CN1682155B - Photoresist stripper composition - Google Patents

Photoresist stripper composition Download PDF

Info

Publication number
CN1682155B
CN1682155B CN038219662A CN03821966A CN1682155B CN 1682155 B CN1682155 B CN 1682155B CN 038219662 A CN038219662 A CN 038219662A CN 03821966 A CN03821966 A CN 03821966A CN 1682155 B CN1682155 B CN 1682155B
Authority
CN
China
Prior art keywords
stripper composition
resist
water
compound
corrosion
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN038219662A
Other languages
Chinese (zh)
Other versions
CN1682155A (en
Inventor
金玮溶
尹锡一
曹三永
朴顺姬
全雨植
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.)
Dongjin Semichem Co Ltd
Original Assignee
Dongjin Semichem Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dongjin Semichem Co Ltd filed Critical Dongjin Semichem Co Ltd
Publication of CN1682155A publication Critical patent/CN1682155A/en
Application granted granted Critical
Publication of CN1682155B publication Critical patent/CN1682155B/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Images

Classifications

    • 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
    • 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
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • 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
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • 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
    • G03F7/426—Stripping or agents therefor using liquids only containing organic halogen compounds; containing organic sulfonic acids or salts thereof; containing sulfoxides
    • 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

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)

Abstract

The present invention relates to a photoresist stripper composition, and particularly relates to a photoresist stripper composition comprising 20-60 wt% of water-soluble organic solvent, (b) 10-45 wt% of water, (c) 5-15 wt% of alkylamine or alcohol, (d) 0.1-10 wt% of acetic acid, (e) 0.01-5 wt% of oxime compound, (f) 1-10 wt% of organic phenol compound containing two or three hydroxyl groups, and (g) 0.5-5 wt% of triazole compound. The photoresist stripper composition of the present invention can easily and rapidly remove the resist film hardened in the hard bake, dry etching, ashing or ion implantation process and the resist film modified by the metal byproduct etched from the underlying metal film in the process in a short time. In addition, the composition can minimize corrosion of the underlying metal wiring during the resist removal process. It can be very effectively used in the manufacturing process of semiconductor devices such as integrated circuits, large scale integrated circuits and very large scale integrated circuits.

