CN1280676C - Positive photoresistive agent composition and method for forming photoresistive pattern - Google Patents
Positive photoresistive agent composition and method for forming photoresistive pattern Download PDFInfo
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- CN1280676C CN1280676C CN 03132821 CN03132821A CN1280676C CN 1280676 C CN1280676 C CN 1280676C CN 03132821 CN03132821 CN 03132821 CN 03132821 A CN03132821 A CN 03132821A CN 1280676 C CN1280676 C CN 1280676C
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Abstract
The present invention provides a positive photoresist compound with uniform reactivity, which can respectively carry out thermal cross-linking reaction and optical decomposition reaction in different production procedures after being coated, and then pattern lines are formed. The novel photoresist compound is prepared from a multicomponent resin compound, a photo-acid generator and reactive monomers. When the photoresist compound is in soft-baking, the reactive monomers and the multicomponent resin compound can firstly form a polymer with a net-shaped structure; subsequently, the photoresist compound is irradiated by an exposure optical source, and the multicomponent resin can respectively carry out chemical amplification resin protection group removing reaction and network structure resin optical decomposition reaction with generated acid. Therefore, the positive photoresist of the present invention has the advantages of good alkaline comparison capacity and uniform reactivity, and the positive photoresist can obtain a good photoresist form ratio and resolution ratio in microimage producing processes.
Description
Technical field
The present invention relates to a kind of multi-component eurymeric Photoresisting agent composition, particularly a kind ofly apply in the yellow photolithographic techniques of thick film eurymeric Photoresisting agent composition with homogeneous reaction.
Background technology
Under the development trend that semiconductor element dwindles towards size, press for and in micro-photographing process, form more accurate patterns, so that semiconductor element can reach more the integrated of height in design.Under this technological trend and the market demand, the substrate technology will develop towards high density distribution, thin typeization, graph thinning and high vertical wide direction such as compare, to satisfy the diversified support plate technical need of following electronics and photoelectricity.
In the micro-photographing process of present high density distribution carrier substrate, generally be to utilize the minus photoresistance to carry out the thick film gold-tinted micro-photographing process of carrier substrate, but because under the requirement of photoresistance thickness and resolution, on processing procedure, use the eurymeric photoresistance to help the raising of photoresistance thick film and resolution, and when utilizing the eurymeric photoresistance to make perforation pattern, has lower defect rate than minus development photoresistance.
The eurymeric photoresist mainly is used in the IC industry at present as the film photoresistance, can be divided into two kinds of the chemical amplification type systems of the DNQ/Novolac system of I-Line and deep UV (ultraviolet light) according to exposure light source.The coating thickness of DNQ/Novolac system photoresist generally is about 0.5～5 μ m, and resolution is between 0.35～5 μ m.And about 0.2～0.5 μ m of coating thickness of the chemical amplification type special ratios protecting group resin of deep UV (ultraviolet light), resolution is between 0.3～0.09 μ m.At present in the micro-photographing process of high density distribution carrier substrate, general required coating thickness is about 10～50 μ m, require optimum resolution between 10～50 μ m, therefore, under the trend of support plate high density distribution and multiple stratification, the restriction of using thin film manufacture process will be used with the eurymeric photoresistance, for example photoresistance can become big (usually greater than 5 μ m because of the photoresistance film thickness of required coating, the scope of application of 0.2 more original μ m to 1 μ m exceeds many) and cause the optics penetration to descend, and then make the required exposure energy too high, cause photoresistance surface and bottom section to be subjected to difference on the light path degree, and Chang Yinwei exposure light source and photoresist react uneven relation, cause photoresistance surface and sidewall out-of-flatness, and can't obtain high-resolution thick film photoresistance.
Resin combination with chemical amplification type characteristic; because of it has the unsettled functional group of acid; under the acid catalyzed reaction after the exposure, can carry out protective reaction; removal is to the unstable functional group of acid, thereby can change the hydrophilic and hydrophobic matter of photoresistance ingredient, and since to the unsettled functional group of acid behind protective reaction; can further discharge acid; can reduce the required exposure energy of photoresist, therefore, often be used as one of component of eurymeric photoresist.Yet, the antilysis ability and the polymerization lack of uniformity of this kind chemical amplification type photoresistance composition, the photoresistance rete that causes unexposed and exposure easily makes the contour of track distortion and causes edge roughness poor.
