Method of forming copper sulfide layer over substrate
View Patent ↗Methods of forming copper sulfide regions or layers over a substrate are disclosed. The copper sulfide regions or layers are formed by contacting a sulfide compound with a substrate containing at least copper and contacting a copper vapor precursor with the substrate to form the copper sulfide layer. Methods of making a memory devices/cells containing a copper sulfide layer, methods of using the memory devices/cells, and devices such as computers containing the memory devices/cells are also disclosed.
1. A method of making a copper sulfide layer on a substrate comprising at least copper, comprising:
contacting a sulfide compound with the substrate; and thereafter
contacting a copper vapor precursor with the substrate to form the copper sulfide layer.
2. The method of claim 1 , wherein the sulfide compound has a general formula of R 2 S, wherein each R is independently a Group IA element or an organic group.
3. The method of claim 1 , wherein the sulfide compound comprises from about 0.1% to about 100% by weight of the sulfide compound and from about 0% to about 99.9% by weight of at least one inert gas.
4. The method of claim 1 , wherein the copper vapor precursor comprises from about 0.1% to about 100% by weight of the copper vapor precursor and from about 0% to about 99.9% by weight of at least one inert gas.
5. The method of claim 1 , wherein the sulfide compound is contacted with the substrate for a time from about 1 second to about 60 minutes at a temperature from about 15° C. to about 500° C.
6. The method of claim 1 , wherein the copper vapor precursor is contacted with the substrate for a time from about 1 second to about 60 minutes at a temperature from about 15° C. to about 500° C.
7. The method of claim 1 , wherein the copper vapor precursor comprises at least one selected from the group consisting of a copper halide, copper acetyl acetonate, copper tetramethyl heptanedionate, cyclopentadienyl-copper-trialkylphosphine, t-butoxy-copper-t-butyldifluorophosphane, t-butoxy-copper-phenyldifluorophosphane, t-butoxy-copper-diethylaminodifluorophosphane, 2-trifluoromethylpropane-2-oxy-copper-t-butylisonitrile, 2-trifluoromethylpropane-2-oxy-copper-trimethylphosphane, perfluoro-t-butoxy-copper-t-butylisonitrile, perfluoro-t-butoxy-copper-trimethylphosphane, C 5 H 5 —Cu-t-BuNC and Cu(hfac)R, where R is at least one of 1,5-cyclooctadiene, hexyne, butyne, trimethylvinylsilyl, bis(trimethylsilyl)acetylene, triethoxyvinylsilane and trimethylallylsilane.
8. The method of claim 1 , wherein the method comprises contacting the sulfide compound with the substrate and forming a copper-sulfur bond on a surface of the substrate; and thereafter contacting the copper vapor precursor with the substrate and forming an additional copper-sulfur bond between a copper element of the copper vapor precursor and a sulfur element that is previously attached to the substrate, and the copper sulfide layer has a thickness of about 2 Å or more and about 0.1 μm or less.
9. The method of claim 2 , wherein the organic group comprises at least one aliphatic or aromatic organic moiety having from about 1 to about 100 carbon atoms which may include one or more oxygen, sulfur, or nitrogen, or fluorine atoms, wherein the aliphatic chain may be linear, branched, saturated or unsaturated, and wherein either the aliphatic chain or the aromatic ring may have substituted groups thereon.
10. A method of making a memory cell comprising:
providing a first electrode comprising at least copper;
contacting a sulfide compound with the first electrode and thereafter contacting a copper vapor precursor with the first electrode to form a copper sulfide layer on the first electrode;
forming an active layer over the copper sulfide layer; and
forming a second electrode over the active layer.
11. The method of claim 10 , wherein the sulfide compound has a general formula of R 2 S, wherein each R is independently a Group IA element or an organic group.
12. The method of claim 10 , wherein the sulfide compound comprises from about 0.1% to about 100% by weight of the sulfide compound and from about 0% to about 99.9% by weight of at least one inert gas.
13. The method of claim 10 , wherein the copper vapor precursor comprises from about 0.1% to about 100% by weight of the copper vapor precursor and from about 0% to about 99.9% by weight of at least one inert gas.
14. The method of claim 10 , wherein the sulfide compound is contacted with the first electrode for a time from about 1 second to about 60 minutes at a temperature from about 15° C. to about 500° C.
15. The method of claim 10 , wherein the copper vapor precursor is contacted with the first electrode for a time from about 1 second to about 60 minutes at a temperature from about 15° C. to about 500° C.
16. The method of claim 10 , wherein the copper vapor precursor comprises at least one selected from the group consisting of a copper halide, copper acetyl acetonate, copper tetramethyl heptanedionate, cyclopentadienyl-copper-trialkylphosphine, t-butoxy-copper-t-butyldifluorophosphane, t-butoxy-copper-phenyldifluorophosphane, t-butoxy-copper-diethylaminodifluorophosphane, 2-trifluoromethylpropane-2-oxy-copper-t-butylisonitrile, 2-trifluoromethylpropane-2-oxy-copper-trimethylphosphane, perfluoro-t-butoxy-copper-t-butylisonitrile, perfluoro-t-butoxy-copper-trimethylphosphane, C 5 H 5 —Cu-t-BuNC and Cu(hfac)R, where R is at least one of 1,5-cyclooctadiene, hexyne, butyne, trimethylvinylsilyl, bis(trimethylsilyl)acetylene, triethoxyvinylsilane and trimethylallylsilane.