Description

Light carving rubber stripper composition
Technical field
The present invention relates to a kind of light carving rubber stripper composition, relate more particularly to a kind ofly in semiconductor devices such as integrated circuit (IC), large scale integrated circuit (LSI) and VLSI (very large scale integrated circuit) (VLSI) manufacture process, be used to remove the light carving rubber stripper composition of resist.
Background technology
In common production process of semiconductor device, on the conductive layer on the Semiconductor substrate, form the resist pattern, then will be not by a part of conductive layer etching of pattern covers to form conductive layer pattern.This process repeats repeatedly.After conductive layer pattern forms, should adopt corrosion inhibitor stripper, remove resist pattern from conductive layer as mask.Yet,, resist is become is difficult to remove owing in the VLSI (very large scale integrated circuit) semiconductor is made recently, mainly adopt dry method etch technology to form conductive layer pattern.
Different with the wet etching that uses the acidic liquid chemicals, dry etching utilizes plasma etching gas and material layer, carries out as the gas phase-solid phase reaction between the conductive layer.Because dry etching control easily also can obtain clear pattern, thereby becomes the main flow of recent etch process.Yet because the ion of plasma etch gases and free radical and resist film react and make its quick-hardening, thereby dry etching is unfavorable for removing resist.Especially, under the situation of the conductive layer that adopts dry etching to constitute,, also be difficult to remove the resist of modification and sclerosis on the sidewall even use various chemicals by tungsten and titanium nitride.
The recent corrosion inhibitor stripper composition that comprises azanol and amino ethoxy ethanol that proposes, it can remove the resist film of most sclerosis relatively effectively.Yet, this remover combination in the semi-conductive large-scale production of 1-gigabit DRAM, the copper wiring metal film of heavy corrosion substitution of Al wiring.In addition, because azanol has high toxicity, so need a kind of eco-friendly novel corrosion inhibitor stripper of exploitation.
Recently also proposed a kind of corrosion inhibitor stripper composition that comprises alkanolamine and diglycol monotertiary alkyl ether, it has less smell and toxicity and has for the resist film of great majority sclerosis and removes performance preferably.Yet this remover combination can not be removed the resist film that is exposed to plasma etching gas or ion beam in dry etching or ion implantation technology well.Therefore, need the development of new corrosion inhibitor stripper, this remover can be removed by the resist film of dry etching or ion implantation technology modification.
As mentioned above, be difficult to use corrosion inhibitor stripper to remove and stand the resist film of ion implantation technology.Especially,, stand the resist film that the high dose ion injection technology forms source/drain region, just more be difficult to remove in the VLSI (very large scale integrated circuit) manufacturing process.During ion implantation technology, harden mainly due to the reaction heat of high dose, high energy ion beam in the surface of resist film.In addition, when ashing was carried out simultaneously, the pressure in the resist film increased, thereby the resist film surface may be owing to remaining solvent in the film breaks (explosion), and explosion causes forming the resist residue.Usually, the semiconductor wafer of ashing treatment is being handled above under 200 ℃ the temperature.In this process, should evaporate and discharge at the inner remaining solvent of resist.But this is impossible for the resist surface of having stood the high dose ion injection, because should form hardened layer on the surface.
Hardened layer after the explosion is difficult to remove.And because hardened layer is owing to adding thermosetting, adulterant just foreign ion may be displaced in the molecular structure of resist and cause cross-linking reaction.Then, reaction site is by O 2The oxidation of plasma institute.The resist of oxidation becomes residue and particle becomes another pollution source, and reduces the output of VLSI (very large scale integrated circuit).
The dry method and the wet processing of many effective removal resist hardened layers have been proposed.One of them is two step ashing methods (Fujimura, Spring Meeting of the Japanese Society of AppliedPhysics, Presentation 1P-13, p574,1989).Yet the dry method etch technology complexity of this method needs large-scale equipment and throughput rate not high.
Proposed to comprise the corrosion inhibitor stripper composition of organic amine compound and various organic solvents, as the corrosion inhibitor stripper that is used for conventional wet cleaning technology.Especially, widely-used organic amine compound, especially monoethanolamine (MEA) the corrosion inhibitor stripper composition that comprises as principal ingredient.
