WO2006056298A1 - Resist stripper and residue remover for cleaning copper surfaces in semiconductor processing - Google Patents
Resist stripper and residue remover for cleaning copper surfaces in semiconductor processing Download PDFInfo
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- WO2006056298A1 WO2006056298A1 PCT/EP2005/011739 EP2005011739W WO2006056298A1 WO 2006056298 A1 WO2006056298 A1 WO 2006056298A1 EP 2005011739 W EP2005011739 W EP 2005011739W WO 2006056298 A1 WO2006056298 A1 WO 2006056298A1
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- 238000004140 cleaning Methods 0.000 title claims abstract description 58
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 22
- 239000010949 copper Substances 0.000 title claims abstract description 22
- 238000012545 processing Methods 0.000 title abstract description 9
- 239000004065 semiconductor Substances 0.000 title abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 65
- 239000000758 substrate Substances 0.000 claims abstract description 9
- 238000001465 metallisation Methods 0.000 claims abstract description 7
- 238000004377 microelectronic Methods 0.000 claims abstract description 6
- 229920000642 polymer Polymers 0.000 claims abstract description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 66
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 54
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 17
- 238000005260 corrosion Methods 0.000 claims description 16
- 230000007797 corrosion Effects 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 230000002401 inhibitory effect Effects 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 7
- 230000000269 nucleophilic effect Effects 0.000 claims description 2
- 229920002120 photoresistant polymer Polymers 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 150000002484 inorganic compounds Chemical class 0.000 abstract description 2
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 2
- 150000002894 organic compounds Chemical class 0.000 abstract description 2
- 150000002902 organometallic compounds Chemical class 0.000 abstract description 2
- 235000012431 wafers Nutrition 0.000 description 21
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 8
- 229910000679 solder Inorganic materials 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000006117 anti-reflective coating Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000006184 cosolvent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 2
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- CETRZFQIITUQQL-UHFFFAOYSA-N dmso dimethylsulfoxide Chemical compound CS(C)=O.CS(C)=O CETRZFQIITUQQL-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012536 packaging technology Methods 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
Classifications
-
- 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
- H01L21/02071—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a delineation, e.g. RIE, 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
- 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
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/426—Stripping or agents therefor using liquids only containing organic halogen compounds; containing organic sulfonic acids or salts thereof; containing sulfoxides
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/263—Ethers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3209—Amines or imines with one to four nitrogen atoms; Quaternized amines
-
- 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
- the present invention relates to new compositions for cleaning of microelectronic substrates, especially for copper metallizations or copper surfaces in semiconductor processing and wafer production. It also relates to the use of such cleaning compositions for stripping photoresists and cleaning residues from plasma generated organic, organometallic and inorganic compounds. Especially the invention relates to compositions of resist strippers or polymer resist removers and their use with better performance.
- BEOL semiconductor back end of line
- interconnects are made on the upper chip surface using metal bumps instead of the side contacted wire bonds.
- a variety of high-end processes are used for bumping or packaging wafers as WLP. Compared to the normal chip structures the dimensions of the bumps have to be relatively huge to meet the requirements of mechanical plugs. They are created by photolithography and metal deposition. In this photolithographic process a structure with deep wholes is produced. These wholes are filled with the solder bump metal (e.g. Sn/Ag). After removal of the resist mask the tower like bumps remain.
- Electroplating of metals and solder deposition use materials such as photoresists and fluxes that need to be completely removed during the manufacturing process. Failure to completely strip these materials can result in a contamination, yield loss, downstream problems in test and board-level assembly, and reliability fallout in the field.
- Bumping and WLP processes based on electroplating and solder paste have rigorous cleaning requirements. Wafers to be processed as flip chip or WLP come with a plethora of different under bump metallization (UBM), ° passivations (organic and inorganic), solders and substrates. All of these materials demand robust cleaning and stripping solutions. Cleaning chemistries and processes must remove polymerized and baked-on films without damaging or disturbing materials exposed in the process.
