Processing a copolymer to form a polymer memory cell
View Patent ↗Disclosed are organic semiconductor devices containing a copolymer layer that contains a polymer dielectric and a semiconducting polymer formed using actinic radiation. As initially formed, the copolymer layer has dielectric properties, but portions may selectively rendered conductive after those portions are exposed to actinic radiation. Also disclosed are methods of making the organic semiconductor devices. Such devices are characterized by light weight and robust reliability.
1. A method of making a memory device, comprising:
providing a first electrode within an insulating material;
forming a passive layer above the first electrode;
forming a copolymer layer above the first electrode, passive layer, and insulating material, the copolymer layer comprising a polymer dielectric and a semiconducting polymer precursor, the copolymer layer having dielectric properties;
exposing a portion of the copolymer layer to actinic radiation thereby forming a semiconducting polymer in the exposed portion of the copolymer layer; and
forming a second electrode aligned above the exposed portion of the copolymer layer comprising the semiconducting polymer,
wherein the semiconducting polymer precursor forms the semiconducting polymer in response to exposure to the actinic radiation.
2. The semiconductor device of claim 1 , wherein the polymer dielectric comprises at least one selected from the group consisting of polyimides, fluorinated polyimides, polysilsequioxanes such as hydrogen polysilsequioxanes, methyl polysilsequioxanes, butyl polysilsequioxanes, phenyl polysilsequioxanes, benzocyclobutenes (BCB), fluorinated benzocyclobutene, polyphenylene, polysilazanes, polyphenylquinoxaline, copolymers of 2,2-bistrifluoromethyl-4,5-difluoro-1,3-dioxole, perfluoroalkoxy resin, fluorinated ethylene propylene, fluoromethacrylate, poly(arylene ether), fuorinated poly(arylene ether), fluorinated parylenes, poly(p-xylxylenes), fluorinated poly(p-xylxylenes), parylene F, parylene N, parylene C, parylene D, amorphous polytetrafluoroethylene, polyquinoline, polyphenylquinoxalines, and polymeric photoresist materials.
3. The semiconductor device of claim 1 , wherein the copolymer layer contains from about 50% to about 90% by weight of a polymer dielectric and from about 10% to about 50% by weight of the semiconducting polymer precursor.
4. The semiconductor device of claim 1 , wherein unexposed portions of the copolymer layer have a dielectric constant below about 3.
5. The semiconductor device of claim 1 , wherein the copolymer layer is formed by depositing a mixture by spin-on techniques.
6. The semiconductor device of claim 5 , wherein the mixture contains from about 0.1% to about 75% by weight of copolymer material and from about 25% to about 99.9% by weight of solvent.
7. The semiconductor device of claim 1 , wherein the semiconducting polymer 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.
8. The semiconductor device of claim 1 , wherein the passive layer comprises at least one selected from the group consisting of copper sulfide, copper rich copper sulfide, copper oxide, copper selenide, copper telluride, manganese oxide, titanium dioxide, indium oxide, silver sulfide, gold sulfide, iron oxide, cobalt arsenide, and nickel arsenide.
9. The semiconductor device of claim 1 , wherein the actinic radiation has a wavelength from about 1 nm to about 1,000 nm.
10. A method of making a polymer memory device, comprising:
providing a first electrode within an insulating material;
forming a passive layer above the first electrode;
forming a copolymer layer above the first electrode, passive layer, and insulating material, the copolymer layer comprising a polymer dielectric and a semiconducting polymer precursor, the copolymer layer having dielectric properties;
patterning an ARC above the copolymer layer so that openings in the ARC are positioned at least partially aligned above the first electrode;
exposing a portion of the copolymer layer through openings in the ARC to actinic radiation thereby forming a semiconducting polymer in the exposed portion of the copolymer layer; and
forming a second electrode aligned above the exposed portion of the copolymer layer comprising the semiconducting polymer,
wherein the semiconducting polymer precursor forms the semiconducting polymer in response to exposure to the actinic radiation.
11. The semiconductor device of claim 10 , wherein the polymer dielectric comprises at least one selected from the group consisting of polyimides, fluorinated polyimides, polysilsequioxanes such as hydrogen polysilsequioxanes, methyl polysilsequioxanes, butyl polysilsequioxanes, phenyl polysilsequioxanes, benzocyclobutenes (BCB), fluorinated benzocyclobutene, polyphenylene, polysilazanes, polyphenylquinoxaline, copolymers of 2,2-bistrifluoromethyl-4,5-difluoro-1,3-dioxole, perfluoroalkoxy resin, fluorinated ethylene propylene, fluoromethacrylate, poly(arylene ether), fuorinated poly(arylene ether), fluorinated parylenes, poly(p-xylxylenes), fluorinated poly(p-xylxylenes), parylene F, parylene N, parylene C, parylene D, amorphous polytetrafluoroethylene, polyquinoline, polyphenylquinoxalines, and polymeric photoresist materials.
12. The semiconductor device of claim 10 , wherein the ARC has thickness from about 250 Å to about 2,000 Å.
13. The semiconductor device of claim 10 , wherein the copolymer layer is formed by spin-on techniques, and unexposed portions of the copolymer layer have a dielectric constant below about 2.4.
14. The semiconductor device of claim 10 , wherein the actinic radiation has a wavelength from about 100 nm to about 500 nm.
15. The semiconductor device of claim 10 , wherein the semiconducting polymer 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.
16. The method of claim 10 , wherein the passive layer comprises at least one selected from the group consisting of copper sulfide, copper rich copper sulfide, copper oxide, copper selenide, copper telluride, manganese oxide, titanium dioxide, indium oxide, silver sulfide, gold sulfide, iron oxide, cobalt arsenide, and nickel arsenide.
17. A method of making a polymer memory device, comprising:
providing a first electrode within an insulating material;
forming a passive layer above the first electrode;
forming a copolymer layer above the first electrode, passive layer, and insulating material, the copolymer layer comprising a polymer dielectric and a semiconducting polymer precursor, the copolymer layer having dielectric properties;
forming a barrier layer aligned above the copolymer layer;
patterning an ARC above the barrier layer so that openings in the ARC are positioned at least partially aligned above the first electrode;
exposing a portion of the copolymer layer through openings in the ARC and through the barrier layer to actinic radiation thereby forming a semiconducting polymer in the exposed portion of the copolymer layer;
removing a portion of the barrier layer at least from partially above the exposed portion of the copolymer layer; and
forming a second electrode aligned above the exposed portion of the copolymer layer comprising the semiconducting polymer,
wherein the semiconducting polymer precursor forms the semiconducting polymer in response to exposure to the actinic radiation.
18. The semiconductor device of claim 17 , wherein the barrier layer has thickness from about 250 Å to about 2,000 Å, and the barrier layer is substantially translucent to the actinic radiation.
19. The semiconductor device of claim 17 , wherein the barrier layer comprises at least one of silica and silicon nitride.
20. The semiconductor device of claim 17 , wherein the polymer dielectric comprises a low k polymer material.