JEONG, Ji-Young (Cheil Industries Inc, 332-2, Gocheon-dong,,Uiwang-s, Gyeonggi-do 437-711, KR)
CHO, Hyun-Yong (Cheil Industries Inc, 332-2, Gocheon-dong,,Uiwang-s, Gyeonggi-do 437-711, KR)
YOO, Yong-Sik (Cheil Industries Inc, 332-2, Gocheon-dong,,Uiwang-s, Gyeonggi-do 437-711, KR)
LEE, Kil-Sung (Cheil Industries Inc, 332-2, Gocheon-dong,,Uiwang-s, Gyeonggi-do 437-711, KR)
CHA, Myoung-Hwan (Cheil Industries Inc, 332-2, Gocheon-dong,,Uiwang-s, Gyeonggi-do 437-711, KR)
JUNG, Doo-Young (Cheil Industries Inc, 332-2, Gocheon-dong,,Uiwang-s, Gyeonggi-do 437-711, KR)
JEONG, Ji-Young (Cheil Industries Inc, 332-2, Gocheon-dong,,Uiwang-s, Gyeonggi-do 437-711, KR)
CHO, Hyun-Yong (Cheil Industries Inc, 332-2, Gocheon-dong,,Uiwang-s, Gyeonggi-do 437-711, KR)
YOO, Yong-Sik (Cheil Industries Inc, 332-2, Gocheon-dong,,Uiwang-s, Gyeonggi-do 437-711, KR)
LEE, Kil-Sung (Cheil Industries Inc, 332-2, Gocheon-dong,,Uiwang-s, Gyeonggi-do 437-711, KR)
CHA, Myoung-Hwan (Cheil Industries Inc, 332-2, Gocheon-dong,,Uiwang-s, Gyeonggi-do 437-711, KR)
| [CLAIMS] [Claim 1]
A positive photosensitive resin composition, comprising:
(A) a polyamic acid or polyamic acid ester compound including a repeating unit represented by the following Formula 1 ;
(B) a photosensitive diazoquinone compound;
(C) a silane compound;
(D) a phenol compound; and
(E) a solvent, [Chemical Formula 1]
Ra, Rb, Rc, Rd, Re, and R f are the same or independently hydrogen or a monovalent organic group, Ri and R2 are the same or independently a single bond, or a substituted or unsubstituted alkylene, and in one embodiment a Ci to C 5 alkylene, a', b', c 1 , d 1 , e', and f are the same or independently O or 1 , a'+b'+c' and d'+e'+f are respectively integers of 2 or 3,
Yi and Y 2 are the same or independently a substituted or unsubstituted aliphatic or alicyclic organic group,
Xi is a substituted or unsubstituted arylene, a substituted or unsubstituted alkylene, or a substituted or unsubstituted cycloalkylene,
X 2 is a divalent to a quadrivalent aromatic or aliphatic organic group, or is a functional group represented by the following Formula 2, mi and ITi 2 are mole ratios, mi+m 2 =100 mol%, mi ranges from 60 to 100 mol%, and m 2 ranges from 0 to 40 mol%:
[Chemical Formula 2]
R 3 and R 4 are the same or independently a substituted or unsubstituted alkyl, a substituted or unsubstituted aryl, a substituted or unsubstituted alkoxy, or a hydroxy,
R 5 and Re are the same or independently a substituted or unsubstituted alkylene or a substituted or unsubstituted arylene, and k is an integer ranging from 1 to 50.
[Claim 2]
The positive photosensitive resin composition of claim 1 , wherein the polyamic acid or polyamic acid ester compound has a weight average molecular weight (Mw) of 3000 to 300,000. [Claim 3]
The positive photosensitive resin composition of claim 1 , wherein the silane compound includes acompound represented by the following Formulae 14 or 15:
[Chemical Formula 14]
[Chemical Formula 15]
wherein in the above Formula 15, R 36 to R 39 are the same or are independently a substituted or unsubstituted alkoxy, R40 and R41 are the same or are independently a substituted or unsubstituted amino, and ni7 and ni 8 are the same or are independently integers ranging from 1 to 5. [Claim 4]
The positive photosensitive resin composition of claim 1 , wherein the solvent comprises N-methyl-2-pyrrolidone, y -butyrolactone, N,N-dimethyl acetamide, dimethylsulfoxide, diethyleneglycol dimethylether, diethyleneglycol diethylether, diethyleneglycol dibutylether, propyleneglycol monomethylether, dipropyleneglycol monomethylether, propyleneglycol monomethylether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1 ,3-butyleneglycol acetate, 1 ,3-butyleneglycol-3-monomethylether, methyl pyruvate, ethyl pyruvate, methyl- 3-methoxy propionate, or combinations thereof.
[Claim 5]
The positive photosensitive resin composition of claim 1 , wherein the resin composition comprises 5 to 100 parts by weight of the (B) photosensitive diazoquinone compound, 0.1 to 30 parts by weight of the (C) silane compound, 1 to 30 parts by weight of the (D) phenol compound, and 50 to 200 parts by weight of the (E) solvent, based on 100 parts by weight of the (A) polyamic acid or polyamic acid ester compound.
[Claim 6] The positive photosensitive resin composition of claim 1 , wherein the polyamic acid or polyamic acid ester compound includes one of compounds represented by the following Formulae 22 to 25: [Chemical Formula 22]
[Chemical Formula 23]
[Chemical Formula 24]
[Chemical Formula 25]
[Claim 7]
A photosensitive resin film fabricated using the positive photosensitive resin composition according to one of claims 1 to 6.
