CN105869997A - Amine-free post-CMP composition and using method thereof - Google Patents

Amine-free post-CMP composition and using method thereof Download PDF

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Publication number
CN105869997A
CN105869997A CN201610274374.1A CN201610274374A CN105869997A CN 105869997 A CN105869997 A CN 105869997A CN 201610274374 A CN201610274374 A CN 201610274374A CN 105869997 A CN105869997 A CN 105869997A
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acid
residue
cleasing compositions
compositions
weight
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杰弗里·A·巴尼斯
刘俊
张鹏
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Entegris Inc
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Mykrolis Corp
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Priority to CN201610274374.1A priority Critical patent/CN105869997A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041—Cleaning
    • H01L21/02057—Cleaning during device manufacture
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/044—Hydroxides or bases
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/43—Solvents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/06—Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5004—Organic solvents
    • C11D7/5009—Organic solvents containing phosphorus, sulfur or silicon, e.g. dimethylsulfoxide
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5004—Organic solvents
    • C11D7/5022—Organic solvents containing oxygen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041—Cleaning
    • H01L21/02057—Cleaning during device manufacture
    • H01L21/0206—Cleaning during device manufacture during, before or after processing of insulating layers
    • H01L21/02063—Cleaning during device manufacture during, before or after processing of insulating layers the processing being the formation of vias or contact holes
    • 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
    • H01L21/02074—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a planarization of conductive layers
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2041—Dihydric alcohols
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2065—Polyhydric alcohols
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2068—Ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3454—Organic compounds containing sulfur containing sulfone groups, e.g. vinyl sulfones
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/261—Alcohols; Phenols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/263—Ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/34—Organic compounds containing sulfur

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  • Chemical Kinetics & Catalysis (AREA)
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  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Microelectronics & Electronic Packaging (AREA)
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  • Manufacturing & Machinery (AREA)
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  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Cleaning Or Drying Semiconductors (AREA)
  • Detergent Compositions (AREA)

Abstract

The invention relates to an amine-free post-CMP (chemical-mechanical polishing) composition and a using method thereof, in particular to a cleaning composition and method for removing residues and contaminants from microelectronic devices with post-CMP residues and contaminants. The cleaning composition hardly contains amine and amine-containing compounds such as quaternary ammonium hydroxide. The composition can efficiently remove post-CMP residues and contaminants from the surfaces of microelectronic devices without damage to low -k dielectric materials or copper interconnection materials.

Description

Compositions and using method thereof after CMP without amine
The application is international filing date October 21, international application no in 2011 PCT/US2011/057287 enters National Phase in China, application number on May 27th, 2014 201180075099.6, denomination of invention " without compositions and using method thereof after amine CMP " point Case application.
Technical field
The present invention relates generally to the microelectronics device for having residue and/or pollutant from it The compositions of described residue and/or pollutant is cleaned on part.
Background technology
Microelectronic device wafer is used to form integrated circuit.Described microelectronic device wafer comprises Substrate such as silicon, has insulation, conduction or semiconductive character by the regions pattern of substrate with deposition Different materials.
In order to obtain appropriate patterning, it is necessary to remove and make during forming each layer on substrate Excess material.It addition, in order to manufacture functional and reliable circuit, it is important that rear Smooth or the microelectronic die surface of plane is prepared before continuous processing.Accordingly, it would be desirable to remove and/or Some surface of polish microelectronic device wafer.
Chemically mechanical polishing or planarization (" CMP ") be wherein by material from microelectronic component The surface of wafer removes and by physical method as ground and chemical method such as oxidation or the connection of chelating It is used for polishing the process on (more specifically planarization) described surface.In its most basic form, CMP includes that the solution using slurry such as abrasive material and active chemical is to polishing pad, polishing microelectronics The surface of device wafer is to complete to remove, planarize and polishing process.By purely physical effect or Removal that purely chemical action is constituted or polishing process are the most unsatisfactory, but need both Synergistic combination is to realize removing rapidly and uniformly.In the fabrication of integrated circuits, CMP slurry should This can also preferentially remove the thin film of the composite bed including metal and other materials, such that it is able to raw Become the surface of elevation plane for photoetching subsequently or patterning, etching and processing film.
Recently, copper has been haveed increasingly been used in the metal interconnection in integrated circuit.It is being usually used in micro-electricity In the manufacture of sub-device in the metallized copper inlaying process of circuit, it is necessary to be removed and flattened Layers of copper that layer comprises the thickness with about 1～1.5mm and there is the thickness of about 0.05～0.15 μm Copper crystal seed layer.These layers of copper pass through typically aboutThick spacer material layer and dielectric material Material surface separates, and this prevents copper to be diffused in oxide dielectric material.After polishing at wafer One that obtains excellent homogeneity on surface it is critical only that use has appropriate removal to various materials Selective CMP slurry.
Above-mentioned include that wafer substrate surface prepares, deposits, electroplates, etches and chemically-mechanicapolish polishes Process operation need clean operation to ensure that microelectronic device products is without any dirt in many aspects Dye thing, not so described pollutant will deleteriously affect product function or even make it be not used to Its predetermined function.The particle of these pollutant is often less than 0.3 μm.
A particular problem in this respect is to stay microelectronic component lining after CMP processes Residue at the end.This kind of residue comprises CMP material and corrosion inhibitor compound such as benzo Triazole (BTA).If be not removed, then these residues may cause copper cash damage or make Copper metallization is the most coarse, and causes layer after-applied for CMP on the device substrate bad viscous ?.The serious coarse of copper metallization is a problem especially, because the copper of excess abrasive can cause micro- The bad electric property of electronic device product.
