Bismuth precursors for EUV film processes

Abstract

Bismuth-containing precursor compositions and a method of depositing the precursor on a substrate to form a bismuth-containing film are provided. The bismuth-containing precursor is of the formula: BiL1L2L3, wherein each of L1, L2, or L3 independently is at least one of a hydrogen, an alkyl, an alkenyl, an alkynyl, an aryl, a cycloalkyl, an alkoxy, an oxysilyl, an alkoxyalkyl, an aralkyl, a thiol, a xanthate, a thioester, an amino, an amidine, a guanidine, a carbonyl, a halogen, or any combination thereof, or at least two of L1, L2, or L3 are bonded to form a cyclic ring.

Description

BISMUTH PRECURSORS FOR EUV FILM PROCESSESFIELD

[0001] The present disclosure relates to bismuth precursors for EUV film processes.CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit under 35 USC 119 of U.S. Provisional Patent Application No. 63 / 729,845, filed Dec. 9, 2024, the disclosure of which is hereby incorporated herein by reference in its entirety.BACKGROUND

[0003] Bismuth-containing precursors can be deposited on a substrate to form a bismuth-containing film.SUMMARY

[0004] Some embodiments relate to a composition. In some embodiments, the composition comprises a bismuth-containing compound. In some embodiments, the composition comprises a compound of the formula:In some embodiments, each of L1, L2, or L3of the formula independently comprises at least one of a hydrogen, an alkyl, an alkenyl, an alkynyl, an aryl, a cycloalkyl, an alkoxy, an oxysilyl, a thiol, a xanthate, a thioester, an amine, an amidine, a guanidine, a carbonyl, a ketone, a halogen, or any combination thereof. In some embodiments, at least two L1, L2, or L3are bonded to form a cyclic ring.

[0005] Some embodiments relate to a method. In some embodiments, the method comprises obtaining a precursor compound. In some embodiments, the precursor compound comprises a compound of the formula:In some embodiments, each of L1, L2, or L3of the formula independently comprises at least one of a hydrogen, an alkyl, an alkenyl, an alkynyl, an aryl, a cycloalkyl, an alkoxy, an oxysilyl, a thiol, a xanthate, a thioester, an amine, an amidine, a guanidine, a carbonyl, a ketone, a halogen, or any combination thereof. In some embodiments, at least two L1, L2, or L3are bonded to form a cyclic ring. In some embodiments, the method comprises contacting the precursor compound with a substrate to form a film.BRIEF DESCRIPTION OF THE DRAWINGS

[0006] FIG. 1 is a flowchart of a method of making a film, according to some embodiments.DETAILED DESCRIPTION

[0007] As used herein, the term “alkyl” refers to a hydrocarbyl having from 1 to 30 carbon atoms. The alkyl may be attached via a single bond. An alkyl having n carbon atoms may be designated as a “Cnalkyl.” For example, a “C3 alkyl” may include n- propyl and isopropyl. An alkyl having a range of carbon atoms, such as 1 to 30 carbon atoms, may be designated as a C1-C30 alkyl. In some embodiments, the alkyl is linear. In some embodiments, the alkyl is branched. In some embodiments, the alkyl is substituted. In some embodiments, the alkyl is unsubstituted. In some embodiments, the alkyl comprises or is selected from the group consisting of at least one of a C1-C30 alkyl, C1-C29 alkyl, C1-C28 alkyl, C1-C27 alkyl, C1-C27 alkyl, C1-C26 alkyl, C1-C25 alkyl, C1-C24 alkyl, C1-C23 alkyl, C1-C22 alkyl, C1-C21 alkyl, C1-C20 alkyl, C1-C19 alkyl, C1-C18 alkyl, C1-C17 alkyl, C1-C16 alkyl, C1-C15 alkyl, C1-C14 alkyl, C1-C13 alkyl, C1-C12 alkyl, C1-C11 alkyl, C1-C10 alkyl, a C1-C9 alkyl, a Ci-Cs alkyl, a C1-C7 alkyl, a C1-C6 alkyl, a C1-C5 alkyl, a C1-C4 alkyl, a C1-C3 alkyl, a C1-C2 alkyl, a C2-C30 alkyl, a C3-C30 alkyl, a C4-C30 alkyl, a C5-C30 alkyl, a C6-C30 alkyl, a C7-C30 alkyl, a Cs-Cso alkyl, a C9-C30 alkyl, a C10-C30 alkyl, a C11-C30 alkyl, a C12-C30 alkyl, a C13-C30 alkyl, a C14-C30 alkyl, a C15- C30 alkyl, a C16-C30 alkyl, a C17-C30 alkyl, a C18-C30 alkyl, a C19-C30 alkyl, a C20-C30 alkyl, a C21-C30 alkyl, a C22-C30 alkyl, a C23-C30 alkyl, a C24-C30 alkyl, a C25-C30 alkyl, aC26-C30 alkyl, a C27-C30 alkyl, a C28-C30 alkyl, a C29-C30 alkyl, a C2-C10 alkyl, a C3-C10 alkyl, a C4-C10 alkyl, a C5-C10 alkyl, a Ce-Cio alkyl, a C7-C10 alkyl, a Cs-Cio alkyl, a C2- C9 alkyl, a C2-C8 alkyl, a C2-C7 alkyl, a C2-C6 alkyl, a C2-C5 alkyl, a C3-C5 alkyl, or any combination thereof. In some embodiments, the alkyl comprises or is selected from the group consisting of at least one of methyl, ethyl, n-propyl, 1 -methylethyl (isopropyl), n-butyl, iso-butyl, sec-butyl, n-pentyl, 1 ,1 -dimethylethyl (t-butyl), n-pentyl, isopentyl, n-hexyl, isohexyl, 3-methylhexyl, 2-methylhexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, or any combination thereof. In some embodiments, the term “alkyl” refers generally to alkyls, alkenyls, alkynyls, and / or cycloalkyls.