[Claim 8]
A semiconductor electronic component comprising the photosensitive resin film according to claim 7. |
[SPECIFICATION]
POSITIVE PHOTOSENSITIVE RESIN COMPOSITION [Technical Field]
The present invention relates to a positive photosensitive resin composition. More particularly, the present invention relates to a positive photosensitive resin composition that can be cured at a low temperature and has high sensitivity, resolution, residue removal, substrate adherence, and pattern-forming capabilities, and low film shrinkage. [Background Art] The conventional surface protective layer and interlayer insulating layer for the semiconductor device includes a polyimide resin having excellent heat resistance and electrical characteristics, mechanical characteristics, and so on,
The polyimide resin has recently been used as a form of a photosensitive polyimide precursor composition, and it is able to be coated and to form a surface protective layer, an interlayer insulating layer, and so on by coating the polyimide precursor composition on a semiconductor device, patterning by ultraviolet (UV) rays, developing, and heat imidizing the same. Accordingly, it is possible to remarkably shorten the process compared to that of the conventional non-photosensitive polyimide precursor composition. The photosensitive polyimide precursor composition can be applied as a positive type in which an exposed part is dissolved by development and a negative type in which the exposed part is cured and maintained. It is preferable to use a positive type since it can be developed by a non-toxic alkali
i
aqueous solution. The positive photosensitive polyimide precursor composition includes a polyimide precursor of polyamic acid, a photosensitive material of diazonaphto quinone, and so on. However, the positive photosensitive polyimide precursor composition has a problem in that a desired pattern is not obtained because the carbonic acid of the polyamidic acid used is too highly soluble to an alkali.
In order to solve this problem, a material to which phenolic hydroxyl acid has been introduced instead of carbonic acid by esterificating polyamidic acid with an alcohol compound having at least one hydroxyl group has been suggested (refer to Japanese Patent Laid-Open Publication No. H 10-30739), but this material is insufficiently developed, causing problems of a layer decrease or resin delamination from the substrate.
Recently, a material of which a polybenzoxazole precursor is mixed with a diazonaphtoquinone compound has drawn attention (Japanese Patent Laid- open Publication No. S63-96162), but when the polybenzoxazole precursor composition is actually used, a layer decrease of an unexposed part is remarkably increased, so it is difficult to obtain a desirable pattern after the developing process. In order to improve this, if the molecular weight of the polybenzoxazole precursor is increased, the layer decrease amount of the unexposed part is reduced, but development residue (scum) is generated so it deteriorates the resolution and prolongs the development duration on the exposed part.
In order to solve the problem, it has been reported that the layer decrease is suppressed by adding a certain phenol compound to a
polybenzoxazole precursor composition (Japanese Patent Laid-Open Publication No. H9-302221 and Japanese Patent Laid-Open Publication No. 2000-292913). However, the effect of suppressing the decreased amount of the unexposed part is insufficient, so research for increasing the effects on suppressing the layer decrease is required, along with preventing generation of the development residue (scum).
After forming the pattern, the conventional photosensitive polyimide or polybenzoxazole is cured at a temperature of around 350° C.
Magnetoresistive RAM (MRAM) that is usable for the next generation memory device is weak at a high temperature, so it requires a low curing process temperature. Accordingly, it needs a material that can be used as a surface protective layer and an interlayer insulating layer and that can be cured at a low temperature of 260° C or below. By using a latent thermal acid generator or a monomer having excellent flexibility, it has been reported that it is possible to be cured at a low temperature by using a polymerized polybenzoxazole precursor
(Japanese Patent Laid-Open Publication No. 2006-349700 and Japanese
Patent Laid-Open Publication No. 2007-079264). However, the obtained polybenzoxazole precursor has poor adherence to the substrate, so research for improving the various characteristics of a layer including the same is required.
[Detailed Description] [Technical Problem]
One exemplary embodiment of the present invention provides a
photosensitive resin composition that can be cured at a low temperature of 260° C or less and has high sensitivity, resolution, residue removal, substrate adherence, and pattern-forming capabilities, and low film shrinkage and excellent film properties after curing. [Technical Solution]
Another embodiment of the present invention provides a photosensitive resin film made using the positive photosensitive resin composition.
A further embodiment of the present invention provides a semiconductor electronic component that is produced using the positive photosensitive resin composition.
The embodiments of the present invention are not limited to the above technical purposes, and a person of ordinary skill in the art can understand other technical purposes.
According to one embodiment of the present invention, provided is a positive photosensitive resin composition that includes (A) a polyamic acid or polyamic acid ester compound including a repeating unit represented by the following Formula 1 , (B) a photosensitive diazoquinone compound, (C) a silane compound, (D) a phenol compound, and (E) a solvent: [Chemical Formula 1]
-NH-C
wherein, in the above Formula 1 ,
Ra, Rb, Rc, Rd, Re, and Rf are the same or independently hydrogen or a monovalent organic group,
Ri and R 2 are the same or independently a single bond, or a substituted or unsubstituted alkylene, a', b 1 , c 1 , d', e 1 , and f are the same or independently 0 or 1 , a'+b'+c 1 and d'+e'+f are respectively integers of 2 or 3,
Y 1 and Y2 are the same or independently a substituted or unsubstituted aliphatic or alicyclic organic group, X 1 is a substituted or unsubstituted arylene, a substituted or unsubstituted alkylene, or a substituted or unsubstituted cycloalkylene,
X 2 is a divalent to quadrivalent aromatic or aliphatic organic group, or a functional group represented by the following Formula 2,
ITi 1 and 1TI2 are mole ratios, mi+m 2 =100 mol%,
ITi 1 ranges from 60 to 100 mol%, and ITi 2 ranges from 0 to 40 mol%, [Chemical Formula 2]
R 3 and R 4 are the same or independently a substituted or unsubstituted alkyl, a substituted or unsubstituted aryl, a substituted or unsubstituted alkoxy,
or a hydroxy,
R 5 and RQ are the same or independently a substituted or unsubstituted alkylene or a substituted or unsubstituted arylene, and k is an integer ranging from 1 to 50. According to another embodiment of the present invention, provided is a photosensitive resin film made using the positive photosensitive resin composition.
