Ethyleneoxide-silane and bridged silane precursors for forming low k films

Abstract

An organosilicon precursor for vapor deposition, e.g., low pressure (<100 Torr), plasma-enhanced chemical vapor deposition (PECVD) of a low k, high strength dielectric film, wherein the precursor includes at least one of: (i) silicon-pendant oxiranyl functionality; and (ii) a disilyl moiety of the formula wherein x is an integer having a value of from 0 to 4 inclusive. These precursors are useful for the formation of dielectric films having dielectric constants on the order of ˜3 and less, and a hardness exceeding ˜1 GigaPascals.

1 . An organosilicon precursor for vapor deposition of a low k, high strength dielectric film, wherein the precursor comprises a disilyl moiety of the formula  
     
       
         
         
             
             
         
       
       wherein x is an integer having a value of from 0 to 4 inclusive.  
     
   
   
       2 . An organosilicon precursor according to  claim 1 , wherein x is 1.  
   
   
       3 . An organosilicon precursor according to  claim 1 , wherein x is 2.  
   
   
       4 . An organosilicon precursor according to  claim 1 , having the formula (III):  
       R 4 R 5 R 6 Si—(CH 2 ) y —SiR 7 R 8 R 9    (III)  wherein:    each of R 4 , R 5 , R 6 , R 7 , R 8  and R 9  can be the same as or different from one another and each is independently selected from the group consisting of H, C 1 -C 8  alkyl, C 1 -C 8  fluoroalkyl, C 1 -C 8  alkoxyl, C 6 -C 10  cycloalkyl, C 6 -C 10  aryl, C 6 -C 10  fluoroaryl, C 2 -C 6  vinyl, C 3 -C 6  allyl, and oxiranylalkylene of formula (IV)                          wherein s is 0 or 1; and    y is an integer having a value of from 0 to 4 inclusive.    
   
   
       5 . The organosilicon precursor of  claim 4 , wherein x is 1.  
   
   
       6 . The organosilicon precursor of  claim 4 , wherein x is 2.  
   
   
       7 . The organosilicon precursor of  claim 4 , wherein x is 0.  
   
   
       8 . An organosilicon precursor composition for vapor deposition of a low k, high strength dielectric film, comprising an organosilicon precursor according to  claim 1 .  
   
   
       9 . The organosilicon precursor composition of  claim 8 , wherein the organosilicon precursor has the formula:  
       R 4 R 5 R 6 Si—(CH 2 ) y —SiR 7 R 8 R 9    (III)  wherein:    each of R 4 , R 5 , R 6 , R 7 , R 8  and R 9  can be the same as or different from one another and each is independently selected from the group consisting of H, C 1 -C 8  alkyl, C 1 -C 8  fluoroalkyl, C 1 -C 8  alkoxyl, C 6 -C 10  cycloalkyl, C 6 -C 10  aryl, C 6 -C 10  fluoroaryl, C 2 -C 6  vinyl, C 3 -C 6  allyl, and oxiranylalkylene of formula (IV)                          wherein s is 0 or 1; and    y is an integer having a value of from 0 to 4 inclusive.    
   
   
       10 . The organosilicon precursor composition of  claim 9 , wherein x is 1.  
   
   
       11 . The organosilicon precursor composition of  claim 9 , wherein x is 2.  
   
   
       12 . The organosilicon precursor composition of  claim 9 , wherein x is 0.  
   
   
       13 . The organosilicon precursor composition according to  claim 8 , further comprising TMCTS.  
   
   
       14 . The organosilicon precursor composition according to  claim 8 , further comprising a porogen.  
   
   
       15 . The organosilicon precursor composition of  claim 14 , wherein said porogen is selected from the group consisting of compounds of the formula (X):  
       R 10 R 11 SiR 12 R 13    (X)  wherein:    each of R 10 , R 11 , R 12  and R 13  can be the same as or different from one another and each is independently selected from the group consisting of H, C 1 -C 8  alkyl, C 1 -C 8  alkoxyl, C 6 -C 10  cycloalkyl, and C 6 -C 10  aryl, with the proviso that at least one of R 10 , R 11 , R 12  and R 13  is C 1 -C 8  alkoxyl.    
   