For example, a kind of bicomponent system corrosion inhibitor stripper composition comprises: a) organic amine compound such as MEA and 2-(2-amino ethoxy) ethanol (AEE) and b) polar solvent such as N, N-dimethyl acetamide (DMAc), N, dinethylformamide (DMF), N-Methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO), carbitol acetate ester and methoxyl acetoxy-propane (United States Patent (USP) 4,617 251); A kind of bicomponent system corrosion inhibitor stripper composition, comprise a) organic amine compound such as MEA, single Propanolamine and methyl amyl alcohol and b) amide solvent such as N-methylacetamide (MAc), N, N-dimethyl acetamide (DMAc), dimethyl formamide (DMF), N, N-diethyl acetamide (DEAc), N, N-Valpromide (DPAc), N, N-dimethyl propylene acid amides, N, N-diethyl butyramide and N-methyl-N-ethyl propionamide (United States Patent (USP) 4,770713); A kind of bicomponent system corrosion inhibitor stripper composition, comprise a) organic amine compound such as alkanolamine (MEA) and b) aprotic polar solvent as 1,3-dimethyl-2-imidazolone (1,3-dimethyl-2-imidazolidinone, DMI) and 1,3-dimethyl-tetrahydro pyrimidine ketone (German patent application No.3,828,513); A kind of corrosion inhibitor stripper composition comprises the alkylene polyamine of a) being introduced by the ethoxy on the alkanolamine, and ethylenediamine, wherein alkanolamine such as MEA, diethanolamine (DEA) and triethanolamine (TEA), b) sulphones such as sulfolane (sulforane), and c) glycol monoalkyl ether such as carbiphene and diglycol monotertiary butyl ether (the clear 62-49355 of Japanese patent application No.); A kind of corrosion inhibitor stripper composition comprises a) water-soluble amine such as MEA and DEA, and b) 1,3-dimethyl-2-imidazolone (the clear 63-208043 of Japanese patent application No.); A kind of positive resist release agent compositions comprises a) amine such as MEA, ethylenediamine, piperidines and benzylamine, b) polar solvent such as DMAc, NMP and DMSO, and c) surfactant (the clear 63-231343 of Japanese patent application No.); A kind of positive resist release agent compositions, comprise a) nitrogenous organic hydroxy compounds such as MEA, b) one or more are selected from carbiphene, diglycol dialkyl ether, gamma-butyrolacton and 1, the solvent of 3-dimethyl-2-imidazolone, and c) DMSO (the clear 64-42653 of Japanese patent application No.); A kind of positive resist release agent compositions comprises a) organic amine compound such as MEA, b) aprotic polar solvent such as diglycol monotertiary alkyl ether, DMAc, NMP and DMSO, and c) phosphate ester surfactants (the flat 4-124668 of Japanese patent application No.); A kind of corrosion inhibitor stripper composition comprises a) 1,3-dimethyl-2-imidazolone (DMI), b) dimethyl sulfoxide (DMSO), and c) water-soluble organic amine compound such as MEA (the flat 4-350660 of Japanese patent application No.); With a kind of corrosion inhibitor stripper composition, comprise a) MEA, b) DMSO, and c) catechol (the flat 5-281753 of Japanese patent application No.).These corrosion inhibitor stripper compositions have good relatively security, workability and resist and remove efficient.
Yet, comprise the various substrates of silicon wafer owing in recent process for fabrication of semiconductor device, under 110-140 ℃ high temperature, handle, and resist tended to by roasting.Yet above-mentioned corrosion inhibitor stripper can not be removed the resist through roasting fully.Proposed with the resist of the corrosion inhibitor stripper composition removal that comprises water or hydroxylamine compound through roasting.For example, the corrosion inhibitor stripper composition that has proposed has: a kind of corrosion inhibitor stripper composition comprises a) azanol, b) alkanolamine and c) water (the flat 4-289866 of Japanese patent application No.); A kind of corrosion inhibitor stripper composition comprises a) azanol, b) alkanolamine, c) water and d) anticorrosive (the flat 6-266119 of Japanese patent application No.); A kind of corrosion inhibitor stripper composition comprises a) polar solvent such as GBL, DMF, DMAc and NMP, b) amino alcohol such as 2-methylamino ethanol, and c) water (the flat 7-69618 of Japanese patent application No.); A kind of remover combination comprises a) amino alcohol such as MEA, b) water and c) butyldiglycol (the flat 8-123043 of Japanese patent application No.); A kind of corrosion inhibitor stripper composition comprises a) alkanolamine and alkoxyalkyl amine, b) glycol monoalkyl ether, c) sugar alcohol, d) quaternary ammonium hydroxide and e) water (the flat 8-262746 of Japanese patent application No.); A kind of remover combination comprises a) one or more as the alkanolamine of MEA and AEE, b) azanol, c) diglycol monotertiary alkyl ether, d) sugar (D-sorbite) and e) water (the flat 9-152721 of Japanese patent application No.); A kind of corrosion inhibitor stripper composition comprises a) azanol, b) water, c) acid dissociation constant (pK a) be 7.5 to 13 amine, d) water-miscible organic solvent and e) anticorrosive (the flat 9-96911 of Japanese patent application No.).
Yet these corrosion inhibitor stripper compositions can not be removed the resist film of modification and sclerosis in dry etching, ashing and ion implantation technology fully, perhaps in this technology by resist film from the etched metal byproducts modification of bottom metal film.And they can endanger environment, also do not stop resist to remove during the technology corrosion to the bottom metal wiring fully.
Summary of the invention
The purpose of this invention is to provide a kind of light carving rubber stripper composition, said composition can be easily and is removed the resist film of modification and sclerosis in dry etching, ashing and ion implantation technology apace, with in this technology, by resist film from the etched metal byproducts modification of underlying metal film.In addition, said composition can minimize the underlying metal wiring, the particularly corrosion of copper wiring, and be environmentally safe.
For reaching this purpose, the invention provides a kind of light carving rubber stripper composition, said composition comprises: (a) water-miscible organic solvent of 20～60wt%, (b) water of 10～45wt%, (c) alkylamine or alkanolamine of 5～15wt%, (d) acetate of 0.1～10wt%, (e) oxime of 0.01～5wt%, (f) 1～10wt% contains organic phenolic compounds of two or three hydroxyls and (g) triazole compounds of 0.5～5wt%.
Description of drawings
Fig. 1 is to use the scanning electron micrograph before the light carving rubber stripper composition.
Fig. 2 is the scanning electron micrograph behind the light carving rubber stripper composition that uses embodiment 1 under 65 ℃.
Fig. 3 is the scanning electron micrograph behind the light carving rubber stripper composition that uses Comparative Examples 1 under 65 ℃.
