Siloxane polymer compositions and their use

Abstract

The present invention relates to siloxane polymer compositions. In particular, the invention relates to siloxane polymer compositions which have suitable properties for use in a lithographic fabrication processes. The invention also relates to synthesis, polymerization and cross-linking of such compositions.

1 . A method of producing a siloxane polymer composition, the method comprising:
 (a) admixing at least four different silane monomers and at least one bi-silane to a first solvent(s) to form a mixture,   with the proviso that at least one of the silane monomers or the bi-silane comprises an active group capable of achieving cross-linking to adjacent siloxane polymer chains of the siloxane polymer composition;   (b) subjecting the mixture to an acid treatment so that the silane monomers are at least partially hydrolysed, and the hydrolysed silane monomers, the silane monomers and the bi-silane are at least partially polymerized and cross-linked;   (c) optionally changing the first solvent to a second solvent; and   (d) subjecting the mixture to further cross-linking of the siloxane polymer to achieve a predetermined degree of cross-linking.   
     
     
         2 . The method according to  claim 1 , wherein the active group is selected from the group consisting of epoxy, vinyl, allyl and methacrylate group. 
     
     
         3 . The method according to  claim 1 , wherein 0.1 to 70% of the silane monomers comprise the active groups based on the molar portion of monomers. 
     
     
         4 . The method according to  claim 1 , wherein the first solvent(s) is/are selected from the group consisting of acetone, methyl ethyl ketone, methyl isobutyl ketone, and 1-methoxy-2-propanol. 
     
     
         5 . The method according to  claim 1 , comprising (c), wherein the second solvent(s) is/are selected from the group consisting of 1-methoxy-2-propanol, PGMEA, methyl ethyl ketone, PnP, methyl isobutyl ketone, and cyclopentatone. 
     
     
         6 . The method according to  claim 1 , wherein the at least four silane monomers are selected from molecules of formula I, II, III and IV:
   R 1   a SiX 4-a    I
     R 2   b SiX 4-b    II,
     R 3   c SiX 4-c    III, and
     R 4   d SiX 4-d    IV
   wherein   R 1 , R 2 , R 3  and R 4  are each independently selected from hydrogen and a group comprising linear and branched alkyl, cycloalkyl, alkenyl, alkynyl, (alk)acrylate, epoxy, allyl, vinyl and alkoxy and aryl having 1 to 6 rings, and wherein the group is substituted or unsubstituted;   X is a hydrolysable group or a hydrocarbon residue; and   a, b, c and d are each independently an integer 1 to 3.   
     
     
         7 . The method according to  claim 6 , wherein the alkoxy groups are selected from the group of radicals having the formula V:
   O—R 5    V
   wherein R 5  is a linear or branched alkyl group having 1 to 10 carbon atoms, and exhibiting one or two substituents selected from the group of halogen, hydroxyl, vinyl, epoxy and allyl.   
     
     
         8 . The method according to  claim 1 , wherein the at least one bi-silane is selected from molecules of formula VI:
   (R 6 ) 3 Si—Y—Si(R 7 ) 3 ,   VI
   wherein   R 6  and R 7  are each independently selected from hydrogen and a group consisting of linear or branched alkyl, cycloalkyl, alkenyl, alkynyl, (alk)acrylate, epoxy, allyl, vinyl, alkoxy and aryl having 1 to 6 rings, and wherein the group is substituted or unsubstituted; and   Y is a linking group selected from bivalent unsubstituted and substituted aliphatic and aromatic groups.   
     
