Aluminum-containing suppressor compounds for selective deposition

Abstract

The present disclosure provides aluminum-containing inhibitor compounds for selective deposition. A method for selective deposition includes obtaining a substrate having a first surface and a second surface, exposing the substrate to an Al-containing inhibitor to modify the first surface, and selectively depositing a film on the second surface. The aluminum-containing inhibitor compound is a compound including a substituted alkyl aluminum. Related systems, related compositions, and related apparatuses are also provided.

Description

Technical Field

[0001] This application relates to an aluminum-containing inhibitor compound for selective deposition.

[0002] Cross-reference of related applications

[0003] This application claims the benefit of U.S. Provisional Patent Application No. 63 / 557,297, filed February 23, 2024, pursuant to 35 USC 119, the entire disclosure of which is incorporated herein by reference. Background Technology

[0004] The precursor is deposited on the substrate surface. During the vapor deposition process, the precursor may be undesirably deposited on some surfaces. When the precursor is undesirably deposited on those surfaces, the deposited precursor must be removed from those surfaces. Summary of the Invention

[0005] Some embodiments relate to a method. In some embodiments, the method includes obtaining a substrate having a first surface and a second surface. In some embodiments, the method includes exposing the substrate to an Al-containing inhibitor to modify the first surface. In some embodiments, the Al-containing inhibitor is a compound comprising substituted alkyl aluminum. In some embodiments, the method includes selectively depositing a film on the second surface.

[0006] Some embodiments relate to a composition. In some embodiments, the composition comprises an Al-containing inhibitor including a compound of the following formula: Q—Al—(R)2. In some embodiments, Q is cyclopentadienyl or indenyl. In some embodiments, R is independently an alkyl group. In some embodiments, when the Al-containing inhibitor is exposed to a substrate having a first surface containing hydroxyl groups and a second surface not containing hydroxyl groups, the Al-containing inhibitor sufficiently modifies the first surface to allow for selective deposition of a film on the second surface.

[0007] Some embodiments relate to an apparatus. In some embodiments, the apparatus includes a membrane. In some embodiments, the apparatus includes an Al-containing inhibitor. In some embodiments, the apparatus includes a substrate having at least a first surface and a second surface. In some embodiments, the Al-containing inhibitor is deposited on the first surface. In some embodiments, the membrane is not deposited on the first surface. In some embodiments, the membrane is deposited on the second surface. Attached Figure Description

[0008] Figure 1 This is a flowchart of a selective deposition method according to some embodiments.

[0009] Figure 2This is a schematic diagram of a cross-section of a substrate according to some embodiments.

[0010] Figure 3 This is a schematic diagram of a selective deposition method according to some embodiments. Detailed Implementation

[0011] As used herein, the term "alkyl" refers to a hydrocarbon group having 1 to 30 carbon atoms. Alkyl groups can be linked by single bonds. Alkyl groups having n carbon atoms can be designated as "C". n Alkyl group. For example, "C3 alkyl" may include n-propyl and isopropyl. Alkyl groups having a series of carbon atoms (e.g., 1 to 30 carbon atoms) may be specified as C1-C6. 30 Alkyl group. In some embodiments, the alkyl group is straight-chain. In some embodiments, the alkyl group is branched. In some embodiments, the alkyl group is substituted. In some embodiments, the alkyl group is not substituted. In some embodiments, the alkyl group comprises or is selected from the group consisting of at least one of the following: C1-C 30 Alkyl, C1-C 29 Alkyl, C1-C 28 Alkyl, C1-C 27 Alkyl, C1-C 27 Alkyl, C1-C 26 Alkyl, C1-C 25 Alkyl, C1-C 24 Alkyl, C1-C 23 Alkyl, C1-C 22 Alkyl, C1-C 21 Alkyl, C1-C 20 Alkyl, C1-C 19 Alkyl, C1-C 18 Alkyl, C1-C 17 Alkyl, C1-C 16 Alkyl, C1-C 15 Alkyl, C1-C 14 Alkyl, C1-C 13 Alkyl, C1-C 12 Alkyl, C1-C 11 Alkyl, 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, C1-C2 alkyl, C2-C 30 Alkyl, C3-C 30 Alkyl, C4-C 30 Alkyl, C5-C 30 Alkyl, C6-C 30 Alkyl, C7-C 30 Alkyl, C8-C 30Alkyl, C9-C 30 Alkyl, C 10 -C 30 Alkyl, C 11 -C 30 Alkyl, C 12 -C 30 Alkyl, C 13 -C 30 Alkyl, C 14 -C 30 Alkyl, C 15 -C 30 Alkyl, C 16 -C 30 Alkyl, C 17 -C 30 Alkyl, C 18 -C 30 Alkyl, C 19 -C 30 Alkyl, C 20 -C 30 Alkyl, C 21 -C 30 Alkyl, C 22 -C 30 Alkyl, C 23 -C 30 Alkyl, C 24 -C 30 Alkyl, C 25 -C 30 Alkyl, C 26 -C 30 Alkyl, C 27 -C 30 Alkyl, C 28 -C 30 Alkyl, C 29 -C 30 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 includes 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, n-hexyl, isohexyl, 3-methylhexyl, 2-methylhexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, or any combination thereof. In some embodiments, the term "alkyl" generally refers to alkyl, alkenyl, ynyl, and / or cycloalkyl.