[0008] As used herein, the term “alkenyl” refers to a hydrocarbyl having from 2 to 30 carbon atoms and at least one carbon-carbon double bond. In some embodiments, the alkenyl comprises or is selected from the group consisting of at least one of a C2- C30 alkenyl, C2-C29 alkenyl, C2-C28 alkenyl, C2-C27 alkenyl, C2-C26 alkenyl, C2-C25 alkenyl, C2-C24 alkenyl, C2-C23 alkenyl, C2-C22 alkenyl, C2-C21 alkenyl, C2-C20 alkenyl, C2-C19 alkenyl, C2-C18 alkenyl, C2-C17 alkenyl, C2-C16 alkenyl, C2-C15 alkenyl, C2-C14 alkenyl, C2-C13 alkenyl, C2-C12 alkenyl, C2-C11 alkenyl, C2-C10 alkenyl, a C2-C9 alkenyl, a C2-C8 alkenyl, a C2-C7 alkenyl, a C2-C6 alkenyl, a C2-C5 alkenyl, a C2-C4 alkenyl, a C2-C3 alkenyl, a C2-C30 alkenyl, a C3-C30 alkenyl, a C4-C30 alkenyl, a C5-C30 alkenyl, a C6-C30 alkenyl, a C7-C30 alkenyl, a Cs-Cso alkenyl, a C9-C30 alkenyl, a C10-C30 alkenyl, a C11-C30 alkenyl, a C12-C30 alkenyl, a C13-C30 alkenyl, a C14-C30 alkenyl, a C15-C30 alkenyl, a C16-C30 alkenyl, a C17-C30 alkenyl, a C18-C30 alkenyl, a C19-C30 alkenyl, aC20-C30 alkenyl, a C21-C30 alkenyl, a C22-C30 alkenyl, a C23-C30 alkenyl, a C24-C30 alkenyl, a C25-C30 alkenyl, a C26-C30 alkenyl, a C27-C30 alkenyl, a C28-C30 alkenyl, aC29-C30 alkenyl, a C2-C10 alkenyl, a C3-C10 alkenyl, a C4-C10 alkenyl, a C5-C10 alkenyl, a Ce-Cio alkenyl, a C7-C10 alkenyl, a Cs-Cw alkenyl, a C3-C5 alkenyl, or any combination thereof. Examples of alkenyl groups include, without limitation, at least one of vinyl, allyl, 1 -methylvinyl, 1 -propenyl, 1 -butenyl, 2-butenyl, 3-butenyl, 1 ,3-butadienyl, 2- methyl-1 -propenyl, 2-methyl-2-propenyl, 1 -pentenyl, 2-pentenyl, 3-pentenyl, 4- pentenyl, 1 ,3-pentadienyl, 2,4-pentadienyl, 1 ,4-pentadienyl, 3-methyl-2-butenyl, 1 - hexenyl, 2-hexenyl, 3-hexenyl, 1 ,3-hexadienyl, 1 ,4-hexadienyl, 2-methylpentenyl, 1 - heptenyl, 3-heptenyl, 1 -octenyl, 1 ,3-octadienyl, 1 -nonenyl, 2-nonenyl, 3-nonenyl, 1 - decenyl, 3-decenyl, 1 -undecenyl, oleyl, linoleyl, linolenyl, or any combination thereof.

[0009] As used herein, the term “alkynyl” refers to a hydrocarbyl having from 2 to 30 carbon atoms and at least one carbon-carbon triple bond. In some embodiments, the alkynyl comprises or is selected from the group consisting of at least one of a C2- C30 alkynyl, C2-C29 alkynyl, C2-C28 alkynyl, C2-C27 alkynyl, C2-C26 alkynyl, C2-C25 alkynyl, C2-C24 alkynyl, C2-C23 alkynyl, C2-C22 alkynyl, C2-C21 alkynyl, C2-C20 alkynyl, C2-C19 alkynyl, C2-C18 alkynyl, C2-C17 alkynyl, C2-C16 alkynyl, C2-C15 alkynyl, C2-C14 alkynyl, C2-C13 alkynyl, C2-C12 alkynyl, C2-C11 alkynyl, C2-C10 alkynyl, a C2-C9 alkynyl, a C2-C8 alkynyl, a C2-C7 alkynyl, a C2-C6 alkynyl, a C2-C5 alkynyl, a C2-C4 alkynyl, a C2-C3 alkynyl, a C3-C30 alkynyl, a C4-C30 alkynyl, a C5-C30 alkynyl, a C6-C30 alkynyl, a C7-C30 alkynyl, a C8-C30 alkynyl, a C9-C30 alkynyl, a C10-C30 alkynyl, a C11-C30 alkynyl, a C12-C30 alkynyl, a C13-C30 alkynyl, a C14-C30 alkynyl, a C15-C30 alkynyl, a C16-C30 alkynyl, a C17-C30 alkynyl, a C18-C30 alkynyl, a C19-C30 alkynyl, a C20-C30 alkynyl, a C21- C30 alkynyl, a C22-C30 alkynyl, a C23-C30 alkynyl, a C24-C30 alkynyl, a C25-C30 alkynyl, a C26-C30 alkynyl, a C27-C30 alkynyl, a C28-C30 alkynyl, a C29-C30 alkynyl, a C3-C10 alkynyl, a C4-C10 alkynyl, a C5-C10 alkynyl, a Ge-Cio alkynyl, a C7-C10 alkynyl, a Cs-Cio alkynyl, a C3-C5 alkynyl, or any combination thereof. Examples of alkynyl groups include, without limitation, at least one of ethynyl, propynyl, n-butynyl, n-pentynyl, 3-methyl-1 - butynyl, n-hexynyl, methyl-pentynyl, or any combination thereof.

