CN108235741B - Anticorrosive additive stripping liquid controlling - Google Patents
Anticorrosive additive stripping liquid controlling Download PDFInfo
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- CN108235741B CN108235741B CN201680042942.3A CN201680042942A CN108235741B CN 108235741 B CN108235741 B CN 108235741B CN 201680042942 A CN201680042942 A CN 201680042942A CN 108235741 B CN108235741 B CN 108235741B
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- hydrazine
- amine
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- 239000000654 additive Substances 0.000 title claims abstract description 104
- 230000000996 additive effect Effects 0.000 title claims abstract description 104
- 239000007788 liquid Substances 0.000 title claims abstract description 93
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract description 349
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims abstract description 339
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 242
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 claims abstract description 73
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 claims abstract description 72
- 239000002798 polar solvent Substances 0.000 claims abstract description 60
- 150000001412 amines Chemical class 0.000 claims abstract description 54
- 150000003335 secondary amines Chemical class 0.000 claims abstract description 43
- 150000003141 primary amines Chemical class 0.000 claims abstract description 29
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical group CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims description 67
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical group NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 41
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 6
- 238000005260 corrosion Methods 0.000 abstract description 6
- 238000004064 recycling Methods 0.000 abstract description 4
- 239000004065 semiconductor Substances 0.000 abstract description 4
- 238000007711 solidification Methods 0.000 abstract description 2
- 230000008023 solidification Effects 0.000 abstract description 2
- 230000008929 regeneration Effects 0.000 abstract 1
- 238000011069 regeneration method Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 103
- 239000000203 mixture Substances 0.000 description 97
- 239000010408 film Substances 0.000 description 95
- 239000010949 copper Substances 0.000 description 60
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine hydrate Chemical compound O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 51
- 238000011156 evaluation Methods 0.000 description 42
- 239000003638 chemical reducing agent Substances 0.000 description 35
- 239000004615 ingredient Substances 0.000 description 30
- 229910052751 metal Inorganic materials 0.000 description 25
- 239000002184 metal Substances 0.000 description 25
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 21
- 238000002360 preparation method Methods 0.000 description 21
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 17
- 229910052802 copper Inorganic materials 0.000 description 17
- 239000000758 substrate Substances 0.000 description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 14
- 239000012528 membrane Substances 0.000 description 14
- -1 DNQ compound Chemical class 0.000 description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 13
- 229910052710 silicon Inorganic materials 0.000 description 13
- 239000010703 silicon Substances 0.000 description 13
- 239000012298 atmosphere Substances 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 11
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 9
- JEYWNNAZDLFBFF-UHFFFAOYSA-N Nafoxidine Chemical compound C1CC2=CC(OC)=CC=C2C(C=2C=CC(OCCN3CCCC3)=CC=2)=C1C1=CC=CC=C1 JEYWNNAZDLFBFF-UHFFFAOYSA-N 0.000 description 9
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 9
- 238000003287 bathing Methods 0.000 description 8
- 238000009835 boiling Methods 0.000 description 8
- 230000003628 erosive effect Effects 0.000 description 8
- 150000003512 tertiary amines Chemical class 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 230000009920 chelation Effects 0.000 description 6
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 6
- 238000005530 etching Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229950002366 nafoxidine Drugs 0.000 description 6
- 229920003986 novolac Polymers 0.000 description 6
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 6
- WFCSWCVEJLETKA-UHFFFAOYSA-N 2-piperazin-1-ylethanol Chemical compound OCCN1CCNCC1 WFCSWCVEJLETKA-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- URQUNWYOBNUYJQ-UHFFFAOYSA-N diazonaphthoquinone Chemical compound C1=CC=C2C(=O)C(=[N]=[N])C=CC2=C1 URQUNWYOBNUYJQ-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 4
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 4
- 229940081974 saccharin Drugs 0.000 description 4
- 235000019204 saccharin Nutrition 0.000 description 4
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000005401 electroluminescence Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- SNWQUNCRDLUDEX-UHFFFAOYSA-N inden-1-one Chemical compound C1=CC=C2C(=O)C=CC2=C1 SNWQUNCRDLUDEX-UHFFFAOYSA-N 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 230000000269 nucleophilic effect Effects 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000005846 sugar alcohols Chemical class 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- WGIAYBNWTYECJD-UHFFFAOYSA-N 1-ethoxypiperazine Chemical compound CCON1CCNCC1 WGIAYBNWTYECJD-UHFFFAOYSA-N 0.000 description 1
- KGWYICAEPBCRBL-UHFFFAOYSA-N 1h-indene-1-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)C=CC2=C1 KGWYICAEPBCRBL-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010021036 Hyponatraemia Diseases 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 235000016127 added sugars Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- HFNQLYDPNAZRCH-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O.OC(O)=O HFNQLYDPNAZRCH-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003196 chaotropic effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002169 ethanolamines Chemical class 0.000 description 1
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000000399 optical microscopy Methods 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Abstract
In the manufacturing process of semiconductor device etc., solidified under high-temperature all the time, the solidification for avoiding resist is bad.Therefore, it is necessary to the strippers stronger than previous peeling force.A kind of anticorrosive additive stripping liquid controlling, it includes: as at least one of the primary amine of amine or secondary amine；Diethylene glycol monoethyl ether (EDG) and propylene glycol (PG) and water as polar solvent；And the hydrazine as additive, aforementioned amine is more than 3.0 mass % and is 20.0 mass % or less, aforementioned diethylene glycol monoethyl ether is more than 39.5 mass % and is 59.5 mass % or less, aforementioned water is more than 5.18 mass % and is lower than 28.18 mass %, aforementioned hydrazine more than 0.064 mass % and be 1.28% hereinafter, the anticorrosive additive stripping liquid controlling can remove through high temperature bake resist film, the corrosion of metallic film surface, section will not occur, in addition, regeneration efficiency when recycling is good.
Description
Technical field
The present invention relates to a kind of stripper, it is used to remove in the display equipment, semiconductor when institute such as manufacture liquid crystal, organic EL
The resist film used is more specifically related to even if to be able to carry out removing resist film through baking firmly, and then can be with
Say the anticorrosive additive stripping liquid controlling that will not substantially corrode to aluminium film and copper film.
Background technique
The flat-panel monitors (FPD) such as liquid crystal, organic EL (Electro-Luminescence) require large screen.It is another
Aspect, as notebook PC, tablet PC, smart phone purposes, it is desirable that small-sized fine screen.As large screen purposes, can make
With being utilized, Cu is routed or Cu/Mo stacking is routed (hereinafter referred to as " Cu wiring ".) thin film transistor (TFT) (TFT:Thin Film
Transistor).In addition, the TFT that Al wiring is utilized can be used as small-sized fine screen purposes.It should be noted that
Following Cu is also referred to as copper, Mo is also referred to as molybdenum, Al is also referred to as aluminium.
In panel manufacturing plant quotient, also there is the TFT for having produced and used Cu wiring in a factory and make Cu wiring and Al
The case where TFT made of wiring is mixed in.When TFT made of production is mixed in Cu wiring and Al wiring, in the removing of resist film
In process, as long as anticorrosive additive stripping liquid controlling can be shared when being routed using Al and when being routed using Cu, it will be able to reduce production
Cost and equipment.
Water-based positive light anti-etching agent is usually the composition for including alkanolamine, polar solvent, water with stripper, anti-
40 DEG C or more and 50 DEG C or less Zuo You are heated in erosion agent stripping off device to use.
Alkanolamine is for making the DNQ as the alkali insolubilizing agent in positive light anti-etching agent film by nucleation
The carbonyl of (diazo naphthoquinone) compound ingredient necessary to solubilising in polar solvent and water.Alkanolamine according to nitrogen knot
The number of substituent group other than the hydrogen of conjunction and be divided into primary amine, secondary amine, tertiary amine.It is known that the smaller then alkaline stronger, nucleophilic of series
Property is also stronger.
Therefore, the small alkanolamine of series, makes the DNQ compound as alkali insolubilizing agent in polar solvent, water
The ability of solubilising is stronger, plays the resist stripping performance (also referred to as " resist peeling force " of strength.).
On the other hand, it is known that alkanolamine has chelation to Cu.Keep Cu solubilized the chelation of Cu, therefore meeting
Corrode Cu film.The series of alkanolamine is smaller stronger for the chelation of Cu in the same manner as alkalinity, nucleophilicity.Therefore,
The small alkanolamine of series more consumingly corrodes Cu film.
At amorphous silicon (hereinafter also referred to " a-Si ".), low temperature polycrystalline silicon (hereinafter also referred to " LTPS ".), oxide partly leads
Body (hereinafter also referred to " IGZO ".) as semiconductor fine in the production technology of TFT, have in dry etch sequence
When resist be modified due to impaired, becomes difficult to remove resist.It is believed that this is because constituting the DNQization of positive-workingresist film
Conjunction object polymerize caused by excessively carrying out with novolac resin.
Al is routed the corrosiveness (chelation) that not will receive alkanolamine.Therefore, in order to remove modified resist,
Usually using the alkanolamine of the primary amine of the resist stripping performance with strength.
