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WO2023040308A1 - 一种铜表面钝化组合物、其用途及包含其的光刻胶剥离液 - Google Patents

一种铜表面钝化组合物、其用途及包含其的光刻胶剥离液 Download PDF

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Publication number
WO2023040308A1
WO2023040308A1 PCT/CN2022/092986 CN2022092986W WO2023040308A1 WO 2023040308 A1 WO2023040308 A1 WO 2023040308A1 CN 2022092986 W CN2022092986 W CN 2022092986W WO 2023040308 A1 WO2023040308 A1 WO 2023040308A1
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Prior art keywords
copper
stripping solution
photoresist stripping
surface passivation
copper surface
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PCT/CN2022/092986
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English (en)
French (fr)
Inventor
侯军
申海艳
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浙江奥首材料科技有限公司
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Priority to EP22868686.1A priority Critical patent/EP4404000A1/en
Priority to US18/691,737 priority patent/US20250180997A1/en
Publication of WO2023040308A1 publication Critical patent/WO2023040308A1/zh

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/02—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using non-aqueous solutions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
    • C23C22/63—Treatment of copper or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C23G1/20—Other heavy metals
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
    • C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
    • C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
    • C23G5/032—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing oxygen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/003—3D structures, e.g. superposed patterned layers
    • 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
    • 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
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
    • H01L21/0274—Photolithographic processes
    • 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
    • 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
    • H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a compound composition used in the semiconductor preparation process and its use, in particular to a copper surface passivation composition used to passivate copper surfaces, its use and photoresist stripping comprising the composition Liquid belongs to the application field of microelectronic technology.
  • Metal copper has a very wide application in the semiconductor field, for example, it is used in the manufacturing process of the semiconductor front-end and the packaging process of the back-end.
  • the front-end process of IC manufacturing with the continuous advancement of the process, the feature size is continuously reduced, and the traditional Al/SiO 2 interconnection system can no longer meet the technical requirements.
  • IBM In order to reduce the interconnection RC delay, in 1997, IBM first adopted the dual damascene process of Cu wire interconnection. From below the 0.13 ⁇ m process node, copper has replaced aluminum as a new interconnect material. Compared with aluminum, copper has better conductivity, which can reduce resistance-capacitance delay, and can experience less electromigration, so it has better interconnection. Good results. Among them, copper electroplating plus chemical mechanical polishing (CMP) is an indispensable process in the preparation of multilayer copper interconnection wiring.
  • CMP chemical mechanical polishing
  • the pitch of the corresponding bumps is required to be continuously reduced.
  • (Cu pillar) as a semiconductor bump technology (bumping) came into being.
  • the original tin bump (Solder bump) can achieve the shortest pitch of 150 ⁇ m, while the copper pillar bump can achieve high-density packaging with the shortest pitch below 40 ⁇ m.
  • copper pillar bumps have better thermal performance and more electron mobility than tin bumps.
  • Copper pillar bumps have been widely used in various types of flip-chip interconnection processes, which can not only provide many design advantages, but also meet the current and future ROHS requirements. Copper pillar bumps are ideally suited for a variety of specific applications requiring a combination of fine pitch, RoHS/green compliance, low cost, and electromigration performance, such as transceivers, embedded processors, application processors, power management , baseband, ASIC and SOC, etc.
  • metal copper is widely used in the front and rear ends of the manufacture of microelectronic devices, and it is inevitable to contact chemical solutions (such as CMP, cleaning fluid, etc.) Corrosion of copper is caused, which in turn leads to a decrease in product yield.
  • CMP treatment there are many kinds of residues left on the semiconductor substrate. These residues can cause damage or severe corrosion to the copper wires, resulting in severe roughening of the metal wiring, and ultimately lead to poor electrical properties of the finished product.
  • CN101815811A discloses a composition for treating copper surfaces, wherein when a dithiocarbamate compound is used together with a chelating agent hydroxybenzene, the corrosion or etching rate of metallic copper is lower than that of using dithiocarbamate alone In the case of salt compounds or other chelating agents, that is, the dithiocarbamate compound and the chelating agent hydroxybenzene have a synergistic effect on the passivation of the copper surface.
  • US7923423A discloses an alkaline aqueous cleaning composition for use after a CMP process, the composition comprising at least one amine, at least one passivator, optionally at least one quaternary base, optionally at least one reducing agent, and water, the passivating agent is selected from a variety of triazole compounds, thiazole compounds, imidazole compounds, imidazolinone compounds, benzoic acid, tricresyl phosphate, ammonium benzoate, etc., which can reduce the Corrosion of metal wiring such as copper wires.
  • CN101874093A discloses a chemical mechanical polishing (CMP) method and composition for polishing copper-containing substrates, wherein the CMP composition comprises a granular abrasive, a copper complexing agent, a copper passivator and an aqueous carrier, the Copper passivators with acidic OH groups and additional oxygen substituents in a 1,6 relationship to the acidic OH groups can be, for example, N-acyl sarcosine compounds or salts thereof, in partially neutralized form.
  • CMP chemical mechanical polishing
  • CN102197124A discloses a cleaning composition and method for cleaning post-chemical mechanical polishing (CMP) residues and contaminants from microelectronic devices having the residues and contaminants thereon.
  • the cleaning composition includes a corrosion inhibitor.
  • the composition achieves efficient cleaning of post-CMP residues and contaminants on the surface of the microelectronic device without damaging low-k dielectric materials or copper interconnect materials, and the corrosion inhibitors include ribosyl purines and their methylation Or deoxy derivatives, degradation products of adenosine and adenosine derivatives, purine-sugar complexes, methylated or deoxypurine derivatives, and reaction or degradation products of these substances, which can achieve good corrosion inhibition of metallic copper.
  • CN104395989A discloses a method for removing residues and contaminants from microelectronic devices using a cleaning composition comprising at least one quaternary base, at least one amine, at least one corrosion inhibitor and at least one Solvents, said corrosion inhibitors comprising pyrazole, pyrazole derivatives, phosphoric acid, phosphoric acid derivatives, ascorbic acid, adenosine, adenosine derivatives and combinations thereof, the cleaning composition has good copper due to the corrosion inhibitor therein Corrosion inhibition effect.
  • CN1784487A discloses a cleaning composition for cleaning photoresists and residues on microelectronic substrates, which comprises a corrosion inhibiting compound with multiple hydroxyl functional groups, whose structure is T 1 -[(CR 1 R 2 ) m -(CR 3 R 4 ) n ] p -(CR 5 R 6 ) q -T 2 , wherein at least one of R 1 and R 2 is OH, if one of R 1 and R 2 is not OH, Then it is selected from H, alkyl and alkoxy, m is an integer of 1 or greater, R and R are selected from H, alkyl and alkoxy, n is a positive integer of 0 or greater, and p is 1 or greater integers; at least one of R and R is OH, and if one of R and R is not OH, it is selected from H, alkyl and alkoxy, and q is 1 or more Large integers; T and T are selected from H, alkyl, hydroxy
  • TW90115043A discloses a method for preparing semiconductor elements that prevent copper from corroding after chemical mechanical polishing, wherein a solution containing a corrosion inhibitor is used, and the corrosion inhibitor is selected from indazole, benzimidazole, mercaptobenzothiazole or imidazoline A group of thiones, which have good performance in preventing copper corrosion.
  • CN1575328A discloses a cleaning formulation after CMP, which can effectively remove residue after the resist ashing step, and will not corrode and possibly strip fine structures intended to remain on the wafer, which include fluoride sources, Organic amines, nitrogen-containing components selected from nitrogen-containing carboxylic acids and imines, water and metal chelating agents, wherein the nitrogen-containing carboxylic acids or imines can provide functional groups that can specifically bind to free copper atoms, so that in the residue-removal process Copper Specific Corrosion Inhibitor C which can be in contact with the copper surface will combine with the copper surface and form a protective layer to prevent the copper surface from being corroded by the cation A + and anion X - in the cleaning agent
  • CN105261554A discloses a copper corrosion inhibiting cleaning composition by using two chemicals: at least one polyfunctional amine having more than one amino group and at least one polyfunctional amine having more than one carboxylic acid group Corrosion inhibition is provided by a combination of acids selected from the group consisting of polyethyleneimine, triamine, pentamine, hexamine, and combinations thereof, and the polyfunctional acid selected from (i) dicarboxylic acids, aromatic Parts of dicarboxylic acids, and combinations thereof; (ii) tricarboxylic acids, tricarboxylic acids with aromatic moieties, and combinations thereof; and (iii) tetracarboxylic acids, tetracarboxylic acids with aromatic moieties, and combinations thereof, the The metal corrosion inhibiting cleaning composition is capable of effectively cleaning residues derived from ashing with an oxygen-containing plasma after high-density plasma etching, and slurry particles and residues remaining after chemical mechanical polishing (CMP), while for metals Copper has a very
  • CN112424327A discloses a cleaning composition for cleaning microelectronic device substrates in the process, the cleaning composition comprises water, an alkali for providing a pH of at least 8, cleaning compounds and selected guanidine functional group compounds, pyrazolone Corrosion inhibitors of functional compounds and hydroxyquinoline compounds, the cleaning composition can cause a higher degree of passivation of copper, thereby greatly reducing the corrosion of copper.