     
         9 . The method according to  claim 1 , wherein the at least four silane monomers are selected from the group consisting of triethoxysilane, tetraethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, n-butyltriethoxysilane, methyldiethoxyvinylsilane, dimethyldiethoxysilane, phenyltrimethoxysilane, phenantrene-9-triethoxysilane, vinyltrimethoxysilane, 3-glysidoxypropyltrimethoxysilane, aminopropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, acryloxypropyltrimethoxysilane, allyltrimethoxysilane, epoxycyclohexylethyltrimethoxysilane, diphenylsilanediol, 1,2-bis(trimethoxysilyl)methane, 1,2-bis(trimethoxysilyl)ethane, glycidylmethacrylate, dimethyldimethoxysilane, 1-(2-(Trimethoxysilyl)ethyl)cyclohexane-3,4-epoxide, 1,2-bis(triethoxysilyl)ethane, 1H,1H,2H,2H-perfluorodecyltrimethoxysilane, trimethoxy (3,3,3-trifluoropropyl)silane, 1,2-bis(trimethoxysilyl)methane, 1,2-bis(triethoxysilyl)methane, 1,2-bis(trimethoxysilyl)ethane, 1,2-bis(triethoxysilyl)ethane, 1-(dimethoxymethylsilyl)-1-(trimethoxysilyl)methane, 1-(diethoxymethylsilyl)-1-(triethoxysilyl)methane, 1-(dimethoxymethylsilyl)-2-(trimethoxysilyl)ethane, 1-(diethoxymethylsilyl)-2-(triethoxysilyl)ethane, bis(dimethoxymethylsilyl)methane, bis(diethoxymethylsilyl)methane, 1,2-bis(dimethoxymethylsilyl)ethane, 1,2-bis(diethoxymethylsilyl)ethane, 1,2-bis(trimethoxysilyl)benzene, 1,2-bis(triethoxysilyl)benzene, 1,3-bis(trimethoxysilyl)benzene, 1,3-bis(triethoxysilyl)benzene, 1,4-bis(trimethoxysilyl)benzene, 1,4-bis(triethoxysilyl)benzene, and combinations thereof, in particular methyltriethoxysilane, phenyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, diphenylsilanediol, and glycidoxypropyltrimethoxysilane. 
     
     
         10 . The method according to  claim 1 , wherein the at least one bi-silane is selected from the group consisting of 1,2-bis(triethoxysilyl)ethane; bis(trimethoxysilyl)methane; 4,4′-Bis(triethoxysilyl)-1,1′-biphenyl; 1,4-Bis(triethoxysilyl)benzene; and 1,3-Bis(triethoxysilyl)benzene. 
     
     
         11 . The method according to  claim 1 , the method further comprising
 (e) admixing with one more substances selected from the group consisting of photoacid initiators and UV sensitizers.   
     
     
         12 . The method according to  claim 1 , further comprising adding a UV initiator in a sufficient amount to initiate cross-linking of the siloxane polymer to provide a cured polymer. 
     
     
         13 . The method according to  claim 1 , the method further comprising admixing with nano- and or/microparticles. 
     
     
         14 . The method according to  claim 13 , wherein the nano and/or microparticles are selected from the group consisting of light scattering pigments, organic and inorganic phosphors, oxides, quantum dots and metals. 
     
     
         15 . A siloxane polymer composition obtained by the method of  claim 1 . 
     
     
         16 . A display or a semiconductor device comprising the siloxane polymer composition according to  claim 15 . 
     
     
         17 . A method for covering a substrate, the method comprising:
 depositing the siloxane polymer composition according to  claim 15  on a substrate, and   optionally curing the deposited siloxane polymer composition.   
     
     
         18 . The method according to  claim 17 , wherein the deposited siloxane polymer composition forms a film on the substrate, and wherein the solvent is evaporated and the film dried. 
     
     
         19 . The method according to  claim 17 , further comprising exposing the siloxane polymer composition to UV light. 
     
     
         20 . The method according to  claim 17 , further comprising developing the siloxane polymer composition. 
     
     
         21 . The method according to  claim 20 , wherein the developing comprises treatment with a basic solution. 
     
     
         22 . The method according to  claim 17 , further comprising curing the siloxane polymer film. 
     
     
         23 . The method according to  claim 20 , wherein the developing is carried out after a pre-curing step and before a final curing step. 
     
     
         24 . The method according to  claim 17 , wherein the curing is performed by heating. 
     
     
         25 . The method according to  claim 17 , wherein the substrate is a material comprising glass, quartz, silicon, silicon nitride, polymers, metals, plastics, or a mixture thereof. 
     
     
         26 . A composition comprising:
 at least four different silane monomers,   at least one bi-silane, wherein at least one of the silane monomers or the bi-silane comprises an active group capable of achieving cross-linking upon a thermal or radiation initiation, and   a solvent.   
     
     
         27 . The composition according to  claim 26 , further comprising an UV sensitizer. 
     
     
         28 . The composition according to  claim 26 , wherein:
 the at least four silane monomers are selected from the group consisting of methyltriethoxysilane, phenyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, diphenylsilanediol, and glycidoxypropyltrimethoxysilane, and   the at least one bis-silane is selected from the group consisting of 1,2-bis(triethoxysilyl)ethane and bis(trimethoxysilyl)methane.