Embodiment
It below is detailed description of the present invention.
The present invention relates to a kind of light carving rubber stripper composition, said composition comprises alkylamine or alkanolamine, acetate and oxime compound.Light carving rubber stripper composition of the present invention can be easily and remove the resist film that hardens apace in violent roasting, dry etching, ashing or ion implantation technology, with in this technology, by resist film from the etched metal byproducts modification of underlying metal film.In addition, remove in the technology at this resist, said composition can minimize the corrosion to the underlying metal wiring.
Alkylamine or alkanolamine is preferably one or more and is selected from compound in following group: ethamine, dimethylamine, diethylamine, trimethylamine, triethylamine, monoethanolamine, diethanolamine and triethanolamine.The content of alkylamine or alkanolamine is preferably 5～15wt%.If the content of alkylamine or alkanolamine is lower than 5wt%, will be difficult to remove fully the sidewall resist polymkeric substance that in dry etching or cineration technics, is modified.In addition, if its content surpasses 15wt%, the bottom metal film of will excessive corrosion making by aluminum or aluminum alloy.
The content of acetate is preferably 0.1～10wt%.If acetic acid content is lower than 0.1wt%, polymkeric substance is removed efficient and will be reduced.In addition, if its content surpasses 10wt%, will the excessive corrosion bottom metal film.
Oxime compound is preferably one or more and is selected from compound in following group: acetaldoxime, acetoxime and diacetylmonoxime.The content of oxime compound is preferably 0.01～5wt%.If the content of oxime compound is lower than 0.01wt%, can not well dissolve the sidewall photoresist polymkeric substance of peeling off.In addition, if its content surpasses 5wt%, the dissolution in low temperature performance of photoresist will reduce owing to the higher boiling of oxime.
The preferred pure water that filters by ion exchange resin that uses among the present invention.More preferably use resistivity to surpass the high purity water of 18M Ω.Liquid water content is preferably 10～45wt%.If liquid water content is lower than 10wt%, can not remove well by the resist of the serious modification of metal byproducts that produces in dry etching and the cineration technics.In addition, if content surpasses 45wt%, may corrode the underlying metal wiring, and because the relative content of alkyl amine and water-miscible organic solvent reduces, the most of common resist except that the resist of modification can not be removed well.
Comprise the compound that organic phenolic compounds of two or three hydroxyls is preferably represented by following Chemical formula 1:
Chemical formula 1
Wherein, m is 2 or 3.
The organic phenolic compounds that comprises two or three hydroxyls can be removed the resist film that hardens in dry etching, ashing and ion implantation technology, and by the resist film of the etched metal byproducts modification of bottom metal film.The hydroxide ion that is produced by reaction between the hydrogen ion of azanol and water makes permeable space of generation between resist film and the Semiconductor substrate.In addition, the hydroxyl that comprises organic phenolic compounds of two or three hydroxyls can prevent the corrosion of bottom metal film light carving rubber stripper composition.
The content that comprises organic phenolic compounds of two or three hydroxyls is preferably 1～10wt%.If the content of organic phenolic compounds is lower than 1wt%, the resist of the serious modification of metal byproducts that is produced in dry etching and ion implantation technology can not be removed well, and can the heavy corrosion bottom metal film.In addition, if its content surpasses 10wt%, the cost of composition will be very high.
Water-miscible organic solvent is preferably one or more and is selected from compound in following group: dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone (NMP), dimethyl acetamide (DMAc) or dimethyl formamide (DMF).Consider dissolubility, prevent the deposition again of resist and, be more preferably dimethyl sulfoxide (DMSO) or dimethyl acetamide (DMAc) owing to being made waste liquid processing aspect easily by biodegradation fast for resist.The content of water-miscible organic solvent is preferably 20～60wt%.
Can prevent that corrosion from taking place by the organic phenolic compounds that comprises two or three hydroxyls effectively.Yet, the sidewall of bottom metal wiring membrane or the partial corrosion of upper surface, the problem of spot corrosion does not in other words also solve fully.Use with triazole compounds if will comprise organic phenolic compounds of two or three hydroxyls, just can prevent that the spot corrosion problem from taking place.
Triazole compounds is preferably one or more and is selected from compound in following group: benzotriazole (BT), azimido-toluene (TT), carboxyl benzotriazole (CBT) and comprise benzotriazole (BT) and the bi-component triazole compounds of azimido-toluene (TT).Wherein, the bi-component triazole compounds that more preferably comprises benzotriazole (BT) and azimido-toluene (TT).Especially, be 1: 1 the bi-component triazole compounds that comprises benzotriazole (BT) and azimido-toluene (TT) if use the fragrant phenolic compounds contain hydroxyl simultaneously and have preferred mixing ratio, can more effectively prevent the spot corrosion of resist film lateral faces.The content of triazole compounds is 0.5～5wt%.If its content is lower than 0.5wt%, can not prevent effectively that spot corrosion from taking place.In addition, if its content surpasses 5wt%, the corrosion inhibitor stripper composition will use inconvenience owing to viscosity increases to cause.