Microelectronic component produces common another residue generation process and includes vapor plasma Etching, it is in order to transfer on following layer by the pattern of the photoresist coating of development, institute Stating following layer can be by hard mask layer, interlayer dielectric (ILD) layer and etch stop layer group Become.May comprise the gas phase etc. of the chemical element being present on substrate and in plasma gas from Daughter post-etch residue be typically deposited on back-end process (BEOL) if in structure and not by Remove, then may interfere with silication subsequently or contact is formed.Conventional cleaning chemical often damages ILD, Absorb and the hole of ILD thus increases dielectric constant, and/or corrosion metal structure.
Summary of the invention
The microelectronic component that the present invention relates generally to have from it residue and pollutant cleans institute State residue and/or the compositions of pollutant and method.The Cleasing compositions of the present invention is substantially free of Amine and ammonium material.After described residue can comprise CMP, etching after and/or post-ash residue.
On the one hand, describe and include at least one basic salt, at least one organic solvent, at least A kind of chelating agent and the Cleasing compositions of water, wherein said compositions is substantially free of amine and ammonium salt-containing.
On the other hand, describe substantially by least one basic salt, at least one organic solvent, At least one chelating agent and the Cleasing compositions of water composition, wherein said compositions is substantially free of amine And ammonium salt-containing.
Another aspect, describes by least one basic salt, at least one organic solvent, at least A kind of chelating agent and the Cleasing compositions of water composition, wherein said compositions is substantially free of amine and contains Ammonium salt.
On the other hand relating to test kit, it is clear for being formed that it is included in one or more container The following reagent of one or more of cleansing composition, one or more reagent described are selected from: at least one Plant basic salt；At least one organic solvent；At least one chelating agen；With optionally at least one table Face activating agent；Wherein said test kit is applicable to form described compositions.
The microelectronic component relating in one aspect to again have from it residue and pollutant removes described Residue and the method for pollutant, described method includes making described microelectronic component and cleaning combination Thing contact time enough with from described microelectronic component clean at least in part described residue and Pollutant, wherein said Cleasing compositions comprises at least one basic salt；At least one is organic molten Agent；At least one chelating agen；Optionally at least one surfactant；And water.
By disclosure below and claims, other aspect, feature and advantage will more Add apparent.
Detailed description of the invention
The present invention relates generally to the microelectronic component that can be used for that there are residue and pollutant from it Remove the compositions of described material.After described compositions is particularly useful for removing CMP, after etching Or post-ash residue.
For the ease of mentioning, " microelectronic component " corresponding to Semiconductor substrate, flat faced display, Phase transformation storage device, solar panel and comprise solar energy substrate, light cell and microelectromechanicpositioning Other products of system (MEMS), it is manufactured for microelectronics, integrated circuit or calculating Machine chip application.Solar energy substrate include but not limited to silicon, non-crystalline silicon, polysilicon, monocrystal silicon, CdTe, copper indium diselenide, sulfuration copper and indium and the GaAs on gallium.Described solar energy substrate is permissible For doping or undoped.It should be understood that term " microelectronic component " is not intended to by any way It is any limitation as, but comprises and finally will become any substrate of microelectronic component or micromodule.
Time used herein, " residue " is corresponding to including but not limited to that plasma loses Carve, be ashed, chemically-mechanicapolish polish, the microelectronic component production period of Wet-type etching and combinations thereof The particle produced.
Time used herein, " pollutant " corresponding to chemicals present in the CMP slurry, The byproduct of reaction of polishing slurries, chemicals, wet type erosion present in the Wet-type etching compositions Carve compositions byproduct of reaction and as CMP process, Wet-type etching, plasma etching or Any other material of the by-product of plasma ashing procedure.
Time used herein, " residue after CMP " is corresponding to the particle from polishing slurries As the particle containing silica, present in this slurry chemicals, polishing slurries reaction secondary Product, rich carbon particle, polishing pad particle, brushing off-load (brush deloading) particle, structure Pelletize the son equipment and materials of (construction particle), copper, copper oxide, organic residue Any other material with the by-product as CMP process.
As defined in this article, " low-k dielectric material " is corresponding in stratiform microelectronic component Any material used as dielectric material, the dielectric that wherein said material has less than about 3.5 is normal Number.Preferably, described low-k dielectric material comprises low polar material, the most siliceous organic polymer Thing, containing silicon hybridization organic/inorganic materials, organic silicate glass (OSG), TEOS, fluoro Oxide (CDO) glass of silicate glass (FSG), silicon dioxide and carbon doping.Ying Liao Solve described low-k dielectric material and can have different density and different porositys.
As defined in this article, " chelating agent " comprises art technology person personnel and is interpreted as complexation Those compounds of agent, chelating agen and/or screening agent.Chelating agent will be intended to use as herein described The metallic atom of compositions removing and/or metal ion chemistry combine or physics keeps described metal admittedly here Atom and/or metal ion.
As defined in this article, term " barrier material " is corresponding to being used in the art sealing Metal wire such as copper-connection (copper interconnect) is so that described metal such as copper is to dielectric material The minimized any material of diffusion.Preferably barrier material comprise tantalum, titanium, ruthenium, hafnium, Tungsten, other refractory metals and their nitride and silicide with and combinations thereof.
As defined in this article, " post-etch residue " is corresponding to etching at vapor plasma The material of residual after the processing of process such as BEOL dual-metal inserting or Wet-type etching process.Institute Stating post-etch residue can be organic residue, organo-metallic residues, organosilicon residue Or substantially inorganic residue such as material, carbon back organic material and etching gas residue be such as Oxygen and fluorine.
