Systems and methods of forming refractory metal nitride layers using disilazanes

Abstract

A method of forming (and apparatus for forming) refractory metal nitride layers (including silicon nitride layers), such as a tantalum (silicon) nitride barrier layer, on a substrate by using a vapor deposition process with a refractory metal precursor compound, a disilazane, and an optional silicon precursor compound.

1 . A method of manufacturing a memory device, the method comprising: 
 providing a substrate comprising a silicon-containing surface;    providing a vapor comprising one or more refractory metal precursor compounds of the formula MY n  (Formula I), wherein M is a refractory metal, each Y is independently a halogen atom, and n is an integer selected to match the valence of the metal M;    directing the vapor comprising the one or more precursor compounds of the Formula I to the substrate and allowing the one or more compounds to chemisorb on the silicon-containing surface;    providing a vapor comprising one or more disilazanes;    providing a vapor comprising one or more silicon precursor compounds other than the one or more disilazanes;    directing the vapors comprising the one or more disilazanes and the one or more silicon precursor compounds other than the one or more disilazanes to the substrate with the chemisorbed compounds thereon to form a refractory metal silicon nitride barrier layer on the silicon-containing surface;    providing a first electrode on the barrier layer;    providing a high dielectric material over at least a portion of the first electrode; and    providing a second electrode over the high dielectric material.    
   
   
       2 . The method of  claim 1  further comprising providing one or more reaction gases other than the one or more disilazanes and the one or more silicon precursor compounds other than the one or more disilazanes, and directing the one or more reaction gases to the substrate.  
   
   
       3 . The method of  claim 2  wherein the one or more disilazanes are of the formula (R) x H 3-x SiNHSi(R) x H 3-x , wherein each R is independently an organic group, and x is 1 to 3.  
   
   
       4 . The method of  claim 3  wherein each R is independently selected from the group consisting of a (C1-C6) organic group.  
   
   
       5 . The method of  claim 4  wherein each R is independently ethyl or methyl.  
   
   
       6 . The method of  claim 5  wherein the one or more disilazanes comprise tetramethyldisilazane (TMDS), (CH 3 ) 2 HSiNHSiH(CH 3 ) 2 , or hexamethyldisilazane.  
   
   
       7 . The method of  claim 6  wherein the one or more disilazanes comprise tetramethyldisilazane.  
   
   
       8 . The method of  claim 1  wherein the substrate is a semiconductor substrate or substrate assembly.  
   
   
       9 . The method of  claim 8  wherein the semiconductor substrate or substrate assembly is a silicon wafer.  
   
   
       10 . The method of  claim 1  wherein providing the vapors and directing the vapors is accomplished using an atomic layer deposition process comprising a plurality of deposition cycles.  
   
   
       11 . The method of  claim 1  further comprising providing one or more metal-containing precursor compounds having a formula different than Formula I and directing the vapor comprising the one or more compounds different than Formula I to the substrate.  
   
   
       12 . The method of  claim 1  wherein the formed layer has a thickness of about 10 Å to about 100 Å.  
   
   
       13 . The method of  claim 1  wherein the formed layer is a diffusion barrier layer.  
   
   
       14 . The method of  claim 1  wherein Y is independently selected from the group consisting of F, Cl, I, and combinations thereof.  
   
   
       15 . The method of  claim 1  wherein each Y is a fluorine atom.  
   
   
       16 . The method of  claim 1  wherein M is selected from the group consisting of Ti, Nb, Ta, Mo, and W.  
   
   
       17 . The method of  claim 1  wherein M is tantalum and n is 5.  
   
   
       18 . The method of  claim 1  wherein the formed layer is a tantalum silicon nitride layer.  
   
   
       19 . The method of  claim 1  wherein one or more silicon precursor compounds other than the one or more disilazanes are selected from the group consisting of silane (SiH 4 ); disilane (Si 2 H 6 ); halogenated silanes; organic silanes of the formula SiH p R 1   q  wherein p=1-4, q=4-p, and each R 1  is independently an organic group having up to six carbon atoms; and combinations thereof.  
   