  • TW200745384A discloses a special cleaning agent for copper wiring with excellent corrosion inhibition effect (copper corrosion inhibition effect) of copper wiring, which contains copper corrosion inhibitor (RE) and water (W), and the pH at 25°C is 3 to 14, and satisfy the formula (1): 0.49 ⁇ E+0.059 ⁇ pH ⁇ 0.93, where E represents the redox potential (V) at 25°C, pH represents the pH at 25°C, and the copper
  • the corrosion inhibitor is at least one selected from free water-soluble reducing agents, complexing agents, namely quaternary ammonium hydroxide; the special cleaning agent can exert excellent copper corrosion inhibition effect, and can be used for semiconductor substrates with copper wiring patterns or in the manufacture of semiconductor components.
  • CN103228775A discloses a substrate cleaning agent for copper wiring, the cleaning agent can fully suppress the dissolution of metallic copper, and can remove copper hydroxide (II), copper oxide ( Impurities or particles such as II) are composed of an aqueous solution containing amino acids and alkylhydroxylamines, and the cleaning agent does not affect monovalent copper such as Cu(I)-BTA coatings and coatings of metal anti-corrosion agents (metal anti-corrosion coatings) On the other hand, it can remove divalent copper such as Cu(II)-QCA film and the film (metal anti-corrosion film layer) of the metal anti-corrosion agent, so it is suitable for cleaning the copper compound with the metal anti-corrosion film layer formed. wire or copper alloy wiring semiconductor substrate.
  • II copper hydroxide
  • Impurities or particles such as II are composed of an aqueous solution containing amino acids and alkylhydroxylamines
  • the cleaning agent does not affect monovalent copper such as Cu(I)-BTA coatings and coatings of
  • CN105143517A discloses a cleaning composition for the field of microelectronics, which comprises at least one solvent, at least one corrosion inhibitor, at least one amine, at least one quaternary base and at least one surfactant, wherein the The corrosion inhibitor comprises a substance selected from the group consisting of adenosine, adenine, methylated adenine, methylated adenine, adenosine derivatives (which are selected from 2-methoxyadenosine, N-methyladenosine , N,N-dimethyladenosine, trimethylated adenosine, trimethyl N-methyladenosine, C-4'-methyladenosine, 3-deoxyadenosine and combinations thereof), adenosine Degradation products, and their combinations, can reduce copper loss while improving cleaning efficiency, and can prevent redeposition of slurry particles, further improving the cleaning performance of various substrates of microelectronics.
  • CN102338994A discloses a cleaning solution suitable for cleaning thicker photoresists with low etchability, which contains potassium hydroxide, pyrrolidone solvents, pentaerythritol, alcohol amine and resorcinol, and this glue cleaning agent can be used to remove metal , photoresist and other residues on metal alloys or dielectric substrates, and has a low etching rate for metals such as Cu (copper), and has good application prospects in microelectronics such as semiconductor wafer cleaning.
  • CN109195720A discloses a stripping composition for removing photoresist from a semiconductor substrate, which comprises: (1) at least one water-soluble polar aprotic organic solvent; (2) at least one quaternary ammonium hydroxide; (3 ) at least one compound containing at least three hydroxyl groups; (4) at least one carboxylic acid; (5) at least one Group II metal cation; (6) selected from the group consisting of 6-substituted-2,4-diamino - at least one copper corrosion inhibitor from the group consisting of 1,3,5-triazines; and (7) water.
  • the composition can effectively strip positive or negative photoresists or photoresist residues, while bumps and underlying metallization materials (such as SnAg, CuNiSn, CuCoCu, CoSn, Ni, Cu, Al , W, Sn, Co, etc.) are non-corrosive.
  • bumps and underlying metallization materials such as SnAg, CuNiSn, CuCoCu, CoSn, Ni, Cu, Al , W, Sn, Co, etc.
  • CN101076760A discloses a non-aqueous cleaning composition for removing photoresist and residue from microelectronic substrates, said cleaning composition comprising: one or more polar organic solvents, one or A plurality of organic hydroxylated amines, and a corrosion inhibiting amount of one or more corrosion inhibitor polymers having a plurality of pendant functional groups on the polymer backbone, and wherein the pendant functional groups are selected from the group consisting of amino groups and hydroxyl groups , such as polyethyleneimine and poly(vinyl alcohol-co-ethylene), etc.
  • said cleaning composition is substantially non-corrosive to copper metallized microelectronic substrates and capable of removing photoinduced In addition to resist, plasma, and etch residues, the composition cleans aluminum metallized microelectronic substrates in a similarly non-corrosive manner.
  • CN103923765A discloses a cleaning agent composition for the process of manufacturing semiconductors and displays, which includes 0.01-3wt% amino acid chelating agent, 0.01-0.5wt% organic acid, 0.01-1.0wt% inorganic acid, 0.01-5wt% alkali compound and 0.01-98 wt% deionized DI water such that the composition is a water-based base with a pH of 8 to 13 and capable of removing particulate and organic contaminants while preventing reverse adsorption and copper corrosion, which Benzoic acid or benzotriazole corrosion inhibitors may further be included, and the composition has improved metal impurity removal and is capable of removing organic contaminants while inhibiting copper corrosion and reverse adsorption. By controlling the etch rate, it can be used for copper etching, residue removal and various other applications.
  • CN105022237A discloses a novel cleaning solution, which contains: a) quaternary amine hydroxide, (b) alcohol amine, (c) solvent and (d) sugar acid or sugar lactone, the cleaning solution contains sugar acid or sugar Acid lactone is the main metal corrosion inhibitor.
  • Sugar acid or sugar lactone can be used alone or in combination with star-shaped copolymers with pigment affinity groups, so that the cleaning solution can effectively remove the corrosion on the wafer.
  • the photoresist it can effectively protect the base material such as metal aluminum, copper, etc. from corrosion. After cleaning the wafer, it can be rinsed directly with water. Therefore, the cleaning solution has a good application prospect in microelectronic fields such as metal cleaning and semiconductor wafer cleaning.
  • CN107664930A discloses a photoresist cleaning solution for semiconductor wafers, which includes the following components in mass percent: quaternary ammonium hydroxide 32-36%, alcohol amine 14-18%, pentaerythritol 7-11%, six 6-8% of polyhydric alcohol, 0.1-1% of 3-amino-5-mercapto-1,2,4-triazole, 22-26% of surfactant, and the rest are auxiliary solvents.
  • this application helps to coordinate the photoresist removal ability and the anticorrosion of metal microspheres by selecting the ratio of suitable quaternary ammonium hydroxide/alcohol amine; It has strong corrosion inhibition ability; alcohol amine is used as solvent to dissolve potassium hydroxide and pentaerythritol, and its removal ability is strong.
  • CN108121175A discloses a fluorine-containing cleaning solution, which contains fluoride, organic amine, organic solvent, water, hydrazine and its derivatives.
  • the cleaning solution has strong cleaning ability and can effectively remove plasma etching residues in the semiconductor manufacturing process, especially It is the residue after ashing in the copper damascene process, and it has a small corrosion rate for non-metallic materials (such as silicon oxynitride and low dielectric materials) and metal materials (such as Cu) in high-speed single-chip cleaning.
  • the purpose of the present invention is to provide a safe, environmentally friendly, high-efficiency, especially copper passivation composition with a very low corrosion rate for copper, so as to reduce the corrosion of metal copper in the semiconductor manufacturing process and help improve production efficiency and product quality. Rate.
  • the composition can be used for the removal of photoresist in the bump process of semiconductor back-end packaging, so the application of the composition and a photoresist stripping solution comprising the composition are further provided, and the photoresist is also provided Preparation method and application of stripping liquid.