Influenced by the requirement of circuit precision, the high density interconnect multilager base plate will become main flow, the resolution of photoresist more necessarily requires to be promoted to 10～25 μ m and reaches, and will adopt the process technique of higher photoresistance film thickness, therefore developing a kind of have high homogeneous reaction and dynamical eurymeric photoresistance, is the technical emphasis of needing research badly of present micro image etching procedure.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of eurymeric Photoresisting agent composition, carry out heat cross-linking reaction and photolysis reactions in different fabrication steps respectively after the coating and form the figure circuit with homogeneous reaction.This eurymeric Photoresisting agent composition is not soluble in the aqueous alkali; under the irradiation of exposure light source; the acid that light acid in the composition is produced can make Photoresisting agent composition carry out multiple reaction; comprise to the reticulate texture resin remove aldolisation and to the protective reaction of chemical amplification type resin; with the hydrophilic and hydrophobic matter that changes the photoresistance ingredient simultaneously and the molecular weight of photoresistance ingredient; reach the purpose that makes eurymeric Photoresisting agent composition homogeneous reaction; thus; when the eurymeric Photoresisting agent composition with homogeneous reaction of the present invention applies to the graphical processing procedure of thick film photoresistance; need not improve exposure energy just can make photoresistance react completely; so can not take place because of exposure light source scattering and the uneven photoresistance defective that is caused of photoresist reaction; and because eurymeric Photoresisting agent composition of the present invention has high homogeneous reaction and preferable antilysis ability, therefore being used for photolithography techniques can obtain better resolution.
For reaching above-mentioned purpose, Photoresisting agent composition of the present invention is the eurymeric Photoresisting agent composition of being made up of various kinds of resin, and this Photoresisting agent composition comprises being dissolved in the organic solvent and forms the homogeneous solution form:
(a) phenolic resin compound, 100 weight portions;
(b) has resin compound, 1 to 100 weight portion to the unstable functional group of acid;
(c) reactive monomer, it is a main structure with vinyl ether or epoxy radicals (cycloaliphatic epoxides), 1 to 100 weight portion; And
(d) light acid producing agent, 1 to 35 weight portion.
Eurymeric Photoresisting agent composition with homogeneous reaction of the present invention mainly combines tradition and is used for the molecular weight change type system of eurymeric photoresist and the advantage of chemical amplification type system.In eurymeric photoresist of the present invention, phenolic resin compound constitutes a polycomponent resin with the resin compound that has the unstable functional group of acid, not only can utilize the resin compound that has the unstable functional group of acid to reduce the required exposure energy of photoresist, and this polycomponent resin also can reduce the sensitivity of exposure back acid catalyzed reaction, and this resin compound that has the unstable functional group of acid can carry out protective reaction under acid catalysis, removal is to the unsettled functional group of acid, thereby change the hydrophilic and hydrophobic matter of photoresistance ingredient, obtain the characteristic of eurymeric photoresistance; This polycomponent resin more can further reduce the alkali lye dissolving power of Photoresisting agent composition integral body; And adding with the vinyl ether in photoresist is the reactive monomer of main structure, in the soft roasting process before exposure, can effectively phenolic resin compound and the resin compound that has the unstable functional group of acid be bound by in the highly cross-linked reticulate texture, can make unexposed preceding photoresistance rete have preferable polymerization homogeneity thus, increased photoresistance contrast ability, required further to make the photoresistance profile meet processing procedure; And the formed highly cross-linked reticulate texture of this reactive monomer and resin combination is under the acid catalysis after the exposure, its bond also can be decomposed, cause photoresistance composition molecular weight to change, make the dissolving power that is exposed photoresistance rise, further increased the high-aspect-ratio and the resolving power of photoresist.
For further specifying content of the present invention, below will be narrated one by one at each component in the eurymeric Photoresisting agent composition under this multiple reaction pattern.
Eurymeric Photoresisting agent composition with homogeneous reaction of the present invention, comprise at least a phenolics as composition (a), its can be have the neighbour,, to the phenolics or the polymkeric substance of cresol-novolak resin structure derivant, also can be compound with the described structure of formula (I)
Formula (I),
R wherein
1Can be identical also can be different, and be selected from one of following groups :-CH
2-,
Alkyl, naphthenic base, alkoxy, thiazolinyl, alkynyl or aryl, and wherein alkyl, alkoxy, alkenyl or alkynyl contain 2-12 carbon atom and are straight chain type or branched chain type, naphthenic base contains 3-12 carbon atom, and the n value is between 1～100.
According to the eurymeric Photoresisting agent composition with homogeneous reaction of the present invention, the phenolic resin compound that wherein has the described structure of formula (I), the hydrogen on its each carbon atom, optionally can by halogen, cyano group, methyl ,-R " ,-CO
2H ,-CO
2R " ,-COR " ,-R " CN ,-CONH
2,-CONHR " ,-CONR "
2,-OCOR " or OR " replaces, R wherein " be selected from the following groups one or more: the replacement or unsubstituted alkyl, alkynyloxy group, alkoxy, thiazolinyl, alkynyl, alkene oxygen base, heterocyclic radical, aryl, aralkyl, heteroaryl or the aliphatic many cyclic groups that contain the 1-12 carbon atom; and this has in the phenolic resin compound of the described structure of formula (I), and the n value is preferably between 2～30.
