Precursors for selective deposition of silicon-containing films

Abstract

The present invention provides precursors for selective deposition of silicon-containing films. The precursor comprises a compound of the formula: R (HO) Si (OR1) (OR2) wherein: R is or comprises an alkyl, alkenyl or alkoxy group; and R1 and R2 are independently hydrogen, alkoxy, or R1 and R2 are bonded to form a heterocyclic ring. Also provided are devices comprising a silicon-containing film, wherein the silicon-containing film comprises a reaction product of the precursor with another reactive species. In addition, the invention also provides a method for depositing a silicon-containing film.

Description

Technical Field

[0001] This disclosure relates to precursors for selectively depositing silicon-containing films, and provides related apparatus, systems and methods.

[0002] Cross-reference to related applications

[0003] This application claims the benefit of U.S. Provisional Patent Application No. 63 / 535,262, filed August 29, 2023, pursuant to 35 USC 119, the disclosure of which is hereby incorporated herein by reference in its entirety. Background Technology

[0004] Forming a film on a substrate suitable for microelectronics fabrication requires depositing the film on certain surfaces. Therefore, the film is deposited on all surfaces and subsequently removed from some. This can involve complex, multi-step methods. Summary of the Invention

[0005] Some embodiments of this disclosure relate to a precursor. In some embodiments, the precursor comprises a compound of the following formula:

[0006] ,

[0007] Wherein: R is alkyl, alkenyl, or alkoxy; and R 1 and R 2 Independently hydrogen, alkyl, or R 1 and R 2 They are bonded to form heterocyclic rings. In some embodiments, the compound is deposited on a material with a dielectric constant of no more than 3.9 when vaporized to form a precursor vapor.

[0008] Some embodiments relate to an apparatus. In some embodiments, the apparatus includes a substrate having a first surface portion and a second surface portion. In some embodiments, the apparatus includes a silicon-containing film located on the first surface portion of the substrate. In some embodiments, the silicon-containing film includes a reaction product of at least one precursor and reactive groups on the first surface portion of the substrate. In some embodiments, the precursor includes a compound of the following formula:

[0009] ,

[0010] Wherein: R is alkyl, alkenyl, or alkoxy; and R 1 and R 2 Independently hydrogen, alkyl, or R 1 and R 2 They are bonded to form heterocyclic rings. In some embodiments, the second surface portion of the substrate does not contain a silicon-containing film.

[0011] Some embodiments relate to a method for depositing a silicon-containing film. In some embodiments, the method includes obtaining a precursor. In some embodiments, the precursor is a compound of the following formula:

[0012] ,

[0013] Wherein: R is alkyl, alkenyl, or alkoxy; and R 1 and R 2 Independently hydrogen, alkyl, or R 1 and R 2 The precursor is bonded to form a heterocyclic ring. In some embodiments, the method includes vaporizing the precursor to obtain a vaporized precursor. In some embodiments, the method includes exposing a substrate to the vaporized precursor in the presence of a catalyst to selectively deposit a silicon-containing film on the substrate. Attached Figure Description

[0014] Some embodiments of this disclosure are described herein with reference to the accompanying drawings, using only examples. Specific references to the drawings will now be detailed, and it should be emphasized that the embodiments are shown by way of example and for the purpose of illustrative discussion of embodiments of this disclosure. In this respect, the description taken in conjunction with the drawings will make it apparent to those skilled in the art how embodiments of this disclosure can be practiced.

[0015] Figure 1 This is a schematic cross-sectional view of a silicon-containing film deposited on a substrate according to some embodiments.

[0016] Figure 2 This is a flowchart of a method for depositing a silicon-containing film according to some embodiments. Detailed Implementation

[0017] Among the benefits and improvements already disclosed, other objects and advantages of this disclosure will become apparent from the following description taken in conjunction with the accompanying drawings. Detailed embodiments of this disclosure are disclosed herein; however, it should be understood that the disclosed embodiments are merely illustrative of the disclosure as it may be embodied in various forms. Furthermore, the various examples given with respect to the embodiments of this disclosure are intended to be illustrative and not restrictive.

[0018] Any prior patents and publications referenced in this document are incorporated herein by reference in their entirety.

[0019] Throughout this specification and claims, unless the context clearly indicates otherwise, the following terms shall have the meanings explicitly associated herein. The phrases “in one embodiment,” “in another embodiment,” and “in some embodiments” as used herein do not necessarily refer to the same embodiment, but may refer to the same embodiment. Furthermore, the phrases “in another embodiment” and “in some other embodiments” as used herein do not necessarily refer to different embodiments, but may refer to different embodiments. All embodiments of this disclosure are intended to be combined without departing from the scope or spirit of this disclosure.

[0020] As used herein, unless the context clearly indicates otherwise, the term "based on" is not exclusive and may be based on other factors not described. Furthermore, throughout this specification, the meanings of "a," "an," and "the" include multiple references. The meaning of "in" includes both "in" and "on."

[0021] As used herein, the term "alkyl" refers to a hydrocarbon compound having 1 to 30 carbon atoms. An alkyl compound having n carbon atoms can be represented as "C". n Alkyl group. For example, "C3 alkyl" can include n-propyl and isopropyl. Alkyl groups having a range of carbon atoms (e.g., 1 to 30 carbon atoms) can be represented as C1-C6. 30 Alkyl group. In some embodiments, the alkyl group is linear. In some embodiments, the alkyl group is branched. In some embodiments, the alkyl group is substituted. In some embodiments, the alkyl group is unsubstituted. In some embodiments, the alkyl group comprises at least one of the following or is selected from the group consisting of at least one of the following: C1-C 10 Alkyl, C1-C9 alkyl, C1-C8 alkyl, C1-C7 alkyl, C1-C6 alkyl, C1-C5 alkyl, C1-C4 alkyl, C1-C3 alkyl, C2-C 10 Alkyl, C3-C 10 Alkyl, C4-C 10 Alkyl, C5-C 10 Alkyl, C6-C 10 Alkyl, C7-C 10 Alkyl, C8-C 10Alkyl, C2-C9 alkyl, C2-C8 alkyl, C2-C7 alkyl, C2-C6 alkyl, C2-C5 alkyl, C3-C5 alkyl, or any combination thereof. In some embodiments, the alkyl group comprises at least one of the following or is selected from the group consisting of at least one of the following: methyl, ethyl, n-propyl, 1-methylethyl (isopropyl), n-butyl, isobutyl, sec-butyl, n-pentyl, 1,1-dimethylethyl (tert-butyl), n-pentyl, isopentyl, tert-pentyl, n-hexyl, isohexyl, 3-methylhexyl, 2-methylhexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, or any combination thereof.

