Selective ruthenium deposition and related systems and methods

Abstract

Selective ruthenium deposition and related systems and methods are provided. The method includes vaporizing at least a portion of a ruthenium precursor to generate a vaporized ruthenium precursor; contacting a first surface portion and a second surface portion of a substrate with the vaporized ruthenium precursor and at least one reducing gas; and depositing ruthenium on the first surface portion of the substrate with a selectivity of at least 25 Å over the second surface portion of the substrate. The device includes a substrate having a first surface portion and a second surface portion adjacent to the first surface portion, and a ruthenium layer located on the first surface portion of the substrate, wherein the ruthenium layer has a thickness of at least 25 Å on the first surface portion of the substrate, and the second surface portion of the substrate is ruthenium-free.

Description

[Technical Field]

[0001]

[0001] This disclosure relates to the selective deposition of ruthenium and related systems and methods.

[0002] Cross-reference with related applications

[0002] This application claims the benefits pursuant to U.S. Provisional Patent Application No. 63 / 472,158, filed on 9 June 2023, 35 U.S.C. 119, the disclosures thereof of which are incorporated herein by reference in their entirety. [Background technology]

[0003]

[0003] Conventional processes for depositing ruthenium films require multiple steps. Furthermore, conventional processes use O2 as a co-reactant to deposit ruthenium, but this is undesirable because the O2 oxidizes the substrate during the deposition process. Depositing ruthenium with high selectivity remains an ongoing challenge. [Overview of the project]

[0004]

[0004] Several embodiments relate to methods for selective deposition of ruthenium. In some embodiments, the method for selective deposition of ruthenium includes vaporizing at least a portion of a ruthenium precursor to produce a vaporized ruthenium precursor. In some embodiments, the method for selective deposition of ruthenium includes contacting a first surface portion and a second surface portion of a substrate with the vaporized ruthenium precursor and at least one reducing gas. In some embodiments, the method for selective deposition of ruthenium includes depositing ruthenium on the first surface portion of the substrate with a selectivity of at least 25 Å relative to the second surface portion of the substrate.

[0005]

[0005] Some embodiments relate to a device. In some embodiments, the device includes a substrate. In some embodiments, the substrate has a first surface portion and a second surface portion adjacent to the first surface portion. In some embodiments, the device includes a ruthenium layer located on the first surface portion of the substrate. In some embodiments, the ruthenium layer has a thickness of at least 25 Å on the first surface portion of the substrate. In some embodiments, the second surface portion of the substrate does not contain ruthenium.

[0006]

[0006] In this disclosure, several embodiments of the disclosure will be described only as examples, with reference to the accompanying drawings. A detailed reference to the drawings will emphasize that the embodiments shown are illustrative and intended to illustrate the embodiments of the disclosure. In this regard, a description in conjunction with the drawings will make it clear to those skilled in the art how embodiments of the disclosure can be carried out. [Brief explanation of the drawing]

[0007] [Figure 1]

[0007] Figure 1 is a flowchart of a method for manufacturing a ruthenium-containing film 100 according to several embodiments. [Figure 2]

[0008] Figure 2 is a graph showing the relationship between ruthenium film thickness and atomic layer deposition cycle in several embodiments. [Figure 3]

[0009] Figure 3 is a graph showing the relationship between ruthenium film thickness and atomic layer deposition cycle in several embodiments. [Figure 4]

[0010] Figure 4 is a graph showing the relationship between ruthenium film thickness and atomic layer deposition cycle in several embodiments. [Modes for carrying out the invention]

[0008]

[0011] Of the advantages and improvements disclosed, other objects and advantages of the present disclosure will become apparent from the following description when taken in conjunction with the accompanying drawings. Although detailed embodiments of the present disclosure are disclosed herein, it should be understood that the disclosed embodiments are merely illustrative of the present disclosure which can be implemented in various forms. Further, each example presented with respect to the various embodiments of the present disclosure is for illustrative purposes and not for purposes of limitation.

[0009]

[0012] The conventional patents and publications referred to herein are incorporated by reference in their entirety.

[0010]

[0013] Throughout this specification and the claims, unless the context clearly dictates otherwise, the following terms have the meanings explicitly associated with them herein. As used herein, the phrases "in one embodiment," "in an embodiment," and "in some embodiments" do not necessarily refer to the same embodiment, although they may. Further, the phrases "in another embodiment" and "in some other embodiments" as used herein do not necessarily refer to different embodiments, although they may. It is intended that all embodiments of the present disclosure be combinable without departing from the scope or spirit of the present disclosure.