[0010] As used herein, the term “cycloalkyl” refers to a non-aromatic carbocyclic ring having from 3 to 8 carbon atoms in the ring. The term includes a monocyclic non- aromatic carbocyclic ring and a polycyclic non-aromatic carbocyclic ring. The term "monocyclic," when used as a modifier, refers to a cycloalkyl having a single cyclic ring structure. The term "polycyclic," when used as a modifier, refers to a cycloalkyl having more than one cyclic ring structure, which may be fused, bridged, spiro, or otherwise bonded ring structures. For example, two or more cycloalkyls may be fused, bridged, or fused and bridged to obtain the polycyclic non-aromatic carbocyclic ring. In some embodiments, the cycloalkyl may comprise, consist of, or consist essentially of, or may be selected from the group consisting of, at least one of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, or any combination thereof.

[0011] As used herein, the term "aryl" refers to a monocyclic or polycyclic aromatic hydrocarbon. The number of carbon atoms of the aryl may be in a range of 5 carbon atoms to 100 carbon atoms. In some embodiments, the aryl has 5 to 20 carbon atoms. For example, in some embodiments, the aryl has 6 to 8 carbon atoms, 6 to 10 carbonatoms, 6 to 12 carbon atoms, 6 to 15 carbon atoms, or 6 to 20 carbon atoms. The term "monocyclic," when used as a modifier, refers to an aryl having a single aromatic ring structure. The term "polycyclic," when used as a modifier, refers to an aryl having more than one aromatic ring structure, which may be fused, bridged, spiro, or otherwise bonded ring structures. In some embodiments, the aryl is — CeHs.

[0012] Non-limiting examples of aryls include, without limitation, at least one of benzene, toluene, xylene (e.g., o-xylene, m-xylene, p-xylene), t-butyltoluene (e.g., o- t-butyltoluene, m-t-butyltoluene, p-t-butyltoluene), ethylmethylbenzene (e.g., 1 -ethyl- 4-methylbenzene, 1 -ethyl-3-methylbenzene), 1 -isopropyl-4-methylbenzene, 1 -t-butyl- 4-methylbenzene, mesitylene, pseudocumene, durene, methylbenzene, dimethylbenzene, trimethylbenzene, ethylbenzene, diethylbenzene (e.g., 1 ,4- diethylbenzene), triethylbenzene, propylbenzene, butylbenzene, iso-butylbenzene, sec-butylbenzene, t-butylbenzene, hexylbenzene, styrene, naphthalene, anthracene, phenanthrene, biphenyl, terphenyl, methylnaphthalene, biphenylene, dimethylnaphthalene, methylanthracene, 4,4'-dimethylbiphenyl, bibenzyl, diphenylmethane, any isomer thereof, or any combination thereof, and the like.

[0013] As used herein, the term “amino” and / or “amine” refers to a functional group of formula — N(RaRb), wherein Raand Rbare independently a hydrogen, an alkyl (as defined herein), an aminoalkyl (as defined herein), or a silyl (as defined herein), or Raand Rbare bonded to each other to form a C3-C20 N-heterocycle. In some embodiments, the amino may comprise an alkylamino or a dialkylamino. In some embodiments, the amino may comprise at least one of methylamino, dimethylamino, ethylamino, diethylamino, isopropylamino, di-isopropylamino, butylamino, secbutylamino, tert-butylamino, di-sec-butylamino, isobutylamino, di-isobutylamino, di- tert-pentylamino, ethylmethylamino, isopropyl-n-propylamino, or any combination thereof. Examples of the alkylamines may include, without limitation, one or more of the following: primary alkylamines, such as, for example and without limitation, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, secbutylamine, isobutylamine, t-butylamine, pentylamine, 2-aminopentane, 3- aminopentane, 1 -amino-2-methylbutane, 2-amino-2-methylbutane, 3-amino-2- methylbutane, 4-amino-2-methylbutane, hexylamine, 5-amino-2-methylpentane, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine,and octadecylamine; secondary alkylamines, such as, for example and without limitation, dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diisobutylamine, di-sec-butylamine, di-t-butylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, methylethylamine, methylpropylamine, methylisopropylamine, methylbutylamine, methylisobutylamine, methyl-sec-butylamine, methyl-t-butylamine, methylamylamine, methylisoamylamine, ethylpropylamine, ethylisopropylamine, ethylbutylamine, ethylisobutylamine, ethyl-sec-butylamine, ethylamine, ethylisoamylamine, propylbutylamine, and propylisobutylamine; and tertiary alkylamines, such as, for example and without limitation, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, dimethylethylamine, methyldiethylamine, and methyldipropylamine. Examples of polyamines may include, without limitation, one or more of the following: ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, 1 ,3-diaminobutane, 2,3-diaminobutane, pentamethylenediamine, 2,4-diaminopentane, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, N- methylethylenediamine, N,N-dimethylethylenediamine, trimethylethylenediamine, N- ethylethylenediamine, N,N-diethylethylenediamine, triethylethylenediamine, 1 ,2,3- triaminopropane, hydrazine, tris(2-aminoethyl)amine, tetra(aminomethyl)methane, diethylenetriamine, triethylenetetramine, tetraethylpentamine, heptaethyleneoctamine, nonaethylenedecamine, and diazabicyloundecene. Unless otherwise provided herein, the terms “amine” and “amino” may be used interchangeably throughout this disclosure.

[0014] As used herein, the term “alkoxy” or “alkoxide” refers to a functional group of formula — ORC, wherein Rcis an alkyl (as defined herein), a silylalkyl, a cycloalkyl, or an aryl. In some embodiments, the alkoxy may comprise, consist of, or consist essentially of, or may selected from the group consisting of, at least one of methoxy, ethoxy, methoxy, ethoxy, n-propoxy, 1 -methylethoxy (isopropoxy), n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, or any combination thereof.

[0015] As used herein, the term “silyl” refers to a functional group of formula — Si(ReRfRg), where each of Re, Rf, and Rgis independently a hydrogen or an alkyl, as defined herein. In some embodiments, the silyl is a functional group of formula — SIHs. In some embodiments, the silyl is a functional group of formula — SiReH2, where Reisnot hydrogen. In some embodiments, the silyl is a functional group of formula — SiReRfH, where Reand Rfare not hydrogen. In some embodiments, the silyl is a functional group of the formula — Si(ReRfRg), where Re, Rf, and Rgare not hydrogen. In some embodiments, the silyl is a functional group of formula — Si(CHs)3.

