CN1820228A - Positive photosensitive resin composition - Google Patents
Positive photosensitive resin composition Download PDFInfo
- Publication number
- CN1820228A CN1820228A CN 200480017404 CN200480017404A CN1820228A CN 1820228 A CN1820228 A CN 1820228A CN 200480017404 CN200480017404 CN 200480017404 CN 200480017404 A CN200480017404 A CN 200480017404A CN 1820228 A CN1820228 A CN 1820228A
- Authority
- CN
- China
- Prior art keywords
- alkyl
- positive type
- type photosensitive
- relief pattern
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
- G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
Abstract
Disclosed is a positive photosensitive resin composition which comprises 100 parts by mass of a hydroxy polyamide, 1-30 parts by mass of a phenolic compound having only one benzene ring, and 1-100 parts by mass of a photosensitive diazoquinone compound.
Description
Technical field
The positive type photosensitive organic compound that the present invention relates to use, the manufacture method of the stable on heating sclerosis relief pattern of having of this positive type photosensitive organic compound and semiconductor devices have been used with this sclerosis relief pattern as the surface protection film of semiconductor devices and interlayer dielectric.
Background technology
All the time, the polyimide resin that has good thermotolerance and electrical characteristics, mechanical property etc. concurrently is used to the surface protection film and the interlayer dielectric of semiconductor devices.This polyimide resin; now generally be to supply with by form with the photosensitive polyimide precursor composition; implement coating, utilize active ray to form pattern, development, hot-imide processing etc.; can on semiconductor devices, easily form surface protection film and interlayer dielectric etc.; compare with non-photosensitive polyimide precursor composition in the past, have the advantages that to shorten operation significantly.
But the photosensitive polyimide precursor composition as developer solution, needs a large amount of organic solvents such as N-N-methyl-2-2-pyrrolidone N-in its developing procedure.Because environmental problem increase in recent years etc., people have begun to seek to remove the countermeasure of organic solvent, and are recently same with photoresist for this reason, proposed the scheme of the thermotolerance photoresist material of various available alkaline aqueous solutions developments.
Wherein, just paid close attention in recent years as the method that positive type photosensitive organic compound uses with following composition, described composition is an aqueous base solubility hydroxypolyamide, and for example the photolytic activity composition of polybenzoxazole (to call PBO in the following text) precursor and photonasty diazonium naphtoquinone compounds etc. mixes the PBO precursor composition (special public clear 63-96162 communique) that forms.
The development mechanism of this positive type photosensitive organic compound is to utilize, the photonasty diazonium naphtoquinone compounds of unexposed portion is insoluble in alkaline aqueous solution, relative therewith, by exposure, this photonasty diazonium naphtoquinone compounds generation chemical change, form indene carboxylic acid's compound and in alkaline aqueous solution, become solvable.Utilize between this exposed portion and the unexposed portion dissolution velocity poor, can make the relief pattern that has only unexposed portion for developer solution.
Above-mentioned PBO precursor composition can develop by exposure and alkaline aqueous solution and form the eurymeric relief pattern, because the PBO film after the sclerosis has the thermmohardening characteristic equal with polyimide film, paid close attention to as the material that is expected to alternative organic solvent developable polyimide precursor.But, pass through to so far and still have a lot of problems in the resulting PBO precursor composition of disclosed method.
For example, when reality was used the PBO precursor composition, what become problem especially was the film reduction of unexposed portion when developing.When the film reduction of unexposed portion was big, the obvious variation of shape of the back relief pattern that develops can not obtain sufficient performance.As countermeasure, if increase as the molecular weight of the PBO precursor of matrix resin, then can reduce the film reduction of unexposed portion to this.But partly developed residual (scum silica frost) with the exposure that developer solution should be able to be removed fully this moment originally, has the shortcoming of resolution variation.In addition, the elongated problem of development time that also has exposed portion.
At this problem, reported by in the PBO precursor composition, adding specific phenolic compound, the film reduction (spy opens flat 9-302221 communique and Te Kai 2000-292913 communique) of the unexposed portion in the time of suppressing to develop.But its effect is insufficient, and when special molecular weight at the PBO precursor was big, people sought not take place to develop residual (scum silica frost), can bring into play the material of the effect that suppresses the film minimizing.
In addition, though carry out heat treated by the relief pattern that the PBO precursor after this development is formed, variable being changed to has the sclerosis relief pattern that stable on heating PBO resin forms, but also has following problems: big variation takes place in unhardened PBO precursor flow, relief pattern shape in its heat-treatment process.
And then when preserving said composition in room temperature etc., each performance such as sensitivity, development time changes significantly, has the problem used with the technology of identical conditions of being difficult to.
Summary of the invention
Problem of the present invention is to provide a kind of sensitivity, resolution, removing property of scum silica frost is good and then sclerosis relief pattern shape is good, preserve the few novel positive type photosensitive organic compound of performance change that causes, used the manufacture method of the sclerosis relief pattern of said composition, and the semiconductor devices that contains this sclerosis relief pattern.
The present inventor furthers investigate in order to solve above-mentioned problem, found that the phenolic compound that has ad hoc structure by combination in having the hydroxypolyamide of ad hoc structure, the positive type photosensitive organic compound of the above-mentioned problem that can be resolved, thus the present invention finished.