[0011]

[0014] As used herein, the term "based on" is not exclusive and allows for being based on additional factors not recited, unless the context clearly dictates otherwise. Further, throughout this specification, the meanings of "a," "an," and "the" include plural references. The meaning of "in" includes "in" and "on."

[0012]

[0015] As used herein, the term "alkyl" refers to a hydrocarbon compound having from 1 to 30 carbon atoms. An alkyl having n carbon atoms is "C" nIt may be denoted as "alkyl". For example, "C3 alkyl" may include n-propyl and isopropyl. Alkyl having a certain range of carbon atoms such as 1 to 30 carbon atoms is C1~C 30 It may be designated as alkyl. In some embodiments, the alkyl is linear. In some embodiments, the alkyl is branched. In some embodiments, the alkyl is substituted. In some embodiments, the alkyl is unsubstituted. In some embodiments, the alkyl is 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 10 alkyl, C2~C9 alkyl, C2~C8 alkyl, C2~C7 alkyl, C2~C6 alkyl, C2~C5 alkyl, C3~C5 alkyl, or at least one of any combination thereof, or is selected from the group consisting of them. In some embodiments, the alkyl is methyl, ethyl, n-propyl, 1-methylethyl (isopropyl), n-butyl, isobutyl, sec-butyl, n-pentyl, 1,1-dimethylethyl (t-butyl), n-pentyl, isopentyl, n-hexyl, isohexyl, 3-methylhexyl, 2-methylhexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, or at least one of any combination thereof, or is selected from the group consisting of it.

[0013]

[0016] Some embodiments relate to depositing ruthenium on a substrate with high selectivity. In some embodiments, ruthenium is selectively deposited as a thin film on the surface of a substrate by an atomic layer deposition process, such as plasma atomic layer deposition, thermal atomic layer deposition, etc., for example. At least one advantage of the embodiments disclosed herein is that ruthenium can be deposited on a desired surface with selectivity of up to 80 Å. At least another advantage of the embodiments disclosed herein is that the deposition process is oxygen-free or substantially oxygen-free. At least a further advantage of the embodiments disclosed herein is that the ruthenium is deposited at a temperature of 450°C or less. At least one additional advantage of the embodiments disclosed herein is that the ruthenium is selectively deposited on surfaces other than, for example, silicon oxides, thermal oxides, silicon nitrides, SiCOH, low dielectric constant dielectrics, porous low dielectric constant dielectrics, and / or polysilicon. These are not limiting, and other advantages of the embodiments disclosed herein will become apparent by examining this disclosure.

[0014]

[0017] As used herein, the term "selectivity," when described in terms of thickness (e.g., thickness in Å units), refers to the maximum thickness of a material on a first surface before it is deposited on any surface other than the first surface. For example, depositing ruthenium on a first surface of a substrate with a selectivity of 80 Å means that once the thickness of ruthenium on the first surface of the substrate exceeds 80 Å, the ruthenium begins to deposit on surfaces other than the first surface (e.g., a second surface).

[0015]

[0018] As used herein, the term “substantially absent” means that the weight or volume of the substance is 5% or less, based on the total weight or total volume. In some embodiments, the term “substantially absent” means that the weight or volume of the substance is 4% or less, 3% or less, 2% or less, 1% or less, 0.9% or less, 0.8% or less, 0.7% or less, 0.6% or less, 0.5% or less, 0.4% or less, 0.3% or less, 0.2% or less, or 0.1% or less, based on the total weight or total volume. In some embodiments, the term “substantially absent” refers to an amount that cannot be detected using standard instruments (e.g., an undetectable amount). As used herein, the term “free” refers to an amount of substance that is not present.

[0016]

[0019] Figure 1 is a flowchart of a method for fabricating a ruthenium-containing film 100 according to several embodiments. As shown in Figure 1, a method for fabricating a ruthenium-containing film 100 includes one or more of the following steps: vaporizing at least a portion of a ruthenium precursor to generate a vaporized ruthenium precursor 102; contacting a first surface portion and a second surface portion of a substrate with the vaporized ruthenium precursor and at least one reducing gas 104; and depositing ruthenium on the first surface portion of the substrate with a selectivity of at least 25 Å relative to the second surface portion of the substrate 106. In some embodiments, the method for fabricating the ruthenium-containing film 100 is an atomic layer deposition (ALD) process. In some embodiments, the method for fabricating the ruthenium-containing film 100 is a plasma-enhanced atomic layer deposition (PEALD) process. In some embodiments, the method for fabricating the ruthenium-containing film 100 is a thermal atomic layer deposition (thermal ALD) process.