[0016] As used herein, the term “oxysilyl” refers to a functional group of formula — OSi(ReRfRg), where each of Re, Rf, and Rgis independently a hydrogen or an alkyl, as defined herein. In some embodiments, the silyl is a functional group of formula — SiHs. In some embodiments, the silyl is a functional group of formula — SiReH2, where Reis not hydrogen. In some embodiments, the silyl is a functional group of formula — SiReRfH, where Reand Rfare not hydrogen. In some embodiments, the silyl is a functional group of the formula — Si(ReRfRg), where Re, Rf, and Rgare not hydrogen. In some embodiments, the silyl is a functional group of formula — Si(CHs)3.

[0017] As used herein, the term “alkoxyalkyl” refers to an alkyl as defined herein, wherein at least one of the hydrogen atoms of the alkyl is replaced with an alkoxy as defined herein. In some embodiments, the term “alkoxyalkyl” refers to a functional group of formula — (alkyl)ORa, wherein the alkyl is defined above and wherein the Rais defined above. In some embodiments, the alkoxyalkyl is a functional group of formula — (CH2)nORa, where n is 1 to 10 and Rais defined above. In some embodiments, the alkoxyalkyl is a functional group of the formula — CH2CH2OCH3.

[0018] As used herein, the term “aralkyl” refers to an alkyl as defined herein, wherein at least one of the hydrogen atoms of the alkyl is replaced with an aryl as defined herein. In some embodiments, the term “aralkyl” refers to a functional group of formula — (alkyl)(aryl), wherein the alkyl is defined herein and the aryl is defined herein. In some embodiments, the aralkyl is — CH2(CeH5).

[0019] As used herein, the term “aminoalkyl” refers to an alkyl as defined herein, wherein at least one of the hydrogen atoms of the alkyl is replaced with an amino as defined herein. In some embodiments, the term “aminoalkyl” refers to a functional group of formula — (alkyl)N(RbRcRd), wherein the alkyl is defined above and wherein Rb, Rc, and Rdare defined above. In some embodiments, the aminoalkyl is — CH2N(CH3)2. In some embodiments, the aminoalkyl is — (CH2)3N(CHs)2. In some embodiments, the aminoalkyl is aminomethyl ( — CH2NH2). In some embodiments, theaminoalkyl is N,N-dimethylaminoethyl ( — CH2CH2N(CH3)2). In some embodiments, the aminoalkyl is 3-(N-cyclopropylamino)propyl ( — CH2CH2CH2NH — Pr).

[0020] As used herein, the term “silylalkyl” refers to an alkyl as defined herein, wherein at least one of the hydrogen atoms of the alkyl is replaced with a silyl as defined herein. In some embodiments, the term “silylalkyl” refers to a functional group of formula — (alkyl)Si(ReRfRg), wherein the alkyl is defined above and wherein Re, Rf, and Rgare defined above. In some embodiments, the silylalky is a functional group of formula — (CH2)mSi(ReRfRg), where m is 1 to 10 and where Re, Rf, and Rgare defined above. In some embodiments, the silylalkyl is a functional group of formula — CH2Si(CH3)3.

[0021] As used herein, the term “haloalkyl” refers to an alkyl as defined here, wherein at least one of the hydrogen atoms of the alkyl is replaced with a halide as defined herein. In some embodiments, the haloalkyl comprises a fluoroalkyl. In some embodiments, the fluoroalkyl comprises at least one of — CH2CF3, — CH(CF3)2, — CH2F, — CH2CH2F, — CF3, — CF2CF3, or any combination thereof.

[0022] As used herein, the term “thiol” refers to a functional group of formula — SRa, wherein Rais a hydrogen, an alkyl (as defined herein), an amino (as described herein), an alkoxy (as described herein), an alkylamino (as described herein), an alkoxyalkyl (as described herein), a carbonyl (as described herein), or any combination thereof. In some embodiments, the term “thiol” refers to a functional group of formula— SH. In some embodiments, the term “thiol” refers to a functional group of formula— SCH3.

[0023] As used herein, the term “alkylthiol” refers to a compound of formula — RaSRb, wherein Rais an alkyl, as described herein, and Rbis a hydrogen, an alkyl (as defined herein), an amino (as described herein), an alkoxy (as described herein), an alkylamino (as described herein), an alkoxyalkyl (as described herein), a carbonyl (as described herein), or any combination thereof. In some embodiments, the term “alkylthiol” refers to a compound of formula — RaSH, wherein Rais an alkyl, as described herein.

[0024] As used herein, the term “thiourea” refers to a compound of formula — RaC(=S)Rb, wherein Raand Rbare independently an amino, as described herein.

[0025] As used herein, the term “thioester” refers to a functional group of formula— SG(=O)Ra, wherein Rais a hydrogen, an alkyl (as defined herein), an amino (as described herein), an alkoxy (as described herein), an alkylamino (as described herein), an alkoxyalkyl (as described herein), or any combination thereof. In some embodiments, the term “thioester” refers to a functional group of formula — SC(=O)H. In some embodiments, the term “thioester” refers to a functional group of formula — SC(=O)CH3.

[0026] As used herein, the term “xanthate” refers to a functional group of formula— SC(=S)ORa, wherein Rais a hydrogen or an alkyl, as defined herein. In some embodiments, the term “xanthate” refers to a functional group of formula — SC(=S)OH. In some embodiments, the term “xanthate” is a functional group of formula — SC(=S)OCH3.

