Binary and ternary metal chalcogenide materials and method of making and using same

1. A process of making a ternary metal chalcogenide alloy film on a substrate comprising steps of:

(a) contacting the substrate with a silyl-chalcogen selected from the group consisting of silyltellurium and silylselenium;

(b) contacting the substrate with at least one germanium compound selected from the group consisting of

GeX 4 ,

wherein X is a neucleophilic group selected from the group consisting of OR (alkoxy), CN (cyano), OCN (cyanate), SCN (thiocyanate), carboxylic groups and mixtures thereof; (R 1 O) 4 Ge or (R 1 O) n GeH 4-n , where R 1 is an alkyl group with 1 to 10 carbons in chain, branched, cyclic, or aromatic group; and n=1 to 3;

and

R n GeX′ 4-n ,

wherein X′ is F (fluorine), Cl (chlorine), or Br (bromine); R is hydrogen, or alkyl groups with 1 to 10 carbons in chain, branched, cyclic or aromatic groups; and n=0-3; and

(c) contacting the substrate with a metal compound having a general formula of: M′X n wherein M′ is selected from the group consisting of Sb, In, Sn, Ga, Bi, Ag, Cu, Zr, Hf, Hg, Cd, and Zn;

X is a neucleophilic group selected from the group consisting of OR (alkoxy), F (fluorine), Cl (chlorine), Br (bromine), CN (cyano), OCN (cyanate), SCN (thiocyanate), diketonate, carboxylic groups and mixtures thereof; and n=1 to 5.

2. The process of claim 1 wherein

the silyltellurium is 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 hydrogen, alkyl groups having 1-10 carbons in linear, branched, or cyclic forms without or with double bonds, or aromatic groups; and

the silylselenium is selected from the group consisting of disilylselenium having a general formula: (R 1 R 2 R 3 Si) 2 Se, alkylsilylselenium having a general formula: (R 1 R 2 R 3 Si)SeR 4 , and mixtures thereof;

wherein R 1 , R 2 , R 3 , and R 4 , are independently hydrogen, alkyl groups having 1-10 carbons in linear, branched, or cyclic forms without or with double bonds, or aromatic groups.

3. The process of claim 2 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; and the silylselenium 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.

4. The process of claim 1 wherein the germanium compound is selected from the group consisting of:

(R 1 O) 4 Ge or (R 1 O) n GeH 4-n , where R 1 is an alkyl group with 1 to 10 carbons in chain, branched, cyclic, or aromatic group; and n=1 to 3.

5. The process of claim 1 wherein the process is selected from the group consisting of atomic layer deposition (ALD) process, Chemical Vapor Deposition (CVD) process and solution wet chemistry.

6. The process of claim 1 , wherein the process is an atomic layer deposition (ALD) in an ALD reactor, and the process further comprising a step of: purging the ALD reactor with inert gas selected from the group consisting of N 2 , Ar and mixtures thereof;

wherein the purging step is performed before the contacting step (a) and after each contacting step.

7. The process of claim 1 , wherein the process is a Chemical Vapor Deposition (CVD) in a CVD reactor, and the process further comprising steps of:

purging the CVD reactor with inert gas selected from the group consisting of N 2 , Ar and mixtures thereof; and

pumping the CVD reactor down to a pressure of less than 1 Torr; wherein the purging and pumping steps are performed before the contacting step (a).

8. The CVD process of claim 7 , wherein the CVD is a cyclic-CVD; and all steps are repeated to achieve a desired thickness of the film.

9. An ALD process of making a ternary metal chalcogenide alloy film on a substrate in an ALD reactor comprising steps of:

(a) contacting the substrate with a silyl-chalcogen selected from the group consisting of silyltellurium and silylselenium;

(b) contacting the substrate with at least one germanium compound selected from the group consisting of

GeX 4 ,

wherein X is a neucleophilic group selected from the group consisting of OR (alkoxy), CN (cyano), OCN (cyanate), SCN (thiocyanate), carboxylic groups and mixtures thereof; (R 1 O) 4 Ge or (R 1 O) n GeH 4-n , where R 1 is an alkyl group with 1 to 10 carbons in chain, branched, cyclic, or aromatic group; and n=1 to 3;

and

R n GeX′ 4-n ,

wherein X′ is F (fluorine), Cl (chlorine), or Br (bromine); R is hydrogen, or alkyl groups with 1 to 10 carbons in chain, branched, cyclic or aromatic groups; and n=0-3;

