Novel Photosensitive Resin Compositions

Abstract

A positive-working photosensitive composition containing one or more polybenzoxazole precursor polymers, a diazonaphthoquinone photoactive compound which is the condensation product of a compound containing from 2 to about 9 aromatic hydroxyl groups with a 5-naphthoquinone diazide sulfonyl compound and a 4-naphthoquinone diazide sulfonyl compound, and at least one solvent, and the use of such compositions to form a relief pattern on a substrate.

1 . A positive photosensitive resin composition, comprising:
 (a) one or more polybenzoxazole precursor polymers having structure (II);   
     
       
         
         
             
             
         
       
     
     wherein Ar 1  is selected from the group consisting of a tetravalent aromatic group, a tetravalent heterocyclic group, and mixtures thereof; Ar 2  is selected from the group consisting of a divalent aromatic group, a divalent heterocyclic group, a divalent alicyclic group, and a divalent aliphatic group that optionally contains silicon; Ar 3  is selected from the group consisting of a divalent aromatic group, a divalent aliphatic group, a divalent heterocyclic group, and mixtures thereof; Ar 4  is selected from the group consisting of Ar 1 (OD) k   1 (OH) k   2  and Ar 2 ; x is from about 10 to about 1000; y is from 0 to about 900; D is selected from the group consisting of one of the following moieties: 
     
       
         
         
             
             
         
       
     
     in which R is selected from the group consisting of H, halogen, C 1 -C 4  alkyl group, C 1 -C 4  alkoxy group, cyclopentyl and cyclohexyl; k 1  is any positive value of up to about 0.5; and k 2  is any value from about 1.5 to about 2 with the proviso that (k 1 +k 2 )=2; and
 (b) a diazonaphthoquinone photoactive compound which is the condensation product of a compound containing from 2 to 9 aromatic hydroxyl groups with a 5-naphthoquinone diazide sulfonyl compound and a 4-naphthoquinone diazide sulfonyl compound. 
 
   
   
       2 . The composition of  claim 1 , wherein diazonaphthoquinone photoactive compound is selected from the group consisting of compounds of the following formulas: 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     in which at least one Q is moiety (IX), at least one Q is moiety (X), and each remainder Q is H, moieties (IX) and (X) being: 
     
       
         
         
             
             
         
       
     
   
   
       3 . The composition of  claim 2 , wherein the diazonaphthoquinone photoactive compound is selected from the group consisting of the compounds of formulas (VII a), (VII b), (VII e), (VII g), (VII h), (VII i), (VII l), (VII n), (VII o), and (VII p). 
   
   
       4 . The composition of  claim 2 , wherein the diazonaphthoquinone photoactive compound is the compound of formula (VII p). 
   
   
       5 . The composition of  claim 2 , wherein the molar ratio of moiety (IX) to moiety (X) is from about 20/80 to 80/20 and from about 2 mol % to about 34 mol % of Q is H. 
   
   
       6 . The composition of  claim 1 , wherein the diazonaphthoquinone photoactive compound has a solubility of at least about 18 wt % in gamma-butyrolactone at room temperature. 
   
   
       7 . The composition of  claim 1 , wherein Ar 1  is a moiety selected from the group consisting of: 
     
       
         
         
             
             
         
       
     
     in which X 1  is selected from the group consisting of —O—, —S—, —C(CF 3 ) 2 —, —CH 2 —, —SO 2 —, —NHCO— and —SiR 9   2 — and each R 9  is independently selected from the group consisting of a C 1 -C 7  linear or branched alkyl and a C 5 -C 8  cycloalkyl group. 
   
   
       8 . The composition of  claim 1 , wherein Ar 3  is a moiety selected from the group consisting of: 
     
       
         
         
             
             
         
       
     
     in which X 2  is selected from the group consisting of —O—, —S—, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —CH 2 —, —SO 2 —, and —NHCO—. 
   
   
       9 . The composition of  claim 1 , further comprising an adhesion promoter. 
   
   
       10 . The composition of  claim 9 , wherein the adhesion promoter is a compound of formula (XI): 
     
       
         
         
             
             
         
       
     
     in which each R 10  is independently selected from the group consisting of a C 1 -C 4  alkyl group and a C 5 -C 7  cycloalkyl group; each R 11  is independently selected from the group consisting of a C 1 -C 4  alkyl group, a C 1 -C 4  alkoxy group, a C 5 -C 7  cycloalkyl group and a C 5 -C 7  cycloalkoxy group; d is an integer from 0 to 3; n is an integer from 1 to 6; and R 12  is a moiety selected from the group consisting of: 
     
       
         
         
             
             
         
       
     
     in which each R 13  and R 14  are independently selected from the group consisting of a C 1 -C 4  alkyl group and a C 5 -C 7  cycloalkyl group, and R 15  is selected from the group consisting of a C 1 -C 4  alkyl group and a C 5 -C 7  cycloalkyl group. 
   