Promptly, the invention provides a kind of positive type photosensitive organic compound, it contains following substances and forms, described material is: the phenolic compound shown in the hydroxypolyamide with the repetitive shown in the general formula (1) of 100 mass parts, the general formula (2) of 1～30 mass parts and the photonasty diazonium naphtoquinone compounds of 1～100 mass parts
(in the formula, X
1Be organic group with 4 valencys of at least 2 carbon atoms, X
2, Y
1And Y
2Be the organic group with divalent of at least 2 carbon atoms, m is 2～1000 integer, and n is 0～500 integer, m/ (m+n)＞0.5; In addition, comprise X
1And Y
1M dihydroxy diamides unit and comprise X
2And Y
2The putting in order arbitrarily of n diamides unit),
(in the formula, R
1Expression is selected from group or the atom in hydrogen atom, alkyl, halogen atom, hydroxyl, alkoxy, alkyl-carbonyl, alkyl carbonyl oxy, the urea groups, R
1Separately can be different when being plural number; In addition, a is 0～5 integer).
In positive type photosensitive organic compound of the present invention, phenolic compound is the compound shown in the general formula (3) more preferably,
(in the formula, R
2Expression is selected from group or the atom in hydrogen atom, alkyl, halogen atom, hydroxyl, alkoxy, alkyl-carbonyl, alkyl carbonyl oxy, the urea groups, R
2Separately can be different when being plural number; In addition, b is 0～4 integer).
In addition, the invention provides a kind of manufacture method of the relief pattern that hardens, comprise: 1) form of above-mentioned positive type photosensitive organic compound with layer or film is formed on the substrate, 2) expose or direct irradiation light, electron ray or ion irradiation with chemical ray by mask, 3) wash-out or remove exposed portion or illuminated portion, 4) relief pattern of gained is carried out heat treated.
And then, the invention provides a kind of semiconductor devices, it contains above-mentioned sclerosis relief pattern layer and forms.
Positive type photosensitive organic compound of the present invention and used the manufacture method of the sclerosis relief pattern of said composition, sensitivity, resolution, removing property of scum silica frost are good, and sclerosis relief pattern shape is good, and it is few to preserve the performance change that causes.In addition, having the semiconductor devices of the present invention of the sclerosis relief pattern that has used said composition, is the semiconductor devices of having used the premium properties of this sclerosis relief pattern.
Embodiment
＜positive type photosensitive organic compound of the present invention 〉
Below each composition that constitutes positive type photosensitive organic compound of the present invention is specifically described.
(1) hydroxypolyamide
The matrix polymer hydroxypolyamide of positive type photosensitive organic compound of the present invention is the polymkeric substance that contains m dihydroxy diamides unit in the following general formula (1).This dihydroxy diamides unit is by having X
1(NH
2)
2(OH)
2Two amino-phenols of structure and have a Y
1(COOH)
2The dicarboxylic acid of structure forms.Here, 2 groups of this pair amino-phenol amino and hydroxyls are mutual respectively to be the ortho position, by making this hydroxypolyamide closed loop in about 300～400 ℃ of heating, becomes the heat-resistant resin polybenzoxazole.M is preferably in 2～1000 scope, more preferably in 3～50 scope.
In this hydroxypolyamide,, can make n diamides unit condensation in the following general formula (1) according to necessity.This diamides unit is by having X
2(NH
2)
2The diamines of structure and have a Y
2(COOH)
2The dicarboxylic acid of structure forms.N is preferably in 0～500 scope, more preferably in 0～10 scope.Because when the ratio of the diamides unit in the hydroxypolyamide is too high, the dissolubility in the alkaline aqueous solution that uses as developer solution is low, equals 0.5 so the value of m/ (m+n) is preferably greater than, more preferably greater than equaling 0.7, most preferably more than or equal to 0.8.
As having X
1(NH
2)
2(OH)
2Two amino-phenols of structure, for example can list, 3,3 '-dihydroxybiphenyl amine, 3,3 '-diamido-4,4 '-dihydroxybiphenyl, 4,4 '-diamido-3,3 '-dihydroxybiphenyl, 3,3 '-diamido-4,4 '-dihydroxydiphenylsulisomer, 4,4 '-diamido-3,3 '-dihydroxydiphenylsulisomer, two (3-amino-4-hydroxy phenyl) methane, 2, two (the 3-amino-4-hydroxy phenyl) propane of 2-, 2, two (the 3-amino-4-hydroxy phenyl) HFC-236fa of 2-, 2, two (the 4-amino-3-hydroxy base) HFC-236fa of 2-, two (4-amino-3-hydroxy base) methane, 2, two (the 4-amino-3-hydroxy base) propane of 2-, 4,4 '-diamido-3,3 '-dihydroxy benaophenonel, 3,3 '-diamido-4,4 '-dihydroxy benaophenonel, 4,4 '-diamido-3,3 '-dihydroxydiphenyl ether, 3,3 '-diamido-4,4 '-dihydroxydiphenyl ether, 1,4-diamido-2, the 5-dihydroxy benzenes, 1,3-diamido-2, the 4-dihydroxy benzenes, 1,3-diamido-4,6-dihydroxy benzenes etc., but be not limited to this.These diamines can be used alone or as a mixture.
Be preferably X in these pairs amino-phenol especially
1For being selected from the compound of following aromatic group.
In addition, as having X
2(NH
2)
2The diamines of structure, can list aromatic diamine, silicon diamines etc.