   
       16 . The organosilicon precursor composition of  claim 14 , wherein said porogen is selected from the group consisting of: 
   t Bu 2 Si(OCH 3 ) 2        t Bu 2 Si(OC 2 H 5 ) 2      (C 6 H 5 ) 2 Si(OCH 3 ) 2      (C 6 H 5 ) 2 Si(OC 2 H 5 ) 2      (C 6 H,  1 ) 2 Si(OCH 3 ) 2      (C 6 H5) 2 Si(OC 2 H 5 ) 2        t BuSi(OCH 3 ) 2 H      t BuSi(OC 2 H 5 ) 2 H    (C 6 H 5 )Si(OCH 3 ) 2 H    (C 6 H 5 )Si(OC 2 H 5 ) 2 H    (C 6 H 5 )Si(OCH 3 ) 2 H    (C 6 H 5 )Si(OC 2 H 5 ) 2 H    ( t Bu)(CH 3 )Si(OCH 3 ) 2      ( t Bu)(CH 3 )Si(OC 2 H 5 ) 2      (C 6 H 5 )(CH 3 )Si(OCH 3 ) 2      (C 6 H 5 )(CH 3 )Si(OC 2 H 5 ) 2      (C 6 H 5 )(CH 3 )Si(OCH 3 ) 2      (C 6 H 5 )(CH 3 )Si(OC 2 H 5 ) 2      wherein  t Bu is tertiary butyl.    
   
   
       17 . A method of synthesizing a bridged disilane compound of formula (II):  
       R 4 R 5 R 6 Si—(CH 2 ) y —SiR 7 R 8 R 9    (III)  wherein:    each of R 4 , R 5 , R 6 , R 7 , R 8  and R 9  can be the same as or different from one another and each is independently selected from the group consisting of H, C 1 -C 8  alkyl, C 1 -C 8  fluoroalkyl, C 1 -C 8  alkoxyl, C 6 -C 10  cycloalkyl, C 6 -C 10  aryl, C 6 -C 10  fluoroaryl, C 2 -C 6  vinyl, C 3 -C 6  allyl, and oxiranylalkylene of formula (IV)                          wherein s is 0 or 1; and    y is an integer having a value of from 0 to 4 inclusive,    said method comprising derivatization of a corresponding bridged chlorosilane.    
   
   
       18 . The method of  claim 17 , wherein said derivatization step comprises reacting said corresponding bridged chlorosilane with tetraalkylsodium to alkylate said corresponding bridged chlorosilane.  
   
   
       19 . The method of  claim 17 , wherein said derivatization step comprises the reaction  
       MeCl 2 SiCH 2 CH 2 SiMeCl 2 +4MeONa→Me(MeO) 2 SiCH 2 CH 2 SiMe(OMe) 2 +4NaCl.  
   
   
       20 . The method of  claim 17 , wherein said derivatization step comprises the reaction  
       Me 2 ClSiCH 2 CH 2 SiMe 2 Cl+2MeONa→Me 2 (MeO)SiCH 2 CH 2 SiMe 2 (OMe)+2NaCl.  
   
   
       21 . The method of  claim 17 , wherein said derivatization step comprises the reaction  
       HSiCl 2 CH 2 HSiCl 2 +4MeONa+2MeOH→(MeO) 3 SiCH 2 Si(OMe) 3 +4NaCl+2H 2 .  
   
   
       22 . A method of forming a low k, high strength dielectric film on a substrate, comprising vapor depositing said film on the substrate from a precursor comprising a disilyl moiety of the formula  
     
       
         
         
             
             
         
       
       wherein x is an integer having a value of from 0 to 4 inclusive.  
     