According to a further embodiment of the present invention, provided is a semiconductor electronic component made using the positive photosensitive resin composition.
Hereinafter, embodiments of the present invention will be described in detail. [Advantageous Effects]
The positive photosensitive resin composition can be cured at a low temperature of 260 ° C or less, and has high sensitivity, resolution, residue removal, substrate adherence, and pattern-forming capabilities, and low film shrinkage. [Best Mode]
Exemplary embodiments of the present invention will hereinafter be described in detail. However, these embodiments are only exemplary but do not limit the present invention.
The photosensitive resin composition according to one embodiment of the present invention includes (A) a polyamic acid or polyamic acid ester
compound including a repeating unit represented by the following Formula 1 , (B) a photosensitive diazoquinone compound, (C) a silane compound, (D) a phenol compound, and (E) a solvent.
As used herein, when specific definition is not provided, the term "substituted" refers to one substituted with at least a substituent including a halogen, an alkyl, an aryl, an alkoxy, an amino, or an alkenyl.
As used herein, when specific definition is not provided, the term "an alkyl" refers to a C1 to C30 alkyl, and preferably a C1 to C15 alkyl, the term "a cycloalkylene" refers to a C3 to C30 cycloalkylene, and preferably a C3 to C18 cycloalkylene, the term "an alkoxy" refers to a C1 to C30 alkoxy, and preferably a C1 to C18 alkoxy, the term "an aryl" refers to a C6 to C30 aryl, and preferably a C6 to C18 aryl, the term "an alkenyl" refers to a C2 to C30 alkenyl, and preferably a C2 to C18 alkenyl, the term "an alkylene" refers to a C1 to C30 alkylene, and preferably a C1 to C18 alkylene, and the term "arylene" refers to a C6 to C30 arylene, and preferably a C6 to C18 arylene.
As used herein, when specific definition is not provided, the term ""divalent to quadrivalent organic group" refers to an organic group including 2 to 4 functional groups. The functional groups are substituents excluding hydrogen. As used herein, the term "aliphatic organic group" refers to a C1 to C30 alkyl, a C2 to C30 alkenyl, or a C2 to C30 alkynyl, the term "alicyclic organic group" refers to a C3 to C30 cycloalkyl, a C3 to C30 cycloalkenyl, or a C3 to C30 cycloalkynyl, and the term "aromatic organic group" refers to a C6 to C30 aryl or a C2 to C30 heteroaryl.
Exemplary components included in photosensitive resin compositions according to embodiments of the present invention will hereinafter be described in detail.
(A) Polvamic acid or polvamic acid ester compound
The polyamic acid or polyamic acid ester compound includes a repeating unit represented by the following Formula 1.
[Chemical Formula 1]
In the above Formula 1 , R 3 , Rb, Rc, R d , Re, and Rf are the same or independently hydrogen or a monovalent organic group, and for example, an alkyl,
Ri and R 2 are the same or independently a single bond, or a substituted or unsubstituted alkylene, and in one embodiment, a Ci to C 5 alkylene, and in another embodiment, a C 2 to C 3 alkylene, a 1 , b', c', d', e', and f are the same or independently O or 1, and a'+b'+c' and d'+e'+f are respectively integers of 2 or 3, mi and m 2 are mole ratios, mi+m 2 =100 mol%, mi ranges from 60 to 100 mol%, and m 2 ranges from 0 to 40 mol%, and
X 1 is a substituted or unsubstituted arylene, a substituted or unsubstituted alkylene, or a substituted or unsubstituted cycloalkylene.
In one embodiment, Xi is derived from a dihydroxy-included diamine compound including 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3 l - dihydroxybiphenyl, bis(3-amino-4-hydroxyphenyl)propane, bis(4-amino-3- hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3- hydroxyphenyl)sulfone, 2,2-bis(3-amino-4-hydroxyphenyl)-1 ,1 ,1 ,3,3,3- hexafluoropropane, 2,2-bis(4-amino-3-hydroxyphenyl)-1 ,1 ,1 ,3,3,3- hexafluoropropane, cyclohexyldiamine, methylenebiscyclohexylamine, or combinations thereof.
For example, Xi may be a compound represented by the following Formula 3 or 4.
[Chemical Formula 3]
i
[Chemical Formula 4]
A 1 includes O, CO, CRi 0 Rn, SO 2 , S, or CONH,
Rg to Ri 3 are the same or independently hydrogen, a substituted or unsubstituted aryl, or a substituted or unsubstituted alkyl, and for example, Ri 0 and R 11 are fluoroalkyls,
n-i is an integer of 1 or 2, and n 2 and n 3 are the same or independently integers from 1 to 3. X 2 is a divalent to quadrivalent aromatic or aliphatic organic group, or a functional group represented by the following Formula 2. [Chemical Formula 2]
In the above Formula 2,
R 3 and R 4 are the same are independently a substituted or unsubstituted alkyl, a substituted or unsubstituted aryl, a substituted or unsubstituted alkoxy, or a hydroxy,
R 5 and Re are the same or independently a divalent substituted or unsubstituted alkylene, or a substituted or unsubstituted arylene, and k is an integer ranging from 1 to 50.