[0012] As used herein, the term "haloalkyl" refers to an alkyl group as defined herein, wherein at least one of the hydrogen atoms of the alkyl group is replaced by a halide as defined herein. In some embodiments, the haloalkyl group includes a fluoroalkyl group. In some embodiments, the fluoroalkyl group includes at least one of CH2CF3, -CH(CF3)2, -CH2F, -CH2CH2F, -CF3, -CF2CF3, or any combination thereof.

[0013] As used herein, the term "metal" means at least one of alkali metals, alkaline earth metals, transition metals, post-transition metals, lanthanides, actinides, or any combination thereof. In some embodiments, for example, the metal comprises or is selected from the group consisting of transition metals. In some embodiments, the transition metal comprises or is selected from the group consisting of at least one of the following: scandium (Sc), yttrium (Y), titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), technetium (Tc), rhenium (Re), iron (Fe), ruthenium (Ru), osmium (Os), cobalt (Co), rhodium (Rh), iridium (Ir), nickel (Ni), palladium (Pd), platinum (Pt), copper (Cu), silver (Ag), gold (Au), zinc (Zn), cadmium (Cd), mercury (Hg), or any combination thereof. In some embodiments, the metal is in ionic form, elemental form, or any combination thereof.

[0014] Some embodiments relate to aluminum (Al-containing) inhibitor compounds for selective deposition processes. In some embodiments, the Al-containing inhibitor compound provides deposition of a precursor on a selected surface. In some embodiments, for example, the Al-containing inhibitor compound selectively inhibits a first surface of the substrate without inhibiting a second surface of the substrate. In some embodiments, the precursor is deposited on the second surface while the first surface of the substrate is exposed to the precursor. That is, in some embodiments, the precursor is not deposited on the first surface of the substrate, and the first surface is still inhibited by the Al-containing inhibitor compound. In some embodiments, the precursor will be deposited on the first surface of the substrate in the absence of the Al-containing inhibitor compound. In some embodiments, the Al-containing inhibitor compounds disclosed herein allow for selective deposition of the precursor on selected areas of a selected surface.

[0015] The Al-containing inhibitors disclosed herein can be used to selectively deposit films on a substrate. In some embodiments, when a first and second surface of the substrate are exposed to a precursor, a film is selectively deposited on the substrate, the precursor is deposited on the second surface of the substrate (e.g., as a film), and the precursor is not deposited on the first surface of the substrate. In some embodiments, the first and second surfaces are different (e.g., chemically different). In some embodiments, the precursor is selectively deposited on the second surface with preference to the first surface. In some embodiments, selectively depositing a film on the second surface includes a process in which the film is not or substantially not deposited on the first surface. In some embodiments, the precursor is selectively deposited on the second surface of the substrate at a range of thicknesses without being deposited on the first surface of the substrate.

[0016] The Al-containing inhibitor compounds, inhibitor compounds, and related systems and methods disclosed herein can be used to manufacture microelectronic devices, including semiconductor devices, etc. For example, the Al-containing inhibitor compounds can be used to form films or layers for area-selective deposition (ASD) during 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) methods, digital or pulsed chemical vapor deposition processes, plasma-enhanced cyclic chemical vapor deposition (PECCVD), flowable chemical vapor deposition (FCVD), 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. The deposition processes may include water-based deposition processes, inflow, and water-based area-selective deposition processes.

[0017] Figure 1 This is a flowchart of a selective deposition method 100 according to some embodiments. Figure 1As shown, in some embodiments, the selective deposition method 100 includes one or more of the following steps: obtaining 102 a substrate having at least a first surface and a second surface; treating 104 at least one of the first surface, the second surface, or any combination thereof; exposing the substrate 106 to an Al inhibitor to modify the first surface; and selectively 108 depositing a film on the second surface. In some embodiments, the selective deposition method does not include any or more of the above steps.

[0018] In step 102, the selective deposition method 100 includes obtaining a substrate having at least a first surface and a second surface.

[0019] The first surface and the second surface may be different. In some embodiments, the first surface is the surface to be suppressed. For example, in some embodiments, the first surface is a surface configured to be suppressed by an Al-containing inhibitor compound. In some embodiments, the first surface is a surface configured to react with an Al-containing inhibitor compound. In some embodiments, when the first surface reacts with an Al-containing inhibitor compound, the resulting surface is the suppressed surface. In some embodiments, the first surface is a functionalized surface, wherein the functionalized surface contains functional groups configured to react with an Al-containing inhibitor compound. In some embodiments, the first surface contains hydroxyl groups. In some embodiments, the functional groups are exposed to an Al-containing inhibitor compound or otherwise made available for reaction with or access to an Al-containing inhibitor compound. In some embodiments, the functionalized surface contains functional groups configured to react with an alkyl group of an Al-containing inhibitor compound. In some embodiments, the functional groups of the functionalized surface include a plurality of hydroxyl groups. Where appropriate, the functional groups may include non-hydroxyl or functional groups other than hydroxyl groups.

[0020] In some embodiments, the second surface is a surface on which a substance is to be deposited. In some embodiments, the substance to be deposited on the second surface is deposited by a deposition process (e.g., any or more of the deposition processes disclosed herein). For example, in some embodiments, the substance to be deposited on the second surface is a precursor for zone-selective deposition deposited during atomic layer deposition and / or chemical vapor deposition. In some embodiments, the second surface is a surface not inhibited by an Al-containing inhibitor compound. In some embodiments, the second surface is a surface that does not react with an Al-containing inhibitor compound. In some embodiments, the second surface is a functionalized surface, wherein the functional groups on the functionalized surface do not react with an Al-containing inhibitor compound. In some embodiments, the second surface does not contain hydroxyl groups. In some embodiments, the second surface does not contain hydroxyl groups exposed to or otherwise available to react with or accessible to an Al-containing inhibitor compound.

