CN103676502B - Thick film negative photoresist release agent constituent - Google Patents
Thick film negative photoresist release agent constituent Download PDFInfo
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- CN103676502B CN103676502B CN201310382409.XA CN201310382409A CN103676502B CN 103676502 B CN103676502 B CN 103676502B CN 201310382409 A CN201310382409 A CN 201310382409A CN 103676502 B CN103676502 B CN 103676502B
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- photoresist
- release agent
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- compound
- thick film
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- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 79
- 239000000470 constituent Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000000126 substance Substances 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- -1 tetramethylammonium hydroxide class compound Chemical class 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 238000001259 photo etching Methods 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N DMA Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims description 3
- 150000003951 lactams Chemical class 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N n-methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- HNJBEVLQSNELDL-UHFFFAOYSA-N 2-Pyrrolidone Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N DETA Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- AJFDBNQQDYLMJN-UHFFFAOYSA-N N,N-diethylacetamide Chemical class CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 claims description 2
- 229960001124 Trientine Drugs 0.000 claims description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N Triethylenetetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxyl anion Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 2
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-ethylpyrrolidin-2-one Chemical class CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 claims 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N Pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 19
- 230000002335 preservative Effects 0.000 abstract description 15
- 239000003755 preservative agent Substances 0.000 abstract description 14
- 238000005516 engineering process Methods 0.000 abstract description 9
- 238000001704 evaporation Methods 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 12
- 238000005260 corrosion Methods 0.000 description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N Diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M Tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 6
- 239000003495 polar organic solvent Substances 0.000 description 6
- 229910052718 tin Inorganic materials 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N tin hydride Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N glycol Chemical class OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-Ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 4
- 206010040844 Skin exfoliation Diseases 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 150000003457 sulfones Chemical class 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N 1,2-ethanediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 210000002381 Plasma Anatomy 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000005468 ion implantation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000002829 reduced Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinone Chemical class CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- NYCCIHSMVNRABA-UHFFFAOYSA-N 1,3-diethylimidazolidin-2-one Chemical class CCN1CCN(CC)C1=O NYCCIHSMVNRABA-UHFFFAOYSA-N 0.000 description 1
- MBDUIEKYVPVZJH-UHFFFAOYSA-N 1-ethylsulfonylethane Chemical compound CCS(=O)(=O)CC MBDUIEKYVPVZJH-UHFFFAOYSA-N 0.000 description 1
- DCALJVULAGICIX-UHFFFAOYSA-N 1-propylpyrrolidin-2-one Chemical compound CCCN1CCCC1=O DCALJVULAGICIX-UHFFFAOYSA-N 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N 2-(2-Ethoxyethoxy)ethanol Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-Methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-Butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- 230000036947 Dissociation constant Effects 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N Hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 229960004011 Methenamine Drugs 0.000 description 1
- HHVIBTZHLRERCL-UHFFFAOYSA-N Methylsulfonylmethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical class CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000009867 copper metallurgy Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N ethanolamine Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 150000002169 ethanolamines Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000000816 ethylene group Chemical class [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- HXHYTNUGRGBKIE-UHFFFAOYSA-N formazan Chemical compound NN=CN=N.NN=CN=N HXHYTNUGRGBKIE-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
- 230000003760 hair shine Effects 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000000670 limiting Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000004433 nitrogen atoms Chemical group N* 0.000 description 1
- 230000000149 penetrating Effects 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000002285 radioactive Effects 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 230000035897 transcription Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Abstract
The present invention provides a kind of chemical formulas by 1 5wt%（1）The photoresist release agent that compound, the polarity organic solvent of 70 95wt%, the tetramethylammonium hydroxide class compound of 0.1 5wt% and the water indicated is formed.By the above results, photoresist release agent constituent of the present invention is free of preservative, contains suitable chemical formula（1）Shown compound even if removing in a short time, also can effectively remove thick film photoresist.The present invention can carry out compared with other techniques at a temperature of relatively high engineering, it is ensured that composition transfer minimizes in stripping technology.In addition, the present invention does not contain preservative, so can avoid evaporation is bad caused by adsorbing water-insoluble preservative from waiting the subsequent techniques problem, electrode damage is prevented.
Description
Technical field
The present invention relates to it is a kind of can be by the constituent for the remover that thick film negative photoresist is effectively removed.