- UBM under bump metallization
- ° passivations organic and inorganic
- solders and substrates All of these materials demand robust cleaning and stripping solutions. Cleaning chemistries and processes must remove polymerized and baked-on films without damaging or disturbing materials exposed in the process.
- the stripping composition requires balancing the rate of attack on the intramolecular bonds controlling the surface adhesion of the film with the attack on the intramolecular bonds in the bulk film.
- the potential for redeposition of dissolved material on the wafer surface is limited by controlling the particulate size of the removed resist film.
- buffers and corrosion inhibitors may be added to reduce or eliminate metal etch.
- buffers and corrosion inhibitors may be added to reduce or eliminate metal etch.
- compositions containing NaOH, KOH, TMAH or amine, organic solvent water and surfactants are used for this application.
- Commercially available products are for example DYNASTRI P ® 7000, SUPER X ® , LOSOLIN IV ® or ORGASOLV STR ® 102 or 104. All these stripper compositions are not capable to remove the residue layer entirely without damaging the metal layer underneath.
- cleaning compositions containing cations of sodium or potassium may be disturbing in further processing steps.
- ammonia free cleaning compositions for cleaning microelectronic substrates containing 0,005 to 30 % by weight of one or more non-ammonium producing strong base like tetraalkylammonium hydroxide or a salt thereof, one or more corrosion inhibiting solvent compounds, water and/or other organic co-solvent, and further additives.
- Suitable tetraalkylammonium hydroxides are ammonium compounds in which alkyl is a alkyl group containing 1 to 22 carbon atoms.
- compositions may be used for stripping in wafer processing, but there is neither a disclosure about the influence of the compositions on layers underneath the resist layer during stripping nor is anything disclosed about remaining particles on the wafer surface.
- compositions comprising dimethyl sulfoxide
- DMSO methyl methoxysulfoxide
- TMAH tetramethylammonium hydroxide
- ethylene glycol as corrosion inhibiting solvent and low amounts of water satisfy this need and lead to very improved cleaning results.
- compositions comprising dimethyl sulfoxide (DMSO) in an amount of from about 85 to 95 % by weight, tetramethylammonium hydroxide (TMAH) in an amount of from about 0,5 to 4 % by weight, ethylene glycol in an amount of from about 1 - 4 % by weight and water in an amount of from about 3 to 9 % by weight satisfy this need and lead to very improved cleaning results.
- DMSO dimethyl sulfoxide
- TMAH tetramethylammonium hydroxide
- ethylene glycol in an amount of from about 1 - 4 % by weight
- water in an amount of from about 3 to 9 % by weight
- compositions which are free of cations of sodium or potassium and of ammonium producing compounds, lead unexpectedly to very improved cleaning results. It has been found, that a composition comprising a suitable solvent, which is stable under alkaline conditions, in combination with a further solvent, having metal-corrosion inhibiting properties which are useful . 5 to remove polymer resists with a thickness of at least 50 ⁇ m from wafer surfaces without damaging the underlying metal layer or prepared metal bumps.
- a non-ammonia producing strong base is added for achieving a strong basic condition during the cleaning process.
- a compound is added, which is a non-nucleophilic, positively charged ion.
- TMAH tetramethylammonium hydroxide
- cleaning compositions containing TMAH show very much improved compatibility with porous and low- ⁇ dielectrics and especially with copper metallization.
- cleaning compositions containing dimethyl sulfoxide (DMSO) as main solvent, ethylene glycol as corrosion inhibitor and water as a co-solvent are surprisingly able to clean wafer surfaces in WLP processes from polymer resists without leaving particles or damaging the metal layer underneath, if tetramethylammonium hydroxide (TMAH) is added as non ammonium producing strong base to this composition in a suitable amount.
- DMSO dimethyl sulfoxide
- ethylene glycol as corrosion inhibitor
- water as a co-solvent
- these improved compositions generally comprise dimethyl sulfoxide (DMSO) in an amount of from about 85 to 95 % by weight.
- Suitable compositions with improved properties comprise ethylene glycol in an amount of from about 1 - 4 % by weight as corrosion inhibiting solvent and water in an amount of from about 3 to 9 % by weight.
