Catalyst and formulations comprising same for alkoxysilanes hydrolysis reaction in semiconductor process
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C09D-001/00
H01L-021/02
B65B-001/04
C08G-077/04
출원번호
US-0738482
(2013-01-10)
등록번호
US-9809711
(2017-11-07)
발명자
/ 주소
Xiao, Manchao
Pearlstein, Ronald Martin
Ho, Richard
Lei, Xinjian
Mayorga, Steven Gerard
Spence, Daniel P.
출원인 / 주소
VERSUM MATERIALS US, LLC
대리인 / 주소
Kiernan, Anne B.
인용정보
피인용 횟수 :
0인용 특허 :
16
초록▼
A stable formulation comprising a silicon containing precursor selected from an alkoxysilane, aryloxysilane, or alkylalkoxysilane and a catalyst compound comprising a haloalkoxyalkylsilane or haloaryloxyalkylsilane wherein the substitutents within the silicon-containing precursor and catalyst compou
A stable formulation comprising a silicon containing precursor selected from an alkoxysilane, aryloxysilane, or alkylalkoxysilane and a catalyst compound comprising a haloalkoxyalkylsilane or haloaryloxyalkylsilane wherein the substitutents within the silicon-containing precursor and catalyst compound are the same are described herein. More specifically, the formulation comprises a silicon-containing precursor comprising an alkoxyalkylsilane or aryloxysilane having a formula of Si(OR1)nR24-n and a catalyst comprising haloalkoxyalkylsilane having a formula of XSi(OR1)nR23-n; or a silicon-containing precursor comprising an alkoxysilane or aryloxysilane having a formula of R23-p(R1O)pSi—R3—Si(OR1)pR23-p and a catalyst comprising a haloalkoxyalkylsilane or haloaryloxyalkylsilane having a formula of (R1O)mR22-m(X)Si—R3—Si(OR4)2R5 wherein at least one or all of the R1 and R2 substituents are the same in both the silicon-containing precursor and catalyst compound are described herein. The formulations can be used in semiconductor deposition process, such as for example, a flowable silicon oxide process.
대표청구항▼
1. A formulation comprising (a) a silicon-containing precursor comprising a compound having a formula R23-p(R1O)pSi—R3—Si(OR1)pR23-p and(b) a catalyst comprising a haloalkoxyalkylsilane having a formula of (R1O)mR22-m(X)Si—R3—Si(OR4)2R5; wherein R1 and R4 are each independently selected from a C1-C1
1. A formulation comprising (a) a silicon-containing precursor comprising a compound having a formula R23-p(R1O)pSi—R3—Si(OR1)pR23-p and(b) a catalyst comprising a haloalkoxyalkylsilane having a formula of (R1O)mR22-m(X)Si—R3—Si(OR4)2R5; wherein R1 and R4 are each independently selected from a C1-C12 linear or branched alkyl group; a C3-C12 aryl group; a C3-C12 cycloalkyl group; a C2-C12 alkenyl group; and a C2-C12 alkynyl group; R2 is selected from a C1-C12 linear or branched alkyl group; a C3-C12 aryl group; a C3-C12 cycloalkyl group; a C2-C12 alkenyl group; a C2-C12 alkynyl group; and a hydrogen atom; wherein R1 and R2 may be the same or different; R3 is selected from a C1-10 alkanediyl group; a C2-10 alkenediyl group; a C2-10 alkynediyl group; a C3-10 cyclic alkanediyl; a C5-10 cyclic alkenediyl group; a C6-10 bi-cyclic alkanediyl group; a C6-10 cyclic alkenediyl group; a C6-10 arenediyl group; and R5 is selected from a linear or branched C1-C12 alkyl group; a C4-C12 aryl group; a C3-C12 cycloalkyl group; a C2-C12 alkenyl group; a C2-C12 alkynyl group; and a linear or branched C1-C12 alkoxy group; X is chosen from F, Cl, Br and I; m is an integer ranging from 1 to 2 inclusive; and p is an integer ranging from 1 to 3 inclusive; and wherein R1 in the silicon containing precursor and R1 in the catalyst are the same substituents and the concentration of the silicon-containing precursor and the catalyst does not change by more than 10 wt %, based upon gas chromatography, after storage for a period of one year. 2. The Formulation of claim 1 wherein R1 and R4 are selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, 2-ethylhexyl, isobutyl, sec-butyl, n-pentyl, isopentyl, neopentyl