SiCOH DIELECTRIC
A porous composite material useful in semiconductor device manufacturing, in which the diameter (or characteristic dimension) of the pores and the pore size distribution (PSD) is controlled in a nanoscale manner and which exhibits improved cohesive strength (or equivalently, improved fracture toughness or reduced brittleness), and increased resistance to water degradation of properties such as stress-corrosion cracking, Cu ingress, and other critical properties is provided. The porous composite material is fabricating utilizing at least one bifunctional organic porogen as a precursor compound.
1 . A dielectric material comprising atoms of Si, C, O, and H and having a covalently bonded tri-dimensional random network structure in which a fraction of the C atoms are bonded as Si—CH 3 functional groups, and another fraction of the C atoms are bonded as Si—R—Si, wherein R is —[CH 2 ] n —, —[HC═CH] n —, —[C≡C] n —, or —[CH 2 C═CH] n —, where n is greater than or equal to and the fraction of the total carbon atoms in the material that is bonded as Si—R—Si is between 0.01 and 0.49, wherein said material is a porous composite material comprising a first solid phase having a first characteristic dimension and a second phase comprised of pores having a second characteristic dimension, wherein the characteristic dimensions of at least one of said phases is controlled to a value of about 5 nm or less.
2 . A method of forming a dielectric material comprising atoms of Si, C, O, and H comprising:
depositing a dielectric film comprising a first phase and a second phase onto a substrate utilizing at least a first precursor and a second precursor, wherein at least one of said first or second precursors is a bifunctional organic molecule forming a porogen in the film; and
removing said porogen from said dielectric film to provide a porous dielectric material comprising a first solid phase having a first characteristic dimension and a second solid phase comprised of pores having at second characteristic dimension, wherein the characteristic dimensions of at least one of said phases is controlled to a value of about 5 nm or less.
3 . The method of claim 2 wherein said bifunctional organic molecule is comprised of a linear, branched, cyclic or polycyclic hydrocarbon backbone of —[CH 2 ] n —, where n is greater than or equal to 1, and is substituted at only two sites by a functional group selected from alkenes, alkynes, ethers, 3 member oxiranes, epoxides, aldehydes, ketones, amines, hydroxyls, alcohols, carboxylic acids, nitriles, esters, amino, azido and azo.
4 . The method of claim 3 wherein the functional groups are alkenes and the bifunctional organic molecule has the general formula [CH 2 ═CH]—[CH 2 ] n —[CH═CH 2 ], where n is 1-8.
5 . The method of claim 2 wherein said bifunctional organic molecule is one of cyclopentene oxide, isobutylene oxide, 2,2,3-trimethyloxirane, butadienemonoxide, bicycloheptadiene, 1,2-epoxy-5-hexene and 2-methyl-2-vinyloxirane, propadiene, butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, cyclopentadiene, cyclohexadiene, dialkynes, butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, cyclopentadiene, cyclohexadiene, propdiyne, butadiyne, diethers, diepoxides, dialdehydes, diketones, diamines, dihydroxyls, dialcohols, dicarboxylic acids, dinitriles, diesters, diazido, or diazo.
6 . The method of claim 2 wherein one of said first or second precursors is a silicon containing molecule selected from the group of silane (SiH 4 ) derivatives having the molecular formulas SiR 4 , disiloxane derivatives having the formula R 3 SiOSiR 3 , trisiloxane derivatives having the formula R 3 SiOSiR 2 SiOSiR 3 , cyclic siloxanes, and cyclic Si containing compounds wherein the R substitutents may or may not be identical and are selected from H, alkyl, alkoxy, epoxy, phenyl, vinyl, allyl alkenyl or alkynyl groups that may be linear, branched, cyclic, polycyclic and may be functionalized with oxygen, nitrogen or fluorine containing substituents.
