Crosslinked polymeric dielectric materials and methods of manufacturing and use thereof

Abstract

Solution-processable dielectric materials are provided, along with precursor compositions and processes for preparing the same. Composites and electronic devices including the dielectric materials also are provided.

1 . A crosslinked polymeric material comprising a thermally cured product of a precursor composition, the precursor composition comprising at least one of (i) a polymeric component and a crosslinker component, the crosslinker component comprising a thermally curable crosslinker having the formula:
   (X) 3-m (Y) m Si-Z-Si(Y) m (X) 3-m ,   
       and (ii) a polymeric crosslinker comprising a pendant group, the pendant group comprising a thermally curable crosslinking moiety having the formula:
   -Q-Si(Y) m (X) 3-m , 
 wherein:
 m, at each occurrence, is independently selected from 0, 1, and 2; 
 X, at each occurrence, is independently selected from a halogen, —NR 1 R 2 , —OR 3 , and —OC(O)R 3 ; 
 Y, at each occurrence, is independently selected from H, a C 1-6  alkyl group, and a C 1-6  haloalkyl group; 
 Z is Q-W-Q; and 
 Q, at each occurrence, is independently selected from -L-, —O—, —O-L-, -L-O—, —NR 4 —, —NR 4 -L-, -L-NR 4 —, and a covalent bond;
 wherein: 
 L, at each occurrence, is independently a divalent C 1-10  alkyl group or a divalent C 1-10  haloalkyl group, each of which is optionally substituted with 1-4 R 4  groups; 
 W is selected from —SiXX—, —SiXY—, —SiYY—, —SiXX—O—, —O—SiXX—, —SiXY—O—, —O—SiXY—, —SiYY—O—, —O—SiYY—, —O—{[(CR 4   2 ) t —O] p —[(CR 5   2 ) t —O] q }—, a divalent C 6-14  aryl group, a divalent 5-14 membered heteroaryl group, and a covalent bond, wherein each of the divalent C 6-14  aryl group and the divalent 5-14 membered heteroaryl group is optionally substituted with 1-4 R 4  groups; 
 R 1  and R 2  are independently selected from H, a C 1-6  alkyl group, a C 6-14  aryl group, a 5-14 membered heteroaryl group, a —C 1-6  alkyl-C 6-14  aryl group, and a —C 1-6  alkyl-5-14 membered heteroaryl group; 
 R 3  is selected from H, a C 1-6  alkyl group, a C 1-6  haloalkyl group, a C 2-6  alkenyl group, a C 2-6  alkynyl group, a C 6-14  aryl group, a 5-14 membered heteroaryl group, a —C 1-6  alkyl-C 6-14  aryl group, and a —C 1-6  alkyl-5-14 membered heteroaryl group; 
 R 4  and R 5 , at each occurrence, are independently selected from H, a halogen, a C 1-6  alkyl group, a C 1-6  haloalkyl group, a C 6-14  aryl group, a 5-14 membered heteroaryl group, a —C 1-6  alkyl-C 6-14  aryl group, a —C 1-6  alkyl-5-14 membered heteroaryl group, and -Q-Si(Y) m (X) 3-m ; 
 t, at each occurrence, is independently 1, 2, 3, 4, 5 or 6; 
 p is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18 or 19; and 
 q is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20, provided that p+q≦20; and 
 
 
 
       provided that Z is not —O—, a divalent C 1-20  alkyl group, or a covalent bond. 
     
     
         2 . The crosslinked polymeric material of  claim 1 , wherein the polymeric component comprises one or more polymers selected from a polyalkylene, a substituted polyalkylene, a siloxane polymer, and a copolymer thereof. 
     
     
         3 . The crosslinked polymeric material of  claim 1 , wherein the polymeric component comprises one or more polymers selected from polyethylene, polypropylene, polyvinylalcohol, polystyrene, a ring-functionalized derivative of polystyrene, polyacrylate, a siloxane polymer, and copolymers thereof. 
     
