WO2013118042A1 - Composition de nettoyage de type post-polissage mécano-chimique (post-cmp) comprenant un composé spécifique contenant du soufre et dépourvue de quantités significatives de composés spécifiques contenant de l'azote - Google Patents

Composition de nettoyage de type post-polissage mécano-chimique (post-cmp) comprenant un composé spécifique contenant du soufre et dépourvue de quantités significatives de composés spécifiques contenant de l'azote Download PDF

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Publication number
WO2013118042A1
WO2013118042A1 PCT/IB2013/050932 IB2013050932W WO2013118042A1 WO 2013118042 A1 WO2013118042 A1 WO 2013118042A1 IB 2013050932 W IB2013050932 W IB 2013050932W WO 2013118042 A1 WO2013118042 A1 WO 2013118042A1
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composition
group
acid
alkyl
post
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PCT/IB2013/050932
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English (en)
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Yuzhuo Li
Shyam Sundar Venkataraman
Mingjie ZHONG
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Basf Se
Basf Schweiz Ag
Basf (China) Company Limited
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Publication of WO2013118042A1 publication Critical patent/WO2013118042A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3245—Aminoacids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/34—Organic compounds containing sulfur

Definitions

  • post-CMP post chemical-mechanical-polishing
  • This invention essentially relates to a post chemical-mechanical-polishing (post-CMP) cleaning composition and its use for removing residues and contaminants from the surface of semiconductor substrates. Moreover, this invention relates to the use of the post CMP cleaning composition for removing residues and contaminants comprising benzotriazole after CMP. Particularly, this invention relates to the use of the post CMP cleaning composition for removing residues and contaminants from the surface of semiconductor substrates comprising electrically conduc- tive layers (such as copper layers), electrically insulating dielectric layers (such as low-k or ultra- low-k dielectric material layers) and barrier layers (such as tantalum, tantalum nitride, titanium nitride or ruthenium layers) after CMP.
  • electrically conduc- tive layers such as copper layers
  • electrically insulating dielectric layers such as low-k or ultra- low-k dielectric material layers
  • barrier layers such as tantalum, tantalum nitride, titanium nitride or ruthenium layers
  • CMP chemical mechanical polishing
  • contaminants and residues comprising particles from the CMP slurries, added chemicals, and reaction by-products remain on the polished substrate surface.
  • These residues that are left on the substrates following CMP processing can also include corrosion inhibitor compounds such as benzotriazole (BTA), which can - if for example the copper ion concentration exceeds the maximum solubility of the copper-inhibitor complexes during CMP - precipitate from solution and coagulate into a surface residue.
  • BTA benzotriazole
  • the polishing of a substrate surface having copper/low-k or ultra- low-k dielectric materials often generates carbon-rich particles that settle onto the surface after CMP.
  • US 2005/0197266 A1 discloses a composition for cleaning a semiconductor workpiece, the composition comprising:
  • a cleaning agent selected from the group consisting of: (i) ammonium citrate; (ii) ammonium oxalate; (iii) aspartic acid; (iv) benzoic acid; (v) citric acid; (vi) cysteine; (vii) glycine; (viii) gluconic acid; (ix) glutamic acid; (x) histidine; (xi) maleic acid; (xii) oxalic acid; (xiii) propionic acid; (xiv) salicylic acid; (xv) tartaric acid; (xvi) and mixtures thereof; and
  • a corrosion-inhibiting compound is selected from the group consisting of: (i) ascorbic acid; (ii) benzotriazole; (iii) caffeic acid; (iv) cinnamic acid; (v) cysteine; (vi) glucose; (vii) imidazole; (viii) mercaptothiazoline; (ix) mercaptoethanol; (x) mercaptopropionic acid; (xi) mercaptobenzo- thiazole; (xii) mercaptomethylimidazole; (xiii) tannic acid; (xiv) thioglycerol; (xv) thiosalicylic acid; (xvi) triazole; (xvii) vanillin; (xviii) vanillic acid; (xix) and mixtures thereof.
  • the cleaning composition comprises ammonium citrate, ascorbic acid, and cysteine.
  • WO 201 1/000694 A1 discloses an aqueous alkaline cleaning composition
  • an aqueous alkaline cleaning composition comprising (a) at least one thioamino acid having at least one primary amino group and at least one mercapto group, (b) at least one quaternary ammonium hydroxide, (c) at least one specific chelating and/or corrosion inhibiting agent, and (d) at least one organic solvent having wetting properties and a melting point below 0°C.
  • the cleaning composition comprises L-cysteine, tetramethylammonium hydroxide (referred to as TMAH in the following), ethylene diamine, and diethylene glycol monobutyl ether.
  • WO 201 1/000758 A1 discloses an aqueous alkaline cleaning composition comprising (a) at least one thioamino acid having at least one secondary or tertiary amino group and at least one mercapto group and, and (b) at least one quaternary ammonium hydroxide.
  • the cleaning composition comprises N-acetylcysteine, TMAH, ethylene diamine, and diethylene glycol monobutyl ether.
  • the cleaning composition comprises N- acetylcysteine, TMAH, diethylene triamine, 1 ,2,4-triazole, citric acid, and a surfactant such as 3,5-dimethyl-1 -hexyn-3-ol or polyoxyethylene sorbitan laurate.
  • post-CMP cleaning compositions comprising
  • One of the objects of the present invention was to provide a post-CMP cleaning composition and a post-CMP cleaning process appropriate for post-CMP cleaning of copper-containing microelectronic substrates and showing an improved cleaning performance, particularly
  • one of the objects of the present invention was to provide a post-CMP cleaning composition containing no or minimal amounts of organic solvents which can cause environmental and safety concerns. Moreover, one of the objects of the present invention was to provide a post-CMP cleaning composition which does not cause an increase of surface roughness of the copper-containing surface or an increase of defects thereon. Last but not least, a post- CMP cleaning process was sought that is easy and safe to apply and requires as few steps as possible.
  • a post-CMP cleaning composition comprising:
  • (A) at least one compound comprising at least one thiol (-SH), thioether (-SR 1 ) or thiocarbonyl (>C S) group, wherein R 1 is alkyl, aryl, alkylaryl or arylalkyl, and
  • composition (Q) wherein the total amounts of Nh , any sulfur-free organic ammonium ions, and any sulfur-free amines comprised in the composition do not exceed 100 ppm ("ppm” stands for "parts per million") based on the total weight of the composition, was found.