- the cleaning composition according to present invention comprises dimethyl sulfoxide (DMSO) in an amount of from about 88 to 92 % by weight as solvent, tetramethylammonium hydroxide (TMAH) ⁇ in an amount of from about 1 to 3 % by weight as non ammonium producing strong base, ethylene glycol in an amount of from about 1 to 3 % by weight as corrosion inhibiting solvent and water in an amount of from about 4 to 8 % by weight.
- DMSO dimethyl sulfoxide
- TMAH tetramethylammonium hydroxide
- the amounts of the comprising compounds may be varied in wide range as well as the processing or operating temperature during effectively removing and cleaning photo resists, adhesion promoters, post plasma etch/ash residues, sacrifical light absorbing materials or anti-reflective coatings (ARC). It has also been found, that compositions composed of compounds mentioned above in a special ratio are particular effective in cleaning, especially in cleaning wafer surfaces with copper layers. Surprisingly it has been found, that said compositions are not corrosive versus these copper layers.
- compositions comprising tetramethylammonium hydroxide (TMAH) in an amount of from about 1 ,5 to 2,5 % by weight.
- TMAH tetramethylammonium hydroxide
- DMSO dimethyl sulfoxide
- the experiments have shown that especially in cleaning procedures in bumping and WLP processes based on electroplating and solder paste ethylene glycol has only to be added to the improved cleaning compositions in an amount of from about 1 ,5 to 2,5 % by weight.
- the cleaning problem is solved by a composition comprising said compounds in about the following amounts: DMSO 90 weight %
- compositions of the present invention may be used in cleaning processes of microelectronic substrates having at least one copper metallization. They lead to improved results cleaning resist layers as well as in applications where polymerized and baked-on films have to be removed without damaging or disturbing materials exposed in the process.
- compositions as described are even suitable to remove photo resist layers of at least 50 ⁇ m thickness and more. Even resist layers of 200 ⁇ m thickness may removed entirely in very short time.
- the wafers are treated with the stripper solution according to the present invention. This can be carried out for example in an immersion bath.
- the cleaning result may be improved by moderate agitation.
- the process temperature and the immersion time may be varied.
- compositions according to the present invention may be used at a temperature in a range between 40 and 90 0 C, and very good cleaning results are achieved already, if the cleaning solution is warmed up to a temperature in the range of from 50 to 65 0 C.
- wafers are treated for at least 20 minutes up to 60 minutes and longer with the cleaning composition. If compositions according to the present invention are used, the time for the cleaning process may be reduced very much. Unexpectedly it has been found, that very improved cleaning results are achievable in reduced time. Already after a cleaning time of 10 minutes at a temperature of 60 0 C residue free wafer surfaces are found.
- the cleaning compositions according to the present invention are able to remove polymer resists and to clean wafer surfaces very fast and selectively. But the compositions according to the invention not only show improved cleaning results, additionally they show a long shelf life, and surprisingly their cleaning activity seems to increase, if they are stored for a longer time. For example compositions, which are stored for six months, lead to better cleaning results than freshly mixed compositions.
- the following application tests are performed in both, a stirred 500 ml glass beaker and in a 7 000 ml PTFE-immersion bath (the claimed chemical compositions are compatible with stainless steel tools).
- the immersion time is determined optically according to the change of colour of the wafer surfaces. Control is done by a following copper etch test, which shows unetched copper isles, if there are remaining resist residues after the stripping process on the treated surfaces. The surfaces are inspected with an optical microscope.
- compositions comprising of about 1 % by weight ethylene glycol in DMSO/TMAH mixtures have a lower oxidation activity versus copper layers than known mixtures and, what is a very unexpected result, show much lower corrosion if a stripper solution is used, containing 1 ,9 % by weight ethylene glycol, which has been stored for 6 months.
- Stripper compositions according to the invention also show superior cleaning behaviour on copper substrates and are suitable for the removal of resist layers of 200 ⁇ m thickness after mushroom plating on wafers.