[0017]

[0020] A method for producing a ruthenium-containing film 100 may include vaporizing at least a portion of the ruthenium precursor 102 in order to generate a vaporized ruthenium precursor.

[0018]

[0021] In some embodiments, vaporization may include heating the ruthenium precursor to a degree sufficient to obtain a vaporized ruthenium precursor. In some embodiments, vaporization may include heating a vessel containing the ruthenium precursor. In some embodiments, the ruthenium precursor exists in at least one of the following states: liquid phase, gas phase, vapor phase, solid phase, or any combination thereof. In some embodiments, vaporization may include heating the ruthenium precursor in a deposition chamber in which a deposition process is carried out. In some embodiments, vaporization may include heating a conduit for supplying the ruthenium precursor, the vaporized ruthenium precursor, or any combination thereof to the deposition chamber, for example. In some embodiments, vaporization may include operating a vapor supply system containing the ruthenium precursor. In some embodiments, vaporization may include heating the ruthenium precursor to a temperature sufficient to vaporize it and obtain a vaporized ruthenium precursor. In some embodiments, vaporization may include heating to a temperature below the decomposition temperature of at least one of the ruthenium precursor, the vaporized ruthenium precursor, or any combination thereof. In some embodiments, the ruthenium precursor may exist in the gas phase, in which case step 102 is optional and not required. For example, the ruthenium precursor may include a vaporized ruthenium precursor.

[0019]

[0022] In some embodiments, the ruthenium precursor is a precursor of the following formula. R 1 R 2 Ru(0)

[0020]

[0023] In the formula, R 1 R is a ligand containing a benzene or aryl group, 2 It is a diene group-containing ligand.

[0021]

[0024] As used herein, “aryl group-containing ligands” comprise at least one aromatic ring and one or more hydrocarbon substituents bonded to the aromatic ring. For example, in some embodiments, the aryl group-containing ligand may be a fused ring structure such as a monoalkylbenzene, dialkylbenzene, or trialkylbenzene, or indan and / or tetrahydronaphthalene (e.g., benzocyclohexane, tetralin).

[0022]

[0025] In this specification, a “diene group-containing ligand” is a compound containing at least two carbon-carbon double bonds separated by at least one carbon-carbon single bond, and may include conjugated dienes and unconjugated dienes. Diene group-containing ligands may optionally contain two or more carbon-carbon double bonds, such as trienes. Diene group-containing ligands include linear compounds and cyclic compounds. Cyclic diene group-containing ligands may have a single ring structure, such as cyclohexadiene, cyclohexadiene, or alkylated derivatives thereof, or they may have a fused ring structure, such as hexahydronaphthalene, tetrahydroindene, dicyclopentadiene, or norbornadiene.

[0023]

[0026] For example, in some embodiments, R 1 This includes at least one of toluene, xylene, ethylbenzene, cumene, cymene, or any combination thereof. In embodiments, R 2 This includes a cyclic non-conjugated diene or a linear non-conjugated diene. In some embodiments, R 2 is a cyclohexadiene or alkylcyclohexadiene. In some embodiments, R 2 This comprises at least one of cyclohexadiene, methylcyclohexadiene, ethylcyclohexadiene, propylcyclohexadiene, or any combination thereof.

[0024]

[0027] In some embodiments, the ruthenium precursor comprises the compound of formula II: TIFF2026521487000002.tif79170

[0028] During the ceremony,

[0029] R 3 ~R 8 Each of these is independently either water or a C1-C6 alkyl group.

[0030] R 9 This is a covalent bond or a divalent alkene group of 1 to 4 carbon atoms.

[0031] R 10 and R 11 These may form one or more ring structures, each independently being hydrogen or a C1-C6 alkyl group. In some embodiments, R 3 ~R 8 One, two, or three of are selected from C1-C6 alkyl or C1-C3 alkyl, and the remaining R3-R8 are hydrogen. In some embodiments, R 9 It is a covalent bond, R 10 and R 11 It forms one or more ring structures.