     
         4 . The crosslinked polymeric material of  claim 1 , wherein Q, at each occurrence, is independently selected from —O—, —CH 2 ) t —, —(CF 2 ) t —, and a covalent bond; and W is selected from —O—[(CH 2 ) 2 —O] t —, —O—[(CF 2 ) 2 —O] t —, a divalent phenyl group, and a covalent bond; wherein t is as defined in  claim 1 . 
     
     
         5 . The crosslinked polymeric material of  claim 1 , wherein X, at each occurrence, is independently selected from Cl, —OCH 3 , —OCH 2 CH 3 , —N(CH 3 ) 2 —, —N(CH 2 CH 3 ) 2 —, —OC(O)CH 3 , and —OC(O)CH 2 CH 3 ; and Y, at each occurrence, is independently selected from H, CF 3 , a methyl group, and an ethyl group. 
     
     
         6 . The crosslinked polymeric material of  claim 1 , wherein the crosslinker component comprises a crosslinker selected from [CH 3 C(O)O] 3 Si—(CH 2 ) 3 —O—(CH 2 ) 2 —O—(CH 2 ) 3 —Si[CH 3 C(O)O] 3 , 
       Cl 3 Si—(CH 2 ) 3 —O—(CH 2 ) 2 —O—(CH 2 ) 3 —SiCl 3 , (CH 3 O) 3 Si—(CH 2 ) 2 -phenyl-(CH 2 ) 2 —Si(OCH 3 ) 3 , Cl 3 Si—(CH 2 ) 2 —(CF 2 ) 2 —(CH 2 ) 2 —SiCl 3 , and [CH 3 C(O)O] 3 Si—CH 2 ) 2 (CF 2 ) 2 (CH 2 ) 2 —Si[CH 3 C(O)O] 3 . 
     
     
         7 . The crosslinked polymeric material of  claim 1 , wherein the polymeric crosslinker has the formula: 
       
         
           
           
               
               
           
         
       
       wherein:
 R 6 , at each occurrence, is independently H, a halogen, or a C 1-6  alkyl group; 
 R 7  is selected from H, OH, a halogen, C(O)O—R 3 , a C 1-6  alkyl group, a C 1-6  haloalkyl group, a C 6-14  aryl group, a 5-14 membered heteroaryl group, a 3-14 membered cycloheteroalkyl group, a —C 1-6  alkyl-C 6-14  aryl group, a —C 1-6  alkyl-5-14 membered heteroaryl group, and a —C 1-6  alkyl-3-14 membered cycloheteroalkyl group, wherein each of the C 6-14  aryl groups, the 5-14 membered heteroaryl groups, and the 3-14 membered cycloheteroalkyl groups is optionally substituted with 1-5 substituents independently selected from a halogen, an oxo group, OH, CN, NO 2 , C(O)O—C 1-6  alkyl, a C 1-6  alkyl group, a C 1-6  alkoxy group, and a C 1-6  haloalkyl group; 
 R 8  is selected from —O—, —C(O)O—, a divalent C 1-6  alkyl group, and a divalent phenyl group; 
 x and y are independently a real number, wherein 0<x<1, 0<y<1, and x+y=1; and 
 Q, X, Y and m are as defined in  claim 1 . 
 
     
     
         8 . The crosslinked polymeric material of  claim 1 , wherein the precursor composition further comprises at least one of (iii) a crosslinker component comprising a photochemically curable crosslinker and (iv) a photochemically curable polymeric crosslinker. 
     
     
         9 . A dielectric material comprising the crosslinked polymeric material of  claim 1 . 
     
     
         10 . The dielectric material of  claim 9  comprising a plurality of metal oxide particles, the metal oxide particles comprising a metal component selected from a Group I metal, a Group II metal, a Group III metal, a Group IV metal, a transition metal, and combinations thereof. 
     
     
         11 . The dielectric material of  claim 9  having a thickness of less than about 50 nm. 
     
     
         12 . A thin film transistor comprising the dielectric material of  claim 9  and an organic semiconductor material. 
     
     
         13 . A thin film transistor comprising the dielectric material of  claim 9  and an inorganic semiconductor material. 
     