- ethylene glycol is active as a corrosion inhibitor for copper in stripper mixtures.
- comparative measurements the influence of ethylene glycol on the corrosion behaviour of stripper compositions is shown and the influence of its concentration is examined.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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- Detergent Compositions (AREA)
- Cleaning Or Drying Semiconductors (AREA)
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Abstract
The present invention relates to new compositions for cleaning of microelectronic substrates, especially for copper metallizations or copper surfaces in semiconductor processing and wafer production. It also relates to the use of such cleaning compositions for stripping photoresists and cleaning residues from plasma generated organic, organometallic and inorganic compounds. Especially the invention relates to compositions of from resist strippers or polymer resist removers and their use with better performance.
Description
Resist Stripper and Residue Remover for Cleaning Copper Surfaces in Semiconductor Processing
FIELD OF THE INVENTION
The present invention relates to new compositions for cleaning of microelectronic substrates, especially for copper metallizations or copper surfaces in semiconductor processing and wafer production. It also relates to the use of such cleaning compositions for stripping photoresists and cleaning residues from plasma generated organic, organometallic and inorganic compounds. Especially the invention relates to compositions of resist strippers or polymer resist removers and their use with better performance.
BACKGROUND TO THE INVENTION
In semiconductor back end of line (BEOL) processing it is necessary to connect microchip conductor lines to the computer periphery.
The common procedure is the wire bonding of chip side contacts to the motherboard. Today this method is partly replaced by the "flip chip technology". "Flip chip" and wafer-level packaging (WLP) technologies have become ubiquitous in recent years in applications from consumer and wireless products to high-performance electronics. As requirements for high performance and reduced form factor grow in these applications, so do the demands on these packaging technologies.
Therefore, interconnects are made on the upper chip surface using metal bumps instead of the side contacted wire bonds. A variety of high-end processes are used for bumping or packaging wafers as WLP. Compared to the normal chip structures the dimensions of the bumps have to be relatively huge to meet the requirements of mechanical plugs. They are created by photolithography and metal deposition. In this photolithographic process a structure with deep wholes is produced. These wholes are filled with the solder bump metal (e.g. Sn/Ag). After removal of the resist mask the tower like bumps remain.
Electroplating of metals and solder deposition use materials such as photoresists and fluxes that need to be completely removed during the
manufacturing process. Failure to completely strip these materials can result in a contamination, yield loss, downstream problems in test and board-level assembly, and reliability fallout in the field.
Bumping and WLP processes based on electroplating and solder paste have rigorous cleaning requirements. Wafers to be processed as flip chip or WLP come with a plethora of different under bump metallization (UBM), ° passivations (organic and inorganic), solders and substrates. All of these materials demand robust cleaning and stripping solutions. Cleaning chemistries and processes must remove polymerized and baked-on films without damaging or disturbing materials exposed in the process.
, n Whereas for photolithographic structuring of underlying chip layers resist thicknesses of less than 1 μm are common, the described solder bump process needs a much higher resist thickness to achieve the required geometries (50 - 100 μm). This resist is applied as a dry film resist (DFR) or in multiple coats of a liquid resist. Removal of thick resists requires long soak
1 C. time and high temperature. Also a special and extremely efficient chemistry is necessary to remove this relatively high amount of photo resist without attacking the top and sides of the copper post. In extreme cases, strippers have disturbed the bus metal and attacked the organic passivations underneath. In case that the underlying substrate is copper, the surrounding
20 copper has to be removed by wet etching after solder bump structuring. The efficacy of a stripping chemistry is a function of the chemistry's constituents and process, time and temperature. Chemistries for stripping in advanced WLP processes do not follow the general rule of "the stronger the better". Removal of these crosslinked polymers from the wafer surface typically pc requires use of a formulated product containing one or more solvents in combination with a source of alkalinity. The combined composition of a suitable solvent and base swells and dissolves the polymer film. This swelling increases the penetration of alkaline components, which in general are NaOH, KOH, TMAH or amine. It may also cause lifting off the film from
30 the wafer. Therefore, the stripping composition requires balancing the rate of attack on the intramolecular bonds controlling the surface adhesion of the film with the attack on the intramolecular bonds in the bulk film. The potential for redeposition of dissolved material on the wafer surface is limited by controlling the particulate size of the removed resist film. Special additives
35 are used to lower surface tension, aid in penetration and redeposition. According to the common state of the art buffers and corrosion inhibitors may be added to reduce or eliminate metal etch.