[0027] As used herein, the term “amidine” refers to a functional group of formula — C(=NRa)N(RbRc), wherein Ra, Rb, and Rcare each independently a hydrogen or an alkyl, as defined here. In some embodiments, the term “amidine” refers to a functional group of formula — C(=NH)N(RbRc), where Rband Rcare not hydrogen. In some embodiments, the term “amidine” refers to a functional group of formula — C(=NRa)N(HRc), where Raand Rcare not hydrogen. In some embodiments, the term “amidine” refers to a functional group of formula — C(=NH)N(HRC), where Rcis not hydrogen. In some embodiments, the term “amidine” refers to a functional group of formula — C(=NRa)N(RbRc), wherein Ra, Rb, and Rcare not hydrogen.

[0028] As used herein, the term “guanidine” refers to a functional group of formula— C(=NRa)N(RbRc)N(RdRe), wherein Ra, Rb, Rc, Rd, and Reare each independently a hydrogen or an alkyl, as defined here. In some embodiments, the term “guanidine” refers to a functional group of formula — C(=NH)N(RbRc)N(RdRe), wherein Rb, Rc, Rd, and Reare not hydrogen. In some embodiments, the term “guanidine” refers to a functional group of formula — C(=NRa)N(HRc)N(RdRe), wherein Ra, Rc, Rd, and R® are not hydrogen. In some embodiments, the term “guanidine” refers to a functional group of formula — C(=NRa)N(H2)N(RdRe), wherein Ra, Rd, and Reare not hydrogen. In some embodiments, the term “guanidine” refers to a functional group of formula — C(=NH)N(HRc)N(RdR®), wherein Rc, Rd, and R® are not hydrogen. In some embodiments, the term “guanidine” refers to a functional group of formula — C(=NRa)N(H2)N(HRe), wherein Raand R® are not hydrogen. In some embodiments,the term “guanidine” refers to a functional group of formula — C(=NH)N(H2)N(HRe), wherein Reis not hydrogen.

[0029] As used herein, the term “carbonyl” refers to a functional group of formula — C(=O)Ra, wherein Rais a hydrogen or an alkyl, as defined herein. In some embodiments, the term “carbonyl” refers to a functional group of formula — C(=O)H. In some embodiments, the term “carbonyl” is a functional group of formula — C(=O)CH3.

[0030] As used herein, the term “halide” refers to a — Cl, — Br, — I, or — F.

[0031] As used herein, the term “ethynyl” refers to — C=CH.

[0032] As used herein, the term “phenyl” refers to — CeHs.

[0033] As used herein, the term “allyl” refers to — CH2CH=CH2.

[0034] As used herein, the term “vinyl” refers to — CH=CH2.

[0035] As used herein, the term “acetoxy” refers to — OC(=O)CH3.

[0036] Some embodiments relate to precursors and related methods. At least some of these embodiments relate to precursors useful in the fabrication of microelectronic devices, including semiconductor devices, and the like. For example, the precursors can be used to form films by one or more deposition processes. Examples of deposition processes include, without limitation, at least one of a chemical vapor deposition (CVD) process, a digital or pulsed chemical vapor deposition process, a plasma-enhanced cyclical chemical vapor deposition (PECCVD) process, a flowable chemical vapor deposition (FCVD) process, an atomic layer deposition (ALD) process, a thermal atomic layer deposition, a plasma-enhanced atomic layer deposition (PEALD) process, a metal organic chemical vapor deposition (MOCVD) process, a plasma-enhanced chemical vapor deposition (PECVD) process, or any combination thereof.

[0037] Some embodiments relate to a composition comprising a bismuth- containing compound. In some embodiments, the composition comprises a compound of the formula:In some embodiments, each of L1, L2, or L3independently comprises at least one of a hydrogen, an alkyl, an alkenyl, an alkynyl, an aryl, a cycloalkyl, an alkoxy, an oxysilyl, an alkoxyalkyl, an aralkyl, a thiol, a xanthate, a thioester, an amino, an amidine, a guanidine, a carbonyl, a halogen, or any combination thereof. In some embodiments, at least two of L1, L2, or L3are bonded to form a cyclic ring. In some embodiments, L1, L2, or L3are coordinated to the bismuth atom.

[0038] In some embodiments, at least one of L1, L2, or L3comprises an amine.

[0039] In some embodiments, at least two of L1, L2, or L3comprises an amine.

[0040] In some embodiments, at least two of L1, L2, or L3comprises an alkoxy.

[0041] In some embodiments, at least two of L1, L2, or L3comprises a thiol.

[0042] In some embodiments, each of L1, L2, or L3comprises an amine.

[0043] In some embodiments, each of L1, L2, or L3comprises an alkoxy.

[0044] In some embodiments, each of L1, L2, or L3comprises a thiol.

[0045] In some embodiments, each of L1, L2, or L3comprises an alkyl.

[0046] In some embodiments, each of L1, L2, or L3comprises a xanthate.

[0047] In some embodiments, two of L1, L2, or L3are bonded to form a cyclic ring. In some embodiments, the cyclic ring is an aromatic ring. In some embodiments, the cyclic ring comprises at least one heteroatom. In some embodiments, the heteroatom comprises a nitrogen, an oxygen, a sulfur, or any combination thereof.

[0048] FIG. 1 is a flowchart of a method for making a film 100, according to some embodiments. As shown in FIG. 1 , the method for making a film 100 may comprise one or more of the following steps: obtaining a precursor compound 102, heating the precursor compound to form a precursor vapor 104, and contacting a substrate with the precursor vapor to form a film on the substrate 106.

[0049] At step 102, in some embodiments, the method comprises obtaining a precursor compound. In some embodiments, the precursor compound is a bismuth-containing precursor compound. In some embodiments, the precursor compound is of the formula:In some embodiments, each of L1, L2, or L3independently comprises at least one of a hydrogen, an alkyl, an alkenyl, an alkynyl, an aryl, a cycloalkyl, an alkoxy, an oxysilyl, an alkoxyalkyl, an aralkyl, a thiol, a xanthate, a thioester, an amino, an amidine, a guanidine, a carbonyl, a halogen, or any combination thereof. In some embodiments, at least two of L1, L2, or L3are bonded to form a cyclic ring. In some embodiments, L1, L2, or L3are coordinated to the bismuth atom.