Wherein, as aromatic diamine, for example can list, m-phenylene diamine, p-phenylenediamine (PPD), 2, the 4-toluene diamine, 3,3 '-diamino-diphenyl ether, 3,4 '-diamino-diphenyl ether, 4,4 '-diamino-diphenyl ether, 3,3 '-diamino-diphenyl sulfone, 4,4 '-diamino-diphenyl sulfone, 3,4 '-diamino-diphenyl sulfone, 3,3 '-diaminodiphenyl-methane, 4,4 '-diaminodiphenyl-methane, 3,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl thioether, 3,3 '-diaminobenzophenone, 4,4 '-diaminobenzophenone, 3,4 '-diaminobenzophenone, 2,2 '-two (4-aminophenyl) propane, 2,2 '-two (4-aminophenyl) HFC-236fa, 1, two (3-amino-benzene oxygen) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 4-, 4-methyl-2, two (4-the aminophenyl)-1-amylenes of 4-, 4-methyl-2, two (4-the aminophenyl)-2-amylenes of 4-, 1, two (the α of 4-, alpha-alpha-dimethyl-4-aminobenzyl) benzene, imino group-di-p-phenylenediamine, 1, the 5-diaminonaphthalene, 2, the 6-diaminonaphthalene, 4-methyl-2, two (4-aminophenyl) pentanes of 4-, 5 (or 6)-amino-1-(4-aminophenyl)-1,3,3-trimethyl indane, two (p-aminophenyl) phosphine oxide, 4,4 '-chrysoidine, 4,4 '-diamino-diphenyl urea, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-, 2, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2-, 2, two [4-(3-amino-benzene oxygen) phenyl] benzophenone of 2-, 4,4 '-two (4-amino-benzene oxygen) diphenylsulphone, 4,4 '-two [4-(α, alpha-alpha-dimethyl-4-aminobenzyl) phenoxy group] benzophenone, 4,4 '-two [4-(α, alpha-alpha-dimethyl-4-aminobenzyl) phenoxy group] diphenylsulphone, 4,4 '-benzidine, 4,4 '-diaminobenzophenone, the phenyl indan diamines, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 3,3 '-dimethyl-4,4 '-benzidine, the ortho-aminotoluene sulfone, 2, two (the 4-amino-benzene oxygen phenyl) propane of 2-, two (4-amino-benzene oxygen phenyl) sulfone, two (4-amino-benzene oxygen phenyl) sulphur, 1,4-(4-amino-benzene oxygen phenyl) benzene, 1,3-(4-amino-benzene oxygen phenyl) benzene, 9, two (4-aminophenyl) fluorenes of 9-, 4,4 '-two (3-amino-benzene oxygen) diphenylsulphone, 4,4 '-diaminobenzene formailide etc., and the hydrogen atom of the aromatic proton of these aromatic diamines is selected from the chlorine atom, fluorine atom, bromine atoms, methyl, methoxyl, cyano group, at least a group in the phenyl or atom replace and the compound of formation, but are not limited to this.
In addition, in order to improve the cohesiveness with matrix material, can select the silicon diamines, as its example, can list, two (4-aminophenyl) dimethylsilane, two (4-aminophenyl) tetramethyl silica alkane, two (p-aminophenyl) tetramethyl disiloxane, two (gamma-amino propyl group) tetramethyl disiloxane, 1, two (the gamma-amino propyl-dimethyl silicyl) benzene of 4-, two (the amino butyl of 4-) tetramethyl disiloxane, two (gamma-amino propyl group) tetramethylphenyl disiloxane etc., but be not limited to this.
In addition, as preferred dicarboxylic acid, can list Y
1And Y
2For being selected from the compound of following aromatic group.
In the hydroxypolyamide with the repetitive shown in the above-mentioned general formula (1), its end group is also contained in scope of the present invention with the compound of specific organic group end-blocking.
As this end-capping group, for example can list, the spy opens the group with unsaturated link such described in the flat 5-197153 communique.When coming the closed end group, can expect that the mechanical properties of filming (particularly length growth rate), the sclerosis relief pattern shape after the heat hardening becomes good with these groups.As the preference in such end-capping group, can list following group, but be not limited to these groups.
(2) photonasty diazonium naphtoquinone compounds
The photonasty diazonium naphtoquinone compounds that uses among the present invention is to contain 1,2-benzoquinones diazido structure or 1, the compound of 2-naphthoquinones diazido structure, according to US Patent specification No. 2772972, No. 2797213, No. 3669658 etc., it is known material.As preferred examples for compounds, can list for example following compounds.
(in the formula, Q is hydrogen atom or naphthoquinones diazido sulphonic acid ester as follows, and all Q is not hydrogen atom simultaneously.)
As particularly preferred compound wherein is following substances.
(Q be hydrogen atom or
, Q is not hydrogen atom simultaneously).
The use level of photonasty diazonium naphtoquinone compounds in hydroxypolyamide with respect to this hydroxypolyamide of 100 mass parts, is preferably 1～100 mass parts.If the use level of photonasty diazonium naphtoquinone compounds is less than 1 mass parts, then the composition performance of resin is bad, in contrast, if surpass 100 mass parts, then the tensile elongation of the film after the sclerosis obviously reduces, and the development of exposed portion residual (scum silica frost) becomes very obvious.
(3) phenolic compound
In positive type photosensitive organic compound of the present invention, it is important further containing the phenolic compound shown in the general formula (2).
(in the formula, R
1Expression is selected from group or the atom in hydrogen atom, alkyl, halogen atom, hydroxyl, alkoxy, alkyl-carbonyl, alkyl carbonyl oxy and the urea groups, R
1Separately can be different during for plural number; In addition, a is 0～5 integer).
This phenolic compound is the phenolic compound shown in the general formula (3) more preferably,
(in the formula, R
2Expression is selected from group or the atom in hydrogen atom, alkyl, halogen atom, hydroxyl, alkoxy, alkyl-carbonyl, alkyl carbonyl oxy and the urea groups, R
2Separately can be different when being plural number; In addition, b is 0～4 integer).
