Methods for producing a dielectric, dielectric having self-generating pores, monomer for porous dielectrics, process for preparing poly-o-hydroxyamides, process for preparing ploybenzoxazoles, and processes for producing an electronic component

Abstract

Poly-o-hydroxyamides include binaphthyl substituents as repeating units. The poly-o-hydroxyamides can be cyclized to give the polybenzoxazole by heating. Pore formation occurs, so that a dielectric having a very low dielectric constant k of less than 2.5 is obtained.

1 . A method for producing a dielectric, which comprises: using a poly-o-hydroxyamides of Formula I  
     
       
         
         
             
             
         
       
     
     where 
 E 1  and E 2 , in each case independently, are substituents selected from the group consisting of hydrogen, a hydroxyl group, a saturated monovalent hydrocarbon, and an unsaturated monovalent hydrocarbon;  
 Y 1  and Y 2 , in each case independently for each position, are a divalent hydrocarbon;  
 Z 1 , in each case independently for each position, is a structural unit having a formula selected from the group consisting of Formula IIa and IIb  
                     
 the bond (-*) and the substituent -GR 5  being disposed in the ortho position relative to one another,  
                     
 Z 2 , in each case independently for each position, is a tetravalent hydrocarbon composed of groups linked to one another and selected from the group consisting of alkyl and aryl groups;  
 R 1 , R 2 , R 3 , and R 4 , in each case independently, are substituents selected from the group consisting of H, —C 6 H 5 , —(CH 2 ) n —CH 3 , -G-(CH 2 ) n —CH 3 , —CH((CH 2 ) n CH 3 ) 2 , —CH(CH 3 ) 2 , -G-CH(CH 3 ) 2 , —C(CH 3 ) 3 , -G-C(CH 3 ) 3 , —(CF 2 ) n —CF 3 , -G-(CF 2 ) n —CF 3 , —CF((CF 2 ) n CF 3 ) 2 , —CF(CF 3 ) 2 , —C(CF 3 ) 3 , —N(CH 3 ) 2 , —N(CF 3 ) 2 ,  
                     
 R 5 , in each case independently, is a substituent selected from the group consisting of H, —CO(CH 2 ) n —CH 3 , —COO—(CH 2 ) n —CH 3 , —(CH 2 ) n —CH 3 , —CH((CH 2 ) n CH 3 ) 2 , —CH(CH 3 ) 2 , —C(CH 3 ) 3 , —(CF 2 ) n —CF 3 , —CF((CF 2 ) n CF 3 ) 2 , —CF(CF 3 ) 2 , —C(CF 3 ) 3 , —(CH 2 ) n —C 6 H 5 , —COO—(CH 2 ) n —C 6 H 5 ;  
 G is a heteroatom selected from the group consisting of oxygen and sulfur;  
 a is an integer from 0 to 1;  
 b has a value from 1 to 200;  
 c has a value from 0 to 200;  
 d is an integer from 0 to 1;  
 n is an integer from 0 to 5;  
 R 6  is a divalent substituent selected from the group consisting of:  
                     
 R 7  is a substituent selected from the group consisting of an alkyl group having from 1 to 10 carbon atoms and an aryl group having from 5 to 22 carbon atoms; and  
 e is an integer from 1 to 10.  
 
   
   
       2 . The method according to  claim 1 , wherein, in E 1  and E 2 , the saturated monovalent hydrocarbon contains a heteroatom.  
   
   
       3 . The method according to  claim 1 , wherein, in E 1  and E 2 , the unsaturated monovalent hydrocarbon contains a heteroatom.  
   
   
       4 . The method according to  claim 1 , wherein at least one of the Y 1  substituents has a heteroatom.  
   
   
       5 . The method according to  claim 1 , wherein at least one of the Y 2  substituents has a heteroatom.  
   
   
       6 . The method according to  claim 1 , wherein, in Z 2,  one of the groups has a heteroatom.  
   
