Method of Making a Multicomponent Film

Abstract

Described herein is a method and liquid-based precursor composition for depositing a multicomponent film. In one embodiment, the method and compositions described herein are used to deposit Germanium Tellurium (GeTe), Antimony Tellurium (SbTe), Antimony Germanium (SbGe), Germanium Antimony Tellurium (GST), Indium Antimony Tellurium (IST), Silver Indium Antimony Tellurium (AIST), Cadmium Telluride (CdTe), Cadmium Selenide (CdSe), Zinc Telluride (ZnTe), Zinc Selenide (ZnSe), Copper indium gallium selenide (CIGS) films or other tellurium and selenium based metal compounds for phase change memory and photovoltaic devices.

1 - 9 . (canceled) 
     
     
         10 . A method of depositing a multicomponent film on a substrate comprising steps of:
 (a) contacting the substrate with an In precursor or a precursor solution comprising the In precursor to react with the substrate to provide a first coating layer comprising In;   (b) rinsing at least a portion of the first coating layer with a rinse solution to remove any unreacted In precursor;   (c) contacting the first coating layer comprising In with a Te precursor or a precursor solution comprising the Te precursor, wherein at least a portion of the Te precursor reacts with the In comprised therein to provide a second coating layer comprising In and Te;   (d) rinsing at least a portion of the second coating layer with rinse solution to remove any unreacted Te precursor;   (e) contacting the second coating layer comprising In and Te with a Sb precursor or a precursor solution comprising the Sb precursor, wherein at least a portion of the Sb precursor reacts with at least a portion of the In and Te comprised therein to provide a third coating layer comprising In, Sb, and Te;   (f) rinsing at least a portion of the third coating layer with rinse solution to remove any unreacted Sb precursor,   (g) contacting the third coating layer comprising In, Te, and Sb with a Te precursor or a precursor solution comprising the Te precursor to provide a fourth coating layer comprising In, Te, and Sb; and   (h) rinsing at least a portion of the fourth coating layer with rinse solution to remove any unreacted Te precursor,   wherein steps (a) through (h) are repeated to form a number of coating layers to provide the film.   
     
     
         11 . The method of  claim 10  further comprising the steps of:
 (i) contacting the fourth coating layer comprising In, Te, and Sb with a Ag precursor or a precursor solution comprising the Ag precursor wherein at least a portion of the Ag precursor reacts with at least a portion of the In, Te, and Sb comprised therein to provide a fifth coating layer comprising In, Te, Sb and Ag; 
 (j) rinsing at least a portion of the fifth coating layer with the rinse solution to remove unreacted Ag precursor; 
 (k) contacting the fifth coating layer comprising In, Te, Sb and Ag with a Te precursor or a precursor solution comprising the Te precursor to react with the fifth coating layer to provide a sixth coating layer comprising In, Te, Sb and Ag; and 
 (l) rinsing at least a portion of the sixth coating layer with rinse solution to remove any unreacted Te precursor, 
 wherein steps (a) through (l) are repeated to form a number of coating layers to provide the film. 
 
     
     
         12 . The method of  claim 10  wherein the In precursor comprises a compound having the following formula: MX n  wherein M is In; X is a nucleophilic group selected from the group consisting of OR(alkoxy), F(fluorine), Cl (chlorine), Br (bromine), NR 2 (amino), CN (cyano), OCN (cyanate), SCN (thiocyanate), diketonate, carboxylic groups and mixtures thereof; and n=1 to 3. 
     
     
         13 . The method of  claim 10  wherein the Te precursor comprises a silyltellurium selected from the group consisting of disilyltellutium having a general formula: (R 1 R 2 R 3 Si) 2 Te; alkylsilyltellurium having a general formula: (R 1 R 2 R 3 Si)TeR 4 ; and mixtures thereof wherein R 1 , R 2 , R 3 , and R 4  are each independently selected from the group consisting of: hydrogen; linear, branched, or unsaturated C 1-10  alkyl groups; C 4-10  cyclic alkyl groups; and C 4-12  aromatic groups. 
     
     
         14 . The method of  claim 10  wherein the Sb precursor comprises a compound having the following formula: MX n  wherein M is Sb; X is a nucleophilic group selected from the group consisting of OR(alkoxy), F(fluorine), Cl (chlorine), Br (bromine), NR 2 (amino), CN (cyano), OCN (cyanate), SCN (thiocyanate), diketonate, carboxylic groups and mixtures thereof; and n=3 to 5. 
     