  • an object of the present invention is to provide a copper surface passivation composition, which includes 4-(2-pyridylazo) resorcinol (also known as “4- (2-pyridylazo)-1,3-resorcinol”) and glucosamine derivatives.
  • the mass ratio of 4-(2-pyridylazo)resorcinol to glucosamine derivatives is 1:1-5, for example, it can be 1:1, 1 :2, 1:3, 1:4 or 1:5.
  • the mass of 4-(2-pyridylazo)resorcinol and glucosamine derivative is 1:2-4, most preferably 1:3.
  • the glucosamine derivative is any one of D-glucosamine, N-acetyl-D-glucosamine, chitosan oligosaccharide or carboxymethyl chitosan One or any combination of multiple, most preferably N-acetyl-D-glucosamine.
  • an object of the present invention is to provide a photoresist stripping solution, in parts by mass, the photoresist stripping solution includes the following components:
  • the copper surface passivation composition is the above-mentioned copper surface passivation composition, which will not be repeated here.
  • the mass part of the copper surface passivation composition is 0.01-1 part, such as 0.01 part, 0.05 part, 0.1 part, 0.5 part or 1 part.
  • the water-soluble organic solvent has 60-90 parts by mass, for example, 60, 70, 80 or 90 parts.
  • the water-soluble organic solvent is any one or a combination of any of sulfones, sulfoxides, alcohol ethers, amides and pyrrolidones.
  • the sulfone is preferably sulfolane.
  • the sulfoxide is preferably dimethyl sulfoxide.
  • the alcohol ether is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, Any one or any combination of propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monobutyl ether.
  • the amide is N-methylformamide, N,N-dimethylformamide, N,N-dimethylacetamide, acetamide, N-formylethylamide or N,N-diethyl Any one or any combination of formamides.
  • the pyrrolidone is N-methylpyrrolidone or N-ethylpyrrolidone, or a combination of these two in any ratio.
  • the mass parts of the alkali are 2-40 parts, for example, 2 parts, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts or 40 parts.
  • the base is an organic base, more specifically, a quaternary ammonium hydroxide or an alkanolamine.
  • the quaternary ammonium hydroxide can be, for example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetra-n-butylammonium hydroxide, benzyltrimethylammonium hydroxide or hydrogen Any one or any combination of choline oxides.
  • the alkanolamine is monoethanolamine, diethanolamine, triethanolamine, N,N-dimethylethanolamine, N-ethylethanolamine, N-n-butylethanolamine, monoisopropanolamine, diisopropanol Any one or any combination of amines, triisopropanolamine or diglycolamine.
  • the mass parts of polyols are 5-30 parts, for example, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts or 30 parts.
  • the polyhydric alcohol is any one of ethylene glycol, diethylene glycol, 1,2-propanediol or 1,3-propanediol or any combination thereof.
  • the mass parts of deionized water is 1-10 parts, such as 1 part, 3 parts, 5 parts, 7 parts, 9 parts or 10 parts.
  • the deionized water can be added separately to form the photoresist stripping solution, and it can also be used in whole or in part as a solvent for other components (such as any water-soluble organic solvent, alkali or polyhydric alcohol) One or more are dissolved therein to form a solution, and when part serves as a solvent, the remaining part may be added separately rather than in the form of a solution) but added in the form of a solution.
  • a solvent for other components such as any water-soluble organic solvent, alkali or polyhydric alcohol
  • the third aspect of the present invention is to provide the preparation method of the photoresist stripping solution, the preparation method is as follows: Weigh the respective components in parts by mass, and then passivate the copper surface at room temperature The composition, the water-soluble organic solvent, the alkali and the polyhydric alcohol are added into the deionized water, and fully stirred and mixed evenly to obtain the uniform and transparent photoresist stripping solution.
  • another preparation method is specifically as follows: Weigh each component in parts by mass respectively, at room temperature, add a water-soluble organic solvent, alkali and polyhydric alcohol into deionized water to obtain a mixed solution, and then add the mixed solution to the mixture under stirring. Add the copper surface passivation composition into the mixed solution, and keep stirring until the mixture is uniform, and then the uniform and transparent photoresist stripping solution is obtained.
  • the fourth aspect of the present invention is to provide the use of the copper surface passivation composition for inhibiting copper corrosion.
  • the fifth aspect of the present invention is to provide the use of the copper surface passivation composition for preparing a photoresist stripping solution.
  • the sixth aspect of the present invention is to provide a method for cleaning photoresist residues on copper substrates.
  • the cleaning method is as follows: at 35-45°C, soak the copper substrate with photoresist in the photo In the resist stripping solution, or spray the photoresist stripping solution onto the copper substrate, the soaking or spraying time is 5-40 minutes, then rinse with ultrapure water, and then blow dry with high-purity nitrogen , that is, the cleaning process of the copper substrate is completed.
  • the soaking or spraying time is 5-40 minutes, such as 5 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes, 30 minutes, 35 minutes or 40 minutes.
  • the ultrapure water is deionized water with a resistance of at least 18 M ⁇ at 25°C.
  • the dosage of the ultrapure water is not particularly strictly limited, as long as the copper substrate can be fully and completely rinsed, those skilled in the art can select an appropriate dosage and determine the washing end point.
  • the high-purity nitrogen gas is nitrogen gas with a volume purity greater than 99.999%.
  • Both the ultrapure water and high-purity nitrogen can be purchased through commercial channels, and will not be described in detail here.
  • the present invention provides a copper surface passivation composition, its use, a photoresist stripping solution containing it, a preparation method and use of the stripping solution, and a copper substrate cleaning method using the stripping solution, etc. , these technical solutions have the following advantages:
  • the copper surface passivation composition has very excellent copper corrosion inhibition performance and a very low copper corrosion rate, so it can be used in the bumping process of copper wiring or copper pillar bumps.
  • the photoresist stripping solution containing the copper surface has excellent photoresist stripping performance, and also has excellent low copper corrosion rate, and can be used for photoresist removal in the bump process of semiconductor back-end packaging.
  • the photoresist stripping solution After the photoresist stripping solution is cleaned, it can be simply processed such as washing with pure water and blowing dry with nitrogen, without using organic solvents to wash, which can greatly reduce the pollution to the environment and avoid a large amount of waste liquid
  • the production has good environmental protection.
  • Accompanying drawing 3 is a magnified scanning electron microscope picture of a single copper pillar bump in accompanying drawing 2, wherein the magnification is 2780 times.
  • the rectangular frame in Figures 3-6 shows the side wall of the copper pillar
  • the rectangular frame in Figures 7-8 shows the bottom area of the copper pillar.
  • each component used in step 2 in each embodiment or comparative example is the corresponding component weighed in corresponding step 1.
  • Embodiment 1 Preparation of photoresist stripping solution
  • Step 1 Weigh the following components by mass respectively: 0.5 parts of copper surface passivation composition (4-(2-pyridylazo) resorcinol and N-acetyl-D - a mixture of glucosamine), 75 parts of water-soluble organic solvent diethylene glycol monoethyl ether, 21 parts of base N-ethylethanolamine, 17.5 parts of polyol 1,3-propylene glycol and 5.5 parts of deionized water;
  • Step 2 Add the copper surface passivation composition, water-soluble organic solvent, alkali and polyhydric alcohol into deionized water at room temperature, and fully stir and mix evenly to obtain a uniform and transparent photoresist stripping solution. Name it G1.
  • Embodiment 2 Preparation of photoresist stripping solution
  • Step 1 Weigh the following components by mass respectively: 1 part of copper surface passivation composition (4-(2-pyridylazo) resorcinol and N-acetyl-D - a mixture of glucosamine), 60 parts of water-soluble organic solvent dimethylsulfoxide, 40 parts of base benzyltrimethylammonium hydroxide, 5 parts of polyol diethylene glycol and 10 parts of deionized water;
  • Step 2 Add water-soluble organic solvent, alkali and polyol to deionized water at room temperature to obtain a mixed solution, then add the copper surface passivation composition to the mixed solution under stirring, and fully stir and mix evenly , to obtain a uniform and transparent photoresist stripping solution, which is named G2.
  • Embodiment 3 Preparation of photoresist stripping solution
  • Step 1 Weigh the following components by mass respectively: 0.01 part of copper surface passivation composition (4-(2-pyridylazo) resorcinol and N-acetyl-D - a mixture of glucosamine), 90 parts of water-soluble organic solvent sulfolane, 2 parts of alkali tetramethylammonium hydroxide, 30 parts of polyol ethylene glycol and 1 part of deionized water;
  • Step 2 Add the copper surface passivation composition, water-soluble organic solvent, alkali and polyhydric alcohol into deionized water at room temperature, and fully stir and mix evenly to obtain a uniform and transparent photoresist stripping solution. Named G3.
