CN103676505A - Photoresist stripper for chip and preparation method and photoresist removing process thereof - Google Patents
Photoresist stripper for chip and preparation method and photoresist removing process thereof Download PDFInfo
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- CN103676505A CN103676505A CN201310719197.XA CN201310719197A CN103676505A CN 103676505 A CN103676505 A CN 103676505A CN 201310719197 A CN201310719197 A CN 201310719197A CN 103676505 A CN103676505 A CN 103676505A
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Abstract
The invention relates to a photoresist stripper for a chip and a preparation method and a photoresist removing process thereof. The stripper comprises a stripping agent, a wetting agent, organic amine or organic ammonium salt, a corrosion inhibitor, an auxiliary and an organic solvent. The stripper has excellent photoresist stripping and dissolving ability on various chips, can completely remove a photoresist and does not generate residues; moreover, the stripper also can ensure no corrosion and has wide industrial application potential and value.
Description
Technical field
The present invention relates to a kind of electronic component cleaning fluid, relate to especially a kind of photoresist lift off liquid, preparation method and degumming process for chip, belong to the precision cleaning field of high precision electronic devices and components.
Background technology
In hyundai electronics retrofit field, integrated circuit (IC), large scale integrated circuit (LSI), VLSI (very large scale integrated circuit) (ULSI), the multiple semiconductor elements such as light emitting diode (LED) chip or liquid crystal board element have a large amount of extremely trickle loop and circuit structures, and in order to form these structures, all need to make to process with photoresist, before and after this photoetching process, conventionally need to carry out tens of times, conventional processing and treating method is normally at substrate, on substrate through multiple processing as electroplated, methods such as chemical vapour desposition and form specific function film, then evenly apply photoresist, then through overexposure, video picture is processed and is formed required line pattern, this functional membrane of final etch and form trickle loop or circuit.And residual photoresist layer needs to use and peels off.
In chip manufacturing proces, cleaning the pollutants such as chip surface photoresist, metallics is the fundamental purpose of removing photoresist, and removing photoresist is the critical process in chip manufacturing process, removes photoresist and not exclusively likely causes scrapping of chip by the gross.Therefore, the removal degree of chip surface state and pollutant is one of most important factor affecting chip acceptance rate and device quality and reliability.
Peeling off of photoresist, clean in research, generally use for a long time dry method to peel off or wet method is peeled off, but dry process exists and easily leave over many defects such as residue, therefore the main wet method of using is peeled off at present.The principle that wet method is peeled off is to use stripper that residual photoresist is dissolved, thereby is removed smoothly.
By further investigation for many years, prepared multiple stripper, and there is advantage and the scope of application separately.
CN101295143B discloses a kind of photoetching glue residue clean-out system, it comprises surfactant, ammonium fluoride, organic sulfonic acid, organic solvent, bleeding agent, containing nitronic acid, corrosion inhibiter and pure water, its wafer after dry method is peeled off has good cleanup action.
CN101295144A discloses a kind of photoresist lift off liquid, and it comprises surfactant, organic amine, organic solvent, sequestrant, corrosion inhibiter and pure water, and this stripper has good cleaning performance.
CN1244023C discloses a kind of photoresist stripper, the HF acid that it comprises certain content and the salt that alkali of metal ion does not form, water-miscible organic solvent, anticorrosive and excess water.This stripper can meet the double requirements of fissility and preventing metal corrosion simultaneously.
CN101251722B discloses a kind of positive photoresist stripper, described stripper AEO, cyclohexanone and monoethanolamine, and this stripper is corrosion-free to aluminium base, glass surface noresidue after cleaning.
CN102147576B discloses a kind of photoresist lift off composition, and described composition is comprised of organosilicon compound, acrylic acid esters co-polymer and organic solvent, and it has good photoresist dissolubility and fissility.
CN102141743A discloses a kind of photoresist lift off composition with metal coating, and it comprises quaternary amines oxyhydroxide, water-soluble alkanolamine, water soluble organic polar solvent and glycitols adjuvant.Said composition is outside excellent photoresist lift off performance, good to the corrosion resistivity of Metal Substrate coating film.