  • This post-CMP cleaning composition of the invention is referred to as (Q) or composition (Q) in the following.
  • the use of the composition (Q) for removing residues and contaminants from the surface of semiconductor substrates useful for manufacturing microelectronic devices was found.
  • composition (Q) and the process (P) were excellently suited for post-processing substrates useful for fabricating electrical devices, in particular, semiconductor integrated circuits (ICs), more preferably ICs with LSI (large-scale integration) or VLSI (very-large-scale integration). It was even more surprising that the composition (Q) and the pro- cess (P) were most excellently suited for high precision fabrication methods involving inter alia surface preparation, pre-plating cleaning, post-etch cleaning and/or post-CMP cleaning steps.
  • ICs semiconductor integrated circuits
  • LSI large-scale integration
  • VLSI very-large-scale integration
  • composition (Q) and the process (P) were most particularly well-suited for carrying out the above-mentioned cleaning steps, in particular, the post-CMP cleaning of semiconductor wafers and the fabrication of ICs with LSI or VLSI, in particular by the copper damascene or dual dam- ascene process.
  • the passivation film especially the ben- zotriazole film, was also completely removed from the copper-containing surfaces by the composition (Q) and the process (P). Moreover, the corrosion of the copper-containing surfaces was prevented by the composition (Q) and the process (P). Last but not least, the composition (Q) and the process (P) were applicable in moderate pH range such as from 4 to 8. Furthermore, it was surprising that the absence of Nh , any sulfur-free organic ammonium ions, and any sulfur-free amines does not affect the cleaning performance of the cleaning composition, although prior art cleaning compositions containing a thiol or thioamino compound also comprise ammonium salts such as TMAH or Nh .
  • TMAH is rather hazardous, and the Nh cation can easily convert into the corrosive and hazardous NH3, so that the absence of these species in the cleaning composition is beneficial to the handling and safety of the cleaning composition.
  • NH4 + can convert into NH3
  • sulfur-free organic ammonium ions can convert into the corresponding amines
  • sulfur-free amines may cause contamination prob- lems in the following manufacturing steps of the semiconductor device, which can be avoided by the absence of these species in the cleaning composition.
  • the composition (Q) is used for removing residues and contaminants from the surface of semiconductor substrates useful for manufacturing microelectronic devices.
  • Said residues and contaminants can be any residues and contaminants, including but not limited to abrasive particles, processing residues, metal oxides including copper oxide, metallic ions, salts, passivation films, and abraded or decomposed low-k or ultra-low-k dielectric materials.
  • Said residues and contaminants preferably comprise a passivation film, more preferably comprise an A/-heterocyclic compound, most preferably comprise diazoles, triazoles, tetrazoles, or a derivative thereof, particularly preferably comprise benzotriazole, or a derivative thereof, for instance comprise benzotria- zole.
  • (Q) is used for removing residues and contaminants comprising benzotriazole or a derivative thereof from the copper-containing surface of semiconductor substrate after CMP.
  • (Q) is used for removing a passivation film comprising benzotriazole from the copper-containing surface of a semiconductor substrate after CMP.
  • the composition (Q) is used for removing residues and contaminants from the sur- face of semiconductor substrates useful for manufacturing microelectronic devices after CMP. More preferably, the composition (Q) is used for removing residues and contaminants from said surface after said surface has been polished in a CMP step.
  • Said semiconductor substrates preferably comprise electrically conductive layers, electrically insulating dielectric layers and barrier layers, more preferably comprise
  • barrier layers containing or consisting of tantalum, tantalum nitride, titanium nitride, cobalt, nickel, manganese, ruthenium, ruthenium-nitride, ruthenium-carbide, or ruthenium tungsten nitride.
  • composition (Q) can be advantageously used for other purposes, it is particularly well-suited for the process (P).
  • Microelectronic devices can be manufactured from semiconductor substrates by the process (P), the process (P) comprises the step of removing residues and contaminants from the surface of semiconductor substrates by contacting them at least once with the composition (Q).
  • Said residues and contaminants preferably comprise a passivation film, more preferably com- prise an A/-heterocyclic compound, most preferably comprise diazoles, triazoles, tetrazoles, or a derivative thereof, particularly preferably comprise benzotriazole, or a derivative thereof, for instance comprise benzotriazole.
  • (P) comprises the step of removing residues and contaminants comprising benzotriazole or a derivative thereof from the copper-containing surface of semiconductor substrates by contacting them at least once with (Q).
  • the process (P) comprises the step of removing residues and contaminants from the surface of semiconductor substrates by contacting them at least once with the composition (Q) after CMP. More preferably, process (P) comprises the step of removing residues and contaminants from the surface of semiconductor substrates by contacting them at least once with the composition (Q) after said surface has been polished in a CMP step.
  • the process (P) cannot only be used for the post-CMP cleaning but also for photoresists stripping and post-etch residue removal. However, the process (P) exhibits its particular advantages in the post-CMP cleaning of the above-described semiconductor substrates.
  • the composition (Q) comprises one compound (A).
  • the compound (A) can be contained in varying amounts in the composition (Q), and the amounts or the concentration of (A) can be adjusted most advantageously according to the particular requirements of a given composition, use and method of the invention.
  • the amount of (A) is preferably not more than 1.5 weight percent (referred to as "wt.%” in the following), more preferably not more than 0.5 wt.%, most preferably not more than 0.1 wt.%, particularly not more than 0.07 wt.%, for example not more than 0.05 wt.%, based on the total weight of the composition (Q).
  • the amount of (A) is preferably at least 0.0005 wt.%, more preferably at least 0.001 wt.%, most preferably at least 0.004 wt.%, particularly at least 0.01 wt.%, for example at least 0.03 wt.%, based on the total weight of the composition (Q).
  • the compound (A) is a compound comprising
  • R 1 , R 2 , R 3 and R 4 is - independently from each other - alkyl, aryl, alkylaryl or arylalkyl.
  • R 1 , R 2 , R 3 and R 4 is - independently from each other - alkyl, aryl, alkylaryl or arylalkyl.