If light carving rubber stripper composition of the present invention is used for process for fabrication of semiconductor device, can remove resist film at an easy rate at short notice.Particularly can easily remove by the resist film of tungsten and titanium nitride film modification.In addition, it is an Environmental security, and energy minimization is removed the corrosion of in the technology bottom metal being connected up at resist.Especially, it can minimize the corrosion that is used for above the copper wiring of the semi-conductive large-scale production of 1 gigabit DRAM VLSI (very large scale integrated circuit).
The present invention is described by the following examples in more detail.Yet the following example only is used to understand the present invention, and is not used in restriction the present invention.Unless otherwise indicated, content in following examples and the Comparative Examples and mixing ratio are based on weight.
Embodiment
Embodiment 1-5 and Comparative Examples 1-2
The light carving rubber stripper composition for preparing embodiment 1-5 and Comparative Examples 1-2 with the component that provides in the table 1 and content:
Table 1
The test implementation example
For the every kind of light carving rubber stripper composition for preparing among embodiment 1-5 and the Comparative Examples 1-2, carry out (1) resist and remove test and the test of (2) copper corrosion.The results are shown in as in following table 2 and 3.
(1) resist removes test
The preparation of sample A
On the surface of 8 inches silicon wafers, sequential aggradation thickness is from bottom to top Tungsten film and Titanium nitride film, the normally used positive corrosion-resisting agent composition of spin coating (Mitsubishi product, name of product: IS401), make final film thickness arrive 1.01 μ m.Then, on 100 ℃ of hot plates with resist film prebaking 90 seconds.The mask that will have predetermined pattern is placed on the resist film, with the ultraviolet ray irradiation.Developed 60 seconds down at 21 ℃ with 2.38% tetramethylammonium hydroxide (TMAH) developer solution, on 120 ℃ of hot plates, the sample of resist pattern was baked (hard-bake) 100 seconds firmly then.As mask, use SF with the resist pattern that on sample, forms 6/ Cl 2(Hitachi, Ltd's product, model name: M318), etching is not by the tungsten of resist pattern covers and titanium nitride film 35 seconds, to form the metal line pattern for mixed gas and dry etching equipment.
Resist removes test
Sample A is immersed in every kind of corrosion inhibitor stripper composition down at 65 ℃.Sample is taken out,, and use nitrogen drying with the ultrapure water washing.Observe the resist residue on pattern sidewalls and line pattern surface with scanning electron microscope (SEM).Remove efficient with following standard evaluation resist.The results are shown in Table 2.
Zero: remove fully at pattern sidewalls and the lip-deep resist residue of line pattern.
△: remove more than 80% at pattern sidewalls and the lip-deep resist residue of line pattern, but small amount of residual is arranged.
*: great majority all are not removed in pattern sidewalls and the lip-deep resist residue of line pattern.
(2) copper corrosion test
The preparation of sample B
The copper lead frame that uses in the preparation package semiconductor technology.
The copper corrosion test
Sample B is immersed in every kind of corrosion inhibitor stripper composition down at 65 ℃.Sample is taken out,, and use nitrogen drying with the ultrapure water washing.Use the sem observation sample surfaces then.With following standard evaluation extent of corrosion.The results are shown in Table 3.
Zero: the not corrosion of copper surface.
△: copper surface portion corrosion.
*: the whole surperficial heavy corrosion of copper.
Table 2: the resist of corrosion inhibitor stripper composition is removed efficient
Figure G038219662D00101
As shown in table 2, the compositions display of embodiment 1 to 5 goes out extraordinary resist and removes efficient, and the resist of the common composition of Comparative Examples 1 and 2 is removed poor efficiency.
Table 3: metal line corrosion test
Figure G038219662D00102
Equally, as shown in table 3, in the metal line corrosion test, the compositions display of embodiment 1 to 5 goes out good result, becomes very poor and the common composition of Comparative Examples 1 and 2 prolongs corrosion resistance in time.
Fig. 1 and Fig. 2 are to use the scanning electron micrograph of the light carving rubber stripper composition front and back of embodiment 1, and Fig. 3 is to use the scanning electron micrograph (adopting the scanning electron microscope of Hitachi, Ltd, model name S-4100) behind the light carving rubber stripper composition of Comparative Examples 1.The test of sample A is carried out under 65 ℃.
There is resist to exist before making with photoresist as can be seen from Figure 1 on the sidewall.
All resists have been removed satisfactorily after using the light carving rubber stripper composition of embodiment 1 as can be seen from Figure 2.
Use as can be seen from Figure 3 on the common corrosion inhibitor stripper composition rear wall of Comparative Examples 1 resist is still arranged.
As mentioned above, light carving rubber stripper composition of the present invention can easily be removed the resist film that hardens and in this technology, by the resist film from the etched metal byproducts modification of underlying metal film in dry etching, ashing and ion implantation technology.In addition, remove in the technology at this resist, said composition can minimize the corrosion to the underlying metal wiring.In addition, in cleaning subsequently, can only make water, and without the organic solvent of isopropyl alcohol or dimethyl sulfoxide and so on.
Although describe the present invention in detail, one skilled in the art will understand that and to carry out various improvement and alternative to the present invention, and do not deviate from as the desired the spirit and scope of the present invention of appended claims according to preferred embodiment.