On the other hand, the case where Cu is routed, if using primary amine or the alkanolamine of secondary amine, the corruption of most cases Cu wiring
Erosion can reach unacceptable degree.Therefore, it is proposed to the stripper of the alkanolamine using tertiary amine.The alkanolamine pair of tertiary amine
The chelation of Cu is weak, can inhibit the corrosion of Cu film in the range of not going wrong in practical.However, alkalinity, nucleophilic
Property is also weak in the same manner as chelation, and compared with having used the anticorrosive additive stripping liquid controlling of alkanolamine of primary amine or secondary amine, there are anti-
Lose the weak such disadvantage of agent peeling force.
Under such technical background, needs and the Al wiring of the alkanolamine of primary amine has been used to have with anticorrosive additive stripping liquid controlling
There is the stripping performance of the same and above degree, and can be used in the anticorrosive additive stripping liquid controlling composition of both Cu wiring, Al wiring.
In addition, disclosing the anticorrosive additive stripping liquid controlling comprising (1) formula compound represented and solvent in patent document 1.This is anti-
Losing agent stripper can also share in the resist stripping process that Cu is routed and Al is routed.
In addition, being disclosed in patent document 2: although using the alkanolamine of tertiary amine, but still have and used primary amine
Alkanolamine the same peeling force of Al wiring anticorrosive additive stripping liquid controlling anticorrosive additive stripping liquid controlling.The stripper include tertiary amine,
Polar solvent, water, cyclic amine, sugar alcohol and reducing agent, the five-membered cyclic amine have nafoxidine or in 3 substds
The composition of nafoxidine.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2012-514765 bulletin (patent 5279921)
Patent document 2: Japanese Unexamined Patent Publication 2016-085378 bulletin (patent 5885041)
Summary of the invention
Problems to be solved by the invention
The stripper of patent document 2 can be routed in Cu (comprising Cu/Mo stacking wiring) and the resist removing of Al wiring
It is shared in process.In addition, can also remove resist film even if implementing hard baking to resist film.
However, disposably to be handled more massive at the scene using resist manufacture semiconductor device, FPD
Substrate.Therefore, the failure in 1 photo-mask process, which will lead to, disposably generates a large amount of substandard products.Therefore, each work of photoetching
Sequence runs operating parameter with secure context.
Specifically, carrying out solidification at a higher temperature in the curing process of resist, consolidating for resist is avoided
Change bad such problems.However, at the same time, it is meant that the resist stronger than previous resist peeling force is needed to remove
Liquid.
The solution to the problem
The present invention is completed in view of the above subject, is provided even if to resist made of baking at a temperature of being higher than previous
Lose agent film, the anticorrosive additive stripping liquid controlling that can also remove.Certainly much less, it is strong but also require pair that resist peeling force is not required nothing more than
The corrosivity as Cu, Mo and Al is low.
More specifically, about anticorrosive additive stripping liquid controlling of the invention, characterized by comprising:
As at least one of the secondary amine other than the primary amine or ring-type of amine；
As polar solvent,
Diethylene glycol monoethyl ether (EDG) and
Propylene glycol (PG) and
Water；And
As the hydrazine of additive,
Aforementioned amine more than 3.0 mass % and be 20.0 mass % hereinafter,
Aforementioned diethylene glycol monoethyl ether more than 39.5 mass % and be 59.5 mass % hereinafter,
Aforementioned water is more than 5.18 mass % and is lower than 28.18 mass %,
Aforementioned hydrazine is more than 0.064 mass % and is 1.28 mass % or less.It should be noted that much less these ratio of components
It is to be prepared with the 100 mass % of total of each material.
The effect of invention
Anticorrosive additive stripping liquid controlling of the invention has used secondary amine or primary amine, therefore even if for be higher than previous high temperature bake and
At resist, also can reliably be removed.In turn, anticorrosive additive stripping liquid controlling of the invention is made comprising diethylene glycol monoethyl ether
For polar solvent, therefore regardless of whether contain secondary amine or primary amine, can inhibit to corrosion of metal as Cu, Mo, Al.
In addition, the boiling point of amine used in anticorrosive additive stripping liquid controlling of the invention and organic polar solvent is higher than water, use
After be able to carry out recycling.In turn, for can be suitable for using amine and as the diethylene glycol monoethyl ether of polar solvent and
Propylene glycol, respective boiling point differs 5 degree or more, therefore can also individually be separated, and is able to carry out effective recycling.
In addition, the bath service life of anticorrosive additive stripping liquid controlling of the invention is excellent, even if placing 12 hours under atmosphere opening state
Above or even if closed save 4 days, resist stripping ability will not change.
Detailed description of the invention
Fig. 1 is the cone angle for illustrating Cu/Mo stacked film and the figure of Mo undercutting.
Specific embodiment
Anticorrosive additive stripping liquid controlling of the invention is illustrated below.It should be noted that the following description shows the present invention
Photoresist stripper an embodiment, without departing from the scope of the subject in the invention can be to embodiment party below
Formula and embodiment are changed.It should be noted that in this specification, indicate to use when range " more than " and " following " be
Refer to " comprising the value and being greater than (or " being more than ") value " and " comprising the value and being less than (or " being less than ") value ".In addition, " being lower than "
Refer to " do not include the value and be less than the value ".In addition, " being more than " refers to " not including the value and more than the value ".
The resist film that anticorrosive additive stripping liquid controlling of the invention is removed is assumed to positive-workingresist.Include in positive-workingresist
The resin of novolaks system uses diazo naphthoquinone (DNQ) compound as resin, as emulsion.When being etched, in substrate
Upper formation resist film, is exposed across pattern.
DNQ compound is set to become indone by the exposure.When indone and water associate, becomes indene carboxylic acid and be dissolved in water.Phenol
The resin of Novolac system has the property for being dissolved in aqueous slkali originally, but protects dissolved click by DNQ compound.DNQ chemical combination
Object goes bad due to exposure, is dissolved in the developer solution comprising water, to also novolac resin be made to dissolve out.Thus resist is completed
The patterning of film.
Patterned substrate warp, which is completed, by resist film bakes and implement later wet etching or dry etching processing.
Bake afterwards be in order to make the novolac resin in resist film and DNQ compound polymerize be able to carry out to a certain extent and
Implement.Heat treatment in 5 minutes or so is carried out usually at 140 DEG C.Hard bake refers at 170 DEG C in the present specification
30 minutes or more heating conditions.When stoving temperature rises, novolac resin and DNQ compound can polymerize rapidly and secured
Ground is bonded to the metal film of substrate, becomes to not readily dissolve.Anticorrosive additive stripping liquid controlling of the invention hard will also be baked by this
Resist film as object.
Anticorrosive additive stripping liquid controlling of the invention includes: the amine of primary amine or the secondary amine without cyclic structure, polar solvent and
Reducing agent as additive.As amine, it is expected that boiling point is higher than water, and not azeotrope with water.The reason is that, being carried out to stripper
When recycling, separated with water.As such substance, as primary amine it is preferable to use monoethanolamines (hereinafter also referred to
"MEA".Boiling point is 170 DEG C.CAS model 141-43-5).
In addition, as secondary amine, it is preferable to use N- methylethanolamine (hereinafter also referred to " MMA ".Boiling point is 155 DEG C.
CAS model 109-83-1), N- ehtylethanolamine (hereinafter also referred to " EEA ".170 DEG C of boiling point.CAS model 110-73-6).It can also
To mix them.
In addition, relative to stripper total amount, the composition ratio of amine more than 3.0 mass % and for 20.0 mass % the following are
It preferably, is preferably 5.0 mass % or more and 20.0 mass % or less, most preferably 10.0 mass % or more and 20.0 mass % or less
It is advisable.When amine is few, the resist baked firmly can not be removed.On the other hand, when excessive, damaged metal becomes larger.
As polar solvent, it is preferable to use water and affinity organic solvent are (referred to as water-soluble organic molten
Agent.).In addition, if the Combination of above-mentioned primary amine and secondary amine well if it is more suitable.
As such water-miscible organic solvent, it is preferable to use diethylene glycol monoethyl ether (hereinafter also referred to " EDG ".
Boiling point is 202 DEG C.CAS model 111-90-0) and propylene glycol (hereinafter also referred to " PG ".Boiling point is 188 DEG C.CAS model 57-55-
6) mixed liquor.Polar solvent is made of water-miscible organic solvent and water.
After the composition ratio of polar solvent is the amount for eliminating amine and aftermentioned reducing agent relative to stripper total amount
Amount.
The composition ratio of each material in polar solvent has desired range as follows.Firstly, relative to resist
Stripper total amount, water are suitably more than 5.18 mass % and lower than 28.18 mass %.If 10.0 mass % or more and 25.0 matter
It is then more suitable to measure % or less.When dilutional hyponatremia, metal film can occur to corrode Al such problems when being Al.
Relative to anticorrosive additive stripping liquid controlling total amount, diethylene glycol monoethyl ether is suitably more than 39.5 mass % and 59.5 mass %
Below.If 44.5 mass % or more and 50.0 mass % or less it is then more suitable.In addition, propylene glycol can be polar solvent
Surplus.