CN102012645A discloses a kind of photoresist lift off liquid, and it comprises hydrazine hydrate or organic amine compound, solvent, resist and pure water.This stripper can stripping photoresist, and the corrosion of metal line is reduced to minimum.
CN103336412A discloses a kind of photoresist lift off liquid, and it comprises organic solvent, separates crosslinking catalyst, anticorrosion preservative and other adjuvant.This stripper can shorten the cycle of removing photoresist, and can thoroughly remove negative photoresist.
As mentioned above, although there is multiple photoresist lift off liquid in prior art, but the mechanism of removing photoresist of these strippers is the single effects based on dissolving, realize the removal of photoresist, thereby cause existing various defects, not thorough etc. such as metal wiring or backing material more or less being existed to burn into photoresist lift off to a certain degree, and wherein there is strong corrosive material (as HF) etc., thereby cause the three wastes many, process and to expend large, contaminated environment etc.
Therefore, under the industry requirement of development of new photoresist lift off liquid, further more efficient, the eco-friendly photoresist lift off liquid of exploitation, is the current place of needing badly, and novel photoresist lift off liquid will be significant to the development of integrated circuit, LED and liquid crystal panel industry.
Summary of the invention
The various defects that existing photoresist lift off liquid based on described above exists, and in order to seek new photoresist lift off liquid, preparation method and degumming process, the present invention is based on the principle of removing photoresist of peeling off and dissolving, a kind of photoresist lift off liquid for chip is provided, have charge stripping efficiency high, remove photoresist completely, the plurality of advantages such as environmental protection, reduction pollution.
Particularly, the invention provides a kind of photoresist lift off liquid, preparation method and degumming process for chip.
More specifically, first object of the present invention is to provide a kind of photoresist lift off liquid for chip, and described photoresist lift off liquid comprises the various components of following weight parts:
It should be noted that, unless otherwise prescribed, " the comprising " while relating to component in this application, that its implication comprises is enclosed " by .... form " or its equivalent definition, and open " comprising ", " comprising " etc. or its equivalent definition, and can not be limited to its simple literal meaning.
Still it should be noted that "or" in component " organic amine or organic ammonium salt ", only to working to component, only plays restriction effect to the selection of " organic amine " and " organic ammonium salt ", and to other component indefinite effect.
Further note that, numerical value, numerical ranges all in the application can be limited by " approximately " word equally.
In described photoresist lift off liquid of the present invention, described remover is perfluoroalkyl ethoxy polyoxyethylene ether, and its structural formula is C
mf
2m+1cH
2cH
2o(C
2h
4o)
nh, the aggregate number that wherein n is oxirane, m and n are all selected from the integer of 6-12, and exemplarily, for example both can be 6,7,8,9,10,11 or 12 independently of one another.
Wherein as the C of end group
mf
2m+1in C-C skeleton form be not particularly limited, can be straight or branched.As a kind of, exemplify indefiniteness ground, described C
mf
2m+1can be perfluor n-hexyl (C
6f
13), perfluor n-octyl (C
8f
17), the positive decyl (C of perfluor
10f
21), perfluor dodecyl (C
12f
25) or (CF
3)
2cF (CF
2)
3-etc.
Described remover can be any one or any multiple potpourri belonging within the scope of this structural formula.
The weight portion of described remover is 1-10 part, and this scope has comprised any concrete point value wherein, as 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 1 part, 9 parts or 10 parts.
In described photoresist lift off liquid of the present invention, described wetting agent is aliphatic alcohol polyethenoxy polyethenoxy ether, and structural formula is R
1o(C
2h
4o)
p(C
3h
6o)
qh, wherein p and q are respectively the aggregate number of oxirane and epoxypropane, and wherein p is the integer between 4-12, and q is the integer between 4-10.
Exemplarily, p can be 4,5,6,7,8,9,10,11 or 12; Q can be 4,5,6,7,8,9 or 10.
R wherein
1for C
10-C
18straight or branched alkyl, exemplarily, R
1for positive decyl, n-undecane base, dodecyl, n-tridecane base, n-tetradecane base, n-pentadecane base, n-hexadecyl, n-heptadecane base or n-octadecane base.