  • Embodiment 4-5 Preparation of photoresist stripping solution
  • Embodiment 4 except that the water-soluble organic solvent diethylene glycol monoethyl ether of embodiment 1 is replaced by N-methylformamide of equal parts, base N-ethylethanolamine is replaced by diisopropanolamine of equal parts Except that, other operations were unchanged, and the obtained photoresist stripping solution was named G4.
  • Embodiment 5 In addition to replacing the water-soluble organic solvent dimethyl sulfoxide of embodiment 2 with N-methylpyrrolidone of equal parts, the base benzyltrimethylammonium hydroxide is replaced with diglycolamine of equal parts Except that, other operations were unchanged, and the obtained photoresist stripping solution was named G5.
  • Embodiment 6-8 Preparation of photoresist stripping solution
  • Embodiment 9-12 Preparation of photoresist stripping solution
  • the copper pillar bump manufacturing process After the copper pillar bump (Cu pillar) is electroplated, it is necessary to clean and remove the photoresist.
  • the specific cleaning method is as follows: at 40 ° C, the copper with photoresist The substrate is directly immersed in each photoresist stripping solution obtained above, or each photoresist stripping solution is sprayed onto the copper substrate, and the soaking or spraying time is 30 minutes, and then ultrapure water (25° C. The lower resistance is at least 18M ⁇ ), and then blown dry with high-purity nitrogen gas (volume purity greater than 99.999%) to complete the cleaning treatment of the copper substrate.
  • the copper pillar bump after cleaning with photoresist stripping solution G1 has no photoresist residue on the surface of the copper pillar side wall, indicating that the cleaning effect of G1 is very good; and the copper pillar side wall The surface is smooth without any corrosion, and the copper surface passivation protection effect is excellent.
  • the scanning electron microscope pictures can be used to accurately and qualitatively judge the passivation protection ability of different photoresist stripping solutions on Cu, among which G1-G5 have very excellent passivation protection ability of copper surface, and when the When the copper surface passivation composition is changed to a single component, the passivation ability is significantly reduced (but the effect of the single component 4-(2-pyridylazo) resorcinol is better than that of the single component N-acetyl base-D-glucosamine), and when the copper surface passivation composition of the present invention is not used, then there is the most severe copper surface corrosion, which proves that only the copper surface passivation composition as defined in the present invention can be used to obtain The best technical effect should be due to the good compound synergistic effect between 4-(2-pyridylazo)resorcinol and N-acetyl-D-glucosamine.
  • the -OH and -NH 2 containing lone electron pairs can be combined with the Cu surface, so that the molecule can be stably adsorbed and fixed on the Cu surface, thereby preventing Cu from being eroded by the outside world, while N-acetyl-D-glucosamine Then it can be adsorbed on the surface of Cu through -OH.
  • the synergistic effect of the combination of the two may be due to the fact that when these two compounds are simultaneously adsorbed on the Cu surface in a certain ratio, the Cu surface can achieve the highest molecular adsorption amount (due to the adsorption sites of different molecules). There are differences, molecules with different structures can form a denser adsorption film when they act together), so as to obtain the best Cu protection effect, the inventor will conduct further in-depth research on this.
  • the photoresist stripping solution has a one-to-one correspondence with the Cu corrosion rate.