[0025]

[0032] In some embodiments, formula R 1 and R 2 The ruthenium precursor does not contain heteroatoms (i.e., atoms other than carbon or hydrogen). For example, in some embodiments, R 1 and R 2 It can be composed of carbon and hydrogen. In some embodiments, formula R 1 R 2 Ru(0) compounds can also be described by their degree of unsaturation, their total carbon atom content, their total hydrogen content, or a combination thereof.

[0026]

[0033] In some embodiments, formula R 1 R 2 The ruthenium precursor of Ru(0) can have a total carbon content in the range of (a1) 12-20, (a2) 14-18, or (a3) ​​15-17. In some embodiments, the ruthenium precursor has a total carbon content of (a4) 16. Formula R 1 R 2The ruthenium precursor of Ru(0) may also have a total hydrogen atom weight in the range of (b1) 16-28, (b2) 19-25, or (b3) 20-24. In some embodiments, the ruthenium precursor has a total hydrogen atom weight of 22. In some embodiments, the ruthenium precursor may have a total carbon and total hydrogen weight of (a1) and (b1), (a2) and (b2), or (a3) ​​and (b3).

[0027]

[0034] In some embodiments, the ruthenium precursor is (cymene)(1,3-cyclohexadiene)Ru(0), (cymene)(1,4-cyclohexadiene)Ru(0), (cymene)(1-methylcyclohexa-1,3-diene)Ru(0), (cymene)(2-methylcyclohexa-1,3-diene)Ru(0), (cymene)(3-methylcyclohexa-1,3-diene)Ru(0), (cymene)(4-methylcyclohexa-1,3-diene)Ru(0), (cymene)(5-methylcyclohexa-1,3-diene)Ru(0), (cymene)(6- (Cymene)(1-methylcyclohexa-1,3-diene)Ru(0), (Cymene)(1-methylcyclohexa-1,4-diene)Ru(0), (Cymene)(2-methylcyclohexa-1,4-diene)Ru(0), (Cymene)(3-methylcyclohexa-1,4-diene)Ru(0), (Cymene)(4-methylcyclohexa-1,4-diene)Ru(0), (Cymene)(5-methylcyclohexa-1,4-diene)Ru(0), (Cymene)(6-methylcyclohexa-1,4-diene)Ru(0), or at least one of any combination thereof. Cymene is also known as 1-methyl-4-(propan-2-yl)benzene or 1-isopropyl-4-methylbenzene.

[0028]

[0035] In some embodiments, the ruthenium precursor is (benzene)(1,3-cyclohexadiene)Ru(0), (toluene)(1,3-cyclohexadiene)Ru(0), (ethylbenzene)(1,3-cyclohexadiene)Ru(0), (1,2-xylene)(1,3-cyclohexadiene)Ru(0), (1,3-xylene)(1,3-cyclohexadiene)Ru(0), (1,4-xylene)(1,3-cyclohexadiene)Ru(0), (p-cymene)(1,3-cy (Crohexadiene)Ru(0), (o-Cymene)(1,3-Cyclohexadiene)Ru(0), (m-Cymene)(1,3-Cyclohexadiene)Ru(0), (Cumene)(1,3-Cyclohexadiene)Ru(0), (n-Propylbenzene)(1,3-Cyclohexadiene)Ru(0), (m-Ethyltoluene)(1,3-Cyclohexadiene)Ru(0), (p-Ethyltoluene)(1,3-Cyclohexadiene)Ru(0), (o-Ethyltoluene)(1,3-Cyclohexadiene (Sadiene)Ru(0), (1,3,5-trimethylbenzene)(1,3-cyclohexadiene)Ru(0), (1,2,3-trimethylbenzene)(1,3-cyclohexadiene)Ru(0), (tert-butylbenzene)(1,3-cyclohexadiene)Ru(0), (isobutylbenzene)(1,3-cyclohexadiene)Ru(0), (sec-butylbenzene)(1,3-cyclohexadiene)Ru(0), (indan)(1,3-cyclohexadiene)Ru(0) This includes at least one of the following: (1,2-diethylbenzene)(1,3-cyclohexadiene)Ru(0), (1,3-diethylbenzene)(1,3-cyclohexadiene)Ru(0), (1,4-diethylbenzene)(1,3-cyclohexadiene)Ru(0), (1-methyl-4-propylbenzene)(1,3-cyclohexadiene)Ru(0), (1,4-dimethyl-2-ethylbenzene)(1,3-cyclohexadiene)Ru(0), or any combination thereof.

