CuS formation by anodic sulfide passivation of copper surface
View Patent ↗Disclosed are methods of making memory cells and semiconductor devices containing the memory cells. The methods involve passivating a portion of a copper containing electrode to form a copper sulfide layer in an electrochemical cell by applying a current through a passivation solution containing a sulfide compound. Such devices containing the memory cells are characterized by light weight and robust reliability.
1. A method of making a memory cell, comprising:
providing a partially fabricated memory structure comprising a patterned dielectric over a first electrode comprising at least copper;
charging the partially fabricated memory structure into an electrochemical cell comprising a cathode and a passivation solution comprising a sulfide compound, the sulfide compound comprising at least one selected from the group consisting of ammonium sulfide, an alkylammonium sulfide, dimethylsulfide, benzylmethylsulfide, sodium sulfide, and lithium sulfide;
applying a current density through the electrochemical cell so that a CuS layer is formed on the first electrode in portions not covered by the patterned dielectric;
forming an organic semiconductor over the CuS layer; and
forming a second electrode over the organic semiconductor.
2. The method of claim 1 , wherein the passivation solution comprises from about 0.1% to about 40% by weight of the sulfide compound.
3. The method of claim 1 , wherein the passivation solution has a temperature from about 10° C. to about 100° C.
4. The method of claim 1 , wherein the current density applied is about 1 ASF or more and about 500 ASF or less for a time of about 1 second or longer and about 120 minutes or shorter.
5. The method of claim 1 , wherein the passivation solution comprises ammonium sulfide.
6. The method of claim 1 , wherein the CuS layer has a thickness of about 2 Å or more and about 0.1 μm or less.
7. The method of claim 1 , wherein the CuS layer comprises at least one compound represented by the formula Cu x S y , where x and y are independently from about 0.5 to about 4.
8. The method of claim 1 , wherein the CuS layer is treated with a plasma before forming the organic semiconductor over the CuS layer.
9. The method of claim 1 , wherein the organic semiconductor 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.
10. A method of making a CuS layer in a memory cell, comprising:
providing an electrochemical cell comprising a cathode, a partially fabricated memory structure comprising a patterned dielectric over an electrode comprising at least copper, and a passivation solution comprising a sulfide compound; and
applying a current density of about 1 ASF or more and about 500 ASF or less for a time of about 1 second or longer and about 120 minutes or shorter to the electrochemical cell whereby sulfide ions are generated in the passivation solution and migrate to the electrode to form the CuS layer.
11. The method of claim 10 , wherein the sulfide compound is selected from the group consisting of ammonium sulfide, an alkylammonium sulfide, dimethylsulfide, benzylmethylsulfide, sodium sulfide, and lithium sulfide.
12. The method of claim 10 , wherein the CuS layer has a thickness of about 10 Å or more and about 0.01 μm or less.
13. The method of claim 10 , wherein the passivation solution has a temperature from about 20° C. to about 80° C.
14. The method of claim 10 , wherein the current density applied is about 2 ASF or more and about 100 ASF or less for a time of about 5 seconds or longer and about 30 minutes or shorter.
15. The method of claim 10 , wherein the passivation solution further comprises a reducing agent.
16. The method of claim 10 , wherein the electrode comprises a copper seed layer thereon having a thickness of about 1 Å or more and about 100 Å or less.
17. A method of making a memory cell, comprising:
providing a first electrode comprising at least 50% by weight copper on a memory substrate;
patterning a dielectric over the first electrode so that portions of the first electrode remain exposed, thereby forming a memory structure;
charging the memory structure into an electrochemical cell comprising a passivation solution, and a cathode, the passivation solution comprising a sulfide compound and a reducing agent;
applying a current density through the electrochemical cell so that a CuS layer is formed on the exposed portions of the first electrode;
forming an organic semiconductor over the CuS layer; and
forming a second electrode over the organic semiconductor.
18. The method of claim 17 , wherein the passivation solution comprises an inorganic sulfide compound.
19. The method of claim 17 , wherein the passivation solution comprises from about 0.5% to about 30% by weight of the sulfide compound.
20. The method of claim 17 , with the proviso that the first electrode is not contacted with H 2 S.