Binary and ternary metal chalcogenide materials and method of making and using same
View Patent ↗This invention discloses the synthesis of metal chalcogenides using chemical vapor deposition (CVD) process, atomic layer deposition (ALD) process, or wet solution process. Ligand exchange reactions of organosilyltellurium or organosilylselenium with a series of metal compounds having neucleophilic substituents generate metal chalcogenides. This chemistry is used to deposit germanium-antimony-tellurium (GeSbTe) and germanium-antimony-selenium (GeSbSe) films or other tellurium and selenium based metal compounds for phase change memory and photovoltaic devices.
1. 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 a germanium compound having a general formula comprising at least one selected from the group consisting of (i) Ge(OR) 2 ,
wherein R is selected from the group consisting of
an alkyl group with 1 to 10 carbons in chain, branched, or cyclic form;
a functionalized alkyl group with the general structure of:
R 5 NR 6 R 7 ;
R 5 OR 6 ; and
R 5 SR 6 ;
wherein R 5 is an alkylene group with 2 to 6 carbons in chain, branched, or cyclic form; R 6-7 are independently selected from the group consisting of hydrogen, alkyl groups with 1 to 6 carbons in chain, branched, or cyclic form; and
(ii) Ge(NR 2 ) 2 , wherein R is a functionalized alkyl group with the general structure of:
R 5 NR 6 R 7 ;
R 5 OR 6 ; and
R 5 SR 6 ;
wherein R 5 is an alkylene group with 2 to 6 carbons in chain, branched, or cyclic form;
R 6-7 are independently selected from the group consisting of hydrogen, alkyl groups with 1 to 6 carbons in chain, branched, or cyclic form;
and
(c) contacting the substrate with a metal compound having a general formula of: MX n ;
wherein: M is selected from the group consisting of Sb, In, Sn, Ga, Bi, Ag, Cu, Zr, Hf, Hg, Cd, Zn and noble metals;
X is a 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, carboxylic groups and mixtures thereof, wherein R is selected from the group consisting of
an alkyl group with 1 to 10 carbons in chain, branched, or cyclic form;
and a functionalized alkyl group with the general structure of:
R 5 NR 6 R 7 ;
R 5 OR 6 ; and
R 5 SR 6 ;
wherein R 5 is an alkylene group with 2 to 6 carbons in chain, branched, or cyclic; R 6-7 are independently selected from the group consisting of hydrogen, alkyl groups with 1 to 6 carbons in chain, branched, or cyclic form; and
n=1 to 5.
2. The process of claim 1 wherein
the silyltellurium is selected from the group consisting of disilyltellurium 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 Ge(OBu t ) 2 , Ge(OCH 2 CH 2 NMe 2 ) 2 , Ge(OCH(Me)CH 2 CH 2 NMe 2 ) 2 , Ge(OC(Me) 2 CH 2 CH 2 NMe 2 ) 2 , Ge(OCH(Me)CH 2 CH 2 NEt 2 ) 2 , Ge(OCMe 2 CH 2 CH 2 NEt 2 ) 2 , Ge(OCH 2 CH 2 OMe) 2 , Ge(OCH 2 CH 2 OEt) 2 , Ge(OCH 2 CH 2 OPr i ) 2 , Ge(OCH(Me)CH 2 CH 2 OMe) 2 , Ge(OCH(Me)CH 2 CH 2 OEt) 2 , Ge(OCH(Me)CH 2 CH 2 OPr i ) 2 , Ge(OC(Me) 2 CH 2 CH 2 OMe) 2 , Ge(OC(Me) 2 CH 2 CH 2 OEt) 2 , Ge(OC(Me) 2 CH 2 CH 2 OPr i ) 2 , Ge(OCH 2 CH 2 SMe) 2 , Ge(MeNCH 2 CH 2 NMe 2 ) 2 , and Ge(MeNCH 2 CH 2 NEt 2 ) 2 .
