Photosensitive resin composition, method for manufacturing cured relief pattern, and semiconductor apparatus

Abstract

A photosensitive resin composition containing a resin and a compound each having a structure specified by the present specification provides a cured film having excellent adhesiveness to copper wiring.

1 . A negative-type photosensitive resin composition, comprising:
 (A) a polyimide precursor in the form of a polyamic acid, polyamic acid ester or polyamic acid salt represented by the following general formula (18):   
       
         
           
           
               
               
           
         
       
       {wherein, X 1  and X 2  respectively and independently represent a tetravalent organic group, Y 1  and Y 2  respectively and independently represent a divalent organic group, n1 and n2 respectively and independently represent an integer of 2 to 150, and R 1  and R 2  respectively and independently represent a hydrogen atom, saturated aliphatic group having 1 to 30 carbon atoms, aromatic group, monovalent organic group represented by the following general formula (2): 
       
         
           
           
               
               
           
         
       
       (wherein, R 3 , R 4  and R 5  respectively and independently represent a hydrogen atom or organic group having 1 to 3 carbon atoms, and m 1  represents an integer of 2 to 10), or monovalent ammonium ion represented by the following general formula (3): 
       
         
           
           
               
               
           
         
       
       (wherein, R 6 , R 7  and R 8  respectively and independently represent a hydrogen atom or organic group having 1 to 3 carbon atoms, and m 2  represents an integer of 2 to 10), provided that X 1  and X 2  are not the same and Y 1  and Y 2  are not the same};
 (B) a photosensitizer; and, 
 (C) a solvent. 
 
     
     
         2 . The negative-type photosensitive resin composition according to  claim 1 , wherein X 1  and X 2  in general formula (18) are at least one selected from the group consisting of a group represented by the following general formula (4): 
       
         
           
           
               
               
           
         
       
       {wherein, a1 represents an integer of 0 to 2, R 9  represents a hydrogen atom, fluorine atom or monovalent organic group having 1 to 10 carbon atoms, and in the case a plurality of R 9  are present, may be mutually the same or different}, a group represented by the following general formula (5): 
       
         
           
           
               
               
           
         
       
       {wherein, a2 and a3 respectively and independently represent an integer of 0 to 4, a4 and a5 respectively and independently represent an integer of 0 to 3, R 10  to R 13  respectively and independently represent a hydrogen atom, fluorine atom or monovalent organic group having 1 to 10 carbon atoms, and in the case a plurality of R 10  to R 13  are present, may mutually be the same or different}, a group represented by the following general formula (6): 
       
         
           
           
               
               
           
         
       
       {wherein, n2 represents an integer of 0 to 5, X n1  represents a single bond or divalent organic group, in the case a plurality of X n1  are present, may mutually be the same or different, X m1  represents a single bond or divalent organic group, at least one of X m1  and X n1  represents a single bond or an organic group selected from the group consisting of an oxycarbonyl group, oxycarbonylmethylene group, carbonylamino group, carbonyl group and sulfonyl group, a6 and a8 respectively and independently represent an integer of 0 to 3, a7 represents an integer of 0 to 4, R 14 , R 15  and R 16  respectively and independently represent a hydrogen atom, fluorine atom or monovalent organic group having 1 to 10 carbon atoms, and in the case a plurality of R 14 , R 15  and R 16  are present, may mutually be the same or different}, and a group represented by the following general formula (8): 
       
         
           
           
               
               
           
         
       
       {wherein, n4 represents an integer of 0 to 5, X m2  and X n3  respectively and independently represent an organic group having 1 to 10 carbon atoms that may contain a fluorine atom but does not contain a heteroatom other than fluorine, an oxygen atom or a sulfur atom, in the case of a plurality of X n3  are present, may be mutually the same or different, all and a13 respectively and independently represent an integer of 0 to 3, a12 represents an integer of 0 to 4, R 19 , R 20  and R 21  respectively and independently represent a hydrogen atom, fluorine atom or monovalent organic group having 1 to 10 carbon atoms, and in the case of a plurality of R 19 , R 20  and R 21  are present, may mutually be the same or different}. 
     
     
         3 . The negative-type photosensitive resin composition according to  claim 1 , wherein Y 1  and Y 2  in general formula (18) represent at least one selected from the group consisting of a group represented by the following general formula (7): 
       
         
           
           
               
               
           
         
       
       {wherein, n3 represents an integer of 1 to 5, Y n2  represents an organic group having 1 to 10 carbon atoms that may contain a fluorine atom but does not contain a heteroatom other than fluorine, an oxygen atom or a sulfur atom, in the case a plurality of Y n2  are present, may mutually be the same or different, a9 and a10 respectively and independently represent an integer of 0 to 4, R 17  and R 18  respectively and independently represent a hydrogen atom, fluorine atom or monovalent organic group having 1 to 10 carbon atoms, and in the case a plurality of R 17  and R 18  are present, may mutually be the same or different}, a group represented by the following general formula (9): 
       
         
           
           
               
               
           
         
       