[0022] As used herein, the term "alkenyl" refers to a hydrocarbon chain group having 1 to 10 carbon atoms and at least one carbon-carbon double bond. Examples of alkenyl groups include, but are not limited to, at least one of the following: 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-Octenyl, 1-Nonenyl, 2-Nonenyl, 3-Nonenyl, 1-Decanenyl, 3-Decanenyl, 1-Undecenyl, Oleyl, Linoleyl, Linolenyl, or any combination thereof.

[0023] As used herein, the term "alkoxy" refers to a group of the formula -OR, where R is an alkyl group as defined herein. In some embodiments, an alkoxy group may comprise at least one of, consist of at least one of, or substantially consist of at least one of, or optionally consist of at least one of the group consisting of: methoxy, ethoxy, methoxy, ethoxy, n-propoxy, 1-methylethoxy (isopropoxy), n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, tert-pentoxy, or any combination thereof.

[0024] As used in this article, the term "allyl" refers to -CH2CH=CH2.

[0025] As used in this article, the term "vinyl" refers to -CH=CH2.

[0026] As used herein, the term "silicon-containing film" refers to a film comprising at least one of the following: silicon, silicon nitride, silicon oxynitride, silicon oxide, silicon dioxide, silicon carbide, silicon carbonitride, silicon carbonitride, carbon-doped silicon nitride, carbon-doped silicon oxide, carbon-doped silicon oxynitride, or any combination thereof. For example, a silicon-containing film may comprise at least one of the following: SiO film, SiO2 film, SiN film, SiOC film, SiOCH film, SiCN film, SiOCN film, or any combination thereof. In some embodiments, the silicon-containing film has a thickness of 20 Å to 2000 Å.

[0027] Some embodiments relate to precursors and related methods. At least some of these embodiments relate to precursors that can be used to manufacture microelectronic devices, including semiconductor devices, etc. For example, the precursor can be used to form a silicon-containing film through one or more deposition processes. Examples of deposition processes include, but are not limited to, at least one of the following: chemical vapor deposition (CVD) processes, digital or pulsed chemical vapor deposition processes, plasma-enhanced cyclic chemical vapor deposition (PECCVD) processes, flowable chemical vapor deposition (FCVD) processes, atomic layer deposition (ALD) processes, fast atomic layer deposition (ALD) processes, thermal atomic layer deposition, plasma-enhanced atomic layer deposition (PEALD) processes, metal-organic chemical vapor deposition (MOCVD) processes, plasma-enhanced chemical vapor deposition (PECVD) processes, or any combination thereof.

[0028] The precursors disclosed herein are applicable to the selective deposition of films on a substrate. In some embodiments, the term "selective deposition" or "selectively depositing" encompasses a process in which more material is deposited on a first material than on a second material, wherein the first material is different from the second material. In some embodiments, the precursor can be used to deposit a film on a first material with greater selectivity than the second material, wherein the second material is different from the first material. In some embodiments, the first material is a dielectric material. In some embodiments, the first material is an insulating material. In some embodiments, selectively depositing a film on the first material is a process in which the film is not deposited or substantially not deposited on the second material. In some embodiments, the precursor is selectively deposited within a certain thickness range on a first surface portion of the substrate (e.g., a low-dielectric-constant material, etc.) and not on a second surface portion of the substrate (e.g., containing a metal, etc.). In some embodiments, the deposited film is a film having a low dielectric constant.

[0029] The precursor may also provide improved control over at least one of film thickness, film uniformity, deposition rate, or any combination thereof. In some embodiments, the precursor exhibits a reduced hydrolysis rate compared to conventional precursors (e.g., but not limited to, tri-(tert-pentoxy)silanol). In some embodiments, the precursor exhibits a reduced crosslinking rate. In some embodiments, the diffusion rate is a rate-determining step of film growth, inversely to the crosslinking rate. In some embodiments, when the diffusion rate is a rate-determining step of film growth, the film thickness is controlled by and / or proportional to the concentration of the precursor.

[0030] Some embodiments relate to a precursor. The precursor may comprise a compound of the following formula:

[0031]

[0032] in:

[0033] R is or includes at least one of the following: alkyl, alkenyl, alkoxy, or any combination thereof;

[0034] R 1 and R 2 Independently hydrogen, alkyl, or R 1 and R 2 They are bonded together to form heterocyclic rings.

[0035] In some embodiments, R is different from OR. 1 OR 2 Or at least one of any combination thereof. In some embodiments, R, OR 1 OR 2 At least one of its combinations is not tert-pentoxy.

[0036] In some embodiments, the precursor comprises a compound of at least one of the following formulas:

[0037] ,

[0038] ,

[0039] ,

[0040] or any combination thereof, wherein:

[0041] R is or includes at least one of the following: alkyl, alkenyl, alkoxy, or any combination thereof;

[0042] R 1 and R 2 Independently hydrogen, alkyl, or R 1 and R 2 They are bonded together to form heterocyclic rings.

[0043] In some embodiments, the precursor comprises a compound of at least one of the following formulas:

[0044] ,

[0045] ,

[0046] ,

[0047] ,

[0048] ,

[0049] ,

[0050] ,

[0051] ,

[0052] Or any combination thereof.