Specifically, X 2 is derived from diamine monomers including an aromatic amine, an alicyclic diamine, an aliphatic diamine, or a silicon diamine.
Examples of the diamine monomers include 3,4'-diaminodiphenylether, 4,4'-diaminodiphenylether, 3,4'-diaminodiphenyl methane, 4,4'-diaminodiphenyl methane, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'- diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, para-phenylenediamine, meta-phenylenediamine, 1 ,5-naphthalenediamine, 2,6-naphthalenediamine, cyclohexyldiamine methylenebiscyclohexylamine, 3,3'-diamino-4,4'- dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxysulfone, 4,4'-diamino-3,3 l -
dihydroxyphenylsulfone, bis(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3- amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4- hydroxyphenyl)hexafluoropropane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'- dihydroxydiphenylether 1 ,4-diamino-2,5-dihydroxybenzene, 1 ,3-diamino-2,4- dihydroxybenzene, or mixtures thereof, but are not limited thereto. These diamine monomers can be used singularly or in combination.
Examples of the silicon diamine include bis(4- aminophenyl)dimethylsilane, bis(4-aminophenyl)tetramethylsiloxane, bis(p- aminophenyl)tetramethyldisiloxane, bis( Y -aminopropyl)tetramethyldisiloxane,
1 ,4-bis( Y -aminopropyldimethylsilyl)benzene, bis(4- aminobutyl)tetramethyldisiloxane, bis( Y -aminopropyl)tetraphenyldisiloxane, 1 ,3-bis(aminopropyl)tetramethyldisiloxane, and so on, but are not limited thereto.
Yi and Y 2 are the same or independently a substituted or unsubstituted aliphatic or alicyclic organic group. The aliphatic or alicyclic organic group may include an aryl, alkenyl, or alkyl substituent, and these substituents may be linked to each other to form a fused ring with an alicyclic cycle.
For example, Yi and Y 2 are derived from tetracarbonic acid dianhydride, or a derivative thereof that reacts with a diamine derivative to produce polyamic acid, or reacts with a diamino phenol derivative to form a polyamic acid ester.
Yi and Y 2 are quadrivalent alicyclic organic groups including 4 to 40 carbon atoms.
For example, the Y 1 and Y 2 are derived from one of the compounds the
following Formulae 5 to 8.
[Chemical Formula 5]
[Chemical Formula 6]
[Chemical Formula 7]
[Chemical Formula 8]
A 2 includes O, CR 14 R 15 , CO, CONH, S, or SO 2 , where R 14 and R 15 are the same or independently a substituted or unsubstituted alkyl, hydrogen, or a fluoroalkyl.
The polyamic acid or polyamic acid ester compound may have a weight average molecular weight (Mw) of 3000 to 300,000. When the weight average molecular weight is less than 3000, sufficient properties cannot be obtained, whereas when it is more than 300,000, solubility with respect to an organic solvent may be reduced and thus it is difficult to handle it.
(B) Photosensitive diazoquinone compound
The photosensitive diazoquinone compound may be a compound including a 1 ,2-benzoquinone diazide or 1 ,2-naphtoquinone diazide structure. These compounds are described in U.S. Patent Nos. 2,772,975, 2,797,213, and 3,669,658, the entire contents of which are incorporated herein by reference.
The photosensitive diazoquinone compound may include the compound represented by the following Formulae 9 to 12, but is not limited thereto.
[Chemical Formula 9]
Q is may be hydrogen, or the following Formula 9-1 or 9-2, provided that all Q are not hydrogen, and
n 4 to nβ are the same or independently integers ranging from 1 to 3. [Chemical Formula 9-1]
[Chemical Formula 9-2]
[Chemical Formula 10]
In the above Formula 10, Ri 9 is hydrogen or a substituted or unsubstituted alkyl, D 4 to D 6 are OQ 1 where Q is the same as defined in Chemical Formula 9, and n 7 to n 9 are the same or independently integers ranging from 1 to 3.
[Chemical Formula 11]
In the above Formula 11 ,
A 3 is CO or CRR 1 , R and R' are the same or independently a substituted
or unsubstituted alkyl,
D 7 to Dio are the same or independently hydrogen, a substituted or unsubstituted alkyl, OQ, or NHQ,
Q is the same as defined in Chemical Formula 9, nio, n-ii, n 12 , and ni 3 are the same or independently integers ranging from 1 to 4, and nio+nn and n-i 2 +n 13 are independently integers of 5 or less, provided that at least one of D 7 to D 8 is OQ, and one aromatic ring includes one to three OQs and the other aromatic ring includes one to four OQs. [Chemical Formula 12]
In the above Formula 12,
R20 to R27 are the same or independently hydrogen or a substituted or unsubstituted alkyl, n-w and ni 5 are the same or independently integers ranging from 1 to 5, and preferably 2 to 4, and Q is the same as defined in Chemical Formula 9.
The photosensitive resin composition includes 5 to 100 parts by weight of the photosensitive diazoquinone compound based on 100 parts by weight of the polyamic acid, or the polyamic acid ester compound. Within the above range, residues do not remain after exposure and there is no film thickness loss during development, resulting in good pattern formation. (C) Silane compound
The silane compound improves adherence between the photosensitive resin composition and a substrate. The silane compound may be represented by the following Formula 13.
[Chemical Formula 13]
In the above Formula 13,
R 2S is vinyl, a substituted or unsubstituted alkyl, or a substituted or unsubstituted aryl, and for example, 3-(meth)acryloxypropyl, p-styryl, or 3- (phenylamino)propyl, and R 2θ to R 31 are the same or independently a substituted or unsubstituted alkoxy, a substituted or unsubstituted alkyl, or a halogen, provided that at least one of R 2θ to R 31 is an alkoxy or a halogen. The alkoxy may be a C1 to C8 alkoxy, and the alkyl may be a C1 to C20 alkyl.