(c) contacting the substrate with a silyl-chalcogen selected from the group consisting of silyltellurium and silylselenium;

(d) contacting the substrate with a metal compound having a general formula of: M′X n ;

wherein: M′ is selected from the group consisting of Sb, In, Sn, Ga, Bi, Ag, Cu, Zr, Hf, Hg, Cd, and Zn; X is a neucleophilic group selected from the group consisting of OR (alkoxy), F (fluorine), Cl (chlorine), Br (bromine), CN (cyano), OCN (cyanate), SCN (thiocyanate), diketonate, carboxylic groups and mixtures thereof; and n=1 to 5; and

(e) purging the ALD reactor with inert gas selected from the group consisting of N 2 , Ar and mixtures thereof;

wherein the purging step (e) is performed before the contacting step (a) and after each contacting step; and

all steps are repeated to achieve a desired thickness of the film.

10. The ALD process of claim 9 wherein

the germanium compound is selected from the group consisting of:

(R 1 O) 4 Ge or (R 1 O) n GeH 4-n , where R 1 is an alkyl group with 1 to 10 carbons in chain, branched, cyclic, or aromatic group; and n=1 to 3;

M′X n is selected from the group consisting of:

(1) (RO) 3 Sb, where R is an alkyl group with 1 to 10 carbons in chain, branched, cyclic, or aromatic group;

(2) antimony halide with the general formula: SbX 3 and SbX 5 , where X is F, Cl, or Br.

11. The ALD process of claim 9 wherein

the silyltellurium is 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 hydrogen, alkyl groups having 1-10 carbons in linear, branched, or cyclic forms without or with double bonds, or aromatic groups; and

the silylselenium is selected from the group consisting of

disilylselenium having a general formula: (R 1 R 2 R 3 Si) 2 Se,

alkylsilylselenium having a general formula: (R 1 R 2 R 3 Si)SeR 4 , and

mixtures thereof;

wherein R 1 , R 2 , R 3 , and R 4 , are independently hydrogen, alkyl groups having 1-10 carbons in linear, branched, or cyclic forms without or with double bonds, or aromatic groups.

12. The ALD process of claim 11 , 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; and the silylselenium 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.

13. The ALD process of claim 9 , wherein the silyl-chalcogen is bis(trimethylsilyl)tellurium, the germanium compound is alkoxygermane, and M′X n is alkoxyantimony.

14. The ALD process of claim 9 wherein deposition temperature ranges from 50° to 400° C.

15. The ALD process of claim 9 wherein M′X n , is (RO) 3 Sb, where R is an alkyl group with 1 to 10 carbons in chain, branched, cyclic, or aromatic group; and

the germanium compound is selected from the group consisting of:

(R 1 O) 4 Ge or (R 1 O) n GeH 4-n , where R 1 is an alkyl group with 1 to 10 carbons in chain, branched, cyclic, or aromatic group; and n=1 to 3;

GeX 4 , or R n GeX 4-n , where X is F, Cl, or Br, R is hydrogen, or alkyl groups with 1 to 10 carbons in chain, branched, cyclic, or aromatic group; and n=0-3.

16. A CVD process of making a ternary metal chalcogenide alloy film on a substrate in an CVD reactor comprising steps of:

(a) contacting the substrate with a silyl-chalcogen selected from the group consisting of silyltellurium and silylselenium; and

(b) contacting the substrate with at least one germanium compound selected from the group consisting of

GeX 4 ,

X is a neucleophilic group selected from the group consisting of OR (alkoxy), CN (cyano), OCN (cyanate), SCN (thiocyanate), carboxylic groups and mixtures thereof; (R 1 O) 4 Ge or (R 1 O) n GeH 4-n , where R 1 is an alkyl group with 1 to 10 carbons in chain, branched, cyclic, or aromatic group; and n=1 to 3;

and

R n GeX′ 4-n ,

wherein X′ is F (fluorine), Cl (chlorine), or Br (bromine); R is hydrogen, or alkyl groups with 1 to 10 carbons in chain, branched, cyclic or aromatic groups; and n=0-3;

