Memory devices based on electric field programmable films

• US 20050058009A1
• Filed: 08/25/2004
• Published: 03/17/2005
• Est. Priority Date: 09/03/2003
• Status: Active Grant

• Current Assignee: Regents of the University of California (University of California)
• Original Assignee: Regents of the University of California (University of California)
• Inventors: Szmanda, Charles R., Yang, Yang, Ouyang, Jianyong
• Granted Patent: US 7,274,035 B2
• Time in Patent Office: Days
• US Class Current: 365/232
• CPC Class Codes: B82Y 10/00 Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
• CPC Class Codes: G11C 13/0009 RRAM elements whose operation depends upon chemical change
• CPC Class Codes: G11C 13/0014 comprising cells based on organic memory material
• CPC Class Codes: G11C 13/0016 comprising polymers
• CPC Class Codes: G11C 2213/71 Three dimensional array
• CPC Class Codes: G11C 2213/72 Array wherein the access device being a diode
• CPC Class Codes: G11C 2213/77 Array wherein the memory element being directly connected to the bit lines and word lines without any access device being used

Abstract

A composition for the formation of an electric field programmable film, the composition comprising a matrix precursor composition or a dielectric matrix material, wherein the dielectric matrix material comprises an organic polymer and/or a inorganic oxide; and an electron donor and an electron acceptor of a type and in an amount effective to provide electric field programming. The films are of utility in data storage devices.

Claims

1. A composition for the formation of an electric field programmable film, the composition comprising

a matrix precursor composition or a dielectric matrix material, wherein the dielectric matrix material comprises an organic polymer and/or a inorganic oxide;

and

an electron donor and an electron acceptor of a type and in an amount effective to provide electric field programming.

2. The composition of claim 1, wherein the matrix precursor composition comprises styrene, 4-hydroxystyrene, C₁-C₁₀ linear, branched or cyclic alkyl, C₁-C₁₀ linear, branched, or cyclic alkoxy, C₁-C₁₀ aryl or aralkyl, or C₆-C₁₀ aryloxy or aralkyloxy substituted styrene, vinyl acetate, vinyl alcohol, (meth)acrylonitrile, (meth)acrylic acid, C₁-C₁₀ linear, branched or cyclic alkyl or C₆-C₁₀ aryl or aralkyl (meth)acrylate esters, C₁-C₁₀ linear, branched or cyclic alkyl or C₆-C₁₀ aryl or aralkyl cyanoacrylate esters, C₁-C₁₀ linear, branched, or cyclic alkoxy, C₆-C₁₀ aryl, arylalkyl, aryloxy or arylalkyloxy dialcohols;

C₁-C₁₀ linear, branched, cyclic alkoxy, C₆-C₁₀ aryl, arylalkyl, aryloxy or arylalkyloxy diacids, C₁-C₁₀ linear, branched, or cyclic alkoxy;

C₁-C₁₀ aryl, arylalkyl, aryloxy or arylalkyloxy clialcohols;

C₁-C₁₀ linear, branched, or cyclic alkoxy, C₆-C₁₀ aryl, arylalkyl, aryloxy or arylalkyloxy diacids, C₁-C₁₀ linear, branched, or cyclic alkoxy, C₆-C₁₀ aryl, arylalkyl, aryloxy or arylalkyloxy diamines, polyinerizable oligomers comprising at least one of the foregoing monomers, polymerizable polymers comprising at least one of the foregoing monomers, or a combination comprising at least one of the foregoing monomers, oligomers, or polymers, and further wherein polymerization of the matrix precursor composition provides a dielectric matrix material.

3. The composition of claim 1 or 2 wherein the dielectric matrix material is a homopolymer or copolymer and has a dielectric constant of greater than 2.

4. The composition of claim 1 or 2 wherein the dielectric matrix material is a homopolymer or copolymer and has a dielectric constant of 2 to 500.

5. The composition of claim 1, wherein the organic polymer is a polyolefins, poly(meth)acrylates, polyesters, polyamides, novolacs, polysiloxanes, polycarbonates, polyimides, polyacetates, polyalkyds, polyamideimides, polyarylates, polyurethanes, polyarylsulfone, polyethersulfone, polyphenylene sulfide, polyvinyl chloride, polysulfone, polyetherimide, polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, polyetherketone, polyether etherketone, polyether ketone ketone or a combination comprising at least one of the foregoing organic polymers.

6. The composition of claim 1, wherein the inorganic oxide is a composition of the formula

A_wB_xC_yO_z

where w, x, and y are 0 to 30, and z is 1 to 60;

A is calcium, strontium, or barium, B is bismuth, zirconium, nickel or lead, and C is titanium, niobium zirconium vanadium, or tantalum and wherein stoichiometry of the inorganic oxides is constrained to give, approximate charge neutrality.