   
   
       23 . The method of  claim 22 , wherein said precursor is selected from the group consisting of disilane compounds of formula (III):  
       R 4 R 5 R 6 Si—(CH 2 ) y —SiR 7 R 8 R 9    (III)  wherein:    each of R 4 , R 5 , R 6 , R 7 , R 8  and R 9  can be the same as or different from one another and each is independently selected from the group consisting of H, C 1 -C 8  alkyl, C 1 -C 8  fluoroalkyl, C 1 -C 8  alkoxyl, C 6 -C 10  cycloalkyl, C 6 -C 10  aryl, C 6 -C 10  fluoroaryl, C 2 -C 6  vinyl, C 3 -C 6  allyl, and oxiranylalkylene of formula (IV)                          wherein s is 0 or 1; and    y is an integer having a value of from 0 to 4 inclusive.    
   
   
       24 . The method of  claim 23 , wherein x is 0.  
   
   
       25 . The method of  claim 23 , wherein x is 1.  
   
   
       26 . The method of  claim 23 , wherein x is 2.  
   
   
       27 . The method of  claim 22 , wherein said vapor depositing step comprises use of a porogen in combination with said precursor.  
   
   
       28 . The method of  claim 27 , wherein said porogen is selected from the group consisting of compounds of the formula (X):  
       R 10 R 11 SiR 12 R 13    (X)  wherein:    each of R 10 , R 11 , R 12  and R 13  can be the same as or different from one another and each is independently selected from the group consisting of H, C 1 -C 8  alkyl, C 1 -C 8  alkoxyl, C 6 -C 10  cycloalkyl, and C 6 -C 10  aryl, with the proviso that at least one of R 10 , R 11 , R 12  and R 13  is C 1 -C 8  alkoxyl.    
   
   
       29 . The method of  claim 27 , wherein said porogen is selected from the group consisting of: 
   t BU 2 Si(OCH 3 ) 2        t Bu 2 Si(OC 2 H 5 ) 2      (C 6 H 5 ) 2 Si(OCH 3 ) 2      (C 6 H 5 ) 2 Si(OC 2 H 5 ) 2      (C 6 H 5 ) 2 Si(OCH 3 ) 2      (C 6 H 5 ) 2 Si(OC 2 H 5 ) 2        t BuSi(OCH 3 ) 2 H      t BuSi(OC 2 H 5 ) 2 H    (C 6 H 5 )Si(OCH 3 ) 2 H    (C 6 H 5 )Si(OC 2 H 5 ) 2 H    (C 6 H 5 )Si(OCH 3 ) 2 H    (C 6 H 5 )Si(OC 2 H 5 ) 2 H    ( t Bu)(CH 3 )Si(OCH 3 ) 2      ( t Bu)(CH 3 )Si(OC 2 H 5 ) 2      (C 6 H 5 )(CH 3 )Si(OCH 3 ) 2      (C 6 H 5 )(CH 3 )Si(OC 2 H 5 ) 2      (C 6 H 5 )(CH 3 )Si(OCH 3 ) 2      (C 6 H 5 )(CH 3 )Si(OC 2 H 5 ) 2      wherein  t Bu is tertiary butyl.    
   
   
       30 . The method of  claim 22 , wherein said vapor depositing step comprises chemical vapor deposition.  
   
   
       31 . The method of  claim 22 , wherein said vapor depositing step comprises plasma-enhanced chemical vapor deposition.  
   
   
       32 . The method of  claim 22 , wherein said vapor depositing step comprises flowing said precursor to a vapor deposition locus in a carrier gas.  
   
   
       33 . The method of  claim 32 , wherein said carrier gas comprises carbon dioxide.  
   
   
       34 . The method of  claim 22 , wherein the precursor and the carrier gas are the only potential sources of oxygen at the vapor deposition locus.  
   
   
       35 . The method of  claim 22 , wherein the precursor is selected from the group consisting of: 
 Me(EtO) 2 SiCHCH 2 O;    Me(MeO) 2 Si CH 2 CHCH 2 O;    Me 2 Si (CHCH 2 O) 2 ;    Me(MeO) 2 SiCH 2 CH 2 SiMe(OMe) 2 ;    Me 2 (MeO)SiCH 2 CH 2 SiMe 2 (OMe); and    (MeO) 3 SiCH 2 Si(OMe) 2 .    
   
   
       36 . The method of  claim 22 , wherein the precursor further comprises TMCTS.