[0050] In some embodiments, the obtaining comprises obtaining a vessel comprising the precursor compound. In some embodiments, the obtaining comprises obtaining a container comprising the precursor compound. In some embodiments, the precursor compound may be obtained in a container or other vessel in which the precursor compound is to be heated.

[0051] At step 104, in some embodiments, the method comprises heating the precursor compound to obtain a precursor vapor. The heating may comprise heating the precursor compound sufficient to obtain the precursor vapor. In some embodiments, the heating comprises heating a container comprising the precursor compound. In some embodiments, the heating comprises heating the precursor compound in a deposition chamber in which the vapor deposition process is performed. In some embodiments, the heating comprises heating a conduit for delivering the precursor compound, the precursor vapor, or any combination thereof to, for example, a deposition chamber. In some embodiments, the heating comprises operating a vapor delivery system comprising the precursor compound. In some embodiments, the heating comprises heating to a temperature sufficient to vaporize the precursor compound to obtain the precursor vapor. In some embodiments, the heating comprises heating to a temperature below a decomposition temperature of at least one of the precursor compound, the precursor vapor, or any combination thereof. In some embodiments, the precursor compound may be present in a gas phase or other vaporizable phase, in which case the step 104 is optional and not required. Forexample, in some embodiments, the precursor compound comprises the precursor vapor.

[0052] At step 106, in some embodiments, the method comprises contacting a substrate with the precursor vapor to form a film on the substrate. In some embodiments, the contacting comprises contacting the substrate under vapor deposition conditions. The contacting may be performed in any system, apparatus, device, assembly, chamber thereof, or component thereof suitable for vapor deposition processes, including, for example and without limitation, a deposition chamber, among others.

[0053] The vapor deposition conditions may comprise conditions for vapor deposition processes. Examples of vapor deposition conditions include, without limitation, vapor deposition conditions for vapor deposition processes including at least one of a chemical vapor deposition (CVD) process, a digital or pulsed chemical vapor deposition process, a plasma-enhanced cyclical chemical vapor deposition (PECCVD) process, a flowable chemical vapor deposition (FCVD) process, an atomic layer deposition (ALD) process, a thermal atomic layer deposition, a plasma-enhanced atomic layer deposition (PEALD) process, a metal organic chemical vapor deposition (MOCVD) process, a plasma-enhanced chemical vapor deposition (PECVD) process, or any combination thereof.

[0054] The vapor deposition conditions may comprise a deposition temperature. The deposition temperature may be a temperature less than the thermal decomposition temperature of the precursor vapor. The deposition temperature may be sufficiently high to reduce or avoid condensation of the precursor vapor. In some embodiments, the substrate may be heated to the deposition temperature. In some embodiments, the chamber or other vessel in which the substrate is contacted with the precursor vapor. In some embodiments, the precursor vapor may be heated to the deposition temperature.

[0055] The deposition temperature may be a temperature of 200 °C to 2500 °C, or any range or subrange between 200 °C and 2500 °C. In some embodiments, the deposition temperature may be a temperature of 500 °C to 700 °C. For example, in some embodiments, the deposition temperature may be a temperature of 500 °C to 680 °C, 500 °C to 660 °C, 500 °C to 640 °C, 500 °C to 620 °C, 500 °C to 600 °C,500 °C to 580 °C, 500 °C to 560 °C, 500 °C to 540 °C, 500 °C to 520 °C, 520 °C to 700 °C, 540 °C to 700 °C, 560 °C to 700 °C, 580 °C to 700 °C, 600 °C to 700 °C, 620 °C to 700 °C, 640 °C to 700 °C, 660 °C to 700 °C, or 680 °C to 700 °C. In other embodiments, the deposition temperature may be a temperature of greater than 200 °C to 2500 °C, such as, for example and without limitation, a temperature of 400 °C to 2000 °C, 500 °C to 2000 °C, 550 °C to 2400 °C, 600 °C to 2400 °C, 625 °C to 2400 °C, 650 °C to 2400 °C, 675 °C to 2400 °C, 700 °C to 2400 °C, 725 °C to 2400 °C, 750 °C to 2400 °C, 775 °C to 2400 °C, 800 °C to 2400 °C, 825 °C to 2400 °C, 850 °C to 2400 °C, 875 °C to 2400 °C, 900 °C to 2400 °C, 925 °C to 2400 °C, 950 °C to 2400 °C, 975 °C to 2400 °C, 1000 °C to 2400 °C, 1025 °C to 2400 °C, 1050 °C to2400 °C, 1075 °C to 2400 °C, 1 100 °C to 2400 °C, 1200 °C to 2400 °C, 1300 °C to2400 °C, 1400 °C to 2400 °C, 1500 °C to 2400 °C, 1600 °C to 2400 °C, 1700 °C to2400 °C, 1800 °C to 2400 °C, 1900 °C to 2400 °C, 2000 °C to 2400 °C, 2100 °C to2400 °C, 2200 °C to 2400 °C, 2300 °C to 2400 °C, 500 °C to 2000 °C, 500 °C to 1900 °C, 500 °C to 1800 °C, 500 °C to 1700 °C, 500 °C to 1600 °C, 500 °C to 1500 °C, 500 °C to 1400 °C, 500 °C to 1300 °C, 500 °C to 1200 °C, 500 °C to 1100 °C, 500 °C to 1000 °C, 500 °C to 1000 °C, 500 °C to 900 °C, or 500 °C to 800 °C.

[0056] The vapor deposition conditions may comprise a deposition pressure. In some embodiments, the deposition pressure may comprise a vapor pressure of the precursor vapor. In some embodiments, the deposition pressure may comprise a chamber pressure.