   
       11 . The composition of  claim 10 , wherein Ar 1  is a moiety derived from a reactant selected from the group consisting of 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropanel, 3,3′-dihydroxy-4,4′-diaminodiphenylether, 3,3′-dihydroxybenzidine, 4,6-diaminoresorcinol, and 2,2-bis(3-amino-4-hydroxyphenyl)propane and mixtures thereof; Ar 3  is a moiety derived from a reactant selected from the group consisting of 4,4′-diphenyletherdicarboxylic acid, terephthalic acid, isophthalic acid, isophthaloyl dichloride, phthaloyl dichloride, terephthaloyl dichloride, 4,4′-diphenyletherdicarboxylic acid dichloride, dimethylisophthalate, dimethylphthalate, dimethylterephthalate, diethylisophthalate, diethylphthalate, and diethylterephthalate and mixtures thereof. 
   
   
       12 . The composition of  claim 1 , further comprising an organic solvent. 
   
   
       13 . The composition of  claim 12 , wherein the organic solvent comprises N-methyl-2-pyrrolidone, gamma-butyrolactone, N,N-dimethylacetamide, dimethyl-2-piperidone, N,N-dimethylformamide, or a mixture thereof. 
   
   
       14 . The composition of  claim 1 , further comprising a dissolution inhibitor. 
   
   
       15 . The composition of  claim 14 , wherein the dissolution inhibitor comprises diphenylsilane diol. 
   
   
       16 . A process, comprising:
 (1) coating on a substrate a positive-working photosensitive composition, thereby forming a coated substrate, the composition comprising:   (a) one or more polybenzoxazole precursor polymers having structure (II);   
     
       
         
         
             
             
         
       
     
     wherein Ar 1  is selected from the group consisting of a tetravalent aromatic group, a tetravalent heterocyclic group, and mixtures thereof; Ar 2  is selected from the group consisting of a divalent aromatic group, a divalent heterocyclic group, a divalent alicyclic group, and a divalent aliphatic group that optionally contains silicon; Ar 3  is selected from the group consisting of a divalent aromatic group, a divalent aliphatic group, a divalent heterocyclic group, and mixtures thereof; Ar 4  is selected from the group consisting of Ar 1 (OD) k   1 (OH) k   2  and Ar 2 ; x is from about 10 to about 1000; y is from 0 to about 900; D is selected from the group consisting of one of the following moieties: 
     
       
         
         
             
             
         
       
     
     in which R is selected from the group consisting of H, halogen, C 1 -C 4  alkyl group, C 1 -C 4  alkoxy group, cyclopentyl and cyclohexyl; k 1  is any positive value of up to about 0.5; and k 2  is any value from about 1.5 to about 2 with the proviso that (k 1 +k 2 )=2; and
 (b) a diazonaphthoquinone photoactive compound which is the condensation product of a compound containing from 2 to 9 aromatic hydroxyl groups with a 5-naphthoquinone diazide sulfonyl compound and a 4-naphthoquinone diazide sulfonyl compound; 
 (2) prebaking the coated substrate; 
 (3) exposing the prebaked coated substrate to actinic radiation; 
 (4) developing the exposed coated substrate with an aqueous developer, thereby forming an uncured relief image on the coated substrate; and 
 (5) baking the developed coated substrate at an elevated temperature, thereby curing the relief image. 
 
   
   
       17 . A device, comprising
 a substrate, and   a relief pattern formed by the process of  claim 16 , the relief pattern being supported by the substrate.   
   
   
       18 . The device of  claim 17 , wherein the device is a memory device, a logic device, or a plating stencil. 
   
   
       19 . A positive photosensitive resin composition, comprising:
 (a) one or more polybenzoxazole precursor polymers having structure (II);   
     
       
         
         
             
             
         
       
     
     wherein Ar 1  is selected from the group consisting of a tetravalent aromatic group, a tetravalent heterocyclic group, and mixtures thereof; Ar 2  is selected from the group consisting of a divalent aromatic group, a divalent heterocyclic group, a divalent alicyclic group, and a divalent aliphatic group that optionally contains silicon; Ar 3  is selected from the group consisting of a divalent aromatic group, a divalent aliphatic group, a divalent heterocyclic group, and mixtures thereof; Ar 4  is selected from the group consisting of Ar 1 (OD) k   1 (OH) k   2  and Ar 2 ; x is from about 10 to about 1000; y is from 0 to about 900; D is selected from the group consisting of one of the following moieties: 
     
       
         
         
             
             
         
       
     
     in which R is selected from the group consisting of H, halogen, C 1 -C 4  alkyl group, C 1 -C 4  alkoxy group, cyclopentyl and cyclohexyl; k 1  is any positive value of up to about 0.5; and k 2  is any value from about 1.5 to about 2 with the proviso that (k 1 +k 2 )=2;
 (b) a diazonaphthoquinone photoactive compound of formula (VIII p): 
 
     
       
         
         
             
             
         
       
     
     in which one Q is moiety (IX) and the other Q is moiety (X), moieties (IX) and (X) being: 
     
       
         
         
             
             
         
       
       (c) an adhesion promoter. 
     
