) of hydrofluorite and metal-free alkali are the alkali more than select from the group that organic amine compound, ammonia and rudimentary the 4th grade of quaternary ammonium base are formed at least a.
5. the detergent remover that is used to remove resist according to claim 1, the content that it is characterized in that the salt (A composition) of hydrofluorite and metal-free alkali is 0.01 quality %～1 quality %.
6. detergent remover that is used to remove resist, it is characterized in that containing salt (A composition), water-miscible organic solvent (B2 composition), phosphonic acids (C1 composition), water (D composition) and metal-free alkali (E composition) of hydrofluorite and metal-free alkali, and pH pH is 2～8.
7. the detergent remover that is used to remove resist according to claim 6 is characterized in that water-miscible organic solvent (B2 composition) is the potpourri of sulfocompound and polyvalent alcohol or its derivant.
8. detergent remover that is used to remove resist, it is characterized in that containing salt (A composition), water-miscible organic solvent (B2 composition), phosphonic acids (C1 composition), water (D composition), metal-free alkali (E composition) and the Cu corrosion inhibitor (F composition) of hydrofluorite and metal-free alkali, and pH pH is 2～8.
9. the detergent remover that is used to remove resist according to claim 8 is characterized in that the Cu corrosion inhibitor contains select at least a from the group who is made up of triazole type, aliphatic carboxylic acid class, aromatic carboxylic acid class and aminocarboxylic acids.
10. the manufacture method of a semiconductor devices, it is characterized in that being included in film forming on the Semiconductor substrate and be with copper major component metal film operation and, in the above form dielectric film operation and and then form thereon resist film operation and, by with this resist film be mask carry out dry corrosion in this dielectric film, be provided with hole or groove operation and, the plasma treatment that produces with gas or the heat treated operation of removing this resist, after above-mentioned operation, use the described detergent remover that is used to remove resist of claim 1 to remove remaining resist residue.
11. the manufacture method of semiconductor devices according to claim 10 is characterized in that using on the resist of the dry corrosion mask in becoming above-mentioned dry corrosion operation chemical amplifying type quasi-molecule resist.
12. the manufacture method of a semiconductor devices, it is characterized in that being included in film forming on the Semiconductor substrate and be the operation of the metal film of major component, form the operation of dielectric film and then form the operation of resist film thereon and in the above, the resist residue that takes place when after above-mentioned operation, using the described detergent remover that is used to remove resist of claim 1 to remove remaining resist film and dry corrosion by being that mask carries out dry corrosion is provided with hole or groove in this dielectric film operation with this resist film with copper.
13. the manufacture method of a semiconductor devices, it is characterized in that being included in film forming on the Semiconductor substrate and be the operation of the metal film of major component, form the operation of dielectric film and the operation in the hole that reaches this metal film is set in this dielectric film in the above, the corrosion residue that takes place when after above-mentioned operation, using the described detergent remover that is used to remove resist of claim 1 to remove dry corrosion by dry corrosion with copper.
CNB031464947A 2002-07-12 2003-07-11 Detergent for removing resist and method for making semiconductor Expired - Fee Related CN100370361C (en)

Applications Claiming Priority (3)

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JP203987/2002 2002-07-12
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CN101156111B (en) * 2005-04-06 2011-04-13 株式会社东进世美肯 Remover composition for photoresist of semiconductor device
CN101000467B (en) * 2006-01-10 2012-07-04 株式会社东进世美肯 Resist remover composition and resist removing method
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CN100370361C (en) 2008-02-20

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