  • the Cu corrosion rate is "0.11/0.17/0.13/0.12/0.13", which means the corrosion rate of G1, G2, G3, G4 and G5 They are 0.11, 0.17, 0.13, 0.12 and 0.13 respectively.
  • Other photoresist strippers and Cu etching rates also have the same corresponding relationship, which will not be described one by one here.
  • the photoresist stripping solution G1-G5 of the present invention has an excellent copper surface passivation protection function, and its corrosion rate is very low, and when changing the glucosamine derivative therein, it is found that the copper corrosion rate is reduced.
  • the present invention provides a copper surface passivation composition and its use, a photoresist stripping solution comprising the copper surface passivation composition, a preparation method of the photoresist stripping solution and its use, and the use of the stripping solution.
  • the cleaning method of the copper substrate of the liquid, the copper surface passivation composition uses the use of the two-component compound, the selection of the preferred component and the optimal selection of the dosage, thereby achieving excellent technical effects, so that the photoresist
  • the stripping solution also has an excellent copper passivation protection effect, so it can be used for photoresist removal and copper surface protection in the convex process of semiconductor back-end packaging, and has a good industrial application in the field of microelectronics technology. Application prospect and promotion potential.

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Abstract

本发明涉及一种铜表面钝化组合物，其包括4-(2-吡啶偶氮)间苯二酚和氨基葡萄糖衍生物，还涉及包含其的光刻胶剥离液和一种铜基板的清洗方法，所述铜表面钝化组合物具有良好的铜钝化保护性能，从而可用于半导体后道封装的凸块工艺中的光刻胶去除和铜表面钝化保护，在微电子技术领域具有良好的工业应用前景和推广潜力。

Description

一种铜表面钝化组合物、其用途及包含其的光刻胶剥离液
相关申请的交叉参考
该申请要求2021年09月14日提交的中国专利申请号为202111076657.2的专利申请的优先权，该专利申请在此被完全引入作为参考。
技术领域
本发明涉及一种用于半导体制备工序的复配组合物及其用途，特别地涉及一种用于钝化铜表面的铜表面钝化组合物、其用途及包含该组合物的光刻胶剥离液，属于微电子技术应用领域。
背景技术
金属铜(Cu)在半导体领域有着非常广泛的应用，例如应用于半导体前道的制造工序和后道的封装工序中。在IC制造的前端工艺中，随着工艺制程不断推进，而导致特征尺寸不断减小，传统的Al/SiO 2互连线系统已无法满足技术要求。为了降低互联RC延迟，1997年IBM公司首次采用了Cu线互连的双镶嵌大马士革工艺。从0.13μm工艺节点以下，铜便代替了铝成为新的互连材料，相较于铝，铜有着更好的导电率，可降低阻容延时，能更少地经历电迁移，从而具有更好的效果。其中铜电镀加化学机械抛光(CMP)是实现多层铜互连布线制备中的必不可少的工艺。
而在后端封装工序中，随着输入/输出(I/O)密度急速增加，相应要求凸块的节距(pitch)不断缩减，顺应微细节距(fine pitch)的要求，铜柱凸块(Cu pillar)作为半导体凸块的凸块技术(bumping)便应运而生。原有的锡凸块(Solder bump)可实现的最短节距为150μm，而铜柱凸块可实现最短节距低于40μm的高密度封装。不仅如此，与锡凸块相比，铜柱凸块的散热性能更好，且电子移动性更强。
也正是因为铜柱凸块具有的上述优点，目前已被广泛运用于多种类型的倒装芯片互连工艺中，其既能提供众多设计优势，且又满足了当前和未来的ROHS要求。铜柱凸块能够完美适用于各种需要小节距、RoHS/绿色合规、低成本和电迁移性能组合的多个具体应用应用中，例如收发器、嵌入式处理器、应用处理器、功率管理、基带、ASIC和SOC等。
如上所述，金属铜在微电子器件的制造前后端中均有着广泛的应用，而在这些前后端的生产制造过程中均不可避免地需要接触化学溶液(例如CMP、清洗液等等)，进而可导致铜的腐蚀，该腐蚀又导致产品良率的下降。此外，经过CMP处理后在半导体基片上都残留有多 种残留物，这些残留物可对铜线造成损伤或严重腐蚀，从而导致金属布线的严重糙化，最终导致成品电性能欠佳。
因此，为了克服该腐蚀、提升产品良率，对金属铜表面的钝化处理是非常必要的，科研工作者也对此进行了大量的深入研究，以降低对金属铜的腐蚀，例如：
CN101815811A公开了一种用来处理铜表面的组合物，其中二硫代氨基甲酸盐化合物与螯合剂羟基苯共同使用时，金属铜的腐蚀或蚀刻速率要低于单独使用二硫代氨基甲酸盐化合物或与其它螯合剂搭配时的情况，即二硫代氨基甲酸盐化合物与螯合剂羟基苯对铜表面的钝化起到了协同作用。
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CN112424327A公开了一种用于清洗工艺内微电子装置衬底的清洗组合物，所述清洗组合物包含水、用来提供至少为8的pH的碱、清洗化合物以及选择胍官能团化合物、吡唑酮官能化合物和羟基喹啉化合物的腐蚀抑制剂，该清洗组合物能够引起较高程度的铜钝化，从而极大降低了对铜的腐蚀。
TW200745384A公开了一种铜配线的腐蚀抑制效果(铜腐蚀抑制效果)优良的铜配线专用清洗剂，其含有铜腐蚀抑制剂(RE)和水(W)，且在25℃下的pH为3～14，并且满足式(1)：0.49≦{E+0.059×pH}≦0.93，式中，E表示25℃下的氧化还原电位(V)，pH表示25℃下的pH，所述铜腐蚀抑制剂为选自自由水溶性还原剂、络合剂即氢氧化季铵中的至少一种；所述专用清洗剂能够发挥优良的铜腐蚀抑制效果，可用于具有铜配线图案的半导体基板或半导体元件的制造中。
CN103228775A公开了一种铜配线用基板清洗剂，所述清洗剂可以充分地抑制金属铜的 溶出、且可以除去在化学机械抛光(CMP)工序中产生的氢氧化铜(II)、氧化铜(II)等杂质或颗粒，其由含有氨基酸和烷基羟胺的水溶液构成，该清洗剂不会对Cu(I)-BTA被膜等1价的铜与金属防腐蚀剂的被膜(金属防腐蚀膜层)造成不良影响，另一方面可以除去Cu(II)-QCA被膜等2价的铜与金属防腐蚀剂的被膜(金属防腐蚀膜层)，因此是适合于清洗形成了金属防腐蚀膜层的铜配线或铜合金配线半导体基板。
CN105143517A公开了一种用于微电子领域的清洁组合物，其包含至少一种溶剂、至少一种腐蚀抑制剂、至少一种胺、至少一种季碱和至少一种表面活性剂，其中所述腐蚀抑制剂包含选自以下的物质：腺苷、腺嘌呤、甲基化腺嘌呤、甲基化腺嘌呤、腺苷衍生物(其选自2-甲氧基腺苷、N-甲基腺苷、N,N-二甲基腺苷、三甲基化腺苷、三甲基N-甲基腺苷、C-4’-甲基腺苷、3-脱氧腺苷及其组合)、腺苷降解产物，及它们的组合，其能够减少铜损失并同时提高清洁效率，并能阻止浆料粒子的重新沉积，进一步提高了微电子各种基板的清洁性能。