5. The process of claim 1 , wherein the metal compound is an antimony compound selected from the group consisting of (a) (RO) 3 Sb, where R is an alkyl group with 1 to 10 carbons in chain, branched, or cyclic; and (b) antimony halide with the general formula: SbX 3 and SbX 5 , where X is F, Cl, or Br.
6. The process of claim 5 , the antimony compound is selected from the group consisting of Sb(OMe) 3 , and Sb(OEt) 3 .
7. 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.
8. The process of claim 1 , wherein the metal chalcogenide alloy film is germanium-antimony-tellurium with a composition of Ge 2 Sb 2 Te 5 .
9. An ALD process of making a 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; and
(b) contacting the substrate with a germanium compound having a general formula comprising at least one selected from the group consisting of (i) Ge(OR) 2 ;
wherein R is selected from the group consisting of
an alkyl group with 1 to 10 carbons in chain, branched, or cyclic form;
a functionalized alkyl group with the general structure of:
R 5 NR 6 R 7 ;
R 5 OR 6 ; and
R 5 SR 6 ;
wherein R 5 is an alkylene group with 2 to 6 carbons in chain, branched, or cyclic form; R 6-7 are independently selected from the group consisting of hydrogen, alkyl groups with 1 to 6 carbons in chain, branched, or cyclic form; and
(ii) Ge(NR 2 ) 2 , wherein R is a functionalized alkyl group with the general structure of:
R 5 NR 6 R 7 ;
R 5 OR 6 ; and
R 5 SR 6 ;
wherein R 5 is an alkylene group with 2 to 6 carbons in chain, branched, or cyclic form;
R 6-7 are independently selected from the group consisting of hydrogen, alkyl groups with 1 to 6 carbons in chain, branched, or cyclic form;
(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: MX n ;
wherein M is selected from the group consisting of Sb, In, Sn, Ga, Bi, Ag, Cu, Zr, Hf, Hg, Cd, Zn and noble metals; X is a 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, carboxylic groups and mixtures thereof, wherein R is selected from the group consisting of
an alkyl group with 1 to 10 carbons in chain, branched, or cyclic form; and
a functionalized alkyl group with the general structure of:
R 5 NR 6 R 7 ;
R 5 OR 6 ; and
R 5 SR 6 ;
wherein R 5 is an alkylene group with 2 to 6 carbons in chain, branched, or cyclic; R 6-7 are independently selected from the group consisting of hydrogen, alkyl groups with 1 to 6 carbons in chain, branched, or cyclic form; and n=1 to 5;
(e) optionally, 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
(f) all steps are repeated to achieve a desired thickness of the film.
10. 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; and
the metal compound is an antimony compound selected from the group consisting of (a) (RO) 3 Sb, where R is an alkyl group with 1 to 10 carbons in chain, branched, or cyclic; and (b) antimony halide with the general formula: SbX 3 and SbX 5 , where X is F, Cl, or Br.
11. The ALD process of claim 10 , 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.
12. The ALD process of claim 10 , wherein the germanium compound is selected from the group consisting of Ge(OBu t ) 2 , Ge(OCH 2 CH 2 NMe 2 ) 2 , Ge(OCH(Me)CH 2 CH 2 NMe 2 ) 2 , Ge(OC(Me) 2 CH 2 CH 2 NMe 2 ) 2 , Ge(OCH(Me)CH 2 CH 2 NEt 2 ) 2 , Ge(OCMe 2 CH 2 CH 2 NEt 2 ) 2 , Ge(OCH 2 CH 2 OMe) 2 , Ge(OCH 2 CH 2 OEt) 2 , Ge(OCH 2 CH 2 OPr i ) 2 , Ge(OCH(Me)CH 2 CH 2 OMe) 2 , Ge(OCH(Me)CH 2 CH 2 OEt) 2 , Ge(OCH(Me)CH 2 CH 2 OPr i ) 2 , Ge(OC(Me) 2 CH 2 CH 2 OMe) 2 , Ge(OC(Me) 2 CH 2 CH 2 OEt) 2 , Ge(OC(Me) 2 CH 2 CH 2 OPr i ) 2 , Ge(OCH 2 CH 2 SMe) 2 , Ge(MeNCH 2 CH 2 NMe 2 ) 2 , and Ge(MeNCH 2 CH 2 NEt 2 ) 2 ; and
the antimony compound is selected from the group consisting of Sb(OMe) 3 , Sb(OEt) 3 , Sb(NMe 2 ) 3 , Sb(NMeEt) 3 , and Sb(NEt 2 ) 2 .