  • R 1 , R 2 , R 3 and R 4 is - independently from each other - alkyl, aryl, alkylaryl or arylalkyl.
  • amino groups -IMH2 and -NHR2 are more preferred, and amino groups -NH2 are most preferred.
  • the compound (A) is preferably a compound comprising
  • R 2 , R 3 and R 4 is - independently from each other - alkyl, aryl, alkylaryl or arylalkyl. More preferably, (A) is a compound comprising
  • (A1 ) one thiocarbonyl (>C S) group and (A2) at least two amino (-NH 2 , -NHR 2 , or -NR 3 R 4 ) groups.
  • (A) is thiourea or a derivative thereof. Particularly, (A) is thiourea.
  • the compound (A) is preferably a compound comprising (A1 ) at least one thiol (-SH), or thioether (-SR 1 ) group, and
  • R 1 , R 2 , R 3 and R 4 is - independently from each other - alkyl, aryl, alkylaryl or arylalkyl. More preferably, (A) is an amino acid comprising at least one thiol (-SH) or thioether (-SR 1 ) group, or a derivative of this amino acid, wherein R 1 is alkyl, aryl, alkylaryl or arylalkyl. Most preferably, (A) is an amino acid comprising at least one thiol (-SH) group or a derivative of this amino acid. Particularly, (A) is an amino acid comprising one thiol (-SH) group or a derivative of this amino acid.
  • (A) is cysteine, cystine, glutathione, N-acetylcysteine, or a derivative thereof.
  • (A) is cysteine or N-acetylcysteine.
  • R 1 can generally be any substituted or unsubstituted alkyl, aryl, alkylaryl, or arylalkyl group.
  • R 1 is preferably alkyl, more preferably unsubstituted alkyl, most preferably Ci to C20 alkyl, particularly Ci to C10 alkyl, for example Ci to C 4 alkyl.
  • R 2 can generally be any substituted or unsubstituted alkyl, aryl, alkylaryl, or arylalkyl group.
  • R 2 is preferably alkyl, more preferably unsubstituted alkyl, most preferably Ci to C20 alkyl, particularly Ci to C10 alkyl, for example Ci to C 4 alkyl.
  • R 3 can generally be any substituted or unsubstituted alkyl, aryl, alkylaryl, or arylalkyl group.
  • R 3 is preferably alkyl, more preferably unsubstituted alkyl, most preferably Ci to C20 alkyl, particularly Ci to C10 alkyl, for example Ci to C 4 alkyl.
  • R 4 can generally be any substituted or unsubstituted alkyl, aryl, alkylaryl, or arylalkyl group.
  • R 4 is preferably alkyl, more preferably unsubstituted alkyl, most preferably Ci to C20 alkyl, particularly Ci to C10 alkyl, for example Ci to C 4 alkyl.
  • the total amounts of NH 4 + , any sulfur-free organic ammonium ions, and any sulfur-free amines comprised in the composition (Q) do not exceed 100 ppm, preferably 40 ppm, more preferably 10 ppm, most preferably 1 ppm, particularly preferably 0.1 ppm, particularly 0.01 ppm, based on the total weight of the composition (Q).
  • the composition (Q) does not comprise any NH 4 + or any sulfur-free organic ammonium ions or any sulfur-free amines.
  • “Sulfur-free” means that the compound does not comprise any covalently bonded sulfur atoms.
  • Organic ammonium ions means a primary, secondary, tertiary, or quaternary ammonium ion.
  • the composition (Q) contains an aqueous medium (B).
  • B can be of one type or a mixture of different types of aqueous media.
  • the aqueous medium (B) can be any medium which contains water.
  • the aqueous medium (B) is a mixture of water and an organic solvent miscible with water (e.g. an alcohol, preferably a Ci to C3 alcohol, or an alkylene glycol derivative). More preferably, the aqueous medium (B) is water. Most preferably, aqueous medium (B) is de-ionized water.
  • the composition (Q) can further optionally contain at least one metal corrosion inhibitor (C), preferably one metal corrosion inhibitor (C).
  • a metal corrosion inhibitor used in post- CMP cleaning compositions is a chemical compound that, when added to said composition, decreases the corrosion rate of a metal or an alloy, for example by forming a protective passivation layer on the surface of the metal or the alloy.
  • the metal corrosion inhibitor (C) is a compound having no nitrogen-containing functional groups, as for example amine, amide, imide, hydrazine, hydroxyl amine, urethane, tria- zole, tetrazole groups and similar nitrogen-containing functional groups as well as cationic groups derived from such nitrogen-containing functional groups.
  • metal corrosion inhibitors (C) preventing the corrosion of copper i.e., copper corrosion inhibitors (C) are used.
  • said metal corrosion inhibitor (C) can be contained in varying amounts in the composition (Q), and the amounts or the concentration of (C) can be adjusted most advantageously according to the particular requirements of a given composition, use and method of the inven- tion.
  • the amount of (C) is not more than 1 .5 wt.%, more preferably not more than 0.5 wt.%, most preferably not more than 0.2 wt.%, particularly not more than 0.1 wt.%, for example not more than 0.06 wt.%, based on the total weight of the composition (Q).
  • the amount of (C) is at least 0.0005 wt.%, more preferably at least 0.001 wt.%, most preferably at least 0.007 wt.%, particularly at least 0.02 wt.%, for example at least 0.04 wt.%, based on the total weight of the composition (Q).
  • the metal corrosion inhibitor (C) is selected from the group consisting of water- soluble and water dispersible, preferably, water-soluble compounds having at least two, most preferably at least three, hydroxyl (-OH) groups which do not dissociate in the aqueous medi- um.
  • the metal corrosion inhibitor (C) is selected from the group consisting of polyhydric alcohols, polyhydric phenols and carboxylic acids having at least two hydroxyl groups.
  • the polyhydric alcohol (C) is selected from the group consisting of glycerol, trimethylolpropane, pentaerythritol, alditols, cyclitols, carbohydrates and the dimers and oligomers of glycerol, trimethylolpropane, pentaerythritol, alditols and cyclitols.
  • the alditol (C) is selected from the group consisting of tetritols, pentitols, hex- itols, heptitols, and octitols.