Be applicable to that composition of the present invention (b) has the resin compound to the unstable functional group of acid, be selected from the acryl resin (being called acrylic resin again) that has the unstable functional group of acid, have polycarboxylated styrene (PHS) resin or its potpourri the unstable functional group of acid.Wherein this refers to go under the positively charged state that the protecting group effect produced in acid catalysis unstable to the unsettled functional group of acid, and easily discharges H voluntarily
+Ion is so that self become the group of a stable molecule, and this can be selected from the following groups one or more to the unsettled functional group of acid: the tert-butyl group, oxinane-2-base, 2-methyl oxinane-2-base tetrahydrofuran-2-base, 2-methyltetrahydrofuran-2-base, the 1-methoxy-propyl, 1-methoxyl-1-Methylethyl, the 1-ethoxycarbonyl propyl, 1-ethoxy-1-Methylethyl, the 1-methoxy ethyl, the 1-ethoxyethyl group, the 1-butoxyethyl group, 1-tert-butoxy ethyl, 1-isobutoxy ethyl, tert-butoxycarbonyl, tert-butoxy carbonyl methyl, TMS, 3-tert-butyl group dimethylsilyl and 2-acetyl
Base-1-base (2-acetylmenth-1-yl).
Preferably, the described acryl resin (being called acrylic resin again) that has the unstable functional group of acid is selected from one or more in the following resin: tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, the dimethyltrimethylene glycol diacrylate, the dimethyltrimethylene glycol dimethylacrylate, polyethyleneglycol diacrylate, polyethylene glycol dimethacrylate, the bisphenol a diacrylate of ethoxylation, the bisphenol a dimethacrylate of ethoxylation, trimethylol-propane trimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, the trimethylolpropane triacrylate of ethoxylation, glyceryl propoxyl group triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol five acrylate, the acrylic acid epoxy propyl ester, the multipolymer of glytidyl methacrylate and composition thereof.
Be applicable to the reactive monomer of component of the present invention (c), be the reactive monomer of main structure preferably with vinyl ether or epoxy radicals, the vinyl ether reactive monomer can be selected from one or more in the following monomer: 1, the 4-cyclohexanedimethanodiglycidyl diglycidyl ether, 1,2-propylene glycol divinyl ether, 1, the ammediol divinyl ether, 1,3-butylene glycol divinyl ether, 1,4-butylene glycol divinyl ether, the tetramethylene glycol divinyl ether, the neopentyl glycol divinyl ether, the hexane diol divinyl ether, the ethylene glycol bisthioglycolate vinyl ether, the diglycol divinyl ether, triethylene glycol divinyl ether, 1,4 cyclohexane dimethanol divinyl ether or lactone; And cycloaliphatic epoxides (cycloaliphatic epoxide) can be N, N-diglycidyl-4-dehydration glyceryl aniline (N, N-diglycidyl-4-glycidyloxyaniline), 3,4-7-oxa-bicyclo[4.1.0 ylmethyl carboxylate, 3,4-epoxycyclohexane carboxylate, 1,2-cyclohexane diglycidyl dicarboxylic ester (1,2-cyclohexane diglycidyldicarboxylate).
Be applicable to the light acid producing agent of component of the present invention (d), be any suitable light acid producing agent, preferable light acid producing agent is selected from one or more in the following salt: salt, triaryl sulfonium salts, alkaryl sulfosalt, diaryl group iodized salt, diaryl villaumite, diaryl bromine salt, sulfonate, diazo salt and diazo naphthoquinone sulfonate thereof.
The object lesson of above-mentioned triaryl sulfonium salts comprises the potpourri of triaryl hexafluorophosphoric acid sulfosalt, triphenyl trifluoro-methanyl sulfonate (triphenyl triflate), antimony triphenyl hydrochlorate, methoxyl triphenyl trifluoro-methanyl sulfonate (methoxytriphenyl triflate), methoxyl antimony triphenyl hydrochlorate, trimethyl triphenyl trifluoro-methanyl sulfonate (trimethyl triphenyltriflate) or above-claimed cpd.
According to the eurymeric Photoresisting agent composition with homogeneous reaction of the present invention, for wherein (a) phenolics and (b) has resin to the unstable functional group of acid, its suitable molecular weight is between 2000 to 150000, and phenolics and have resin to the unstable functional group of acid, its preferable molecular weight is between 3000 to 100000.
The present invention has the eurymeric Photoresisting agent composition of homogeneous reaction, carries out a multiple reaction pattern after the exposure light source irradiation, and this multiple reaction pattern comprises the synchronous reaction that photoresistance ingredient hydrophilic and hydrophobic matter changes and photoresistance ingredient molecular weight changes.
According to the eurymeric Photoresisting agent composition with homogeneous reaction of the present invention, can comprise the multiple resin that different molecular weight distributes that has more simultaneously, with further increase photoresistance homogeneity, and increase the preceding antilysis ability of exposure.