   
       7 . A monomer for the preparation of a poly-o-hydroxyamide usable in dielectrics, comprising a backbone having a formula selected from the group consisting of Formula IVa and IV  
     
       
         
         
             
             
         
       
     
     where 
 R 1 , R 2 , R 3 , and R 4 , in each case independently, are selected from the group of substituents selected from the group consisting of H, —C 6 H 5 , —(CH 2 ) n —CH 3 , -G-(CH 2 ) n —CH 3 , —CH((CH 2 ) n CH 3 ) 2 , —CH(CH 3 ) 2 , -G-CH(CH 3 ) 2 , —C(CH 3 ) 3 , -G-C(CH 3 ) 3 , —(CF 2 ) n —CF 3 , -G-(CF 2 ) n —CF 3 , —CF((CF 2 ) n CF 3 ) 2 , —CF(CF 3 ) 2 , —C(CF 3 ) 3 , —N(CH 3 ) 2 , —N(CF 3 ) 2 ,  
                     
 R 5 , in each case independently, is a substituent selected from the group consisting of H, —CO(CH 2 ) n —CH 3 , —COO—(CH 2 ) n —CH 3 , —(CH 2 ) n —CH 3 , —CH((CH 2 ) n CH 3 ) 2 , —CH(CH 3 ) 2 , —C(CH 3 ) 3 , —(CF 2 ) n —CF 3 , —CF((CF 2 ) n CF 3 ) 2 , —CF(CF 3 ) 2 , —C(CF 3 ) 3 , —(CH 2 ) n —C 6 H 5 , —COO—(CH 2 ) n —C 6 H 5 ; and  
 G is a heteroatom selected from the group consisting of oxygen and sulfur.  
 
   
   
       8 . A process for preparing poly-o-hydroxyamides, which comprises: 
 reacting the monomer according to  claim 7  with a dicarboxylic acid having a formula selected from the group consisting of Formulae Va and Vb                          where    L is a substituent selected from the group consisting of a hydroxyl group and an activating group; and    Y 1  and Y 2 , in each case independently for each position, are a divalent hydrocarbon.    
   
   
       9 . A process for preparing poly-o-hydroxyamides, which comprises: 
 reacting the monomer according to  claim 7  with an activated dicarboxylic acid derivative having a formula selected from the group consisting of Formulae Va and Vb                          where    L is a substituent selected from the group consisting of a hydroxyl group and an activating group; and    Y 1  and Y 2 , in each case independently for each position, are a divalent hydrocarbon.    
   
   
       10 . The process according to  claim 8 , which further comprises carrying out the reacting step with a base.  
   
   
       11 . The process according to  claim 9 , which further comprises carrying out the reacting step with a base.  
   
   
       12 . A process for preparing polybenzoxazoles having a Formula III  
     
       
         
         
             
             
         
       
     
     where 
 Z 1  has a formula selected from the group consisting of  
                     
 E 1  and E 2 , in each case independently, are substituents selected from the group consisting of hydrogen, a hydroxyl group, a saturated monovalent hydrocarbon, and an unsaturated monovalent hydrocarbon;  
 Y 1  and Y 2 , in each case independently for each position, are a divalent hydrocarbon;  
 Z 2,  in each case independently for each position, is a tetravalent hydrocarbon composed of groups linked to one another and selected from the group consisting of alkyl and aryl groups;  
 R 1 , R 2 , R 3 , and R 4 , in each case independently, are substituents selected from the group consisting of H, —C 6 H 5 , —(CH 2 ) n —CH 3 , -G-(CH 2 ) n —CH 3 , —CH((CH 2 ) n CH 3 ) 2 , —CH (CH 3 ) 2 , -G-CH(CH 3 ) 2 , —C(CH 3 ) 3 , -G-C(CH 3 ) 3 , —(CF 2 ) n —CF 3 , -G-(CF 2 ) n —CF 3 , —CF((CF 2 ) n CF 3 ) 2 , —CF(CF 3 ) 2 , —C(CF 3 ) 3 , —N(CH 3 ) 2 , —N(CF 3 ) 2 ,  
                     