[0029]

[0036] In some embodiments, the ruthenium precursor includes at least one of the following: TIFF2026521487000003.tif186170

[0037] Any combination of those.

[0030]

[0038] In some embodiments, the ruthenium precursor may also be described with reference to the melting and / or boiling point of the compound. In some embodiments, the ruthenium precursor is liquid at room temperature (25°C). In some embodiments, the ruthenium precursor may have a boiling point in the temperature range of about 100°C to about 175°C, or about 120°C to about 150°C.

[0031]

[0039] In some embodiments, when the ruthenium precursor of formula I is in liquid form at room temperature (25°C), it can be described in terms of its vapor pressure. The vapor pressure of a liquid is the equilibrium pressure of the vapor above the liquid. The vapor pressure is produced by the vaporization of the liquid, measured in a sealed container at a specific temperature. For example, the precursor may have a vapor pressure of at least about 0.01 Torr, or at least about 0.05 Torr, for example, in the range of about 0.05 Torr to about 0.50 Torr, or in the range of about 0.1 Torr to about 0.30 Torr, at 100°C.

[0032]

[0040] In some embodiments, ruthenium precursors are produced by reacting a ruthenium-containing reactant, such as a ruthenium salt hydrate, with a first hydrocarbon-containing ligand (R1) to form an intermediate, and then reacting this intermediate with a second hydrocarbon-containing ligand (R2) to form the final product. For example, (6-1-isopropyl-4-methylbenzene)-(4-cyclohexa-1,3-diene)Ru(0)(IMBCHRu) can be produced by preparing an ethanol solution of ruthenium trichloride hydrate and α-terpene, refluxing for 5 hours to form a microcrystalline product of m-chloro-bis(chloro(1-isopropyl-4-methylbenzene)ruthenium(II)), drying this product, and then adding it to an ethanol solution containing Na2CO3 and 1,3-cyclohexadiene, and refluxing for 4.5 hours.

[0033]

[0041] A method for producing a ruthenium-containing film 100 may include vaporizing at least a portion of at least one reducing agent to produce at least one reducing gas.

[0034]

[0042] In some embodiments, vaporization may include heating at least one reducing agent to a degree sufficient to obtain at least one reducing gas. In some embodiments, vaporization may include heating a container containing at least one reducing agent. In some embodiments, vaporization may include heating at least one reducing agent within a deposition chamber in which the deposition process is carried out. In some embodiments, vaporization may include heating a conduit for supplying at least one reducing agent, at least one reducing gas, or any combination thereof, to, for example, the deposition chamber. In some embodiments, vaporization may include operating a vapor supply system containing at least one reducing agent. In some embodiments, vaporization may include heating at least one reducing agent to a temperature sufficient to vaporize it and obtain at least one reducing gas. In some embodiments, vaporization may include heating at least one reducing agent, at least one reducing gas, or any combination thereof to a temperature below the decomposition temperature of at least one of them. In some embodiments, at least one reducing agent may be present in the gas phase, in which case this step is optional and not required. For example, at least one reducing agent may contain at least one reducing gas.

[0035]

[0043] A desired ruthenium-containing film can be obtained by selecting at least one reducing agent, at least one reducing gas, or any combination thereof. In some embodiments, the at least one reducing agent, at least one reducing gas, or any combination thereof may include at least one 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 radicals, or any combination thereof. In some embodiments, the method for producing the ruthenium-containing film does not involve the use of oxygen. In some embodiments, the at least one reducing agent, at least one reducing gas, or any combination thereof does not contain oxygen. For example, in some embodiments, at least one reducing agent, at least one reducing gas, or any combination thereof does not include at least one of H2, O2, O3, H2O, H2O2, NO, N2O, NO2, CO, CO2, carboxylic acids, alcohols, diols, their radicals, or any combination thereof. In some embodiments, at least one reducing agent, at least one reducing gas, or any combination thereof is present in a container or other container. At least one reducing agent, at least one reducing gas, or any combination thereof may exist as a solid, liquid, gas, vapor, or any combination thereof.

[0036]

[0044] A method for producing a ruthenium-containing film 100 may include contacting a first surface portion and a second surface portion of a substrate with a vaporized ruthenium precursor and at least one reducing gas 104.