17. The method of claim 10 , wherein the active layer comprises at least one selected from the group consisting of polyacetylene; polydiphenylacetylene; poly(t-butyl)diphenylacetylene; poly(trifluoromethyl)diphenylacetylene; polybis(trifluoromethyl)acetylene; polybis(t-butyldiphenyl)acetylene; poly(trimethylsilyl)diphenylacetylene; poly(carbazole)diphenylacetylene; polydiacetylene; polyphenylacetylene; polypyridineacetylene; polymethoxyphenylacetylene; polymethylphenylacetylene; poly(t-butyl)phenylacetylene; polynitro-phenylacetylene; poly(trifluoromethyl)phenylacetylene; poly(trimethylsilyl)pheylacetylene; polydipyrrylmethane; polyindoqiunone; polydihydroxyindole; polytrihydroxyindole; furane-polydihydroxyindole; polyindoqiunone-2-carboxyl; polyindoqiunone; polybenzobisthiazole; poly(p-phenylene sulfide); polyaniline; polythiophene; polypyrrole; polysilane; polystyrene; polyfuran; polyindole; polyazulene; polyphenylene; polypyridine; polybipyridine; polyphthalocyanine; polysexithiofene; poly(siliconoxohemiporphyrazine); poly(germaniumoxohemiporphyrazine); poly(ethylenedioxythiophene); polymetallocene complexes; and polypyridine metal complexes.
18. The method of claim 10 , wherein the method comprises contacting the sulfide compound with the first electrode and forming a copper-sulfur bond on a surface of the first electrode; and thereafter contacting the copper vapor precursor with the first electrode and forming an additional copper-sulfur bond between a copper element of the copper vapor precursor and a sulfur element that is previously attached to the first electrode, and the copper sulfide layer has a thickness of about 2 Å or more and about 0.1 μm or less.
19. The method of claim 11 , wherein the organic group comprises at least one aliphatic or aromatic organic moiety having from about 1 to about 100 carbon atoms which may include one or more oxygen, sulfur, or nitrogen, or fluorine atoms, wherein the aliphatic chain may be linear, branched, saturated or unsaturated, and wherein either the aliphatic chain or the aromatic ring may have substituted groups thereon.
20. A copper sulfide layer on a substrate comprising at least copper, the copper sulfide layer made by contacting a sulfide compound with the substrate and thereafter contacting a copper vapor precursor with the substrate.
21. The method of claim 20 , wherein the sulfide compound has a general formula of R 2 S, wherein each R is independently a Group IA element or an organic group.
22. The method of claim 20 , wherein the sulfide compound comprises from about 0.1% to about 100% by weight of the sulfide compound and from about 0% to about 99.9% by weight of at least one inert gas.
23. The method of claim 20 , wherein the copper vapor precursor comprises from about 0.1% to about 100% by weight of the copper vapor precursor and from about 0% to about 99.9% by weight of at least one inert gas.
24. The method of claim 20 , wherein the sulfide compound is contacted with the first electrode for a time from about 1 second to about 60 minutes at a temperature from about 15° C. to about 500° C.
25. The method of claim 20 , wherein the copper vapor precursor is contacted with the first electrode for a time from about 1 second to about 60 minutes at a temperature from about 150° C. to about 500° C.
26. The method of claim 20 , wherein the copper vapor precursor comprises at least one selected from the group consisting of a copper halide, copper acetyl acetonate, copper tetramethyl heptanedionate, cyclopentadienyl-copper-trialkylphosphine, t-butoxy-copper-t-butyldifluorophosphane, t-butoxy-copper-phenyldifluorophosphane, t-butoxy-copper-diethylaminodifluorophosphane, 2-trifluoromethylpropane-2-oxy-copper-t-butylisonitrile, 2-trifluoromethylpropane-2-oxy-copper-trimethylphosphane, perfluoro-t-butoxy-copper-t-butylisonitrile, perfluoro-t-butoxy-copper-trimethylphosphane, C 5 H 5 —Cu-t-BuNC and Cu(hfac)R, where R is at least one of 1,5-cyclooctadiene, hexyne, butyne, trimethylvinylsilyl, bis(trimethylsilyl)acetylene, triethoxyvinylsilane and trimethylallylsilane.
27. The method of claim 20 , wherein the copper sulfide layer is made by contacting the sulfide compound with the substrate and forming a copper-sulfur bond on a surface of the substrate, and thereafter contacting the copper vapor precursor with the substrate and forming an additional copper-sulfur bond between a copper element of the copper vapor precursor and a sulfur element that is previously attached to the substrate, and the copper sulfide layer has a thickness of about 2 Å or more and about 0.1 μm or less.
28. The method of claim 21 , wherein the organic group comprises at least one aliphatic or aromatic organic moiety having from about 1 to about 100 carbon atoms which may include one or more oxygen, sulfur, or nitrogen, or fluorine atoms, wherein the aliphatic chain may be linear, branched, saturated or unsaturated, and wherein either the aliphatic chain or the aromatic ring may have substituted groups thereon.