The weight portion of described wetting agent is 3-10 part, and this scope comprises any concrete point value wherein, as 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts.
In described photoresist lift off liquid of the present invention, described organic amine or organic ammonium salt are selected from any or any multiple potpourri in diethylamine, triethylamine, ethylenediamine, monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, diisopropanolamine, triisopropanolamine, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, TBAH.
The weight portion of described organic amine or organic ammonium salt is 3-30 part, and this scope comprises any concrete point value wherein, as 3 parts, 7 parts, 11 parts, 15 parts, 19 parts, 23 parts, 27 parts or 30 parts.
In described photoresist lift off liquid of the present invention, described corrosion inhibiter is benzotriazole, 1-C
1-C
6alkylbenzotriazole, 1-hydroxy benzo triazole, 1-methylol benzotriazole, 3-sulfydryl-1, any or any multiple potpourri in 2,4-triazole, 5-carboxy benzotriazole, the chloro-1-hydroxy benzo triazole of 6-.
Wherein, 1-C
1-C
6alkylbenzotriazole is such as can be 1-methyl benzotriazazole, 1-ethyl benzotriazole, 1-n-pro-pyl benzo triazole, 1-normal-butyl benzo triazole, 1-n-pentyl benzo triazole, 1-n-hexyl benzo triazole etc.
Described corrosion inhibiter is preferably 1-hydroxy benzo triazole, the chloro-1-hydroxy benzo triazole of 6-, most preferably is the chloro-1-hydroxy benzo triazole of 6-.
The weight portion of described corrosion inhibiter is 0.01-5 part, and this scope comprises any concrete point value wherein, as 0.01 part, 0.05 part, 0.1 part, 0.5 part, 1 part, 2 parts, 3 parts, 4 parts or 5 parts.
In described photoresist lift off liquid of the present invention, described auxiliary agent is crown ether compound, and it is selected from any or any multiple potpourri in open chain crown ether, benzo-crown ether, hydroxy benzo crown ether, naphthenic base crown ether.
Wherein, open chain crown ether can be 15-hat-5,18-hat-6; Benzo-crown ether can be dibenzo-18-hat-6; Hydroxy benzo crown ether can be hydroxyl-dibenzo-14-crown-4; Naphthenic base crown ether can be dicyclohexyl-18-crown-6.
Described auxiliary agent is preferably hydroxy benzo crown ether or naphthenic base crown ether, most preferably is dicyclohexyl-18-crown-6.
The weight portion of described auxiliary agent is 0.05-3 part, this scope comprises any concrete point value wherein, as 0.05 part, 0.1 part, 0.3 part, 0.5 part, 0.7 part, 0.9 part, 1.1,1.3 parts, 1.5 parts, 1.7 parts, 1.9 parts, 2.1 parts, 2.3 parts, 2.5 parts, 2.7 parts, 2.9 parts or 3 parts.
In described photoresist lift off liquid of the present invention, described organic solvent is alcohol ether compound, sulfone compound or pyrrolidones.
Wherein, described alcohol ether compounds compound had both comprised alcohol compound, ether compound, also comprised the alcohol ether compound that alcohol forms.For example, it can be methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, normal butyl alcohol, isobutyl alcohol, ethylene glycol, propylene glycol, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, DPE, dipropylene glycol list propyl ether, Dipropylene glycol mono-n-butyl Ether, methyl phenyl ethers anisole, phenetol, diphenyl ether any or any multiple potpourri wherein.
Described sulfone compound can be dimethyl sulfoxide (DMSO), diethyl sulfoxide, dipropyl sulfoxide, dibutyl sulfoxide, sulfolane, 2-methyl sulfolane, 2-ethyl sulfolane, 2-propyl group sulfolane, 2-butyl sulfolane, 3-methyl sulfolane, 3-ethyl sulfolane, 3-propyl group sulfolane, 3-butyl sulfolane, 4-methyl sulfolane, 4-ethyl sulfolane, 4-propyl group sulfolane, 4-butyl sulfolane, 2,4-dimethylsulfolane, 2,4-diethyl sulfolane, 2,4-dipropyl sulfolane, 2, any or any multiple potpourri in 4-dibutyl sulfolane.