As defined in this article, corresponding at oxygen when " post-ash residue " is used herein Change or reduction plasma ashing is to remove photoresist and/or the anti-reflective coating of bottom of hardening The material of residual after layer (BARC) material.Described post-ash residue can be organic residue Thing, organo-metallic residues, organosilicon residue or substantially inorganic residue.
" be substantially free of " be defined herein as being based on the total weight of the composition less than 2 weight %, Preferably smaller than 1 weight %, more preferably less than 0.5 weight % and more preferably less than 0.1 weight %.
Time used herein, " about " be intended to corresponding to described value ± 5%.
Time used herein, there is the microelectronic component cleaning of residue and pollutant from it " fitness " of described residue and pollutant is corresponding to from this microelectronic component at least in part Remove described residues/contaminants.Cleaning efficiency is come by the minimizing of object on microelectronic component It is evaluated.Such as, analyze before cleaning and cleaning post analysis can use atomic force microscope to enter OK.Particle on sample can be registered as pixel coverage.Rectangular histogram can be applied (such as, Sigma Scan Pro) filter pixel count particles number with a certain intensity such as 231～235.Grain Son minimizing can use following formula to calculate:
It should be noted that and determine that the method for cleaning efficiency is only used as example and provides, and be not wishing to It is any limitation as.Or, cleaning efficiency can be considered as the summary table covered by particle matter The percent in face.For example, it is possible to by AFM programming to carry out z-plane scanning to identify a certain Target shaped area on height threshold and calculate the summary table covered by described target area subsequently The area in face.Those skilled in the art is covered by described target area after will be apparent from cleaning Area the least, then the efficiency of Cleasing compositions is the highest.Preferably, combination as herein described is used Thing removes the residues/contaminants of at least 75% from microelectronic component, more preferably at least 90%, The residues/contaminants of even more desirably at least 95% and most preferably at least 99% is removed.
As described more fully below, compositions as herein described can be with various concrete preparations Embody.
In all such compositions, wherein with regard to the percetage by weight model of concrete component of compositions Enclosing and be described it, described scope comprises 0 lower limit, it should be appreciated that such component exists The various detailed description of the invention of described compositions there may be or do not exist, and existing In the case of stating component, they may be low in terms of the gross weight of the compositions using such component Concentration to 0.001 weight % exists.
Described Cleasing compositions includes following material, is made up of following material or substantially by following Material form: at least one basic salt, at least one organic solvent, at least one chelating agent, Water and optionally at least one surfactant.The most described water is deionized water.Described cleaning group Compound is residual after being particularly useful for residue after residue contamination and pollutant, such as CMP, etching Stay thing, post-ash residue and the pollutant from microelectronic device structure.
In one embodiment, described Cleasing compositions includes following material, by following material Composition or be substantially made up of following material: at least one basic salt, at least one organic solvent, At least one chelating agent and water.In another embodiment, described Cleasing compositions includes following Material, it is made up of following material or is substantially made up of following material: at least one basic salt, At least one organic solvent, at least one chelating agent, water and at least one surfactant.? In another embodiment, described Cleasing compositions includes following material, be made up of following material or Substantially it is made up of following material: at least one basic salt, at least one organic solvent, at least Two kinds of chelating agent and water.
Regardless of embodiment, described Cleasing compositions is all substantially free of amine and ammonium salt-containing, example Such as quaternary ammonium base.It addition, described compositions before use, as before cleaning chemical preferably without with At least one in lower material: oxidant；Source containing fluoride；Grinding-material；Alkaline earth Metal base；The organic polymer particle of crosslinking；And combinations thereof.It addition, described Cleasing compositions Should not solidify to form polymer/solid, such as photoresist.For the purpose of the present invention, " amine " is defined as at least one primary amine, secondary amine or tertiary amine, ammonia and/or quaternary ammonium hydroxide chemical combination Thing (such as, ammonium hydroxide, alkyl ammonium hydroxide, hydroxide alkylaryl ammonium etc.), its limit Condition processed is: (i) amide group, (ii) comprise hydroxy-acid group and the material of amido, (iii) surfactant and (iv) wherein amido of comprising amido are that substituent group (such as, connects Receive aryl or heterocyclic moiety) material be not viewed as " amine " according to this definition.Amine formula can With by NR1R2R3Represent, wherein R1、R2And R3Can be same to each other or different to each other, and selected from hydrogen, Straight or branched C1-C6Alkyl (such as, methyl, ethyl, propyl group, butyl, amyl group, hexyl), C6-C10Aryl (such as, benzyl), straight or branched C1-C6Alkanol (such as, methanol, second Alcohol, propanol, butanol, amylalcohol, hexanol) and combinations thereof, its restrictive condition is R1、R2And R3 Hydrogen can not be all.Quaternary phosphonium hydroxides ammonium compounds has general formula R1R2R3R4NOH, wherein R1、R2、 R3And R4It is same to each other or different to each other and for hydrogen, C1-C6Alkyl (such as, methyl, ethyl, third Base, butyl, amyl group or hexyl) and substituted or unsubstituted C6-C10Aryl is (such as, Benzyl)；And alkanolamine.
For compositions as herein described and the purpose of method, at least one basic salt described is permissible Comprise Cesium hydrate., rubidium hydroxide, potassium hydroxide and combinations thereof, preferably Cesium hydrate. and/or hydrogen Rubidium oxide, even more preferably Cesium hydrate..Preferably select at least one basic salt described so that Even if compositions as herein described maintains its initial pH after dilution several times the most substantially, the dilutest The pH=initial pH ± 2pH unit released, the pH initial for pH=more preferably diluted ± About 1pH unit.