[0021] The substrate may have more than one first surface and one second surface. Furthermore, the substrate may comprise at least one of a dielectric material, an insulating material, a conductive material, or any combination thereof. In some embodiments, the first surface of the substrate is constructed of or comprises at least one of a dielectric material, an insulating material, a conductive material, or any combination thereof. In some embodiments, the second surface of the substrate is constructed of or comprises at least one of a dielectric material, an insulating material, a conductive material, or any combination thereof. In some embodiments, the substrate comprises at least one of 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 comprises other silicon-based substrates, for example, one or more of a polycrystalline silicon substrate, a metal substrate, and a dielectric substrate. In some embodiments, at least one of the first surface, the second surface, or any combination thereof comprises a metal. In some embodiments, at least one of the first surface, the second surface, or any combination thereof is a metallic surface. In some embodiments, at least one of the first surface, the second surface, or any combination thereof is a non-metallic surface. In some embodiments, at least one of the first surface, the second surface, or any combination thereof does not contain metal.

[0022] In step 104, the selective deposition method 100 includes processing at least one of the first surface, the second surface, or any combination thereof.

[0023] The first surface of the substrate may be subjected to various treatments. For example, when the first surface of the substrate is not configured to be inhibited by an Al-containing inhibitor compound (e.g., when the first surface does not have hydroxyl groups), in some embodiments, the method may include functionalizing the first surface of the substrate. In some embodiments, the functionalization includes forming functional groups on the first surface of the substrate. In some embodiments, for example, the functionalization includes forming hydroxyl groups on the first surface of the substrate. In some embodiments, the functionalization includes surface hydroxyl functionalization. In some embodiments, the functionalization includes exposing the first surface to plasma (e.g., H2 / O2 plasma treatment) to form hydroxyl groups on the first surface. In some embodiments, the functionalization includes contacting the first surface with a solvent to form hydroxyl groups on the first surface. In some embodiments, the functionalization includes contacting the first surface with anhydrous peroxide to form hydroxyl groups on the first surface. In some embodiments, the functionalization includes exposing the first surface to water vapor to form hydroxyl groups on the first surface. It should be understood that any technique known in the art for surface functionalization may be used herein without departing from the scope of this disclosure. In some embodiments, the functionalization does not include functionalizing a second surface of the substrate.

[0024] The second surface can be subjected to various treatments. In some embodiments, the selective deposition method 100 includes removing functional groups from the second surface of the substrate such that the second surface is not configured to be suppressed. In some embodiments, the removal includes contacting the second surface of the substrate with a solvent to remove functional groups that react with Al-containing inhibitor compounds. In some embodiments, the removal includes exposing the second surface to a reactive gas and / or reactive vapor to remove functional groups that react with Al-containing inhibitor compounds. In some embodiments, the selective deposition method 100 includes functionalizing the second surface of the substrate such that the second surface is not configured to be suppressed. In some embodiments, the functionalization includes functionalizing the second surface of the substrate such that the second surface does not react with Al-containing inhibitor compounds. In some embodiments, the functionalization includes functionalizing the second surface of the substrate with functional groups other than hydroxyl groups.

[0025] In step 106, the selective deposition method 100 includes exposing the substrate to an Al inhibitor to modify the first surface.

[0026] In some embodiments, the exposure includes contacting the substrate with an Al-containing inhibitor compound. In some embodiments, contact means bringing the substrate and the Al-containing inhibitor compound into close or direct proximity. In some embodiments, contact means bringing the substrate and the Al-containing inhibitor compound into direct physical contact. In some embodiments, the exposure includes reacting the Al-containing inhibitor compound with hydroxyl groups on a first surface. In some embodiments, the exposure does not include reacting the Al-containing inhibitor compound with a second surface. In some embodiments, the exposure includes introducing the Al-containing inhibitor compound into a chamber containing the substrate. In some embodiments, the exposure includes pumping the Al-containing inhibitor compound from one location into a chamber containing the substrate. In some embodiments, the exposure includes supplying the Al-containing inhibitor compound to the substrate. In some embodiments, the exposure includes vaporizing the Al-containing inhibitor compound. In some embodiments, the exposure includes allowing the Al-containing inhibitor compound to flow from one location into a chamber containing the substrate. In some embodiments, the exposure includes feeding the Al-containing inhibitor compound into a chamber containing the substrate. In some embodiments, exposing the substrate to the Al-containing inhibitor compound includes pulsed the Al-containing inhibitor compound into a chamber containing the substrate.

[0027] In some embodiments, the exposure is continued at temperatures ranging from 100°C to 400°C or any range or subrange between 100°C and 400°C. In some embodiments, the temperature is a temperature within the range of 100°C to 380°C, 100°C to 360°C, 100°C to 340°C, 100°C to 320°C, 100°C to 300°C, 100°C to 280°C, 100°C to 260°C, 100°C to 240°C, 100°C to 220°C, 100°C to 200°C, 100°C to 180°C, 100°C to 160°C, 100°C to 140°C, or 100°C to 120°C. In some embodiments, the temperature is a temperature within the range of 120°C to 400°C, 140°C to 400°C, 160°C to 400°C, 180°C to 400°C, 200°C to 400°C, 220°C to 400°C, 240°C to 400°C, 260°C to 400°C, 280°C to 400°C, 300°C to 400°C, 320°C to 400°C, 340°C to 400°C, 360°C to 400°C, or 380°C to 400°C.

