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US 8,507,040 B2Granted
Binary and ternary metal chalcogenide materials and method of making and using same
AssigneeAir Products and Chemicals, Inc.
InventorsManchao Xiao, Xinjian Lei, Liu Yang
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Abstract
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.
Claims20
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:
- R5NR6R7;
- R5OR6;
- and
- R5SR6;
- wherein R5 is an alkylene group with 2 to 6 carbons in chain, branched, or cyclic form;
- R6-7 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(NR2)2, wherein R is a functionalized alkyl group with the general structure of:
- R5NR6R7;
- R5OR6;
- and
- R5SR6;
- wherein R5 is an alkylene group with 2 to 6 carbons in chain, branched, or cyclic form;
- R6-7 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:
- MXn;
- 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), NR2 (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:
- R5NR6R7;
- R5OR6;
- and
- R5SR6;
- wherein R5 is an alkylene group with 2 to 6 carbons in chain, branched, or cyclic;
- R6-7 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.
32 more elements
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:
- R5NR6R7;
- R5OR6;
- and
- R5SR6;
- wherein R5 is an alkylene group with 2 to 6 carbons in chain, branched, or cyclic form;
- R6-7 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(NR2)2, wherein R is a functionalized alkyl group with the general structure of:
- R5NR6R7;
- R5OR6;
- and
- R5SR6;
- wherein R5 is an alkylene group with 2 to 6 carbons in chain, branched, or cyclic form;
- R6-7 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:
- MXn;
- 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), NR2 (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:
- R5NR6R7;
- R5OR6;
- and
- R5SR6;
- wherein R5 is an alkylene group with 2 to 6 carbons in chain, branched, or cyclic;
- R6-7 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 N2, 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.
36 more elements
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:
- R5NR6R7;
- R5OR6;
- and
- R5SR6;
- wherein R5 is an alkylene group with 2 to 6 carbons in chain, branched, or cyclic form;
- R6-7 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(NR2)2 wherein R is a functionalized alkyl group with the general structure of:
- R5NR6R7;
- R5OR6;
- and
- R5SR6;
- wherein R5 is an alkylene group with 2 to 6 carbons in chain, branched, or cyclic form;
- R6-7 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:
- MXn;
- 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:
- R5NR6R7;
- R5OR6;
- and
- R5SR6;
- wherein R5 is an alkylene group with 2 to 6 carbons in chain, branched, or cyclic;
- R6-7 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 N2, 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).
34 more elements
Dependencies are inferred from the claim text.