Usually compositions containing NaOH, KOH, TMAH or amine, organic solvent water and surfactants are used for this application. Commercially available products are for example DYNASTRI P® 7000, SUPER X®, LOSOLIN IV® or ORGASOLV STR® 102 or 104. All these stripper compositions are not capable to remove the residue layer entirely without damaging the metal layer underneath. Besides, cleaning compositions containing cations of sodium or potassium may be disturbing in further processing steps.
In WO 03/006598 A ammonia free cleaning compositions for cleaning microelectronic substrates are described, containing 0,005 to 30 % by weight of one or more non-ammonium producing strong base like tetraalkylammonium hydroxide or a salt thereof, one or more corrosion inhibiting solvent compounds, water and/or other organic co-solvent, and further additives. Suitable tetraalkylammonium hydroxides are ammonium compounds in which alkyl is a alkyl group containing 1 to 22 carbon atoms. From the description of this application someone skilled in the art is informed, that a variety of compositions may be used for stripping in wafer processing, but there is neither a disclosure about the influence of the compositions on layers underneath the resist layer during stripping nor is anything disclosed about remaining particles on the wafer surface.
BRIEF SUMMARY OF THE INVENTION
Therefore, there is a need for improved cleaning or stripper compositions suitable for residue free removal of an at least 50 μm thick photoresist layer without attacking the underlying copper surface whereas conventional resist strippers show copper attack before removal.
Now it has been found, that compositions, comprising dimethyl sulfoxide
(DMSO) as solvent, tetramethylammonium hydroxide (TMAH) as non ammonium producing strong base, and ethylene glycol as corrosion inhibiting solvent and low amounts of water satisfy this need and lead to very improved cleaning results.
Especially, compositions comprising dimethyl sulfoxide (DMSO) in an amount of from about 85 to 95 % by weight, tetramethylammonium hydroxide (TMAH) in an amount of from about 0,5 to 4 % by weight,
ethylene glycol in an amount of from about 1 - 4 % by weight and water in an amount of from about 3 to 9 % by weight satisfy this need and lead to very improved cleaning results.
After cleaning, rinsing and drying the wafer surfaces are particle free and cleaned without attack of the deeper metal surfaces. 5
DETAILED DESCRIPTION OF THE INVENTION
Experiments have shown, that in advanced WLP processes cleaning , 0 compositions, which are free of cations of sodium or potassium and of ammonium producing compounds, lead unexpectedly to very improved cleaning results. It has been found, that a composition comprising a suitable solvent, which is stable under alkaline conditions, in combination with a further solvent, having metal-corrosion inhibiting properties which are useful .5 to remove polymer resists with a thickness of at least 50 μm from wafer surfaces without damaging the underlying metal layer or prepared metal bumps. For achieving a strong basic condition during the cleaning process a non-ammonia producing strong base is added. Preferably a compound is added, which is a non-nucleophilic, positively charged ion. Especially ?n preferred is the addition of tetramethylammonium hydroxide (TMAH) or a suitable salt of it. Cleaning compositions containing TMAH show very much improved compatibility with porous and low-κ dielectrics and especially with copper metallization.
According to the present invention cleaning compositions containing dimethyl sulfoxide (DMSO) as main solvent, ethylene glycol as corrosion inhibitor and water as a co-solvent are surprisingly able to clean wafer surfaces in WLP processes from polymer resists without leaving particles or damaging the metal layer underneath, if tetramethylammonium hydroxide (TMAH) is added as non ammonium producing strong base to this composition in a suitable amount. Compositions containing tetramethylammonium hydroxide in an amount of from about 0,5 to 4 % by weight show much improved cleaning results in comparison to commercially available compositions for this purpose.
