Amino Vinylsilane Precursors for Stressed SiN Films

Abstract

The present invention is a method to increase the intrinsic compressive stress in plasma enhanced chemical vapor deposition (PECVD) silicon nitride (SiN) and silicon carbonitride (SiCN) thin films, comprising depositing the film from an amino vinylsilane-based precursor. More specifically the present invention uses the amino vinylsilane-based precursor selected from the formula: [RR 1 N] x SiR 3 y (R 2 ) z , where x+y+z=4, x=1-3, y=0-2, and z=1-3; R, R 1 and R 3 can be hydrogen, C 1 to C 10 alkane, alkene, or C 4 to C 12 aromatic; each R 2 is a vinyl, allyl or vinyl-containing functional group.

1 . A method to increase the intrinsic compressive stress in plasma enhanced chemical vapor deposition (PECVD) of silicon nitride (SiN) and silicon carbonitride (SiCN) thin films, comprising depositing the film from an amino vinylsilane-based precursor. 
     
     
         2 . The method of  claim 1  wherein the amino vinylsilane-based precursor is selected from the formula: [RR 1 N] x SiR 3   y (R 2 ) z  
 where x+y+z=4, x=1-3, y=0-2, and z=1-3; R, R 1  and R 3  can be hydrogen, C 1  to C 10  alkane, alkene, or C 4  to C 12  aromatic; each R 2  is a vinyl, allyl or vinyl-containing functional group. 
 
     
     
         3 . The method of  claim 2  wherein the amino vinylsilane based precursor is selected from the group consisting of Bis(iso-propylamino)vinylmethylsilane (BIPAVMS), Bis(iso-propylamino)divinylsilane (BIPADVS) and mixtures thereof. 
     
     
         4 . The method of  claim 1  wherein the compressively stressed films have a compressive stress of −4 GPa or higher. 
     
     
         5 . The method of  claim 1  wherein a nitrogen containing reactant is reacted with the amino vinylsilane-based precursor. 
     
     
         6 . The method of  claim 5  wherein the nitrogen containing reactant is selected from the group consisting of ammonia, nitrogen and mixtures thereof. 
     
     
         7 . The method of  claim 1  wherein the deposition is conducted at an elevated temperature at or below 500° C. 
     
     
         8 . The method of  claim 1  wherein the deposition is conducted in the presence of a diluent gas selected from the group consisting of helium, argon, neon, xenon and mixtures thereof. 
     
     
         9 . The method of  claim 1  wherein the flow rate of the amino vinylsilane-based precursor is 50 to 1000 mg/min. 
     
     
         10 . The method of  claim 5  wherein the flow rate of the nitrogen containing reactant is 500 to 10,000 mg/min. 
     
     
         11 . The method of  claim 8  wherein the flow rate of the diluents gas is 50 to 50,000 mg/min. 
     
     
         12 . The method of  claim 1  wherein the deposited thin film has a compressive stress of −700 to −2400 MPa. 
     
     
         13 . The method of  claim 1  wherein the deposited thin film has a N—H to Si—H ratio of 25 to 85. 
     
     
         14 . The method of  claim 1  wherein the deposited thin film has a N—H derived H content/cm 3 ×10 22  in the range of 3.3 to 3.6. 
     
     
         15 . The method of  claim 1  wherein the deposited thin film has a compressive stress of −700 to −4500 MPa. 
     
     
         16 - 18 . (canceled) 
     
     
         19 . A method for depositing a film selected from a silicon nitride film or a silicon carbonitride film comprising:
 reacting a nitrogen-containing gas with a precursor having the general formula:
   [RR 1 N] x SiR 3   y (R 2 ) z    
   where x+y+z=4, x=1-3, y=0-2, and z=1-3 and wherein R, R 1  and R 3  are individually selected from the group consisting of hydrogen, C 1  to C 10  alkane, O 2  to C 10  alkene, or C 4  to C 12  aromatic; R 2  is selected from the group consisting of a vinyl, allyl or other vinyl-containing functional group and wherein when R 2  is vinyl, x=2, y=0, and z=2, R and R 1  cannot both be methyl to provide the film.   
     