Described pyrrolidones can be any or any multiple potpourri in 1-METHYLPYRROLIDONE, N-ethyl pyrrolidone, N-propyl pyrrole alkane ketone, N-butyl pyrrolidine ketone, N-dodecylpyrrolidone, NVP, N-propenyl pyrrolidone.
The weight portion of described organic solvent is 5-90 part, for example, can be 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts or 90 parts.Be preferably 20-80 part, most preferably be 40-60 part.
Second object of the present invention relates to the preparation method of above-mentioned photoresist lift off liquid, and described preparation method comprises the steps:
(1) take respectively the various components of above-mentioned weight portion separately;
(2) organic solvent is joined in stirred tank, then add in turn organic amine or organic ammonium salt, remover, be stirred to homogeneous transparent;
(3) in the homogeneous transparent potpourri in step (2), add in turn wetting agent, corrosion inhibiter and auxiliary agent, be stirred to homogeneous transparent, obtain described photoresist lift off liquid.
Wherein, in above-mentioned steps (2) and (3), stirring rate can be 50-100rpm/min, is preferably 60-80rpm/min.
The 3rd object of the present invention relates to the degumming process of the chip photoresist lift off liquid that uses photoresist lift off liquid of the present invention, and described degumming process comprises the steps:
(1) chip is soaked at 60-90 ℃ in photoresist lift off liquid to ultrasound wave 10-30 minute;
(2) by pure water rinsing 3-10 minute for the chip after removing photoresist, rinsing 1-3 time, then nitrogen dries up.
Wherein, in above-mentioned steps (1), temperature is 60-90 ℃, for example, can be 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃ or 90 ℃; Time is 10-30 minute, for example, can be 10 minutes, 15 minutes, 20 minutes, 25 minutes or 30 minutes.
Optionally, when being difficult to remove photoresist, can repeating step (1) repeatedly, for example 2-4 time.
In above-mentioned steps (2), pure water rinsing time is 3-10 minute, for example, can be 3 minutes, 5 minutes, 7 minutes or 10 minutes.
In sum, the present invention is by providing its degumming process of photoresist lift off liquid, its preparation method and use with specific components, content, and developed a kind of novel photoresist lift off liquid, the plurality of advantages such as it has that charge stripping efficiency is high, noresidue, cleanliness are good, be suitable for the photoresist lift off of various chips, at microelectronic, there is wide application potential and value.
Accompanying drawing explanation
Fig. 1 is the microphotograph after the photoresist lift off liquid of the use embodiment of the present invention 1 removes photoresist to LED chip.
Embodiment
Below by specific embodiment, the present invention is described in detail; but the purposes of these exemplary embodiments and object are only used for exemplifying the present invention; not real protection scope of the present invention is formed to any type of any restriction, more non-protection scope of the present invention is confined to this.
Wherein, in the step (2) of each embodiment and the component in (3), be the respective components taking in step (1).
Embodiment 1
(1) take respectively 1 weight portion remover C
6f
13cH
2cH
2o(C
2h
4o)
6h (C wherein
6f
13for perfluor n-hexyl), 3 weight portion wetting agent C
10h
21o(C
2h
4o)
4(C
3h
6o)
4h (C wherein
10h
21for positive decyl), 3 weight portion organic amine diethylamine, the chloro-1-hydroxy benzo triazole of 0.01 weight portion corrosion inhibiter 6-, 0.05 weight portion auxiliary agent dicyclohexyl-18-crown-6 and 5 weight portion organic solvent ethanol.
(2) organic solvent of step (1) is joined in stirred tank, then add in turn organic amine, remover, be stirred to homogeneous transparent, stirring rate is 60rpm/min;
(3) in the homogeneous transparent potpourri in step (2), add in turn wetting agent, corrosion inhibiter and auxiliary agent, be stirred to homogeneous transparent, stirring rate is 60rpm/min, obtains described photoresist lift off liquid, by its called after BLY1.