7. The composition of claim 1, wherein the electron acceptor is 8-hydroxyquinoline, phenothiazine, 9,10-dimethylanthracene, pentafluoroaniline, phthalocyanine, perfluorophthalicyanine, tetraphenylporphine, copper phthalocyanine, copper perfluorophthalocyanine, copper tetraphenylporphine, 2-(9-dicyanomethylene-spiro[5.5]undec-3-ylidene)-malononitrile, 4-phenylazo-benzene-1,3-diol, 4-(pyridin-2-ylazo)-benzene-1,3-diol, benzo[1,2,5]thiadiazole-4,7-dicarbonitrile, tetracyanoquinodimethane, quinoline, chlorpromazine, tetraphenylporphine, or a combination comprising at least one of the foregoing electron acceptors.

8. The composition of claim 1, wherein the electron donor is an organic electron donor or an inorganic electron donor.

9. The composition of claim 8, wherein the organic electron donors are tetrathiafulvalene, 4,4′

,5-trimethyltetrathiafulvalene, bis(ethylenedithio)tetrathiafulvalene, p-phenylenediamine, N-ethylcarbazole, tetrathiotetracene, hexamethylbenzene, tetramethyltetraseleno fulvalene, or hexamethylenetetraselenofulvalene.

10. The composition of claim 8, wherein the inorganic electron donor comprises metal-halide salts or the acetylacetonate complexes of transition metals that are reduced by K⁺BEt₃H⁻

or NR4⁺BEt₃H⁻

and stabilized using tetrahydrofuran, tetrahydrothiophene, quaternary ammonium salts or betaine surfactants.

11. The composition of claims 8, 9, or 10, wherein the electron donor has a protective organic or inorganic shell.

12. The composition of claim 1, further comprising donor-acceptor complexes, wherein the donor-acceptor complexes are tetrathiafulvalene—

tetracyanoquinodimethane;

hexamethylenetetrathiafulvalene—

tetracyanoquinodimethane;

tetraselenafulvalene—

tetracyanoquinodimethane;

hexamethylenetetraselenafulvalene—

tetracyanoquinodimethane;

methylcarbazoletetracyanoquinodimethane;

tetramethyltetraselenofulvalene—

tetracyanoquinodimethane;

metal nanoparticle-tetracyanoquinodimethane complexes comprising gold, copper, silver or iron, ferrocene-tetracyanoquinodimethane complexes;

tetrathiotetracene, tetramethyl-p-phenylenediamine, or hexamethylbenzene—

tetracyanoquinodimethane complexes;

tetrathiafulvalene, hexamethylenetetrathiafulvalene, tetraselenafulvalene, hexamethylenetetraselenafulvalene, or tetramethyltetraselenofulvalene—

N-alkylcarbazole(C₁-C₁₀, linear or branched) complexes;

tetrathiotetracene, tetramethyl-p-phenylenediamine, or hexamethylbenzene—

Buckminsterfullerene C₆₀ complexes;

tetrathiafulvalene, hexamethylenetetrathiafulvalene, tetraselenafulvalene, hexamethylenetetraselenafulvalene, tetramethyltetraselenofulvalene—

N-alkylcarbazole(C₁-C₁₀,-linear-or branched) complexes;

tetrathiotetracene, tetramethyl-p-phenylenediamine, or hexamethylbenzene-tetracyanobenzene complexes;

tetrathiafulvalene, hexamethylenetetrathiafulvalene, tetraselenafulvalene, hexamethylenetetraselenafulvalene, or tetramethyltetraselenofulvalene—

N-alkylcarbazole(C₁-C₁₀, linear or branched) complexes;

tetrathiotetracene, tetramethyl-p-phenylenediamine, or hexamethylbenzene—

tetracyanoethylene complexes;

tetrathiafulvalene, hexamethylenetetrathiafulvalene, tetraselenafulvalene, hexamethylenetetraselenafulvalene, or tetramethyltetraselenofulvalene—

N-alkylcarbazole(C₁-C₁₀, linear or branched) complexes;

tetrathiotetracene, tetramethyl-p-phenylenediamine, hexamethylbenzene-p-chloranil complexes, or a combination comprising at least one of the foregoing donor-acceptor complexes.

13. The composition of claim 1, further comprising a solvent.

17. A method for manufacturing an electric field programmable film comprising:

applying the composition of claim 1 to a substrate; and

removing the solvent from the applied-composition to form a film.

18. A film manufactured by the method of claim 17.

14. An electric field programmable film comprises:

a dielectric matrix material, wherein the dielectric matrix material comprises an organic polymer and/or a inorganic oxide;

an electron donor; and

an electron acceptor.

15. A data storage device comprising the film of claim 14.

16. A cross point array comprising the film of claim 14.