[0053] In some embodiments, R is or comprises an alkyl group. In some embodiments, R is or comprises an alkenyl group. In some embodiments, R is or comprises an alkoxy group. In some embodiments, R 1 It may contain hydrogen. In some embodiments, R 1 It may be or contain alkyl groups. In some embodiments, R 2 It may contain hydrogen. In some embodiments, R 2 It may be or contain alkyl groups. In some embodiments, R 1 and R 2 They are bonded to form heterocycles. In some embodiments, the heterocycle is a 5-membered heterocycle. In some embodiments, the heterocycle is a 6-membered heterocycle. In some embodiments, the heterocycle is a 7-membered heterocycle. In some embodiments, the heterocycle is an 8-membered heterocycle. In some embodiments, the heterocycle is a 9-membered heterocycle. In some embodiments, the heterocycle is a 10-membered heterocycle. In some embodiments, R 1 With R 2 Same. In some embodiments, R 1 With R 2 different.

[0054] In some embodiments, the compound is deposited on a material with a dielectric constant not greater than 3.9, 3.8, 3.7, 3.6, 3.5, 3.4, 3.3, 3.2, 3.1, 3, 2.9, 2.8, 2.7, 2.6, 2.5, 2.4, 2.3, 2.2, 2.1, 2, 1.9, 1.8, 1.7, 1.6, 1.5, 1.4, 1.3, 1.2, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1 when vaporized to form a precursor. In some embodiments, the film is selectively deposited on a low dielectric constant or low-k material. In some embodiments, the compound is deposited on a material with a dielectric constant of 0.1 to 3.9, or any range or subrange between 0.1 and 3.9, when vaporized to form a precursor. In some embodiments, the compound is not deposited on a surface containing a material with a dielectric constant greater than 3.9 when vaporized to form a precursor vapor.

[0055] In some embodiments, the compound is deposited on a material having a dielectric constant of 0.1 to 3.9, or any range or subrange between 0.1 and 3.9, when vaporized to form a precursor. In some embodiments, the compound is deposited on a material having a dielectric constant of 0.1 to 3.8, 0.1 to 3.7, 0.1 to 3.6, 0.1 to 3.5, 0.1 to 3.4, 0.1 to 3.3, 0.1 to 3.2, 0.1 to 3.1, 0.1 to 3, 0.1 to 2.9, 0.1 to 2.8, 0.1 to 2.7, 0.1 to 2.6, 0.1 to 2.5, 0.1 to 2.4, 0.1 to 2.3, or 0.1 to 2. 2. On materials with a strength of 0.1 to 2.1, 0.1 to 2, 0.1 to 1.9, 0.1 to 1.8, 0.1 to 1.7, 0.1 to 1.6, 0.1 to 1.5, 0.1 to 1.4, 0.1 to 1.3, 0.1 to 1.2, 0.1 to 1.1, 0.1 to 1, 0.1 to 0.9, 0.1 to 0.8, 0.1 to 0.7, 0.1 to 0.6, 0.1 to 0.5, 0.1 to 0.4, 0.1 to 0.3, or 0.1 to 0.2. In some embodiments, the compound is deposited on surfaces with dielectric constants of 0.2 to 3.9, 0.3 to 3.9, 0.4 to 3.9, 0.5 to 3.9, 0.6 to 3.9, 0.7 to 3.9, 0.8 to 3.9, 0.9 to 3.9, 1 to 3.9, 1.1 to 3.9, 1.2 to 3.9, 1.3 to 3.9, 1.4 to 3.9, 1.5 to 3.9, 1.6 to 3.9, 1.7 to 3.9, and 1.8 to 3.9 when vaporized to form a precursor. 9. On materials ranging from 1.9 to 3.9, 2 to 3.9, 2.1 to 3.9, 2.2 to 3.9, 2.3 to 3.9, 2.4 to 3.9, 2.5 to 3.9, 2.6 to 3.9, 2.7 to 3.9, 2.8 to 3.9, 2.9 to 3.9, 3 to 3.9, 3.1 to 3.9, 3.2 to 3.9, 3.3 to 3.9, 3.4 to 3.9, 3.5 to 3.9, 3.6 to 3.9, 3.7 to 3.9, or 3.8 to 3.9.

[0056] In some embodiments, the purity of the precursor is at least 90%, at least 95%, at least 99%, at least 99.9%, at least 99.99%, at least 99.999%, at least 99.999% to 100%, or any range or subrange between 90% and 100%.

[0057] Some embodiments relate to an apparatus. In some embodiments, the apparatus, for example, is a fully self-aligned via and other apparatus that may have a recessed feature. The apparatus may include a substrate. The substrate may have a first surface portion and a second surface portion, wherein the first surface portion is different from the second surface portion. In some embodiments, the first surface portion and the second surface portion are made of different materials. In some embodiments, the first surface portion and the second surface portion are adjacent. In some embodiments, the first surface portion is adjacent to the second surface portion. In some embodiments, an intermediate surface portion is located between the first surface portion and the second surface portion. In some embodiments, the first surface portion and the second surface portion are made of materials with different dielectric constants. In some embodiments, the first surface portion is made of a material with a dielectric constant not greater than 3.9. In some embodiments, the first surface portion is made of a material with a dielectric constant from 0.1 to 3.9.

[0058] The substrate may comprise at least one of the following: dielectric material, insulating material, conductive material, or any combination thereof. In some embodiments, a first surface portion of the substrate is composed of or comprises at least one of the following: dielectric material, insulating material, or any combination thereof. In some embodiments, a second surface portion of the substrate comprises a conductive material (e.g., electrically conducting material). In some embodiments, a second surface portion of the substrate is composed of or comprises a metallic material (e.g., one or more metals). In some embodiments, the substrate may comprise at least one of the following: Si, Co, Cu, Al, W, WN, WC, TiN, Mo, MoC, SiO2, SiOC, Ge, SiN, WCN, Al2O3, AlN, ZrO2, La2O3, TaN, RuO2, IrO2, Nb2O3, Y2O3, hafnium oxide, or any combination thereof. In some embodiments, the substrate may comprise one or more other silicon-based substrates, such as polycrystalline silicon substrates, metal substrates, and dielectric substrates.