13. The ALD process of claim 11 , wherein the germanium compound is selected from the group consisting of Ge(OBu t ) 2 , Ge(OCH 2 CH 2 NMe 2 ) 2 , Ge(OC(Me) 2 CH 2 CH 2 NMe 2 ) 2 , Ge(OCH(Me)CH 2 CH 2 NEt 2 ) 2 , Ge(OCMe 2 CH 2 CH 2 NEt 2 ) 2 , (OCMe 2 CH 2 CH 2 NEt 2 ) 2 , Ge(OCH 2 CH 2 OMe) 2 , Ge(OCH 2 CH 2 OEt) 2 , Ge(OCH 2 CH 2 OPr i ) 2 , Ge(OCH(Me)CH 2 CH 2 OMe) 2 , Ge(OCH(Me)CH 2 CH 2 OEt) 2 , Ge(OCH(Me)CH 2 CH 2 OPr i ) 2 , Ge(OC(Me) 2 CH 2 CH 2 OMe) 2 , Ge(OC(Me) 2 CH 2 CH 2 OEt) 2 , Ge(OC(Me) 2 CH 2 CH 2 OPr i ) 2 , Ge(OCH 2 CH 2 SMe) 2 , Ge(MeNCH 2 CH 2 NMe 2 ) 2 , and Ge(MeNCH 2 CH 2 NEt 2 ) 2 ; and
the antimony compound is selected from the group consisting of Sb(OMe) 3 , Sb(OEt) 3 , Sb(NMe 2 ) 3 , Sb(NMeEt) 3 , and Sb(NEt 2 ) 2 .
14. The ALD process of claim 13 , wherein the metal chalcogenide alloy film is germanium-antimony-tellurium with a composition of Ge 2 Sb 2 Te 5 .
15. A CVD process of making a 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;
(b) contacting the substrate with a germanium compound having a general formula comprising at least one selected from the group consisting of (i) Ge(OR) 2
wherein R is selected from the group consisting of
an alkyl group with 1 to 10 carbons in chain, branched, or cyclic form;
a functionalized alkyl group with the general structure of:
R 5 NR 6 R 7 ;
R 5 OR 6 ; and
R 5 SR 6 ;
wherein R 5 is an alkylene group with 2 to 6 carbons in chain, branched, or cyclic form; R 6-7 are independently selected from the group consisting of hydrogen, alkyl groups with 1 to 6 carbons in chain, branched, or cyclic form; and
(ii) Ge(NR 2 ) 2 wherein R is a functionalized alkyl group with the general structure of:
R 5 NR 6 R 7 ;
R 5 OR 6 ; and
R 5 SR 6 ;
wherein R 5 is an alkylene group with 2 to 6 carbons in chain, branched, or cyclic form;
R 6-7 are independently selected from the group consisting of hydrogen, alkyl groups with 1 to 6 carbons in chain, branched, or cyclic form;
(c) contacting the substrate with a metal compound having a general formula of: MX n ;
wherein M is selected from the group consisting of Sb, In, Sn, Ga, Bi, Ag, Cu, Zr, Hf, Hg, Cd, Zn and noble metals; 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, wherein R is selected from the group consisting of
an alkyl group with 1 to 10 carbons in chain, branched, or cyclic form; and
a functionalized alkyl group with the general structure of:
R 5 NR 6 R 7 ;
R 5 OR 6 ; and
R 5 SR 6 ;
wherein R 5 is an alkylene group with 2 to 6 carbons in chain, branched, or cyclic; R 6-7 are independently selected from the group consisting of hydrogen, alkyl groups with 1 to 6 carbons in chain, branched, or cyclic form; 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).