If the phenolic compound shown in general formula (2) or the general formula (3) is joined in the positive type photosensitive organic compound that is made of above-mentioned hydroxypolyamide and photonasty diazonium naphtoquinone compounds, then the dissolution velocity of exposed portion increases, and sensitivity improves.In addition, being seen when improving sensitivity as the molecular weight that reduces matrix resin PBO precursor, the film reduction of unexposed portion also very little (dissolution velocity of unexposed portion is increased greatly).In addition, under the situation that has added this phenolic compound, do not observe the development residual (scum silica frost) at the molecular weight that increases the PBO precursor, the exposed portion that takes place when reducing the film reduction of unexposed portion substantially, resolution is improved significantly.As this phenolic compound, can list following compounds as preferred compound.
As preferred especially person wherein, can list following phenolic compound.
As the addition of phenolic compound,, be preferably 1～30 mass parts with respect to 100 mass parts hydroxypolyamides.If addition less than 1 mass parts, then can not obtain the effect of high sensitivityization, high resolving powerization, on the other hand, if addition surpasses 30 mass parts, it is big that the film when then developing reduces quantitative change, lacks practicality.
(4) other compositions
In positive type photosensitive organic compound of the present invention, according to necessity, can also add all the time dyestuff, surfactant, stabilizing agent that the adjuvant as photosensitive polymer combination uses, be used to improve and the close-burning bonding assistant of substrate, crosslinking chemical etc.
Below, above-mentioned adjuvant is described more specifically.
As dyestuff, for example can list methyl violet, crystal violet, peacock green etc.
As surfactant, can list the polyethylene glycols of polypropylene glycol or polyoxyethylene lauryl ether etc. or the nonionic class surfactant that forms by its derivant.In addition, the fluorine class surfactant of Off ロ ラ one De (trade name, Sumitomo 3M society system), メ ガ Off ア Star Network (trade name, big Japanese イ Application キ chemical industry society system) or ス Le Off ロ Application (trade name, Asahi Glass society system) etc.And then, can list the organosiloxane surfactant of KP341 (trade name, chemical industry society of SHIN-ETSU HANTOTAI system), DBE (trade name, チ Star ソ society system), グ ラ ノ one Le (trade name, chemistry society of common prosperity society system) etc.
As the bonding assistant, for example can list alkyl imidazoline, butyric acid, alkyl acid, polycarboxylated styrene, polyvinyl methyl ether, tert-butyl group novolac, epoxy silane, epoxy polymer etc., and various silane coupling agent.
As the concrete preference of silane coupling agent, for example can list N-phenyl-3-aminopropyl trialkoxy silane, 3-sulfydryl propyl trialkoxy silane, 2-(trialkoxysilyl ethyl) pyridine, 3-methacryloxypropyl trialkoxy silane, 3-methacryloxypropyl dialkoxy alkyl silane, 3-glycidoxy propyl trialkoxy silane, 3-glycidoxy propyl group dialkoxy alkyl silane, 3-aminopropyl trialkoxy silane or 3-aminopropyl dialkoxy alkyl silane (following they are collectively referred to as amino silane), the reactant of amino silane and acid anhydrides or acid dianhydride, and the amino of amino silane is transformed to carbamate groups or urea groups and the compound that forms etc.In addition, the alkyl as this moment can list methyl, ethyl, butyl etc., as acid anhydrides, can list maleic anhydride, phthalate anhydride etc., as acid dianhydride, can list pyromellitic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic acid dianhydride, 4,4 '-oxygen, two phthalic acid dianhydrides etc. as carbamate groups, can list tert-butoxycarbonyl amino etc., as urea groups, can list phenyl amino carbonylamino etc.
As crosslinking chemical, have 1,1,2,2-four (p-hydroxybenzene) ethane, four glycidol ethers, T 55,1, two (2, the 3-glycidoxy) naphthalenes of 6-, diglycerol polyglycidylether, the epoxy compound of Polyethylene Glycol Bisglycidyl Ether etc., aluminium acetylacetonate (III) salt, titanium acetylacetone (IV) salt, chromium acetylacetonate (III) salt, magnesium acetylacetonate (II) salt, nickel acetylacetonate (II) salt, trifluoroacetylacetone (TFA) aluminium (III) salt, trifluoroacetylacetone (TFA) titanium (IV) salt, trifluoroacetylacetone (TFA) chromium (III) salt, trifluoroacetylacetone (TFA) magnesium (II) salt, the metal-chelator of trifluoroacetylacetone (TFA) nickel (II) salt etc., ニ カ ラ Star Network MW-30MH, MW-100LH (trade name, three and ケ ミ カ Le chemistry society system), サ イ メ Le 300, サ イ メ Le 303 (trade names, Mitsui サ イ テ Star Network society system) etc. alkylated melamine resin.
In the present invention, these compositions are dissolved in formation varnish shape in the solvent, use as positive type photosensitive organic compound.As such solvent, can be used alone or as a mixture N-N-methyl-2-2-pyrrolidone N-, gamma-butyrolacton, N, N-dimethyl acetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diglycol dibutyl ethers, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl isophthalic acid, 3-butylene glycol acetate, 1,3 butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxy propyl acid esters etc.In these solvents, from the little viewpoint of influence to photoresist etc., preferred non-amides compound as concrete preferred example, can list, gamma-butyrolacton, cyclopentanone, cyclohexanone, isophorone etc.
＜used the preparation method of the sclerosis relief pattern of positive type photosensitive organic compound of the present invention 〉
Then, to positive type photosensitive organic compound of the present invention being coated on the substrate, carry out following specifying to make the method for sclerosis relief pattern.
The first,, positive type photosensitive organic compound of the present invention is coated on the substrate of for example silicon wafer, ceramic substrate, aluminium base etc. by with the spin coating of spinner, the roller coat of roller coat device.Use baking oven, electric hot plate 50～140 ℃ of dryings, remove it to desolvate.