[0059] The device may include a silicon-containing film located on a first surface portion of a substrate. In some embodiments, the silicon-containing film is a reaction product of at least one precursor and reactive groups on the first surface portion of the substrate. In some embodiments, the precursor comprises a compound of the following formula:

[0060]

[0061] in:

[0062] R is or includes at least one of the following: alkyl, alkenyl, alkoxy, or any combination thereof;

[0063] R 1and R 2 Independently hydrogen, alkyl, or R 1 and R 2 They are bonded to form heterocyclic rings. In some embodiments, the reactive groups on the first surface portion of the substrate are inherent to the substrate. In some embodiments, the reactive groups are functional groups added to the substrate and / or the first surface portion of the substrate. In some embodiments, the reactive groups comprise reactive precursors, wherein the reactive precursors are attached to the surface of the substrate.

[0064] In some embodiments, the precursor comprises a compound of at least one of the following formulas:

[0065] ,

[0066] ,

[0067] ,

[0068] or any combination thereof, wherein:

[0069] R 1 and R 2 Independently hydrogen, alkyl, or R 1 and R 2 They are bonded together to form heterocyclic rings.

[0070] In some embodiments, the precursor comprises a compound of at least one of the following formulas:

[0071] ,

[0072] ,

[0073] ,

[0074] ,

[0075] ,

[0076] ,

[0077] ,

[0078] ,

[0079] Or any combination thereof.

[0080] In some embodiments, R is or comprises an alkyl group. In some embodiments, R is or comprises an alkenyl group. In some embodiments, R is or comprises an alkoxy group. In some embodiments, R 1 It may contain hydrogen. In some embodiments, R1 It may be or contain alkyl groups. In some embodiments, R 2 It may contain hydrogen. In some embodiments, R 2 It may be or contain alkyl groups. In some embodiments, R 1 and R 2 They are bonded to form heterocycles. In some embodiments, the heterocycle is a 5-membered heterocycle. In some embodiments, the heterocycle is a 6-membered heterocycle. In some embodiments, the heterocycle is a 7-membered heterocycle. In some embodiments, the heterocycle is an 8-membered heterocycle. In some embodiments, the heterocycle is a 9-membered heterocycle. In some embodiments, the heterocycle is a 10-membered heterocycle. In some embodiments, R 1 With R 2 Same. In some embodiments, R 1 With R 2 different.

[0081] A silicon-containing film is located on a first surface portion of the substrate. In some embodiments, the first surface portion of the substrate comprises at least one of a dielectric material, an insulating material, or any combination thereof. In some embodiments, the first surface portion of the substrate comprises at least one of SiO2, SiN, or any combination thereof. In some embodiments, the first surface portion of the substrate is composed of or contains a material with a dielectric constant not greater than 3.9, 3.8, 3.7, 3.6, 3.5, 3.4, 3.3, 3.2, 3.1, 3, 2.9, 2.8, 2.7, 2.6, 2.5, 2.4, 2.3, 2.2, 2.1, 2, 1.9, 1.8, 1.7, 1.6, 1.5, 1.4, 1.3, 1.2, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1.

[0082] In some embodiments, a first surface portion of the substrate is constituted or contains a material with a dielectric constant of 0.1 to 3.9, or any range or subrange between 0.1 and 3.9. In some embodiments, the first surface portion of the substrate is composed of or contains a material with a dielectric constant of 0.1 to 3.8, 0.1 to 3.7, 0.1 to 3.6, 0.1 to 3.5, 0.1 to 3.4, 0.1 to 3.3, 0.1 to 3.2, 0.1 to 3.1, 0.1 to 3, 0.1 to 2.9, 0.1 to 2.8, 0.1 to 2.7, 0.1 to 2.6, 0.1 to 2.5, 0.1 to 2.4, 0.1 to 2.3, 0.1 to 2.2, or 0.1 to 2... The material comprises or contains the material in the following quantities: 0.1 to 2, 0.1 to 1.9, 0.1 to 1.8, 0.1 to 1.7, 0.1 to 1.6, 0.1 to 1.5, 0.1 to 1.4, 0.1 to 1.3, 0.1 to 1.2, 0.1 to 1.1, 0.1 to 1, 0.1 to 0.9, 0.1 to 0.8, 0.1 to 0.7, 0.1 to 0.6, 0.1 to 0.5, 0.1 to 0.4, 0.1 to 0.3, or 0.1 to 0.2. In some embodiments, the first surface portion of the substrate is composed of dielectric constants of 0.2 to 3.9, 0.3 to 3.9, 0.4 to 3.9, 0.5 to 3.9, 0.6 to 3.9, 0.7 to 3.9, 0.8 to 3.9, 0.9 to 3.9, 1 to 3.9, 1.1 to 3.9, 1.2 to 3.9, 1.3 to 3.9, 1.4 to 3.9, 1.5 to 3.9, 1.6 to 3.9, 1.7 to 3.9, 1.8 to 3.9, 1.9 to 3.9. The material constitutes or contains the material in the following ranges: 0.9, 2 to 3.9, 2.1 to 3.9, 2.2 to 3.9, 2.3 to 3.9, 2.4 to 3.9, 2.5 to 3.9, 2.6 to 3.9, 2.7 to 3.9, 2.8 to 3.9, 2.9 to 3.9, 3 to 3.9, 3.1 to 3.9, 3.2 to 3.9, 3.3 to 3.9, 3.4 to 3.9, 3.5 to 3.9, 3.6 to 3.9, 3.7 to 3.9, or 3.8 to 3.9.

[0083] In some embodiments, the second surface portion of the substrate does not contain a silicon-containing film. In some embodiments, the second surface portion of the substrate is made of or contains a material with a dielectric constant greater than 3.9. For example, in some embodiments, the second surface portion of the substrate is made of or contains a material with a dielectric constant of 4 or greater. In some embodiments, the second surface portion of the substrate is made of or contains a metal.