CN102338994A公开了一种低蚀刻性的适用于较厚光刻胶清洗的清洗液，其包含氢氧化钾、吡咯烷酮类溶剂、季戊四醇、醇胺和间苯二酚，该胶清洗剂可以用于除去金属、金属合金或电介质基材上的光刻胶和其它残留物，同时对于Cu(铜)等金属具有较低的蚀刻速率，在半导体晶片清洗等微电子领域具有良好的应用前景。
CN109195720A公开了一种从半导体基板上去除光刻胶的剥离组合物，其包含：(1)至少一种水溶性极性非质子性有机溶剂；(2)至少一种氢氧化季铵；(3)至少一种含有至少三个羟基基团的化合物；(4)至少一种羧酸；(5)至少一种第Ⅱ族金属阳离子；(6)选自由6-取代-2,4-二氨基-1,3,5-三嗪所构成的群组的至少一种铜腐蚀抑制剂；以及(7)水。所述组合物能有效地剥离正或负型光刻胶或光刻胶残余物，而对半导体基板上的凸块及底层金属化材料(诸如SnAg、CuNiSn、CuCoCu、CoSn、Ni、Cu、Al、W、Sn、Co等)是非腐蚀性的。
CN101076760A公开了一种非水清洁组合物，其用于从微电子衬底上清除光致抗蚀剂和残余物，所述清洁组合物包括：一种或多种极性有机溶剂，一种或多种有机羟基化胺，和抑制腐蚀量的一种或多种腐蚀抑制剂聚合物，该聚合物在聚合物主链上具有多个官能团侧基，且其中该官能团侧基选自氨基和羟基，例如可为聚乙烯亚胺和聚(乙烯醇-共聚-乙烯)等，所述清洁组合物除了基本上对铜金属化的微电子衬底无腐蚀性并能够从该衬底上清除光致抗蚀剂、等离子体和蚀刻残余物之外，该组合物还能以类似的无腐蚀性方式清洁铝金属化的微电子衬底。
CN103923765A公开了一种用于制造半导体和显示器的工艺的清洁剂组合物，其包括0.01-3wt％氨基酸螯合剂、0.01-0.5wt％有机酸、0.01-1.0wt％无机酸、0.01-5wt％碱化合物和0.01-98wt％去离子DI水，从而使得所述组合物是pH为8到13的、基于水的碱且能在 防止反向吸附和铜腐蚀的同时移除颗粒和有机污染物，其还可进一步包括苯甲酸或苯并三唑腐蚀抑制剂，该组合物具有改良的金属杂质移除能力且能在抑制铜腐蚀和反向吸附的同时移除有机污染物。通过控制蚀刻速率，能用于铜蚀刻、残余物移除和各种其它应用。
CN105022237A公开了一种新型清洗液，其含有：a)季胺氢氧化物、(b)醇胺、(c)溶剂和(d)糖酸或糖酸内酯，该清洗液含有糖酸或糖酸内酯作为主要的金属腐蚀抑制剂，糖酸或糖酸内酯可单独使用，也可以与具有颜料亲和基团的星状共聚物复配使用，使得该清洗液在有效去除晶圆上的光刻胶的同时，能有效的保护基材如金属铝、铜等基本无腐蚀，在对晶圆清洗后可以用水直接漂洗。因此该清洗液在金属清洗和半导体晶片清洗等微电子领域具有良好的应用前景。
CN107664930A公开了一种用于半导体晶圆的光刻胶清洗液，其包括以下质量百分比的组份：季铵氢氧化物32-36％、醇胺14-18％、季戊四醇7-11％、六元醇6-8％、3-氨基-5-巯基-1，2，4-三氮唑0.1-1％、表面活性剂22-26％，其余为助溶剂。与现有技术相比，该申请通过选用合适的季铵氢氧化物/醇胺的比例有利于协调光刻胶去除能力和金属微球的防腐蚀；采用了六元醇对金属铝和铜同时具有较强的腐蚀抑制能力；采用了醇胺作为溶剂溶解氢氧化钾和季戊四醇，去除能力强。
CN108121175A公开了一种含氟清洗液，其含有氟化物、有机胺、有机溶剂、水和肼及其衍生物，该清洗液清洗能力强，可有效去除半导体制程过程中等离子刻蚀残留物，尤其是在铜大马士革工艺中灰化后的残留物，并且在高转速单片机清洗中对非金属材料(如氮氧化硅和低介质材料)和金属材料(如Cu)等有较小的腐蚀速率，适用于批量浸泡式、批量旋转喷雾式清洗方式，尤其适用于高转速单片旋转式的清洗方式，克服了传统清洗液铜腐蚀抑制的缺陷，在半导体晶片清洗等微电子领域具有良好的应用前景。
如上所述，现有技术中已经公开了多种用于降低铜腐蚀的半导体生产不同阶段中的助剂溶液，但对于新型的铜钝化组合物仍存在继续研究的需求和必要，也正是在如此的行业需求和行业研发的内在动力驱动之下，本发明得以完成。
发明内容
本发明的目的在于提供一种安全、环保、高效，尤其是对铜具有非常低腐蚀速率的铜钝化组合物，以减轻半导体制造过程中金属铜的腐蚀，有助于提高生产效率和产品良率。该组合物可用于半导体后道封装的凸块工艺中光刻胶的去除，因此进一步提供了该组合物的用途及包含该组合物的一种光刻胶剥离液，还提供了该光刻胶剥离液的制备方法和应用。涉及上述的组合物、用途、光刻胶剥离液及其制备方法和应用的多个技术方案在半导体技术领域具有潜在的巨大应用前景和潜力。
需要注意的是，在本发明中，除非另有规定，涉及组成限定和描述的“包括”的具体含义，既包含了开放式的“包括”、“包含”等及其类似含义，也包含了封闭式的“由…组成”等及其类似含义。
第一个方面，本发明的一个目的在于提供一种铜表面钝化组合物，所述铜表面钝化组合物包括4-(2-吡啶偶氮)间苯二酚(也称为“4-(2-吡啶偶氮)-1,3-间苯二酚”)和氨基葡萄糖衍生物。
在所述铜表面钝化组合物中，优选的，4-(2-吡啶偶氮)间苯二酚与氨基葡萄糖衍生物的质量比为1:1-5，例如可为1:1、1:2、1:3、1:4或1:5。
在所述铜表面钝化组合物中，更优选的，4-(2-吡啶偶氮)间苯二酚与氨基葡萄糖衍生物的质量为1:2-4，最优选为1:3。
在所述铜表面钝化组合物中，优选的，所述氨基葡萄糖衍生物为D-氨基葡萄糖、N-乙酰基-D-氨基葡萄糖、壳寡糖或羧甲基壳聚糖中的任意一种或任意多种的组合，最优选为N-乙酰基-D-氨基葡萄糖。
第二个方面，本发明的一个目的在于提供一种光刻胶剥离液，以质量份计，所述光刻胶剥离液包括如下组分：
Figure PCTCN2022092986-appb-000001
在所述光刻胶剥离液中，铜表面钝化组合物即为上述的铜表面钝化组合物，在此不再进行赘述。
其中，所述铜表面钝化组合物的质量份为0.01-1份，例如可为为0.01份、0.05份、0.1份、0.5份或1份。
在所述光刻胶剥离液中，水溶性有机溶剂的质量份为60-90份，例如可为60份、70份、80份或90份。
其中，所述水溶性有机溶剂为砜、亚砜、醇醚、酰胺和吡咯烷酮中的任意一种或任意多种的组合。
其中，所述砜优选为环丁砜。
其中，所述亚砜优选二甲基亚砜。
其中，所述醇醚为乙二醇单甲醚、乙二醇单乙醚、乙二醇单丁醚、二乙二醇单甲醚、二乙二醇单乙醚、二乙二醇单丁醚、丙二醇单甲醚、丙二醇单乙醚、丙二醇单丁醚中的任意一种或任意多种的组合。
其中，所述酰胺为N-甲基甲酰胺、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、乙酰胺、N-甲酰乙胺或N,N-二乙基甲酰胺中的任意一种或任意多种的组合。
其中，所述吡咯烷酮为N-甲基吡咯烷酮或N-乙基吡咯烷酮，或者为这两种的任意比例的组合。
在所述光刻胶剥离液中，碱的质量份为2-40份，例如可为2份、5份、10份、15份、20份、25份、30份、35份或40份。
其中，所述碱为有机碱，更具体地，为季铵盐氢氧化物或链烷醇胺。
其中，所述季铵氢氧化物例如可为四甲基氢氧化铵、四乙基氢氧化铵、四正丙基氢氧化铵、四正丁基氢氧化铵、苄基三甲基氢氧化铵或氢氧化胆碱中的任意一种或任意多种的组合。
其中，所述链烷醇胺为单乙醇胺、二乙醇胺、三乙醇胺、N,N-二甲基乙醇胺、N-乙基乙醇胺、N-正丁基乙醇胺、单异丙醇胺、二异丙醇胺、三异丙醇胺或二甘醇胺中的任意一种或任意多种的组合。
在所述光刻胶剥离液中，多元醇的质量份为5-30份，例如可为5份、10份、15份、20份、25份或30份。
其中，所述多元醇为乙二醇、二乙二醇、1,2-丙二醇或1,3-丙二醇的任意一种或任意多种的组合。
在所述光刻胶剥离液中，去离子水的质量份为1-10份，例如可为1份、3份、5份、7份、9份或10份。
需要注意的是，所述去离子水可单独加入以形成该光刻胶剥离液，也可将其全部或部分作为其它组分的溶剂(如将水溶性有机溶剂、碱或多元醇中的任意一种或多种溶于其中形成溶液，当部分作为溶剂时，剩余部分可单独加入而非以溶液的形式加入)而以溶液的形式加入。
本发明的第三个方面，在于提供所述光刻胶剥离液的制备方法，所述制备方法具体如下：分别称取各自质量份的各个组份，然后在室温下将所述铜表面钝化组合物、水溶性有机溶剂、碱和多元醇加入到去离子水中，并充分搅拌混合均匀，即得均匀透明的所述光刻胶剥离液。
或者，另一种制备方法具体如下：分别称取各自质量份的各个组份，室温下，将水溶性有机溶剂、碱和多元醇加入到去离子水中，得到混合溶液，然后在搅拌下向所述混合溶液中 加入铜表面钝化组合物，并持续搅拌至混合均匀，即得均匀透明的所述光刻胶剥离液。