[0057] The deposition pressure may be a pressure of 0.001 Torr to 100 Torr, or any range or subrange between 0.001 Torr and 100 Torr. For example, in some embodiments, the deposition pressure may be a pressure of 1 Torr to 30 Torr, 1 Torr to 25 Torr, 1 Torr to 20 Torr, 1 Torr to 15 Torr, 1 Torr to 10 Torr, 5 Torr to 50 Torr, 5 Torr to 40 Torr, 5 Torr to 30 Torr, 5 Torr to 20 Torr, or 5 Torr to 15 Torr. In other embodiments, the deposition pressure may be a pressure of 1 Torr to 100 Torr, 5 Torr to 100 Torr, 10 Torr to 100 Torr, 15 Torr to 100 Torr, 20 Torr to 100 Torr, 25 Torr to 100 Torr, 30 Torr to 100 Torr, 35 Torr to 100 Torr, 40 Torr to 100 Torr, 45 Torr to 100 T orr, 50 T orr to 100 T orr, 55 T orr to 100 T orr, 60 Torr to 100 T orr, 65 T orr to 100 T orr, 70 Torr to 100 Torr, 75 Torr to 100 Torr, 80 T orr to 100 T orr, 85 T orr to 100 Torr, 90 Torr to 100 Torr, 95 Torr to 100 Torr, 1 Torr to 95 Torr, 1 Torr to 90 Torr, 1 Torr to 85 Torr, 1 Torr to 80 Torr, 1 Torr to 75 Torr, or 1 Torr to 70 Torr. In other furtherembodiments, the deposition pressure may be a pressure of 1 mTorr to 100 mTorr, 1 mTorr to 90 mTorr, 1 mTorr to 80 mTorr, 1 mTorr to 70 mTorr, 1 mTorr to 60 mTorr, 1 mTorr to 50 mTorr, 1 mTorr to 40 mTorr, 1 mTorr to 30 mTorr, 1 mTorr to 20 mTorr, 1 mTorr to 10 mTorr, 100 mTorr to 300 mTorr, 150 mTorr to 300 mTorr, 200 mTorr to 300 mTorr, or 150 mTorr to 250 mTorr, or 150 mTorr to 225 mTorr.

[0058] The substrate may comprise at least one of Bi, Bi2O3, BiaSs, Si, Co, Cu, Al, W, WN, WC, TiN, Mo, MoC, SiO2, W, SiN, WCN, AI2O3, AIN, ZrO2, La2O3, TaN, RuO2, I rO2, Nb2Os, Y2O3, hafnium oxide, or any combination thereof.

[0059] In some embodiments, the silicon-containing film comprises at least one of at least one of silicon, silicon nitride, silicon oxynitride, silicon oxide, silicon dioxide, silicon carbide, silicon carbonitride, silicon oxycarbonitride, carbon-doped silicon nitride, carbon-doped silicon oxide, carbon-doped silicon oxynitride, or any combination thereof. In some embodiments, the substrate may comprise other silicon- based substrates, such as, for example, one or more of polysilicon substrates, metallic substrates, and dielectric substrates.

[0060] Some embodiments relate to a film on a substrate. In some embodiments, the film comprises any film formed according to the methods disclosed herein. In some embodiments, the film comprises any film prepared from any one or more of the precursors disclosed herein.

[0061] Any one or more of the embodiments disclosed herein shall be understood to be combinable without departing from the scope or spirit of the disclosure.

[0062] EXAMPLE 1

[0063] BiCis is dissolved in THF and cooled to -20 °C. Isopropyl MgCI (~3 eq) is added slowly to produce triisopropylbismuthane. After addition is complete the mixture is allowed to warm to room temperature and stirred overnight (about 12 to 20 hours). The volatiles are then removed under reduced pressure. The residues are then extracted with hexanes and filtered. The hexane washings are then combined and thevolatiles removed under reduced pressure. Further purification of the material through crystallization, sublimation, distillation or other methods may be taken.

[0064] A solution of triisopropylbismuthane dissolved in THF is cooled to -20 °C. A solution of Bismuth(lll) chloride in THF is added slowly. Upon completion of the addition the mixture continues to be stirred and allowed to warm to room temperature overnight. The mixture is then filtered and volatiles removed under reduced pressure to obtain the desired product, dichloro(isopropyl)bismuthane. Further purification through crystallization, sublimation, distillation, or other methods may be taken.

[0065] LiNMea is produced in-situ by bubbling HNMe? through a solution of nBuLi in hexanes at 0 °C. The suspension then is cooled to -20 °C and a solution of dichloro(isopropyl)bismuthane in THF is added slowly. The mixture is then allowed to stir and warm to room temperature overnight (about 12 to 20 hours). The mixture is then filtrated and volatiles removed under reduced pressure to obtain the desired product, isopropylbis(dimethylamine)bismuthane. The resulting crude material may be further purified through crystallization, sublimation, distillation, or other methods.

[0066] EXAMPLE 2

[0067] Sodium tert-butoxide is suspended in THF then is cooled to 0 °C followed by slow addition of a solution of dichloro(isopropyl)bismuthane in THF. The mixture is then allowed to stir and warm to room temperature overnight (about 12 to 20 hours).The mixture is then filtrated and volatiles removed under reduced pressure to obtain the desired product, isopropylbis(di-tert-butoxy)bismuthane. The resulting crude material may be further purified through crystallization, sublimation, distillation, or other methods.

[0068] EXAMPLE 3

[0069] A solution of potassium ethylxanthate in THF is cooled to 0 °C. A solution of dichloro(isopropyl)bismuthane in THF is added slowly. The mixture is then allowed to stir and warm to room temperature overnight (about 12 to 20 hours). The mixture is then filtrated and volatiles removed under reduced pressure to obtain the desired product, isopropylbismuth(lll) ethyl xanthate. The resulting crude material may be further purified through crystallization, sublimation, distillation, or other methods.