  • the tetritol (C) is selected from erythritol, threitol and stereoisomers and mixtures thereof; the pentitol (C) is selected from the group consisting of arabinitol, ribitol and xylitol and stereoisomers and mixtures thereof, the hexitol (C) is selected from the group consisting of galactitol, mannitol, glucitol, allitol, altritol, iditol and stereoisomers and mixtures thereof.
  • the dimer (C) is selected from the group consisting of the dimers of glycerol, trimethylolpropane, erythritol, threitol and pentaerythritol and stereoisomers and mixtures thereof as well as maltitol, isomalt, lactitol and stereoisomers and mixtures thereof.
  • the oligomer (C) is selected from the group consisting of tri-, tetra-, pen- ta-, hexa-, hepta-, octa-, nona-, deca-, undeca- and dodecaglycerol, -trimethylolpropane, - erythritol, -threitol and -pentaerythritol and stereoisomers and mixtures thereof.
  • the cyclitols (C) are selected from 1 ,2,3,4-tetrahydroxycyclohexane, 1 ,2,3,4,5-pentahydroxycyclohexane, inositols and stereoisomers and mixtures thereof.
  • the inositol (C) is selected from the group consisting of myo-, scyllo-, muco-, chiro-, neo-, alio-, epi- and cis-inositol and mixtures thereof. Most preferably, myoinositol (C) is used. Even more preferably, the carbohydrate (C) is selected from the group consisting of monosaccharides.
  • the monosaccharide (C) is selected from the group consisting of allose, altrose, glucose, mannose, idose, galactose and talose, in particular galactose.
  • the polyhydric phenol (C) is selected from the group consisting of pyro- catechol, resorcinol, hydroquinone, pyrogallol, 1 ,2,4-trishydroxybenzene and phloroglucinol.
  • the carboxylic acids (C) having at least 2 hydroxy groups are selected from the group consisting of sugar acids and benzene carboxylic acids having at least 2 hydroxy groups.
  • the sugar acid (C) is selected from the group consisting of glyceric acid, tartaric acid, threonic acid, erythronic acid, xylonic acid, glucuronic acid, ascorbic acid, gluconic acid, galacturonic acid, iduronic acid, mannuronic acid, glucuronic acid, guluronic acid, gly- curonic acid, glucaric acid, ulusonic acid, lactobionic acid and mixtures thereof.
  • the benzene carboxylic acid (C) is selected from the group consisting of 2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5-dihydroxybenzoic acid and 2,4,6-, 2,4,5-, 2,3,4- and 3,4,5- trihydroxybenzoic acid (gallic acid).
  • erythritol or a stereoisomer thereof, or gallic acid is used as metal corrosion inhibitor (C).
  • erythritol or a stereoisomer thereof is used as metal corrosion inhibitor (C).
  • the composition (Q) can further optionally contain at least one metal chelating agent (D), pref- erably one metal chelating agent (D).
  • a metal chelating agent used in a post-CMP cleaning composition is a chemical compound that forms soluble, complex molecules with certain metal ions, inactivating the ions so that they cannot normally react with other elements or ions to produce precipitates or scale.
  • said metal chelating agent (D) can be contained in varying amounts in the composition (Q), and the amounts or the concentration of (D) can be adjusted most advantageously according to the particular requirements of a given composition, use and method of the invention.
  • the amount of (D) is not more than 1 .5 wt.%, more preferably not more than 0.5 wt.%, most preferably not more than 0.2 wt.%, particularly not more than 0.1 wt.%, for example not more than 0.06 wt.%, based on the total weight of the composition (Q).
  • the amount of (D) is at least 0.0005 wt.%, more preferably at least 0.001 wt.%, most preferably at least 0.007 wt.%, particularly at least 0.02 wt.%, for example at least 0.04 wt.%, based on the total weight of the composition (Q).
  • the metal chelating agent (D) is a compound comprising at least two carboxylic acid
  • (D) is a compound comprising at least three carboxylic acid (-COOH) or carboxylate (-COO-) groups.
  • the metal chelating agent (D) is selected from the group consisting of
  • (D9) oligomeric or polymeric polycarboxylic acids.
  • (D) is selected from the group consisting of (D1 ), (D2), (D3), (D4), (D5), (D6), (D7) and (D8).
  • (D) is selected from the group consisting of (D1 ), (D2), (D3) and (D4).
  • the metal chelating agent (D) is citric acid (D2).
  • (D9) is preferably an oligomeric or polymeric polycarboxylic acid containing acrylic acid and/or methacrylic acid - preferably acrylic acid - monomeric units.
  • the weight average molecular weight of (D9) as determined by gel permeation chromatography is preferably less than 20,000 Dalton, more preferably less than 15,000 Dalton, most preferably less than 10,000 Dalton, particularly less than 5,000 Dalton, and preferably more than 500 Dalton, more preferably more than 1 ,000 Dalton, most preferably more than 2,000 Dalton, particularly more than 2,500 Dalton.
  • (D9) can be homopolymers, i.e., polyacrylic acid or polymethacrylic acid - preferably polyacrylic acid - homopolymers or copolymers.
  • Said copolymer containing acrylic acid monomeric units may contain essentially any suitable other monomeric units, preferably monomeric units comprising at least one carboxylic acid group, in particular, monomeric units derived from fumaric acid, maleic acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid, methylenemalonic acid or maleic anhydride. Most preferably, said copolymer is a maleic acid / acrylic acid copolymer. For example, said copolymer is Sokalan ® CP 12 S.
  • An oligomeric polycarboxylic acid is a polycarboxylic acid having at least 7 carboxylic acid groups.
  • a polymeric polycarboxylic acid is a polycarboxylic acid having at least 30 carboxylic acid groups.
  • composition (Q) can further optionally contain at least one surfactant (E), preferably one surfactant (E), more preferably one surfactant (E) which is selected from the group of water- soluble or water-dispersible - preferably water-soluble - amphiphilic nonionic surfactants (E1 ), (E2) and (E3).
  • surfactant preferably one surfactant (E)
  • E more preferably one surfactant (E) which is selected from the group of water- soluble or water-dispersible - preferably water-soluble - amphiphilic nonionic surfactants (E1 ), (E2) and (E3).