 R 5 , in each case independently, is a substituent selected from the group consisting of H, —CO(CH 2 ) n —CH 3 , —COO—(CH 2 ) n —CH 3 , —(CH 2 ) n —CH 3 , —CH((CH 2 ) n CH 3 ) 2 , —CH(CH 3 ) 2 , —C(CH 3 ) 3 , —(CF 2 ) n —CF 3 , —CF((CF 2 ) n CF 3 ) 2 , —CF(CF 3 ) 2 , —C(CF 3 ) 3 , —(CH 2 ) n —C 6 H 5 , —COO—(CH 2 ) n —C 6 H 5 ;  
 G is a heteroatom selected from the group consisting of oxygen and sulfur;  
 a is an integer from 0 to 1;  
 b has a value from 1 to 200;  
 c has a value from 0 to 200; and  
 d is an integer from 0 to 1;  
 the method which comprises:  
 heating poly-o-hydroxyamides having a Formula I  
                     
 where  
 E 1  and E 2 , in each case independently, are substituents selected from the group consisting of hydrogen, a hydroxyl group, a saturated monovalent hydrocarbon, and an unsaturated monovalent hydrocarbon;  
 Y 1  and Y 2 , in each case independently for each position, are a divalent hydrocarbon;  
 Z 1 , in each case independently for each position, is a structural unit having a formula selected from the group consisting of Formula IIa and IIb  
                     
 in which the bond (-*) and the substituent -GR 5  are disposed in the ortho position relative to one another,  
                     
 Z 2,  in each case independently for each position, is a tetravalent hydrocarbon composed of groups linked to one another and selected from the group consisting of alkyl and aryl groups;  
 R 1 , R 2 , R 3 , and R 4 , in each case independently, are substituents selected from the group consisting of H, —C 6 H 5 , —(CH 2 ) n —CH 3 , -G-(CH 2 ) n —CH 3 , —CH((CH 2 ) n CH 3 ) 2 , —CH(CH 3 ) 2 , -G-CH(CH 3 ) 2 , —C(CH 3 ) 3 , -G-C(CH 3 ) 3 , —(CF 2 ) n —CF 3 , -G-(CF 2 ) n —CF 3 , —CF((CF 2 ) n CF 3 ) 2 , —CF(CF 3 ) 2 , —C(CF 3 ) 3 , —N(CH 3 ) 2 , —N(CF 3 ) 2 ,  
                     
 R 5 , in each case independently, is a substituent selected from the group consisting of H, —CO (CH 2 ) n —CH 3 , —COO—(CH 2 ) n —CH 3 , —(CH 2 ) n —CH 3 , —CH((CH 2 ) n CH 3 ) 2 , —CH(CH 3 ) 2 , —C(CH 3 ) 3 , —(CF 2 ) n —CF 3 , —CF((CF 2 ) n CF 3 ) 2 , —CF(CF 3 ) 2 , —C(CF 3 ) 3 , —(CH 2 ) n —C 6 H 5 , —COO—(CH 2 ) n —C 6 H 5 ;  
 G is a heteroatom selected from the group consisting of oxygen and sulfur;  
 a is an integer from 0 to 1;  
 b has a value from 1 to 200;  
 c has a value from 0 to 200;  
 d is an integer from 0 to 1;  
 n is an integer from 0 to 5;  
 R 6  is a divalent substituent selected from the group consisting of:  
                     
 R 7  is a substituent selected from the group consisting of an alkyl group having from 1 to 10 carbon atoms and an aryl group having from 5 to 22 carbon atoms; and p 1  e is an integer from 1 to 10.  
 