7 . The method of claim 6 wherein said organosilicon precursor is one of silane, methylsilane, dimethylsilane, trimethylsilane, tetramethylsilane, ethylsilane, diethylsilane, triethylsilane, tetraethylsilane, ethylmethylsilane, triethylmethylsilane, ethyldimethylsilane, ethyltrimethylsilane, diethyldimethylsilane, diethoxymethylsilane (DEMS), dimethylethoxysilane, dimethyldimethoxysilane, tetramethylcyclotetrasiloxane (TMCTS), octamethylcyclotetrasiloxane (OMCTS), ethoxyltrimethylsilane, ethoxydimethylsilane, dimethoxydimethylsilane, dimethoxymethylsilane, trimethoxymethylsilane, methoxysilane, dimethoxysilane, trimethoxysilane, tetramethoxysilane, ethoxysilane, diethoxysilane, triethoxysilane, tetraethoxysilane, methoxymethylsilane, dimethoxymethylsilane, trimethoxymethylsilane, methoxydimethylsilane, methoxytrimethylsilane, dimethoxyldimethylsilane, ethoxymethylsilane, ethoxydimethylsilane, ethoxytrimethylsilane, triethoxymethylsilane, diethoxydimethylsilane, ethylmethoxysilane, diethylmethoxysilane, triethylmethoxysilane, ethyldimethoxysilane, ethyltrimethoxysilane, diethyldimethoxysilane, ethoxymethylsilane, diethoxymethylsilane, triethoxymethylsilane, ethoxydimethylsilane, ethoxytrimethylsilane, diethoxyldimethylsilane, ethyldimethoxylmethylsilane, diethoxyethylmethylsilane, 1,3-disilolane, 1,1,3,3-tetramethoxy(ethoxy)-1,3-disilolane 1,1,3,3-tetramethyl-1,3-disilolane, vinylmethyldiethoxysilane, vinyltriethoxysilane, vinyldimethylethoxysilane, cyclohexenylethyltriethoxysilane, 1,1-diethoxy-1-silacyclopent-3-ene, divinyltetramethyldisiloxane, 2-(3,4-epoxyeyclohexyl)ethyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, epoxyhexyltriethoxysilane, hexavinyldisiloxane, trivinylmethoxysilane, trivinylethoxysilane, vinylmethylethoxysilane, vinylmethyldiethoxysilane, vinylmethyldimethoxysilane, vinylpentamethyldisiloxane, vinyltetramethyldisiloxane, vinyltriethoxysilane, vinyltrimethoxysilane, 1,1,3,3,-tetrahydrido-1,3-disilacyclobutane; 1,1,3,3-tetramethoxy(ethoxy)-1,3 disilacyclobutane; 1,3-dimethyl-1,3-dimethoxy-1,3 disilacyclobutane; 1,3-disilacyclobutane, 1,3-dimethyl-1,3-dihydrido-1,3-disilylcyclobutane, 1,1,3,3, tetramethyl-1,3-disilacyclobutane, 1,1,3,3,5,5-hexamethoxy-1,3,5-trisilane, 1,1,3,3,5,5-hexahydrido-1,3,5-trisilane, 1,1,3,3,5,5-hexamethyl-1,3,5-trisilane, 1,1,1,3,3,3-hexamethoxy(ethoxy)-1,3-disilapropane, 1,1,3,3-tetramethoxy-1-methyl-1,3-disilabutane, 1,1,3,3-tetramethoxy-1,3-disilapropane, 1,1,1,3,3,3-hexahydrido-1,3-disilapropane, 3-(1,1-dimethoxy-1-silaethyl)-1,4,4-trimethoxy-1-methyl-1,4-disilpentane, methoxymethane 2-(dimethoxysilamethyl)-1,1,4-trimethoxy-1,4-disilabutane, methoxymethane 1,1,4-trimethoxy-1,4-disila-2-(trimethoxysilylmethyl)butane, dimethoxymethane, methoxymethane, 1,1,1,5,5,5-hexamethoxy-1,5-disilapentane, 1,1,5,5-tetramethoxy-1,5-disilahexane, 1,1,5,5-tetramethoxy-1,5-disilapentane, 1,1,1,4,4,4-hexamethoxy(ethoxy)-1,4-disilylbutane, 1,1,1,4,4,4,-hexahydrido-1,4-disilabutane, 1,1,4,4-tetramethoxy(ethoxy)-1,4-dimethyl-1,4-disilabutane, 1,4-bis-trimethoxy (ethoxy)silyl benzene, 1,4-bis-dimethoxymethylsilyl benzene, 1,4-bis-trihydrosilyl benzene, 1,1,1,4,4,4-hexamethoxy(ethoxy)-1,4-disilabut-2-ene, 1,1,1,4,4,4-hexamethoxy(ethoxy)-1,4-disilabut-2-yne, 1,1,3,3-tetramethoxy(ethoxy)-1,3-disilolane 1,3-disilolane, 1,1,3,3-tetramethyl-1,3-disilolane, 1,1,3,3-tetramethoxy(ethoxy)-1,3-disilane, 1,3-dimethoxy(ethoxy)-1,3-dimethyl-1,3-disilane, 1,3-disilane; 1,3-dimethoxy-1,3-disilane, 1,1-dimethoxy(ethoxy)-3,3-dimethyl-1-propyl-3-silabutane, 2-silapropane, 1,3-disilacyclobutane, 1,3-disilapropane, 1,5-disilapentane, or 1,4-bis-trihydrosilyl benzene.
8 . The method of claim 2 wherein said removing said porogen comprises treating said dielectric film with at least one energy source which comprises a thermal energy source, UV light, electron beam, chemical, microwave or plasma.
9 . The method of claim 8 wherein the at least one energy source is a UV light, that may be pulsed or continuous, and said step is performed at a substrate temperature from 3000° 450° C., and with light that includes at least a UV wavelength between 150-370 nm.