     
         20 . The precursor of  claim 19  selected from the group consisting of Bis(isopropylamino)divinylsilane (BIPADVS), Bis(isopropylamino)diallylsilane, Bis(t-butylamino)divinylsilane, Bis(t-butylamino)diallylsilane, Bis(diethylamino)diallylsilane, Bis(methyethylamino)diallylsilane, and Bis(methyethylamino)divinylsilane 
     
     
         21 . A composition for depositing a film selected from a silicon nitride and a silicon carbonitride film comprising:
 an aminosilane precursor which is at least one selected from the group consisting of Bis(isopropylamino)divinylsilane (BIPADVS), Bis(isopropylamino)vinylmethylsilane (BIPAVNS), Bis(isopropylamino)vinylsilane, Bis(isopropylamino)allylmethylsilane, Bis(isopropylamino)allylsilane, Bis(t-butylamino)vinylmethylsilane, Bis(t-butylamino)vinylsilane, Bis(t-butylamino)allylmethylsilane, Bis(t-butylamino)allylsilane, Bis(diethylamino)vinylmethylsilane, Bis(diethylamino)divinylsilane, Bis(diethylamino)vinylsilane, Bis(diethylamino)allylmethylsilane, Bis(diethylamino)allylsilane, Bis(dimethylamino)vinylmethylsilane, Bis(dimethylamino)divinylsilane, Bis(dimethylamino)vinylsilane, Bis(dimethylamino)allylmethylsilane, Bis(dimethylamino)diallylsilane, Bis(dimethylamino)allylsilane, Bis(methylethylamino)vinylmethylsilane, Bis(methyethylamino)vinylsilane, Bis(methyethylamino)allylmethylsilane, Bis(methyethylamino)allylsilane, Dipiperidinovinylmethylsilane, Dipiperidinovinylsilane, Dipiperidinoallylmethylsilane, Dipiperidinodiallylsilane, Dipiperidinoallylsilane, Dipyrrolidinovinylmethylsilane, Dipyrrolidinovinylsilane, Dipyrrolidinoallylmethylsilane, Dipyrrolidinodiallylsilane, and Dipyrrolidinoallylsilane.   
     
     
         22 . The composition of  claim 21  further comprising a nitrogen-containing gas. 
     
     
         23 . The composition of  claim 21  further comprising an inert gas. 
     
     
         24 . A method for depositing a film selected from a silicon nitride film or a silicon carbonitride film comprising:
 reacting a nitrogen-containing gas with an aminosilane precursor to provide the film wherein the amino silane precursor is at least one selected from the group consisting of Bis(isopropylamino)vinylmethylsilane (BIPAVNS), Bis(isopropylamino)vinylsilane, Bis(isopropylamino)allylmethylsilane, Bis(isopropylamino)allylsilane, Bis(t-butylamino)vinylmethylsilane, Bis(t-butylamino)vinylsilane, Bis(t-butylamino)allylmethylsilane, Bis(t-butylamino)allylsilane, Bis(diethylamino)vinylmethylsilane, Bis(diethylamino)divinylsilane, Bis(diethylamino)vinylsilane, Bis(diethylamino)allylmethylsilane, Bis(diethylamino)allylsilane, Bis(dimethylamino)vinylmethylsilane, Bis(dimethylamino)divinylsilane, Bis(dimethylamino)vinylsilane, Bis(dimethylamino)allylmethylsilane, Bis(dimethylamino)diallylsilane, Bis(dimethylamino)allylsilane, Bis(methylethylamino)vinylmethylsilane, Bis(methyethylamino)vinylsilane, Bis(methyethylamino)allylmethylsilane, Bis(methyethylamino)allylsilane, Dipiperidinovinylmethylsilane, Dipiperidinovinylsilane, Dipiperidinoallylmethylsilane, Dipiperidinodiallylsilane, Dipiperidinoallylsilane, Dipyrrolidinovinylmethylsilane, Dipyrrolidinovinylsilane, Dipyrrolidinoallylmethylsilane, Dipyrrolidinodiallylsilane, and Dipyrrolidinoallylsilane.