[0084] The thickness of the silicon-containing film can be from 100 Å to 100 µm, or any range or subrange between 100 Å and 100 µm. In some embodiments, the thickness of the silicon-containing film is 0.1 μm to 100 μm, 1 μm to 100 μm, 10 μm to 100 μm, 20 μm to 100 μm, 30 μm to 100 μm, 40 μm to 100 μm, 50 μm to 100 μm, 60 μm to 100 μm, 70 μm to 100 μm, 80 μm to 100 μm, or 90 μm to 100 μm. In some embodiments, the thickness of the silicon-containing film is 20 Å to 90 μm, 20 Å to 80 μm, 20 Å to 70 μm, 20 Å to 60 μm, 20 Å to 50 μm, 20 Å to 40 μm, 20 Å to 30 μm, 20 Å to 20 μm, 20 Å to 10 μm, 20 Å to 1 μm, or 20 Å to 0.1 μm. In some embodiments, the thickness of the silicon-containing film is 20 Å to 900 Å, 20 Å to 800 Å, 20 Å to 700 Å, 20 Å to 600 Å, 20 Å to 500 Å, 20 Å to 400 Å, 20 Å to 300 Å, 20 Å to 200 Å, 200 Å to 900 Å, 300 Å to 900 Å, 400 Å to 900 Å, 500 Å to 900 Å, 600 Å to 900 Å, 700 Å to 900 Å, or 800 Å to 900 Å. In some embodiments, the thickness mentioned above refers to the average thickness of the silicon-containing film.

[0085] Figure 1 This is a schematic cross-sectional view of a silicon-containing film deposited on a substrate according to some embodiments. Figure 1 As shown, substrate 102 includes a silicon-containing film 104 deposited on the surface of substrate 102. Any of the silicon-containing films and / or substrates disclosed herein may be used without departing from the scope of this disclosure.

[0086] Figure 2 This is a flowchart of a method 200 for preparing a silicon-containing film according to some embodiments. Figure 2As shown, a method 200 for preparing a silicon-containing film may include one or more of the following steps: obtaining a precursor 202; obtaining at least one co-reactant precursor 204; vaporizing the precursor 206 to obtain a vaporized precursor; vaporizing at least one co-reactant precursor 208 to obtain at least one vaporized co-reactant precursor; and exposing a substrate 210 to at least one of the vaporized precursor, at least one vaporized co-reactant precursor, or any combination thereof under vapor deposition conditions to selectively deposit a silicon-containing film on the substrate. In some embodiments, the method does not include an etching step (e.g., a selective etching step). In some embodiments, the method further includes selecting or adjusting the concentration of the precursor in the vapor to control the thickness of the silicon-containing film.

[0087] Step 202 may include, consist of, or substantially consist of: obtaining a precursor. The precursor may include, consist of, or substantially consist of any one or more of the precursors disclosed herein. Obtaining may include obtaining a container or other vessel containing the precursor. In some embodiments, the precursor may be obtained in the container or other vessel to which it is to be vaporized.

[0088] Step 204 may include, consist of, or substantially consist of: obtaining at least one co-reactant precursor. In some embodiments, the at least one co-reactant precursor comprises, consists of, or substantially consists of, or is selected from the group consisting of at least one of: oxidizing gas, reducing gas, hydrocarbon, or any combination thereof. At least one co-reactant precursor may be selected to obtain the desired silicon-containing film. In some embodiments, the at least one co-reactant precursor may comprise, consist of, or substantially consists of: N2, H2, NH3, N2H4, CH3HNNH2, CH3HNNHCH3, NCH3H2, NCH3CH2H2, N(CH3)2H, N(CH3CH2)2H, N(CH3)3, N(CH3CH2)3, Si(CH3)2NH, pyrazoline, pyridine, ethylenediamine, their groups, or any combination thereof. In some embodiments, at least one co-reactant precursor may comprise, consist of, or substantially consist of at least one of the following: H2, O2, O3, H2O, H2O2, NO, N2O, NO2, CO, CO2, carboxylic acids, alcohols, glycols, their groups, or any combination thereof. In some embodiments, at least one co-reactant precursor may comprise, consist of, or substantially consist of at least one of the following: methane, ethane, ethylene, acetylene, or any combination thereof. Obtaining may include obtaining a container or other vessel containing at least one co-reactant precursor. In some embodiments, at least one co-reactant precursor may be obtained in a container or other vessel in which at least one co-reactant precursor is to be vaporized. In some embodiments, the method further includes an inert gas, such as at least one of argon, helium, nitrogen, or any combination thereof.

[0089] Step 206 may include, consist of, or substantially consist of: vaporizing the precursor to obtain a vaporized precursor. Vaporization may include, consist of, or substantially consist of: heating the precursor to a level sufficient to obtain a vaporized precursor. In some embodiments, vaporization may include, consist of, or substantially consist of: heating a container containing the precursor. In some embodiments, vaporization may include, consist of, or substantially consist of: heating the precursor in a deposition chamber where a vapor deposition process is performed. In some embodiments, vaporization may include, consist of, or substantially consist of: heating a conduit for delivering the precursor, the vaporized precursor, or any combination thereof to, for example, a deposition chamber. In some embodiments, vaporization may include, consist of, or substantially consist of: operating a vapor delivery system containing the precursor. In some embodiments, vaporization may include, consist of, or substantially consist of: heating to a temperature sufficient to vaporize the precursor to obtain a vaporized precursor. In some embodiments, vaporization may include, consist of, or substantially consist of: heating to a temperature below the decomposition temperature of at least one of the precursor, the vaporized precursor, or any combination thereof. In some embodiments, the precursor may be present in a gaseous form, in which case step 206 is optional and not required. For example, the precursor may comprise, consist of, or substantially consist of a vaporized precursor.