and tert-pentyl, allyl (2-propenyl), homoallyl (3-butenyl), propargyl (2-propynyl), 2-hydroxyethyl, 2-hydroxypropyl, 2-methoxyethyl, phenyl, tolyl, xylyl, hydroxyphenyl, lauryl, napthyl, indenyl, benzyl, and mixtures thereof, and R2 is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, 2-ethylhexyl, isobutyl, sec-butyl, n-pentyl, isopentyl, neopentyl and tert-pentyl, vinyl (ethenyl), allyl (2-propenyl), homoallyl (3-butenyl), propargyl (2-propynyl), 2-hydroxyethyl, 2-hydroxypropyl, 2-methoxyethyl, phenyl, tolyl, xylyl, hydroxyphenyl, lauryl, napthyl, indenyl, benzyl, hydrogen and mixtures thereof. 3. The formulation of claim 1 wherein R1 and R4 are selected from the group consisting of methyl, ethyl, isopropyl, tert-butyl, phenyl, and mixtures thereof; R2 is selected from the group consisting of methyl, ethyl, isopropyl, vinyl, tert-butyl, phenyl, hydrogen, and mixtures thereof; R3 is selected from the group consisting of methylene (—CH2—), ethanediyl (—CH2CH2—), ethylenediyl (—CH═CH—), cyclopentenediyl, cyclohexenediyl, cycloctenediyl, tricycloheptanediyl. 4. The formulation of claim 1 wherein R1 and R4 are selected from the group consisting of methyl and ethyl; R2 is selected from the group consisting of methyl, ethyl, vinyl, tert-butyl, hydrogen, and mixtures thereof; R3 is selected from the group consisting of methylene, ethanediyl, ethenediyl, cyclopentenediyl, cyclohexenediyl, cycloctenediyl, bi-cycloheptanediyl, benzenediyl; R5 is selected from methyl, ethyl, methoxy, ethoxy, and X is Cl. 5. The formulation of claim 1 wherein (R1O)mR22-m(X)Si—R3—Si(OR4)2R5 is selected from the group consisting of bis(trimethoxysilyl)(dimethoxychlorosilyl)methane (MeO)2ClSi—CH2—Si(OMe)3, (triethoxysilyl)(diethoxychlorosilyl)methane (EtO)2ClSi—CH2—Si(OEt)3, 1-(trimethoxysilyl)-2-(dimethoxychlorosilyl)ethane (MeO)2ClSi—CH2CH2—Si(OMe)3, 1-(triethoxysilyl)-2-(diethoxychlorosilyl)ethane (EtO)2ClSi—CH2CH2—Si(OEt)3, (chloromethoxymethylsilyl)(dimethoxymethylsilyl)methane (MeO)ClMeSi-CH2SiMe(OMe)2, (chloroethoxymethylsilyl)(diethoxymethylsilyl)methane (EtO)CI MeSi—CH2—SiMe(OEt)2, 1-(chloromethoxymethylsilyl)-2-(dimethoxymethylsilyl)ethane (MeO)ClMeSi—CH2CH2—SiMe(OMe)2, 1-(chloroethoxymethylsilyl)-2-(diethoxymethylsilyl)ethane (EtO)ClMeSi—CH2CH2—SiMe(OEt)2, and combinations thereof. 6. The formulation of claim 1 wherein R23-p(R1O)pSi—R3—Si(OR1)pR23p is selected from the group consisting of bis(trimethoxysilyl)methane (MeO)3Si—CH2—Si(OMe)3, bis(triethoxysilyl)methane (EtO)3Si—CH2—Si(OEt)3, bis(trimethoxysilyl)ethane (MeO)3Si—CH2CH2—Si(OMe)3, bis(triethoxysilyl)ethane (EtO)3Si—CH2CH2—Si(OEt)3, bis(dimethoxymethylsilyl)methane (MeO)2MeSi—CH2—SiMe(OMe)2, bis(diethoxymethylsilyl)methane (EtO)2MeSi—CH2—SiMe(OEt)2, bis(dimethoxymethylsilyl)ethane (MeO)2MeSi—CH2CH2—SiMe(OMe)2, bis(diethoxymethylsilyl)ethane (EtO)2MeSi—CH2CH2—SiMe(OEt)2, and combinations thereof. 7. The formulation of claim 1 wherein the formulation is selected from the group consisting of bis(trimethoxysilyl)methane and (trimethoxysilyl)(dimethoxychlorosilyl)methane; bis(triethoxysilyl)methane and (triethoxysilyl)(diethoxychlorosilyl)methane; 1,2-bis(trimethoxysilyl)ethane and 1-(trimethoxysilyl)-2-(dimethoxychlorosilyl)ethane; 1,2-bis(triethoxysilyl)ethane and 1-(triethoxysilyl)-2-(diethoxychlorosilyl)ethane; bis(dimethoxymethylsilyl)methane and (trimethoxysilyl(dimethoxychlorosilyl)methane; bis(diethoxymethylsilyl)methane and (triethoxysilyl)(diethoxychlorosilyl)methane; 1,2-bis(dimethoxymethylsilyl)methane and 1-(trimethoxysilyl)-2-(dimethoxychlorosilyl)methane; 1,2-bis(diethoxymethylsilyl)ethane and 1-(triethoxysilyl)-2-(diethoxychlorosilyl)ethane. 8. The formulation of claim 1 wherein the amount of the silicon-containing precursor present in the formulation is 50 wt % or greater. 