Method of depositing silicon oxide films

Abstract

Methods of depositing a silicon oxide film are disclosed. One embodiment is a plasma enhanced atomic layer deposition (PEALD) process that includes supplying a vapor phase silicon precursor, such as a diaminosilane compound, to a substrate, and supplying oxygen plasma to the substrate. Another embodiment is a pulsed hybrid method between atomic layer deposition (ALD) and chemical vapor deposition (CVD). In the other embodiment, a vapor phase silicon precursor, such as a diaminosilane compound, is supplied to a substrate while ozone gas is continuously or discontinuously supplied to the substrate.

1 . A method of depositing a silicon oxide film over a substrate, the method comprising one or more of deposition cycles, each of the cycles comprising:
 supplying a plurality of pulses of silicon source gas of a compound represented by Formula 1 into a reactor in which a substrate is loaded,   
     
       
         
         
             
             
         
       
     
     wherein R is a straight or branched alkyl group having 1 to 4 carbons; and
 providing an oxygen-containing gas over the substrate in the reactor. 
 
   
   
       2 . The method of  claim 1 , wherein the compound comprises N, N, N′, N′-tetraethyldiaminosilane (SiH 2  [N(C 2 H 5 ) 2 ] 2 ). 
   
   
       3 . The method of  claim 1 , wherein at least one of the cycles comprises providing the oxygen-containing gas after supplying the silicon source gas. 
   
   
       4 . The method of  claim 3 , wherein the at least one of the cycles further comprises supplying a purge gas into the reactor after supplying the silicon source gas and before providing the oxygen-containing gas. 
   
   
       5 . The method of  claim 3 , wherein the at least one of the cycles further comprises providing a purge gas into the reactor after providing the oxygen-containing gas. 
   
   
       6 . The method of  claim 1 , wherein providing the oxygen-containing gas comprises providing oxygen plasma. 
   
   
       7 . The method of  claim 6 , wherein providing the oxygen plasma comprises generating the oxygen plasma in-situ in the reactor. 
   
   
       8 . The method of  claim 7 , wherein generating the oxygen plasma comprises supplying oxygen gas into the reactor, and applying plasma power to the reactor to activate the oxygen gas. 
   
   
       9 . The method of  claim 8 , wherein applying the plasma power comprises applying plasma power between about 0.05 W/cm 2  and about 2 W/cm 2 . 
   
   
       10 . The method of  claim 1 , wherein the oxygen-containing gas comprises ozone. 
   
   
       11 . The method of  claim 1 , wherein at least one of the cycles comprises, in sequence:
 supplying the silicon source gas; and   supplying a purge gas into the reactor to purge the silicon source gas from the reactor.   
   
   
       12 . The method of  claim 11 , wherein the at least one of the cycles comprises providing the oxygen-containing gas substantially continuously throughout the at least one cycle. 
   
   
       13 . The method of  claim 11 , wherein the at least one of the cycles comprises: providing the oxygen-containing gas during supplying the silicon source gas; and providing the oxygen-containing gas during supplying the purge gas. 
   
   
       14 . The method of  claim 13 , wherein the one or more of deposition cycles comprise a first cycle and a second cycle,
 wherein the first cycle comprises flowing at least one of the silicon source gas or the oxygen-containing gas in a first direction relative to the orientation of the substrate, and   wherein the second cycle comprises flowing at least one of the silicon source gas or the oxygen-containing gas in a second direction relative to the orientation of the substrate, the second direction being different from the first direction.   
   
   
       15 . The method of  claim 1 , wherein each of the cycles is conducted at a process temperature between room temperature and about 400° C. 
   
   
       16 . The method of  claim 1 , wherein each of the cycles is conducted at a process pressure between about 0.1 torr and about 10 torr. 
   
   
       17 . The method of  claim 1 , wherein providing the oxygen-containing gas comprises supplying the oxygen-containing gas at a gas flow rate between about 50 sccm and about 300 sccm. 
   
   
       18 . The method of  claim 1 , wherein providing the oxygen-containing gas comprises supplying the oxygen-containing gas at a gas flow rate between about 50 sccm and about 1000 sccm. 
   
   
       19 . An apparatus comprising:
 a silicon oxide film made by the method of  claim 1 ,   wherein the silieon oxide film has an atomic ratio of silicon to oxygen of about 1:1, and   wherein the silicon oxide film has a refractive index between about 1.459 and about 1.483.   
   
   
       20 . A method of forming a thin film over a substrate, the method comprising a first cycle which comprises:
 supplying a vapor phase silicon precursor comprising diaminosilane over a substrate;   purging the vapor phase silicon precursor from the substrate; and   supplying ozone gas to the substrate during supplying the vapor phase silicon precursor and after purging and before a subsequent cycle.   
   
   
       21 . The method of  claim 20 , wherein supplying ozone gas is conducted substantially continuously during the first cycle. 
   
   
       22 . The method of  claim 20 , wherein the silicon precursor is represented by Formula 1: 
     
       
         
         
             
             
         
       
       wherein R is a straight or branched alkyl group having 1 to 4 carbons. 
     
   
   
       23 . The method of  claim 22 , wherein the silicon precursor comprises N, N, N′,N′-tetraethyldiaminosilane (SiH 2 [N(C 2 H 5 ) 2 ] 2 ). 
   
   
       24 . The method of  claim 20 , wherein the first cycle comprises flowing the precursor and the ozone gas in a first direction relative to the orientation of the substrate. 
   
   
       25 . The method of  claim 20 , further comprising a second cycle which comprises:
 supplying the vapor phase silicon precursor over the substrate;   purging the vapor phase silicon precursor from the substrate; and   supplying ozone gas to the substrate during supplying the vapor phase silicon precursor, after purging and before a subsequent cycle,   wherein the second cycle comprises flowing the precursor and the ozone gas in a second direction relative to the orientation of the substrate, the second direction being different from the first direction.   
   
   
       26 . The method of  claim 25 , wherein the first cycle comprises flowing purge gas in the first direction, and wherein the second cycle comprises flowing the purge gas in the second direction. 
   
   
       27 . The method of  claim 20 , wherein the deposition rate of the silicon oxide film is more than about 1.1 Å/cycle. 
   
   
       28 . A method of depositing a thin film over a substrate, the method comprising;
 supplying a silicon source gas to a substrate; and   supplying an excited oxygen species to the substrate to form a film, such that the film has an atomic ratio of Si to O of about 0.5:1 to about 1.1:1.