  • a surfactant used in a post-CMP cleaning composition is a surface-active compound which decreases the surface tension of a liquid, the interfacial tension between two liquids, or that between a liquid and a solid.
  • said surfactant (E) can be contained in varying amounts in the composition (Q), and the amounts or the concentration of (E) can be adjusted most advantageously according to the particular requirements of a given composition, use and method of the invention.
  • the amount of (E) is not more than 5 wt.%, more preferably not more than 2 wt.%, most preferably not more than 1 wt.%, particularly not more than 0.5 wt.%, for example not more than 0.3 wt.%, based on the total weight of the composition (Q).
  • the amount of (E) is at least 0.0005 wt.%, more preferably at least 0.005 wt.%, most preferably at least 0.01 wt.%, particularly at least 0.05 wt.%, for example at least 0.1 wt.%, based on the total weight of the composition (Q).
  • the amphiphilic nonionic surfactant (E1) comprises at least one hydrophobic group (e11). This means that (E1) can have more than one hydrophobic group (e11), e.g., 2, 3 or more groups (e11), which are separated from each other by at least one hydrophilic group (e12) hereinbelow described.
  • the hydrophobic group (e11) is selected from the group consisting of branched alkyl groups having 5 to 20, preferably 7 to 16 and, most preferably 8 to 15 carbon atoms.
  • the branched alkyl groups (e11) have on the average a degree of branching of from 1 to 5, preferably 1 to 4 and, most preferably, 1 to 3.
  • Suitable branched alkyl groups are derived from isopentane, neopentane and the branched hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetrade- cane, pentadecane, hexadecane, heptadecane, nonadecane and eicosane isomers.
  • the branched alkyl groups (e11) are derived from Guerbet-alcohols having 8 to 15, preferably, 10 carbon atoms (cf. Rompp Online 2011, "Guerbet-Recision”).
  • (E1) comprises at least one hydrophilic group (e12). This means that (E1) can contain more than one group (e12), e.g., 2, 3 or more groups (e12), which are separated from each other by hydrophobic groups (e11).
  • the hydrophilic groups (e12) consist of oxyethylene monomer units.
  • the degree of polymerization of the hydrophilic groups (e12) can vary broadly and, therefore, can be adapted most ad- vantageously to the particular requirements of a given composition, use and method of the invention.
  • the degree of ethoxylation is in the range of from 4 to 20, more preferably 6 to 16 and, most preferably, 7 to 8.
  • (E1) can have different blocklike general structures.
  • Examples of such general blocklike struc- tures are: e11-e12,
  • the blocklike general structure e11-e12 is used.
  • the weight average molecular weight of (E1 ) is in the range of from 300 to 800 Dalton, preferably 400 to 750 Dalton and, most preferably, 400 to 600 Dalton, as determined by size exclusion chromatography.
  • the hydrophilic-lipophilic balance (HLB) value is in the range of 8 to 16, preferably 9 to 15 and, most preferably, 1 1 to 14.
  • amphiphilic nonionic surfactants are customary and known materials and are available from BASF SE under the trademark Lutensol ® .
  • (E1 ) is particularly Lutensol ® XP80 or Lutensol ® XP70, for example Lutensol ® XP80.
  • the amphiphilic nonionic surfactant (E2) also comprises at least one hydrophobic group (e21 ) and at least one hydrophilic group (e22). This means that the amphiphilic nonionic surfactant (E2) contains more than one group (e22), e.g., 2, 3 or more groups (e22) which are separated from each other by hydrophobic groups (e21 ) or it contains more than one group (e22), e.g., 2, 3 or more groups (e22), which are separated from each other by hydrophobic groups (e21 ).
  • the amphiphilic nonionic surfactant (E2) can have different blocklike general structures. Examples of such general blocklike structures are: e21 -e22,
  • hydrophobic groups (e1 1 ) described above are used as the hydrophobic groups (e21 ).
  • the hydrophilic group (e22) comprises oxyethylene monomer units (e221 ).
  • the hydrophilic group (e22) comprises at least one type of substituted oxyalkylene monomer units (e222), wherein the substituents are selected from the group consisting of alkyl, cycloalkyl, aryl, alkyl-cycloalkyl, alkyl-aryl, cycloalkyl-aryl and alkyl-cycloalkyl-aryl groups.
  • the oxyalkylene monomer units (e222) are derived from substituted oxiranes wherein the substituents are selected from the group consisting of alkyl, cycloalkyi, aryl, alkyl- cycloalkyl, alkyl-aryl, cycloalkyl-aryl and alkyl-cycloalkyl-aryl groups.
  • the substituents of the oxiranes are preferably selected from the group consisting of alkyl groups having 1 to 10 carbon atoms, cycloalkyi groups having 5 to 10 carbon atoms in spirocy-rod, exocyclic and/or annealed configuration, aryl groups having 6 to 10 carbon atoms, alkyl- cycloalkyl groups having 6 to 20 carbon atoms, alkyl-aryl groups having 7 to 20 carbon atoms, cycloalkyl-arylgroup having 1 1 to 20 carbon atoms, and alkyl-cycloalkyl-aryl groups having 12 to 30 carbon atoms.
  • suitable alkyl groups are methyl, ethyl, propyl, isopropyl, n-butyl, n-pentyl, and n- hexyl.
  • suitable cycloalkyi groups are cyclopentyl, and cyclohexyl.
  • suitable aryl groups are phenyl and 1 - and 2-naphthyl.
  • Examples for particularly preferred substituted oxiranes are methyl oxirane (propyleneoxide) and ethyl oxirane (butylene oxide).
  • the hydrophilic group (e22) consists of the monomer units (e221 ) and (e222).
  • the polyoxyalkylene group contains the monomer units (e221 ) and (e222) in random, alternating, gradient and/or blocklike distribution. This means, that one hydrophilic group (e22) can have only one type of distribution, i.e., - random: ...-e221 -e221 -e222-e221 -e222-e222-e222-e221 -e222-...;
  • hydrophilic group (e22) can contain at least two types of distributions, e.g., an oligomeric or polymeric segment having a random distribution and an oligomeric or polymeric segment having an alternating distribution.