As additive, it is preferable to use the hydrazines of reducing agent (to be also denoted as " HN " below.CAS model 302-01-2).Also
The addition of former agent inhibits the surface corrosion of the undercutting and metal film of the Mo as caused by amine (evaluation assessment is aftermentioned).It is shelled relative to resist
Chaotropic total amount, reducing agent are desired for more than 0.064 mass % and 1.28 mass % ranges below.More preferably 0.128 matter
Measure % or more and 0.64 mass % range below.It should be noted that hydrazine can also use from the viewpoint of safety operation
Water and object (one water of hydrazine and object: are denoted as " HNH2O".).When being converted with one water of hydrazine and object, the range of above-mentioned hydrazine is desired for more
In 0.1 mass % and 2.0 mass % range below, if 0.2 mass % or more and 1.0 mass % ranges below then more
It is preferred that.
[embodiment]
The embodiment and comparative example of anticorrosive additive stripping liquid controlling of the invention described below.For " resist fissility ", " metal
The corrosivity of film " and this 3 points of " bath service life " have rated anticorrosive additive stripping liquid controlling.
< resist fissility >
The silicon thermal oxidation film for forming 100nm on a silicon substrate, forms 300nm thickness using sputtering method on silicon thermal oxidation film
Copper film.Positive-workingresist liquid is coated on the copper film by rotary coating and has made resist film.Keep resist film dry
After dry, it is exposed using the mask of wiring pattern.Then the resist of photosensitive part is removed by developer solution.That is, being copper film
The state for the part that the upper remaining part of resist film and copper film with wiring pattern is exposed.Then to silicon substrate at 170 DEG C
Plate integrally carries out rear baking in 30 minutes.
Then, using the etchant of the copper of hydrogen peroxide system, the copper film of exposing is etched, is removed.The etching of copper film
After, using the sample anticorrosive additive stripping liquid controlling just prepared (in aftermentioned table " new liquid ".) to against corrosion on the pattern of remaining copper
Agent film is removed.The processing time for removing is set as 15 minutes, and measurement is until the time removed.With optical microscopy side into
Row interference edges see whether to remove, and are thus judged.
Even across 15 minutes, it is "×" (fork) the case where also confirming resist film residual on copper film, is confirmed
It is "○" (" circle " or " circle evaluation ") to the case where resist film residual.In the case, also record removing complete when
Between.It should be noted that "○" (circle) indicates successfully or qualified, "×" (" fork " or " fork evaluation ") indicates failure or does not conform to
Lattice.Evaluation below is also identical.
The corrosivity > of < metal film
The corrosivity (metal membrane damage) of metal film is evaluated as follows.Firstly, forming 100nm thickness on a silicon substrate
Silicon thermal oxidation film.Then, the molybdenum film that 20nm thickness is formed on silicon thermal oxidation film on a silicon substrate, is then formed on
The copper film of 300nm thickness has made the stacking membrane sample of Cu/Mo.It is denoted as " Cu/Mo ".In addition, silicon heat on a silicon substrate
The aluminium film that 300nm thickness is formed on oxidation film, has made Al membrane sample.It is denoted as " Al ".
The resist film that patterned wiring shape is formed on these evaluation samples, the base as erosion analysis
Material.That is, erosion analysis with Cu/Mo film is formed by the silicon thermal oxidation film that substrate includes on a silicon substrate, appointing in Al film
The layer of one；And the resist layer being formed on as wiring shape.
Copper film with or the etchant of aluminium film in these erosion analysis with substrate carry out accurately etching during make
It impregnates, etches.Then the erosion analysis after etching is immersed in sample anticorrosive additive stripping liquid controlling 4 minutes with substrate, is removed
Resist film.The erosion analysis for being immersed in 4 minutes in sample anticorrosive additive stripping liquid controlling is cleaned with substrate, is dried, so
After observe film surface.In addition, cutting off wiring portion and observing section.
It should be noted that the judgement accurately etched is to play to be able to confirm that by visual observation to silicon thermal oxidation since etching
At the time of when film.
The observation of film surface and section uses scanning electron microscope (SEM:Scanning Electron
Microscope) (Hitachi's system: SU8020 type) carries out under conditions of acceleration voltage 1kV, 30000~50000 times.
The signal of section shape is illustrated in Fig. 1.(a) of Fig. 1 shows the section shape of the case where " Al ".Accurate erosion
The section shape of the part at quarter forms the almost cone angle 5 at 30 ° to 60 ° angles relative to substrate 1.Film portion 2 is Al film.
(b) of Fig. 1 shows the case where " Cu/Mo ".The case where " Cu/Mo ", at least the film portion 2 (Cu) on upper layer, have cone angle 5.
It is expected that the tapered surface 6 along film portion 2 is etched basal layer 3 (Mo).However, as shown in (b) of Fig. 1, basal layer 3 and film portion
2 compare, and etch residue is also possible.
About corrosive evaluation, the case where the case where " Cu/Mo " is known as " Cu/Mo damage ", " Al ", is referred to as " Al damage ".
They are referred to as " metal membrane damage ".In addition, by observing above-mentioned cross sectional shape, observe film portion 2, film portion 2 surface 4 or
Any one of basal layer 3 does not observe that there is a situation where corrode to be judged as circle there is a situation where corroding to be judged as fork (×)
(○)。
Especially " Cu/Mo " the case where, as shown in (c) of Fig. 1, sent out between basal layer 3 (Mo) and film portion 2 (Cu) sometimes
Raw corrosion.That is, sometimes since film portion 2 and the interface of basal layer 3 the Mo of basal layer 3 dissolution, Mo (basal layer 3) is earlier than layers of copper
(film portion 2) is selectively etched.Therefore, the case where gap 10 will be confirmed between basal layer 3 and film portion 2, is evaluated as
It pitches (×).
< bathes service life >
Anticorrosive additive stripping liquid controlling is the blend compositions of amine, organic solvent, material as reducing agent.Titanium dioxide in air
Carbon dissolution becomes carbonate bicarbonate ion in stripper or reacts with amine and generate carbamate ions, ties
Tab phenolphthaleinum causes peeling force reduction or damaged metal to become larger.
Especially in large-scale factory, a large amount of anticorrosive additive stripping liquid controlling is used under atmosphere opening environment.In addition, due to
Anticorrosive additive stripping liquid controlling is recycled, therefore the chance that anticorrosive additive stripping liquid controlling associates with air increases.Therefore, if the bath service life is short,
Then need to frequently replace or supplement anticorrosive additive stripping liquid controlling.
As test method, with after just preparing each anticorrosive additive stripping liquid controlling (=0 hour), place under room temperature atmospheric environment
The test that resist fissility is carried out after 6 hours, after 12 hours passes through SEM observation " Cu/Mo ", the surface of " Al " and section shape
State.The case where evaluation method is with for < resist fissility > and < corrosivity > is identical.It should be noted that 0
Hour refers to (i.e. " new liquid ") immediately after preparation.
In addition, anticorrosive additive stripping liquid controlling is put into and is moved in container.However, if container preservation cannot be carried out at normal temperature,
Then the availability in factory becomes very poor.Therefore, it also studied through the closed composition transfer being stored at room temperature.
It about evaluation method, is put into closed container, places 4 days at normal temperature, determine the stability of hydrazine.With rigid preparation
After compare, the situation that hydrazine reduces 1% or more is " × (fork evaluation) ", is if lower than 1% " zero (circle evaluation) ".
Successively carry out these evaluations.However, the case where result before also with good grounds is without carrying out subsequent evaluation.It will
The situation is not carried out as evaluation and is denoted as "-".
< sample anticorrosive additive stripping liquid controlling >
Sample anticorrosive additive stripping liquid controlling is prepared for by following main points.
(embodiment 1)
The N- methylethanolamine of secondary amine is used as amine.
20.0 mass % of N- methylethanolamine (MMA)
Polar solvent is mixed with water, diethylene glycol monoethyl ether and propylene glycol.
49.5 mass % of diethylene glycol monoethyl ether (EDG)
10.0 mass % of propylene glycol (PG)
20.0 mass % of water
The hydrazine of reducing agent is used as additive.
One water of hydrazine and object (HNH2O) 0.5 mass %
The above ingredient is mixed and is made the sample anticorrosive additive stripping liquid controlling of embodiment 1.
It should be noted that 0.5 mass % of one water of hydrazine and object is equivalent to 0.32 mass % of hydrazine.One water of hydrazine and object are remaining
The amount of 0.18 mass % is water.It therefore, can be with when the ratio of components of above-mentioned water also includes the amount put into the form of hydrazine monohydrate
It says as 20.18 mass %.In following all embodiment and comparative example, the case where having used hydrazine monohydrate, contains to be identical
Justice.
(embodiment 2)
The N- ehtylethanolamine of secondary amine is used as amine.
20.0 mass % of N- ehtylethanolamine (EEA)
Polar solvent is mixed with water, diethylene glycol monoethyl ether and propylene glycol.
49.5 mass % of diethylene glycol monoethyl ether (EDG)
10.0 mass % of propylene glycol (PG)
20.0 mass % of water
Hydrazine is used as reducing agent.