[0090] Step 208 may include, consist of, or substantially consist of: vaporizing at least one co-reactant precursor to obtain at least one vaporized co-reactant precursor. In some embodiments, vaporization may include, consist of, or substantially consist of: heating at least one co-reactant precursor to sufficient extent to obtain at least one vaporized co-reactant precursor. In some embodiments, vaporization may include, consist of, or substantially consist of: heating a container containing at least one co-reactant precursor. In some embodiments, vaporization may include, consist of, or substantially consist of: heating at least one co-reactant precursor in a deposition chamber where a vapor deposition process is performed. In some embodiments, vaporization may include, consist of, or substantially consist of: heating a conduit for delivering at least one co-reactant precursor, at least one vaporized co-reactant precursor, or any combination thereof to, for example, a deposition chamber. In some embodiments, vaporization may include, consist of, or substantially consist of: operating a vapor delivery system containing at least one co-reactant precursor. In some embodiments, vaporization may comprise, consist of, or substantially consist of heating to a temperature sufficient to vaporize at least one co-reactant precursor to obtain at least one vaporized co-reactant precursor. In some embodiments, vaporization may comprise, consist of, or substantially consist of heating to a temperature below the decomposition temperature of at least one co-reactant precursor, at least one vaporized co-reactant precursor, or any combination thereof. In some embodiments, at least one co-reactant precursor may be present in a gaseous form, in which case step 208 is optional and not required. For example, at least one co-reactant precursor may comprise, consist of, or substantially consist of at least one vaporized co-reactant precursor.

[0091] Step 210 may include, consist of, or substantially consist of exposing a substrate 210 to at least one of a vaporized precursor, at least one vaporized co-reactant precursor, or any combination thereof under vapor deposition conditions to selectively deposit a silicon-containing film on the substrate. The substrate may include any of the substrates disclosed herein. In some embodiments, exposure includes contacting at least one of a vaporized precursor, at least one vaporized co-reactant precursor, or any combination thereof with the substrate under vapor deposition conditions sufficient to form a silicon-containing film on the surface of the substrate. In some embodiments, exposure is performed in the presence of a catalyst. Non-limiting examples of catalysts include, for example, but not limited to, catalysts comprising at least one of: aluminum, alumina, hafnium, hafnium oxide, zirconium, zirconium oxide, dimethylaluminum isopropylidene oxide, and others. In some embodiments, exposure includes contacting a first surface portion and a second surface portion of the substrate with the vaporized precursor in the presence of a catalyst. In some embodiments, a silicon-containing film is formed on the first surface portion of the substrate. In some embodiments, a silicon-containing film is formed on the first surface portion of the substrate without depositing a silicon-containing film on the second surface portion of the substrate. In some embodiments, the catalyst covers a first surface portion of the substrate but is not present on a second surface portion of the substrate. In some embodiments, the first surface portion is different from the second surface portion.

[0092] Exposure can be performed in any system, apparatus, device, assembly, chamber, or component thereof (including, for example, but not limited to, deposition chambers and others) suitable for vapor deposition processes. The substrate may be exposed to the vaporized precursor and at least one co-reactant precursor simultaneously or at different times. For example, each of the vaporized precursor, at least one vaporized co-reactant precursor, and the substrate may be present simultaneously in the deposition chamber. That is, in some embodiments, exposure may include simultaneously or synchronously exposing the substrate to the vaporized precursor and at least one vaporized co-reactant precursor. Alternatively, each of the vaporized precursor and at least one vaporized co-reactant precursor may be present in the deposition chamber at different times. That is, in some embodiments, exposure may include alternating and / or sequentially exposing the vaporized precursor and substrate in one or more cycles, followed by exposing at least one vaporized co-reactant precursor to the substrate.

[0093] Vapor deposition conditions may include conditions for vapor deposition processes. Examples of vapor deposition conditions include, but are not limited to, vapor deposition conditions for vapor deposition processes comprising at least one of the following: chemical vapor deposition (CVD) processes, digital or pulsed chemical vapor deposition processes, plasma-enhanced cyclic chemical vapor deposition (PECCVD) processes, flowable chemical vapor deposition (FCVD) processes, atomic layer deposition (ALD) processes, thermal atomic layer deposition, plasma-enhanced atomic layer deposition (PEALD) processes, metal-organic chemical vapor deposition (MOCVD) processes, plasma-enhanced chemical vapor deposition (PECVD) processes, or any combination thereof.

[0094] Vapor deposition conditions may include, consist of, or substantially consist of a deposition temperature. The deposition temperature may be a temperature below the thermal decomposition temperature of at least one of the vaporized precursor, at least one of the vaporized co-reactant precursors, or any combination thereof. The deposition temperature may be high enough to reduce or avoid condensation of at least one of the vaporized precursor, at least one of the vaporized co-reactant precursors, or any combination thereof. In some embodiments, the substrate may be heated to the deposition temperature. In some embodiments, a chamber or other vessel in which the substrate is in contact with the vaporized precursor and at least one of the vaporized co-reactant precursors may be heated to the deposition temperature. In some embodiments, at least one of the vaporized precursor, at least one of the vaporized co-reactant precursors, or any combination thereof may be heated to the deposition temperature.

[0095] The deposition temperature can be from 50°C to 500°C. In some embodiments, the deposition temperature can be from 50°C to 500°C. For example, in some embodiments, the deposition temperature can be the following temperatures: 50°C to 500°C, 50°C to 450°C, 50°C to 400°C, 50°C to 350°C, 50°C to 300°C, 50°C to 250°C, 50°C to 200°C, 50°C to 150°C, 50°C to 100°C, 100°C to 500°C, 150°C to 500°C, 200°C to 500°C, 250°C to 500°C, 300°C to 500°C, 350°C to 500°C, 400°C to 500°C, or 450°C to 500°C.

[0096] Vapor deposition conditions may include, consist of, or substantially consist of deposition pressure. In some embodiments, deposition pressure may include, consist of, or substantially consist of the vapor pressure of at least one of a vaporized precursor, at least one vaporized co-reactant precursor, or any combination thereof. In some embodiments, deposition pressure may include, consist of, or substantially consist of chamber pressure.