According to the present invention these improved compositions generally comprise dimethyl sulfoxide (DMSO) in an amount of from about 85 to 95 % by weight. Suitable compositions with improved properties comprise
ethylene glycol in an amount of from about 1 - 4 % by weight as corrosion inhibiting solvent and water in an amount of from about 3 to 9 % by weight.
In a preferred embodiment the cleaning composition according to present invention comprises dimethyl sulfoxide (DMSO) in an amount of from about 88 to 92 % by weight as solvent, tetramethylammonium hydroxide (TMAH) ^ in an amount of from about 1 to 3 % by weight as non ammonium producing strong base, ethylene glycol in an amount of from about 1 to 3 % by weight as corrosion inhibiting solvent and water in an amount of from about 4 to 8 % by weight.
^ ° Thus, depending on the nature of the wafer surface to be cleaned the amounts of the comprising compounds may be varied in wide range as well as the processing or operating temperature during effectively removing and cleaning photo resists, adhesion promoters, post plasma etch/ash residues, sacrifical light absorbing materials or anti-reflective coatings (ARC). It has also been found, that compositions composed of compounds mentioned above in a special ratio are particular effective in cleaning, especially in cleaning wafer surfaces with copper layers. Surprisingly it has been found, that said compositions are not corrosive versus these copper layers.
Especially good cleaning results could be achieved with compositions comprising tetramethylammonium hydroxide (TMAH) in an amount of from about 1 ,5 to 2,5 % by weight. For the preparation of these compositions dimethyl sulfoxide (DMSO) may be especially varied in the range of from about 89 to 91 % by weight. The experiments have shown that especially in cleaning procedures in bumping and WLP processes based on electroplating and solder paste ethylene glycol has only to be added to the improved cleaning compositions in an amount of from about 1 ,5 to 2,5 % by weight.
Although in general no further water needs to be added to compositions on according to the present invention by using in an aqueous solution comprising TMAH in an amount of 25 % by weight, it has been found, that very improved cleaning results may be achieved, if the water content is in a range between 5 to 7 % by weight.
35
In a very preferred embodiment the cleaning problem is solved by a composition comprising said compounds in about the following amounts:
DMSO 90 weight %
TMAH 2 weight %
Ethylenglycol 2 weight %
Water 6 weight %
It is self-explaining that the summed-up total amount of all compounds of the whole composition shall not exceed 100 % by weight and it will be apparent to those skilled in the art that various modifications and variations can be made to the composition of the present invention without departing from the scope or spirit of the invention. In view of the foregoing, it is self-explaining that the present invention covers modifications and variations of this invention provided they fall within the scope of the following claims and their equivalents.
Compositions of the present invention may be used in cleaning processes of microelectronic substrates having at least one copper metallization. They lead to improved results cleaning resist layers as well as in applications where polymerized and baked-on films have to be removed without damaging or disturbing materials exposed in the process.
Depending on the complete manufacturing process and depending on the surfaces, which have to be cleaned someone skilled in the art may vary the amount of the added compounds, and if it is needed he may add suitable surfactants, further chelating agents or other additives, but in general this should not be necessary, because the compositions as described are even suitable to remove photo resist layers of at least 50 μm thickness and more. Even resist layers of 200 μm thickness may removed entirely in very short time.
In order to clean wafer surfaces the wafers are treated with the stripper solution according to the present invention. This can be carried out for example in an immersion bath. The cleaning result may be improved by moderate agitation. The process temperature and the immersion time may be varied. In general compositions according to the present invention may be used at a temperature in a range between 40 and 90 0C, and very good cleaning results are achieved already, if the cleaning solution is warmed up to a temperature in the range of from 50 to 65 0C.
Usually wafers are treated for at least 20 minutes up to 60 minutes and longer with the cleaning composition. If compositions according to the present invention are used, the time for the cleaning process may be reduced very much. Unexpectedly it has been found, that very improved cleaning results are achievable in reduced time. Already after a cleaning time of 10 minutes at a temperature of 60 0C residue free wafer surfaces are found.