Claims (4)

1. light carving rubber stripper composition, comprise: (a) water-miscible organic solvent of 20～60wt%, (b) water of 10～45wt%, (c) alkylamine or alkanolamine of 5～15wt%, (d) acetate of 1～10wt%, (e) acetaldoxime of 0.5wt%, the acetaldoxime of 3.5wt%, the diacetylmonoxime of 1wt%, the acetoxime of 0.5wt% or the acetoxime of 3wt%, (f) the organic phenolic compounds that contains two or three hydroxyls represented by following Chemical formula 1 of 1～10wt%, (g) triazole compounds of 0.5～5wt%
Chemical formula 1
Wherein m is 2 or 3.
2. light carving rubber stripper composition according to claim 1, wherein alkylamine or alkanolamine is that one or more are selected from the compound in following group: ethamine, dimethylamine, diethylamine, trimethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine.
3. light carving rubber stripper composition according to claim 1, wherein triazole compounds is that one or more are selected from the compound in following group: benzotriazole (BT), azimido-toluene (TT), carboxyl benzotriazole (C BT), comprise the compound of the bi-component triazole of benzotriazole and tolyl-triazole.
4. light carving rubber stripper composition according to claim 1, wherein water miscible organic solvent are that one or more are selected from the compound in following group: dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone (NMP), dimethyl acetamide (DMAc), dimethyl formamide (DMF).
CN038219662A 2002-09-30 2003-09-30 Photoresist stripper composition Expired - Fee Related CN1682155B (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR1020020059552 2002-09-30
KR1020020059552A KR100862988B1 (en) 2002-09-30 2002-09-30 Photoresist remover composition
KR10-2002-0059552 2002-09-30
PCT/KR2003/002007 WO2004029723A1 (en) 2002-09-30 2003-09-30 Photoresist remover composition