     
         15 . The method of  claim 10  wherein the at least one of the In, the Te, and the Sb precursors in the contacting steps comprises a precursor solution. 
     
     
         16 . The method of  claim 15  wherein the precursor solution comprises the precursor and at least one solvent selected from the group consisting of a hydrocarbon, a halogenated hydrocarbon, and an ether. 
     
     
         17 . The method of  claim 16  wherein the solvent comprises a hydrocarbon. 
     
     
         18 . The method of  claim 17  wherein the solvent is at least one selected from the group consisting of hexane, octane, toluene, and combinations thereof. 
     
     
         19 . The method of  claim 16  wherein the amount of solvent in the precursor solution ranges from about 0.01 to about 90 weight percent. 
     
     
         20 . A method of depositing a multicomponent film onto at least a portion of a substrate comprising steps of:
 (a) contacting the substrate with an Cd precursor or a precursor solution comprising the Cd precursor to react with the substrate to provide a first coating layer comprising Cd;   (b) rinsing at least a portion of the first coated layer with a rinse solution to remove any unreacted Cd precursor;   (c) contacting the first coating layer comprising Cd with a Te precursor or a precursor solution comprising the Te precursor, wherein at least a portion of the Te precursor reacts with at least a portion of the Cd comprised therein to provide a second coating layer comprising Cd and Te;   (d) rinsing at least a portion of the second coating layer with rinse solution to remove any unreacted Te precursor,   wherein steps (a) through (d) are repeated to form a number of coating layers to provide the film.   
     
     
         21 . The method of  claim 20  wherein Te precursor comprises a silyltellurium selected from the group consisting of disilyltellutium having a general formula: (R 1 R 2 R 3 Si) 2 Te, alkylsilyltellurium having a general formula: (R 1 R 2 R 3 Si)TeR 4 , and mixtures thereof wherein R 1 , R 2 , R 3  and R 4  are independently selected from the group consisting of: hydrogen; linear, branched, or unsaturated C 1-10  alkyl groups; C 4-10  cyclic alkyl groups; and C 4-12  aromatic groups. 
     
     
         22 . The method of  claim 20  wherein the silyltellurium is selected from the group consisting of bis(trimethylsilyl)tellurium, bis(dimethylsilyl)tellurium, bis(triethylsilyl)tellurium, bis(diethylsilyl)tellurium, bis(phenyldimethylsilyl)tellurium, bis(t-butyldimethylsilyl)tellurium, dimethylsilylmethyltellurium, dimethylsilylphenyltellurium, dimethylsilyl-n-butyltellurium, dimethylsilyl-t-butyltellurium, trimethylsilylmethyltellurium, trimethylsilylphenyltellurium, trimethylsilyl-n-butyltellurium, and trimethylsilyl-t-butyltellurium. 
     
     
         23 . A method of depositing a multicomponent film on at least a portion of a substrate comprising the steps of:
 (a) contacting the substrate with a Sb precursor or a precursor solution comprising the Sb precursor to react with the substrate to provide a first coating layer comprising Sb;   (b) rinsing at least a portion of the first coated layer with a rinse solution to remove any unreacted Sb precursor;   (c) contacting the first coating layer comprising Sb with a Te precursor or a precursor solution comprising the Te precursor, wherein at least a portion of the Te precursor reacts with the Sb comprised therein to provide a second coating layer comprising Sb and Te;   (d) rinsing at least a portion of the second coating layer with rinse solution to remove any unreacted Te precursor;   (e) contacting the second coating layer comprising Sb and Te with a Ge precursor or a precursor solution comprising the Ge precursor, wherein at least a portion of the Ge precursor reacts with at least a portion of the Sb and Te comprised therein to provide a third coating layer comprising Ge, Te, and Sb;   (f) rinsing at least a portion of the third coating layer with rinse solution to remove any unreacted Ge precursor;   (g) contacting the third coating layer comprising Sb, Te, and Ge with a Te precursor or a precursor solution comprising the Te precursor to react with the third coating layer to provide a fourth coating layer comprising Sb, Te, and Ge; and   (h) rinsing at least a portion of the fourth coating layer with rinse solution to remove any unreacted Te precursor,   wherein steps (a) through (h) are repeated to form a number of coating layers and provide the film.   
     