One water of hydrazine and object (HNH2O) 0.5 mass %
The above ingredient is mixed and is made the sample anticorrosive additive stripping liquid controlling of embodiment 2.
Embodiment 2 is the composition that the N- methylethanolamine (MMA) of embodiment 1 is changed to N- ehtylethanolamine (EEA).It needs
It is noted that 0.5 mass % of one water of hydrazine and object is equivalent to 0.32 mass % of hydrazine.0.18 mass % of one water of hydrazine and object remnants
Amount be water.Therefore, when the ratio of components of above-mentioned water also includes the amount put into the form of hydrazine monohydrate it may be said that for 20.18 matter
Measure %.
(embodiment 3)
The monoethanolamine of primary amine is used as amine.
20.0 mass % of monoethanolamine (MEA)
Polar solvent is mixed with water, diethylene glycol monoethyl ether and propylene glycol.
49.5 mass % of diethylene glycol monoethyl ether (EDG)
10.0 mass % of propylene glycol (PG)
20.0 mass % of water
Hydrazine is used as reducing agent.
One water of hydrazine and object (HNH2O) 0.5 mass %
The above ingredient is mixed and is made the sample anticorrosive additive stripping liquid controlling of embodiment 3.
Embodiment 3 is the composition that the N- methylethanolamine (MMA) of embodiment 1 is changed to monoethanolamine (MEA).It needs
Bright, 0.5 mass % of one water of hydrazine and object is equivalent to 0.32 mass % of hydrazine.The amount of the 0.18 mass % of one water of hydrazine and object remnants
For water.Therefore, when the ratio of components of above-mentioned water also includes the amount put into the form of hydrazine monohydrate it may be said that for 20.18 matter
Measure %.
(embodiment 4)
The N- methylethanolamine of secondary amine is used as amine.
20.0 mass % of N- methylethanolamine (MMA)
Polar solvent is mixed with water, diethylene glycol monoethyl ether and propylene glycol.
49.8 mass % of diethylene glycol monoethyl ether (EDG)
10.0 mass % of propylene glycol (PG)
20.0 mass % of water
Hydrazine is used as reducing agent.
One water of hydrazine and object (HNH2O) 0.2 mass %
The above ingredient is mixed and is made the sample anticorrosive additive stripping liquid controlling of embodiment 4.
Embodiment 4 is to reduce one water of hydrazine and object (HNH in embodiment 12O the composition of composition ratio).HN·H2O's
Increase EDG with reducing partial response.It should be noted that 0.2 mass % of one water of hydrazine and object is equivalent to 0.128 mass % of hydrazine.
The amount of the 0.072 mass % of one water of hydrazine and object remnants are water.Therefore, the ratio of components of above-mentioned water also includes the shape with hydrazine monohydrate
It may be said that being 20.072 mass % when the amount of formula investment.
(embodiment 5)
The N- methylethanolamine of secondary amine is used as amine.
20.0 mass % of N- methylethanolamine (MMA)
Polar solvent is mixed with water, diethylene glycol monoethyl ether and propylene glycol.
48.0 mass % of diethylene glycol monoethyl ether (EDG)
10.0 mass % of propylene glycol (PG)
20.0 mass % of water
Hydrazine is used as reducing agent.
One water of hydrazine and object (HNH2O) 2.0 mass %
The above ingredient is mixed and is made the sample anticorrosive additive stripping liquid controlling of embodiment 5.
Embodiment 5 is one water of hydrazine and object (HNH for increasing embodiment 12O the composition of composition ratio).With HNH2O
Increase partial response reduce EDG.It should be noted that 2.0 mass % of one water of hydrazine and object are equivalent to 1.28 mass % of hydrazine.
The amount of the 0.72 mass % of one water of hydrazine and object remnants are water.Therefore, the ratio of components of above-mentioned water also includes the shape with hydrazine monohydrate
It may be said that being 20.72 mass % when the amount of formula investment.
(embodiment 6)
The N- methylethanolamine of secondary amine is used as amine.
5.0 mass % of N- methylethanolamine (MMA)
Polar solvent is mixed with water, diethylene glycol monoethyl ether and propylene glycol.
54.5 mass % of diethylene glycol monoethyl ether (EDG)
20.0 mass % of propylene glycol (PG)
20.0 mass % of water
Hydrazine is used as reducing agent.
One water of hydrazine and object (HNH2O) 0.5 mass %
The above ingredient is mixed and is made the sample anticorrosive additive stripping liquid controlling of embodiment 6.
Embodiment 6 is the composition for reducing the composition ratio of N- methylethanolamine (MMA) in embodiment 1.The reduction portion of MMA
Divide and correspondingly increases EDG and PG.It should be noted that 0.5 mass % of one water of hydrazine and object is equivalent to 0.32 mass % of hydrazine.Hydrazine one
The amount of the 0.18 mass % of water and object remnants are water.Therefore, the ratio of components of above-mentioned water is also included and is thrown in the form of hydrazine monohydrate
It may be said that being 20.18 mass % when the amount entered.
(embodiment 7)
The N- methylethanolamine of secondary amine is used as amine.
10.0 mass % of N- methylethanolamine (MMA)
Polar solvent is mixed with water, diethylene glycol monoethyl ether and propylene glycol.
49.5 mass % of diethylene glycol monoethyl ether (EDG)
20.0 mass % of propylene glycol (PG)
20.0 mass % of water
Hydrazine is used as reducing agent.
One water of hydrazine and object (HNH2O) 0.5 mass %
The above ingredient is mixed and is made the sample anticorrosive additive stripping liquid controlling of embodiment 7.
Embodiment 7 is the composition for reducing the composition ratio of N- methylethanolamine (MMA) in embodiment 1.The reduction portion of MMA
Divide and correspondingly increases PG.It should be noted that 0.5 mass % of one water of hydrazine and object is equivalent to 0.32 mass % of hydrazine.One water of hydrazine and
The amount of the 0.18 mass % of object remnants is water.Therefore, the ratio of components of above-mentioned water is also included and is put into the form of hydrazine monohydrate
It may be said that being 20.18 mass % when amount.
(embodiment 8)
The monoethanolamine of primary amine is used as amine.
5.0 mass % of monoethanolamine (MEA)
Polar solvent is mixed with water, diethylene glycol monoethyl ether and propylene glycol.
49.5 mass % of diethylene glycol monoethyl ether (EDG)
25.0 mass % of propylene glycol (PG)
20.0 mass % of water
The hydrazine of reducing agent is used as additive.
One water of hydrazine and object (HNH2O) 0.5 mass %
The above ingredient is mixed and is made the sample anticorrosive additive stripping liquid controlling of embodiment 8.
Embodiment 8 is that the N- methylethanolamine (MMA) of embodiment 1 is changed to the monoethanolamine (MEA) of primary amine, is reduced
The composition of composition ratio.Increase PG to the reduction partial response of MEA.It should be noted that 0.5 mass % phase of one water of hydrazine and object
When in 0.32 mass % of hydrazine.The amount of the 0.18 mass % of one water of hydrazine and object remnants are water.Therefore, the ratio of components of above-mentioned water also includes
It may be said that being 20.18 mass % when the amount put into the form of hydrazine monohydrate.
(embodiment 9)
The monoethanolamine of primary amine is used as amine.
10.0 mass % of monoethanolamine (MEA)
Polar solvent is mixed with water, diethylene glycol monoethyl ether and propylene glycol.
49.5 mass % of diethylene glycol monoethyl ether (EDG)
20.0 mass % of propylene glycol (PG)
20.0 mass % of water
The hydrazine of reducing agent is used as additive.
One water of hydrazine and object (HNH2O) 0.5 mass %
The above ingredient is mixed and is made the sample anticorrosive additive stripping liquid controlling of embodiment 9.
Embodiment 9 is that the N- methylethanolamine (MMA) of embodiment 1 is changed to the monoethanolamine (MEA) of primary amine, is reduced
The composition of composition ratio.Increase PG to the reduction partial response of MEA.It should be noted that 0.5 mass % phase of one water of hydrazine and object
When in 0.32 mass % of hydrazine.The amount of the 0.18 mass % of one water of hydrazine and object remnants are water.Therefore, the ratio of components of above-mentioned water also includes
It may be said that being 20.18 mass % when the amount put into the form of hydrazine monohydrate.
(embodiment 10)
The N- methylethanolamine of secondary amine is used as amine.
20.0 mass % of N- methylethanolamine (MMA)
Polar solvent is mixed with water, diethylene glycol monoethyl ether and propylene glycol.
44.5 mass % of diethylene glycol monoethyl ether (EDG)
10.0 mass % of propylene glycol (PG)
25.0 mass % of water
The hydrazine of reducing agent is used as additive.
One water of hydrazine and object (HNH2O) 0.5 mass %
The above ingredient is mixed and is made the sample anticorrosive additive stripping liquid controlling of embodiment 10.
Embodiment 10 is the composition for increasing the composition ratio of water of embodiment 1.Reduce to the increase partial response of water
EDG.It should be noted that 0.5 mass % of one water of hydrazine and object is equivalent to 0.32 mass % of hydrazine.The 0.18 of one water of hydrazine and object remnants
The amount of quality % is water.Therefore, it may be said that being when the ratio of components of above-mentioned water also includes the amount put into the form of hydrazine monohydrate
25.18 quality %.