At least one organic solvent described is preferably polyhydric alcohol, sulfone or a combination thereof, the most described many Unit's alcohol can include at least one material selected from following material: ethylene glycol, propylene glycol, new penta Glycol, glycerol (also referred to as glycerol), diethylene glycol, dipropylene glycol, 1,4-butanediol, 2,3- Butanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 3-methyl isophthalic acid, 5-pentanediol and Combination.Described sulfone can include at least one material selected from following material: tetramethylene sulfone (ring Fourth sulfone), dimethyl sulfone, diethyl sulfone, double (2-hydroxyethyl) sulfone, methyl sulfolane, second Base sulfolane and combinations thereof.At least one organic solvent preferably described includes as single solvent Tetramethylene sulfone, glycerol, propylene glycol, ethylene glycol or its combination in any.The most described at least A kind of organic solvent is methylene sulfone.
Described chelating agent can include at least one in following material: ethylenediaminetetraacetic acid (EDTA), 1,2-cyclohexane diamine-N, N, N', N'-tetraacethyl (CDTA), glycine, anti- Bad hematic acid, iminodiacetic acid (IDA), nitrilotriacetic acid(NTA), alanine, arginine, sky Asparagine, aspartic acid, cysteine, glutamic acid, glutamine, histidine, different Leucine, leucine, lysine, methionine, phenylalanine, proline, serine, Soviet Union Propylhomoserin, tryptophan, tyrosine, valine, gallic acid, boric acid, acetic acid, acetone oxime, Acrylic acid, adipic acid, glycine betaine, dimethyl glyoxime, formic acid, fumaric acid, gluconic acid, 1,3-propanedicarboxylic acid, glyceric acid, glycolic, glyoxalic acid, M-phthalic acid, itaconic acid, lactic acid, horse Come sour, maleic anhydride, malic acid, malonic acid, mandelic acid, 2,4-pentanedione, phenylacetic acid, Phthalic acid, proline, propanoic acid, catechol (pyrocatecol), PMA, Kui Buddhist nun's acid, Sorbitol, succinic acid, tartaric acid, p-phthalic acid, trimellitic acid, benzene equal three Acid, tyrosine, xylitol, 1,5,9-triazododecane-N, N', N "-three (methylene phosphonic acids) (DOTRP), Cyclen-N, N', N ", N' "-four (methylene phosphonic acids) (DOTP), nitrilo-three (methylene) tri methylene phosphonic acid, diethylenetriamines five (methylene phosphine Acid) (DETAP), amino three (methylene phosphonic acid), 1-hydroxy ethylene-1,1-di 2 ethylhexyl phosphonic acid (HEDP), double (hexa-methylene) triamine phosphonic acids, 1,4,7-7-triazacyclononane-N, N', N "- Three (methylene phosphonic acid) (NOTP), its salt and derivant, and combinations thereof.The most described extremely Few a kind of chelating agent include the iminodiacetic acid as single chelating agent, boric acid, gallic acid, HEDP or its any combination.At least one chelating agent most preferably described include boric acid, HEDP or Boric acid and the combination of HEDP.
The illustrative surfactant used in compositions as herein described includes but not limited to two Property salt, cationic surfactant, anion surfactant, fluoroalkyl surfactants, Nonionic surfactant and combinations thereof, includes but not limited to104、CF-21、UR、FSO-100、 FSN-100,3M Fluorad fluorine-containing surfactant (that is, FC-4430 and FC-4432), Dioctyl sulfosuccinate, 2,3-dimercapto-1-propane sulfonic acid salt, DBSA, poly-second Glycol, polypropylene glycol, Polyethylene Glycol or polypropylene glycol ether, carboxylate, R1Benzenesulfonic acid or its salt (wherein, R1For straight or branched C8-C18Alkyl), amphipathic fluoride polymer, poly-second two Alcohol, polypropylene glycol, Polyethylene Glycol or polypropylene glycol ether, carboxylate, DBSA, The poly-silica of polyacrylate polymers, dinonylphenyl polyoxyethylene, polysiloxanes or modification The alkylammonium salt of the acetylenic glycols of alkane polymer, acetylenic glycols or modification, alkylammonium salt or modification, with And include the combination of at least one in following material: above-mentioned surfactant, dodecyl sulfur Acid sodium, zwitterionic surfactant, aerosol-OT (AOT) and fluoro analogs thereof, Alkylammonium, perfluoropolyether surfactants, 2-sulfosuccinate, based on phosphatic surface live Property agent, surfactant based on sulfur and polymer based on acetoacetic ester.It is being preferable to carry out In mode, described surfactant comprises alkyl benzene sulphonate, more preferably DBSA.
The pH of Cleasing compositions as herein described is more than 7, preferably in the range of about 8～about 14, More preferably in the range of about 8～about 13.
In a preferred embodiment, described Cleasing compositions includes following material, by following material Composition or be substantially made up of following material: at least one basic salt, at least one organic solvent, At least two chelating agent and water.Such as, described Cleasing compositions includes following material, by following Material composition or be substantially made up of following material: CsOH, at least one organic solvent, at least Two kinds of chelating agent and water.In another embodiment, described Cleasing compositions include following material, It is made up of following material or is substantially made up of following material: CsOH, sulfone, at least two complexation Agent and water.In another embodiment, described Cleasing compositions includes following material, by following Material composition or be substantially made up of following material: CsOH, sulfone, phosphonic acids and at least one additionally Chelating agent and water.