[0097] The deposition pressure can be from 0.001 Torr to 100 Torr. For example, in some embodiments, the deposition pressure can be the following pressures: 0.001 Torr to 10 Torr, 0.01 Torr to 10 Torr, 0.1 Torr to 1 Torr, 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 one of the following: 1 to 100 Torr, 5 to 100 Torr, 10 to 100 Torr, 15 to 100 Torr, 20 to 100 Torr, 25 to 100 Torr, 30 to 100 Torr, 35 to 100 Torr, 40 to 100 Torr, 45 to 100 Torr, 50 to 100 Torr, 55 to 100 Torr, 60 to 100 Torr, 65 to 100 Torr, 70 to 100 Torr, 75 to 100 Torr, 80 to 100 Torr, 85 to 100 Torr, 90 to 100 Torr, 95 to 100 Torr, 1 to 95 Torr, 1 to 85 Torr, 1 to 80 Torr, 1 to 75 Torr, or 1 to 70 Torr. In other embodiments, the deposition pressure may be one of the following: 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.

[0098] Some embodiments relate to silicon-containing films on a substrate surface. In some embodiments, the silicon-containing film comprises any film formed according to the methods disclosed herein. In some embodiments, the silicon-containing film comprises any film prepared from the precursors disclosed herein.

[0099] Example 1

[0100] A 300 mm silicon oxide substrate was placed in a CVD / ALD chamber and heated to 150 °C in a controlled flow of Ar at 500 sccm, with the pressure controlled to 1 Torr using a throttle valve. The substrate was first exposed to 50 sccm of H₂O vapor added to the Ar flow for 0.5 s. The substrate was then purged with a continuous Ar flow for 5 s. Next, a 20 sccm pulse of DMAI (dimethylaluminum isopropylidene oxide) vapor was applied for 3 s. The substrate was then purged with a continuous Ar flow for 5 s. A 300 s pulse of 20 sccm of 1,1-bis(1,1-dimethylethoxy)-1-vinylsilanol vapor was then applied to deposit a 50 Å low-k (k < 3.9) SiOCH film. The substrate was then purged with a continuous Ar flow for 500 s. If a higher thickness was required, the DMAI and 1,1-bis(1,1-dimethylethoxy)-1-vinylsilanol vapor pulses were repeated until the desired thickness was achieved.

[0101] Example 2

[0102] A 300 mm substrate with some OH-terminated dielectric regions and some CH3-terminated metal regions was placed in a CVD / ALD chamber and heated to 150 °C in a flowing Ar stream controlled to 500 sccm, with the pressure controlled to 1 Torr using a throttle valve. The substrate was first exposed to 50 sccm of H2O vapor added to the Ar stream for 0.5 s. The substrate was then purged with a continuous Ar stream for 5 s. This was followed by a 3-s pulse of 20 sccm of DMAI (dimethylaluminum isopropylidene) vapor. Under these conditions, Al was deposited only on the OH-terminated dielectric surface, and the metal did not accept any of the catalysts. The substrate was then purged with a continuous Ar stream for 5 s. A 300-s pulse of 20 sccm of 1,1-bis(1,1-dimethylethoxy)-1-vinylsilanol vapor deposited only a 50 Å low-k (k < 3.9) SiOCH film on the dielectric surface, with no significant deposition on the metal surface. Next, purge the substrate with a continuous flow of Ar for 500 s. If additional thickness is required, repeat the DMAI and 1,1-bis(1,1-dimethylethoxy)-1-vinylsilanol vapor pulses until the desired thickness is achieved.

[0103] aspect

[0104] The following describes various aspects. It should be understood that any one or more of the features described in the following aspects may be combined with any one or more other aspects.

[0105] Aspect 1. A precursor comprising:

[0106] The following compounds:

[0107] ,

[0108] in:

[0109] R is alkyl, alkenyl, or alkoxy; and

[0110] R 1 and R 2 Independently hydrogen, alkyl, or R 1 and R 2 They are bonded together to form heterocyclic rings;

[0111] Where R is different from OR 1 OR 2 or at least one of any combination thereof;

[0112] The compound is deposited on a material with a dielectric constant of no more than 3.9 when it is vaporized to form a precursor vapor.

[0113] Aspect 2. The precursor according to aspect 1, wherein R is vinyl, allyl or alkoxy.

[0114] Aspect 3. The precursor according to any one of aspects 1 to 2, wherein R is vinyl, allyl, tert-butoxy or tert-pentoxy.

[0115] Aspect 4. The precursor according to any one of aspects 1 to 3, wherein R 1 and R 2 It is tert-pentyl.

[0116] Aspect 5. The precursor according to any one of aspects 1 to 4, wherein R 1 and R 2 It is tert-butyl.

[0117] Aspect 6. The precursor according to any one of aspects 1 to 5, wherein R 1 and R 2 They are bonded to form a 5-membered heterocycle.

[0118] Aspect 7. The precursor according to any one of aspects 1 to 6, wherein the precursor comprises a compound of the following formula:

[0119]

[0120] or,

[0121]

[0122] in:

[0123] R 1 and R 2 Independently hydrogen, alkyl, or R 1 and R 2They are bonded together to form heterocyclic rings.

[0124] Aspect 8. The precursor according to any one of aspects 1 to 7, wherein the precursor comprises a compound of the following formula:

[0125]

[0126]

[0127] .

[0128] Aspect 9. An apparatus comprising:

[0129] A substrate having a first surface portion and a second surface portion; and

[0130] A silicon-containing film is located on the first surface portion of the substrate.

[0131] The silicon-containing film comprises a reaction product of at least one precursor and reactive groups on the first surface portion of the substrate.

[0132] The precursor comprises a compound of the following formula:

[0133] ,

[0134] in:

[0135] R is alkyl, alkenyl, or alkoxy; and

[0136] R 1 and R 2 Independently hydrogen, alkyl, or R 1 and R 2 They are bonded together to form heterocyclic rings;

[0137] Where R is different from OR 1 OR 2 or at least one of any combination thereof;

[0138] The second surface portion of the substrate does not contain the silicon-containing film.