According to the eurymeric Photoresisting agent composition with homogeneous reaction of the present invention, it more can comprise:
(e) photoresist additive, 0.1 to 100 weight portion.
This photoresist additive can be selected from one or more in the following adjuvant: dissolution inhibitor, antioxidant, thermal stabilizer, light stabilizer, lubricant, colorant, defoamer, levelling agent, filling agent and thickening agent.
In the eurymeric Photoresisting agent composition of multiple reaction pattern of the present invention, described have the unstable functional group's of acid the resin compound and the weight ratio of described phenolic resin compound are preferably 1: 6 to 1: 1.
The invention still further relates to a kind of this eurymeric Photoresisting agent composition with homogeneous reaction that makes and form the photoresistance method of patterning, this method may further comprise the steps: apply this and have the eurymeric Photoresisting agent composition of homogeneous reaction on treated base material; Formed thick film photoresistance optionally is exposed under the exposure light source; And with the thick film photoresistance of alkaline aqueous solution development after exposure.Described eurymeric Photoresisting agent composition with homogeneous reaction as defined above.
Description of drawings
Fig. 1 a to Fig. 1 b is that the Photoresisting agent composition of comparing embodiment 1 is coated the figure of the SEM behind exposure imaging on the copper clad laminate, and photoresist resolution is respectively 10.5 μ m and 15 μ m in regular turn, and resulting live width/gap is respectively 1/1.8 and 1/1.6;
Fig. 2 a to Fig. 2 b is that the Photoresisting agent composition of comparing embodiment 2 is coated the figure of the SEM behind exposure imaging on the copper clad laminate, and photoresist resolution is respectively 9.8 μ m and 13.3 μ m in regular turn, and resulting live width/gap is respectively 1/2.1 and 1/2.
Fig. 3 a to Fig. 3 c coats the figure of the SEM behind exposure imaging on the copper clad laminate for the Photoresisting agent composition of embodiment 1, and photoresist resolution is in regular turn respectively at 9.5 μ m, 15 μ m and 20 μ m, and resulting live width/gap is respectively 1/1.1,1/1 and 1/1.
Fig. 4 a figure to Fig. 4 b coats the figure of the SEM behind exposure imaging on the copper clad laminate for the Photoresisting agent composition of embodiment 2, and photoresist resolution is in regular turn respectively at 14.3 μ m and 17 μ m, and resulting live width/gap is respectively 1/1.1 and 1/1.35.
Embodiment
Below and in conjunction with the accompanying drawings, illustrating further method of the present invention, feature and advantage, but be not to be used for limiting the scope of the invention by several embodiment and comparing embodiment.
Comparing embodiment 1
The cresol-novolak resin (available from Bordeone company, numbering DPD-193A) of getting molecular weight (Mw) 3300 is dissolved in the gamma-butyrolacton, and resin concentration is 66.6wt%.Get above-mentioned resin solution 25 grams, add polycarboxylated styrene (PHS) copolymer resin 2.72 grams that the hydrogen on the part hydroxyl is replaced by the tert-butyl group, utilize supersonic oscillations that it is dissolved fully again, at last, the 50% carbonate propanediol ester solution (Triaryl Sulfonium Hexafluorophosphate 50% inPropylene Carbonate) that adds light inlet acid triaryl hexafluorophosphoric acid sulfosalt (available from U.S. Sartomer chemical company (SARTOMERChemical), is numbered SarCat
K185) 0.27 gram is stirred to and mixes, and so far finishes preparation of compositions.The composition of this Photoresisting agent composition and weight percent are such as table 1:
Table 1
| The photoresist composition | Percentage by weight (wt%) |
| D_PD-193A PHS SarCat The K185 gamma-butyrolacton | 35.73 9.72 0.97 53.58 |
Photoresisting agent composition is coated on the 1/2oz copper clad laminate, and thickness is 10 μ m; Above-mentioned photoresistance rete is carried out soft roasting (soft baking), and soft roasting condition is for to carry out under 80 ℃ 10 minutes; Exposure light source is directional light UV (wavelength 365nm ± 10%), exposure energy 200mJ/cm
2, photoresist is exposed; Exposing to the sun afterwards, (post-exposure bake, PEB), the back baking condition that exposes to the sun is for to carry out under 120 ℃ 10 minutes in the back baking.
After the photoresistance film exposes to the sun the back baking, utilize 2.38% tetramethyl ammonium hydroxide aqueous solution (SD-1, electron level) that this photoresistance film is developed in the supersonic oscillations groove, development time is controlled to be 300 seconds.Please refer to Fig. 1 a to Fig. 1 b, it is for showing photoresistance figure resulting scanning type electron microscope (SEM) figure behind exposure imaging, scheming as can be known by SEM, the photoresistance width is respectively 10.5 μ m and 15 μ m, and resulting live width/gap is respectively 1/1.8 and 1/1.6, and the photoresistance of former figure live width/gap ratio is set at 1/1.