In particularly preferred embodiments, described Cleasing compositions include following material, by with Lower material forms or is substantially made up of following material: (a) Cesium hydrate., glycerol, imido Base oxalic acid and water；(b) Cesium hydrate., glycerol, boric acid and water；(c) Cesium hydrate., Propylene glycol, gallic acid and water；(d) Cesium hydrate., ethylene glycol, iminodiacetic acid and Water；(e) Cesium hydrate., propylene glycol, boric acid and water；(f) Cesium hydrate., HEDP, Tetramethylene sulfone, boric acid and water.In each case, described compositions is substantially free of: amine and Ammonium salt-containing, such as quaternary ammonium base；Oxidant；The source of fluoride；Grinding-material；Alkaline earth gold Belong to alkali；And combinations thereof.
The example of compositions as herein described is selected from preparation A-R:
Preparation A:4.0 weight %CsOH (50%), 12 weight % ethylene glycol, 0.8 weight %IDA, 83.2 weight % water, the pH=12.22 of concentration, the pH (30:1)=10.36 of dilution
Preparation B:7.1 weight %CsOH (50%), 5 weight % ethylene glycol, 1.6 weight %IDA, 86.3 weight % water, the pH=11.88 of concentration, the pH (30:1)=10.27 of dilution
Formulation C: 5.7 weight %CsOH (50%), 12 weight % ethylene glycol, 0.8 weight % IDA, 1 weight % ascorbic acid, 80.5 weight % water, the pH=11.41 of concentration, dilution PH (30:1)=9.89
Preparation D:9.1 weight %CsOH (50%), 12 weight % ethylene glycol, 1.6 weight %IDA, 1 weight % ascorbic acid, 76.3 weight % water, the pH=11.16 of concentration, dilution PH (30:1)=10.1
Preparation E:3.9 weight %CsOH (50%), 5.0 weight % glycerol, 0.8 weight %IDA, 90.3 weight % water, the pH=12.0 of concentration, the pH (30:1)=10.16 of dilution
Preparation F:4.0 weight %CsOH (50%), 12.0 weight % glycerol, 0.8 weight % IDA, 83.2 weight % water, the pH=11.1 of concentration, the pH (30:1)=9.5 of dilution
Preparation G:7.1 weight %CsOH (50%), 5.0 weight % glycerol, 1.6 weight %IDA, 86.3 weight % water, the pH=11.5 of concentration, the pH (30:1)=10.29 of dilution
Preparation H:5.7 weight %CsOH (50%), 12.0 weight % glycerol, 0.8 weight % IDA, 1.0 weight % ascorbic acid, 80.5 weight % water, the pH=10.8 of concentration, dilution PH (30:1)=9.61
Preparation I:8.8 weight %CsOH (50%), 5.0 weight % glycerol, 1.6 weight %IDA, 1.0 weight % ascorbic acid, 83.6 weight % water, the pH=12.3 of concentration, the pH (30:1) of dilution =10.64
Preparation J:7.4 weight %CsOH (50%), 12.0 weight % glycerol, 1.6 weight %IDA, 79.0 weight % water, the pH=10.7 of concentration, the pH (30:1)=9.81 of dilution
Formulation K: 6.3 weight %CsOH (50%), 4.8 weight % propylene glycol, 2 weight % Gallic acid, 86.9 weight % water, the pH=9.71 of concentration
Preparation L:6.6 weight %CsOH (50%), 10 weight % propylene glycol, 2 weight % Gallic acid, 81.4 weight % water, the pH=10.32 of concentration
Preparation M:15.7 weight %CsOH (50%), 4.8 weight % propylene glycol, 5 weight % gallic acid, 74.5 weight % water, the pH=10.14 of concentration
Preparation N:16.2 weight %CsOH (50%), 4.8 weight % propylene glycol, 5 weight % gallic acid, 1 weight % ascorbic acid, 73 weight % water, the pH=9.28 of concentration
Preparation O:2.1 weight %CsOH (50%), 8.5 weight % glycerol, 0.4 weight % Iminodiacetic acid, 89.0 weight % water
Preparation P:2.5 weight %CsOH (50%), 12 weight % ethylene glycol, 0.6 weight % Iminodiacetic acid, 84.9 weight % water
Preparation Q:4 weight %CsOH (50%), 12 weight % glycerol, 3.3 weight % boron Acid, 80.7 weight % water, the pH=7.17 of concentration, the pH (100:1)=8.54 of dilution
Preparation R:4 weight %CsOH (50%), 4.8 weight % propylene glycol, 3.3 weight % Boric acid, 87.9 weight % water, the pH=8.4 of concentration, the pH (100:1)=8.59 of dilution
Preparation S:3 weight %CsOH, 1.2 weight %HEDP, 9 weight % tetramethylene sulfone, 0.25 weight % boric acid, 86.55 weight % water
In concentrate, the concentration of component is preferably as follows:
Component Preferred weight % More preferably weight %
Basic salt (undiluted) About 1～about 9 weight % About 1～about 5 weight %
Organic solvent About 4～about 12 weight % About 7～about 11 weight %
Chelating agent About 0.1～about 4 weight % About 0.5～about 2 weight %
Water About 75～about 99 weight % About 82～about 91.5 weight %
About the amount of composition, the percentage by weight of each component is preferably as follows: basic salt: chelating agent is About 0.1:1～about 10:1, preferably from about 0.5:1～about 4:1 and most preferably about 1:1～about 3:1；And Organic solvent: chelating agent is about 0.1:1～about 25:1, preferably from about 1:1～about 20:1, and most preferably It is about 2:1～about 15:1.
The weight percentage ranges of described component will contain all possible concentration of described compositions Or dilution embodiment.About this, in one embodiment, it is provided that the cleaning combination of concentration Thing, it can be diluted to use as clean solution.The compositions concentrated or " concentrate " Advantageously allow for user such as CMP engineer the dilution of described concentrate to be expired in use The intensity hoped and pH.The dilution factor of the Cleasing compositions of described concentration can at about 1:1～about In the range of 2500:1, preferably from about 5:1～about 1500:1 and most preferably about 10:1～about 1000:1, Wherein said Cleasing compositions such as goes with solvent when for instrument or before will being used for instrument Ionized water dilutes.It will be apparent to those skilled in the art that after the dilution, component is relative to each other The scope of percentage by weight will keep constant.