9. The formulation of claim 8, wherein the amount of the silicon-containing precursor present in the formulation is 80 wt % or greater. 10. The formulation of claim 1, wherein the amount of the catalyst compound in the formulation is 10 parts per million (ppm) by weight or greater. 11. The formulation of claim 10, wherein the amount of the catalyst compound in the formulation ranges from 25 ppm to 10 wt %. 12. The formulation of claim 11, wherein the amount of the catalyst compound in the formulation ranges from 50 ppm to 5 wt %. 13. A stable formulation comprising: (a) a silicon-containing precursor comprising an alkoxyalkylsilane having a formula of Si(OR1)nR24-n; and(b) a catalyst comprising a haloalkoxyalkylsilane having a formula of XSi(OR1)nR23-n; wherein R1 is selected from the group consisting of a C1-C12 linear or branched alkyl group; a C3-C12 aryl group, a C3-C12 cycloalkyl group, a C2-C12 alkenyl group, and a C2-C12 alkynyl group; R2 is selected from the group consisting of a C1-C12 linear or branched alkyl group; a C3-C12 aryl group; a C3-C12 cycloalkyl group; a C2-C12 alkenyl group; a C2-C12 alkynyl group; and a hydrogen atom; wherein when R1 is methyl, R2 is not hydrogen; n is an integer ranging from 1 to 4 inclusive; and X is selected from the group consisting of from F, Cl, Br and I; wherein at least one or both of substituents R1 and R2 in the silicon-containing precursor and the R1 and R2 in the catalyst are the same and wherein the formulation does not change by greater than 10 wt % after being stored for six months. 14. A formulation for use in forming a silicon containing film comprising: (a) a silicon-containing precursor comprising an alkoxyalkylsilane having a formula of Si(OR1)nR24-n; and(b) a catalyst comprising a haloalkoxyalkylsilane having a formula of XSi(OR1)nR23-n; wherein R1 is selected from the group consisting of a C1-C12 linear or branched alkyl group; a C3-C12 aryl group, a C3-C12 cycloalkyl group, a C2-C12 alkenyl group, and a C2-C12 alkynyl group; R2 is selected from the group consisting of a C1-C12 linear or branched alkyl group; a C3-C12 aryl group; a C3-C12 cycloalkyl group; a C2-C12 alkenyl group; a C2-C12 alkynyl group; and a hydrogen atom; wherein when R1 is methyl, R2 is not hydrogen; n is an integer ranging from 1 to 4 inclusive; and X is selected from the group consisting 6 of 11 of from F, Cl, Br and I wherein at least one or both of substituents R1 and R2 in the silicon-containing precursor and the R1 and R2 in the catalyst are the same; wherein the formulation is a fluid and the concentration of the precursor or the catalyst do not compositionally change by more than 10% after storage for one year. 15. The formulation of claim 14 wherein R1 is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, tert-butyl, n-butyl, 2-ethylhexyl, isobutyl, sec-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, allyl (2-propenyl), homoallyl (3-butenyl), propargyl (2-propynyl), 2-hydroxyethyl, 2-hydroxypropyl, 2-methoxyethyl, phenyl, tolyl, xylyl, hydroxyphenyl, lauryl, napthyl, indenyl, benzyl, and mixtures thereof, and R2 is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-ethylhexyl, isobutyl, sec-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, vinyl, allyl, homoallyl (3-butenyl), propargyl (2-propynyl), 2-hydroxyethyl, 2-hydroxypropyl, 2-methoxyethyl, phenyl, tolyl, xylyl, hydroxyphenyl, lauryl, napthyl, indenyl, benzyl, hydrogen and mixtures thereof. 16. The formulation of claim 14 wherein R1 is selected from the group consisting of methyl, ethyl, iso-propyl, tert-butyl, phenyl, and mixtures thereof. 17. The formulation of claim 14 wherein R1 is selected from the group consisting of methyl and ethyl; and X is Cl. 18. The formulation of claim 14 comprising at least one member selected from the group consisting of methyltriethoxysilane and chlorodiethoxymethylsilane (CI-DEMS); bis(tert-butoxy)silane and bis(tert-butoxy)chlorosilane; methyltrimethoxysilane and methyldimethoxybromosilane; n-hexyltrimethoxysilane with methyldimethoxychlorosilane; and tetramethoxysilane with trimethoxychlorosilane. 