Fluorinated photoresist with integrated sensitizer

Abstract

A method of patterning a device comprises providing on a device substrate a layer of a fluorinated photopolymer comprising at least three distinct repeating units including a first repeating unit having a fluorine-containing group, a second repeating unit having an acid- or alcohol-forming precursor group, and a third repeating unit having a sensitizing dye. The photopolymer has a total fluorine content in a range of 15 to 60% by weight. The photopolymer layer is exposed to patterned light and contacted with a developing agent to remove a portion of exposed photopolymer layer in accordance with the patterned light, thereby forming a developed structure having a first pattern of photopolymer covering the substrate and a complementary second pattern of uncovered substrate corresponding to the removed portion of photopolymer. The developing agent comprises at least 50% by volume of a fluorinated solvent.

1 . A composition comprising:
 a fluorinated solvent; and   a fluorinated photopolymer comprising at least three distinct repeating units, including a first repeating unit having a fluorine-containing group, a second repeating unit having an acid- or alcohol-forming precursor group, and a third repeating unit having a sensitizing dye, wherein the photopolymer has a total fluorine content in a range of 15 to 60% by weight and wherein the fluorinated third monomer is provided in a range of 1 to 20% by weight relative to the photopolymer.   
     
     
         2 . The composition of  claim 1  wherein the third monomer has one or more fluorine atoms. 
     
     
         3 . The composition of  claim 1  wherein the third monomer has no fluorine atoms and is provided in a range of 1 to 10% by weight relative to the photopolymer. 
     
     
         4 . The composition of  claim 1  further comprising a photoacid generator provided in a range of 0.1 to 6% by weight relative to the copolymer. 
     
     
         5 . The composition of  claim 4  wherein the photoacid generator is fluorinated and non-ionic. 
     
     
         6 . The composition of  claim 1  wherein the fluorinated solvent is a hydrofluoroether. 
     
     
         7 . The composition of  claim 1  wherein the sensitizing dye is a coumarin-based sensitizing dye. 
     
     
         8 . The composition of  claim 7  wherein the fluorinated solvent is a hydrofluoroether and the fluorinated photopolymer is formed from a first monomer having a fluorine-containing group, a second monomer having an acid- or alcohol forming precursor group, and a third monomer having a structure according to formula (3): 
       
         
           
           
               
               
           
         
         wherein at least one of substituents R 1  through R 6  is a polymerizable group and the remaining substituents independently represent a hydrogen atom, a halogen atom, a cyano group, or a substituted or unsubstituted alkyl, alkoxy, alkylthio, aryl, aryloxy, amino, alkanoate, benzoate, alkyl ester, aryl ester, alkanone, alkyl sulfone, aryl sulfone or monovalent heterocyclic group. 
       
     
     
         9 . A method of patterning a device comprising:
 providing on a device substrate a layer of a fluorinated photopolymer comprising at least three distinct repeating units including a first repeating unit having a fluorine-containing group, a second repeating unit having an acid- or alcohol-forming precursor group, and a third repeating unit having sensitizing dye, wherein the photopolymer has a total fluorine content in a range of 15 to 60% by weight and wherein the fluorinated third monomer is provided in a range of 1 to 20% by weight relative to the photopolymer.   exposing the photopolymer layer to patterned light to form an exposed photopolymer layer;   contacting the exposed photopolymer layer with a developing agent to remove a portion of the exposed photopolymer layer in accordance with the patterned light, thereby forming a developed structure having a first pattern of photopolymer covering the substrate and a complementary second pattern of uncovered substrate corresponding to the removed portion of photopolymer, the developing agent comprising at least 50% by volume of a fluorinated solvent.   
     
     
         10 . The method of  claim 9  wherein the fluorinated solvent is a hydrofluoroether. 
     
     
         11 . The method of  claim 9  wherein the photopolymer has a total fluorine content in a range of 30 to 60% by weight. 
     
     
         12 . The method of  claim 9  wherein the device substrate comprises a support and a layer of active organic material, and wherein the fluorinated photopolymer layer is in contact with the layer of active organic material. 
     
     
         13 . The method of  claim 9  further including:
 treating the developed structure to form a treated structure; and 
 contacting the treated structure with a stripping agent to remove the first pattern of photopolymer. 
 
     
     
         14 . The method of  claim 13  wherein the substrate comprises a support and a layer of active organic material, and wherein the photopolymer layer is in contact with the layer of active organic material. 
     
     
         15 . The method of  claim 14  wherein the treating includes chemical or physical etching of the active organic material in the second pattern of uncovered substrate, thereby forming a patterned layer of active organic material corresponding to the first pattern. 
     
     
         16 . The method of  claim 13  wherein the treating includes providing a layer of active organic material over both the first pattern of photopolymer and the second pattern of uncovered substrate, wherein the removal of the first pattern of photopolymer further removes active organic material formed over the first pattern of photopolymer, thereby forming a patterned layer of active organic material corresponding to the second pattern. 
     
     
         17 . The method of  claim 9  wherein the sensitizing dye is a coumarin-based sensitizing dye. 
     
     
         18 . The method of  claim 1  wherein the third monomer has one or more fluorine atoms. 
     
     
         19 . The composition of  claim 1  wherein the third monomer has no fluorine atoms and is provided in a range of 1 to 10% by weight relative to the photopolymer.