   
   
       13 . A process for producing an electronic component, which comprises: 
 preparing a solution of a poly-o-hydroxyamide having a Formula I in a solvent                          where    E 1  and E 2 , in each case independently, are substituents selected from the group consisting of hydrogen, a hydroxyl group, a saturated monovalent hydrocarbon, and an unsaturated monovalent hydrocarbon;    Y 1  and Y 2 , in each case independently for each position, are a divalent hydrocarbon;    Z 1 , in each case independently for each position, is a structural unit having a formula selected from the group consisting of Formula IIa and IIb                          in which the bond (-*) and the substituent -GR 5  are disposed in the ortho position relative to one another,                          Z 2 , in each case independently for each position, is a tetravalent hydrocarbon composed of groups linked to one another and selected from the group consisting of alkyl and aryl groups;    R 1 , R 2 , R 3 , and R 4 , in each case independently, are substituents selected from the group consisting of H, —C 6 H 5 , —(CH 2 ) n —CH 3 , -G-(CH 2 ) n —CH 3 , —CH((CH 2 ) n CH 3 ) 2 , —CH(CH 3 ) 2 , -G-CH(CH 3 ) 2 , —C(CH 3 ) 3 , -G-C(CH 3 ) 3 , —(CF 2 ) n —CF 3 , -G-(CF 2 ) n —CF 3 , —CF((CF 2 ) n CF 3 ) 2 , —CF(CF 3 ) 2 , —C(CF 3 ) 3 , —N(CH 3 ) 2 , —N(CF 3 ) 2 ,                          R 5 , in each case independently, is a substituent selected from the group consisting of H, —CO(CH 2 ) n —CH 3 , —COO—(CH 2 ) n —CH 3 , —(CH 2 ) n —CH 3 , —CH((CH 2 ) n CH 3 ) 2 , —CH(CH 3 ) 2 , —C(CH 3 ) 3 , —(CF 2 ) n —CF 3 , —CF((CF 2 ) n CF 3 ) 2 , —CF(CF 3 ) 2 , —C(CF 3 ) 3 , —(CH 2 ) n —C 6 H 5 , —COO—(CH 2 ) n —C 6 H 5 ;    G is a heteroatom selected from the group consisting of oxygen and sulfur;    a is an integer from 0 to 1;    b has a value from 1 to 200;    c has a value from 0 to 200;    d is an integer from 0 to 1;    n is an integer from 0 to 5;    R 6  is a divalent substituent selected from the group consisting of:                          R 7  is a substituent selected from the group consisting of an alkyl group having from 1 to 10 carbon atoms and an aryl group having from 5 to 22 carbon atoms; and    e is an integer from 1 to 10;    applying the solution to a substrate;    evaporating the solvent to obtain a film;    heating the film to cyclize the poly-o-hydroxyamide having the Formula I to yield a polybenzoxazole having a Formula III                          where    Z 1  has a formula selected from the group consisting of                          E 1  and E 2 , in each case independently, are substituents selected from the group consisting of hydrogen, a hydroxyl group, a saturated monovalent hydrocarbon, and an unsaturated monovalent hydrocarbon;    Y 1  and Y 2 , in each case independently for each position, are a divalent hydrocarbon;    Z 2 , in each case independently for each position, is a tetravalent hydrocarbon composed of groups linked to one another and selected from the group consisting of alkyl and aryl groups;    R 1 , R 2 , R 3 , and R 4 , in each case independently, are substituents selected from the group consisting of H, —C 6 H 5 , —(CH 2 ) n —CH 3 , -G-(CH 2 ) n —CH 3 , —CH((CH 2 ) n CH 3 ) 2 , —CH(CH 3 ) 2 , -G-CH(CH 3 ) 2 , —C(CH 3 ) 3 , -G-C(CH 3 ) 3 , —(CF 2 ) n —CF 3 , -G-(CF 2 ) n —CF 3 , —CF((CF 2 ) n CF 3 ) 2 , —CF(CF 3 ) 2 , —C(CF 3 ) 3 , —N(CH 3 ) 2 , —N(CF 3 ) 2 ,                          R 5 , in each case independently, is a substituent selected from the group consisting of H, —CO (CH 2 ) n —CH 3 , —COO—(CH 2 ) n —CH 3 , —(CH 2 ) n —CH 3 , —CH((CH 2 ) n CH 3 ) 2 , —CH(CH 3 ) 2 , —C(CH 3 ) 3 , —(CF 2 ) n —CF 3 , —CF((CF 2 ) n CF 3 ) 2 , —CF(CF 3 ) 2 , —C(CF 3 ) 3 , —(CH 2 ) n —C 6 H 5 , —COO—(CH 2 ) n —C 6 H 5 ;    G is a heteroatom selected from the group consisting of oxygen and sulfur;    a is an integer from 0 to 1;    b has a value from 1 to 200;    c has a value from 0 to 200; and    d is an integer from 0 to 1;    structuring the film to obtain a resist structure having trenches;    depositing a conductive material on the resist structure so that the trenches are filled with a conductive material; and    removing excess of the conductive material.    
   