Background technology
Under normal conditions, micro- circuit of semiconductor/LED/LCD elements is completed by a series of photoetching process.Photoetching
Technique needs are evenly coated with metal film or insulating film on substrate, on it after uniform butcher's photoresist, make illumination saturating
It crosses and carves figuratum template, after completing developing process, ultimately form the photoresist of required pattern.At this point, pass through dry type/wet
Formula etches, the transcription pattern on the metal film and insulating film positioned at photoresist lower part, then implements stripping technology, removes not
Necessary photoresist.
Photoresist is divided into positive photoresist according to the difference of developer solubility under the irradiation of radioactive ray
And negative photoresist.Positive photoresist is formed and imaged because exposed portion solubility increases, and negative photoresist
Solubility reduction is imaged caused by then being hardened using exposed portion, so as to leave template pattern.
It, usually can be easily clear with remover in general wet etch process for positive photoresist
It removes.But it after dry-etching or ion implantation technology are hardened or be denatured, is just difficult to clean off.Dry etch process is lost with wet type
Quarter is compared, and convenient for removing, and can obtain anisotropy template, therefore is the main occupation mode that micro- template is formed.But due to dry
Formula etching is completed by steam-solid phase reaction between the substances film such as plasma gas and conductive layer, therefore plasma loses
The ion and atomic group for carving gas can be chemically reacted with photoresist, cause photoresist layer hardening, denaturation, so as to
It is difficult to clean off.In addition, manufacturing process of the ion implantation technology as semiconductor/LED/LCD elements, in order in the particular portion of substrate
Divide and add in electric conductivity, therefore phosphorus, arsenic, boron element are diffused, can cause ion that chemistry occurs instead with positive photoresist
It should and be denatured, cause to be difficult to clean off.
Negative photoresist is then using techniques such as strippings, generates reflection of building bridge by exposing, can not be filled using solvent
It distinguishes and removes, that is, allow to remove, it is also desirable to 100 DEG C or more of high temperature and dipping, therefore technical process is difficult to ensure that surely for a long time
It is qualitative.
In addition, in general, the photoresist film thickness that etch process uses is used for salient pole within 2 μm
Formation process or redistributing layer technique（RDL:ReDistribution Line）Electrode on photoresist film thickness be more than
5 μm, up to tens of μm, therefore the stripping technology for removing photoresist must carry out for a long time, cause engineering inefficiency.
If photoresist is not removed due to remover is using unevenness, the failure of semiconductor element may be caused, therefore,
The constituent that photoresist removes the remover used in technique allows for taking into account uniform stripping and dissolving work simultaneously
With.
There are many photoresist removers at present.For example, No. 2004-0104033 invention of patent application publication is introduced
Include the photoresist release agent constituent of monoethanolamine, ethylene glycol compounds, polarity solvent and preservative.It is above-mentioned
Although constituent can remove positive photoresist, negative photoresist can not be removed.
No. 2007-0019897 invention of patent application publication is described by hydrazine, polar organic solvent and slag compound
The negative photoresist of composition remover constituent.But because wherein including environmental management substance hydrazine, therefore, it is difficult to suitable
Among actual process.
No. 2006-117219 invention of patent application publication is described by hydroxide-type compounds, glycols and diformazan
The negative photoresist remover constituent of sulfoxide composition.Mentioned component can remove negative photoresist, if but needing
Thick film photoresist of the thickness more than 120 μm is removed, it is necessary at least 60 minutes, engineering inefficiency.
No. 10-0770217 invention of Pat. Registration is described to be had by tetramethylammonium hydroxide (TMAH), alkanolamine and polarity
The salient pole of machine solvent composition forms the constituent with thick film photoresist scavenger.Above-mentioned constituent bears thick film
The peeling effect of property photoresist is good, and the damage of Kapton can will be minimized.But because to metal electricity
The corrosivity of pole is larger, is difficult to be applicable in the technique for not implementing salient pole protection.
No. 1997-016836 invention of patent application publication is described by azanol, water, acid dissociation constant (pKa) in 7.5-13
In the range of amine, the remover constituent of water-soluble organic solvent and preservative composition.But because wherein including environment pipe
Substance azanol is managed, there is waste water treatmentntrol difficult.Meanwhile because the invention uses preservative, cause material composition complicated,
It is easily adsorbed in operation process, subsequent technique evaporation may be caused bad.
Prior art literature
Patent document
（Patent document 1）Patent application publication 2004-0104033
（Patent document 2）Patent application publication 2007-0019897
（Patent document 3）Patent application publication 2006-117219
（Patent document 4）Pat. Registration 10-0770217
（Patent document 5）Patent application publication 1997-016836
The content of the invention
In order to solve problem above, the present invention wants to provide can be effectively peeled off thick film negative photoresist in a short time
Remover constituent.