10 . A method of forming a dielectric material including atoms of Si, C, O and H comprising:
depositing a dielectric film comprising a first phase and a second phase onto a substrate utilizing at least a first precursor and a second precursor, wherein at least one of said first or second precursors is a bifunctional organic molecule comprised of a linear, branched, cyclic or polycyclic hydrocarbon backbone of —[CH 2 ] n —, where n is greater than or equal to 1, and is substituted at only two sites by a functional group selected from alkenes, alkynes, ethers, 3 member oxiranes, epoxides, aldehydes, ketones, amines, hydroxyls, alcohols, carboxylic acids, nitriles, esters, amino, azido and azo forming a porogen in the film; and
removing said porogen from said dielectric film to provide a porous composite material comprising a first solid phase having a first characteristic dimension and a second solid phase comprised of pores having at second characteristic dimension, wherein the characteristic dimensions of at least one of said phases is controlled to a value of about 5 nm or less.
11 . The method of claim 10 wherein the bifunctional organic molecule has the general formula [CH 2 ═CH]—[CH 2 ] n —[CH═CH 2 ], wherein n is 1-8 and the functional groups are alkenes.
12 . The method of claim 10 wherein said bifunctional organic molecule is one of cyclopentene oxide, isobutylene oxide, 2,2,3-trimethyloxirane, butadienemonoxide, bicycloheptadiene, 1,2-epoxy-5-hexene and 2-methyl-2-vinyloxirane, propadiene, butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, cyclopentadiene, cyclohexadiene, dialkynes, butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, cyclopentadiene, cyclohexadiene, propdiyne, butadiyne, diethers, diepoxides, dialdehydes, diketones, diamines, dihydroxyls, dialcohols, dicarboxylic acids, dinitriles, diesters, diazido, or diazo.
13 . The method of claim 10 wherein one of said first or second precursors is a silicon containing molecule selected from silane (SiH 4 ) derivatives having the molecular formulas SiR 4 , disiloxane derivatives having the formula R 3 SiOSiR 3 , trisiloxane derivatives having the formula R 3 SiOSiR 2 SiOSiR 3 , cyclic siloxanes, and cyclic Si containing compounds including cyclosiloxanes, cyclocarbosiloxanes cyclocarbosilanes wherein the R substitutents may or may not be identical and are selected from H, alkyl, alkoxy, epoxy, phenyl, vinyl, allyl, alkenyl or alkynyl groups that may be linear, branched, cyclic, polycyclic and may be functionalized with oxygen, nitrogen or fluorine containing substituents.
14 . The method of claim 10 wherein said removing said porogen comprises treating said dielectric film with at least one energy source which comprises a thermal energy source, UV light, electron beam, chemical, microwave or plasma.
15 . A method of forming a dielectric material including atoms of Si, C, O and H comprising:
depositing a dielectric film comprising a first phase and a second phase onto a substrate utilizing at least a first precursor and a second precursor, wherein at least one of said first or second precursors is a bifunctional organic molecule has the general formula [CH 2 ═CH]—[CH 2 ] n —[CH═CH 2 ], wherein n is 1-8 and the functional groups are alkenes to form a porogen in said film; and
removing said porogen from said dielectric film to provide a porous composite material comprising a first solid phase having a first characteristic dimension and a second solid phase comprised of pores having at second characteristic dimension, wherein the characteristic dimensions of at least one of said phases is controlled to a value of about 5 nm or less.
16 . The method of claim 15 wherein said bifunctional organic molecule is one of cyclopentene oxide, isobutylene oxide, 2,2,3-trimethyloxirane, butadienemonoxide, bicycloheptadiene, 1,2-epoxy-5-hexene and 2-methyl-2-vinyloxirane, propadiene, butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, cyclopentadiene, cyclohexadiene, dialkynes, butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, cyclopentadiene, cyclohexadiene, propdiyne, butadiyne, diethers.
17 . The method of claim 15 wherein one of said first or second precursors is any silicon containing molecule selected from the group any Si containing compound including molecules selected from silane (SiH 4 ) derivatives having the molecular formulas SiR 4 , disiloxane derivatives having the formula R 3 SiOSiR 3 , trisiloxane derivatives having the formula R 3 SiOSiR 2 SiOSi R 3 , cyclic siloxanes, and cyclic Si containing compounds wherein the R substitutents may or may not be identical and are selected from H, alkyl, alkoxy, epoxy, phenyl, vinyl, allyl, alkenyl or alkynyl groups that may be linear, branched, cyclic, polycyclic and may be functionalized with oxygen, nitrogen or fluorine containing substituents.
18 . The method of claim 15 wherein said removing said porogen comprises treating said dielectric film with at least one energy source which comprises a thermal energy source, UV light, electron beam, chemical, microwave or plasma.
19 . The method of claim 18 wherein the at least one energy source is a UV light, that may be pulsed or continuous, and said step is performed at a substrate temperature from 300°-450° C., and with light that includes at least a UV wavelength between 150-370 nm.