PROCESS FOR DEPOSITING POROUS ORGANOSILICATE GLASS FILMS FOR USE AS RESISTIVE RANDOM ACCESS MEMORY
A process for forming a resistive random-access memory device, the process comprising the steps of: depositing a first electrode on a substrate; forming a porous resistive memory material layer on the first electrode, wherein the porous resistive memory layer is formed by (i) depositing a gaseous composition comprising a silicon precursor and a porogen precursor and, once deposited, (ii) removing the porogen precursor by exposing the composition to UV radiation; and depositing a second electrode on top of the porous resistive memory material layer.
1 . A process for forming a resistive random-access memory device, the process comprising the steps of:
depositing a first electrode on a substrate;
forming a porous resistive memory material layer on the first electrode, wherein the porous resistive memory layer is formed by (i) depositing a gaseous composition comprising a silicon precursor and a porogen precursor and, once deposited, (ii) removing the porogen precursor by exposing the composition to UV radiation; and
depositing a second electrode on top of the porous resistive memory material layer.
2 . The process of claim 1 wherein the silicon precursor is at least one selected from the group consisting of: tetraethoxysilane, diethoxymethylsilane, dimethoxymethylsilane, di-(tertiary)butoxymethylsilane, di-tertiarypentoxymethylsilane, di-tertiarybutoxysilane, di-tertiarypentoxysilane, methyltriacetatoxysilane, dimethylacetatoxysilane, dimethyldiacetoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, neohexyltriethoxysilane, neopentyltrimethoxysilane, diacetoxymethylsilane, phenyldimethoxysilane, phenyldiethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, phenylmethyldimethoxysilane, 1,3,5,7-tetramethyltetracyclosiloxane, octamethyltetracyclosiloxane, 1,1,3,3-tetramethyldisiloxane, 1-neohexyl-1,3,5,7-tetramethylcyclotetrasiloxane, hexamethyldisiloxane, 1,3-dimethyl-1-acetoxy-3-ethoxydislioxane, 1,2-diemthyl-1,2-diacetoxy-1,2-diethoxydisilane, 1,3-dimethyl-1,3-diethoxydisiloxane, 1,3-dimethyl-1,3-diacetoxydisilxane, 1,2-dimethyl,1,1,2,2-tetraacetoxydisilane, 1,2-dimethyl-1,1,2,2-tetraethoxydisilane, 1,3-dimethyl-1-acetoxy-3-ethoxydisiloxane, 1,2-dimethyl-1-acetoxy-2-ethoxydisilane, methylacetoxy(tertiary)butoxysilane, methylsilane, dimethylsilane, trimethylsilane, tetramethylsilane, hexamethyldisilane, tetramethyldisilane, dimethyldisilane, hexamethyldisiloxane (HMDSO), octamethylcyclotetrasiloxane (OMCTS), tetramethylcyclotetrasiloxane (TMCTS), bis(triethoxysilyl)methane, bis(triethoxysilyl)ethane, bis(trimethoxysilyl)methane, bis(trimethoxysilyl)ethane, bis(diethoxymethylsilyl)methane, bis(diethoxymethylsilyl)ethane, bis(methyldiethoxysilyl)methane, (diethoxymethylsilyl)(diethoxysilyl)methane, and mixtures thereof.
3 . The process of claim 2 wherein the silicon precursor is selected from the group consisting of di-tertiarybutoxysilane, di-tertiarypentoxysilane, tetraethoxysilane (TEOS), tetramethoxysilane and a mixture thereof.
4 . The process of claim 1 wherein the porogen is at least one selected from the group consisting of: alpha-terpinene, limonene, cyclohexane, cyclooctane, gamma-terpinene, camphene, dimethylhexadiene, ethylbenzene, norbornadiene, cyclopentene oxide, 1,2,4-trimethylcyclohexane, 1,5-dimethyl-1,5-cyclooctadiene, camphene, adamantane, 1,3-butadiene, substituted dienes, and decahydronaphthelene.
5 . The process of claim 3 wherein the porogen comprises norbornadiene, alpha-terpinene or cyclooctane.
6 . The process of claim 1 wherein the gaseous composition comprising a silicon precursor and a porogen precursor is deposited by either a plasma enhanced chemical vapor deposition (PECVD) or a plasma enhanced cyclic chemical vapor deposition (PECCVD) process.