Examples of the silane compound include compounds represented by the following Formulae 14 to 15; vinyltrimethoxysilane, vinyltriethoxysilane, vinyl trichlorosilane, vinyltris(β -methoxyethoxy)silane; or 3- methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryl trimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3- methacryloxypropylmethyl diethoxysilane, or trimethoxy[3- (phenylamino)propyl]silane. In one embodiment, vinyltrimethoxysilane or vinyltriethoxysilane may be appropriate.
[Chemical Formula 14]
In the above Formula 14, R 32 is NH 2 or CH 3 CONH,
R 33 to R 35 are the same or independently a substituted or unsubstituted alkoxy, where for example, the alkoxy may be OCH 3 or OCH 2 CH 3 , and niβ is an integer ranging from 1 to 5. [Chemical Formula 15]
i8
In the above Formula 15,
R 36 to R 39 are the same or independently a substituted or unsubstituted alkoxy such as OCH 3 ,
R 40 and R 41 are the same or independently a substituted or unsubstituted amino such as NH 2 or CH 3 CONH, and ni 7 and ni 8 are the same or independently integers ranging from 1 to 5.
The photosensitive resin composition includes 0.1 to 30 parts by weight of the silane compound based on 100 parts by weight of the polyamic acid, or the polyamic acid ester compound. When the amount of the silane compound is less than 0.1 parts by weight, adherence between lower and upper layers is
not sufficient, whereas when it is more than 30 parts by weight, residue film may remain after development, and photo characteristics (transmittance), and mechanical properties such as tensile strength, elongation, Young's modulus, and so on may be reduced. (D) Phenol compound
The phenol compound increases dissolution and sensitivity of exposed parts during development using an alkali aqueous solution, and plays a role of forming high resolution patterns without residues (scum).
The phenol compound may be represented by the following Formulae 16 to 21 , but is not limited thereto.
[Chemical Formula 16]
In the above Formula 16, R 42 to R44 are the same or independently hydrogen or a substituted or unsubstituted alkyl, F Mδ to R 49 are the same or independently hydrogen, OH, or a substituted or unsubstituted alkyl such as CH 3 , and n 19 is an integer ranging from 1 to 5.
[Chemical Formula 17]
In the above Formula 17,
R 50 to R 55 are the same or independently hydrogen, OH, or a substituted or unsubstituted alkyl,
A 4 is CR 56 R 57 or a single bond, where R 56 and R 57 are the same or independently hydrogen or a substituted or unsubstituted alkyl such as CH 3 , and n 2 o+n2i+n22 and n 23 +n 24 +n 25 are the same or independently integers of 5 or less.
[Chemical Formula 18]
In the above Formula 18,
R 5 S to Rβo are the same or independently hydrogen or a substituted or unsubstituted alkyl, n 26 , n 27 , and n 30 are the same or independently integers ranging from 1 to 5, and
n 28 and n 29 are the same or independently integers ranging from 1 to 4. [Chemical Formula 19]
In the above Formula 19,
R 6 i to R 6 3 are the same or independently hydrogen, OH, or a substituted or unsubstituted alkyl, and n 3 i to n 35 are the same or independently integers ranging from 1 to 4, provided that n 33 +n 3 i and n 32 +n 35 are independently integers of 5 or less.
[Chemical Formula 20]
In the above Formula 20,
R 64 is a substituted or unsubstituted alkyl such as CH 3 ,
Res to R δ7 are the same or independently hydrogen or a substituted or unsubstituted alkyl, n 36> n 38 , and n 40 are the same or independently integers ranging from 1 to 5, and n 37 , n 39 , and n 4 i are the same or independently integers ranging from 1
to 4, provided that n 36 +n 37 , n 38 +n 39 , and n 4 o + n 4 i are independently integers of 5 or less.
[Chemical Formula 21]
In the above Formula 21 ,
Res, R δ9 , and R 7 o are the same or independently a substituted or unsubstituted alkyl such as CH 3 ,
R 7 i to R 74 are the same or independently hydrogen or a substituted or unsubstituted alkyl, n 42 , n 44 , and n 47 are the same or independently integers ranging from 1 to 5, n 43 , n 45 , and n 46 are the same or independently integers ranging from 1 to 4, and n 48 is an integer ranging from 1 to 5, provided that n 42 +n 43 , n 44 +n 45 , and n 46 +n 47 are independently integers of 5 or less.
The photosensitive resin composition includes 1 to 30 parts by weight of the phenol compound based on 100 parts by weight of the polyamic acid, or the polyamic acid ester compound having the above Formula 1. When the amount of the phenol compound is less than 1 part by weight, residues (scum) may
remains during development to obtain a poor pattern profile. When it is more than 30 parts by weight, development rate of non- exposed part increases to obtain a distinct pattern and mechanical properties of a film after thermal curing may be remarkably deteriorated. (E) Solvent
The solvent may include N-methyl-2-pyrrolidone, Y -butyrolactone, N 1 N- dimethyl acetamide, dimethylsulfoxide, diethyleneglycol dimethylether, diethyleneglycol diethylether, diethyleneglycol dibutylether, propyleneglycol monomethylether, dipropyleneglycol monomethylether, propyleneglycol monomethylether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1 ,3- butyleneglycol acetate, 1 ,3-butyleneglycol-3-monomethylether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxy propionate, and so on. The solvent may be used singularly or in combination.
The solvent is included in an amount of 50 to 200 parts by weight based on 100 parts by weight of the polyamic acid, or the polyamic acid ester compound of the above Formula 1.