Comparing embodiment 2
Get 8 gram molecular weights (Mw) and be 330 cresol-novolak resin (available from Bordeone company, numbering D_PD-193A), and 2 gram molecular weights (Mw) are that 6000～8500 cresol-novolak resin is (available from Bordeone company, numbering D_PD-140A), they are dissolved in the 15 gram gamma-butyrolactons, and resin concentration is 66.6wt%.Then, add polycarboxylated styrene (PHS) random copolymer resin 2.72 grams that the hydrogen on the part hydroxyl is replaced by the tert-butyl group, utilize supersonic oscillations that it is dissolved fully again, at last, the 50% propylene glycol carbonate solution (TriarylSulfonium Hexafluorophosphate 50% in PropyleneCarbonate) that adds light inlet acid triaryl hexafluorophosphoric acid sulfosalt (available from U.S. Sartomer chemical company (SARTOMERChemical), is numbered SarCat
K185) 0.27 gram is stirred to and mixes, and so far finishes preparation of compositions.The composition of this Photoresisting agent composition and weight percent are such as table 2:
Table 2
| The photoresist composition | Percentage by weight (wt%) |
| D_PD-193A D_PD-193A PHS SarCat The K185 gamma-butyrolacton | 28.58 7.15 9.72 0.97 53.58 |
Photoresisting agent composition is coated on the 1/2oz copper clad laminate, and thickness is 10 μ m; Above-mentioned photoresistance rete is carried out soft baking, and soft roasting condition is for to carry out under 80 ℃ 10 minutes; Exposure light source is directional light UV (wavelength 365nm ± 10%), exposure energy 300mJ/cm
2, photoresist is exposed; Baking (PEB) after exposing to the sun then, the condition of the back baking of exposing to the sun is for to carry out under 120 ℃ 10 minutes.
Expose to the sun after the baking of back, utilize 2.38% tetramethyl ammonium hydroxide aqueous solution (SD-1, electron level) that this photoresistance film is developed in the supersonic oscillations groove, development time is controlled to be 160 seconds.Please refer to Fig. 2 a to Fig. 2 b, it is for showing photoresistance figure resulting scanning type electron microscope (SEM) figure behind exposure imaging, scheming as can be known by SEM, the photoresistance width is respectively 9.8 μ m and 13.3 μ m, and resulting live width/gap is respectively 1/2.1 and 1/2, and the photoresistance of former figure live width/gap is set at 1/1 than system.
Eurymeric photoresist described in the above-mentioned comparing embodiment is that character is close, and has the photoresistance composition of chemical amplification type characteristic, and it can reduce the required exposure energy of photoresist when micro-photographing process.Yet, the antilysis ability and the polymerization lack of uniformity of this kind chemical amplification type photoresistance composition, cause unexposed and the exposure the photoresistance rete between to poor, therefore the tetramethyl ammonium hydroxide aqueous solution has also been dissolved the two side portions thickness of the unexposed photoresistance rete of part when removal is exposed photoresist, make the obviously more previous default photoresistance live width of photoresistance live width behind the exposure imaging reduce many, to cause the distortion of pattern definition in the processing procedure thus, and easily cause the phenomenon of contour of track distortion and edge roughness.
Embodiment 1
Get molecular weight (Mw) and be 3300 cresol-novolak resin (available from Bordeone company, numbering D_PD-193A) and be dissolved in the gamma-butyrolacton, resin solution concentration is 66.6wt%.Get above-mentioned resin solution 25 grams, in polycarboxylated styrene (PHS) random copolymer resin 2.72 grams that the hydrogen on the adding part hydroxyl is replaced by the tert-butyl group, utilize supersonic oscillations that it is dissolved fully again.Then, add triethylene glycol tetrem alkene ether 0.3 gram, at last, the 50% propylene glycol carbonate solution (Triaryl Sulfonium Hexafluorophosphate 50% inPropylene Carbonate) that adds light inlet acid triaryl hexafluorophosphoric acid sulfosalt again (available from U.S. Sartomer chemical company (SARTOMERChemical), is numbered SarCat
K185) 0.27 gram is stirred to and mixes, and so far finishes preparation of compositions.The composition of this Photoresisting agent composition and weight percent are such as table 3:
Table 3
| The photoresist composition | Percentage by weight (wt%) |
| D_PD-193A PHS SarCat K185 triethylene glycol tetrem alkene ether gamma-butyrolacton | 35.35 9.61 0.95 1.06 53.03 |
Photoresisting agent composition is coated on the 1/2oz copper clad laminate, and thickness is 10 μ m; Above-mentioned photoresistance rete is carried out soft baking, and soft roasting condition is for to carry out under 130 ℃ 15 minutes; Exposure light source is directional light UV (wavelength 365nm ± 10%), exposure energy 200mJ/cm
2, photoresist layer is exposed; Baking after exposing to the sun then, the back baking condition that exposes to the sun is for to carry out under 130 ℃ 15 minutes.