Publications (2)

Publication Number Publication Date
CN1682155A CN1682155A (en) 2005-10-12
CN1682155B true CN1682155B (en) 2010-05-26

Family

ID=32040946

Family Applications (1)

Application Number Title Priority Date Filing Date
CN038219662A Expired - Fee Related CN1682155B (en) 2002-09-30 2003-09-30 Photoresist stripper composition

Country Status (5)

Country Link
KR (1) KR100862988B1 (en)
CN (1) CN1682155B (en)
AU (1) AU2003265098A1 (en)
TW (1) TWI228640B (en)
WO (1) WO2004029723A1 (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050032657A1 (en) * 2003-08-06 2005-02-10 Kane Sean Michael Stripping and cleaning compositions for microelectronics
TWI299513B (en) * 2004-11-04 2008-08-01 Nec Lcd Technologies Ltd Method of processing substrate and chemical used in the same (1)
EP1913448B1 (en) * 2005-08-13 2010-10-13 Techno Semichem Co., Ltd. Photoresist stripper composition for semiconductor manufacturing
WO2010118916A1 (en) * 2009-04-16 2010-10-21 Basf Se Organic photoresist stripper composition
KR102012464B1 (en) * 2013-09-06 2019-08-20 동우 화인켐 주식회사 Resist stripper composition and method of manufacturing flat panel display devices using the same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1258730A (en) * 1998-12-31 2000-07-05 东进化成工业株式会社 Photoresist scavenger composition
CN1277682A (en) * 1998-03-03 2000-12-20 硅谷化学实验室公司 Composition and method for removing resist and etching residues using hydroxylammonium carboxylates
WO2001096964A1 (en) * 2000-06-12 2001-12-20 Dongjin Semichem Co., Ltd. Photoresist remover composition

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05259066A (en) * 1992-03-13 1993-10-08 Texas Instr Japan Ltd Positive photoresist removing liquid and manufacture of semiconductor device
JPH07130700A (en) * 1993-10-29 1995-05-19 Sanyo Electric Co Ltd Manufacture of semiconductor device
US6500605B1 (en) * 1997-05-27 2002-12-31 Tokyo Electron Limited Removal of photoresist and residue from substrate using supercritical carbon dioxide process
JP4308959B2 (en) * 1998-02-27 2009-08-05 関東化学株式会社 Photoresist stripping composition
JP3477390B2 (en) * 1999-01-22 2003-12-10 花王株式会社 Release agent composition
US6562726B1 (en) * 1999-06-29 2003-05-13 Micron Technology, Inc. Acid blend for removing etch residue
CN1218222C (en) * 2000-07-10 2005-09-07 Ekc技术公司 Compsns. for cleaning organic and plasma etched residues for semiconductor devices
KR100742119B1 (en) * 2001-02-16 2007-07-24 주식회사 동진쎄미켐 Photoresist remover composition
KR100416657B1 (en) * 2001-06-26 2004-01-31 동부전자 주식회사 Method for manufacturing a contact hole of semiconductor device

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1277682A (en) * 1998-03-03 2000-12-20 硅谷化学实验室公司 Composition and method for removing resist and etching residues using hydroxylammonium carboxylates
CN1258730A (en) * 1998-12-31 2000-07-05 东进化成工业株式会社 Photoresist scavenger composition
WO2001096964A1 (en) * 2000-06-12 2001-12-20 Dongjin Semichem Co., Ltd. Photoresist remover composition

Also Published As

Publication number Publication date
TWI228640B (en) 2005-03-01
TW200424760A (en) 2004-11-16
CN1682155A (en) 2005-10-12
KR100862988B1 (en) 2008-10-13
KR20040028382A (en) 2004-04-03
AU2003265098A1 (en) 2004-04-19
WO2004029723A1 (en) 2004-04-08

Similar Documents

Publication Publication Date Title
JP2001523356A (en) Non-corrosive compositions for resist stripping and cleaning
KR100360985B1 (en) Resist stripper composition
JP2002523546A (en) Non-corrosive stripping and cleaning compositions
JPH09197681A (en) Resist peeling liquid composition
JP2004133153A (en) Cleaning liquid for photolithography and method for processing substrate
IL183648A (en) Non-aqueous, non-corrosive microelectronic cleaning compositions
JP2005043873A (en) Photoresist stripping liquid composition and method for stripping photoresist by using the same
WO2006019402A1 (en) Non-aqueous microelectronic cleaning compositions containing fructose
JP3929518B2 (en) Stripping composition for resist
JPH1184686A (en) Resist removing agent composition
KR100363271B1 (en) Photoresist remover composition
CN1682155B (en) Photoresist stripper composition
JP4698123B2 (en) Resist remover composition
CN1271475C (en) Resist remover composition
JP3742624B2 (en) Photoresist remover composition containing ammonium fluoride
JPH11251214A (en) Manufacture of tantalum thin-film circuit element
TW520470B (en) Photoresist remover composition
CN1248057C (en) Resist remover compsn.
KR20020019813A (en) Photoresist remover composition comprising ammonium fluoride

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20100526

CF01 Termination of patent right due to non-payment of annual fee