   
       20 . The method of  claim 19  wherein each R 1  is independently an organic group having up to two carbon atoms.  
   
   
       21 . The method of  claim 20  wherein each R 1  is independently an organic moiety.  
   
   
       22 . The method of  claim 1  wherein one or more silicon precursor compounds other than the one or more disilazanes are selected from the group consisting of silane (SiH 4 ), disilane (Si 2 H 6 ), dichlorosilane (SiH 2 Cl 2 ), trichlorosilane (SiHCl 3 ), trimethylsilane (SiH(CH 3 ) 3 ), and combinations thereof.  
   
   
       23 . A method of manufacturing a memory device, the method comprising: 
 providing a substrate comprising a silicon-containing surface;    providing a vapor comprising one or more refractory metal precursor compounds of the formula MY n  (Formula I), wherein M is a refractory metal, each Y is independently a halogen atom, and n is an integer selected to match the valence of the metal M;    providing a vapor comprising one or more metal-containing precursor compounds having a formula different than Formula I;    providing a vapor comprising one or more disilazanes;    contacting the vapors comprising the one or more refractory metal precursor compounds of Formula I, the one or more metal-containing precursor compounds having a formula different than Formula I, and the one or more disilazanes with the substrate to form a refractory metal nitride barrier layer on the silicon-containing surface;    providing a first electrode on the barrier layer;    providing a high dielectric material over at least a portion of the first electrode; and    providing a second electrode over the high dielectric material.    
   
   
       24 . The method of  claim 23  wherein the substrate is a semiconductor substrate or substrate assembly.  
   
   
       25 . The method of  claim 23  further comprising providing a vapor comprising one or more silicon precursor compounds other than the one or more disilazanes and contacting the vapor with the substrate to form a refractory metal silicon nitride barrier layer.  
   
   
       26 . The method of  claim 25  wherein the one or more disilazanes are of the formula (R) x H 3-x SiNHSi(R) x H 3-x , wherein each R is independently an organic group, and x is 1 to 3.  
   
   
       27 . The method of  claim 23  wherein providing the vapors and contacting the vapors is accomplished using a chemical vapor deposition process.  
   
   
       28 . The method of  claim 23  wherein providing the vapors and contacting the vapors is accomplished using an atomic layer deposition process comprising a plurality of deposition cycles.  
   
   
       29 . A method of manufacturing a memory device, the method comprising: 
 providing a substrate comprising a silicon-containing surface;    providing a vapor comprising one or more refractory metal precursor compounds of the formula MY n  (Formula I), wherein M is a refractory metal, each Y is independently a halogen atom, and n is an integer selected to match the valence of the metal M;    providing a vapor comprising one or more metal-containing precursor compounds having a formula different than Formula I;    contacting the vapors comprising the one or more precursor compounds of Formula I and the one or more metal-containing precursor compounds having a formula different than Formula I with the substrate and allowing one or more compounds to chemisorb on the silicon-containing surface;    providing a vapor comprising one or more disilazanes;    contacting the vapor comprising the one or more disilazanes with the substrate with the one or more chemisorbed compounds thereon to form a refractory metal nitride barrier layer on the silicon-containing surface;    providing a first electrode on the barrier layer;    providing a high dielectric material over at least a portion of the first electrode; and    providing a second electrode over the high dielectric material.    
   
   
       30 . The method of  claim 29  wherein the substrate is a semiconductor substrate or substrate assembly.  
   
   
       31 . The method of  claim 29  further comprising providing a vapor comprising one or more silicon precursor compounds other than the one or more disilazanes and contacting the vapor with the substrate with the chemisorbed compounds thereon to form a refractory metal silicon nitride barrier layer.  
   
   
       32 . The method of  claim 31  wherein the one or more disilazanes are of the formula (R) x H 3-x SiNHSi(R) x H 3-x , wherein each R is independently an organic group, and x is 1 to 3.  
   
   
       33 . The method of  claim 29  wherein providing the vapors and contacting the vapors is accomplished using an atomic layer deposition process comprising a plurality of deposition cycles.