CN103676502B - Thick film negative photoresist release agent constituent - Google Patents

Thick film negative photoresist release agent constituent Download PDF

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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
present
compound
thick film
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CN103676502A (en
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姜荣汉
朴永真
李相大
柳炫圭
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ENF Technology CO Ltd
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ENF Technology CO Ltd
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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

Thick film negative photoresist release agent constituent
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.
CN201310382409.XA 2012-08-31 2013-08-28 Thick film negative photoresist release agent constituent Active CN103676502B (en)

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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