The second, by mask, use contact float device (contact aligner), stepper etc., utilize chemical light to expose, or direct irradiation light, electron ray or ion irradiation.
Three,, then utilize washing fluid to wash, the relief pattern that obtains wishing by removing illuminated portion with developing solution dissolution.As developing method, can be modes such as spraying, the stirring of oar formula, dipping, ultrasound wave.Washing fluid can use distilled water, deionized water etc.
The developer solution that uses for the photosensitive resin film that is formed by positive type photosensitive organic compound of the present invention is developed must be to dissolve the liquid of removing the alkali-soluble polymkeric substance, must be the alkaline aqueous solution that has dissolved alkali compounds.The alkali compounds that is dissolved in the developer solution can be any in inorganic alkaline compound, the organic basic compound.
As this inorganic alkaline compound, for example can list lithium hydroxide, NaOH, potassium hydroxide, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, sodium hydrogen phosphate, lithium metasilicate, sodium silicate, potassium silicate, lithium carbonate, sodium carbonate, sal tartari, lithium borate, sodium borate, potassium borate, ammonia etc.
In addition, as this organic basic compound, for example can list tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, hydroxide trimethyl hydroxyethyl ammonium, methylamine, dimethylamine, trimethylamine, mono aminoethane, diethylamine, triethylamine, n-propylamine, di-n-propylamine, isopropylamine, diisopropylamine, methyl-diethyl-amine, dimethylethanolamine, monoethanolamine, triethanolamine etc.
And then, as required, can in above-mentioned alkaline aqueous solution, add water-miscible organic solvents such as methyl alcohol, ethanol, propyl alcohol, ethylene glycol, surfactant, stable storage agent, dissolving resin inhibitor etc. in right amount.
At last, the resulting relief pattern of heat treated can form the thermotolerance sclerosis relief pattern with polybenzoxazole structure.
The sclerosis relief pattern of producing by said method; as surface protection film, interlayer dielectric, again wiring with dielectric film, flip chip devices with diaphragm or have the diaphragm of the device of bump structure; make up by manufacture method, can make semiconductor devices with known semiconductor devices.In addition, also be useful as the seal coat of the interlayer dielectric of multilayer circuit, flexible copper plate, soldering-resistance layer, liquid crystal orientation film etc.
(embodiment)
Below, according to reference example, embodiment the present invention is described.
Reference example 1＜hydroxypolyamide P-1's is synthetic 〉
In the many mouthfuls of flasks of capacity 3L (separable flask), mix stirring 183.1g (0.5 mole) 2 in room temperature (25 ℃), 2 '-two (3-amino-4-hydroxy phenyl) HFC-236fa, the N,N-dimethylacetamide (DMAC) of 640.9g, 63.3g (0.8 mole) pyridine form homogeneous solution.In 354g diethylene glycol dimethyl ether (DMDG), be dissolved with 118.0g (0.4 mole) 4, the material of 4 '-diphenyl ether dimethyl chloride by tap funnel to wherein dripping.At this moment, many mouthfuls of flasks of cooling in 15～20 ℃ water-bath.Dripping the needed time is 40 minutes, and reacting liquid temperature is 30 ℃ to the maximum.
After dropping liquid finished 3 hours, in reactant liquor, add 30.8g (0.2 mole) 1,2-cyclohexyl dicarboxylic acid anhydride was placed 15 hours in stirring at room, seal with carboxyl cyclohexyl amide group polymer chain whole amine end groups 99%.Input 1 by monitoring with HPLC, the surplus of 2-cyclohexyl dicarboxylic acid anhydride can easily calculate the reaction rate of this moment.Then, above-mentioned reactant liquor is added drop-wise under high-speed stirred in the 2L water, disperses to separate out polymkeric substance, with its recovery, suitably vacuum drying is carried out in washing after the dehydration, obtains the hydroxypolyamide (P-1) of GPC molecular weight 9000 (polystyrene correction).
In addition, when polymkeric substance need be further purified, available following method was implemented.Promptly, after being dissolved into the above-mentioned polymkeric substance that obtains in the gamma-butyrolacton (GBL) again, it is used Zeo-karb and anion exchange process, the solution that obtains is thus put in the ion exchange water, then by the polymkeric substance of separating out is filtered, washing, vacuum drying, can obtain the polymkeric substance of purifying.
Reference example 2＜hydroxypolyamide P-1's is synthetic 〉
In the many mouthfuls of flasks of capacity 2L, mix the DMAC that stirs 197.8g (0.54 mole) 2,2 '-two (3-amino-4-hydroxy phenyl)-HFC-236fa, 75.9g (0.96 mole) pyridine, 692g, make its dissolving in room temperature (25 ℃).Be dissolved with 19.7g (0.12 mole) 5-norborene-2, the material of 3-dicarboxylic acid anhydride to wherein dripping in addition among the DMDG at 88g by tap funnel.Dripping the needed time is 40 minutes, and reacting liquid temperature is 28 ℃ to the maximum.
After dropping liquid finishes, with 50 ℃ of heating of hot bath, stirs after 18 hours, the infrared spectrum of assaying reaction liquid, affirmation has occurred 1385 and 1772cm
-1The characteristic absorption of imino group.