[0037]

[0045] In some embodiments, contact involves bringing at least one of a vaporized ruthenium precursor, at least one reducing gas, or any combination thereof, into contact with the substrate under deposition conditions sufficient to form a ruthenium-containing film on a selected surface of the substrate. Contact can be performed in any system, apparatus, device, assembly, its chamber, or its components (e.g., a deposition chamber, etc.) suitable for the deposition process. In some embodiments, the method further includes bringing at least one inert gas into contact with the substrate. In some embodiments, the at least one inert gas includes at least one of argon, helium, nitrogen, or any combination thereof.

[0038]

[0046] In some embodiments, contact includes bringing at least one of the vaporized ruthenium precursor, at least one reducing gas, at least one inert gas, or any combination thereof, to the immediate vicinity of the first and second surface portions of the substrate. In some embodiments, contact includes bringing at least one of the vaporized ruthenium precursor, at least one reducing gas, at least one inert gas, or any combination thereof, into direct contact with the first and second surface portions of the substrate. In some embodiments, contact includes introducing at least one of the vaporized ruthenium precursor, at least one reducing gas, at least one inert gas, or any combination thereof, into a chamber containing the substrate. In some embodiments, contact includes pumping at least one of the vaporized ruthenium precursor, at least one reducing gas, at least one inert gas, or any combination thereof, into a chamber containing the substrate. In some embodiments, contact includes injecting at least one of the vaporized ruthenium precursor, at least one reducing gas, at least one inert gas, or any combination thereof, into a chamber containing the substrate. In some embodiments, contact involves introducing at least one of a vaporized ruthenium precursor, at least one reducing gas, at least one inert gas, or any combination thereof, into a chamber containing the substrate.

[0039]

[0047] In some embodiments, contact involves mixing at least one of the vaporized ruthenium precursor, at least one reducing gas, at least one inert gas, or any combination thereof, to obtain at least one gas mixture. In some embodiments, for example, at least two of the vaporized ruthenium precursor, at least one reducing gas, and at least one inert gas are mixed and supplied to the deposition chamber via a gas line. In some embodiments, if one of the vaporized ruthenium precursor, at least one reducing gas, or at least one inert gas is not mixed, the unmixed gas and / or vapor species are supplied to the deposition chamber via another gas line. In other embodiments, the vaporized ruthenium precursor is supplied to the deposition chamber via a first gas line. In some embodiments, at least one reducing gas is supplied to the deposition chamber via a second gas line. In some embodiments, at least one inert gas is supplied to the deposition chamber via a third gas line. In some embodiments, the first, second, and third gas lines are different.

[0040]

[0048] The vaporized ruthenium precursor and at least one reducing gas may be in contact with the substrate at different times. For example, each of the vaporized ruthenium precursor and at least one reducing gas may be present in the deposition chamber with the substrate at different times. That is, in some embodiments, contact does not involve simultaneously contacting the vaporized ruthenium precursor and at least one reducing gas with the substrate. In some embodiments, contact may involve alternately and / or sequentially contacting the vaporized ruthenium precursor with the substrate in one or more cycles, followed by contacting the substrate with at least one reducing gas. For example, in some embodiments, contact may include one or more of the following steps: contacting the substrate with the vaporized ruthenium precursor in the deposition chamber; purging the deposition chamber (e.g., by introducing at least one inert gas into the deposition chamber); contacting the substrate with at least one reducing gas in the deposition chamber; and purging the deposition chamber (e.g., by introducing at least one inert gas into the deposition chamber). In some embodiments, a vaporized ruthenium precursor and at least one reducing gas are brought into contact with the substrate simultaneously, either as a gas / vapor mixture or via separate gas lines.

