Spin on memory cell active layer doped with metal ions
View Patent ↗A method of making organic memory cells made of two electrodes with a controllably conductive media between the two electrodes is disclosed. The controllably conductive media contains an active layer and passive layer. The active layer is formed using spin on techniques and contains an organic semiconductor doped with a metal salt.
1. A method of making an organic memory cell comprising:
providing a first electrode;
forming a passive layer comprising a conductivity facilitating compound over the first electrode;
forming an active layer over the passive layer using a spin-on technique, the spin-on technique comprising applying a mixture of i) from about 0.1% to about 75% by weight of an organic semiconductor material, ii) from about 0.1% to about 20% by weight of an inorganic metal salt, and iii) from about 25% to about 99.9% by weight of at least one solvent selected from the group consisting of glycol ether esters, glycol ethers, furans, and alkyl alcohols containing from about 4 to about 7 carbon atoms;
contacting the active layer with hydrogen sulfide gas to permit hydrogen sulfide to react with the inorganic metal salt to form a metal sulfide; and
providing a second electrode over the active layer.
2. The method of claim 1 , wherein the inorganic metal salt comprises at least one selected from the group consisting of copper salts, manganese salts, titanium salts, indium salts, gold salts, silver salts, iron salts, cobalt salts, nickel salts, palladium salts, platinum salts, zirconium salts, zinc salts, tungsten salts, molybdenum salts, and osmium salts.
3. The method of claim 1 , wherein the inorganic metal salt comprises at least one selected from the group consisting of copper halogens, copper sulfate, copper persulfate, copper nitrate, and copper phosphate.
4. The method of claim 1 , wherein the solvent comprises at least one glycol ether selected from the group consisting of poly(ethylene glycol) methyl ether, poly(ethylene glycol) ethyl ether, poly(ethylene glycol) propyl ether, poly(ethylene glycol) butyl ether, poly(propylene glycol) methyl ether, poly(propylene glycol) ethyl ether, poly(propylene glycol) propyl ether, poly(propylene glycol) butyl ether, ethylene glycol methyl ether, ethylene glycol methylbutyl ether, ethylene glycol ethylbutyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, and propylene glycol dibutyl ether.
5. The method of claim 1 , wherein the solvent comprises at least one glycol ether ester selected from the group consisting of ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol propyl ether acetate, ethylene glycol butyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, poly(ethylene glycol) methyl ether acetate, poly(ethylene glycol) ethyl ether acetate, poly(ethylene glycol) propyl ether acetate, poly(ethylene glycol) butyl ether acetate, poly(propylene glycol) methyl ether acetate, poly(propylene glycol) ethyl ether acetate, poly(propylene glycol) propyl ether acetate, and poly(propylene glycol) butyl ether acetate.
6. The method of claim 1 , wherein the solvent comprises at least one selected from the group consisting of tetrahydrofuran, n-butanol, iso-butanol, n-pentanol, iso-pentanol, cyclopentanol, n-hexanol, cyclohexanol, and heptanol.
7. The method of claim 1 , wherein the active layer comprises at least one conjugated organic polymer selected from the group consisting of poly(p-phenylene vinylene); polyporphyrins; porphyrinic macrocycles, thiol-derivatized polyporphyrins; polymetallocenes such as polyferrocenes, polyphthalocyanines; polyvinylenes; polystiroles; 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; polyfluorene; polyphenylene and alkyl- or alkoxy-substituted derivates thereof; polythiophene and alkyl- or alkoxy-substituted derivates thereof; polypyrrole; polysilane; polystyrene; polyfuran; polyindole; polyazulene; polyphenylene; polyfluorenes, polypyridine; polybipyridine; polyphthalocyanine; polysexithiophene; poly(siliconoxohemiporphyrazine); poly(germaniumoxohemiporphyrazine); and poly(ethylenedioxythiophene).
8. The method of claim 1 , wherein the conductivity facilitating compound comprises at least one selected from the group consisting of copper sulfide, copper oxide, manganese oxide, titanium dioxide, indium oxide, silver sulfide, gold sulfide, nickel arsenide, cobalt arsenide, and iron oxide.
9. A method of making an active layer for an organic memory cell comprising:
forming an active layer using a spin on technique, the spin on technique comprising applying to a surface a mixture of i) from about 0.1% to about 75% by weight of at least one of a conjugated organic polymer, ii) from about 0.1% to about 20% by weight of a metal salt selected from the group consisting of copper salts, manganese salts, titanium salts, indium salts, gold salts, silver salts, iron salts, cobalt salts, nickel salts, palladium salts, platinum salts, zirconium salts, zinc salts, tungsten salts, molybdenum salts, and osmium salts, and iii) from about 25% to about 99.9% by weight of at least one solvent selected from the group consisting of glycol ether esters, glycol ethers, furans, and alkyl alcohols containing from about 4 to about 7 carbon atoms; and
contacting the active layer with hydrogen sulfide gas to permit hydrogen sulfide to react with the inorganic metal salt to form a metal sulfide.