Then it is cooled to 8 ℃ in water-bath, is dissolved with 142.3g (0.48 mole) 4, the material of 4 '-diphenyl ether, two formyl dichloros to wherein dripping in addition among the DMDG at 398g by tap funnel.Dripping the needed time is 80 minutes, and reacting liquid temperature is 12 ℃ to the maximum.After dropping liquid finishes 3 hours, under high-speed stirred, above-mentioned reactant liquor is added drop-wise in the 12L water, disperse to separate out polymkeric substance, with its recovery, suitably washing, vacuum drying is implemented in the dehydration back, obtains hydroxypolyamide (P-2).The weight-average molecular weight of utilizing GPC to obtain of He Cheng hydroxypolyamide is 14000 with the polystyrene correction like this.
The modulation of embodiment 1～3 and comparative example 1～2＜positive type photosensitive organic compound 〉
The phenolic compound that photonasty diazonium naphtoquinone compounds, 10 mass parts of the hydroxypolyamide (P-1 or P-2) that obtains in above-mentioned each reference example of 100 mass parts, structure that 20 mass parts have following formula Q-1 is had following formula F-1～F-4 structure is dissolved among the 170 mass parts GBL, filter with 0.2 μ m filters then, modulates the embodiment 1～3 of table 1 record and the positive type photosensitive organic compound of comparative example 1～2.
The evaluation of＜positive type photosensitive organic compound 〉
(1) composition evaluating characteristics
Make on the silicon wafer that society's system rotary coating machine (Dspin636) is spun onto above-mentioned positive type photosensitive organic compound 5 inches with big Japanese ス Network リ one Application, 130 ℃ of prebake conditions of carrying out 180 seconds, form filming of 10.7 μ m with electric hot plate.Make society's system determining film thickness device (ラ system ダ エ one ス) with big Japanese ス Network リ one Application and measure thickness.
By having the mask of test pattern, use the ニ コ Application society system ledex (NSR2005i8A) of exposure wavelength with i-line (365nm), make the exposure phasic Chang, next this is filmed exposed.Use Network ラ リ ア Application ト ヅ ヤ パ Application society system alkaline-based developer (AZ300MIF デ ベ ロ Star パ one, 2.38 quality % tetramethyl ammonium hydroxide aqueous solution), being that 9.1 μ m adjust development time like that and come above-mentioned film is developed under 23 ℃ of conditions, according to the thickness after developing, formed the relief pattern of eurymeric.The sensitivity of positive type photosensitive organic compound, resolution and removing property of scum silica frost are as shown in table 2.
In addition, the sensitivity of positive type photosensitive organic compound, the following evaluation of resolution.
Sensitivity (mJ/cm
2
)
In above-mentioned development time, can dissolve the minimum exposure amount of removing the exposed portion of filming fully.
Resolution (μ m)
Minimum under the above-mentioned exposure is differentiated pattern dimension.
And then in vertical hardening furnace (light sun リ Application De バ one グ society system), in blanket of nitrogen, 320 ℃ of sclerosis (heat hardening processings) of implementing 1 hour, formation is as polybenzoxazole (PBO) film of thermotolerance tunicle with the relief pattern that obtains.Observe owing to sclerosis makes the shape of relief pattern and the shape of presclerotic relief pattern what degree change take place with microscope, the result also is shown in table 2.
As shown in Table 2, the positive type photosensitive organic compound of the application of the invention can form high sensitivity, high-resolution sclerosis relief pattern.And then, do not observe the back of developing and produce scum silica frost, the variation of the yet basic relief pattern shape that does not cause by sclerosis.Relative therewith, do not contain the comparative example 1 of the phenolic compound that satisfies necessary condition of the present invention and 2 composition, sensitivity, resolution are all low, produce scum silica frost after development, and great changes will take place owing to sclerosis makes the relief pattern shape.
(2) storage stability evaluation
After the positive type photosensitive organic compound that will modulate by aforesaid operations filters, placed for two weeks at 25 ℃, carry out above-mentioned composition evaluating characteristics then.At this moment, with placed for 2 weeks before be coated with (rotation number) under the identical condition, develop (hour), thickness after coating film thickness, the development and sensitivity through the time rate of change as shown in table 3.Rate of change calculates as following.
(rate of change)={ (placed 2 weeks after value)-(value at initial stage) }/(value at initial stage) * 100
As shown in Table 3, positive type photosensitive organic compound of the present invention has shown good storage stability.On the other hand, do not contain the comparative example 1 of the phenolic compound that satisfies necessary condition of the present invention and 2 composition, great changes have taken place for coating film thickness, development back thickness and sensitivity.
Table 1
| Hydroxypolyamide | Phenolic compound | |
| Embodiment 1 | P-1 | F-1 |
| Embodiment 2 | P-2 | F-2 |
| Embodiment 3 | P-2 | F-3 |
| Comparative example 1 | P-1 | Do not have |
| Comparative example 2 | P-2 | F-4 |
Table 2
| Sensitivity (mJ/cm 2) | Resolution (μ m) | Removing property of scum silica frost (1) | The sclerosis shape (2) | |
| Embodiment 1 | 350 | 2 | ○ | ○ |
| Embodiment 2 | 350 | 2 | ○ | ○ |
| Embodiment 3 | 400 | 2 | ○ | ○ |
| Comparative example 1 | 500 | 5 | × | × |
| Comparative example 2 | 800 | 12 | × | × |
(1) removing property of scum silica frost zero: do not observe the scum silica frost in the pattern
*: observe the scum silica frost in the pattern
(2) sclerosis shape zero: the basic no change of pattern before and after the sclerosis
*: great changes have taken place for pattern before and after the sclerosis
Table 3
| Coating film thickness rate of change (%) | Back thickness rate of change (%) develops | Sensitivity rate of change (%) | |
| Embodiment 1 | +1.1 | +1.0 | 0 |
| Embodiment 2 | +0.8 | +1.0 | 0 |
| Embodiment 3 | +0.7 | +0.7 | 0 |
| Comparative example 1 | +4.2 | +5.1 | +30 |
| Comparative example 2 | +3.8 | +3.6 | +25 |
The industry utilizability
Positive type photosensitive organic compound of the present invention, be suitable as the surface protection film, interlayer dielectric of semiconductor devices, again wiring with dielectric film, flip chip devices with diaphragm and seal coat, soldering-resistance layer, liquid crystal orientation film etc. with interlayer dielectric, flexible copper plate of diaphragm, the multilayer circuit of the device of bump structure.