(embodiment 11)
The N- methylethanolamine of secondary amine is used as amine.
20.0 mass % of N- methylethanolamine (MMA)
Polar solvent is mixed with water, diethylene glycol monoethyl ether and propylene glycol.
59.5 mass % of diethylene glycol monoethyl ether (EDG)
10.0 mass % of propylene glycol (PG)
10.0 mass % of water
The hydrazine of reducing agent is used as additive.
One water of hydrazine and object (HNH2O) 0.5 mass %
The above ingredient is mixed and is made the sample anticorrosive additive stripping liquid controlling of embodiment 11.
Embodiment 11 is the composition for reducing the composition ratio of water in embodiment 1.Increase to the reduction partial response of water
EDG.It should be noted that 0.5 mass % of one water of hydrazine and object is equivalent to 0.32 mass % of hydrazine.The 0.18 of one water of hydrazine and object remnants
The amount of quality % is water.Therefore, it may be said that being when the ratio of components of above-mentioned water also includes the amount put into the form of hydrazine monohydrate
10.18 quality %.
(comparative example 1)
The N- methylethanolamine of secondary amine is used as amine.
20.0 mass % of N- methylethanolamine (MMA)
Polar solvent is mixed with water, diethylene glycol monobutyl ether (hereinafter also referred to " BDG ".CAS model 112-34-5) and third
Glycol.
49.5 mass % of diethylene glycol monobutyl ether (BDG)
10.0 mass % of propylene glycol (PG)
20.0 mass % of water
The hydrazine of reducing agent is used as additive.
One water of hydrazine and object (HNH2O) 0.5 mass %
The above ingredient is mixed and is made the sample anticorrosive additive stripping liquid controlling of comparative example 1.
Comparative example 1 is that the polar solvent diethylene glycol monoethyl ether (EDG) of embodiment 1 is changed to diethylene glycol monobutyl ether
(BDG) composition.It should be noted that 0.5 mass % of one water of hydrazine and object is equivalent to 0.32 mass % of hydrazine.One water of hydrazine and object are residual
The amount of 0.18 remaining mass % is water.Therefore, when the ratio of components of above-mentioned water also includes the amount put into the form of hydrazine monohydrate
It may be said that being 20.18 mass %.
(comparative example 2)
The N- methylethanolamine of secondary amine is used as amine.
20.0 mass % of N- methylethanolamine (MMA)
Polar solvent is mixed with water and diethylene glycol monoethyl ether.
59.5 mass % of diethylene glycol monoethyl ether (EDG)
20.0 mass % of water
The hydrazine of reducing agent is used as additive.
One water of hydrazine and object (HNH2O) 0.5 mass %
The above ingredient is mixed and is made the sample anticorrosive additive stripping liquid controlling of comparative example 2.
Comparative example 2 is the composition that polar solvent propylene glycol (PG) is eliminated in embodiment 1.Increase EDG and replaces the part PG.It needs
It is noted that 0.5 mass % of one water of hydrazine and object is equivalent to 0.32 mass % of hydrazine.0.18 mass % of one water of hydrazine and object remnants
Amount be water.Therefore, when the ratio of components of above-mentioned water also includes the amount put into the form of hydrazine monohydrate it may be said that for 20.18 matter
Measure %.
(comparative example 3)
The N- methylethanolamine of secondary amine is used as amine.
20.0 mass % of N- methylethanolamine (MMA)
Polar solvent is mixed with water, diethylene glycol monoethyl ether and propylene glycol.
39.5 mass % of diethylene glycol monoethyl ether (EDG)
20.0 mass % of propylene glycol (PG)
20.0 mass % of water
The hydrazine of reducing agent is used as additive.
One water of hydrazine and object (HNH2O) 0.5 mass %
The above ingredient is mixed and is made the sample anticorrosive additive stripping liquid controlling of comparative example 3.
Comparative example 3 is the composition for reducing the composition ratio of polar solvent diethylene glycol monoethyl ether (EDG) in embodiment 1.
Increase PG to the reduction partial response of EDG.It should be noted that 0.5 mass % of one water of hydrazine and object is equivalent to 0.32 matter of hydrazine
Measure %.The amount of the 0.18 mass % of one water of hydrazine and object remnants are water.Therefore, the ratio of components of above-mentioned water also includes with hydrazine monohydrate
Form investment amount when it may be said that be 20.18 mass %.
(comparative example 4)
The N- methylethanolamine of secondary amine is used as amine.
20.0 mass % of N- methylethanolamine (MMA)
Polar solvent is mixed with water, N-METHYLFORMAMIDE (hereinafter also referred to " NMF ".CAS model 123-39-7) and the third two
Alcohol.
49.5 mass % of N-METHYLFORMAMIDE (NMF)
10.0 mass % of propylene glycol (PG)
20.0 mass % of water
The hydrazine of reducing agent is used as additive.
One water of hydrazine and object (HNH2O) 0.5 mass %
The above ingredient is mixed and is made the sample anticorrosive additive stripping liquid controlling of comparative example 4.
Comparative example 4 is that the polar solvent diethylene glycol monoethyl ether (EDG) of embodiment 1 is changed to N-METHYLFORMAMIDE
(NMF) composition.It should be noted that 0.5 mass % of one water of hydrazine and object is equivalent to 0.32 mass % of hydrazine.One water of hydrazine and object are residual
The amount of 0.18 remaining mass % is water.Therefore, when the ratio of components of above-mentioned water also includes the amount put into the form of hydrazine monohydrate
It may be said that being 20.18 mass %.
(comparative example 5)
The N- methylethanolamine of secondary amine is used as amine.
20.0 mass % of N- methylethanolamine (MMA)
Polar solvent is mixed with water, N,N-dimethylformamide (hereinafter also referred to " DMF ".CAS model 68-12-2) and third
Glycol.
49.5 mass % of N,N-dimethylformamide (DMF)
10.0 mass % of propylene glycol (PG)
20.0 mass % of water
The hydrazine of reducing agent is used as additive.
One water of hydrazine and object (HNH2O) 0.5 mass %
The above ingredient is mixed and is made the sample anticorrosive additive stripping liquid controlling of comparative example 5.
Comparative example 5 is that the polar solvent diethylene glycol monoethyl ether (EDG) of embodiment 1 is changed to N,N-dimethylformamide
(DMF) composition.It should be noted that 0.5 mass % of one water of hydrazine and object is equivalent to 0.32 mass % of hydrazine.One water of hydrazine and object are residual
The amount of 0.18 remaining mass % is water.Therefore, when the ratio of components of above-mentioned water also includes the amount put into the form of hydrazine monohydrate
It may be said that being 20.18 mass %.
(comparative example 6)
The N- methylethanolamine of secondary amine is used as amine.
20.0 mass % of N- methylethanolamine (MMA)
Polar solvent be mixed with water, ethylene carbonate (: ethylene carbonate, hereinafter also referred to " EC ".CAS model 96-49-
And propylene glycol 1).
49.5 mass % of ethylene carbonate (EC)
10.0 mass % of propylene glycol (PG)
20.0 mass % of water
The hydrazine of reducing agent is used as additive.
One water of hydrazine and object (HNH2O) 0.5 mass %
The above ingredient is mixed and is made the sample anticorrosive additive stripping liquid controlling of comparative example 6.
Comparative example 6 is that the polar solvent diethylene glycol monoethyl ether (EDG) of embodiment 1 is changed to ethylene carbonate (EC)
Composition.It should be noted that 0.5 mass % of one water of hydrazine and object is equivalent to 0.32 mass % of hydrazine.One water of hydrazine and object are remaining
The amount of 0.18 mass % is water.It therefore, can be with when the ratio of components of above-mentioned water also includes the amount put into the form of hydrazine monohydrate
It says as 20.18 mass %.
(comparative example 7)
The nafoxidine (hereinafter also referred to " PRL " of cyclic amine is used as amine.CAS model 123-75-1).
20.0 mass % of nafoxidine (PRL)
Polar solvent is mixed with water, diethylene glycol monoethyl ether and propylene glycol.
49.5 mass % of diethylene glycol monoethyl ether (EDG)
10.0 mass % of propylene glycol (PG)
20.0 mass % of water
The hydrazine of reducing agent is used as additive.
One water of hydrazine and object (HNH2O) 0.5 mass %
The above ingredient is mixed and is made the sample anticorrosive additive stripping liquid controlling of comparative example 7.
Comparative example 7 is the nafoxidine that the N- methylethanolamine (MMA) of the secondary amine of embodiment 1 is changed to cyclic amine
(PRL) composition.It should be noted that 0.5 mass % of one water of hydrazine and object is equivalent to 0.32 mass % of hydrazine.One water of hydrazine and object are residual
The amount of 0.18 remaining mass % is water.Therefore, when the ratio of components of above-mentioned water also includes the amount put into the form of hydrazine monohydrate
It may be said that being 20.18 mass %.
(comparative example 8)
As amine use cyclic amine hydroxyethyl piperazine (: 1- (2- ethoxy) piperazine, hereinafter also referred to " OH-PIZ ".