In summary the cleaning compositions according to the present invention are able to remove polymer resists and to clean wafer surfaces very fast and selectively. But the compositions according to the invention not only show improved cleaning results, additionally they show a long shelf life, and surprisingly their cleaning activity seems to increase, if they are stored for a longer time. For example compositions, which are stored for six months, lead to better cleaning results than freshly mixed compositions.
Now, the present invention will be described in further detail with reference to
Examples. However, it should be understood that the present invention is not limited to such specific examples within the scope of the subject matter of the present invention.
Examples
Depending on the size of the processed wafer-sample the following application tests are performed in both, a stirred 500 ml glass beaker and in a 7 000 ml PTFE-immersion bath (the claimed chemical compositions are compatible with stainless steel tools). In each case the immersion time is determined optically according to the change of colour of the wafer surfaces. Control is done by a following copper etch test, which shows unetched copper isles, if there are remaining resist residues after the stripping process on the treated surfaces. The surfaces are inspected with an optical microscope.
List of abbreviations: DMSO Dimethylsulfoxide
TMAH Tetramethylammoniumhydroxide EG Ethylenglycole
(unless otherwise described, solutions of 90 % by weight DMSO and 2 % by weight TMAH are used)
Table 1 :
In the following Table 2 results of stripping experiments with compositions according to the present invention are compared with those of traded compositions.
Table 2: Processing and Results
=> change of concentration towards
Examination of corrosion properties:
By measuring cyclovoltaic properties of compositions it is possible to find out something about the cleaning activity and about the corrosion activity versus metal surfaces. A configuration of a suitable measuring fixture for measuring cytovoltagramms is given in Fig. 1.
Surprisingly measurements of cyclovoltaic properties show that compositions comprising of about 1 % by weight ethylene glycol in DMSO/TMAH mixtures have a lower oxidation activity versus copper layers than known mixtures and, what is a very unexpected result, show much lower corrosion if a stripper solution is used, containing 1 ,9 % by weight ethylene glycol, which has been stored for 6 months.
Stripper compositions according to the invention also show superior cleaning behaviour on copper substrates and are suitable for the removal of resist layers of 200 μm thickness after mushroom plating on wafers. As can be shown in cyclovoltametric measurements ethylene glycol is active as a corrosion inhibitor for copper in stripper mixtures. In comparative measurements the influence of ethylene glycol on the corrosion behaviour of stripper compositions is shown and the influence of its concentration is examined.
In Fig. 2 the influence of ethylene glycol (2%) in DMSO/TMAH-solution on corrosion inhibition of copper is shown.
Claims
1. Cleaning composition for microelectronic substrates and for removal of polymer resist layers or plasma etch residues comprising dimethyl sulfoxide (DMSO), tetramethylammonium hydroxide (TMAH), ethylene glycol and water.
2. Cleaning composition according to claim 1 , comprising tetramethylammonium hydroxide (TMAH) in an amount of from about 1 ,5 to 2,5 % by weight.
3. Cleaning composition according to one of the preceding claims 1 to 2, comprising dimethyl sulfoxide (DMSO) in an amount of from about 87 to 93 % by weight.
4. Cleaning composition according to one of the preceding claims 1 to 3, comprising ethylene glycol in an amount of from about 1 ,5 to 2,5 % by weight.
5. Cleaning composition according to one of the preceding claims 1 to 4, comprising water in an amount of from about 3 to 9 % by weight.
6. Cleaning composition according to claim 1 , comprising dimethyl sulfoxide (DMSO) in an amount of from about 85 to 95 % by weight as solvent, tetramethylammonium hydroxide (TMAH) in an amount of from about 0,5 to 4 % by weight as non ammonium producing strong base, ethylene glycol in an amount of from about 1 - 4 % by weight as corrosion inhibiting solvent and water in an amount of from about 3 to 9 % by weight.