Claims (4)
1. positive type photosensitive organic compound, it contains following substances and forms, described material is: 100 mass parts contain phenolic compound and 1～100 mass parts photonasty diazonium naphtoquinone compounds shown in the hydroxypolyamide of repetitive shown in the general formula (1) and 1～30 mass parts general formula (2)
(in the formula, X
1Be 4 valency organic groups with at least 2 carbon atoms, X
2, Y
1And Y
2Be the divalent organic group with at least 2 carbon atoms, m is 2～1000 integer, and n is 0～500 integer, m/ (m+n)＞0.5; In addition, comprise X
1And Y
1M dihydroxy diamides unit and comprise X
2And Y
2The putting in order arbitrarily of n diamides unit),
(in the formula, R
1Expression by hydrogen atom, alkyl, halogen atom, hydroxyl, alkoxy, alkyl-carbonyl, alkyl carbonyl oxy, and the group formed of urea groups in group or the atom selected, R
1Separately can be different when being plural number; In addition, a is 0～5 integer).
2. positive type photosensitive organic compound as claimed in claim 1, phenolic compound is shown in general formula (3):
(in the formula, R
2Expression is selected from group or the atom in hydrogen atom, alkyl, halogen atom, hydroxyl, alkoxy, alkyl-carbonyl, alkyl carbonyl oxy and the urea groups, R
2Separately can be different when being plural number; In addition, b is 0～4 integer).
3. the manufacture method of the relief pattern that hardens comprises:
1) claim 1 or the 2 described positive type photosensitive organic compounds form with layer or film is formed on the substrate,
2) expose or direct irradiation light, electron ray or ion irradiation with chemical ray by mask,
3) wash-out or remove exposed portion or illuminated portion,
4) relief pattern that obtains is carried out heat treated.
4. semiconductor devices contains the sclerosis relief pattern layer that manufacture method according to claim 3 obtains and forms.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP282213/2003 | 2003-07-29 | ||
| JP2003282213A JP4128116B2 (en) | 2003-07-29 | 2003-07-29 | Positive photosensitive resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1820228A true CN1820228A (en) | 2006-08-16 |
| CN100549828C CN100549828C (en) | 2009-10-14 |
Family
ID=34101002
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800174046A Active CN100549828C (en) | 2003-07-29 | 2004-07-29 | Positive type photosensitive organic compound |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP4128116B2 (en) |
| KR (1) | KR100676360B1 (en) |
| CN (1) | CN100549828C (en) |
| WO (1) | WO2005010616A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102053498A (en) * | 2009-11-10 | 2011-05-11 | 第一毛织株式会社 | Positive photosensitive resin composition |
| CN102292675A (en) * | 2009-12-28 | 2011-12-21 | 东丽株式会社 | Positive-type photosensitive resin composition |
| CN101727006B (en) * | 2008-10-20 | 2014-06-25 | 第一毛织株式会社 | Positive type photosensitive resin composition |
| CN104204120A (en) * | 2012-03-28 | 2014-12-10 | 日产化学工业株式会社 | Composition for forming cured film, orientation material, and phase difference material |
| CN104402751A (en) * | 2014-10-17 | 2015-03-11 | 威海经济技术开发区天成化工有限公司 | Photosensitive imaging composition of amide phenol-containing compound or oligomer thereof |
| TWI492976B (en) * | 2012-12-26 | 2015-07-21 | Cheil Ind Inc | Photosensitive resin composition for insulating film of display device, insulating film using the same, and display device using the same |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101273303B (en) | 2005-10-26 | 2011-07-06 | 旭化成电子材料株式会社 | Positive photosensitive resin composition |
| JP4804329B2 (en) * | 2005-12-22 | 2011-11-02 | 旭化成イーマテリアルズ株式会社 | Positive photosensitive resin composition |
| JP4918312B2 (en) * | 2006-09-01 | 2012-04-18 | 旭化成イーマテリアルズ株式会社 | Photosensitive resin composition |
| US20100119969A1 (en) * | 2007-06-05 | 2010-05-13 | Nissan Chemical Industries Ltd. | Positive photosensitive resin composition and dpolyhydroxyamide resin |
| KR101413076B1 (en) | 2011-12-23 | 2014-06-30 | 제일모직 주식회사 | Positive photosensitive resin composition, photosensitive resin film prepared by using the same, and semiconductor device including the photosensitive resin film |
| KR102337564B1 (en) * | 2018-09-28 | 2021-12-13 | 삼성에스디아이 주식회사 | Photosensitive resin composition, photosensitive resin layer and electronic device using the same |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2931297A1 (en) * | 1979-08-01 | 1981-02-19 | Siemens Ag | HEAT-RESISTANT POSITIVE RESISTS AND METHOD FOR PRODUCING HEAT-RESISTANT RELIEF STRUCTURES |
| EP0291779B1 (en) * | 1987-05-18 | 1994-07-27 | Siemens Aktiengesellschaft | Heat-resistant positive resist, and process for the production of heat-resistant resist patterns |
| JPH0213953A (en) * | 1988-07-01 | 1990-01-18 | Mitsubishi Kasei Corp | Positive type photoresist composition |
| EP0450189B1 (en) * | 1990-03-29 | 1996-10-30 | Siemens Aktiengesellschaft | High temperature stable negative resists and process for the production of high temperature stable relief structure |