Embodiment 2
(1) take respectively 5 weight portion remover C
8f
17cH
2cH
2o(C
2h
4o)
8h (C wherein
8f
17for perfluor n-octyl), 6 weight portion wetting agent C
12h
25o(C
2h
4o)
6(C
3h
6o)
6h (C wherein
12h
25for dodecyl), 10 weight portion organic amine monoethanolamines, the chloro-1-hydroxy benzo triazole of 0.05 weight portion corrosion inhibiter 6-, 0.1 weight portion auxiliary agent dicyclohexyl-18-crown-6 and 40 weight portion organic solvent ethylene glycol monomethyl ethers.
(2) organic solvent of step (1) is joined in stirred tank, then add in turn organic amine, remover, be stirred to homogeneous transparent, stirring rate is 70rpm/min;
(3) in the homogeneous transparent potpourri in step (2), add in turn wetting agent, corrosion inhibiter and auxiliary agent, be stirred to homogeneous transparent, stirring rate is 70rpm/min.Obtain described photoresist lift off liquid, by its called after BLY2.
Embodiment 3
(1) take respectively 10 weight portion remover C
10f
21cH
2cH
2o(C
2h
4o)
10h (C wherein
10f
21for the positive decyl of perfluor), 10 weight portion wetting agent C
14h
29o(C
2h
4o)
8(C
3h
6o)
8h (C wherein
14h
29for n-tetradecane base), 20 weight portion organic amine diisopropanolamines, the chloro-1-hydroxy benzo triazole of 0.2 weight portion corrosion inhibiter 6-, 0.2 weight portion auxiliary agent dicyclohexyl-18-crown-6 and 60 weight portion organic solvent dipropylene glycol monomethyl ethers.
(2) organic solvent of step (1) is joined in stirred tank, then add in turn organic amine, remover, be stirred to homogeneous transparent, stirring rate is 80rpm/min;
(3) in the homogeneous transparent potpourri in step (2), add in turn wetting agent, corrosion inhibiter and auxiliary agent, be stirred to homogeneous transparent, stirring rate is 80rpm/min.Obtain described photoresist lift off liquid, by its called after BLY3.
Embodiment 4
(1) take respectively 3 weight portion remover C
12f
25cH
2cH
2o(C
2h
4o)
12h (C wherein
12f
25for perfluor dodecyl), 5 weight portion wetting agent C
16h
33o(C
2h
4o)
10(C
3h
6o)
10h (C wherein
16h
33for n-hexadecyl), 30 weight portion organic ammonium salt Tetramethylammonium hydroxide, the chloro-1-hydroxy benzo triazole of 1 weight portion corrosion inhibiter 6-, 1 weight portion auxiliary agent dicyclohexyl-18-crown-6 and 80 weight portion organic solvent diphenyl ether.
(2) organic solvent of step (1) is joined in stirred tank, then add in turn organic ammonium salt, remover, be stirred to homogeneous transparent, stirring rate is 50rpm/min;
(3) in the homogeneous transparent potpourri in step (2), add in turn wetting agent, corrosion inhibiter and auxiliary agent, be stirred to homogeneous transparent, stirring rate is 50rpm/min.Obtain described photoresist lift off liquid, by its called after BLY4.
Embodiment 5
(1) take respectively 6 weight portion remover C
6f
13cH
2cH
2o(C
2h
4o)
8h (C wherein
6f
13for perfluor n-hexyl), 7 weight portion wetting agent C
18h
37o(C
2h
4o)
12(C
3h
6o)
4h (C wherein
18h
37for n-octadecane base), 7 weight portion organic amine ethylenediamines, the chloro-1-hydroxy benzo triazole of 3 weight portion corrosion inhibiter 6-, 2 weight portion auxiliary agent dicyclohexyl-18-crown-6s and 10 weight portion organic solvent dimethyl sulfoxide (DMSO)s.
(2) organic solvent of step (1) is joined in stirred tank, then add in turn organic amine, remover, be stirred to homogeneous transparent, stirring rate is 90rpm/min;
(3) in the homogeneous transparent potpourri in step (2), add in turn wetting agent, corrosion inhibiter and auxiliary agent, be stirred to homogeneous transparent, stirring rate is 90rpm/min.Obtain described photoresist lift off liquid, by its called after BLY5.