   
   
       20 . The composition of  claim 19 , wherein the adhesion promoter is a compound of formula (XI): 
     
       
         
         
             
             
         
       
     
     in which each R 10  is independently selected from the group consisting of a C 1 -C 4  alkyl group and a C 5 -C 7  cycloalkyl group; each R 11  is independently selected from the group consisting of a C 1 -C 4  alkyl group, a C 1 -C 4  alkoxy group, a C 5 -C 7  cycloalkyl group and a C 5 -C 7  cycloalkoxy group; d is an integer from 0 to 3; n is an integer from 1 to 6; and R 12  is a moiety selected from the group consisting of: 
     
       
         
         
             
             
         
       
     
     in which each R 13  and R 14  are independently selected from the group consisting of a C 1 -C 4  alkyl group and a C 5 -C 7  cycloalkyl group, and R 15  is selected from the group consisting of a C 1 -C 4  alkyl group and a C 5 -C 7  cycloalkyl group. 
   
   
       21 . The composition of  claim 19 , further comprising an organic solvent. 
   
   
       22 . The composition of  claim 21 , wherein the organic solvent comprises N-methyl-2-pyrrolidone, gamma-butyrolactone, N,N-dimethylacetamide, dimethyl-2-piperidone, N,N-dimethylformamide, or a mixture thereof. 
   
   
       23 . The composition of  claim 19 , wherein the molar ratio of moiety (IX) to moiety (X) is from about 20/80 to 80/20 and from about 2 mol % to about 34 mol % of Q is H. 
   
   
       24 . The composition of  claim 19 , wherein the diazonaphthoquinone photoactive compound has a solubility of at least about 18 wt % in gamma-butyrolactone at room temperature. 
   
   
       25 . The composition of  claim 19 , wherein Ar 1  is a moiety selected from the group consisting of: 
     
       
         
         
             
             
         
       
     
     in which X 1  is selected from the group consisting of —O—, —S—, —C(CF 3 ) 2 —, —CH 2 —, —SO 2 —, —NHCO— and —SiR 9   2 — and each R 9  is independently selected from the group consisting of a C 1 -C 7  linear or branched alkyl and a C 5 -C 8  cycloalkyl group. 
   
   
       26 . The composition of  claim 19 , wherein Ar 3  is a moiety selected from the group consisting of: 
     
       
         
         
             
             
         
       
     
     in which X 2  is selected from the group consisting of —O—, —S—, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —CH 2 —, —SO 2 —, and —NHCO—. 
   
   
       27 . The composition of  claim 19 , further comprising a dissolution inhibitor. 
   
   
       28 . The composition of  claim 27 , wherein the dissolution inhibitor comprises diphenylsilane diol. 
   
   
       29 . A process, comprising:
 (1) coating on a substrate a positive-working photosensitive composition, thereby forming a coated substrate, the composition comprising:   (a) one or more polybenzoxazole precursor polymers having structure (II);   
     
       
         
         
             
             
         
       
     
     wherein Ar 1  is selected from the group consisting of a tetravalent aromatic group, a tetravalent heterocyclic group, and mixtures thereof; Ar 2  is selected from the group consisting of a divalent aromatic group, a divalent heterocyclic group, a divalent alicyclic group, and a divalent aliphatic group that optionally contains silicon; Ar 3  is selected from the group consisting of a divalent aromatic group, a divalent aliphatic group, a divalent heterocyclic group, and mixtures thereof; Ar 4  is selected from the group consisting of Ar 1 (OD) k   1 (OH) k   2  and Ar 2 ; x is from about 10 to about 1000; y is from 0 to about 900; D is selected from the group consisting of one of the following moieties: 
     
       
         
         
             
             
         
       
     
     in which R is selected from the group consisting of H, halogen, C 1 -C 4  alkyl group, C 1 -C 4  alkoxy group, cyclopentyl and cyclohexyl; k 1  is any positive value of up to about 0.5; and k 2  is any value from about 1.5 to about 2 with the proviso that (k 1 +k 2 )=2;
 (b) a diazonaphthoquinone photoactive compound of formula (VII p): 
 
     
       
         
         
             
             
         
       
     
     in which one Q is moiety (IX) and the other Q is moiety (X), moieties (IX) and (X) being: 
     
       
         
         
             
             
         
       
       (c) an adhesion promoter; 
       (2) prebaking the coated substrate; 
       (3) exposing the prebaked coated substrate to actinic radiation; 
       (4) developing the exposed coated substrate with an aqueous developer, thereby forming an uncured relief image on the coated substrate; and 
       (5) baking the developed coated substrate at an elevated temperature, thereby curing the relief image. 
     
   
   
       30 . A device, comprising
 a substrate, and   a relief pattern formed by the process of  claim 29 , the relief pattern being supported by the substrate.   
   
   
       31 . The device of  claim 30 , wherein the device is a memory device, a logic device, or a plating stencil.