(c) contacting the substrate with a metal compound having a general formula of: M′X n ;

wherein: M′ is selected from the group consisting of Sb, In, Sn, Ga, Bi, Ag, Cu, Zr, Hf, Hg, Cd, and Zn; X is a neucleophilic group selected from the group consisting of OR (alkoxy), F (fluorine), Cl (chlorine), Br (bromine), CN (cyano), OCN (cyanate), SCN (thiocyanate), diketonate, carboxylic groups and mixtures thereof; and n=1 to 5;

(d) purging the CVD reactor with inert gas selected from the group consisting of N 2 , Ar and mixtures thereof; and

(e) pumping the CVD reactor down to a pressure of less than 1 Torr;

wherein the purging and pumping steps (d) and (e) are performed before the contacting step (a).

17. The CVD process of claim 16 , wherein the contacting steps are carried out sequentially or concurrently.

18. The CVD process of claim 16 wherein

the germanium compound is selected from the group consisting of:

(R 1 O) 4 Ge or (R 1 O) n GeH 4-n , where R 1 is an alkyl group with 1 to 10 carbons in chain, branched, cyclic, or aromatic group; and n=1 to 3; and

M′X n is selected from the group consisting of:

(1) (RO) 3 Sb, where R is an alkyl group with 1 to 10 carbons in chain, branched, cyclic, or aromatic group;

(2) antimony halide with the general formula: SbX 3 and SbX 5 , where X is F, Cl, or Br.

19. The CVD process of claim 16 wherein

the silyltellurium is 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 hydrogen, alkyl groups having 1-10 carbons in linear, branched, or cyclic forms without or with double bonds, or aromatic groups; and

the silylselenium is selected from the group consisting of:

disilylselenium having a general formula: (R 1 R 2 R 3 Si) 2 Se,

alkylsilylselenium having a general formula: (R 1 R 2 R 3 Si)SeR 4 , and

mixtures thereof;

wherein R 1 , R 2 , R 3 , and R 4 , are independently hydrogen, alkyl groups having 1-10 carbons in linear, branched, or cyclic forms without or with double bonds, or aromatic groups.

20. The CVD process of claim 19 , 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; and the silylselenium 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.

21. The CVD process of claim 16 , wherein the silyl-chalcogen is bis(trimethylsilyl)tellurium, the germanium compound is alkoxygermane, and M′X n is alkoxyantimony.

22. The process of claim 16 , wherein the CVD is a cyclic-CVD; and all steps are repeated to achieve a desired thickness of the film.

23. The CVD process of claim 16 wherein

M′X n is (RO) 3 Sb, where R is an alkyl group with 1 to 10 carbons in chain, branched, cyclic, or aromatic group; and n=1 to 3;

the germanium compound is selected from the group consisting of:

(R 1 O) 4 Ge or (R 1 O) n GeH 4-n , where R 1 is an alkyl group with 1 to 10 carbons in chain, branched, cyclic, or aromatic group; and n=1 to 3; and

GeX 4 , or R n GeX 4-n where X is F, Cl, or Br, R is hydrogen, or alkyl groups with 1 to 10 carbons in chain, branched, cyclic, or aromatic group; and n=0-3.

24. A process of making a metal chalcogenide alloy film on a substrate comprising steps of:

(a) contacting the substrate with a silyl-chalcogen selected from the group consisting of silyltellurium and silylselenium;

(b) contacting the substrate with at least one metal compound selected from the group consisting of:

(R 1 O) 4 Ge or (R 1 O) n GeH 4-n , where R 1 is an alkyl group with 1 to 10 carbons in chain, branched, cyclic, or aromatic group; and n=1 to 3; and

R n GeX′ 4-n ;

wherein X′ is F (fluorine), Cl (chlorine), or Br (bromine); R is hydrogen, or alkyl groups with 1 to 10 carbons in chain, branched, cyclic or aromatic groups; and n=0-3; and

(c) contacting the substrate with a metal compound having a general formula of: M′X n selected from the group consisting of:

(RO) 3 Sb, where R is an alkyl group with 1 to 10 carbons in chain, branched, cyclic, or aromatic group; and

antimony halide with the general formula: SbX 3 and SbX 5 , where X is F, Cl, or Br.