The technical solution adopted by the present invention to solve the technical problems is：The present invention provides the chemistry by weight ratio 1-5%
Formula（1）Compound, the polarity organic solvent of weight ratio 70-95%, the tetramethylammonium hydroxide class of weight ratio 0.1-5% indicated
Compound and remaining weight than the photoresist release agent that forms of water.
In above-mentioned chemical formula, n is the integer in the range of 2-8.
Even if the photoresist release agent constituent of the present invention is removed in a short time, thick film also can be effectively removed
Photoresist, saves money the compression process flow time.Compared with other techniques, the present invention can be in relatively high work
It is carried out at a temperature of journey, it is ensured that composition transfer minimizes in stripping technology.In addition, the present invention does not include preservative, so can avoid
Evaporation is bad caused by adsorbing water-insoluble preservative waits the subsequent techniques problem, prevents electrode damage.
Description of the drawings
The FE-SEM on the salient pole surface of 1 stripper composition of the example evaluation carried out according to Fig. 1 according to the present invention shines
Piece.
The salient pole surface of the 1 stripper composition performance evaluation of comparative example carried out according to Fig. 2 not according to the present invention
FE-SEM photos.
1 stripper composition of comparative example carried out according to Fig. 3 not according to the present invention carries out the convex of Metallic film corrosion evaluation
The FE-SEM photos of block electrode surface.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to the accompanying drawings and embodiments, it is right
The present invention is further elaborated.It should be appreciated that specific embodiment described herein is only to explain the present invention, not
For limiting the present invention.
The present invention provides a kind of remover constituent that can be effectively removed, decompose thick film negative photoresist.
In the present invention, thick film refers in general photoetching process, and thickness is more than 1~2 μm of stacking photoresist film.
The present invention provides the chemical formulas by 1-5wt%（1）The compound that is indicated, the polarity organic solvent of 70-95wt%,
The photoresist release agent that the tetramethylammonium hydroxide class compound and water of 0.1-5wt% is formed.
Preservative is free of in remover constituent.Because containing chemical formula（1）The compound of expression, the present invention can be short
Stripping technology is efficiently accomplished in time.Compared with other techniques, the present invention can carry out at a temperature of relatively high engineering, really
Composition transfer in stripping technology is protected to minimize.In addition, the present invention does not include preservative, so can avoid water-insoluble anti-because adsorbing
Evaporation caused by rotten agent is bad to wait the subsequent techniques problem, prevents electrode damage.
In general, preservative is that one kind is attached to metal surface, for inhibiting the surface layer protective agent of corrosion.Preservative
Action principle is that polar group is attached to metal surface, by nonpolar base arrangement generation moved or prevented by membrane change charge and
Corrode the movement in relation to substance.Therefore, the chemical formula used in the present invention（1）Compound represented is by multiple N（Nitrogen-atoms）
The amine component of composition, alkali（alkali）Degree can maximize stripping performance, and multiple-N bases can then protect metal surface, by gold
Belong to electrode damage to be preferably minimized.
The chemical formula used in the present invention（1）Compound represented is different from other preservatives because with water solubility, can be with
Prevent the appearance of unfavorable condition in subsequent technique.Such as ethylenediamine, Diethylenetriamine, triethylene tetramine, tetraethylenepentamine, five ethylenes
Hexamine, six second, seven amine etc., these substances may be used singly or in combination of two or more.In chemical formula（1）In, it is proposed that selection
N is the ethanolamines substance of 2-8.The compound that n is 1 is ethylenediamine, the N included in compound（Nitrogen-atoms）Deficiency is not prevented
The effect only corroded；When n is more than 9, with the increase of molecular weight, the penetrating power of photoresist is low, causes fissility
It can reduce.
For the remover of the present invention, it is proposed that wherein chemical formula（1）Compounds content account for the 1- of component total weight
5%.When weight ratio is less than 1%, anti-corrosion effect is relatively low；And when weight ratio is more than 5%, the content of polar organic solvent is reduced, from
And cause stripping performance low.