Compositions as herein described may be used for including but not limited to post-etch residue removal, ash After change removing residues surface prepare, electroplate after cleaning and CMP after removing residues application in.
Another preferred embodiment in, Cleasing compositions as herein described also comprises residue And/or pollutant.Importantly, described residue and pollutant can dissolve and/or be suspended in described In compositions.The most described residue comprises residue, post-etch residue, ashing after CMP Rear residue, pollutant or a combination thereof.Such as, described Cleasing compositions can include following thing Matter, it is made up of following material or is substantially made up of following material: at least one basic salt, extremely Few a kind of organic solvent, at least one chelating agent, water, optionally at least one surfactant and Residue and/or pollutant.
Described Cleasing compositions is by being simply added into corresponding composition and being mixed into uniform state and hold Change places preparation.It addition, described compositions can be easily formulated as single packaged preparation or be made Many certain formulations of mixing before used time or use, such as, each portion of described many certain formulations Divide and can mix at instrument or in the storage tank of instrument upstream.The concentration of corresponding composition can be with The concrete multiple of described compositions is widely varied, the dilutest or richer, it is to be understood that described herein Compositions can diversely and alternatively include the composition consistent with disclosure herein Combination in any, be made up of the combination in any of described composition or substantially by described composition appoint Meaning combination composition.
Therefore, on the other hand relating to test kit, what it was included in one or more container is suitable for Form one or more components of compositions as herein described.Described test kit can be included in one At least one basic salt in individual or multiple container, at least one organic solvent, at least one network Mixture, optionally at least one surfactant, and optionally water, in order to adding man-hour or using Combine with make-up water at Dian.The container of described test kit must be appropriate for storing and transporting described removal Compositions, such asContainer (Advanced Technology Materials Inc (Advanced Technology Materials,Inc.),Danbury,Conn.,USA)。
The one or more container of component containing described removal compositions preferably comprises and makes Component flow connection in the one or more container is to blend and assigned unit.Such as, AboutContainer, can be applied to gas pressure in the one or more container The outside of lining to promote being discharged at least partially and thus making of the inclusions of described lining Obtain and can be in fluid communication to blend and distributing.Or, gas pressure can be applied to routine The headroom of pressurisable container, maybe can use pump to be capable of fluid communication.It addition, Described system is preferably included for being assigned to the removal compositions blended the distribution of process tool Mouthful.
Basic chemical inertness, free from foreign meter, flexible and elastic polymeric film material are preferably used As high density polyethylene (HDPE) manufactures the lining for the one or more container.Desirable The processing of lining material need not coextrusion or barrier layer, and without negatively affecting desire cloth Put any pigment of purity requirement, UV inhibitor or the processing aid of component in lining.Close The inventory of the lining material needed comprises and includes pure (additive-free) polyethylene, pure polytetrafluoro Ethylene (PTFE), polypropylene, polyurethane, polyvinylidene chloride, polrvinyl chloride, polyacetals, The thin film of polystyrene, polyacrylonitrile, polybutene etc..The preferred thickness of such lining material In the range of about 5 mils (0.005 inch)～about 30 mils (0.030 inch), such as thick Degree is 20 mils (0.020 inches).
About test kit container, by the disclosure of following patents and patent applications with it each During form in full is expressly incorporated herein by reference: entitled " make the particle in ultrarapture liquid produce Minimized equipment and method (APPARATUS AND METHOD FOR MINIMIZING THE GENERATION OF PARTICLES IN ULTRAPURE LIQUIDS) U.S. Patent number 7,188,644 "；Entitled " recyclable and reusable In Tong pocket type fluid storage and distribution containment system (RETURNABLE AND REUSABLE, BAG-IN-DRUM FLUID STORAGE AND DISPENSING CONTAINER SYSTEM) U.S. Patent number 6,698,619 "；John E.Q.Hughes was at 2007 5 Entitled " system and method (the SYSTEMS blending for material and distributing submitted to by the moon 9 AND METHODS FOR MATERIAL BLENDING AND DISTRIBUTION) U.S. Patent Application No. 60/916,966 "；Have with advanced techniques material Limit company on May 9th, 2008 submit to entitled " for material blend and distribution system and Method (SYSTEMS AND METHODS FOR MATERIAL BLENDING AND DISTRIBUTION) PCT/US08/63276 ".
When being applied to microelectronics production operation when, Cleasing compositions as herein described is useful Ground for from the surface cleaning residue (such as, residue after CMP) of microelectronic component and/ Or pollutant.Importantly, described Cleasing compositions does not damage low-k dielectric material or corrosion at device Metal interconnection on part surface.Additionally, described Cleasing compositions will not easily remove silicon or poly- Silicone compositions.The most described Cleasing compositions removes and deposited on device before removing residues At least 85%, more preferably at least 90%, even more desirably at least 95% and most preferably at least The residue of 99%.