CAS model 103-76-4).
20.0 mass % of hydroxyethyl piperazine (OH-PIZ)
Polar solvent is mixed with water, diethylene glycol monoethyl ether and propylene glycol.
49.5 mass % of diethylene glycol monoethyl ether (EDG)
10.0 mass % of propylene glycol (PG)
20.0 mass % of water
The hydrazine of reducing agent is used as additive.
One water of hydrazine and object (HNH2O) 0.5 mass %
The above ingredient is mixed and is made the sample anticorrosive additive stripping liquid controlling of comparative example 8.
Comparative example 8 is the hydroxyethyl piperazine that the N- methylethanolamine (MMA) of the secondary amine of embodiment 1 is changed to cyclic amine
(OH-PIZ) composition.It should be noted that 0.5 mass % of one water of hydrazine and object is equivalent to 0.32 mass % of hydrazine.One water of hydrazine and
The amount of the 0.18 mass % of object remnants is water.Therefore, the ratio of components of above-mentioned water is also included and is put into the form of hydrazine monohydrate
It may be said that being 20.18 mass % when amount.
(comparative example 9)
The N methyldiethanol amine (hereinafter also referred to " MDEA " of tertiary amine is used as amine.CAS model 105-59-9).
20.0 mass % of N methyldiethanol amine (MDEA)
Polar solvent is mixed with water, diethylene glycol monoethyl ether and propylene glycol.
49.5 mass % of diethylene glycol monoethyl ether (EDG)
10.0 mass % of propylene glycol (PG)
20.0 mass % of water
The hydrazine of reducing agent is used as additive.
One water of hydrazine and object (HNH2O) 0.5 mass %
The above ingredient is mixed and is made the sample anticorrosive additive stripping liquid controlling of comparative example 9.
Comparative example 9 is the N methyldiethanol amine that the N- methylethanolamine (MMA) of the secondary amine of embodiment 1 is changed to tertiary amine
(MDEA) composition.It should be noted that 0.5 mass % of one water of hydrazine and object is equivalent to 0.32 mass % of hydrazine.One water of hydrazine and object
The amount of 0.18 remaining mass % is water.Therefore, the ratio of components of above-mentioned water also includes the amount put into the form of hydrazine monohydrate
When it may be said that be 20.18 mass %.
(comparative example 10)
The N- methylethanolamine of secondary amine is used as amine.
20.0 mass % of N- methylethanolamine (MMA)
Polar solvent is mixed with water, diethylene glycol monoethyl ether and propylene glycol.
49.9 mass % of diethylene glycol monoethyl ether (EDG)
10.0 mass % of propylene glycol (PG)
20.0 mass % of water
The hydrazine of reducing agent is used as additive.
One water of hydrazine and object (HNH2O) 0.1 mass %
The above ingredient is mixed and is made the sample anticorrosive additive stripping liquid controlling of comparative example 10.
Comparative example 10 is to reduce one water of hydrazine and object (HNH in embodiment 12O the composition of composition ratio).It needs to illustrate
, 0.1 mass % of one water of hydrazine and object is equivalent to 0.064 mass % of hydrazine.The amount of the 0.036 mass % of one water of hydrazine and object remnants
For water.Therefore, when the ratio of components of above-mentioned water also includes the amount put into the form of hydrazine monohydrate it may be said that for 20.036 matter
Measure %.
(comparative example 11)
The N- methylethanolamine of secondary amine is used as amine.
20.0 mass % of N- methylethanolamine (MMA)
Polar solvent is mixed with water, diethylene glycol monoethyl ether and propylene glycol.
50.0 mass % of diethylene glycol monoethyl ether (EDG)
10.0 mass % of propylene glycol (PG)
20.0 mass % of water
It is not added as the hydrazine reducing agent of additive.
The above ingredient is mixed and is made the sample anticorrosive additive stripping liquid controlling of comparative example 11.Comparative example 11 is from reality
It applies and eliminates one water of hydrazine and object (HNH in the composition of example 12O composition).
(comparative example 12)
The N- methylethanolamine of secondary amine is used as amine.
20.0 mass % of N- methylethanolamine (MMA)
Polar solvent is mixed with water, diethylene glycol monoethyl ether and propylene glycol.
49.5 mass % of diethylene glycol monoethyl ether (EDG)
10.0 mass % of propylene glycol (PG)
20.0 mass % of water
Saccharin (: o-benzoic sulfimide, CAS model 81-07-2) is used as additive.
0.5 mass % of saccharin
The above ingredient is mixed and is made the sample anticorrosive additive stripping liquid controlling of comparative example 12.Comparative example 12 is by reality
Apply the additive (reducing agent: one water of hydrazine and object (HNH of example 12O)) it is changed to the composition of saccharin.
(comparative example 13)
The N- methylethanolamine of secondary amine is used as amine.
20.0 mass % of N- methylethanolamine (MMA)
Polar solvent is mixed with water, diethylene glycol monoethyl ether and propylene glycol.
49.5 mass % of diethylene glycol monoethyl ether (EDG)
10.0 mass % of propylene glycol (PG)
20.0 mass % of water
D-sorbite (hereinafter referred to as " Stol " is used as additive.CAS model 50-70-4).
0.5 mass % of D-sorbite (Stol)
The above ingredient is mixed and is made the sample anticorrosive additive stripping liquid controlling of comparative example 13.Comparative example 13 is by reality
Apply the additive (reducing agent: one water of hydrazine and object (HNH of example 12O)) it is changed to the composition of D-sorbite (Stol).
(comparative example 14)
The N- methylethanolamine of secondary amine is used as amine.
20.0 mass % of N- methylethanolamine (MMA)
Polar solvent is mixed with water, diethylene glycol monoethyl ether and propylene glycol.
49.5 mass % of diethylene glycol monoethyl ether (EDG)
10.0 mass % of propylene glycol (PG)
20.0 mass % of water
As additive use diglycerol (: Diglycerol, CAS model 627-82-7).
0.5 mass % of diglycerol
The above ingredient is mixed and is made the sample anticorrosive additive stripping liquid controlling of comparative example 14.Comparative example 14 is by reality
Apply the additive (reducing agent: one water of hydrazine and object (HNH of example 12O)) it is changed to the composition of diglycerol.
(comparative example 15)
The N- methylethanolamine of secondary amine is used as amine.
3.0 mass % of N- methylethanolamine (MMA)
Polar solvent is mixed with water, diethylene glycol monoethyl ether and propylene glycol.
49.5 mass % of diethylene glycol monoethyl ether (EDG)
27.0 mass % of propylene glycol (PG)
20.0 mass % of water
The hydrazine of reducing agent is used as additive.
One water of hydrazine and object (HNH2O) 0.5 mass %
The above ingredient is mixed and is made the sample anticorrosive additive stripping liquid controlling of comparative example 15.
Comparative example 15 is the composition for reducing the composition ratio of N- methylethanolamine (MMA) in embodiment 1.The reduction of MMA
Increase 2P to partial response.It should be noted that 0.5 mass % of one water of hydrazine and object is equivalent to 0.32 mass % of hydrazine.One water of hydrazine
Amount with the 0.18 mass % of object remnants is water.Therefore, the ratio of components of above-mentioned water is also included and is put into the form of hydrazine monohydrate
Amount when it may be said that be 20.18 mass %.
(comparative example 16)
The monoethanolamine of primary amine is used as amine.
3.0 mass % of monoethanolamine (MEA)
Polar solvent is mixed with water, diethylene glycol monoethyl ether and propylene glycol.
49.5 mass % of diethylene glycol monoethyl ether (EDG)
27.0 mass % of propylene glycol (PG)
20.0 mass % of water
The hydrazine of reducing agent is used as additive.
One water of hydrazine and object (HNH2O) 0.5 mass %
The above ingredient is mixed and is made the sample anticorrosive additive stripping liquid controlling of comparative example 16.
Comparative example 16 is the monoethanolamine (MEA) that the N- methylethanolamine (MMA) of embodiment 1 is changed to primary amine, reduces
The composition of composition ratio.Increase PG to the reduction partial response of MEA.It should be noted that 0.5 mass % of one water of hydrazine and object
It is equivalent to 0.32 mass % of hydrazine.The amount of the 0.18 mass % of one water of hydrazine and object remnants are water.Therefore, the ratio of components of above-mentioned water also wraps
It may be said that being 20.18 mass % when containing the amount put into the form of hydrazine monohydrate.
(comparative example 17)
The N- methylethanolamine of secondary amine is used as amine.
20.0 mass % of N- methylethanolamine (MMA)
Polar solvent is mixed with water, diethylene glycol monoethyl ether and propylene glycol.
64.5 mass % of diethylene glycol monoethyl ether (EDG)
10.0 mass % of propylene glycol (PG)
5.0 mass % of water
The hydrazine of reducing agent is used as additive.
One water of hydrazine and object (HNH2O) 0.5 mass %
The above ingredient is mixed and is made the sample anticorrosive additive stripping liquid controlling of comparative example 17.