Embodiment 6
(1) take respectively 8 weight portion remover C
8f
17cH
2cH
2o(C
2h
4o)
12h (C wherein
8f
17for perfluor n-octyl), 4 weight portion wetting agent C
10h
21o(C
2h
4o)
4(C
3h
6o)
8h (C wherein
10h
21for positive decyl), 15 weight portion organic amine triethanolamines, the chloro-1-hydroxy benzo triazole of 2 weight portion corrosion inhibiter 6-, 3 weight portion auxiliary agent dicyclohexyl-18-crown-6s and 90 weight portion organic solvent 3-methyl sulfolanes.
(2) organic solvent of step (1) is joined in stirred tank, then add in turn organic amine, remover, be stirred to homogeneous transparent, stirring rate is 60rpm/min;
(3) in the homogeneous transparent potpourri in step (2), add in turn wetting agent, corrosion inhibiter and auxiliary agent, be stirred to homogeneous transparent, stirring rate is 60rpm/min.Obtain described photoresist lift off liquid, by its called after BLY6.
Embodiment 7
(1) take respectively 2 weight portion remover C
10f
21cH
2cH
2o(C
2h
4o)
6h (C wherein
10f
21for the positive decyl of perfluor), 8 weight portion wetting agent C
12h
25o(C
2h
4o)
6(C
3h
6o)
10h (C wherein
12h
25for dodecyl), 25 weight portion organic ammonium salt TBAH, the chloro-1-hydroxy benzo triazole of 5 weight portion corrosion inhibiter 6-, 0.5 weight portion auxiliary agent dicyclohexyl-18-crown-6 and 50 weight portion organic solvent 1-METHYLPYRROLIDONEs.
(2) organic solvent of step (1) is joined in stirred tank, then add in turn organic ammonium salt, remover, be stirred to homogeneous transparent, stirring rate is 100rpm/min;
(3) in the homogeneous transparent potpourri in step (2), add in turn wetting agent, corrosion inhibiter and auxiliary agent, be stirred to homogeneous transparent, stirring rate is 100rpm/min.Obtain described photoresist lift off liquid, by its called after BLY7.
Embodiment 8
(1) take respectively 9 weight portion remover C
12f
25cH
2cH
2o(C
2h
4o)
10h (C wherein
12f
25for perfluor dodecyl), 9 weight portion wetting agent C
14h
29o(C
2h
4o)
10(C
3h
6o)
6h (C wherein
14h
29for n-tetradecane base), 5 weight portion organic amine triethylamines, the chloro-1-hydroxy benzo triazole of 4 weight portion corrosion inhibiter 6-, 0.25 weight portion auxiliary agent dicyclohexyl-18-crown-6 and 70 weight portion organic solvent N-propenyl pyrrolidone.
(2) organic solvent of step (1) is joined in stirred tank, then add in turn organic amine, remover, be stirred to homogeneous transparent, stirring rate is 70rpm/min;
(3) in the homogeneous transparent potpourri in step (2), add in turn wetting agent, corrosion inhibiter and auxiliary agent, be stirred to homogeneous transparent, stirring rate is 70rpm/min.Obtain described photoresist lift off liquid, by its called after BLY8.
Embodiment 9
(1) take respectively 4 weight portion remover C
6f
13cH
2cH
2o(C
2h
4o)
12h (C wherein
6f
13for perfluor n-hexyl), 10 weight portion wetting agent C
16h
33o(C
2h
4o)
12(C
3h
6o)
10h (C wherein
16h
33for n-hexadecyl), 8 weight portion organic ammonium salt TPAOH, the chloro-1-hydroxy benzo triazole of 0.1 weight portion corrosion inhibiter 6-, 2.5 weight portion auxiliary agent dicyclohexyl-18-crown-6s and 30 weight portion organic solvent N-dodecylpyrrolidones.
(2) organic solvent of step (1) is joined in stirred tank, then add in turn organic ammonium salt, remover, be stirred to homogeneous transparent, stirring rate is 80rpm/min;
(3) in the homogeneous transparent potpourri in step (2), add in turn wetting agent, corrosion inhibiter and auxiliary agent, be stirred to homogeneous transparent, stirring rate is 80rpm/min.Obtain described photoresist lift off liquid, by its called after BLY9.