Expose to the sun after the baking of back, utilize 2.38% tetramethyl ammonium hydroxide aqueous solution (SD-1, electron level) that this photoresistance film is developed in the supersonic oscillations groove, development time is controlled to be 180 seconds.Please refer to Fig. 3 a to Fig. 3 c, it is for showing photoresistance figure resulting scanning type electron microscope (SEM) figure behind exposure imaging, scheming as can be known by SEM, the photoresistance width is respectively 9.5 μ m, 15 μ m and 20 μ m, and resulting live width/gap is respectively 1/1.1,1/1 and 1/1, and the photoresistance of former figure live width/gap ratio is set at 1/1.
Embodiment 2
Get molecular weight (Mw) and be 3300 cresol-novolak resin (available from Bordeone company, numbering D_PD-193A) and be dissolved in the cyclopentanone (cyclopentanone), resin concentration is 66.6wt%.Get above-mentioned resin solution 25 grams, add polycarboxylated styrene (PHS) random copolymer resin 2.72 grams that the hydrogen on the part hydroxyl is replaced by the tert-butyl group, utilize supersonic oscillations that it is dissolved fully again.Then, add triethylene glycol tetrem alkene ether 0.4 gram, the 50% propylene glycol carbonate solution (Triaryl Sulfonium Hexafluorophosphate 50% inPropylene Carbonate) that adds light inlet acid triaryl hexafluorophosphoric acid sulfosalt again (available from U.S. Sartomer chemical company (SARTOMERChemical), is numbered SarCat
K185) 0.27 gram is stirred to and mixes, and so far finishes preparation of compositions.The composition of its Photoresisting agent composition and weight percent are such as table 4:
Table 4
| The photoresist composition | Percentage by weight (wt%) |
| D_PD-193A PHS SarCat K185 triethylene glycol tetrem alkene ether ring pentanone | 35.23 9.58 0.95 1.41 52.83 |
Photoresisting agent composition is coated on the 1/2oz copper clad laminate, and thickness is 10 μ m; Above-mentioned photoresistance rete is carried out soft baking, and soft roasting condition is for to carry out under 130 ℃ 15 minutes; Exposure light source is directional light UV (wavelength 365nm ± 10%), exposure energy 200mJ/cm
2, photoresist layer is exposed; Baking after exposing to the sun then, the back baking condition that exposes to the sun is for to carry out under 130 ℃ 15 minutes.
Expose to the sun after the baking of back, utilize 2.38% tetramethyl ammonium hydroxide aqueous solution (SD-1, electron level) that this photoresistance film is developed in the supersonic oscillations groove, development time is controlled to be 260 seconds.Please refer to Fig. 4 a to Fig. 4 b, it is for showing photoresistance figure resulting scanning type electron microscope (SEM) figure behind exposure imaging, scheming as can be known by SEM, the photoresistance width is respectively 14.3 μ m and 17 μ m, and resulting live width/gap is respectively 1/1.1 and 1/1.35, and the photoresistance of former figure live width/gap ratio is set at 1/1.
In sum, the present invention relates to a kind of eurymeric Photoresisting agent composition with multicomponent resin height cross-linked structure, it has splendid antilysis ability for aqueous alkali. This photoresist is under the exposure light source irradiation; the acid that produces can make the chemical amplification type resin in the multicomponent resin carry out protective reaction and make the aggretion type resin remove aldolisation; thereby the hydrophilic and hydrophobic matter of photoresistance ingredient and the molecular weight of photoresistance ingredient have been changed simultaneously; make unexposed photoresistance rete with exposure have better contrast, when carrying out the photoresist processing procedure, can obtain higher resolution ratio. Relatively the time, do not have the similar practice at the present invention and known technology in the known technology, its reason is that multicomponent resin that this photoresist need have proper proportion simultaneously carries out the aldolisation that goes of the protective reaction of chemical amplification type resin and aggretion type resin; In addition, for the crosslinked network structure of height of formation to promote the polymerization uniformity of photoresist before unexposed, also must in the photoresistance composition, add the network structure reactive monomer of proper proportion. Therefore, the ratio of each component of allotment under a specific proportion makes its purpose that reaches the light reaction efficient of control photoresist and increase the reaction uniformity, especially feature place of eurymeric Photoresisting agent composition of the present invention.
Claims (22)
1. eurymeric Photoresisting agent composition with homogeneous reaction comprises being dissolved in forming the homogeneous solution form in the organic solvent:
(a) phenolic resin compound, 100 weight portions;
(b) has resin compound, 1 to 100 weight portion to the unstable functional group of acid;
(c) reactive monomer, it is a main structure with vinyl ether reactive monomer or cycloaliphatic epoxides, 1 to 100 weight portion; And
(d) light acid producing agent, 1 to 35 weight portion.