Comparative example 17 is the composition for reducing the composition ratio of water in embodiment 1.Increase to the reduction partial response of water
EDG.It should be noted that 0.5 mass % of one water of hydrazine and object is equivalent to 0.32 mass % of hydrazine.The 0.18 of one water of hydrazine and object remnants
The amount of quality % is water.Therefore, it may be said that being when the ratio of components of above-mentioned water also includes the amount put into the form of hydrazine monohydrate
5.18 quality %.
(comparative example 18)
The N- methylethanolamine of secondary amine is used as amine.
20.0 mass % of N- methylethanolamine (MMA)
Polar solvent is mixed with water, diethylene glycol monoethyl ether and propylene glycol.
41.5 mass % of diethylene glycol monoethyl ether (EDG)
10.0 mass % of propylene glycol (PG)
28.0 mass % of water
The hydrazine of reducing agent is used as additive.
One water of hydrazine and object (HNH2O) 0.5 mass %
The above ingredient is mixed and is made the sample anticorrosive additive stripping liquid controlling of comparative example 18.
Comparative example 18 is the composition that the composition ratio of water is increased in embodiment 1.Reduce to the increase partial response of water
EDG.It should be noted that 0.5 mass % of one water of hydrazine and object is equivalent to 0.32 mass % of hydrazine.The 0.18 of one water of hydrazine and object remnants
The amount of quality % is water.Therefore, it may be said that being when the ratio of components of above-mentioned water also includes the amount put into the form of hydrazine monohydrate
28.18 quality %.
By the composition of embodiment 1 and comparative example 1~6 and evaluation result is shown in table 1, in addition, by Examples 1 to 3 and comparing
The composition of example 7~9 and evaluation result is shown in table 2.In addition, the composition and evaluation of embodiment 1,4~5 and comparative example 10~14 are tied
Fruit is shown in table 3.In addition, by the composition and evaluation result is shown in table 4 of embodiment 1,6~9 and comparative example 15~16.In addition, by real
Apply the composition and evaluation result is shown in table 5 of example 1,10~11 and comparative example 17~18.
[table 1]
Table 1 shows the composition and result of embodiment 1 and comparative example 1~4.Referring to the embodiment 1 of table 1.By making as amine
With the N- methylethanolamine (MMA) of secondary amine, diethylene glycol monoethyl ether (EDG), propylene glycol (PG) and water are used as polar solvent
Mixed liquor, the resist of (hard to bake) is baked under the conditions of so as to remove as 170 DEG C, 30 minutes in 3 minutes
Film.In addition, the damage of " Cu/Mo " and " Al " film is also circle evaluation.
In addition, for placing bath service life when stripper under atmosphere opening state, even across 12 hours peeling forces
It does not change.In turn, the reduction of hydrazine is not observed in the case where closed save 4 days yet.
Comparative example 1~6 is the type for changing water-miscible organic solvent.Comparative example 1 is by the polar solvent two of embodiment 1
Ethylene glycol monoethyl ether (EDG) is changed to the composition of diethylene glycol monobutyl ether (BDG).Comparative example 1 can not even be removed immediately after preparation
The resist film that (new liquid) extremely bakes under conditions of 170 DEG C, 30 minutes.For comparative example 1, as amine and 1 phase of embodiment
N- methylethanolamine (MMA) has been used together.I.e., it is known that the resist through baking firmly can be not removed as long as using secondary amine
Film, the combination with polar solvent are necessary.
Comparative example 2 is the composition that polar solvent propylene glycol (PG) is eliminated in embodiment 1.For comparative example 2, immediately after preparation
The resist peeling force of (new liquid), in an atmosphere place after be " circle " to the evaluation of the damage of Cu/Mo and Al.However,
In the case where closed placement 4 days, the reduction of hydrazine is observed.As described above, the presence of propylene glycol (PG) has the stabilization for improving hydrazine
The effect of property.
Comparative example 3 is to reduce the amount of the polar solvent diethylene glycol monoethyl ether of embodiment 1 to 39.5 from 49.5 mass %
The composition of quality %.Comparative example 3 fails to remove the resist film through baking firmly from (new liquid) immediately after preparation.Therefore, for bath
Service life is not tested.When diethylene glycol monoethyl ether (EDG) is 39.5 mass % or less, relative to the resist through baking firmly
The resist peeling force of film reduces.
Comparative example 4 is that the polar solvent diethylene glycol monoethyl ether (EDG) of embodiment 1 is changed to N-METHYLFORMAMIDE
(NMF) composition.For comparative example 4, problem does not occur for the resist peeling force of (new liquid), metal membrane damage immediately after preparation,
For circle evaluation.However, the case where placing 6 hours in an atmosphere, resist peeling force is reduced, for fork evaluation.In addition, due to
It is placed 6 hours in atmosphere, and evaluates the fork that is evaluated as of the damage on the surface and section of Cu/Mo.It should be noted that Al is damaged
It does not observe.In addition, observing the reduction of hydrazine in the case where closed place 4 days.
Comparative example 5 is that the polar solvent diethylene glycol monoethyl ether (EDG) of embodiment 1 is changed to N,N-dimethylformamide
(DMF) composition.For comparative example 5, problem does not occur for the resist peeling force of (new liquid), metal membrane damage immediately after preparation,
For circle evaluation.However, the case where placing 6 hours in an atmosphere, resist peeling force is reduced, for fork evaluation.In addition, due to
It is placed 6 hours in atmosphere, and evaluates the fork that is evaluated as of the damage on the surface and section of Cu/Mo.It should be noted that not observing
To the damage to Al.In addition, observing the reduction of hydrazine in the case where closed place 4 days.
Comparative example 6 is that the polar solvent diethylene glycol monoethyl ether (EDG) of embodiment 1 is changed to ethylene carbonate (EC)
Composition.Comparative example 6 is also to fail to remove the resist film through baking firmly from (new liquid) immediately after preparation.Therefore, for bathing the service life,
It is not tested.
As knowen from these results, as polar solvent, by combination diethylene glycol monoethyl ether (EDG), propylene glycol (PG) and
Water will not damage metal so as to remove the resist film through baking firmly, and the hydrazine when bathing service life, closed keeping 4 days is steady
Qualitative aspect also obtains circle evaluation.
[table 2]
Table 2 shows the composition and evaluation result of Examples 1 to 3 and comparative example 7~9.Embodiment 1 is to disclose again, therefore
It is indicated with bracket.Embodiment 2 is that the N- methylethanolamine (MMA) of embodiment 1 is changed to the group of N- ehtylethanolamine (EEA)
At.Embodiment 2 is also similarly to Example 1 round in whole assessment items of resist peeling force, damaged metal and bath service life
Circle evaluation.
Embodiment 3 is the composition that the N- methylethanolamine (MMA) of embodiment 1 is changed to the monoethanolamine (MEA) of primary amine.
Embodiment 3 is also similarly to Example 1 circle in resist peeling force and damaged metal and whole assessment items in bath service life
Evaluation.
It can be seen from the above result that N- ehtylethanolamine (EEA) can be used as secondary amine.In addition it not only can be used secondary
Amine can also use the monoethanolamine (MEA) of primary amine.
Comparative example 7~9 is the composition for having used other amines.Comparative example 7 is the nafoxidine (PRL) for having used cyclic amine
The case where.In addition, the case where comparative example 8 is hydroxyethyl piperazine (OH-PIZ) for having used cyclic amine, comparative example 9 is to have used uncle
The case where N methyldiethanol amine (MDEA) of amine.
Comparative example 7,8,9 fails to remove the resist film baked firmly.In addition, these comparative examples surface observe for
The damage of Cu/Mo.However, not observing the damage for Al.It should be noted that due to failing to remove the resist baked firmly
Film, therefore for bathing the service life, it is not tested.It can be seen from the above result that even if as secondary amine, for cyclic structure amine and
The case where tertiary amine, can not also remove the resist film through baking firmly.
[table 3]
Table 3 shows the composition and evaluation result of embodiment 1,4~5 and comparative example 10~14.Embodiment 1 is to disclose again,
Therefore it is indicated with bracket.Embodiment 4 is to reduce the composition ratio of the hydrazine of embodiment 1 to the group of 0.2 mass % from 0.5 mass %
At.Increase EDG to the reduction partial response of hydrazine.Embodiment 4 also similarly to Example 1 in resist peeling force and damaged metal and
It bathes in whole assessment items in service life and is evaluated for circle.
Embodiment 5 is the composition that the composition ratio of the hydrazine of embodiment 1 is increased to 2.0 mass % from 0.5 mass %.Hydrazine
Reduce EDG with increasing partial response.Embodiment 5 is also similarly to Example 1 in resist peeling force and damaged metal and bath service life
Whole assessment items in for circle evaluate.
Comparative example 10 is by one water of hydrazine and object (HNH of embodiment 12O composition ratio) from 0.5 mass % reduce to
The composition of 0.1 mass %.For the resist peeling force of (new liquid) immediately after preparation of comparative example 10, in an atmosphere placement 6 hours
Afterwards problem is not occurred to metal membrane damage.However, resist peeling force reduces after placing 12 hours in an atmosphere, for fork evaluation.