10. The method of claim 9 , wherein the active layer is formed over a passive layer comprising a conductivity facilitating compound selected from the group consisting of copper sulfide, copper oxide, manganese oxide, titanium dioxide, indium oxide, silver sulfide, gold sulfide, nickel arsenide, cobalt arsenide, and iron oxide.
11. The method of claim 10 , wherein the conductivity facilitating compound comprises a metal that is the same as the metal of the metal salt.
12. The method of claim 11 , wherein the metal is copper.
13. The method of claim 9 , wherein the conjugated organic polymer comprises at least one selected from the group consisting of poly(p-phenylene vinylene); polyporphyrins; porphyrinic macrocycles, thiol-derivatized polyporphyrins; polymetallocenes such as polyferrocenes, polyphthalocyanines; polyvinylenes; polystiroles; 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; polyfluorene; polyphenylene and alkyl- or alkoxy-substituted derivates thereof; polythiophene and alkyl- or alkoxy-substituted derivates thereof; polypyrrole; polysilane; polystyrene; polyfuran; polyindole; polyazulene; polyphenylene; polyfluorenes, polypyridine; polybipyridine; polyphthalocyanine; polysexithiophene; poly(siliconoxohemiporphyrazine); poly(germaniumoxohemiporphyrazine); and poly(ethylenedioxythiophene).
14. A method of making an organic memory cell comprising:
providing a first electrode;
forming a passive layer comprising a conductivity facilitating compound over the first electrode;
forming an active layer over the passive layer using a spin-on technique, the spin-on technique comprising applying a mixture of i) from about 0.1% to about 75% by weight of an organic semiconductor material, ii) from about 0.1% to about 20% by weight of a copper salt, and iii) from about 25% to about 99.9% by weight of at least one solvent selected from the group consisting of glycol ether esters, glycol ethers, furans, and alkyl alcohols containing from about 4 to about 7 carbon atoms;
contacting the active layer with hydrogen sulfide gas to permit hydrogen sulfide to react with the copper salt to form copper sulfide; and
providing a second electrode over the active layer.
15. The method of claim 14 , wherein the solvent comprises at least one glycol ether selected from the group consisting of poly(ethylene glycol) methyl ether, poly(ethylene glycol) ethyl ether, poly(ethylene glycol) propyl ether, poly(ethylene glycol) butyl ether, poly(propylene glycol) methyl ether, poly(propylene glycol) ethyl ether, poly(propylene glycol) propyl ether, poly(propylene glycol) butyl ether, ethylene glycol methyl ether, ethylene glycol methylbutyl ether, ethylene glycol ethylbutyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, and propylene glycol dibutyl ether.
16. The method of claim 14 , wherein the solvent comprises at least one glycol ether ester selected from the group consisting of ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol propyl ether acetate, ethylene glycol butyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, poly(ethylene glycol) methyl ether acetate, poly(ethylene glycol) ethyl ether acetate, poly(ethylene glycol) propyl ether acetate, poly(ethylene glycol) butyl ether acetate, poly(propylene glycol) methyl ether acetate, poly(propylene glycol) ethyl ether acetate, poly(propylene glycol) propyl ether acetate, and poly(propylene glycol) butyl ether acetate.
17. The method of claim 14 , wherein the solvent comprises at least one selected from the group consisting of tetrahydrofuran, n-butanol, iso-butanol, n-pentanol, iso-pentanol, cyclopentanol, n-hexanol, cyclohexanol, and heptanol.
18. The method of claim 14 , wherein the active layer comprises at least one conjugated organic polymer selected from the group consisting of poly(p-phenylene vinylene); polyporphyrins; porphyrinic macrocycles, thiol-derivatized polyporphyrins; polymetallocenes such as polyferrocenes, polyphthalocyanines; polyvinylenes; polystiroles; 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; polyfluorene; polyphenylene and alkyl- or alkoxy-substituted derivates thereof; polythiophene and alkyl- or alkoxy-substituted derivates thereof; polypyrrole; polysilane; polystyrene; polyfuran; polyindole; polyazulene; polyphenylene; polyfluorenes, polypyridine; polybipyridine; polyphthalocyanine; polysexithiophene; poly(siliconoxohemiporphyrazine); poly(germaniumoxohemiporphyrazine); and poly(ethylenedioxythiophene).
19. The method of claim 14 , wherein the conductivity facilitating compound comprises at least one selected from the group consisting of copper sulfide, copper oxide, manganese oxide, titanium dioxide, indium oxide, silver sulfide, gold sulfide, nickel arsenide, cobalt arsenide, and iron oxide.
20. The method of claim 14 , wherein the active layer is formed over a passive layer comprising copper sulfide.