After cmp in residue and pollutant clean applications, described Cleasing compositions can with respectively Plant conventional burnisher such as mega sonic wave and brush scrubbing to be used together, include but not limited to Verteq Single-chip mega sonic wave Goldfinger, OnTrak systems DDS (bilateral scrubber), SEZ Or other single-chip spray irrigations (single wafer spray rinse), Applied Materials Mirra-MesaTM/ReflexionTM/Reflexion LKTMDesktop system is washed with mega sonic wave batch (Megasonic batch wet bench system)。
Using compositions as herein described after residue, etching after having CMP from it The microelectronic component of residue, post-ash residue and/or pollutant clean these residues and/or During pollutant, described Cleasing compositions typically with described device at about 20 DEG C～about 90 DEG C, in the range of preferably from about 20 DEG C～about 50 DEG C at a temperature of contact about 5 seconds～about 10 minutes, Preferably from about 1 second～20 minutes, preferably from about 15 seconds～the time of about 5 minutes.Such time of contact It is illustrative with temperature, and any other suitable time and temperature conditions, institute can be used Condition of stating cleans institute from described device in the broad practice of described method effectively at least in part State residues/contaminants after CMP." cleaning at least in part " and " substantially removing " are the most right Should in remove before removing residues present on device at least 85%, more preferably at least 90%, even more desirably at least 95% and the residue of most preferably at least 99%.
As in applying in the appointment final use of compositions as herein described it may be desirable to and effectively Ground, after realizing desired cleaning action, described Cleasing compositions can be used from previously Its device easily removes.Preferably, rinse solution comprises deionized water.Subsequently, described device Part can use nitrogen or Rotary drying cyclic drying.
The advantage of the compositions and methods of the invention includes but not limited to substantially remove grain from surface Son, from surface basic organic and metal residue, passive metal such as the copper surface, substantially of removing Do not change porous low-k dielectric material and low metal surface roughening.It addition, described compositions is excellent Elect environmental protection as.
Relate in one aspect to again the microelectronic component of improvement made according to method described herein and contain There is the product of described microelectronic component.
On the other hand relating to the Cleasing compositions of recirculation, wherein said Cleasing compositions can be again Circulation is until residue and/or pollutant burden reach those skilled in the art such as is readily determined The maximum that can accommodate of described Cleasing compositions.
Another aspect is directed to use with Cleasing compositions as herein described, produces and includes microelectronic component The method of goods, described method includes making described microelectronic component contact foot with Cleasing compositions The enough time, to have the microelectronic component described residual of removing of residue and pollutant from it Thing and pollutant, and described microelectronic component is incorporated in described goods.
On the other hand, describe and there is residue and the microelectronics device of pollutant from it after CMP Part removes residue and the method for pollutant after described CMP, and described method includes:
Described microelectronic component is polished with CMP slurry；
Described microelectronic component is made to contact time enough with Cleasing compositions, with from described micro-electricity After sub-device removing CMP, residue and pollutant are to be formed containing the combination of residue after CMP Thing, described Cleasing compositions includes following material, is made up of following material or substantially by following Material form: at least one basic salt, at least one organic solvent, at least one chelating agent, Optionally at least one surfactant and water；With
Described microelectronic component is made to contact continuously containing the compositions of residue after CMP with described Time enough cleans to realize the basic of described microelectronic component,
Wherein said Cleasing compositions is substantially free of: amine and ammonium salt-containing, such as quaternary ammonium base；Oxidation Agent；Source containing fluoride；Grinding-material；Alkaline earth metal alkali；And combinations thereof.
On the other hand relating to the goods produced, it includes Cleasing compositions, microelectronic device wafer With the material selected from residue, pollutant and combinations thereof, wherein said Cleasing compositions include to Few a kind of basic salt, at least one organic solvent, at least one chelating agent, optionally at least one Surfactant and water, and wherein said residue include residue after CMP, etching after remain At least one in thing and post-ash residue.
Although diversely disclosing this by reference to illustrated embodiment and feature in this article Bright, it is to be appreciated that embodiments described above and feature are not intended to limit the present invention, and And on the basis of disclosure, other change, improvement and other embodiments are to this Field those of ordinary skill will be apparent to.Therefore need to be broadly construed as the present invention to cover institute There are change, improvement and optional embodiment party such, in the spirit and scope of claims Formula.

Claims (25)

  1. Residue and micro-electricity of pollutant (after CMP) after there is chemically mechanical polishing the most from it Sub-device removes residue and the method for pollutant after described CMP, and described method includes making described Microelectronic component contacts time enough with Cleasing compositions, with from described microelectronic component at least Partly clean residue and pollutant after described CMP, wherein said Cleasing compositions include to Few a kind of basic salt, at least one organic solvent, at least one chelating agent and water, wherein said Cleasing compositions is substantially free of amine and ammonium salt-containing.
  2. 2. the method for claim 1, uses solvent dilution when it is additionally included in use or before using Described Cleasing compositions.
  3. 3. the process of claim 1 wherein that at least one basic salt described includes selected from following Material: Cesium hydrate., rubidium hydroxide, potassium hydroxide and combinations thereof.
  4. 4. the process of claim 1 wherein that at least one basic salt described includes Cesium hydrate..
  5. 5. the process of claim 1 wherein at least one organic solvent described include polyhydric alcohol, Sulfone or a combination thereof.
  6. 6. the process of claim 1 wherein that at least one organic solvent described includes selected from following Material: ethylene glycol, propylene glycol, neopentyl glycol, glycerol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 2,3-butanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, four Asias Methyl sulfone (sulfolane), dimethyl sulfone, diethyl sulfone, double (2-hydroxyethyl) sulfone, methyl Sulfolane, ethylsulfolane and combinations thereof.