     
         14 . A method for preparing a dielectric material, the method comprising applying a precursor composition onto a substrate and curing thermally the precursor composition to provide a dielectric material, the precursor composition comprising at least one of (i) a polymeric component and a crosslinker component and (ii) a polymeric crosslinker dissolved in one or more solvents, wherein the crosslinker component comprises a thermally curable crosslinker having the formula:
   (X) 3-m (Y) m Si-Z-Si(Y) m (X) 3-m ,   
       and the polymeric crosslinker comprises a pendant group comprising a thermally curable crosslinking moiety having the formula:
   -Q-Si(Y) m (X) 3-m , 
 wherein:
 m, at each occurrence, is independently selected from 0, 1, and 2; 
 X, at each occurrence, is independently selected from a halogen, —NR 1 R 2 , —OR 3 , and —OC(O)R 3 ; 
 Y, at each occurrence, is independently selected from H, a C 1-6  alkyl group, and a C 1-6  haloalkyl group; 
 Z is Q-W-Q; and 
 Q, at each occurrence, is independently selected from -L-, —O—, —O-L-, -L-O—, —NR 4 —, —NR 4 -L-, -L-NR 4 —, and a covalent bond;
 wherein: 
 L, at each occurrence, is independently a divalent C 1-10  alkyl group or a divalent C 1-10  haloalkyl group, each of which is optionally substituted with 1-4 R 4  groups; 
 W is selected from —SiXX—, —SiXY—, —SiYY—, —SiXX—O—, —O—SiXX—, —SiXY—O—, —O—SiXY—, —SiYY—O—, —O—SiYY—, —O—{[(CR 4   2 ) t —O] p —[(CR 5   2 ) t —O] q }—, a divalent C 6-14  aryl group, a divalent 5-14 membered heteroaryl group, and a covalent bond, wherein each of the divalent C 6-14  aryl group and the divalent 5-14 membered heteroaryl group is optionally substituted with 1-4 R 4  groups; 
 R 1  and R 2  are independently selected from H, a C 1-6  alkyl group, a C 6-14  aryl group, a 5-14 membered heteroaryl group, a —C 1-6  alkyl-C 6-14  aryl group, and a —C 1-6  alkyl-5-14 membered heteroaryl group; 
 R 3  is selected from H, a C 1-6  alkyl group, a C 1-6  haloalkyl group, a C 2-6  alkenyl group, a C 2-6  alkynyl group, a C 6-14  aryl group, a 5-14 membered heteroaryl group, a —C 1-6  alkyl-C 6-14  aryl group, and a —C 1-6  alkyl-5-14 membered heteroaryl group; 
 R 4  and R 5 , at each occurrence, are independently selected from H, a halogen, a C 1-6  alkyl group, a C 1-6  haloalkyl group, a C 6-14  aryl group, a 5-14 membered heteroaryl group, a —C 1-6  alkyl-C 6-14  aryl group, 
 
 a —C 1-6  alkyl-5-14 membered heteroaryl group, and -Q-Si(Y) m (X) 3-m ;
 t, at each occurrence, is independently 1, 2, 3, 4, 5 or 6; 
 p is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18 or 19; and 
 
 
 q is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20, provided that p+q≦20; and 
 
       provided that Z is not —O—, a divalent C 1-20  alkyl group, or a covalent bond. 
     
     
         15 . The method of  claim 14 , wherein the one or more solvents are selected from ethyl acetate, dioxane, bis(2-methoxyethyl)ether, and tetrahydrofuran. 
     
     
         16 . The method of  claim 14  comprising spin-coating the precursor composition onto the substrate. 
     
     
         17 . The method of  claim 14  comprising printing the precursor composition onto the substrate. 
     
     
         18 . The method of  claim 14  comprising heating the precursor composition at a temperature within a range of about 70° C. and about 150° C. in a high humidity atmosphere. 
     
     
         19 . The method of  claim 14 , wherein the precursor composition further comprises at least one of (iii) a crosslinker component comprising a photochemically curable crosslinker and (iv) a photochemically curable polymeric crosslinker, the method further comprising curing photochemically the precursor composition. 
     
     
         20 . The method of  claim 19  comprising exposing the precursor composition to ultraviolet light.