16. The CVD process of claim 15 , wherein the contacting steps are carried out sequentially or concurrently.
17. The CVD process of claim 15 , 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.
18. The CVD process of claim 15 , wherein the germanium compound is selected from the group consisting of Ge(OBu t ) 2 , Ge(OCH 2 CH 2 NMe 2 ) 2 , Ge(OCH(Me)CH 2 CH 2 NMe 2 ) 2 , Ge(OC(Me) 2 CH 2 CH 2 NMe 2 ) 2 , Ge(OCH(Me)CH 2 CH 2 NEt 2 ) 2 , Ge(OCMe 2 CH 2 CH 2 NEt 2 ) 2 , Ge(OCH 2 CH 2 OMe) 2 , Ge(OCH 2 CH 2 OEt) 2 , Ge(OCH 2 CH 2 OPr i ) 2 , Ge(OCH(Me)CH 2 CH 2 OMe) 2 , Ge(OCH(Me)CH 2 CH 2 OEt) 2 , Ge(OCH(Me)CH 2 CH 2 OPr i ) 2 , Ge(OC(Me) 2 CH 2 CH 2 OMe) 2 , Ge(OC(Me) 2 CH 2 CH 2 OEt) 2 , Ge(OC(Me) 2 CH 2 CH 2 OPr i ) 2 , Ge(OCH 2 CH 2 SMe) 2 , Ge(MeNCH 2 CH 2 NMe 2 ) 2 , and Ge(MeNCH 2 CH 2 NEt 2 ) 2 ; and
the antimony compound is selected from the group consisting of Sb(OMe) 3 , Sb(OEt) 3 , Sb(NMe 2 ) 3 , Sb(NMeEt) 3 , and Sb(NEt 2 ) 2 .
19. The CVD process of claim 17 , wherein the germanium compound is selected from the group consisting of Ge(OBu t ) 2 , Ge(OCH 2 CH 2 NMe 2 ) 2 , Ge(OCH(Me)CH 2 CH 2 NMe 2 ) 2 , Ge(OC(Me) 2 CH 2 CH 2 NMe 2 ) 2 , Ge(OCH(Me)CH 2 CH 2 NEt 2 ) 2 , Ge(OCMe 2 CH 2 CH 2 NEt 2 ) 2 , Ge(OCH 2 CH 2 OMe) 2 , Ge(OCH 2 CH 2 OEt) 2 , Ge(OCH 2 CH 2 OPr i ) 2 , Ge(OCH(Me)CH 2 CH 2 OMe) 2 , Ge(OCH(Me)CH 2 CH 2 OEt) 2 , Ge(OCH(Me)CH 2 CH 2 OPr i ) 2 , Ge(OC(Me) 2 CH 2 CH 2 OMe) 2 , Ge(OC(Me) 2 CH 2 CH 2 OEt) 2 , Ge(OC(Me) 2 CH 2 CH 2 OPr i ) 2 , Ge(OCH 2 CH 2 SMe) 2 , Ge(MeNCH 2 CH 2 NMe 2 ) 2 , and Ge(MeNCH 2 CH 2 NEt 2 ) 2 ; and
the antimony compound is selected from the group consisting of Sb(OMe) 3 , Sb(OEt) 3 , Sb(NMe 2 ) 3 , Sb(NMeEt) 3 , and Sb(NEt 2 ) 2 .
20. The CVD process of claim 19 , wherein the metal chalcogenide alloy film is germanium-antimony-tellurium with a composition of Ge 2 Sb 2 Te 5 .