       {wherein, n5 represents an integer of 0 to 5, Y n4  represents a single bond or a divalent organic group, in the case of a plurality of Y n4  are present, may be mutually the same or different, in the case n4 is 2 or more, at least one of Y n4  represents a single bond or an organic group selected from the group consisting of an oxycarbonyl group, oxycarbonylmethylene group, carbonylamino group, carbonyl group and sulfonyl group, a14 and a15 respectively and independently represent an integer of 0 to 4, R 22  and R 23  respectively and independently represent a hydrogen atom, fluorine atom or monovalent organic group having 1 to 10 carbon atoms, and in the case a plurality of R 22  and R 23  are present, may be mutually the same or different}, and a group represented by the following general formula (10): 
       
         
           
           
               
               
           
         
       
       {wherein, a16 to a19 respectively and independently represent an integer of 0 to 4, R 24  to R 27  respectively and independently represent a hydrogen atom, fluorine atom or monovalent organic group having 1 to 10 carbon atoms, and in the case a plurality of R 24  to R 27  are present, may mutually be the same or different}. 
     
     
         4 . The negative-type photosensitive resin composition according to  claim 2 , wherein at least one of X 1  and X 2  in general formula (18) is selected from the group consisting of those represented by general formulas (4), (5), (6) and (8), and at least one of Y 1  and Y 2  in general formula (18) is selected from the group consisting of those represented by the following general formulas (7), (9) and (10): 
       
         
           
           
               
               
           
         
       
       {wherein, n3 represents an integer of 1 to 5, Y n2  represents an organic group having 1 to 10 carbon atoms that may contain a fluorine atom but does not contain a heteroatom other than fluorine, an oxygen atom or a sulfur atom, in the case a plurality of Y n2  are present, may mutually be the same or different, a9 and a10 respectively and independently represent an integer of 0 to 4, R 17  and R 18  respectively and independently represent a hydrogen atom, fluorine atom or monovalent organic group having 1 to 10 carbon atoms, and in the case a plurality of R 17  and R 18  are present, may mutually be the same or different}, 
       
         
           
           
               
               
           
         
       
       {wherein, n5 represents an integer of 0 to 5, Y n4  represents a single bond or a divalent organic group, in the case of a plurality of Y n4  are present, may be mutually the same or different, in the case n4 is 2 or more, at least one of Y n4  represents a single bond or an organic group selected from the group consisting of an oxycarbonyl group, oxycarbonylmethylene group, carbonylamino group, carbonyl group and sulfonyl group, a14 and a15 respectively and independently represent an integer of 0 to 4, R 22  and R 23  respectively and independently represent a hydrogen atom, fluorine atom or monovalent organic group having 1 to 10 carbon atoms, and in the case a plurality of R 22  and R 23  are present, may be mutually the same or different}, and 
       
         
           
           
               
               
           
         
       
       {wherein, a16 to a19 respectively and independently represent an integer of 0 to 4, R 24  to R 27  respectively and independently represent a hydrogen atom, fluorine atom or monovalent organic group having 1 to 10 carbon atoms, and in the case a plurality of R 24  to R 27  are present, may mutually be the same or different}. 
     
     
         5 . The negative-type photosensitive resin composition according to  claim 2 , wherein, in general formula (18), at least one of X 1  and X 2  is represented by general formula (8) and at least one of Y 1  and Y2 is represented by the following general formula (7): 
       
         
           
           
               
               
           
         
       
       {wherein, n3 represents an integer of 1 to 5, Y n2  represents an organic group having 1 to 10 carbon atoms that may contain a fluorine atom but does not contain a heteroatom other than fluorine, an oxygen atom or a sulfur atom, in the case a plurality of Y n2  are present, may mutually be the same or different, a9 and a10 respectively and independently represent an integer of 0 to 4, R 17  and R 18  respectively and independently represent a hydrogen atom, fluorine atom or monovalent organic group having 1 to 10 carbon atoms, and in the case a plurality of R 17  and R 18  are present, may mutually be the same or different}. 
     
     
         6 . The negative-type photosensitive resin composition according to  claim 2 , wherein, in general formula (18), X 1  is represented by general formula (8) and Y 1  is represented by the following general formula (7): 
       
         
           
           
               
               
           
         
       
       {wherein, n3 represents an integer of 1 to 5, Y n2  represents an organic group having 1 to 10 carbon atoms that may contain a fluorine atom but does not contain a heteroatom other than fluorine, an oxygen atom or a sulfur atom, in the case a plurality of Y n2  are present, may mutually be the same or different, a9 and a10 respectively and independently represent an integer of 0 to 4, R 17  and R 18  respectively and independently represent a hydrogen atom, fluorine atom or monovalent organic group having 1 to 10 carbon atoms, and in the case a plurality of R 17  and R 18  are present, may mutually be the same or different}. 
     
     
         7 . The negative-type photosensitive resin composition according to  claim 1 , wherein the solvent (C) includes at least one selected from the group consisting of N-methyl-2-pyrrolidone, γ-butyrolactone, dimethylsulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoacetate, dimethyl succinate, dimethyl malonate, N,N-dimethylacetoacetamide, ε-caprolactone, and 1,3-dimethyl-2-imidazolidinone. 
     