   
       14 . A process for producing an electronic component, which comprises: 
 preparing a solution of a poly-o-hydroxyamide in a solvent, the poly-o-hyroxyamide having a Formula I                          where    E 1  and E 2 , in each case independently, are substituents selected from the group consisting of hydrogen, a hydroxyl group, a saturated monovalent hydrocarbon, and an unsaturated monovalent hydrocarbon;    Y 1  and Y 2 , in each case independently for each position, are a divalent hydrocarbon;    Z 1 , in each case independently for each position, is a structural unit having a formula selected from the group consisting of Formula IIa and IIb                          in which the bond (-*) and the substituent -GR 5  are disposed in the ortho position relative to one another,                          Z 2 , in each case independently for each position, is a tetravalent hydrocarbon composed of groups linked to one another and selected from the group consisting of alkyl and aryl groups;    R 1 , R 2 , R 3 , and R 4 , in each case independently, are substituents selected from the group consisting of H, —C 6 H 5 , —(CH 2 ) n —CH 3 , -G-(CH 2 ) n —CH 3 , —CH((CH 2 ) n CH 3 ) 2 , —CH (CH 3 ) 2 , -G-CH(CH 3 ) 2 , —C(CH 3 ) 3 , -G-C(CH 3 ) 3 , —(CF 2 ) n —CF 3 , -G-(CF 2 ) n —CF 3 , —CF((CF 2 ) n CF 3 ) 2 , —CF(CF 3 ) 2 , —C(CF 3 ) 3 , —N(CH 3 ) 2 , —N(CF 3 ) 2 ,                          R 5 , in each case independently, is a substituent selected from the group consisting of H, —CO(CH 2 ) n —CH 3 , —COO—(CH 2 ) n —CH 3 , —(CH 2 ) n —CH 3 , —CH((CH 2 ) n CH 3 ) 2 , —CH(CH 3 ) 3 ) 2 , —C(CH 3 ) 3 , —(CF 2 ) n —CF 3 , —CF((CF 2 ) n CF 3 ) 2 , —CF(CF 3 ) 2 , —C(CF 3 ) 3 , —(CH 2 ) n —C 6 H 5 , —COO—(CH 2 ) n —C 6 H 5 ;    G is a heteroatom selected from the group consisting of oxygen and sulfur;    a is an integer from 0 to 1;    b has a value from 1 to 200;    c has a value from 0 to 200;    d is an integer from 0 to 1;    n is an integer from 0 to 5;    R 6  is a divalent substituent selected from the group consisting of:                          R 7  is a substituent selected from the group consisting of an alkyl group having from 1 to 10 carbon atoms and an aryl group having from 5 to 22 carbon atoms; and    e is an integer from 1 to 10;    applying the solution to a substrate having a surface with metallic structures and trenches formed between the metallic structures;    evaporating the solvent to fill the trenches with the poly-o-hydroxyamide of the Formula I; and    heating the substrate to cyclize the poly-o-hydroxyamide of the formula I to yield the polybenzoxazole having a Formula III.