[0028] In some embodiments, the exposure to pressures ranging from 0.1 Torr to 50 Torr, or any range or subrange thereof, continues. In some embodiments, the pressure is within the range of 0.1 Torr to 45 Torr, 0.1 Torr to 40 Torr, 0.1 Torr to 35 Torr, 0.1 Torr to 30 Torr, 0.1 Torr to 25 Torr, 0.1 Torr to 20 Torr, 0.1 Torr to 15 Torr, 0.1 Torr to 10 Torr, 0.1 Torr to 5 Torr, 0.1 Torr to 1 Torr, 0.1 Torr to 0.2 Torr, 0.1 Torr to 50 Torr, 0.2 Torr to 50 Torr, 5 Torr to 50 Torr, 10 Torr to 50 Torr, 15 Torr to 50 Torr, 20 Torr to 50 Torr, 25 Torr to 50 Torr, 30 Torr to 50 Torr, 35 Torr to 50 Torr, 40 Torr to 50 Torr, or 45 Torr to 50 Torr.

[0029] In some embodiments, the Al-containing inhibitor compound includes compounds of the following formula:

[0030] ,

[0031] in:

[0032] Q includes cyclopentadienyl or indenyl; and

[0033] R independently includes alkyl groups.

[0034] In some embodiments, the cyclopentadienyl group comprises a substituted cyclopentadienyl group. In some embodiments, the cyclopentadienyl group comprises one (1) to four (4) substituents. In some embodiments, the substituted cyclopentadienyl group comprises at least one of an alkylcyclopentadienyl group, a fluorinated cyclopentadienyl group, or any combination thereof. In some embodiments, when the cyclopentadienyl group comprises a fluorinated cyclopentadienyl group, the cyclopentadienyl group is substituted with at least one fluoroalkyl group. In some embodiments, the fluoroalkyl group comprises at least one of -CH2CF3, -CH(CF3)2, -CH2F, -CH2CH2F, -CF3, -CF2CF3, or any combination thereof.

[0035] In some embodiments, the cyclopentadienyl group comprises an unsubstituted cyclopentadienyl group.

[0036] In some embodiments, the indenyl group comprises a substituted indenyl group. In some embodiments, the indenyl group comprises one (1) to seven (7) substituents. In some embodiments, the substituted indenyl group comprises at least one of an alkyl indenyl group, a fluorinated indenyl group, or any combination thereof. In some embodiments, when the indenyl group comprises a fluorinated indenyl group, the indenyl group is substituted with at least one fluoroalkyl group. In some embodiments, the fluoroalkyl group comprises at least one of -CH2CF3, -CH(CF3)2, -CH2F, -CH2CH2F, -CF3, -CF2CF3, or any combination thereof.

[0037] In some embodiments, the indenyl group comprises an unsubstituted indenyl group.

[0038] In some embodiments, the Al-containing inhibitor compound comprises a cyclopentadienyl group and a C1-C5 alkyl group. In some embodiments, the Al-containing inhibitor compound comprises a substituted cyclopentadienyl group and a C1-C5 alkyl group. In some embodiments, the Al-containing inhibitor compound comprises an alkylcyclopentadienyl group and a C1-C5 alkyl group. In some embodiments, the Al-containing inhibitor compound comprises a fluorinated cyclopentadienyl group and a C1-C5 alkyl group. In some embodiments, the Al-containing inhibitor compound comprises an unsubstituted cyclopentadienyl group and a C1-C5 alkyl group.

[0039] In some embodiments, the Al-containing inhibitor compound comprises an indenyl group and a C1-C5 alkyl group. In some embodiments, the Al-containing inhibitor compound comprises a substituted indenyl group and a C1-C5 alkyl group. In some embodiments, the Al-containing inhibitor compound comprises an alkyl indenyl group and a C1-C5 alkyl group. In some embodiments, the Al-containing inhibitor compound comprises a fluorinated indenyl group and a C1-C5 alkyl group. In some embodiments, the Al-containing inhibitor compound comprises an unsubstituted indenyl group and a C1-C5 alkyl group.

[0040] In some embodiments, the Al-containing inhibitor compound includes compounds of the following formula:

[0041] .

[0042] In step 108, the selective deposition method 100 includes selectively depositing a film 106 on the second surface.

[0043] In some embodiments, the film is deposited on a second surface of a substrate. In some embodiments, the deposition does not include depositing a film on a first surface. In some embodiments, the film is deposited on the second surface of a substrate via a vapor deposition process. For example, in some embodiments, the deposition includes vaporizing a precursor to obtain a vaporized precursor. The vaporization may include sufficiently heating the precursor to obtain a vaporized precursor. In some embodiments, the vaporization includes heating a container containing the precursor. In some embodiments, the vaporization includes heating the precursor in a deposition chamber in which a vapor deposition process is performed. In some embodiments, the vaporization includes heating a conduit for delivering the precursor, the vaporized precursor, or any combination thereof to, for example, a deposition chamber. In some embodiments, the vaporization includes operating a vapor delivery system containing the precursor. In some embodiments, the vaporization includes heating to a temperature sufficient to vaporize the precursor to obtain a vaporized precursor. In some embodiments, the vaporization includes 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 gas phase or other vaporizable phase, in which case vaporization is optional and not necessary. For example, in some embodiments, the precursor includes a vaporized precursor.