Within the range, a sufficiently thick film can be obtained and good solubility and coating can be provided.
(F) Other additives The photosensitive resin composition may include (F) other additives in addition to the (A) to (D) components.
The other additives include a latent thermal acid generator. The latent thermal acid generator includes an arylsulfonic acid such as p-toluene sulfonic acid, or a benzene sulfonic acid; a perfluoroalkyl sulfonic acid such as
trifluoromethanesulfonic acid or fluorobutane sulfonic acid; alkane sulfonic acid, methane sulfonic acid, ethane sulfonic acid, or butane sulfonic acid; and mixtures thereof.
The latent thermal acid generator promotes dehydration reactions ofthe hydroxyl group-contained polyamide structure of the polybenzoxazole precursor and cyclization, and it can prevent the phenomenon of decreasing the cyclization degree even if the curing temperature is decreased.
In addition, it may further include an additive such as a suitable surfactant or leveling agent to prevent the stain of film or to improve the development.
The process for forming a pattern using a positive photosensitive resin composition includes: coating a positive photosensitive resin composition on a supporting substrate; drying the coated composition to provide a photosensitive polyamic acid or polyamic acid ester compound layer; exposing the polyamic acid or polyamic acid ester compound layer; developing the exposed polyamic acid or polyamic acid ester compound layer in an alkali aqueous solution to provide a photosensitive resin film; and heating the photosensitive resin film. The conditions of processes for coating, exposing, and developing a photosensitive resin composition to provide a pattern are widely known in this art, so detailed descriptions thereof will be omitted in this specification. The photosensitive resin film may be heated at a low temperature of 260° C or below. The polyamic acid and polyamic acid ester compound present in the photosensitive resin film are respectively transformed to a polyimide and polybenzoxazole by dehydrogenation.
According to another embodiment of the present invention, provided is a photosensitive resin film such as insulation layer or protective layer prepared by a positive photosensitive resin compound. In addition, according to a further embodiment of the present invention, provided is a semiconductor member prepared by the photosensitive resin composition according to the present invention. The photosensitive resin composition according to the present invention can be applied to an insulation layer, a passivation layer, or a buffer coating layer in a semiconductor member, or a surface protective layer and an interlayer insulating layer in a semiconductor device. [Mode for Invention]
The following examples illustrate the present invention in more detail. However, it is understood that the present invention is not limited by these examples.
Synthesis Example 1 : Polyamic acid ester compound (PAE-1) synthesis
18.0 g of 1 ,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxofuran-3- yl)naphto[1 ,2-c]furan-1 ,3-dione was added into a four-necked flask mounted with an agitator, a temperature controlling device, a nitrogen gas injector, and a condenser while nitrogen was flowing, and 132 g of N-methyl-2-pyrrolidone (NMP) was introduced therein and dissolved. The solid amount was 20 wt% in the obtained solution.
When the solid was completely dissolved, 9.9 g of pyridine was introduced into the solution, and 5.7 g of ethyl alcohol was slowly dripped into the solution for 30 minutes while the temperature was maintained between 0
and 5° C. After adding the ethyl alcohol, the solution was reacted at a temperature of 25° C for 12 hours to provide an ethyl ester solution of tetracarboxylic acid dianhydride. 14.9 g of thionyl chloride was slowly dripped for 30 minutes while the temperature was maintained between 0 and 5° C. The solution was agitated after the dripping process while the temperature was maintained for 30 minutes, then the temperature of the solution was increased to 25 ° C and further agitated for one and half hour to provide a diethyl ester dichloride solution of tetra carboxylic acid dianhydride. A solution in which 22.0 g of 2,2-bis(3-amino-4-hydroxyphenyl)-1 ,1 ,1 ,3,3,3-hexafluoro propane and 19 g of pyridine were dissolved in168g of NMP was slowly dripped for 30 minutes while the temperature of solution was maintained at 0 to 5 ° C. The temperature was increased to 40 ° C after the dripping, and the reaction was completed while agitating at this temperature for 2 hours. The reaction mixture was introduced into a solution of water/methanol = 10/1 (volume ratio) to produce a precipitate. Then the precipitate was sufficiently filtered, washed, and dried at 80 ° C under vacuum for 24 hours to synthesize a polyamic acid ester compound (PAE-1) represented by Compound Formula 22 having an average molecular weight (Mw) of 13,900 and polydispersity (PD) of 1.8. [Chemical Formula 22]
Synthesis Example 2: Synthesizing polyamic acid ester compound (PAE-2)
A polyamic acid ester compound (PAE-2) represented by Compound Formula 23 having an average molecular weight of 12,300 and polydispersity of 1.6 was synthesized in accordance with the same procedure as in Synthesis Example 1 , except that 22.Og of 2,2-bis(3-amino-4-hydroxyphenyl)-1 , 1 ,1 , 3,3,3- hexafluoropropane was substituted with 15.16 g of 2,2-bis(3-amino-4- hydroxyphenyl)-1 ,1 ,1,3,3,3-hexafluoropropane and 3.68 g of 4,4-diamino phenyl methane, mi was 70 mol%, and m 2 was 30mol% in Chemical Formula 23. [Chemical Formula 23]
Synthesis Example 3: Synthesizing polyamic acid ester compound (PAE-3)
A polyamic acid ester compound (PAE-3) represented by Compound Formula 23 having an average molecular weight of 11 ,500 and polydispersity of
1.7 was synthesized in accordance with the same procedure as in Synthesis
Example 1 , except that 22.0 g of 2,2-bis(3-amino-4-hydroxyphenyl)-1 , 1 ,1 , 3,3,3- hexafluoropropane was substituted with 17.58 g of 2,2-bis(3-amino-4- hydroxyphenyl)-1 ,1 ,1 ,3,3,3-hexafluoropropane and 2.38 g of 4,4-diamino phenyl methane. In Chemical Formula 23, mi was 80mol% and m 2 was 20mol%.