  • the hydrophilic group (e22) has only one type of distribution. Most preferably, the distribution is random or blocklike.
  • the molar ratio of oxyethylene monomer units (e221 ) to oxyalkylene monomer units (e222) can vary broadly and, therefore, can be adjusted most advantageously to the particular requirements of a given composition, the method and the use of the invention.
  • the molar ratio (e221 ):(e222) is from 100:1 to 1 :1 , more preferably, from 60:1 to 1 .5:1 and, most preferably, from 50:1 to 1.5:1 .
  • the degree of polymerization of the oligomeric or polymeric polyoxyalkylene groups (e22) can vary broadly and, therefore, can be adjusted most advantageously to the particular requirements of a given composition, the method and the use of the invention.
  • the degree of polymerization is in the range of from 5 to 100, preferably 5 to 90, and most prefera- bly, 5 to 80.
  • amphiphilic nonionic surfactants (E2) are customary and known materials and are commercially available from BASF SE under the trademark PlurafacTM or from Dow under the trademark TritonTM.
  • the amphiphilic nonionic surfactants (E3) are alkyl polyglucosides (APG).
  • APG preferably have an average degree of polymerization of 1 to 5, preferably 1 .2 to 1 .5.
  • the alkyl groups of the APG have 8 to 16 carbon atoms and, most preferably, 12 to 14 carbon atoms.
  • the APG are customary and known materials and are available from Cognis under the trade- mark GlucoponTM.
  • the surfactant (E) is selected from the group consisting of:
  • (e1 1 ) at least one hydrophobic group selected from the group consisting of branched alkyl groups having 5 to 20 carbon atoms;
  • (e21 ) at least one hydrophobic group selected from the group consisting of branched alkyl groups having 5 to 20 carbon atoms;
  • (e222) at least one type of substituted oxyalkylene monomer units wherein the substituents are selected from the group consisting of alkyl, cycloalkyl, aryl, alkyl-cycloalkyl, alkyl-aryl, cycloalkyl-aryl and alkyl-cycloalkyl-aryl groups;
  • the surfactant (E) is
  • (e1 1 ) at least one hydrophobic group selected from the group consisting of branched alkyl groups having 5 to 20 carbon atoms;
  • the properties of the composition (Q) and of the process (P), such as cleaning performance in general and the efficiency of removing passivation films, may depend on the pH of the corresponding composition.
  • the pH value of the composition (Q) is preferably at least 2, more preferably at least 3, most preferably at least 4, particularly at least 5, for example at least 5.5.
  • the pH value of the composition (Q) is preferably not more than 1 1 , more preferably not more than 10, most preferably not more than 9, particularly preferably not more than 8, particularly not more than 7, for example not more than 6.5.
  • the composition (Q) can further optionally contain at least one pH adjusting agent (G).
  • the pH adjusting agent (G) is a compound which is added to the composition (Q) to have its pH value adjusted to the required value.
  • the composition (Q) contains at least one pH adjusting agent (G).
  • Preferred pH adjusting agents (G) are inorganic acids, carboxylic acids, and alkali hydroxides.
  • the pH adjusting agent (G) is sulfuric acid, sodium hydroxide, or potassium hydroxide.
  • the pH adjusting agent (G) is sulfuric acid, or potassium hydroxide.
  • the pH adjusting agent (G) can be contained in varying amounts. If present, the amount of (G) is preferably not more than 10 wt.%, more preferably not more than 2 wt.%, most preferably not more than 0.5 wt.%, particularly not more than 0.1 wt.%, for example not more than 0.05 wt.%, based on the total weight of the composition (Q). If present, the amount of (G) is preferably at least 0.0005 wt.%, more preferably at least 0.005 wt.%, most preferably at least 0.025 wt.%, particularly at least 0.1 wt.%, for example at least 0.4 wt.%, based on the total weight of the composition (Q).
  • composition (Q) may also contain, if necessary, various other additives, including but not limited to stabilizers, friction reducing agents, biocides, or preservatives etc.
  • Said other additives are for instance those commonly employed in post-CMP cleaning compositions and thus known to the person skilled in the art. Such addition can for example stabilize the post-CMP cleaning compositions, or improve the cleaning performance.
  • said other additive can be contained in varying amounts.
  • the total amount of said other additives is not more than 10 wt.%, more preferably not more than 2 wt.%, most preferably not more than 0.5 wt.%, particularly not more than 0.1 wt.%, for example not more than 0.01 wt.%, based on the total weight of the composition (Q).
  • the total amount of said other additives is at least 0.0001 wt.%, more preferably at least 0.001 wt.%, most preferably at least 0.008 wt.%, particularly at least 0.05 wt.%, for example at least 0.3 wt.%, based on the total weight of the composition (Q).
  • (A-ii) stands for "cysteine, cystine, glutathione, N-acetylcysteine, or a derivative thereof";
  • (C-i) stands for "a water-soluble compound having at least two hydroxyl (-OH) groups which do not dissociate in the aqueous medium"
  • N-i stands for "the total amounts of NH 4 + , any sulfur-free organic ammonium ions, and any sulfur-free amines".
  • composition (Q) comprises
  • composition (Q) comprises
  • composition (Q) comprises
  • composition (Q) comprises
  • composition (Q) does not comprise NH 4 + or any sulfur-free organic am- monium ions or any sulfur-free amines.
  • composition (Q) comprises
  • composition (Q) comprises
  • composition (Q) comprises
  • composition (N-i) does not exceed 100 ppm based on the total weight of the composition (Q) and wherein the composition (Q) has a pH value of from 4 to 8.
  • composition (Q) comprises
  • composition (N-i) does not exceed 100 ppm based on the total weight of the composition (Q) and wherein the composition (Q) has a pH value of from 4 to 8.
  • composition (Q) comprises
  • a metal chelating agent selected from the group consisting of propane-1 ,2,3- tricarboxylic acid, citric acid, butane-1 ,2,3,4-tetracarboxylic acid, pentane- 1 ,2,3,4,5-pentacarboxylic acid, trimellitic acid, trimesinic acid, pyromellitic acid, mellitic acid and oligomeric or polymeric polycarboxylic acids,
  • composition (Q) comprises
  • composition (Q) comprises
  • composition (Q) comprises
  • composition (Q) comprises
  • composition (Q) comprises
  • composition (Q) comprises
  • composition (Q) comprises
  • composition (Q) does not comprise NH 4 + or any sulfur-free organic ammonium ions or any sulfur-free amines.