发明人发现，当所述光刻胶剥离液中包含所述铜表面钝化组合物时，能够在取得优异光刻胶剥离效果的同时，具有非常优异的铜低腐蚀速率性能。
因此，本发明的第四个方面，在于提供所述铜表面钝化组合物用于抑制铜腐蚀的用途。
也因此，本发明的第五个方面，在于提供所述铜表面钝化组合物用于制备光刻胶剥离液的用途。
本发明的第六个方面，在于提供一种铜基板光刻胶残留物的清洗方法，所述清洗方法具体如下：在35-45℃下，将带光刻胶的铜基板浸泡在所述光刻胶剥离液中，或将所述光刻胶剥离液喷淋到所述铜基板上，浸泡或喷淋的时间为5-40分钟，继而使用超纯水冲洗，再用高纯氮气吹干，即完成铜基板的清洗处理。
在所述清洗方法中，所述浸泡或喷淋的时间为5-40分钟，例如可为5分钟、10分钟、15分钟、20分钟、25分钟、30分钟、35分钟或40分钟。
在所述清洗方法中，所述超纯水为25℃下电阻至少为18MΩ的去离子水。
其中，所述超纯水的用量并未特别的严格限定，只要能够将铜基板充分冲洗彻底、完全即可，本领域技术人员可进行合适的用量选择和确定冲洗终点。
在所述清洗方法中，所述高纯氮气即体积纯度大于99.999％的氮气。
所述超纯水和高纯氮气都可通过商业渠道购买获得，在此不再进行详细描述。
如上所述，本发明提供了一种铜表面钝化组合物、其用途，以及包含其的光刻胶剥离液和该剥离液的制备方法及用途，以及使用该剥离液的铜基板清洗方法等，这些技术方案具有如下优点：
1、该铜表面钝化组合物具有非常优异的抑制铜腐蚀性能，具有非常低的铜腐蚀速率，从而可以用于铜配线或铜柱凸块的凸块工艺中。
2、包含该铜表面的光刻胶剥离液在具有优异的光刻胶剥离性能之外，也具有优异的低铜腐蚀速率，可用于半导体后道封装的凸块工艺中的光刻胶去除。
3、所述光刻胶剥离液在清洗完毕后，仅仅通过简单的处理如纯水冲洗、氮气吹干即可，而无需使用有机溶剂冲洗，可大大降低对环境的污染，避免了大量废液的产生，具有良好的环保性。
4、对清洗工艺并无特殊要求，也无需超声处理，仅经过浸泡或喷淋即可除去铜基板上的各种杂质，去污效果彻底，无污染物残留。
附图说明
附图1是未去胶的铜柱凸块的扫描电镜图片，其中，放大倍数为500倍。
附图2是使用光刻胶剥离液G1清洗后的铜柱凸块的扫描电镜图片，其中，放大倍数为250倍。
附图3是附图2中单个铜柱凸块的放大扫描电镜图片，其中，放大倍数为2780倍。
附图4是使用光刻胶剥离液D1清洗后的铜柱凸块的扫描电镜图片，其中，放大倍数为2800倍。
附图5是使用光刻胶剥离液D6清洗后的铜柱凸块的扫描电镜图片，其中，放大倍数为2800倍。
附图6是使用光刻胶剥离液D11清洗后的铜柱凸块扫描电镜图片，其中，放大倍数为2800倍。
附图7为附图3的铜柱凸块的底部区域的局部放大扫描电镜图片，其中，放大倍数为10000倍。
附图8为附图4的铜柱凸块的底部区域的局部放大扫描电镜图片，其中，放大倍数为10000倍。
其中，附图3-6中矩形框示出的为铜柱侧壁，而附图7-8中矩形框示出的即为铜柱底部区域。
具体实施方式
下面通过具体的实施例对本发明进行详细说明，但这些例举性实施方式的用途和目的仅用来例举本发明，并非对本发明的实际保护范围构成任何形式的任何限定，更非将本发明的保护范围局限于此。
其中，除非另有规定，否则各个实施例或对比例中步骤2所使用的各个组份均为相应步骤1中称取的相应组份。
实施例1：光刻胶剥离液的制备
步骤1：分别称取如下质量份的各个组份：0.5份铜表面钝化组合物(为质量比1:3的4-(2-吡啶偶氮)间苯二酚与N-乙酰基-D-氨基葡萄糖的混合物)、75份水溶性有机溶剂二乙二醇单乙醚、21份碱N-乙基乙醇胺、17.5份多元醇1,3-丙二醇和5.5份去离子水；
步骤2：在室温下将所述铜表面钝化组合物、水溶性有机溶剂、碱和多元醇加入到去离子水中，并充分搅拌混合均匀，即得均匀透明的光刻胶剥离液，将其命名为G1。
实施例2：光刻胶剥离液的制备
步骤1：分别称取如下质量份的各个组份：1份铜表面钝化组合物(为质量比1:3的4-(2-吡啶偶氮)间苯二酚与N-乙酰基-D-氨基葡萄糖的混合物)、60份水溶性有机溶剂二甲基亚砜、40份碱苄基三甲基氢氧化铵、5份多元醇二乙二醇和10份去离子水；
步骤2：在室温下，将水溶性有机溶剂、碱和多元醇加入到去离子水中，得到混合溶液，然后在搅拌下向所述混合溶液中加入铜表面钝化组合物，并充分搅拌混合均匀，即得均匀透明的光刻胶剥离液，将其命名为G2。
实施例3：光刻胶剥离液的制备
步骤1：分别称取如下质量份的各个组份：0.01份铜表面钝化组合物(为质量比1:3的4-(2-吡啶偶氮)间苯二酚与N-乙酰基-D-氨基葡萄糖的混合物)、90份水溶性有机溶剂环丁砜、2份碱四甲基氢氧化铵、30份多元醇乙二醇和1份去离子水；
步骤2：在室温下将所述铜表面钝化组合物、水溶性有机溶剂、碱和多元醇加入到去离子水中，并充分搅拌混合均匀，即得均匀透明的光刻胶剥离液，将其命名为G3。
实施例4-5：光刻胶剥离液的制备
实施例4：除将实施例1的水溶性有机溶剂二乙二醇单乙醚替换为等质量份的N-甲基甲酰胺、碱N-乙基乙醇胺替换为等质量份的二异丙醇胺外，其它操作均不变，将得到的光刻胶剥离液命名为G4。
实施例5：除将实施例2的水溶性有机溶剂二甲基亚砜替换为等质量份的N-甲基吡咯烷酮、碱苄基三甲基氢氧化铵替换为等质量份的二甘醇胺外，其它操作均不变，将得到的光刻胶剥离液命名为G5。
实施例6-8：光刻胶剥离液的制备
除分别将实施例1-3中的N-乙酰基-D-氨基葡萄糖依次替换为D-氨基葡萄糖、壳寡糖和羧甲基壳聚糖外，其它操作均不变，将得到的光刻胶剥离液顺次命名为G6、G7和G8。
实施例9-12：光刻胶剥离液的制备
除分别将实施例1中4-(2-吡啶偶氮)间苯二酚与N-乙酰基-D-氨基葡萄糖的质量比由1:3依次改变为1:2、1:4、1:1和1:5外，其它操作均不变，将得到的光刻胶剥离液顺次命名为G9、G10、G11和G12。
对比例1-5：光刻胶剥离液的制备
除分别将实施例1-5中铜表面钝化组合物替换为相同质量份的单一组份4-(2-吡啶偶氮)间苯二酚外，其它操作均不变，将得到的光刻胶剥离液顺次命名为D1、D2、D3、D4和D5。
对比例6-10：光刻胶剥离液的制备
除分别将实施例1-5中铜表面钝化组合物替换为相同质量份的单一组份N-乙酰基-D-氨基葡萄糖外，其它操作均不变，将得到的光刻胶剥离液顺次命名为D6、D7、D8、D9和D10。
对比例11-15：光刻胶剥离液的制备
除分别将实施例1-5中铜表面钝化组合物予以省略外，其它操作均不变，将得到的光刻 胶剥离液顺次命名为D11、D12、D13、D14和D15。
各个光刻胶剥离液的清洗性能测试
在铜柱凸块制造工艺中，当完成铜柱凸块(Cu pillar)的电镀后，需要进行光刻胶的清洗去除，具体清洗方法如下：在40℃下，分别将带光刻胶的铜基板直接浸泡在上述得到的各个光刻胶剥离液中，或将各个光刻胶剥离液喷淋到所述铜基板上，浸泡或喷淋的时间为30分钟，继而使用超纯水(25℃下电阻至少为18MΩ)冲洗，再用高纯氮气(体积纯度大于99.999％)吹干，即完成铜基板的清洗处理。
各个光刻胶剥离液的清洗与铜表面钝化结果的定性分析
1、如附图1所示，为铜柱凸块的电镀工艺完成后，光刻胶清洗前。其中，凸块的高度低于光刻胶的高度。
2、如附图2所示，使用光刻胶剥离液G1清洗后的凸块表面无任何残留，光刻胶清除彻底、完全。
3、如附图3所示，使用光刻胶剥离液G1清洗后的铜柱凸块，铜柱侧壁表面无任何光刻胶残留物，说明G1的清洗效果非常优异；且铜柱侧壁表面光滑，无任何腐蚀，铜表面钝化保护效果优异。
同时也可看出，其铜柱底部区域未被腐蚀。
而G2-G5的清洗后放大图片的效果完全相同于附图2，故不再一一列出。
G6-G8和G9-G12的清洗后放大图片类似于附图2，但铜柱侧壁底部区域均有非常轻微的腐蚀(但无法从放大图片中清晰看出，故在随后的铜腐蚀速率测试中进行数据定量)，这证明铜表面钝化组合物中，4-(2-吡啶偶氮)间苯二酚与N-乙酰基-D-氨基葡萄糖的质量比最优选为1:3，但1:1-5的整个范围仍具有优异的铜表面钝化保护功效，仍可用于后续工序的继续加工。
4、如附图4所示，使用光刻胶剥离液D1清洗后的铜柱凸块，可以明显看出，整个铜柱凸块上的光刻胶清洗彻底、完全，无任何残留，说明其清洗效果良好。
还可看出，其铜柱底部区域有所腐蚀。
同时可见在铜柱侧壁出现了凹凸不平，腐蚀明显，这证明仅仅使用4-(2-吡啶偶氮)间苯二酚时，对铜表面的钝化保护效果有明显的降低，已不能用于后续工序中。
D2-D5的清洗后放大图片的效果高度类似于附图3，故不再一一列出。
5、如附图5所示，使用光刻胶剥离液D6清洗后的铜柱凸块，可以明显看出，整个铜柱凸块上的光刻胶清洗彻底、完全，无任何残留，说明其清洗效果良好。
但在铜柱侧壁出现了凹凸不平，腐蚀明显，且腐蚀程度要稍严重于附图4，这证明仅仅使用N-乙酰基-D-氨基葡萄糖时，对铜表面的钝化保护效果有更为明显的降低，已不能用于后续工序中。