2. have the eurymeric Photoresisting agent composition of homogeneous reaction according to claim 1, it is characterized in that, the compound of described phenolic resin compound for having the described structure of formula (I)
Formula (I),
R wherein
1Can be identical also can be different, and be selected from one of following groups:
-CH
2-,
Alkyl, naphthenic base, alkoxy, thiazolinyl, alkynyl and aryl, wherein alkyl, alkoxy, thiazolinyl, alkynyl contain 2-12 carbon atom and are straight chain type or branched chain type, and naphthenic base contains 3-12 carbon atom, and the n value is 1～100.
3. the eurymeric Photoresisting agent composition as having homogeneous reaction as described in the claim 2 is characterized in that, the hydrogen in the described phenolic resin compound with formula (I) structure on each carbon atom, optional by halogen, cyano group ,-R " ,-CO
2H ,-CO
2R " ,-COR " ,-R " CN ,-CONH
2,-CONHR " ,-CONR "
2,-OCOR " or OR " replaces, and wherein R " is selected from the replacement or unsubstituted alkyl, alkynyloxy group, alkoxy, thiazolinyl, alkynyl, alkene oxygen base, heterocyclic radical, aryl, aralkyl, heteroaryl, aliphatic many cyclic groups or its combination that contain 1-12 carbon atom.
4. have homogeneous reaction eurymeric Photoresisting agent composition as described in claim 2, it is characterized in that, in the described phenolic resin compound with formula (worker) structure, the n value is 2～30.
5. the eurymeric Photoresisting agent composition that has homogeneous reaction according to claim 1, it is characterized in that, described the unsettled functional group of acid is selected from the following groups one or more: the tert-butyl group, oxinane-2-base, 2-methyl oxinane-2-base, tetrahydrofuran-2-base, 2-methyltetrahydrofuran-2-base, the 1-methoxy-propyl, 1-methoxyl-1-Methylethyl, the 1-ethoxycarbonyl propyl, 1-ethoxy-1-Methylethyl, the 1-methoxy ethyl, the 1-ethoxyethyl group, the 1-butoxyethyl group, 1-tert-butoxy ethyl, 1-isobutoxy ethyl, tert-butoxycarbonyl, tert-butoxy carbonyl methyl, TMS, 3-tert-butyl group dimethylsilyl and 2-acetyl base-1-base.
6. have the eurymeric Photoresisting agent composition of homogeneous reaction according to claim 1, it is characterized in that, the described resin compound that has the unstable functional group of acid is the acrylic resin that has the unstable functional group of acid.
7. have the eurymeric Photoresisting agent composition of homogeneous reaction according to claim 1, it is characterized in that, the described resin compound that has the unstable functional group of acid is the polyhydroxystyrene resin that has the unstable functional group of acid.
8. the eurymeric Photoresisting agent composition as having homogeneous reaction as described in the claim 6, it is characterized in that the described acrylic resin that has the unstable functional group of acid is selected from one or more in the following resin: tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, the dimethyltrimethylene glycol diacrylate, the dimethyltrimethylene glycol dimethylacrylate, polyethyleneglycol diacrylate, polyethylene glycol dimethacrylate, the bisphenol a diacrylate of ethoxylation, the bisphenol a dimethacrylate of ethoxylation, trimethylol-propane trimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, the trimethylolpropane triacrylate of ethoxylation, glyceryl propoxyl group triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol five acrylate, the acrylic acid epoxy propyl ester, the multipolymer of glytidyl methacrylate and composition thereof.
9. have the eurymeric Photoresisting agent composition of homogeneous reaction according to claim 1, it is characterized in that, described smooth acid producing agent is selected from salt, sulfonate, diazo salt, diazo naphthoquinone sulfonate or its potpourri.
10. the eurymeric Photoresisting agent composition as having homogeneous reaction as described in the claim 9 is characterized in that described salt is selected from triaryl sulfonium salts, alkaryl sulfosalt, diaryl group iodized salt, diaryl villaumite, diaryl bromine salt or its potpourri.
11. the eurymeric Photoresisting agent composition as having homogeneous reaction as described in the claim 10 is characterized in that described triaryl sulfonium salts is a triaryl hexafluorophosphoric acid sulfosalt.
12. as the eurymeric Photoresisting agent composition that has homogeneous reaction as described in the claim 9, it is characterized in that described salt is selected from the group of being made up of triphenyl trifluoro-methanyl sulfonate, antimony triphenyl hydrochlorate, methoxyl triphenyl trifluoro-methanyl sulfonate, methoxyl antimony triphenyl hydrochlorate, trimethyl triphenyl trifluoro-methanyl sulfonate and composition thereof.