  • composition (Q) comprises
  • composition (Q) comprises
  • composition wherein the composition has a pH value of from 4 to 8.
  • composition (Q) comprises
  • composition wherein (N-i) does not exceed 100 ppm based on the total weight of the composition (Q) and wherein the composition has a pH value of from 4 to 8.
  • composition (Q) comprises
  • composition (Q) does not comprise Nh or any sulfur-free organic ammonium ions or any sulfur-free amines.
  • composition (Q) comprises
  • (N-i) does not exceed 100 ppm based on the total weight of the composition (Q)
  • the amounts of (A), (C), (D) are - independently from each other - each in the range of from 0.001 wt. % to 0.5 wt.% based on the total weight of composition (Q)
  • the amount of (E) is in the range of from 0.005 wt. % to 2 wt.% based on the total weight of composition (Q).
  • the preparation of the composition (Q) does not exhibit any particularities but can be carried out by dissolving or dispersing the above-described ingredients (A) and (B) and optionally (D) and/or (E) and/or other additives in the aqueous medium (C), in particular, in de-ionized water and, most preferably, in ultra-pure water.
  • the customary and standard mixing processes and mixing apparatuses such as agitated vessels, in-line dissolvers, high shear impellers, ultrasonic mixers, homogenizer nozzles or counterflow mixers, can be used.
  • a large variety of conventional cleaning tools and methods can be used for the process (P) or for the application of the composition (Q) in a post-CMP cleaning step.
  • cleaning tools include megasonic cleaners, brush cleaners and combinations thereof.
  • the brushes are made up of soft and porous polyvinyl alcohol materials.
  • the brushes may have different shapes depending on the manufacturer of the processing tool. Most common shapes are rollers, discs and pencils.
  • the semiconductor sub- strates are removed from the composition and dried.
  • the drying step can be carried out as described, for example, in the American patent application US 2009/02191873 A1 , page 4, paragraph [0022].
  • the cleaning or removal performance i.e., the degree of the removal of residues and contami- nants, of the composition (Q) and the process (P) can be determined in accordance with various methods.
  • the performance is evaluated by comparing untreated semiconductor surfaces with the respective semiconductor surfaces that have been treated with the composition (Q) and the process (P).
  • SCM scanning electron microscopy
  • AFM atomic force microscopy
  • Ludox ® TM50 is colloidal silica in form of a 50 wt. % suspension in H2O and is obtained from Sigma-Aldrich.
  • Lutensol ® XP80 is a branched amphiphilic nonionic surfactant provided by BASF SE. It is alkyl polyethylene glycol ether based on Cio-Guerbet alcohol and ethylene oxide. Sokalan ® CP 12 S is a polymeric polycarboxylic acid provided by BASF SE. It is a maleic acid / acrylic acid copolymer.
  • silica slurry was composed of 0.5 wt.% Ludox ® TM50 at pH 4.
  • a sample coupon was first dipped into 0.02 wt.% HNO3 for 35s, rinsed by deionized water, and thereafter dipped into silica slurry for 5min, then rinsed by deionized water for 15s.
  • Each coupon was then dipped into the subject surfactant solution for 2min, rinsed by deionized water for 15s.
  • the coupons were hung to air dry under ambient conditions. Dried coupons were evaluated by scanning electron microscopy (SEM) for evidence of remaining silica abrasive. The dried coupons were com- pared.
  • SEM scanning electron microscopy
  • the contact angle for deionized water (deionized water is referred to as "DIW” in the following) on treated and untreated copper wafer surface was determined.
  • the electrochemical plating copper wafer copper surface without any treatment has a DIW contact angle of approximately 80°, implying that there was organic residues adsorption on copper surface.
  • Copper coupon was immersed in 0.02wt.% HNO3 for 35s and rinsed with DIW to get fresh surface.
  • the fresh copper surface has a DIW contact angle of approximately 50°, indicating that the surface was relative hydrophilic.
  • the copper coupon with HNO3 pre-treatment was immersed in 0.2wt.% benzotriazole solution (benzotriazole is referred to as "BTA" in the following) for 5min, rinsed by DIW and compressed air drying.
  • BTA benzotriazole
  • the Cu-BTA surface has a DIW contact angle of approximately 89°, indicating that the surface was relative hydrophobic (i.e., non-wetting).
  • the Cu-BTA surface was dipped in a variety of compositions as listed in table A for 5min, rinsed with DIW for 15s and followed by compressed air drying for 1 min, thereafter the contact angle of DIW was deter- mined immediately. For comparison, the contact angle of DIW on fresh copper surface treated with the same composition was also determined.
  • Table A The surfaces examined are summarized below in Table A.
  • Cu-BTA surfaces treated with citric acid, serine, urea have a contact angle of approximately 64°, 75°, 67°, respectively, indicating that the treated surfaces were still relative hydrophobic.
  • fresh Cu surface treated with citric acid, serine, urea have contact angle of 41 °, 46°, 38°, respectively, implying that the treated surfaces were hydrophilic.
  • both Cu-BTA surface and fresh Cu surface treated with cysteine have DIW contact angle of approximate 34° and 32°.
  • Acetyl-cysteine treated Cu-BTA surface has a DIW contact angle of 43°, which is the same with acetyl-cysteine treated fresh copper surface.
  • thiourea treated Cu-BTA surface has a DIW contact angle of approximately 63°, which is close to DIW contact angle on thiourea treated fresh copper surface.
  • the cleaning efficiency of BTA film on Cu surface was evaluated by Tafel plot measurement.
  • Fresh Cu wafer coupon was immersed in 0.2% BTA solution having a natural pH 5.8 for 15min, rinsed by DIW and followed by compressed air drying.
  • As working electrode, relative to Ag/AgCI reference electrode, the BTA treated copper coupon was immersed in a variety of compositions for measurement.
  • fresh copper coupon was also dipped in the variety of compositions for measurement.
  • the corrosion potential and corrosion current of substrates in differ- ent solutions are summarized below in Table B.