同时也可看出，其铜柱底部区域有所腐蚀。
D7-D10的清洗后放大图片的效果高度类似于附图5，故不再一一列出。
6、如附图6所示，使用光刻胶剥离液D11清洗后的铜柱凸块，可以明显看出，整个铜柱凸块上的光刻胶清洗彻底、完全，无任何残留，说明其清洗效果良好。
但在铜柱侧壁出现了最为明显的凹凸不平，且腐蚀严重程度要更甚于附图4-5，这证明当省略掉本发明的铜表面钝化组合物后，导致了非常严重的铜表面腐蚀，已经完全不能用于后续工序中。
同时也可看出，其底部区域出现了非常明显的腐蚀，且明显严重于附图4-5(此时已明显看出腐蚀最为严重，故无必要对其进行放大扫描显示了)。
D12-D15的清洗后放大图片的效果高度类似于附图6，故不再一一列出。
7、附图7为使用光刻胶剥离液G1后附图3的铜柱底部区域的局部放大(放大10000倍)扫描电镜图片，从中可见，铜柱底部区域未被腐蚀，分别使用光刻胶剥离液G2-G5后的相同局部同样放大10000倍后，铜也未被腐蚀，故不再一一列出。
8、附图8为使用光刻胶剥离液D1后附图4的铜柱底部区域的局部放大(放大10000倍)扫描电镜图片，从中可见，铜柱底部区域出现了明显的腐蚀凹孔，分别使用光刻胶剥离液D2-D10后的相同局部同样放大10000倍后，也出现了大体类似(腐蚀情况和凹孔深浅等都基本相同)的腐蚀凹孔，故不再一一列出。
综上所述，通过扫描电镜的图片可准确地定性判断不同光刻胶剥离液液对Cu的钝化保护能力强弱，其中G1-G5有着非常优异的铜表面钝化保护能力，而当将铜表面钝化组合物改为单一组份时均导致钝化能力有显著的降低(但单一组分4-(2-吡啶偶氮)间苯二酚的效果要优于单一组份N-乙酰基-D-氨基葡萄糖)，而当不使用本发明的铜表面钝化组合物时，则有着最为严重的铜表面腐蚀，这证明只有使用本发明如此限定的铜表面钝化组合物，才能取得最好的技术效果，这应是因4-(2-吡啶偶氮)间苯二酚和N-乙酰基-D-氨基葡萄糖之间产生了良好的复配协同作用。发明人认为应是因4-(2-吡啶偶氮)间苯二酚的吡啶环与苯环之间通过共轭的氮氮双键相连，形成了具有高电子云密度的大共轭网络，而其中含有孤电子对的-OH和-NH 2可与Cu表面结合，使得该分子可稳定地吸附固定在Cu表面，从而避免了Cu受到外界的侵蚀，而N-乙酰基-D-氨基葡萄糖则可通过-OH吸附在Cu表面。二者复配时起到的协同作用，在此推测或许是由于这两种化合物以一定的比例同时吸附在Cu表面时，可使 Cu表面达到最高的分子吸附量(因不同分子的吸附位点存在差异，结构不同的分子共同作用时可形成密度更大的吸附膜)，从而可取得最好的Cu保护效果，发明人对此将进行进一步的深入研究。
各个光刻胶剥离液对铜表面钝化的定量测试
为了得到更加精确的铜表面钝化保护数据，发明人使用ICP-MS(电感耦合等离子体质谱法)进行了更为精确的定量测试，具体测试方法如下：将带有光刻胶且尺寸为4×4cm的铜柱凸块样片在40℃下直接浸泡在上述得到的各个光刻胶剥离液中，浸泡时间为30分钟，然后采用ICP-MS法测量剥离液中的金属离子浓度，并计算各自的腐蚀速率(
Figure PCTCN2022092986-appb-000002
即
Figure PCTCN2022092986-appb-000003
分钟，也可称为“刻蚀速率”)，从而考察了不同光刻胶剥离液对金属铜的腐蚀速率，测试结果见下表1所示：
表1.不同剥离液的金属Cu腐蚀速率
Figure PCTCN2022092986-appb-000004
其中，光刻胶剥离液与Cu腐蚀速率有着一一对应关系，例如以G1-G5为例，Cu腐蚀速率
Figure PCTCN2022092986-appb-000005
为“0.11/0.17/0.13/0.12/0.13”，意指G1、G2、G3、G4和G5的腐蚀速率
Figure PCTCN2022092986-appb-000006
分别为0.11、0.17、0.13、0.12和0.13，其它光刻胶剥离液与Cu腐蚀速率亦有同样的对应指代关系，在此不再一一进行描述。
由上表1可见，本发明的光刻胶剥离液G1-G5具有优异的铜表面钝化保护功能，其腐蚀速率非常低，而当改变其中的氨基葡萄糖衍生物时，发现铜腐蚀速率有所上升(见G6-G8)，这证明最优选N-乙酰基-D-氨基葡萄糖(尤其是对于G6而言，仅仅是将N-乙酰基-D-氨基葡萄糖替换为D-氨基葡萄糖，腐蚀速率便有了明显的增大)；而当改变4-(2-吡啶偶氮)间苯二酚与氨基葡萄糖衍生物的质量比，腐蚀速率也有所增大，且从中可看出，越是偏离1:3的最佳质量比，则腐蚀速率越大(G9-G12的质量比分别为1:2、1:4、1:1和1:5，但腐蚀速率依次为0.25、0.28、0.45、0.52，证明偏离1:3越大则腐蚀速率越大)；而当将铜表面钝化组合物由双组份改变为单一组份时，则腐蚀速率由非常显著的增大(见D1-D5和D6-D10，但D6-D10 要显著大于D1-D5，也与附图的定性表征相符合)；最为显著的是，当不使用本发明的铜表面钝化组合物时，则腐蚀速率达到最大(见D11-D15)，有着最为严重的Cu腐蚀。
如上所述，本发明提供了一种铜表面钝化组合物及其用途、包含该铜表面钝化组合物的光刻胶剥离液、光刻胶剥离液的制备方法及其用途和使用该剥离液的铜基板的清洗方法，所述铜表面钝化组合物通过双组份化合物的使用、优选组份的选择和用量的最优选择，从而取得了优异的技术效果，使得所述光刻胶剥离液在具有优异清洗性能之外，还有着优异的铜钝化保护效果，从而可用于半导体后道封装的凸工艺中的光刻胶去除和铜表面保护，在微电子技术领域具有良好的工业应用前景和推广潜力。
应当理解，这些实施例的用途仅用于说明本发明而非意欲限制本发明的保护范围。此外，也应理解，在阅读了本发明的技术内容之后，本领域技术人员可以对本发明作各种改动、修改和/或变型，所有的这些等价形式同样落于本申请所附权利要求书所限定的保护范围之内。

Claims (10)

  1. 一种铜表面钝化组合物，其特征在于：所述铜表面钝化组合物包括4-(2-吡啶偶氮)间苯二酚和氨基葡萄糖衍生物。
  2. 如权利要求1所述的铜表面钝化组合物，其特征在于：所述4-(2-吡啶偶氮)间苯二酚与氨基葡萄糖衍生物的质量比为1:1-5，优选为1:2-4，最优选为1:3。
  3. 一种光刻胶剥离液，以质量份计，所述光刻胶剥离液包括如下组分：
    Figure PCTCN2022092986-appb-100001
    其中，所述铜表面钝化组合物为权利要求1-2任一项中所述的铜表面钝化组合物。
  4. 如权利要求3所述的光刻胶剥离液，其特征在于：所述水溶性有机溶剂为砜、亚砜、醇醚、酰胺和吡咯烷酮中的任意一种或任意多种的组合；
    其中，所述砜优选为环丁砜；
    其中，所述亚砜优选二甲基亚砜；
    其中，所述醇醚为乙二醇单甲醚、乙二醇单乙醚、乙二醇单丁醚、二乙二醇单甲醚、二乙二醇单乙醚、二乙二醇单丁醚、丙二醇单甲醚、丙二醇单乙醚、丙二醇单丁醚中的任意一种或任意多种的组合；
    其中，所述酰胺为N-甲基甲酰胺、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、乙酰胺、N-甲酰乙胺或N,N-二乙基甲酰胺中的任意一种或任意多种的组合；
    其中，所述吡咯烷酮为N-甲基吡咯烷酮或N-乙基吡咯烷酮，或者为这两种的任意比例的组合。
  5. 如权利要求3或4所述的光刻胶剥离液，其特征在于：所述碱为有机碱，更具体地，为季铵盐氢氧化物或链烷醇胺。
  6. 如权利要求3-5任一项所述的光刻胶剥离液，其特征在于：所述多元醇为乙二醇、二乙二醇、1,2-丙二醇或1,3-丙二醇的任意一种或任意多种的组合。
  7. 如权利要求3-6任一项所述的光刻胶剥离液的制备方法，所述制备方法具体如下：分别称取各自质量份的各个组份，然后在室温下将所述铜表面钝化组合物、水溶性有机溶剂、碱和多元醇加入到去离子水中，并充分搅拌混合均匀，即得均匀透明的所述光刻胶剥离液；
    或者，另一种制备方法具体如下：分别称取各自质量份的各个组份，室温下，将水溶性 有机溶剂、碱和多元醇加入到去离子水中，得到混合溶液，然后在搅拌下向所述混合溶液中加入铜表面钝化组合物，并持续搅拌至混合均匀，即得均匀透明的所述光刻胶剥离液。
  8. 权利要求1或2所述的铜表面钝化组合物用于抑制铜腐蚀的用途。
  9. 权利要求1或2所述的铜表面钝化组合物用于制备光刻胶剥离液的用途。
  10. 一种铜基板光刻胶残留物的清洗方法，所述清洗方法具体如下：在35-45℃下，将带光刻胶的铜基板浸泡在权利要求3-6任一项所述的光刻胶剥离液中，或将权利要求3-6任一项所述的光刻胶剥离液喷淋到所述铜基板上，浸泡或喷淋的时间为5-40分钟，继而使用超纯水冲洗，再用高纯氮气吹干，即完成铜基板的清洗处理。
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