In addition, since the fork that is evaluated as of the damage on the surface and section that make Cu/Mo after placing in an atmosphere 12 hours is evaluated.It needs
It is bright, do not observe that Al is damaged.In addition, not observing the reduction of hydrazine in the case where closed save 4 days yet.
Comparative example 11 is that hydrazine (one water of hydrazine and object (HNH are not added2O composition)).Comparative example 11 is certainly (new immediately after preparation
Liquid) rise fail to remove the resist film baked firmly.In addition, the membrane damage of " Cu/Mo " occurs.It should be noted that not observing
Al damage.For bathing the service life, experiment is not carried out.
Comparative example 12 is that saccharin is added to replace example of the hydrazine of embodiment 1 as additive.Comparative example 13 is that sorb is added
Sugar alcohol (Stol) replaces example of the hydrazine of embodiment 1 as additive.In addition, comparative example 14 is that diglycerol is added to replace embodiment
Example of 1 hydrazine as additive.Comparative example 12, comparative example 13, comparative example 14 fail the moment from (new liquid) immediately after preparation
Remove the resist film baked firmly.In addition, Cu/Mo damage occurs.It should be noted that not observing that Al is damaged.For bathing the longevity
Life, is not carried out experiment.
By result above, it can be said that hydrazine (one water of hydrazine and object (HNH2It O)) is the necessary material of stripper of the invention,
Ratio of components be 0.064 mass % (one water of hydrazine and object be 0.1 mass %) below when, pass through stripping performance, the gold of bath life test
Belong to damage aspect and is unable to get circle evaluation.On the other hand, at least in the hydrazine comprising 1.28 mass %, (one water of hydrazine and object are 2.0
Quality %) in the case where, characteristic will not be had an impact.
[table 4]
Table 4 shows 15,16 composition and evaluation result of embodiment 1,6~9 and comparative example.Embodiment 1 is to disclose again,
Therefore it is indicated with bracket.Embodiment 6 is to subtract the composition ratio of the N- methylethanolamine (MMA) of embodiment 1 from 20.0 mass %
The as little as composition of 5.0 mass %.Increase EDG and PG to the reduction partial response of MMA.Embodiment 6 is by immediately after preparation (new liquid)
The resist film through baking firmly can be removed in 8 minutes.In addition, also there is no problem and is circle metal membrane damage and bath service life
Evaluation.In addition, closed the case where placing 4 days, does not observe the reduction of hydrazine yet.
Embodiment 7 is to reduce the composition ratio of the N- methylethanolamine (MMA) of embodiment 1 to 10.0 from 20.0 mass %
The composition of quality %.Increase PG to the reduction partial response of MMA.Embodiment 7 is by the way that (new liquid) can be in 5 minutes immediately after preparation
Remove the resist film through baking firmly.In addition, also there is no problem and is circle evaluation metal membrane damage and bath service life.Closed placement
4 days the case where, do not observe the reduction of hydrazine yet.
Embodiment 8 is monoethanolamine (MEA), the ratio of components that the N- methylethanolamine (MMA) of embodiment 1 is changed to primary amine
Rate is also reduced from 20.0 mass % to the composition of 5.0 mass %.Increase PG to the reduction partial response of MEA.Embodiment 8 passes through rigid
(new liquid) can remove the resist film through baking firmly in 5 minutes after preparation.In addition, metal membrane damage and bath service life do not have yet
Problem and be circle evaluation.Closed the case where placing 4 days, does not observe the reduction of hydrazine yet.
Embodiment 9 is monoethanolamine (MEA), the ratio of components that the N- methylethanolamine (MMA) of embodiment 1 is changed to primary amine
Rate is also reduced from 20.0 mass % to the composition of 10.0 mass %.Increase PG to the reduction partial response of MEA.Embodiment 9 passes through
(new liquid) can remove the resist film through baking firmly in 2 minutes immediately after preparation.In addition, metal membrane damage and bath service life do not have yet
It is problematic and be circle evaluation.In addition, closed the case where placing 4 days, does not observe the reduction of hydrazine yet.
Comparative example 15 is to reduce the composition ratio of the N- methylethanolamine (MMA) of embodiment 1 to 3.0 from 20.0 mass %
The composition of quality %.Increase PG to the reduction partial response of MMA.Comparative example 15 fails removing through hard by (new liquid) immediately after preparation
The resist film of baking.Therefore, for bathing the service life, test is not carried out.It follows that the ratio of components of N- methylethanolamine (MMA)
When for 3.0 mass % or less, circle evaluation cannot be obtained about peeling force.
Comparative example 16 is the monoethanolamine (MEA) that the N- methylethanolamine (MMA) of embodiment 1 is changed to primary amine, composition
Ratio is reduced from 20.0 mass % to the composition of 3.0 mass %.Increase PG to the reduction partial response of MEA.Comparative example 16 passes through
(new liquid) fails to remove the resist film through baking firmly immediately after preparation.Therefore, for bathing the service life, test is not carried out.Thus can recognize
When composition ratio is 3.0 mass % or less, also to become not removing and be dried firmly even if the monoethanolamine (MEA) as primary amine
The anticorrosive additive stripping liquid controlling of roasting.
[table 5]
Table 5 shows the composition and evaluation result of embodiment 1,10~11 and comparative example 17~18.Embodiment 1 is to take off again
Show, therefore is indicated with bracket.Embodiment 10 is that the composition ratio of the water of embodiment 1 is increased to 25.0 matter from 20.0 mass %
Measure the composition of %.Reduce EDG to the increase partial response of water.Embodiment 10 can be by (new liquid) immediately after preparation in 5 minutes
Remove the resist film through baking firmly.In addition, also there is no problem and is circle evaluation metal membrane damage and bath service life.In addition, close
Close the reduction that the case where placing 4 days does not observe hydrazine yet.
Embodiment 11 is to reduce the composition ratio of the water of embodiment 1 to the composition of 10.0 mass % from 20.0 mass %.
Increase EDG to the reduction partial response of water.Embodiment 11 can removing be baked firmly in 3 minutes by (new liquid) immediately after preparation
Resist film.In addition, also there is no problem and is circle evaluation metal membrane damage and bath service life.In addition, the closed feelings for placing 4 days
Condition does not observe the reduction of hydrazine yet.
Comparative example 17 is to reduce the composition ratio of the water of embodiment 1 to the composition of 5.0 mass % from 20.0 mass %.Water
Reduction partial response increase EDG.Comparative example 17 fails to remove the resist film through baking firmly by (new liquid) immediately after preparation.
Therefore, for bathing the service life, test is not carried out.It follows that when the composition ratio of water is 5.18 mass % or less, for peeling force
It is unable to get circle evaluation.
Comparative example 18 is the composition that the composition ratio of the water of embodiment 1 is increased to 28.0 mass % from 20.0 mass %.
Water is 28.18 mass % after counting the water of one water of hydrazine and object in.Reduce EDG to the increase partial response of water.Comparative example 18 can lead to
It crosses and removes the resist film through baking firmly in 5 minutes immediately after preparation (new liquid).In addition, the damage to Cu/Mo is also commented for circle
Valence.However, Al is damaged.It follows that when the composition ratio of water is 28.18 mass % or more, in terms of the damage of Al film
It is unable to get circle evaluation.
Industrial availability
Anticorrosive additive stripping liquid controlling of the invention can be reliably peeled the especially resist film through baking firmly, can suitably use
In using photoresist the case where.
Description of symbols
1 substrate
2 film portions
3 basal layers
4 (film portion) surfaces
5 cone angles
10 (between the Mo layer of substrate and Cu layers) gaps
Claims (2)
1. a kind of anticorrosive additive stripping liquid controlling, it includes:
As at least one of the secondary amine other than the primary amine or ring-type of amine；
As polar solvent
Diethylene glycol monoethyl ether,
Propylene glycol and
Water；And
As the hydrazine of additive,
The amine is more than 3.0 mass % and is lower than 20.0 mass %,
The diethylene glycol monoethyl ether more than 39.5 mass % and be 59.5 mass % hereinafter,
The water is more than 5.18 mass % and is lower than 28.18 mass %,
The hydrazine is more than 0.064 mass % and is 1.28 mass % or less.
2. anticorrosive additive stripping liquid controlling according to claim 1, wherein
When the amine includes primary amine, the primary amine is monoethanolamine,
When the amine includes the secondary amine other than ring-type, the secondary amine other than the ring-type is N- methylethanolamine and N- ethyl hexanol
At least one of amine.
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| PCT/JP2016/089014 WO2018122992A1 (en) | 2016-12-28 | 2016-12-28 | Resist removal solution |
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- 2016-12-28 WO PCT/JP2016/089014 patent/WO2018122992A1/en active Application Filing
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| CN105676602A (en) * | 2010-12-02 | 2016-06-15 | Ltc有限公司 | Photoresist stripping composition comprising primary alkanolamine for liquid crystal display manufacturing process |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP6213803B1 (en) | 2017-10-18 |
| WO2018122992A1 (en) | 2018-07-05 |
| TWI640842B (en) | 2018-11-11 |
| JPWO2018122992A1 (en) | 2018-12-27 |
| TW201827952A (en) | 2018-08-01 |
| CN108235741A (en) | 2018-06-29 |
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