7 . The process of claim 1 wherein the substrate is a material selected from the group consisting of: silicon, germanium, silicon oxide, silicon nitride, silicon carbide, silicon carbonitride, carbon doped silicon oxide, boron doped silicon, phosphorous doped silicon, boron doped silicon oxide, phosphorous doped silicon oxide, boron doped silicon nitride, phosphorous doped silicon, silicon nitride, copper, tungsten, aluminum, cobalt, nickel, tantalum, titanium nitride, tantalum nitride, metal oxide, GaAs, InP GaP and GaN, and a combination thereof.
8 . The process of claim 1 wherein the first electrode is a metal deposited from a precursor selected from the group consisting of an alkyl metal, a metal amides, a metal alkoxide, and a metal halide.
9 . The process of claim 1 further comprising adding a dopant when depositing the gaseous composition comprising the silicon precursor and the porogen precursor.
10 . The process of claim 9 wherein the dopant is selected from the group consisting of Zn, Mg, B, P, As, S, Se, and Te.
11 . The process of claim 1 further comprising adding a metal or metal oxide precursor when depositing the gaseous composition comprising the silicon precursor and the porogen precursor.
12 . The process of claim 11 wherein the metal or metal oxide is selected from the group consisting of diethyl zinc, trimethylaluminum, (2,4-dimethylpentadienyl)(ethylcyclopentadienyl) ruthenium, bis(2,4-dimethylpentadienyl) ruthenium, 2,4-dimethylpentadienyl) (methylcyclopentadienyl) ruthenium, bis (ethylcyclopentadienyl) ruthenium, dicobalt hexacarbonyl t-butylacetylene (CCTBA) or cyclopentadienyl cobalt dicarbonyl (CpCo(CO) 2 ), Ru 3 (CO) 12 ; metal amides such as tetrakis(dimethylamino)zirconium (TDMAZ), tetrakis(diethylamino)zirconium (TDEAZ), tetrakis(ethylmethylamino)zirconium (TEMAZ), tetrakis(dimethylamino)hafnium (TDMAH), tetrakis(diethylamino)hafnium (TDEAH), and tetrakis(ethylmethylamino)hafnium (TEMAH), tetrakis(dimethylamino)titanium (TDMAT), tetrakis(diethylamino)titanium (TDEAT), tetrakis(ethylmethylamino)titanium (TEMAT), tert-butylimino tri(diethylamino)tantalum (TBTDET), tert-butylimino tri(dimethylamino)tantalum (TBTDMT), tert-butylimino tri(ethylmethylamino)tantalum (TBTEMT), ethylimino tri(diethylamino)tantalum (EITDET), ethylimino tri(dimethylamino)tantalum (EITDMT), ethylimino tri(ethylmethylamino)tantalum (EITEMT), tert-amylimino tri(dimethylamino)tantalum (TAIMAT), tert-amylimino tri(diethylamino)tantalum, pentakis(dimethylamino)tantalum, tert-amylimino tri(ethylmethylamino)tantalum, bis(tert-butylimino)bis(dimethylamino)tungsten (BTBMW), bis(tert-butylimino)bis(diethylamino)tungsten, bis(tert-butylimino)bis(ethylmethylamino)tungsten, hafnium tetrachloride, tantalum pentachloride, and tungsten hexachloride.
13 . The process of claim 1 further comprising the step of depositing a second porous silicon-containing layer.
14 . The process of claim 13 wherein the second porous silicon-containing layer is formed by depositing at least one second silicon-containing precursor selected from the group consisting of monochlorosilane, monochlorodisilane, di-iso-propylaminosilane, di-sec-butylaminosilane, di-iso-propylaminodisilane, di-sec-butylaminodisilane, bis(tert-butylamino)silane, bis(dimethylamino)silane, bis(diethylamino)silane, bis(ethylmethylamino)silane, trisilyamine and its derivatives, bis(disilylamino)silane, and H 2 Si((NSiH 3 ) 2 ) 2 .
15 . The process of claim 1 wherein the porous resistive memory material layer is selected from the group consisting of SiO x , SiO x H, Si, O x N y , SiO x N y H, SiO x C z , SiO x C z H, and combinations thereof, wherein each of x, y, and z are equal or greater than 1 or equal or less than 2.