[0044] In some embodiments, the deposition includes vaporizing at least one co-reactant precursor to obtain at least one vaporized co-reactant precursor. In some embodiments, the vaporization includes sufficiently heating at least one co-reactant precursor to obtain at least one vaporized co-reactant precursor. In some embodiments, the vaporization includes heating a container containing at least one co-reactant precursor. In some embodiments, the vaporization includes heating at least one co-reactant precursor in a deposition chamber in which a vapor deposition process is performed. In some embodiments, the vaporization includes 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, the vaporization includes operating a vapor delivery system containing at least one co-reactant precursor. In some embodiments, the vaporization includes 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, the vaporization includes heating to a temperature below the decomposition temperature of at least one of the at least one co-reactant precursor, at least one vaporized co-reactant precursor, or any combination thereof. In some embodiments, the at least one co-reactant precursor may be present in a gas phase or other vaporizable phase, in which case vaporization is optional and unnecessary. For example, in some embodiments, the at least one co-reactant precursor comprises at least one vaporized co-reactant precursor.

[0045] In some embodiments, the deposition includes exposing a substrate to at least one of a vaporized precursor, at least one vaporized co-reactant precursor, or any combination thereof under vapor deposition conditions to form a film on a first surface of the substrate. The exposure can be performed in any system, apparatus, device, assembly, chamber, or component thereof suitable for a vapor deposition process, particularly including, but not limited to, a deposition chamber. In some embodiments, the exposure includes contacting the substrate with at least one of a vaporized precursor, at least one vaporized co-reactant precursor, or any combination thereof. The vaporized precursor and at least one co-reactant precursor may be in contact with the substrate simultaneously or at different times. For example, the vaporized precursor, at least one vaporized co-reactant precursor, and the substrate may each be present in the deposition chamber simultaneously. That is, in some embodiments, the contact may include simultaneous or concurrent contact of the vaporized precursor and at least one vaporized co-reactant precursor with the substrate. Alternatively, the vaporized precursor and at least one vaporized co-reactant precursor may each be present in the deposition chamber at different times. That is, in some embodiments, the contact may include alternating and / or sequentially contacting the vaporized precursor with the substrate in one or more cycles and subsequently contacting at least one vaporized co-reactant precursor with the substrate.

[0046] Vapor deposition conditions may include conditions for vapor deposition processes (including selective region deposition during vapor deposition processes). Examples of vapor deposition conditions include (but are not limited to) vapor deposition conditions for vapor deposition processes that include at least one of the following: chemical vapor deposition (CVD) processes, digital or pulsed chemical vapor deposition processes, pulse-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.

[0047] Vapor deposition conditions may include 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 vaporized co-reactant precursor, 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 vaporized co-reactant precursor, or any combination thereof. In some embodiments, the substrate may be heated to the deposition temperature. In some embodiments, a chamber or other container in which the substrate is in contact with the vaporized precursor and at least one vaporized co-reactant precursor may be heated to the deposition temperature. In some embodiments, at least one of the vaporized precursor, at least one vaporized co-reactant precursor, or any combination thereof may be heated to the deposition temperature.

[0048] The deposition temperature can be from 200°C to 2500°C or any range or subrange between 200°C and 2500°C. In some embodiments, the deposition temperature can be from 500°C to 700°C. For example, in some embodiments, the deposition temperature can be from 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 greater than 200°C to 2500°C, such as (but not limited to) 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, and 825°C to 2400°C. 850℃ to 2400℃, 875℃ to 2400℃, 900℃ to 2400℃, 925℃ to 2400℃, 950℃ to 2400℃, 975℃ to 2400℃, 1000℃ to 2400℃, 1025℃ to 2400℃, 1050℃ to 2400℃, 1075℃ to 2400℃, 1100℃ to 2400℃, 1200℃ to 2400℃, 130℃ 0℃ to 2400℃, 1400℃ to 2400℃, 1500℃ to 2400℃, 1600℃ to 2400℃, 1700℃ to 2400℃, 1800℃ to 2400℃, 1900℃ to 2400℃, 2000℃ to 2400℃, 2100℃ to 2400℃, 2200℃ to 2400℃, 2300℃ to 2400℃, 500℃ to 2000℃, 50 Temperatures from 0°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.

[0049] Vapor deposition conditions may include deposition pressure. In some embodiments, the deposition pressure may include 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, the deposition pressure may include chamber pressure.

[0050] The deposition pressure can be from 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 can be 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 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 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.

[0051] The precursor may include at least one of the following: dimethylhydrazine, trimethylaluminum (TMA), hafnium chloride (HfCl4), zirconium chloride (ZrCl4), indium trichloride, indium monochloride, aluminum trichloride, titanium iodide, carbonyl tungsten, Ba(DPM)2, bis(di-neopentylmethane)strontium (Sr(DPM)2), TiO(DPM)2, tetra(di-neopentylmethane)strontium (Zr(DPM)4), decaborane, octadecborane, boron, magnesium, gallium, indium, antimony, copper, phosphorus, arsenic, lithium, sodium tetrafluoroborate, precursors incorporating alkyl-amidinium ligands, organometallic precursors, Zirconium tert-butoxide (Zr(t-OBu)4), zirconium tetradiethylamino(Zr(Net2)4), hafnium tetradiethylamino(Hf(Net2)4), tetra(dimethylamino)titanium (TDMAT), tert-butyliminotris(diethylamino)tantalum (TBTDET), penta(dimethylamino)tantalum (PDMAT), penta(ethylmethylamino)tantalum (PEMAT), zirconium tetradimethylamino(Zr(NMe2)4), hafnium tert-butoxide (Hf(tOBu)4), xenon difluoride (XeF2), xenon tetrafluoride (XeF4), xenon hexafluoride (XeF6), or any combination thereof.