[0139] Aspect 10. The apparatus according to aspect 9, wherein the first surface portion of the substrate comprises at least one of a dielectric material, an insulating material, or any combination thereof.

[0140] Aspect 11. The apparatus according to any one of aspects 9 to 10, wherein the first surface portion of the substrate comprises at least one of SiO2, SiN, or any combination thereof.

[0141] Aspect 12. The apparatus according to any one of aspects 9 to 11, wherein the first surface portion of the substrate comprises a material having a dielectric constant of 3.9 or less; and wherein the second surface portion of the substrate comprises a material having a dielectric constant greater than 3.9.

[0142] Aspect 13. The apparatus according to any one of aspects 9 to 12, wherein the silicon-containing film has a thickness of 20 Å to 100 µm.

[0143] Aspect 14. The apparatus according to any one of aspects 9 to 13, wherein the silicon-containing film comprises SiO2.

[0144] Aspect 15. The apparatus according to any one of aspects 9 to 14, wherein the silicon-containing film comprises SiCOH.

[0145] Aspect 16. The apparatus according to any one of aspects 9 to 15, wherein the apparatus is a self-aligning through-hole.

[0146] Aspect 17. A method comprising:

[0147] Obtain the precursor,

[0148] The precursor is a compound of the following formula:

[0149] ,

[0150] in:

[0151] R is alkyl, alkenyl, or alkoxy; and

[0152] R 1 and R 2 Independently hydrogen, alkyl, or R 1 and R 2 They are bonded together to form heterocyclic rings;

[0153] Where R is different from OR 1 OR 2 or at least one of any combination thereof;

[0154] The precursor is vaporized to produce a vaporized precursor; and

[0155] In the presence of a catalyst, the substrate is exposed to the vaporized precursor to selectively deposit a silicon-containing film on the substrate.

[0156] Aspect 18. The method according to aspect 17, wherein the method does not include an etching step.

[0157] Aspect 19. The method according to any one of aspects 17 to 18, wherein the catalyst comprises at least one of alumina, hafnium oxide, zirconium oxide, or any combination thereof.

[0158] Aspect 20. The method according to any one of aspects 17 to 19, wherein the catalyst covers a first surface portion of the substrate and is not present in a second surface portion of the substrate.

[0159] It should be understood that detailed changes may be made without departing from the scope of this disclosure, particularly in terms of the building materials used and the shape, size, and arrangement of components. This specification and the described embodiments are examples, wherein the true scope and spirit of this disclosure are indicated by the appended claims.

Claims

1. A precursor comprising: The following compounds: ， in: R is alkyl, alkenyl, or alkoxy; and R 1 and R 2 Independently alkyl, or R 1 and R 2 They are bonded together to form heterocyclic rings; Where R is different from OR 1 OR 2 or at least one of any combination thereof; The compound is deposited on a material with a dielectric constant of no more than 3.9 when it is vaporized to form a precursor vapor.

2. The precursor according to claim 1, wherein R is vinyl, allyl, or alkoxy.

3. The precursor according to claim 1, wherein R is vinyl, allyl, tert-butoxy, or tert-pentoxy.

4. The precursor according to claim 1, wherein R 1 and R 2 It is tert-pentyl.

5. The precursor according to claim 1, wherein R 1 and R 2 It is tert-butyl.

6. The precursor according to claim 1, wherein R 1 and R 2 They are bonded to form a 5-membered heterocycle.

7. The precursor according to claim 1, wherein the precursor comprises a compound of the following formula: 、 or, ， in: R 1 and R 2 Independently alkyl, or R 1 and R 2 They are bonded together to form heterocyclic rings.

8. The precursor according to claim 1, wherein the precursor comprises a compound of the following formula: 、 、 、 、 、 、 or, 。 9. An apparatus comprising: A substrate having a first surface portion and a second surface portion; and A silicon-containing film is located on the first surface portion of the substrate. The silicon-containing film comprises a reaction product of at least one precursor and reactive groups on the first surface portion of the substrate. The precursor comprises a compound of the following formula: ， in: R is alkyl, alkenyl, or alkoxy; and R 1 and R 2 Independently alkyl, or R 1 and R 2 They are bonded together to form heterocyclic rings; Where R is different from OR 1 OR 2 or at least one of any combination thereof; The second surface portion of the substrate does not contain the silicon-containing film.

10. The apparatus of claim 9, wherein the first surface portion of the substrate comprises at least one of a dielectric material, an insulating material, or any combination thereof.

11. The apparatus of claim 9, wherein the first surface portion of the substrate comprises at least one of SiO2, SiN, or any combination thereof.

12. The apparatus of claim 9, wherein the first surface portion of the substrate comprises a material having a dielectric constant of 3.9 or less; wherein the second surface portion of the substrate comprises a material having a dielectric constant greater than 3.

9.

13. The apparatus of claim 9, wherein the silicon-containing film has a thickness of 20 Å to 100 µm.

14. The apparatus of claim 9, wherein the silicon-containing film comprises SiO2.

15. The apparatus of claim 9, wherein the silicon-containing film comprises SiCOH.

16. The apparatus of claim 9, wherein the apparatus is a self-aligning through-hole.

17. A method comprising: Obtain a precursor, The precursor is a compound of the following formula: ， in: R is alkyl, alkenyl, or alkoxy; and R 1 and R 2 Independently alkyl, or R 1 and R 2 They are bonded together to form heterocyclic rings; Where R is different from OR 1 OR 2 or at least one of any combination thereof; The precursor is vaporized to produce a vaporized precursor; and In the presence of a catalyst, the substrate is exposed to the vaporized precursor to selectively deposit a silicon-containing film on the substrate.

18. The method of claim 17, wherein the method does not include an etching step.

19. The method of claim 17, wherein the catalyst comprises at least one of alumina, hafnium oxide, zirconium oxide, or any combination thereof.

20. The method of claim 17, wherein the catalyst covers a first surface portion of the substrate and is not present in a second surface portion of the substrate.

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