Radiation durable organic compounds with high transparency in the vaccum ultraviolet, and method for preparing

Abstract

This invention concerns radiation durable organic compositions which are well-suited for use in 157 nm lithography by virtue of their high transparency and excellent radiation durability, and to a process for the preparation thereof.

1 . An organic composition comprising less than 20 parts per million of water, less than 90 ppm of oxygen, and one or more compounds selected from the group consisting of: 
 i) cyclic, linear, or branched hydrofluorocarbons having 2 to 10 carbon atoms in which there are more fluorines than hydrogen, no runs of adjacent C—H bonds longer than two (CH—CH), no runs of adjacent C—F bonds longer than 6 (CF—CF—CF—CF—CF—CF), and no —CH 2 CH 3  radicals;    ii) X—R f   a [OR f   b ]nOR f   c Y wherein X and Y can be hydrogen or fluorine and R f   a , R f   b , and R f   c  are 1 to 3 carbon fluorocarbon radicals, linear or branched    in which there are more fluorines than hydrogens, no runs of adjacent C—H bonds longer than two are present, no —CH 2 CH 3  radicals are present and no sequences with hydrogen on both sides of an ether oxygen (CH—O—CH) are present;    iii) C n F 2n−v+2 H v  wherein n=2 to 10, v<n+1, the number of fluorines equals or exceeds the number of hydrogens, no runs of adjacent C—H bonds longer than two are present, no runs of adjacent C—F bonds longer than 6 are present, and no CH 2 CH 3  radicals are present;    iv) C n F 2n+1 CFHCFHC m F 2m+1  where n equals 1 to 4; and m equals 1 to 4;    v) CF 3 CH 2 CF 2 CH 3 ;    vi) F[CF(CF 3 )CF 2 O] n CFHCF 3  where n=1 to 5;    vii) F[CF(CF 3 )CF 2 O] n CF 2 CF 3  where n 1 to 5;    viii) HCF 2 (OCF 2 ) n (OCF 2 CF 2 ) m OCF 2 H where n+m=1 to 8; and,    ix) cyclic, linear, or branched perfluorocarbon and hydrofluorocarbon amines, and ether-amines in which there are more fluorines than hydrogens, no runs of hydrogen longer than two (CH—CH), no —CH 2 CH 3  radicals are present, no runs of adjacent C—F bonds longer than 6 (CF—CF—CF—CF—CF—CF), and no C—H bonds immediately adjacent to either nitrogen or oxygen.    
     
     
         2 . The composition of  claim 1  wherein said one or more compounds are selected from the group consisting of perfluorotributylamine, perfluoro-N-methymorpholine, C n F 2n+1 CFHCFHC m F 2m+1  where n equals 1 to 4; and m equals 1 to 4 and HCF 2 (OCF 2 ) n (OCF 2 CF 2 ) m OCF 2 H where n+m=1 to 8.  
     
     
         3 . The composition of  claim 1  wherein said one or more compounds are selected from the group consisting of perfluorotributylamine, perfluoro-N-methymorpholine, CF 3 CFHCFHCF 2 CF 3 , CF 3 CH 2 CF 2 CH 3  and HCF 2 O(CF 2 O) n (CF 2 CF 2 O) m CF 2 H where n+m=2 to 6.  
     
     
         4 . The composition of  claim 1  wherein at least one of said one or more compounds is a liquid.  
     
     
         5 . A process for preparing an organic composition for use in optical imaging applications comprising subjecting to treatment with one or more means for extracting one or more photochemically active species, a compound selected from the group consisting of: 
 i) cyclic, linear, or branched hydrofluorocarbons having 2 to 10 carbon atoms in which there are more fluorines than hydrogen, no runs of adjacent C—H bonds longer than two (CH—CH), no runs of adjacent C—F bonds longer than 6 (CF—CF—CF—CF—CF—CF), and no —CH 2 CH 3  radicals;    ii) X—R f   a [OR f   b ]nOR f   c Y wherein X and Y can be hydrogen or fluorine and R f   a , R f   b , and R f   c  are 1 to 3 carbon fluorocarbon radicals, linear or branched    in which there are more fluorines than hydrogens, no runs of adjacent C—H bonds longer than two are present, no —CH 2 CH 3  radicals are present and no sequences with hydrogen on both sides of an ether oxygen (CH—O—CH) are present;    iii) C n F 2n−v+2 H v  wherein n=2 to 10, v<n+1, no runs of adjacent C—H bonds longer than two are present, no runs of adjacent C—F bonds longer than 6 are present, and no CH 2 CH 3  radicals are present;    iv) C n F 2n+1 CFHCFHC m F 2m+1  where n equals 1 to 4; and m equals 1 to 4;    v) CF 3 CH 2 CF 2 CH 3 ;    vi) F[CF(CF 3 )CF 2 O] n CFHCF 3  where n=1 to 5;    vii) F[CF(CF 3 )CF 2 O] n CF 2 CF 3  where n=1 to 5;    viii) HCF 2 (OCF 2 ) n (OCF 2 CF 2 ) m OCF 2 H where n+m=1 to 8; and,    ix) cyclic, linear, or branched perfluorocarbon and hydrofluorocarbon amines, and ether-amines in which there are more fluorines than hydrogens, no runs of hydrogen longer than two (CH—CH), no —CH 2 CH 3  radicals are present and no runs of adjacent C—F bonds longer than 6 (CF—CF—CF—CF—CF—CF), and no C—H bonds immediately adjacent to either nitrogen or oxygen;    at least until the desired concentration of said one or more photochemically active species is achieved.    
     