19. The formulation of claim 14 wherein the formulation is stored in a container selected from the group consisting of glass, plastic, metallic, and plastic or glass lined metallic container. 20. A stable formulation for use in forming a silicon-containing film; selected from the group consisting of: (1) a formulation comprising:(a) a silicon-containing precursor comprising an alkoxyalkylsilane having a formula of Si(OR1)nR24-n;and (b) a catalyst comprising a haloalkoxyalkylsilane having a formula of XSi(OR1)nR23-n; wherein R1 is selected from the group consisting of a C1-C12 linear or branched alkyl group; a C3-C12 aryl group, a C3-C12 cycloalkyl group, a C2-C12 alkenyl group, and a C2-C12 alkynyl group; R2 is selected from the group consisting of a C1-C12 linear or branched alkyl group; a C3-C12 aryl group; a C3-C12 cycloalkyl group; a C2-C12 alkenyl group; a C2-C12 alkynyl group; and a hydrogen atom; wherein when R1 is methyl, R2 is not hydrogen; n is an integer ranging from 1 to 4 inclusive; and X is selected from the group consisting of from F, Cl, Br and I and wherein at least one or both of substituents R1 and R2 in the silicon-containing precursor and the R1 and R2 in the catalyst are the same;and(2) a formulation comprising(a) a silicon-containing precursor comprising a compound having a formula R23-p(R1O)pSi—R3—Si(OR1)pR23-p and(b) a catalyst comprising a haloalkoxyalkylsilane having a formula of (R1O)mR22-m(X)Si—R3—Si(OR4)2R5; wherein R1 and R4 are each independently selected from a C1-C12 linear or branched alkyl group; a C3-C12 aryl group; a C3-C12 cycloalkyl group; a C2-C12 alkenyl group;and a C2-C12 alkynyl group; R2 is selected from a C1-C12 linear or branched alkyl group; a C3-C12 aryl group; a C3-C12 cycloalkyl group; a C2-C12 alkenyl group; a C2-C12 alkynyl group; and a hydrogen atom; wherein R1 and R2 may be the same or different; R3 is selected from a C1-10 alkanediyl group; a C2-10 alkenediyl group; a C2-10 alkynediyl group; a C3-10 cyclic alkanediyl; a C5-10 cyclic alkenediyl group; a C6-10 bi-cyclic alkanediyl group; a C6-10 cyclic alkenediyl group; a C6-10 arenediyl group; and R5 is selected from a linear or branched C1-C12 alkyl group; a C4-C12 aryl group; a C3-C12 cycloalkyl group; a C2-C12 alkenyl group; a C2-C12 alkynyl group; and a linear or branched C1-C12 alkoxy group; X is chosen from F, Cl, Br and I; m is an integer ranging from 1 to 2 inclusive; and p is an integer ranging from 1 to 3 inclusive; wherein the stable formulation is reactive under chemical vapor conditions to form the silicon containing film. 21. The formulation of claim 20 wherein the process for forming the silicon containing film comprises a flowable chemical vapor deposition of silicon dioxide. 22. The formulation of claim 20 wherein the formulation is a fluid and the catalyst of formulation 1 or 2 reacts with at least one of water, ethanol or compositions thereof to generate HX wherein the concentration of HX is sufficient to accelerate hydrolysis of alkoxy groups in the silicon-containing precursor and catalyst in a process for forming the silicon containing film. 23. The formulation of claim 20 further comprising water. 24. The formulation of claim 1 wherein the formulation reacts with water under chemical vapor deposition conditions to deposit a silicon containing film. 25. The formulation of claim 13 wherein the formulation reacts with water under chemical vapor deposition conditions to deposit the silicon containing film. 26. The formulation of claim 14 wherein the formulation reacts with water under chemical vapor deposition conditions to deposit the silicon containing film.
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