For the polar organic solvent contained in the constituent of remover shown in the present invention, formed if remover
The polar organic solvent used in ingredient can be used unlimitedly.Specifically have,
Include the sulfoxide type of diformazan sulfone etc.；Including dimethyl sulfone, diethyl sulfone, double（2- ethoxys）Sulfone, tetramethylene
The sulfone class of sulfone etc.；Including n,N-Dimethylformamide, N-METHYLFORMAMIDE, n,N-dimethylacetamide, N- methylacetamides, N,
The amides of N- diethyl acetamides etc.；Including N, N- diformazans lactams, 2-Pyrrolidone, n-methyl-2-pyrrolidone, N- second
Base -2-Pyrrolidone, N- propyl -2-Pyrrolidone, N- methylols -2-Pyrrolidone, N- ethoxys -2-Pyrrolidone etc. it is interior
Amides；Including 1,3- dimethyl -2- imidazolidinones, 1,3- diethyl -2- imidazolidinones, 1,3- diisopropyl -2- imidazolidines
The imidazolidine ketone of ketone etc.；Including ethylene glycol, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol list first
Ether acetic acid ester, ethylene glycol monoethylether acetate, diethylene glycol (DEG), diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono butyl
The multivalence glycols and its derivative of ether etc..
These substances can be used alone, and also may be selected to be used in combination.If in diformazan sulfone, N, N- dimethyl methyls
Amide, n,N-dimethylacetamide, N, N- diethyl acetamides, N-METHYLFORMAMIDE, N, N- diformazans lactams, 1,3- diformazans
Base -2- imidazolidinones, glycol monoethyl ether, ethylene glycol monoethyl ether, N-Methyl pyrrolidone, N- and pyrrolidones, 2- pyrroles
More than one uses are selected in alkanone, then can show more superior fissility.
The polar organic solvent weight ratio contained in the constituent of remover shown in the present invention is 70-95%, if 80-
95% more.If the weight ratio of above-mentioned content, less than 70%, photoresist solubility reduces, and causes preservative fully erased
Totally；If the weight ratio of above-mentioned content is more than 95%, the content of other compositions opposite will be reduced, and stripping performance weakens, and may go out
The problems such as existing corrosion phenomenon.
The tetramethylammonium hydroxide class compound contained in remover shown in the present invention is to further improve negativity
Photoresist stripping performance and add, it is recommended to use quaternary ammonium cation hydroxide, at this moment alkyl should be in the alkyl of C1-C5
Selection.
It is recommended that the content of tetramethylammonium hydroxide class compound accounts for the weight of the 0.1-5% of remover total composition ingredient, weight
Than for 1-4% it is optimal.If it is low to may result in stripping performance less than 0.1% for the weight ratio of above-mentioned content；If the weight of above-mentioned content
When amount is than more than 5%, then the possibility of corrosion lower metal film is likely to occur.
Water in constituent of the present invention is not particularly limited, but should use deionized water.It is recommended that using values of resistivity in 18M
The deionized water of more than Ω/㎝.
Following content is present example.Though will be to detailed description, these examples are only that the present invention is drilled
Show, and be not merely limited in following examples.
<Example 1 to 13 and comparative example 1 to 7>
By chemical formula（1）Compound, polar organic solvent, tetramethylammonium hydroxide class and water situation cooperation as shown in table 1,
Produce negative photoresist remover.
【Table 1】
<Photoresist stripping performance is evaluated>
Photoresist stripping performance is carried out to the photoresist stripper constituent made according to above-mentioned table 1 to comment
Valency.
In order to evaluate the stripping performance of the photoresist with above-mentioned constituent, one layer is formed on copper-plated disk
Photoresist about 50~60 μm thick and tin salient pole.Specifically, first in UBM (the Under Bump formed by copper
Metallurgy the photoresist film of about 50~60 μm of a thickness) is formed on layer disk.Pass through on above-mentioned photoresist
After exposure process forms template, by developing process, the salient pole of galvanoplastic formation tin material is utilized.
Then, the disk being made of photoresist and salient pole is cut into 3cm x3cm sizes, makes assessment sample
Plate.By above-mentioned sample at a temperature of 60 DEG C, immerse and placed 3 minutes according in each remover constituent made of table 1, so as to go
Except photoresist film.The above-mentioned sample for being removed photoresist film is put into ultra-pure water after washing about 1 minute, is made with nitrogen
It is dried.Confirm whether dried sample has removed photoresist with FE-SEM（With reference to diagram 1 and diagram 2）.Illustrating 1 is
According to the FE-SEM photos on the salient pole surface that 1 stripper composition of example carried out according to the present invention is evaluated, it is illustrated that according to 2
Not according to the FE-SEM photos on the salient pole surface of the comparative example 1 stripper composition performance evaluation of the invention carried out.