13. have the eurymeric Photoresisting agent composition of homogeneous reaction according to claim 1, it is characterized in that, described vinyl ether reactive monomer is selected from 1, the 4-cyclohexanedimethanodiglycidyl diglycidyl ether, 1,2-propylene glycol divinyl ether, 1, the ammediol divinyl ether, 1,3-butylene glycol divinyl ether, 1,4-butylene glycol divinyl ether, the tetramethylene glycol divinyl ether, the neopentyl glycol divinyl ether, the hexylene glycol divinyl ether, the ethylene glycol bisthioglycolate vinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,4 cyclohexane dimethanol divinyl ether or its potpourri.
14. have the eurymeric Photoresisting agent composition of homogeneous reaction according to claim 1, it is characterized in that, described cycloaliphatic epoxides is selected from N, N-diglycidyl-4-dehydration glyceryl aniline, 3,4-7-oxa-bicyclo[4.1.0 ylmethyl carboxylate, 3,4-epoxycyclohexane carboxylate, 1,2-cyclohexane diglycidyl dicarboxylic ester or its potpourri.
15. have the eurymeric Photoresisting agent composition of homogeneous reaction according to claim 1, it is characterized in that described composition (a) phenolics and composition (b) have the resin to the unstable functional group of acid, its molecular weight is between 2000 to 150000.
16. have the eurymeric Photoresisting agent composition of homogeneous reaction according to claim 1, it is characterized in that described composition (a) phenolics and composition (b) have the resin to the unstable functional group of acid, its molecular weight is between 3000 to 100000.
17. have the eurymeric Photoresisting agent composition of homogeneous reaction according to claim 1, it is characterized in that, described eurymeric Photoresisting agent composition with homogeneous reaction carries out a multiple reaction pattern after the exposure light source irradiation, and this multiple reaction pattern comprises the synchronous reaction that photoresistance ingredient hydrophilic and hydrophobic matter changes and photoresistance ingredient molecular weight changes.
18. have the eurymeric Photoresisting agent composition of homogeneous reaction according to claim 1, it is characterized in that described Photoresisting agent composition also comprises:
(e) photoresist additive, 0.1 to 100 weight portion.
19. as the eurymeric Photoresisting agent composition that has homogeneous reaction as described in the claim 18, it is characterized in that described photoresist additive is selected from one or more in dissolution inhibitor, antioxidant, thermal stabilizer, light stabilizer, lubricant, colorant, defoamer, levelling agent, filling agent and the thickening agent.
20. have the eurymeric Photoresisting agent composition of homogeneous reaction according to claim 1, it is characterized in that described have weight ratio scope to the unstable functional group's of acid resin compound and described phenolic resin compound between 1: 6 to 1: 1.
21. one kind forms the photoresistance method of patterning, may further comprise the steps successively:
On treated base material, apply an eurymeric Photoresisting agent composition with homogeneous reaction;
Formed photoresistance is optionally shone with an exposure light source; And
With the photoresistance of alkaline aqueous solution processing after exposure,
Wherein, described eurymeric Photoresisting agent composition with homogeneous reaction comprises:
(a) phenolic resin compound, 100 weight portions;
(b) has resin compound, 1 to 100 weight portion to the unstable functional group of acid;
(c) reactive monomer, it is main structure with the vinyl ether, 1 to 100 weight portion; And
(d) light acid producing agent, 1 to 35 weight portion.
22. as formation photoresistance method of patterning as described in the claim 21, it is characterized in that, described eurymeric Photoresisting agent composition with homogeneous reaction carries out a multiple reaction pattern after described exposure light source irradiation, and this multiple reaction pattern comprises the synchronous reaction that photoresistance ingredient hydrophilic and hydrophobic matter changes and photoresistance ingredient molecular weight changes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03132821 CN1280676C (en) | 2003-07-21 | 2003-07-21 | Positive photoresistive agent composition and method for forming photoresistive pattern |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03132821 CN1280676C (en) | 2003-07-21 | 2003-07-21 | Positive photoresistive agent composition and method for forming photoresistive pattern |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1570765A CN1570765A (en) | 2005-01-26 |
| CN1280676C true CN1280676C (en) | 2006-10-18 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 03132821 Expired - Lifetime CN1280676C (en) | 2003-07-21 | 2003-07-21 | Positive photoresistive agent composition and method for forming photoresistive pattern |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1904736B (en) * | 2005-07-25 | 2012-06-13 | 日产化学工业株式会社 | Positive-type photosensitive resin composition and cured film manufactured therefrom |
| KR101388998B1 (en) * | 2006-06-15 | 2014-04-24 | 닛산 가가쿠 고교 가부시키 가이샤 | Positive photosensitive resin composition containing polymer having ring structure |
| FR2964102B1 (en) * | 2010-09-01 | 2013-03-29 | Commissariat Energie Atomique | USE OF DIAZONIUM SALTS FOR THE FORMATION OF THICK LAYERS ON AT LEAST ONE SURFACE OF A SUBSTRATE |
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