  • the corrosion current of copper treated with 0.2 wt.% BTA in DIW pH 6 is 0.018 ⁇ /cm 2 , which is much lower than the corrosion current of fresh copper in the same solution, indicating that the high passivation efficiency of BTA film on Cu surface.
  • the corrosion current of fresh copper in citric acid and serine is much higher than corrosion current of copper in blank solution (DIW pH 6).
  • the corrosion current of Cu-BTA surface in citric acid and serine is lower than the corrosion current of Cu surface in the same solution, but relative higher than the Cu-BTA surface in blank solution.
  • the corrosion potential of Cu-BTA is higher than Cu surface, implying that the citric acid and serine could remove some amount of BTA layer but BTA film was still on copper surface.
  • corrosion current of Cu-BTA in acetyl-cysteine, cysteine, and thiourea solution were almost identical to the corrosion current of Cu surface in the same solution, indicating that Cu-BTA film was removed by the solutions completely.
  • the BTA removal efficiency may be predicted simply by measuring corrosion potential and corrosion current of Cu-BTA and Cu surface.
  • the nitrogen to copper ratio indicates the amount of BTA remaining on the copper surface.
  • the citric acid and serine could remove some layer of BTA, but still left BTA on the wafer surface.
  • compounds comprising at least one thiol, thioether or thiocarbonyl group for example acetyl-cysteine, cysteine, and thiourea have high BTA removal efficiency.
  • Tests were conducted to evaluate the relative cleaning performance of different formulations as listed in table D. Copper coupon was dipped in 0.02wt.% HNO3 for 35s, rinsed with DIW and followed by compress air drying. The coupon was dipped in 0.2 wt.% BTA for 5min, rinsed with
  • Control sample Z was a coupon which was dipped in 0.2 wt.% BTA for 5min, rinsed with DIW, thereafter the Cu-BTA surface of this coupon was immersed in 0.5 wt.%
  • the cleaning compositions S32 and S33 show an improved cleaning performance. Dip test series no. 2 Tests were conducted to evaluate the cleaning performance of various cleaning compositions at different pH condition. These test compositions were prepared as set forth in Table E. All the compositions were adjusted by diluted KOH or HNO3. The prepared cleaning compositions were evaluated using electrochemical plating copper wafer according to the following procedure. The wafer was polished by barrier slurry containing silica particles, H2O2, BTA. Thereafter, the pol- ished wafer was cut into coupons. Copper coupons were dipped into cleaning compositions for 5min and then rinsed by Dl water for 15s followed by compress air drying for 1 min.
  • compositions containing a compound comprising at least one thiol, thioether or thiocarbonyl group have good performance at pH 3, 6 and 10.5. Therefore, the post-CMP cleaning compositions of the invention are suited for application in acidic, neutral and alkaline conditions.
  • the cleaning compositions S35, S36, S37, S44, S45 and S46 show an improved cleaning per- formance.
  • Figure 1 shows the SEM analysis results of the dip test series no. 1 using the cleaning composi- tions S31 , S32, S33, S34 as well as the SEM analysis results of control sample Z.
  • Figure 2 shows the SEM analysis results of the dip test series no. 2 using the cleaning compositions S35, S36, S37, S38, S39, S40 as well as the SEM analysis results of control sample Y.
  • Figure 3 shows the SEM analysis results of the dip test series no. 2 using the cleaning compositions S41 , S42, S43, S44, S45, and S46.

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Abstract

Cette invention concerne une composition de nettoyage de type post-polissage mécano-chimique (post-CMP) comprenant : (A) au moins un composé contenant au moins un groupe thiol (-SH), thioéther (-SR1) ou thiocarbonyle (>C=S), R1 étant un alkyle, un aryle, un alkylaryle ou un arylalkyle, et (B) un milieu aqueux. Les quantités totales de NH4+, de tout ion ammonium organique sans soufre et de toute amine sans soufre contenus dans la composition ne dépassent pas 100 ppm sur la base du poids total de la composition.
PCT/IB2013/050932 2012-02-06 2013-02-04 Composition de nettoyage de type post-polissage mécano-chimique (post-cmp) comprenant un composé spécifique contenant du soufre et dépourvue de quantités significatives de composés spécifiques contenant de l'azote WO2013118042A1 (fr)

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CN116262889A (zh) * 2021-12-13 2023-06-16 上海新阳半导体材料股份有限公司 等离子刻蚀清洗后中和清洗剂在清洗半导体器件中的应用

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JP6880047B2 (ja) * 2016-09-21 2021-06-02 株式会社フジミインコーポレーテッド 表面処理組成物

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WO2005093031A1 (fr) * 2004-03-05 2005-10-06 L'air Liquide-Societe Anonyme A Directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation Des Procedes Georges Claude Chimie acide amelioree destinee au nettoyage post-planarisation chimico-mecanique
CN101130876A (zh) * 2006-08-25 2008-02-27 安集微电子（上海）有限公司 用于半导体制程中的金属防腐蚀清洗液
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WO2010048139A2 (fr) * 2008-10-21 2010-04-29 Advanced Technology Materials, Inc. Formules de nettoyage et de protection du cuivre

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WO2005093031A1 (fr) * 2004-03-05 2005-10-06 L'air Liquide-Societe Anonyme A Directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation Des Procedes Georges Claude Chimie acide amelioree destinee au nettoyage post-planarisation chimico-mecanique
CN101130876A (zh) * 2006-08-25 2008-02-27 安集微电子（上海）有限公司 用于半导体制程中的金属防腐蚀清洗液
US20090088361A1 (en) * 2007-09-28 2009-04-02 Fujifilm Corporation Cleaning agent for semiconductor device and cleaning method using the same
WO2010048139A2 (fr) * 2008-10-21 2010-04-29 Advanced Technology Materials, Inc. Formules de nettoyage et de protection du cuivre

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CN116262889A (zh) * 2021-12-13 2023-06-16 上海新阳半导体材料股份有限公司 等离子刻蚀清洗后中和清洗剂在清洗半导体器件中的应用
CN116262889B (zh) * 2021-12-13 2024-02-23 上海新阳半导体材料股份有限公司 等离子刻蚀清洗后中和清洗剂在清洗半导体器件中的应用

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