Above-mentioned experimental condition with conventional salient pole photoresist stripping process need 10 minutes or more compared with more
Simplicity, and have a distinct increment compared with the peeling effect of common remover.The results are shown in Table 2.
◎：Photoresist removal 100%, noresidue
○：Photoresist removal more than 80%, basic noresidue
△：Photoresist removal more than 50%, there is a certain amount of residue
×：Photoresist removal amount has a large amount of photoresist residues less than 50%
<Metallic film corrosion is evaluated>
As above-mentioned table 1, by the photoresist stripper constituent of making to salient pole corrosivity
It is evaluated.
In order to evaluate above-mentioned constituent to salient pole corrosivity, a thickness is formed on copper-plated disk about
50~60 μm of photoresist and tin salient pole.Then, the disk that photoresist and salient pole are formed is cut
Into the test sample of 3x3cm sizes.
By above-mentioned sample at a temperature of 60 DEG C, immerse and placed 3 minutes according in each remover constituent made of table 1,
So as to remove photoresist film.The above-mentioned sample for being removed photoresist film is put into ultra-pure water after washing about 1 minute,
Make its drying with nitrogen.Confirm whether dried sample has removed photoresist with FE-SEM.Not according to this according to diagram 3
1 stripper composition of comparative example that invention carries out carries out the FE-SEM photos on the salient pole surface of Metallic film corrosion evaluation.
Above-mentioned experimental condition with conventional salient pole photoresist stripping process need 10 minutes or more compared with more
Simplicity, and have a distinct increment compared with the peeling effect of common remover.The results are shown in Table 2.
◎：The corrosion to copper and tin is not observed
○：Observe the corrosion a little to copper and tin
△：Observe the corrosion to copper and tin part metals
×：It observes to copper and tin whole corrosion of metal
【Table 2】
| Photoresist extent of exfoliation | Metallic film corrosion degree | |
| Example 1 | ◎ | ○ |
| Example 2 | ◎ | ◎ |
| Example 3 | ◎ | ◎ |
| Example 4 | ◎ | ○ |
| Example 5 | ◎ | ◎ |
| Example 6 | ○ | ◎ |
| Example 7 | ◎ | ◎ |
| Example 8 | ◎ | ◎ |
| Example 9 | ◎ | ◎ |
| Example 10 | ◎ | ◎ |
| Example 11 | ◎ | ◎ |
| Example 12 | ○ | ◎ |
| Example 13 | ○ | ◎ |
| Comparative example 1 | △ | × |
| Comparative example 2 | ◎ | △ |
| Comparative example 3 | × | ◎ |
| Comparative example 4 | △ | × |
| Comparative example 5 | △ | ◎ |
| Comparative example 6 | △ | △ |
| Comparative example 7 | △ | ◎ |
By the above results, photoresist release agent constituent of the present invention is free of preservative, containing suitable
Chemical formula（1）Shown compound even if removing in a short time, also can effectively remove thick film photoresist, compression process
Flow time saves money.
Claims (3)
1. a kind of photoresist release agent, which is characterized in that by 1-X wt%, wherein X is less than 5, chemical formula (1) indicated
Compound, the polarity organic solvent of 70-95wt%, the tetramethylammonium hydroxide class compound of 0.1-5wt% and water structure
Into：
In above-mentioned chemical formula, n is the integer in the range of 2-8；
The constituent of the photoresist release agent can be used for removing thick film negative photoresist, and the thick film refers to
In photoetching process, thickness is 1-60 μm of stacking photoresist film；
The polarity organic solvent can in n,N-Dimethylformamide, n,N-dimethylacetamide, N, N- diethyl acetamides,
N-METHYLFORMAMIDE, N select one in N- diformazans lactams, N-Methyl pyrrolidone, N- ethyl pyrrolidones, 2-Pyrrolidone
Kind is two or more.
2. photoresist release agent according to claim 1, which is characterized in that chemical formula (1) compound represented can
It is selected in Diethylenetriamine, triethylene tetramine, tetraethylenepentamine, penten, six second, seven amine one or more kinds of.
3. photoresist release agent according to claim 1, which is characterized in that tetramethylammonium hydroxide class compound is
Quaternary ammonium cation hydroxide, alkyl are the alkyl of C1-C5.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2012-0096430 | 2012-08-31 | ||
| KR1020120096430A KR101375100B1 (en) | 2012-08-31 | 2012-08-31 | Stripper composition for thick negative photoresist |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103676502A CN103676502A (en) | 2014-03-26 |
| CN103676502B true CN103676502B (en) | 2018-06-01 |
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