Embodiment 10
(1) take respectively 7 weight portion remover C
8f
17cH
2cH
2o(C
2h
4o)
10h (C wherein
8f
17for perfluor n-octyl), 3 weight portion wetting agent C
18h
37o(C
2h
4o)
4(C
3h
6o)
12h (C wherein
18h
37for n-octadecane base), 10 weight portion organic amine isopropanolamines, the chloro-1-hydroxy benzo triazole of 3.5 weight portion corrosion inhibiter 6-, 1.5 weight portion auxiliary agent dicyclohexyl-18-crown-6s and 15 weight portion organic solvents 2,4-dibutyl sulfolane.
(2) organic solvent of step (1) is joined in stirred tank, then add in turn organic amine, remover, be stirred to homogeneous transparent, stirring rate is 90rpm/min;
(3) in the homogeneous transparent potpourri in step (2), add in turn wetting agent, corrosion inhibiter and auxiliary agent, be stirred to homogeneous transparent, stirring rate is 90rpm/min.Obtain described photoresist lift off liquid, by its called after BLY10.
Comparative example 1-10
Except respectively the chloro-1-hydroxy benzo triazole of 6-wherein being replaced with other following triazole, with the same way with embodiment 1-10, implemented comparative example 1-10, made respectively 10 photoresist lift off liquid, called after D1-D10, its corresponding relation is as follows:
Comparative example 11-20
Except respectively dicyclohexyl-18-crown-6 wherein being replaced with following crown ether, with the same way with embodiment 1-10, implemented comparative example 11-20, made respectively 10 photoresist lift off liquid, called after D11-D20, its corresponding relation is as follows:
Comparative example 21-30
Except not adding auxiliary agent, [ do not comprise auxiliary agent], with the same way with embodiment 1-10, implemented comparative example 21-30 respectively, made respectively 10 photoresist lift off liquid, in turn called after D21-D30.
Chip photoresist stripping process and method of testing
Stripping technology:
LED chip after gluing is carried out to lithography stripping processing in accordance with the following steps:
(1) chip is soaked at 80 ℃ in photoresist lift off liquid to ultrasound wave 20 minutes;
(2) by pure water rinsing 8 minutes for the chip after removing photoresist, rinsing 2 times, then nitrogen dries up.
Method of testing:
40 times of LED chip amplifications after above-mentioned peeling off are carried out to microscope scanning, observe and whether remove photoresist completely and whether metal wiring and surface generation wherein corroded.
Test result:
According to above-mentioned stripping technology, use respectively above-described embodiment and comparative example gained sample BLY1-BLY10, comparative sample D1-D30 to carry out photoresist lift off to LED chip, and according to above-mentioned method of testing, observe it and whether remove photoresist completely.
The stripping performance of weighing each stripper to peel off rate, it is defined as follows: peel off rate (%)=[(peeling off the area of the front photoresist total area-residual photoresist)/(peeling off the front photoresist total area)] * 100%.
Accompanying drawing 1 is the microphotograph using after BLY1 peels off, and as can be seen here, completely, thoroughly, the rate of peeling off is 100% in photoresist lift off; To ITO and SiO
2surface is corrosion-free.
The data of peeling off of the stripper of all embodiment and comparative example see the following form 1.
The performance of the different strippers of table 1.
Note: wherein, the extent of corrosion of " corrosion " will be seriously in " slightly corrosion ".
By upper table data, proved while there is the chloro-1-hydroxy benzo triazole of 6-and dicyclohexyl-18-crown-6 in stripper simultaneously, can bring into play beyond thought synergy between the two, thereby obtain the excellent effect of removing photoresist (100%) and anticorrosion ability (corrosion-free).
In addition, when the chloro-1-hydroxy benzo triazole of 6-is replaced with to other benzotriazole, obvious corrosion has occurred, this has proved that the chloro-1-hydroxy benzo triazole of 6-has best anticorrosion ability.