| JPH09281702A (en) * | 1996-04-16 | 1997-10-31 | Nippon Zeon Co Ltd | Positive type resist composition |
| JP3207352B2 (en) * | 1996-05-13 | 2001-09-10 | 住友ベークライト株式会社 | Positive photosensitive resin composition |
| JPH1138625A (en) * | 1997-07-16 | 1999-02-12 | Hitachi Chem Co Ltd | Positive chemically sensitized photosensitive resin composition and manufacture of resist pattern |
| KR20010071149A (en) * | 1998-04-15 | 2001-07-28 | 야마모토 카즈모토 | Positive Resist Composition |
| JP4314335B2 (en) * | 1999-04-02 | 2009-08-12 | 旭化成イーマテリアルズ株式会社 | Positive photosensitive resin composition |
| JP4408984B2 (en) * | 1999-04-21 | 2010-02-03 | 旭化成イーマテリアルズ株式会社 | Aromatic polyhydroxyamide |
| JP3460679B2 (en) * | 1999-12-17 | 2003-10-27 | 東レ株式会社 | Positive photosensitive resin precursor composition |
| JP3636059B2 (en) * | 2000-10-19 | 2005-04-06 | 東レ株式会社 | Positive photosensitive resin precursor composition |
-
2003
- 2003-07-29 JP JP2003282213A patent/JP4128116B2/en not_active Expired - Lifetime
-
2004
- 2004-07-29 WO PCT/JP2004/011198 patent/WO2005010616A1/en active Application Filing
- 2004-07-29 KR KR20067001993A patent/KR100676360B1/en active IP Right Grant
- 2004-07-29 CN CNB2004800174046A patent/CN100549828C/en active Active
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101727006B (en) * | 2008-10-20 | 2014-06-25 | 第一毛织株式会社 | Positive type photosensitive resin composition |
| CN102053498A (en) * | 2009-11-10 | 2011-05-11 | 第一毛织株式会社 | Positive photosensitive resin composition |
| CN102053498B (en) * | 2009-11-10 | 2013-05-15 | 第一毛织株式会社 | Positive photosensitive resin composition |
| CN102292675A (en) * | 2009-12-28 | 2011-12-21 | 东丽株式会社 | Positive-type photosensitive resin composition |
| CN102292675B (en) * | 2009-12-28 | 2012-08-22 | 东丽株式会社 | Positive-type photosensitive resin composition |
| CN104204120A (en) * | 2012-03-28 | 2014-12-10 | 日产化学工业株式会社 | Composition for forming cured film, orientation material, and phase difference material |
| TWI492976B (en) * | 2012-12-26 | 2015-07-21 | Cheil Ind Inc | Photosensitive resin composition for insulating film of display device, insulating film using the same, and display device using the same |
| CN104402751A (en) * | 2014-10-17 | 2015-03-11 | 威海经济技术开发区天成化工有限公司 | Photosensitive imaging composition of amide phenol-containing compound or oligomer thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005049661A (en) | 2005-02-24 |
| KR100676360B1 (en) | 2007-02-01 |
| WO2005010616A1 (en) | 2005-02-03 |
| JP4128116B2 (en) | 2008-07-30 |
| CN100549828C (en) | 2009-10-14 |
| KR20060033919A (en) | 2006-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101495919B (en) | Positive photosensitive resin composition, method for preparing cured relief pattern, semiconductor device | |
| JP6252174B2 (en) | Positive photosensitive resin composition and method for manufacturing semiconductor device including cured film using the same | |
| CN102047178B (en) | Photosensitive resin composition | |
| JP4780586B2 (en) | Positive photosensitive resin composition | |
| JP2010097220A (en) | Positive photosensitive resin composition | |
| CN1356356A (en) | Normal Photosensitive resin precursor composition and display using it | |
| TWI743478B (en) | Negative resin composition and method for producing cured film | |
| CN102047181B (en) | Photosensitive resin composition | |
| CN101273303A (en) | Positive photosensitive resin composition | |
| KR100913058B1 (en) | Composition for positive photosensitive resin, method of forming pattern and semiconductor device | |
| TW200403532A (en) | Highly heat-resistant negative-type photosensitive resin composition | |
| CN1820228A (en) | Positive photosensitive resin composition | |
| JP4804312B2 (en) | Positive photosensitive resin composition | |
| JP2001329061A (en) | Hydroxylated polyamide | |
| JP4627030B2 (en) | Positive photosensitive resin composition | |
| JP2005338481A (en) | Positive photosensitive resin composition | |
| TWI711648B (en) | Method for manufacturing substrate and method for manufacturing light-emitting element using the same | |
| JP4726730B2 (en) | Positive photosensitive resin composition | |
| JP4488611B2 (en) | Positive photosensitive resin composition | |
| JP4836607B2 (en) | Positive photosensitive resin composition | |
| JP4578369B2 (en) | Positive photosensitive resin composition | |
| JP5571914B2 (en) | Photosensitive resin composition, method for producing cured relief pattern, and semiconductor device | |
| JP4744318B2 (en) | Positive photosensitive resin composition | |
| JP5111223B2 (en) | Negative photosensitive resin composition | |
| JP2007225942A (en) | Positive photosensitive resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20160504 Address after: Tokyo, Japan, Japan Patentee after: Asahi Kasei Kogyo K. K. Address before: Tokyo, Japan, Japan Patentee before: Asahi Chemical Corp. |