  7. 7. the process of claim 1 wherein that at least one chelating agent described includes selected from following Material: ethylenediaminetetraacetic acid (EDTA), 1,2-cyclohexane diamine-N, N, N', N'-tetraacethyl (CDTA), glycine, ascorbic acid, iminodiacetic acid (IDA), nitrilo-three second Acid, alanine, arginine, asparagine, aspartic acid, cysteine, glutamic acid, Glutamine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, Proline, serine, threonine, tryptophan, tyrosine, valine, gallic acid, boron Acid, acetic acid, acetone oxime, acrylic acid, adipic acid, glycine betaine, dimethyl glyoxime, formic acid, Fumaric acid, gluconic acid, 1,3-propanedicarboxylic acid, glyceric acid, glycolic, glyoxalic acid, M-phthalic acid, Itaconic acid, lactic acid, maleic acid, maleic anhydride, malic acid, malonic acid, mandelic acid, 2,4-penta Diketone, phenylacetic acid, phthalic acid, proline, propanoic acid, catechol, PMA, Quinic acid, Sorbitol, succinic acid, tartaric acid, p-phthalic acid, trimellitic acid, benzene are equal Three acid, tyrosine, xylitol, its salt and derivant, and combinations thereof.
  8. 8. the process of claim 1 wherein that described Cleasing compositions is substantially free of oxidant, contains Have the source of fluoride, grinding-material, alkaline earth metal alkali, the organic polymer particle of crosslinking and A combination thereof.
  9. 9. the method for claim 2, wherein said Cleasing compositions is at about 10:1～about 1000:1 In the range of dilute.
  10. 10. the process of claim 1 wherein that the pH of described Cleasing compositions is about 8～about 14 In the range of.
  11. 11. Cleasing compositions, it includes CsOH, sulfone, phosphonic acids, complexation that at least one is other Agent and water, wherein said compositions is substantially free of amine and ammonium salt-containing.
  12. The Cleasing compositions of 12. claim 11, wherein said sulfone includes selected from following material: Tetramethylene sulfone, dimethyl sulfone, diethyl sulfone, double (2-hydroxyethyl) sulfone, methyl sulfolane, Ethylsulfolane and combinations thereof.
  13. The Cleasing compositions of 13. claim 11, wherein said phosphonic acids includes selected from following thing Matter: 1,5,9-triazododecane-N, N', N "-three (methylene phosphonic acid) (DOTRP), Cyclen-N, N', N ", N " '-four (methylene phosphonic acid) (DOTP), secondary Nitrilo three (methylene) tri methylene phosphonic acid, diethylene triamine penta(methylene phosphonic acid) (DETAP), Amino three (methylene phosphonic acid), 1-hydroxy ethylene-1,1-di 2 ethylhexyl phosphonic acid (HEDP), double (six Methylene) triamine phosphonic acids, 1,4,7-7-triazacyclononane-N, N', N "-three (methylene phosphonic acids) (NOTP), its salt and derivant, and combinations thereof.
  14. The Cleasing compositions of 14. claim 11, at least one other chelating agent wherein said Including selected from following material: ethylenediaminetetraacetic acid (EDTA), 1,2-cyclohexane diamine -N, N, N', N'-tetraacethyl (CDTA), glycine, ascorbic acid, iminodiacetic acid (IDA), Nitrilotriacetic acid(NTA), alanine, arginine, asparagine, aspartic acid, half Guang ammonia Acid, glutamic acid, glutamine, histidine, isoleucine, leucine, lysine, egg ammonia Acid, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine, Gallic acid, boric acid, acetic acid, acetone oxime, acrylic acid, adipic acid, glycine betaine, dimethyl Glyoxime, formic acid, fumaric acid, gluconic acid, 1,3-propanedicarboxylic acid, glyceric acid, glycolic, glyoxalic acid, M-phthalic acid, itaconic acid, lactic acid, maleic acid, maleic anhydride, malic acid, malonic acid, Mandelic acid, 2,4-pentanedione, phenylacetic acid, phthalic acid, proline, propanoic acid, adjacent benzene two Phenol, PMA, quinic acid, Sorbitol, succinic acid, tartaric acid, p-phthalic acid, Trimellitic acid, trimesic acid, tyrosine, xylitol, its salt and derivant, and combinations thereof.
  15. The Cleasing compositions of 15. claim 11, wherein said compositions be substantially free of oxidant, Source containing fluoride, grinding-material, alkaline earth metal alkali, the organic polymer particle of crosslinking And combinations thereof.
  16. The Cleasing compositions of 16. claim 11, wherein said compositions comprise Cesium hydrate., HEDP, tetramethylene sulfone, boric acid and water.
  17. The Cleasing compositions of 17. claim 11, it also includes residue and pollutant, wherein Described residue includes residue after CMP, post-etch residue, post-ash residue or its group Close.
  18. The Cleasing compositions of 18. claim 11, wherein said compositions is at about 10:1～about Dilute in the range of 1000:1.
  19. The Cleasing compositions of 19. claim 11, wherein said Cleasing compositions does not solidify formation Polymer/solid.
  20. The Cleasing compositions of 20. claim 11, it also includes at least one surfactant.
  21. The Cleasing compositions of 21. claim 11, wherein pH is in the range of about 8～about 14.
  22. 22. have from it residue and pollutant microelectronic components remove described residues and The method of pollutant, described method includes making described microelectronic component and claim 11～21 The Cleasing compositions contact time enough of one, with from described microelectronic component at least in part Clean described residue and pollutant.
  23. The method of 23. claim 22, wherein said residue include residue after CMP, Post-etch residue, post-ash residue or a combination thereof.
  24. The method of 24. claim 22, wherein said contact includes selected from following condition: time Between be about 15 seconds～about 5 minutes；Temperature is in the range of about 20 DEG C～about 50 DEG C；And combinations thereof.
  25. The method of 25. claim 22, uses solvent dilute when it is additionally included in use or before using Release described Cleasing compositions.
CN201610274374.1A 2011-10-21 2011-10-21 Amine-free post-CMP composition and using method thereof Pending CN105869997A (en)

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