7. Cleaning composition according to claim 1, comprising dimethyl sulfoxide (DMSO) in an amount of from about 88 to 92 % by weight as solvent, tetramethylammonium hydroxide (TMAH) in an amount of from about 1 to 3 % by weight as non ammonium producing strong base, ethylene glycol in an amount of from about 1 to 3 % by weight as corrosion inhibiting solvent and water in an amount of from about 4 to 8 % by weight.
8. Cleaning composition according to claim 1 , comprising dimethyl sulfoxide (DMSO) in an amount of from about 89 to 91 % by weight as solvent tetramethylammonium hydroxide (TMAH) in an amount of from about 1 ,5 to 2,5 % by weight as non nucleophilic strong base, ethylene glycole in an amount of from about 1,5 to 2,5 % by weight as corrosion inhibiting solvent and water in an amount of from about 5 to 7 % by weight.
9. Use of a cleaning composition according one or more of the preceding claims 1 to 8 in a cleaning process of a microelectronic substrate having at least a copper metallization.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP04027980.4 | 2004-11-25 | ||
| EP04027980 | 2004-11-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2006056298A1 true WO2006056298A1 (en) | 2006-06-01 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2005/011739 WO2006056298A1 (en) | 2004-11-25 | 2005-11-03 | Resist stripper and residue remover for cleaning copper surfaces in semiconductor processing |
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|---|---|
| TW (1) | TW200634450A (en) |
| WO (1) | WO2006056298A1 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2460860A1 (en) | 2010-12-02 | 2012-06-06 | Basf Se | Use of mixtures for removing polyurethanes from metal surfaces |
| CN101685274B (en) * | 2008-09-26 | 2012-08-22 | 安集微电子（上海）有限公司 | Cleaning agent for thick-film photoresist |
| CN101685273B (en) * | 2008-09-26 | 2014-06-04 | 安集微电子（上海）有限公司 | Cleanout fluid for removing photoresist layer residue |
| CN111162001A (en) * | 2018-11-08 | 2020-05-15 | 三星电子株式会社 | Method for cleaning semiconductor chip |
| WO2020219334A1 (en) * | 2019-04-24 | 2020-10-29 | Fujifilm Electronic Materials U.S.A., Inc. | Stripping compositions for removing photoresists from semiconductor substrates |
| US10947484B2 (en) | 2016-05-23 | 2021-03-16 | Fujifilm Electronic Materials U.S.A., Inc. | Stripping compositions for removing photoresists from semiconductor substrates |
| US11986853B2 (en) | 2015-06-03 | 2024-05-21 | SCREEN Holdings Co., Ltd. | Substrate processing apparatus, film formation unit, substrate processing method and film formation method |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101685274B (en) * | 2008-09-26 | 2012-08-22 | 安集微电子（上海）有限公司 | Cleaning agent for thick-film photoresist |
| CN101685273B (en) * | 2008-09-26 | 2014-06-04 | 安集微电子（上海）有限公司 | Cleanout fluid for removing photoresist layer residue |
| EP2460860A1 (en) | 2010-12-02 | 2012-06-06 | Basf Se | Use of mixtures for removing polyurethanes from metal surfaces |
| US11986853B2 (en) | 2015-06-03 | 2024-05-21 | SCREEN Holdings Co., Ltd. | Substrate processing apparatus, film formation unit, substrate processing method and film formation method |
| US10947484B2 (en) | 2016-05-23 | 2021-03-16 | Fujifilm Electronic Materials U.S.A., Inc. | Stripping compositions for removing photoresists from semiconductor substrates |
| CN111162001A (en) * | 2018-11-08 | 2020-05-15 | 三星电子株式会社 | Method for cleaning semiconductor chip |
| WO2020219334A1 (en) * | 2019-04-24 | 2020-10-29 | Fujifilm Electronic Materials U.S.A., Inc. | Stripping compositions for removing photoresists from semiconductor substrates |
| US11208616B2 (en) | 2019-04-24 | 2021-12-28 | Fujifilm Electronic Materials U.S.A., Inc. | Stripping compositions for removing photoresists from semiconductor substrates |
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| Publication number | Publication date |
|---|---|
| TW200634450A (en) | 2006-10-01 |
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