[0052] In some embodiments, the precursor comprises at least one of the following: decaborane, hafnium tetrachloride, zirconium tetrachloride, indium trichloride, organometallic β-diketone complex, tungsten hexafluoride, cyclopentadienylcycloheptadienyl-titanium (CpTiCht), aluminum trichloride, titanium iodide, cyclooctatetraenylcyclopentadienyltitanium, dicyclopentadienyltitanium diazide, trimethylgallium, trimethylindium, alkylaluminum (such as trimethylaluminum, triethylaluminum), trimethylamine aluminum hydride, dimethylzinc, tetramethyltin, trimethylantimony, diethylcadmium, carbonyltungsten, or any combination thereof.

[0053] In some embodiments, the precursor comprises at least one of an elemental metal, a metal halide, a metal oxyhalide, an organometallic complex, or any combination thereof. For example, in some embodiments, the precursor comprises at least one of the following: elemental boron, copper, phosphorus, decaborane, gallium halide, indium halide, antimony halide, arsenic halide, gallium halide, aluminum iodide, titanium iodide, MoO2Cl2, MoOCl4, MoCl5, WCl5, WOCl4, WCl6, cyclopentadienylcycloheptadienyl titanium (CpTiCht), cyclooctatetraenylcyclopentadienyl titanium, dicyclopentadienyl titanium diazide, In(CH3)2(hfac), dibromomethyl tungsten, carbonyl tungsten, organometallic β-diketone complexes, organometallic alkanolate complexes, organometallic carboxylate complexes, organometallic aryl complexes, organometallic amide complexes, or any combination thereof.

[0054] In some embodiments, the precursor comprises at least one of any type of source material that can be liquefied by heating or dissolving in a solvent, including (for example, but not limited to) decaborane (B 10 H 14 ), pentaborane (B5H9), octadecborane (B 18 H 22 The precursor comprises at least one of boric acid (H3BO3), SbCl3, SbCl5, or any combination thereof. In some embodiments, the precursor comprises at least one of the following: AsCl3, AsBr3, AsF3, AsF5, AsH3, As4O6, As2Se3m, As2S2, As2S3, As2S5, As2Te3, B4H 11 B4H 10 , B3H6N3, BBr3, BCl3, BF3, BF3.O(C2H5)2, BF3.HOCH3, B2H6, F2, HF, GeBr4, GeCl4, Ge F4, GeH4, H2, HCl, H2Se, H2Te, H2S, WF6, SiH4, SiH2Cl2, SiHCl3, SiCl4, SiH3Cl, NH3, N H3, Ar, Br2, HBr, BrF5, CO2, CO, COCl2, COF2, Cl2, ClF3, CF4, C2F6, C3F8, C4F8, C5F8, CHF3, CH2F2, CH3F, CH4, SiH6, He, HCN, Kr, Ne, Ni(CO)4, HNO3, NO, N2, NO2, NF3, N2O, C8H 24 O4Si4, PH3, POCl3, PCl5, PF3, PFS, SbH3, SO2, SF6, SF4, Si(OC2H5)4, C4H16Si4O4, Si(CH3)4, SiH(CH3)3, TiCl4, Xe, SiF4, WOF4, TaBr5, TaCl5, TaF5, Sb(C2H5)3, Sb(CH3)3, In(CH3)3, PBr5, PBr3, RuF5, or any combination thereof.

[0055] The at least one co-reactant precursor may include at least one of an oxidizing gas, a reducing gas, a hydrocarbon, or any combination thereof. The at least one co-reactant precursor may be selected to obtain the desired membrane. In some embodiments, the at least one co-reactant precursor includes at least one of the following: 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, its free radical, or any combination thereof. In some embodiments, the at least one co-reactant precursor includes at least one of the following: H2, O2, O3, H2O, H2O2, NO, N2O, NO2, CO, CO2, carboxylic acid, alcohol, diol, its free radical, or any combination thereof. In some embodiments, the at least one co-reactant precursor comprises at least one of methane, ethane, ethylene, acetylene, or any combination thereof. The obtaining process may include obtaining a container or other container containing the at least one co-reactant precursor. In some embodiments, the at least one co-reactant precursor may be obtained in the container or other container in which the at least one co-reactant precursor is to be vaporized. In some embodiments, the method further comprises an inert gas, for example, at least one of argon, helium, nitrogen, or any combination thereof.

[0056] Figure 2 This is a schematic cross-sectional view of a device 200 according to some embodiments. Figure 2 As shown, the device 200 includes a substrate 202. In some embodiments, the substrate 202 has a first surface 204 and a second surface 206. In some embodiments, an Al inhibitor 208 is deposited on the first surface 204. In some embodiments, a film 210 is deposited on the second surface 206. In some embodiments, the film 210 is not deposited on the first surface 204.