     
         24 . A method of depositing a multicomponent film onto at least a portion of a substrate comprising steps of:
 (a) contacting the substrate with a Ge precursor or a precursor solution comprising the Ge precursor to react with the substrate to provide a first coating layer comprising Ge;   (b) rinsing at least a portion of the first coated layer with a rinse solution to remove any unreacted Ge precursor;   (c) contacting the first coating layer comprising Ge with a Sb precursor or a precursor solution comprising the Sb precursor, wherein at least a portion of the Sb precursor reacts with at least a portion of the Sb comprised therein to provide a second coating layer comprising Ge and Sb;   (d) rinsing at least a portion of the second coating layer with rinse solution to remove any unreacted Sb precursor,   wherein steps (a) through (d) are repeated to form a number of coating layers to provide the film.   
     
     
         25 . The method of  claim 24  wherein the Ge precursor comprises a compound having the following formula: MX n  wherein M is Ge; X is a nucleophilic group selected from the group consisting of OR(alkoxy), F(fluorine), Cl (chlorine), Br (bromine), NR 2 (amino), CN (cyano), OCN (cyanate), SCN (thiocyanate), diketonate, carboxylic groups and mixtures thereof; and n=2 to 4. 
     
     
         26 . The method of  claim 24  wherein the Sb precursor comprises a silyl antimony compound. 
     
     
         27 . A method of depositing a multicomponent film onto at least a portion of a substrate comprising steps of:
 (a) contacting the substrate with a MX n  wherein M is a metal or metalloid selected from the group consisting of: Ge, Sb, In, Sn, Ga, Bi, Ag, Cu, Zr, Hf, Hg, Cd, Zn, Ru, Rh, Pd, Os, Ir, Pt and Au; and X is neucleophilic group selected from the group consisting of: OR(alkoxy), F(fluorine), Cl (chlorine), Br (bromine), NR 2 (amino), CN (cyano), OCN (cyanate), SCN (thiocyanate), diketonate, and carboxylic groups;   (b) rinsing at least a portion of the first coated layer with a rinse solution to remove any unreacted precursor;   (c) contacting the first coating layer comprising an organosilyl precursor or a precursor solution;   (d) rinsing at least a portion of the second coating layer with rinse solution to remove any unreacted precursor,   wherein steps (a) through (d) are repeated to form a number of coating layers to provide the film and the metal or metalloid can be selected independently from step to step.   
     
     
         28 . The method of  claim 27  wherein the organosilyl is selected from the group consisting of bis(trimethylsilyl)tellurium, bis(dimethylsilyl)tellurium, bis(triethylsilyl)tellurium, bis(diethylsilyl)tellurium, bis(phenyldimethylsilyl)tellurium, bis(t-butyldimethylsilyl)tellurium, dimethylsilylmethyltellurium, dimethylsilylphenyltellurium, dimethylsilyl-n-butyltellurium, dimethylsilyl-t-butyltellurium, trimethylsilylmethyltellurium, trimethylsilylphenyltellurium, trimethylsilyl-n-butyltellurium, and trimethylsilyl-t-butyltellurium. 
     
     
         29 . The method of  claim 27  wherein the organosilyl is selected from the group consisting of bis(trimethylsilyl)selenium, bis(dimethylsilyl)selenium, bis(triethylsilyl)selenium, bis(diethylsilyl) selenium, bis(phenyldimethylsilyl) selenium, bis(t-butyldimethylsilyl) selenium, dimethylsilylmethyl selenium, dimethylsilylphenyl selenium, dimethylsilyl-n-butyl selenium, dimethylsilyl-t-butyl selenium, trimethylsilylmethyl selenium, trimethylsilylphenyl selenium, trimethylsilyl-n-butyl selenium, and trimethylsilyl-t-butylselenium. 
     
     
         30 . The deposited films of  claim 27  is selected from the group selected from Germanium Tellurium (GeTe), Antimony Tellurium (SbTe), Antimony Germanium (SbGe), Germanium Antimony Tellurium (GST), Indium Antimony Tellurium (IST), Silver Indium Antimony Tellurium (AIST), Cadmium Telluride (CdTe), Cadmium Selenide (CdSe), Zinc Telluride (ZnTe), Zinc Selenide (ZnSe), Copper indium gallium selenide (CIGS).