Synthesis Example 4: Synthesizing polyamic acid ester compound
(PAE-4)
A polyamic acid ester compound (PAE-4) represented by Compound Formula 24 having an average molecular weight of 13,700 and polydispersity of 1.7 was synthesized in accordance with the same procedure as in Synthesis Example 1 , except that 22.0 g of 2,2-bis(3-amino-4-hydroxyphenyl)-1 ,1 ,1 ,3,3,3- hexafluoropropane was substituted with 20.88 g of 2,2-bis(3-amino-4- hydroxyphenyl)-1 ,1 ,1 ,3,3,3-hexafluoropropane and 1.03 g of 1 ,3- bis(aminopropyl)tetramethyldisiloxane. In Chemical Formula 24, mi was 95mol% and m 2 was 5mol%. [Chemical Formula 24]
Synthesis Example 5: Synthesizing polyamic acid ester compound (PAE-5)
A polyamic acid ester compound (PAE-5) represented by the following Formula 25 having an average molecular weight of 14,100 and polydispersity of
1.9 was synthesized in accordance with the same procedure as in Synthesis
Example 1 , except that 7.42 g of isopropyl alcohol was used instead of ethyl alcohol.
[Chemical Formula 25]
Comparative Synthesis Example 1: Synthesizing polyamic acid ester compound (PAE-6)
A polyamic acid ester compound (PAE-6) represented by the following Chemical Formula 26 having an average molecular weight of 14,000 and polydispersity of 1.6 was synthesized in accordance with the same procedure as in Synthesis Example 1 , except that 18.0 g of 1 ,3,3a,4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxofuran-3-yl)naphto[1 ,2-c]furan-1 ,3-dione was substituted with 19.32 g of 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride.
[Chemical Formula 26]
Comparative Synthesis Example 2: Synthesizing polyamic acid ester compound (PAE-7)
A polyamic acid ester compound (PAE-7) represented by the following Formula 27 having an average molecular weight of 13,300 and polydispersity of 1.7 was synthesized in accordance with the same procedure as in Synthesis
Example 1 , except that 18.0 g of 1 ,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5- dioxofuran-3-yl)naphto[1 ,2-c]furan-1 ,3-dione was substituted with 17.64 g of 3,4:3',4'-biphenyl tetracarboxylic acid dianhydride. [Chemical Formula 27]
Comparative Synthesis Example 3: Synthesizing polybenzo- oxazole precursor (PBO-1)
18.3 g of 2,2-bis (3-amino-4-hydroxyphenyl)-1 ,1 ,1 ,3,3,3-hexafluoro propane was added to a four-necked flask mounted with an agitator, a temperature controller, a nitrogen gas injector, and a condenser while nitrogen was flowing, and 280 g of N-methyl-2-pyrrolidone (NMP) was introduced therein and dissolved. The solid amount was 9 wt% in the obtained solution.
When the solid was completely dissolved, 9.9 g of pyridine was introduced into the solution, and a solution in which 14.8 g of 4,4'-oxydibenzonyl chloride was dissolved in 142 g of N-methyl-2-pyrrolidone (NMP) was slowly dripped into the obtained solution for 30 minutes while the temperature was maintained between 0 and 5 ° C. After dripping, it was reacted at a temperature ranging from 0 to 5° C for one hour and heated to a room temperature. It was agitated for one hour to complete the reaction. The reaction mixture was introduced into a solution of water/methanol = 10/1
(volume ratio) to produce a precipitate. Then the precipitate was filtered, sufficiently washed, and dried at 80° C under vacuum for 24 hours or more to synthesize a polybenzoxazole precursor (PBO-1) represented by Compound Formula 28 having an average molecular weight (Mw) of 10,900 and polydispersity of 1.7.
[Chemical Formula 28]
Example 1
15 g of the polyamic acid ester compound (PAE-1) obtained from Synthesis Example 1 was added to and dissolved in 30 g of Y -butyrolactone
(GBL), then 3 g of photosensitive diazoquinone represented by the following
Chemical Formula 29, 0.75 g of trimethoxy[3-(phenylamino)propyl]silane represented by the following Chemical Formula 30, and 0.75 g of a phenol compound represented by the following Chemical Formula 31 were added to and dissolved therein, and filtered through 0.45 μ m fluorine resin-made filter to provide a positive photosensitive polybenzoxazole precursor composition.
[Chemical Formula 29]
In the above formula, two of Qi, Q 2 , and Q 3 are substituted with the following Chemical Formula 29-1 , and the remaining one is hydrogen. [Chemical Formula 29-1]
[Chemical Formula 30]
3 ) 3
[Chemical Formula 31]
Example 2
A positive photosensitive polybenzoxazole precursor composition was prepared in accordance with the same procedure as in Example 1 , except that 15 g of the polyamic acid ester compound (PAE-1) according to Synthesis
Example 1 was substituted with 15 g of the polyamic acid ester compound (PAE-2) according to Synthesis Example 2. Example 3
A positive photosensitive polybenzoxazole precursor composition was prepared in accordance with the same procedure as in Example 1 , except that
15 g of the polyamic acid ester compound (PAE-1) according to Synthesis
Example 1 was substituted with 15 g of the polyamic acid ester compound
(PAE-3) according to Synthesis Example 3.