[0057] Some embodiments relate to a composition. In some embodiments, the composition comprises an Al-containing inhibitor compound. In some embodiments, the Al-containing inhibitor compound comprises a compound of the following formula:

[0058] ,

[0059] in:

[0060] Q includes cyclopentadienyl or indenyl; and

[0061] R independently includes alkyl groups.

[0062] In some embodiments, the cyclopentadienyl group comprises a substituted cyclopentadienyl group. In some embodiments, the substituted cyclopentadienyl group comprises at least one of an alkylcyclopentadienyl group, a fluorinated cyclopentadienyl group, or any combination thereof.

[0063] In some embodiments, the cyclopentadienyl group comprises an unsubstituted cyclopentadienyl group.

[0064] In some embodiments, the indenyl group comprises a substituted indenyl group. In some embodiments, the substituted indenyl group comprises at least one of an alkyl indenyl group, a fluorinated indenyl group, or any combination thereof.

[0065] In some embodiments, the indenyl group comprises an unsubstituted indenyl group.

[0066] In some embodiments, the Al-containing inhibitor compound comprises a cyclopentadienyl group and a C1-C5 alkyl group. In some embodiments, the Al-containing inhibitor compound comprises a substituted cyclopentadienyl group and a C1-C5 alkyl group. In some embodiments, the Al-containing inhibitor compound comprises an alkylcyclopentadienyl group and a C1-C5 alkyl group. In some embodiments, the Al-containing inhibitor compound comprises a fluorinated cyclopentadienyl group and a C1-C5 alkyl group. In some embodiments, the Al-containing inhibitor compound comprises an unsubstituted cyclopentadienyl group and a C1-C5 alkyl group.

[0067] In some embodiments, the Al-containing inhibitor compound comprises an indenyl group and a C1-C5 alkyl group. In some embodiments, the Al-containing inhibitor compound comprises a substituted indenyl group and a C1-C5 alkyl group. In some embodiments, the Al-containing inhibitor compound comprises an alkyl indenyl group and a C1-C5 alkyl group. In some embodiments, the Al-containing inhibitor compound comprises a fluorinated indenyl group and a C1-C5 alkyl group. In some embodiments, the Al-containing inhibitor compound comprises an unsubstituted indenyl group and a C1-C5 alkyl group.

[0068] In some embodiments, the Al-containing inhibitor compound includes compounds of the following formula:

[0069] .

[0070] In some embodiments, the Al-containing inhibitor compound is present in the composition with a purity of at least 95%. In some embodiments, the Al-containing inhibitor compound is present in the composition with a purity of 95% to 99.9999%, 95% to 99.99%, 95% to 99.9%, 95% to 99%, 95% to 98%, 95% to 97%, 95% to 96%, 96% to 99.9999%, 97% to 99.9999%, 98% to 99.9999%, 99% to 99.9999%, 99.9% to 99.9999%, 99.99% to 99.9999%, 99.99% to 99.9999%, or any range or subrange between 95% and 99.9999%.

[0071] Without departing from the scope or spirit of this disclosure, any or more of the embodiments disclosed herein should be understood as composable.

[0072] Example

[0073] Figure 3 This is a schematic diagram of a selective deposition method according to some embodiments. Figure 3 As shown, a substrate 302 having a first surface 304 and a second surface 306 is exposed to an aluminum-containing inhibitor compound 308 of the following formula:

[0074] .

[0075] The first surface 304 has exposed hydroxyl groups 310, while the second surface 306 does not have any exposed hydroxyl groups. After exposing the substrate 302 to the aluminum-containing inhibitor compound 308, the hydroxyl groups 310 on the first surface 304 react with the aluminum-containing inhibitor compound 308 to form the inhibited surface 312.

[0076] aspect

[0077] The following describes various aspects. It should be understood that any one or more of the features detailed in the following aspects may be combined with any or more other aspects.

[0078] Aspect 1. A method comprising:

[0079] Obtain a substrate having a first surface and a second surface;

[0080] The substrate is exposed to an Al inhibitor to modify the first surface.

[0081] The Al-containing inhibitor is a compound comprising substituted alkyl aluminum; and

[0082] A film is selectively deposited on the second surface.

[0083] Aspect 2. The method according to aspect 1, wherein the first surface has hydroxyl groups and wherein the second surface does not have hydroxyl groups.

[0084] Aspect 3. The method according to any one of aspects 1 to 2, wherein the exposure comprises reacting the Al-containing inhibitor with hydroxyl groups on the first surface.

[0085] Aspect 4. The method according to any one of aspects 1 to 2, wherein the exposure does not include reacting the Al-containing inhibitor with the second surface.

[0086] Aspect 5. The method according to any one of aspects 1 to 4, further comprising forming hydroxyl groups on the first surface of the substrate prior to the exposure step.

[0087] Aspect 6. The method according to any one of aspects 1 to 5, wherein the Al-containing inhibitor comprises a compound of the following formula:

[0088] ,

[0089] in:

[0090] Q is cyclopentadienyl or indenyl; and

[0091] R is independently an alkyl group.

[0092] Aspect 7. The method according to aspect 6, wherein the cyclopentadienyl group comprises a substituted cyclopentadienyl group.

[0093] Aspect 8. The method according to aspect 7, wherein the substituted cyclopentadienyl group comprises at least one of alkylcyclopentadienyl, fluorinated cyclopentadienyl, or any combination thereof.

[0094] Aspect 9. The method according to aspect 6, wherein the indenyl group comprises a substituted indenyl group.