And while containing other auxiliary agent, significantly reduced its performance of removing photoresist; When not containing auxiliary agent, the performance of removing photoresist further reduces, and this has proved that dicyclohexyl-18-crown-6 has the best synergisticing performance that removes photoresist.
In sum, the invention provides the photoresist lift off liquid of a class novelty, by specific components as the selection of remover, auxiliary agent, corrosion inhibiter and/or solvent, and brought into play beyond thought peeling off, act synergistically with anticorrosion, obtained excellent peeling off and anticorrosion ability, can be used for the photoresist lift off of various chips, thereby provide the foundation for the preparation of final precision electronic element.
The purposes that should be appreciated that these embodiment only limits the scope of the invention for the present invention being described but not being intended to.In addition; also should understand; after having read technology contents of the present invention, those skilled in the art can make various changes, modification and/or modification to the present invention, within these all equivalent form of values fall within the protection domain that the application's appended claims limits equally.
Claims (9)
1. for a photoresist lift off liquid for chip, described photoresist lift off liquid comprises the various components of following weight parts:
2. photoresist lift off liquid as claimed in claim 1, is characterized in that:
Described remover is perfluoroalkyl ethoxy polyoxyethylene ether, and its structural formula is C
mf
2m+1cH
2cH
2o(C
2h
4o)
nh, m and n are all selected from the integer of 6-12.
3. the photoresist lift off liquid as described in claim 1-2 any one, is characterized in that:
Described wetting agent is aliphatic alcohol polyethenoxy polyethenoxy ether, and structural formula is R
1o(C
2h
4o)
p(C
3h
6o)
qh, wherein R
1for C
10-C
18straight or branched alkyl, p is the integer between 4-12, q is the integer between 4-10.
4. the photoresist lift off liquid as described in claim 1-3 any one, is characterized in that:
Described organic amine or organic ammonium salt are selected from any or any multiple potpourri in diethylamine, triethylamine, ethylenediamine, monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, diisopropanolamine, triisopropanolamine, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, TBAH.
5. the photoresist lift off liquid as described in claim 1-4 any one, is characterized in that:
Described corrosion inhibiter is benzotriazole, 1-C
1-C
6alkylbenzotriazole, 1-hydroxy benzo triazole, 1-methylol benzotriazole, 3-sulfydryl-1, any or any multiple potpourri in 2,4-triazole, 5-carboxy benzotriazole, the chloro-1-hydroxy benzo triazole of 6-.
6. the photoresist lift off liquid as described in claim 1-5 any one, is characterized in that:
Described auxiliary agent is crown ether compound, and it is selected from any or any multiple potpourri in open chain crown ether, benzo-crown ether, hydroxy benzo crown ether, naphthenic base crown ether.
7. the photoresist lift off liquid as described in claim 1-6 any one, is characterized in that:
Described organic solvent is alcohol ether compound, sulfone compound or pyrrolidones.
8. the preparation method of photoresist lift off liquid as described in claim 1-7 any one, described method comprises the steps:
(1) take respectively the various components of above-mentioned weight portion separately;
(2) organic solvent is joined in stirred tank, then add in turn organic amine or organic ammonium salt, remover, be stirred to homogeneous transparent;
(3) in the homogeneous transparent potpourri in step (2), add in turn wetting agent, corrosion inhibiter and auxiliary agent, be stirred to homogeneous transparent, obtain described photoresist lift off liquid.
9. right to use requires the degumming process of chip photoresist lift off liquid described in 1-8 any one, and described degumming process comprises the steps:
(1) chip is soaked at 60-90 ℃ in photoresist lift off liquid to ultrasound wave 10-30 minute;
(2) by pure water rinsing 3-10 minute for the chip after removing photoresist, rinsing 1-3 time, then nitrogen dries up.
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| CN201310719197.XA CN103676505B (en) | 2013-12-23 | 2013-12-23 | A kind of photoresist lift off liquid for chip, preparation method and degumming process |
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| CN111142341A (en) * | 2019-12-31 | 2020-05-12 | 江苏中德电子材料科技有限公司 | Environment-friendly high-stability aqueous photoresist stripping liquid for panels and preparation method thereof |
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