     
         6 . The process of  claim 5  wherein said one or more photochemically active species comprises moisture, and the desired concentration is below 20 parts per million.  
     
     
         7 . The process of  claim 5  wherein said one or more photochemically active species comprises oxygen, and the desired concentration is below 90 parts per million.  
     
     
         8 . The process of  claim 5  wherein said one or more photochemically active species comprises moisture and oxygen and the desired concentrations are below 20 parts per million and below 90 parts per million, respectively.  
     
     
         9 . The process of  claim 5  wherein said one or more compounds are selected from the group consisting of perfluorotributylamine, perfluoro-N-methymorpholine, C n F 2n+1 CFHCFHC m F 2m+1  where n equals 1 to 4; and m equals 1 to 4 and HCF 2 (OCF 2 ) n (OCF 2 CF 2 ) m OCF 2 H where n+m=1 to 8.  
     
     
         10 . The process of  claim 5  wherein said one or more compounds are selected from the group consisting of perfluorotributylamine, perfluoro-N-methymorpholine, CF 3 CFHCFHCF 2 CF 3 , CF 3 CH 2 CF 2 CH 3  and HCF 2 O(CF 2 O) n (CF 2 CF 2 O) m CF 2 H where n+m=2 to 6.  
     
     
         11 . The process of Ca 5 wherein at least one of said one or more compounds is a liquid.  
     
     
         12 . The process of  claim 5  wherein said means comprises contacting said compound with molecular sieves.  
     
     
         13 . The process of  claim 5  wherein said means comprises sparging with an inert gas.  
     
     
         14 . The process of  claim 5  wherein said means comprises contacting said compound with molecular sieves and sparging said compound with an inert gas.  
     
     
         15 . A process for forming an optical image on a substrate, the process comprising: 
 a) radiating electromagnetic radiation from a source capable of radiating electromagnetic radiation in the range of 140-260 nm;    b) receiving said radiation on a target disposed to receive at least a portion of said radiation; and    wherein one or more optically transparent compositions is disposed between said radiation source and said target, at least one of said optically transparent compositions comprising a composition treated with one or more means for extracting one or more photochemically active species and one or more compounds selected from the group consisting of:    i) cyclic, linear, or branched hydrofluorocarbons having 2 to 10 carbon atoms in which there are more fluorines than hydrogen, no runs of adjacent C—H bonds longer than two (CH—CH), no runs of adjacent C—F bonds longer than 6 (CF—CF—CF—CF—CF—CF), and no —CH 2 CH 3  radicals;    ii) X—R f   a [OR f   b ]nOR f   c Y wherein X and Y can be hydrogen or fluorine and R f   a , R f   b  and R f   c  are 1 to 3 carbon fluorocarbon radicals, linear or branched in which there are more fluorines than hydrogens, no runs of adjacent C—H bonds longer than two are present, no —CH 2 CH 3  radicals are present and no sequences with hydrogen on both sides of an ether oxygen (CH—O—CH) are present;    iii) C n F 2n+2 H v  wherein n=2 to 10, v<n+1, no runs of adjacent C—H bonds longer than two are present, no runs of adjacent C—F bonds longer than 6 are present, and no CH 2 CH 3  radicals are present;    iv) C n F 2n+1 CFHCFHC m F 2m+1  where n equals 1 to 4; and m equals 1 to 4;    v) CF 3 CH 2 CF 2 CH 3 ;    vi) F[CF(CF 3 )CF 2 O] n CFHCF 3  where n=1 to 5;    vii) F[CF(CF 3 )CF 2 O] n CF 2 CF 3  where n=1 to 5;    viii) HCF 2 (OCF 2 ) n (OCF 2 CF 2 ) m OCF 2 H where n+m 1 to 8; and,    ix) cyclic, linear, or branched perfluorocarbon and hydrofluorocarbon amines, and ether-amines in which there are more fluorines than hydrogens, no runs of hydrogen longer than two (CH—CH), no —CH 2 CH 3  radicals are present and no runs of adjacent C—F bonds longer than 6 (CF—CF—CF—CF—CF—CF), and no C—H bonds immediately adjacent to either nitrogen or oxygen.    
     
     
         16 . The process of  claim 15  wherein said one or more compounds are selected from the group consisting of perfluorotributylamine, perfluoro-N-methymorpholine, C n F 2n+1 CFHCFHC m F 2m+1  where n equals 1 to 4; and m equals 1 to 4 and HCF 2 (OCF 2 ) n (OCF 2 CF) m OCF 2 H where n+m=1 to 8.  
     
     
         17 . The process of  claim 15  wherein said one or more compounds are selected from the group consisting of perfluorotributylamine, perfluoro-N-methymorpholine, CF 3 CFHCFHCF 2 CF 3 , CF 3 CH 2 CF 2 CH 3  and HCF 2 O(CF 2 O) n (CF 2 CF 2 O) m CF 2 H where n+m=2 to 6.  
     
     
         18 . The process of  claim 15  wherein at least one of said one or more compounds is a liquid.  
     
     
         19 . The process of  claim 15  wherein said at least one of said radiation source and said target are immersed in said optically transparent composition.  
     
     
         20 . The process of  claim 15  wherein both radiation source and target are immersed in said optically transparent composition.  
     
     
         21 . The process of  claim 15  wherein said treated composition comprises less than 20 parts per million of water, less than 90 parts per million of oxygen.  
     
     
         22 . The process of  claim 15  wherein said means comprises contacting said compound with molecular sieves.  
     
     
         23 . The process of  claim 15  wherein said means comprises sparging with an inert gas.  
     
     
         24 . The process of  claim 15  wherein said means comprises contacting said compound with molecular sieves and sparging said compound with an inert gas.