     
         8 . The negative-type photosensitive resin composition according to  claim 7 , wherein the solvent (C) includes at least two selected from the group consisting of N-methyl-2-pyrrolidone, γ-butyrolactone, dimethylsulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoacetate, dimethyl succinate, dimethyl malonate, N,N-dimethylacetoacetamide, ε-caprolactone, and 1,3-dimethyl-2-imidazolidinone. 
     
     
         9 . The negative-type photosensitive resin composition according to  claim 8 , wherein the solvent (C) includes γ-butyrolactone and dimethylsulfoxide. 
     
     
         10 . A photosensitive resin composition containing a photosensitive polyimide precursor, wherein a focus margin of a rounded-out concave relief pattern is 8 μm or more, the rounded-out concave relief pattern being obtained by carrying out the following in order:
 spin-coating the resin composition onto a sputtered Cu wafer substrate; 
 obtaining a spin-coated film having a film thickness of 13 μm by heating the spin-coated wafer substrate on a hot plate for 270 seconds at 110° C.; 
 exposing a rounded-out concave pattern with a mask size of 8 μm by changing the focus from the surface of the film to the bottom of the film 2 μm at a time using the surface of the spin-coated film as a reference; 
 forming a relief pattern by developing the exposed wafer; and 
 heat-treating the developed wafer in a nitrogen atmosphere for 2 hours at 230° C. 
 
     
     
         11 . The photosensitive resin composition according to  claim 10 , wherein the focus margin is 12 μm or more. 
     
     
         12 . The photosensitive resin composition according to  claim 10 , wherein the cross-sectional angle of a cured product of the photosensitive polyimide precursor in the form of a cured relief pattern is 60° to 90°. 
     
     
         13 . The photosensitive resin composition according to  claim 10 , wherein the photosensitive polyimide precursor is a polyamic acid derivative having a radical-polymerizable substituent in a side chain thereof. 
     
     
         14 . The photosensitive resin composition according to  claim 10 , wherein the photosensitive polyimide precursor contains a structure represented by the following general formula (21): 
       
         
           
           
               
               
           
         
       
       {wherein, X 1a  represents a tetravalent organic group, Y 1a  represents a divalent organic group, n 1a  represents an integer of 2 to 150, and R 1a  and R 2a  respectively and independently represent a hydrogen atom, monovalent organic group represented by the following general formula (22): 
       
         
           
           
               
               
           
         
       
       (wherein, R 3a , R 4a  and R 5a  respectively and independently represent a hydrogen atom or organic group having 1 to 3 carbon atoms, and m 1a  represents an integer of 2 to 10), or a saturated aliphatic group having 1 to 4 carbon atoms, provided that R 1a  and R 2a  are not both simultaneously hydrogen atoms}. 
     
     
         15 . The photosensitive resin composition according to  claim 14 , wherein, in general formula (21), X 1a  represents at least one tetravalent organic group selected from group consisting of the following formulas (23) to (25): 
       
         
           
           
               
               
           
         
       
       and Y 1a  represents at least one divalent organic group selected from the group consisting of a group represented by the following general formula (26): 
       
         
           
           
               
               
           
         
       
       {wherein, R 6a  to R 9a  represent hydrogen atoms or monovalent aliphatic groups having 1 to 4 carbon atoms and may mutually be the same or different}, a group represented by the following formula (27): 
       
         
           
           
               
               
           
         
       
       and a group represented by the following formula (28): 
       
         
           
           
               
               
           
         
       
       {wherein, R 10a  and R 11a  respectively and independently represent a fluorine atom, trifluoromethyl group or methyl group}. 
     
     
         16 . The photosensitive resin composition according to  claim 10 , further containing a photopolymerization initiator. 
     
     
         17 . The photosensitive resin composition according to  claim 16 , wherein the photopolymerization initiator contains a component represented by the following general formula (29): 
       
         
           
           
               
               
           
         
       
       {wherein, Z represents a sulfur atom or oxygen atom, R 12a  represents a methyl group, phenyl group or divalent organic group, and R 13a  to R 15a  respectively and independently represent a hydrogen atom or monovalent organic group}. 
     
     
         18 . The photosensitive resin composition according to  claim 10 , further containing an inhibitor. 
     
     
         19 . The photosensitive resin composition according to  claim 18 , wherein the inhibitor is at least one selected from the group consisting of a hindered phenol-type inhibitor and nitroso-type inhibitor. 
     
     
         20 . A method for producing a cured relief pattern comprising:
 forming a photosensitive resin layer on a substrate by coating the photosensitive resin composition according to  claim 10  on the substrate;   exposing the photosensitive resin layer to light;   forming a relief pattern by developing the photosensitive resin layer after exposing to light; and   forming a cured relief pattern by heat-treating the relief pattern.   
     
     
         21 . The method according to  claim 20 , wherein the substrate comprises copper or copper alloy.