[0095] Aspect 10. The method according to aspect 9, wherein the substituted indenyl group comprises at least one of alkyl indenyl, fluorinated indenyl, or any combination thereof.

[0096] Aspect 11. The method according to aspect 6, wherein the cyclopentadienyl group comprises an unsubstituted cyclopentadienyl group or an unsubstituted indenyl group.

[0097] Aspect 12. The method according to aspect 6, wherein the alkyl group comprises C1-C5 alkyl groups.

[0098] Aspect 13. The method according to any one of aspects 1 to 12, wherein the Al-containing inhibitor comprises a compound of the following formula:

[0099] .

[0100] Aspect 14. The method according to any one of aspects 1 to 13, wherein selective deposition of the film does not include deposition of the film on the first surface.

[0101] Aspect 15. A composition comprising:

[0102] Al-containing inhibitors, including compounds of the following formula:

[0103] ,

[0104] in:

[0105] Q is cyclopentadienyl or indenyl; and

[0106] R is independently an alkyl group;

[0107] When the Al-containing inhibitor is exposed to a substrate having a first surface containing hydroxyl groups and a second surface not containing hydroxyl groups, the Al-containing inhibitor sufficiently modifies the first surface to selectively deposit a film on the second surface.

[0108] Aspect 16. The composition according to aspect 15, wherein the cyclopentadienyl group comprises a substituted cyclopentadienyl group or a substituted indenyl group.

[0109] Aspect 17. The composition according to aspect 16, wherein the substituted cyclopentadienyl group comprises at least one of alkylcyclopentadienyl, fluorinated cyclopentadienyl, or any combination thereof.

[0110] Aspect 18. The composition according to aspect 16, wherein the substituted indenyl group comprises at least one of alkyl indenyl, fluorinated indenyl, or any combination thereof.

[0111] Aspect 19. The composition according to any one of aspects 15 to 18, wherein the alkyl group comprises C1-C5 alkyl groups.

[0112] Aspect 20. The composition according to any one of aspects 15 to 19, wherein the Al-containing inhibitor comprises a compound of the following formula:

[0113] .

[0114] Aspect 21. An apparatus comprising:

[0115] membrane;

[0116] Contains Al inhibitors; and

[0117] Substrate having at least a first surface and a second surface

[0118] The Al-containing inhibitor is deposited on the first surface;

[0119] The film is not deposited on the first surface;

[0120] The film is deposited on the second surface.

Claims

1. A method comprising: Obtain a substrate having a first surface and a second surface; The substrate is exposed to an Al inhibitor to modify the first surface. The Al-containing inhibitor is a compound comprising substituted alkyl aluminum; and A film is selectively deposited on the second surface.

2. The method of claim 1, wherein the first surface has hydroxyl groups and wherein the second surface does not have hydroxyl groups.

3. The method of claim 2, wherein the exposure comprises reacting the Al-containing inhibitor with hydroxyl groups on the first surface.

4. The method of claim 2, wherein the exposure does not include reacting the Al-containing inhibitor with the second surface.

5. The method of claim 1, further comprising forming hydroxyl groups on the first surface of the substrate prior to the exposure step.

6. The method of claim 1, wherein the Al-containing inhibitor comprises a compound of the following formula: ， in: Q is cyclopentadienyl or indenyl; and R is independently an alkyl group.

7. The method of claim 6, wherein the cyclopentadienyl group comprises a substituted cyclopentadienyl group.

8. The method of claim 7, wherein the substituted cyclopentadienyl group comprises at least one of alkylcyclopentadienyl, fluorinated cyclopentadienyl, or any combination thereof.

9. The method of claim 6, wherein the indenyl group comprises a substituted indenyl group.

10. The method of claim 9, wherein the substituted indenyl group comprises at least one of alkyl indenyl, fluorinated indenyl, or any combination thereof.

11. The method of claim 6, wherein the cyclopentadienyl group comprises an unsubstituted cyclopentadienyl group or an unsubstituted indenyl group.

12. The method of claim 6, wherein the alkyl group comprises C1-C5 alkyl groups.

13. The method of claim 1, wherein the Al-containing inhibitor comprises a compound of the following formula: 。 14. The method of claim 1, wherein selective deposition of the film does not include depositing the film on the first surface.

15. A composition comprising: Al-containing inhibitors, including compounds of the following formula: ， in: Q is cyclopentadienyl or indenyl; and R is independently an alkyl group; When the Al-containing inhibitor is exposed to a substrate having a first surface containing hydroxyl groups and a second surface not containing hydroxyl groups, the Al-containing inhibitor sufficiently modifies the first surface to selectively deposit a film on the second surface.

16. The composition of claim 15, wherein the cyclopentadienyl group comprises a substituted cyclopentadienyl group or a substituted indenyl group.

17. The composition of claim 16, wherein the substituted cyclopentadienyl group comprises at least one of alkylcyclopentadienyl, fluorinated cyclopentadienyl, or any combination thereof.

18. The composition of claim 16, wherein the substituted indenyl group comprises at least one of alkyl indenyl, fluorinated indenyl, or any combination thereof.

19. The composition according to claim 15, wherein the Al-containing inhibitor comprises a compound of the following formula: 。 20. An apparatus comprising: membrane; Contains Al inhibitors; and A substrate having at least a first surface and a second surface, The Al-containing inhibitor is deposited on the first surface; The film is not deposited on the first surface; The film is deposited on the second surface.

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