Example 4 A positive photosensitive polybenzoxazole precursor composition was prepared in accordance with the same procedure as in Example 1 , except that 15 g of the polyamic acid ester compound (PAE-1) according to Synthesis Example 1 was substituted with 15 g of the polyamic acid ester compound (PAE-4) according to Synthesis Example 4. Example 5
A positive photosensitive polybenzoxazole precursor composition was prepared in accordance with the same procedure as in Example 1 , except that 15 g of the polyamic acid ester compound (PAE-1) according to Synthesis Example 1 was substituted with 15 g of the polyamic acid ester compound (PAE-5) according to Synthesis Example 5. Comparative Example 1
A positive photosensitive polybenzoxazole precursor composition was prepared in accordance with the same procedure as in Example 1 , except that 15 g of the polyamic acid ester compound (PAE-1) according to Synthesis
Example 1 was substituted with 15 g of the polyamic acid ester compound (PAE-6) according to Comparative Synthesis Example 1.
Comparative Example 2
A positive photosensitive polybenzoxazole precursor composition was prepared in accordance with the same procedure as in Example 1 , except that
15 g of the polyamic acid ester compound (PAE-1) according to Synthesis
Example 1 was substituted with 15 g of the polyamic acid ester compound
(PAE-7) according to Comparative Synthesis Example 2.
Comparative Example 3 A positive photosensitive polybenzoxazole precursor composition was prepared in accordance with the same procedure as in Example 1 , except that 15 g of the polyamic acid ester compound (PAE-1) according to Synthesis Example 1 was substituted with 15 g of the polybenzoxazole precursor (PBO-1) according to Comparative Synthesis Example 3. Measuring Physical Properties
Each of the photosensitive polybenzoxazole precursor compositions prepared from Examples 1 to 5 and Comparative Examples 1 to 3 was coated on an 8-inch wafer by a spin coater manufactured by Mikasa (1 H-DX2), then it was heated on a hot plate to 120 ° C for 4 minutes to provide a photosensitive polyimide precursor film.
The polyimide precursor film was exposed through a mask having various patterns by an l-line stepper (NSR MOC) manufactured by Nikon Japan for 250 ms, dissolved in a 2.38% tetramethyl ammonium hydroxide aqueous solution at room temperature for 60 seconds (2 puddles) to remove the exposed
part, and washed with pure water for 30 seconds.
The resolution of the obtained film pattern was observed through an optical microscope, and the film thickness was measured by equipment manufactured by ST4000-DLX (K-MAC, Korea Materials & Analysis Corp). The results are shown in the following Table 1.
As the decrease of the film thickness affected by the development, and the resulting film thickness, it is preferable that the film thickness is less decreased during the development. In order to measure this, the pre-baked film was immersed in 2.38% tetramethyl ammonium hydroxide (TMAH) aqueous solution for different times and washed with water, so the change of film thickness was measured to calculate the residual film ratio (thickness after development / thickness before development, unit: %). The results are shown in the following Table 1.
The sensitivity and resolution were measured, and the results are shown in Table 1.
In order to measure the sensitivity, the optimal exposure time was determined when a 10 μ m L/S (line and space) pattern was formed in a line width of 1 to 1 , and the resolution was determined as the minimum pattern size at the optimal exposure time.
[Table 1]
In addition, the obtained patterns were cured in an electronic furnace under an oxygen concentration of IOOOppm or below at 120 ° C for 30 minutes and at a high temperature of 200 ° C or above for 30 minutes to provide a patterned films.
The change of film thickness after curing was measured by equipment
manufactured by ST4000-DLX (K-MAC, Korea Materials & Analysis Corp) as above.
The adherence to the substrate was determined by measuring the degree of separation from the substrate after heating the cured film at 121 ° C under an atmospheric pressure of 2 for a certain time in accordance with a cross-cut method in JISK-5400, and by measuring the time that the separation began.
The ring closure ratio stands for the degree in percent that polyamic acid is closed and transformed to "polyimide" or polyamic acid ester is closed and transformed to "polybenzoxazole." In order to measure the ring closure ratio, the cured film was peeled off and dissolved in a DMSO-d6 solvent to observe 1 H NMR and compared to 1 H NMR of a precursor that was not cured, and it compared to the integration value of -NH and -OH peaks shown at 9.5 to 11.0 ppm. The shrinkage ratio stands for the percentage of the differentiation between the film thickness before the baking and the film thickness after the baking. The film thickness was measured by equipment manufactured by ST4000-DLX (K-MAC, Korea Materials & Analysis Corp).
The results of measured ring closure ratio, film thickness, shrinkage ratio, and adherence are shown in the following Table 2.
[Table 2]
In Table 2, * means that the results are obtained after curing at 320° C/30 minutes in order to completely cure the obtained pattern.
As shown in Table 1 , it is understood that the photosensitive resin compositions according to Examples 1 to 5 had similar optical characteristics
such as sensitivity, residual film ratio, and resolution to those of photosensitive resin compositions according to Comparative Examples 1 to 3. However, in Table 2, it is shown that Examples 1 to 5 had high ring closure ratios when they were subjected to a curing process at a low temperature of 260 ° C, while Comparative Examples 1 to 3 had very low ring closure ratios. In other words, the photosensitive resin compositions according to Examples 1 to 5 could have comparative or superior photosensitivity to those of the photosensitive resin compositions according to Comparative Examples 1 to 3, and it is possible for them to be adapted to a surface protective layer and an interlayer insulating layer by curing the pattern at a lower temperature. In addition, since the compositions had higher adherence to the substrate than the cured film of polybenzoxazole according to Comparative Example 3, it is understood that they can provide a more stable surface protective layer and interlayer insulating layer. While this invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.
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