[0070] ASPECTS

[0071] Various Aspects are described below. It is to be understood that any one or more of the features recited in the following Aspect(s) can be combined with any one or more other Aspect(s).Aspect 1 . A composition comprising: a compound of the formula:wherein each of L1, L2, or L3independently comprises: at least one of a hydrogen, an alkyl, an alkenyl, an alkynyl, an aryl, a cycloalkyl, an alkoxy, an oxysilyl, an alkoxyalkyl, an aralkyl, a thiol, a xanthate, a thioester, an amino, an amidine, a guanidine, a carbonyl, a halogen, or any combination thereof, orat least two of L1, L2, or L3are bonded to form a cyclic ring.Aspect 2. The composition according to Aspect 1 , wherein at least one of L1, L2, or L3comprises an amine.Aspect 3. The composition according to any one of Aspects 1-2, wherein at least two of L1, L2, or L3comprises an amine.Aspect 4. The composition according to any one of Aspects 1-3, wherein at least two of L1, L2, or L3comprises an alkoxy.Aspect 5. The composition according to any one of Aspects 1-4, wherein at least two of L1, L2, or L3comprises a thiol.Aspect 6. The composition according to any one of Aspects 1-5, wherein each of L1, L2, and L3comprises an amine.Aspect 7. The composition according to any one of Aspects 1-6, wherein each of L1, L2, and L3comprises an alkoxy.Aspect 8. The composition according to any one of Aspects 1-7, wherein each of L1, L2, and L3comprises a thiol.Aspect 9 The composition according to any one of Aspects 1-8, wherein each of L1, L2, and L3comprises an alkyl.Aspect 10. The composition according to any one of Aspects 1 -9, wherein each of L1, L2, and L3comprises a xanthate.Aspect 11 . The composition according to any one of Aspects 1 -10, wherein two of L1, L2, or L3are bonded to form a cyclic ring.Aspect 12. The composition according to any one of Aspects 1 -11 , wherein the cyclic ring is an aromatic ring.Aspect 13. The composition according to any one of Aspects 1 -12, wherein the cyclic ring comprises at least one heteroatom.Aspect 14. The composition according to Aspect 13, wherein the heteroatom comprises a nitrogen, an oxygen, a sulfur, or any combination thereof.Aspect 15. A method comprising: obtaining a precursor compound of the formula:wherein each of L1, L2, or L3independently comprises: at least one of a hydrogen, an alkyl, an alkenyl, an alkynyl, an aryl, a cycloalkyl, an alkoxy, an oxysilyl, an alkoxyalkyl, an aralkyl, a thiol, a xanthate, a thioester, an amino, an amidine, a guanidine, a carbonyl, a halogen, or any combination thereof, or at least two of L1, L2, or L3are bonded to form a cyclic ring; heating the precursor compound to form a precursor vapor; and contacting a substrate with the precursor compound to form a film on the substrate.Aspect 16. The method according to Aspect 15, wherein at least one of L1, L2, or L3comprises an amine.Aspect 17. The method according to any one of Aspects 15-16, wherein at least two of L1, L2, or L3comprises an amine.Aspect 18. The method according to any one of Aspects 15-17, wherein at least two of L1, L2, or L3comprises an alkoxy.Aspect 19. The method according to any one of Aspects 15-18, wherein at least two of L1, L2, or L3comprises a thiol.Aspect 20. The method according to any one of Aspects 15-19, wherein each of L1, L2, and L3comprises a xanthate.

Claims

CLAIMSWHAT IS CLAIMED IS:1 . A composition comprising: a compound of the formula:wherein each of L1, L2, or L3independently comprises: at least one of a hydrogen, an alkyl, an alkenyl, an alkynyl, an aryl, a cycloalkyl, an alkoxy, an oxysilyl, an alkoxyalkyl, an aralkyl, a thiol, a xanthate, a thioester, an amino, an amidine, a guanidine, a carbonyl, a halogen, or any combination thereof, or at least two of L1, L2, or L3are bonded to form a cyclic ring.

2. The composition of claim 1 , wherein at least one of L1, L2, or L3comprises an amine.

3. The composition of claim 1 , wherein at least two of L1, L2, or L3comprises an amine.

4. The composition of claim 1 , wherein at least two of L1, L2, or L3comprises an alkoxy.

5. The composition of claim 1 , wherein at least two of L1, L2, or L3comprises a thiol.

6. The composition of claim 1 , wherein each of L1, L2, and L3comprises an amine.

7. The composition of claim 1 , wherein each of L1, L2, and L3comprises an alkoxy.

8. The composition of claim 1 , wherein each of L1, L2, and L3comprises a thiol.

9. The composition of claim 1 , wherein each of L1, L2, and L3comprises an alkyl.

10. The composition of claim 1 , wherein each of L1, L2, and L3comprises a xanthate.11 . The composition of claim 1 , wherein two of L1, L2, or L3are bonded to form a cyclic ring.

12. The composition of claim 1 1 , wherein the cyclic ring is an aromatic ring.

13. The composition of claim 1 1 , wherein the cyclic ring comprises at least one heteroatom.

14. The composition of claim 13, wherein the heteroatom comprises a nitrogen, an oxygen, a sulfur, or any combination thereof.

15. A method comprising: obtaining a precursor compound of the formula:wherein each of L1, L2, or L3independently comprises: at least one of a hydrogen, an alkyl, an alkenyl, an alkynyl, an aryl, a cycloalkyl, an alkoxy, an oxysilyl, an alkoxyalkyl, an aralkyl, a thiol, a xanthate, a thioester, an amino, an amidine, a guanidine, a carbonyl, a halogen, or any combination thereof, or at least two of L1, L2, or L3are bonded to form a cyclic ring; heating the precursor compound to form a precursor vapor; and contacting a substrate with the precursor compound to form a film on the substrate.

16. The method of claim 15, wherein at least one of L1, L2, or L3comprises an amine.

17. The method of claim 15, wherein at least two of L1, L2, or L3comprises an amine.

18. The method of claim 15, wherein at least two of L1, L2, or L3comprises an alkoxy.

19. The method of claim 15, wherein at least two of L1, L2, or L3comprises a thiol.

20. The method of claim 15, wherein each of L1, L2, and L3comprises a xanthate.

Images