[0041]

[0049] Contact may be performed at the deposition temperature. The deposition temperature may be lower than the thermal decomposition temperature of at least one of the vaporized ruthenium precursor, at least one reducing gas, or any combination thereof. The deposition temperature may be high enough to reduce or avoid condensation of at least one of the vaporized ruthenium precursor, at least one reducing gas, or any combination thereof. In some embodiments, the substrate may be heated to the deposition temperature. In some embodiments, the chamber or other container in which the substrate comes into contact with the vaporized ruthenium precursor and at least one reducing gas is heated to the deposition temperature. In some embodiments, at least one of the vaporized ruthenium precursor, at least one reducing gas, or any combination thereof can be heated to the deposition temperature. The deposition temperature may be 150°C to 450°C, or any range or subrange between 150°C and 450°C. In some embodiments, the deposition temperature may be 150°C to 425°C, 150°C to 400°C, 150°C to 375°C, 150°C to 350°C, 150°C to 325°C, 150°C to 300°C, 150°C to 275°C, 150°C to 250°C, 150°C to 225°C, 150°C to 200°C, 150°C to 175°C, 175°C to 450°C, 200°C to 450°C, 225°C to 450°C, 250°C to 450°C, 275°C to 450°C, 300°C to 450°C, 325°C to 450°C, 350°C to 450°C, 375°C to 450°C, 400°C to 450°C, or 425°C to 450°C.

[0042]

[0050] Contact may be performed at the deposition pressure. In some embodiments, the deposition pressure may include the vapor pressure of at least one of the following: a vaporized ruthenium precursor, at least one reducing gas, or any combination thereof. In some embodiments, the deposition pressure may include the chamber pressure. The deposition pressure may be a pressure of 0.5 Torr to 100 Torr. For example, in some embodiments, the deposition pressure is 1 Torr~100 Torr, 5 Torr~100 Torr, 10 Torr~100 Torr, 15 Torr~100 Torr, 20 Torr~100 Torr, 25 Torr~100 Torr, 30 Torr~100 Torr, 35 Torr~100 Torr, 40 Torr~100 Torr, 45 Torr~100 Torr, 50 Torr~100 Torr, 55 Torr~100 Torr, 60 Torr~100 Torr, 65 Torr~100 Torr, 70 Torr~100 Torr, 75 Torr~100 Torr, 80 Torr~100 Torr, 85 Torr~100 Torr, 90 Torr~100 Torr, 95 Torr~10 The pressure may be 0 Torr, 0.5 Torr to 95 Torr, 0.5 Torr to 90 Torr, 0.5 Torr to 85 Torr, 0.5 Torr to 80 Torr, 0.5 Torr to 75 Torr, 0.5 Torr to 70 Torr, 0.5 Torr to 65 Torr, 0.5 Torr to 60 Torr, 0.5 Torr to 55 Torr, 0.5 Torr to 50 Torr, 0.5 Torr to 45 Torr, 0.5 Torr to 40 Torr, 0.5 Torr to 35 Torr, 0.5 Torr to 30 Torr, 0.5 Torr to 25 Torr, 0.5 Torr to 20 Torr, 0.5 Torr to 15 Torr, 0.5 Torr to 10 Torr, 0.5 Torr to 5 Torr, or 0.5 Torr to 1 Torr.

[0043]

[0051] The first and second surface portions of the substrate may be surface portions of an electronic device. In some embodiments, the electronic device is a partially completed electronic device (e.g., manufacturing / processing of the electronic device has been started but is not yet complete). In some embodiments, the electronic device is a completed electronic device (e.g., manufacturing / processing of the electronic device is complete or at least substantially complete). In some embodiments, the first and second surface portions are surface portions of a gate-all-around transistor. In some embodiments, the ruthenium-containing film is deposited during the manufacturing and / or fabrication of the gate-all-around transistor, so the first and second surface portions of the gate-all-around transistor may be surface portions of an incomplete gate-all-around transistor. That is, in some embodiments, the ruthenium-containing film is deposited on the surface portion of a partially constructed gate-all-around transistor. In some embodiments, the ruthenium-containing film is deposited on the surface portion of a fully constructed gate-all-around transistor. In some embodiments, the gate-all-around transistor, whether partially or fully fabricated, has multiple exposed surfaces (e.g., two exposed surfaces, up to several hundred exposed surfaces), and at least two of the exposed surfaces are formed with different chemical compositions. Therefore, it will be understood that the substrate may have multiple surface portions (e.g., exposed surface portions) in addition to the first and second surface portions.

[0044]

[0052] In some embodiments, the first surface portion and the second surface portion can be any two surfaces of a partially constructed or fully constructed gate-all-around transistor. In some embodiments, the substrate is at least part of the gate-all-around transistor. The first surface portion and the second surface portion can have any spatial arrangement of any two surfaces of the gate-all-around transistor. In some embodiments, the first surface portion and the second surface portion are adjacent to or close to each other. In some embodiments, the first surface portion is adjacent to the second surface portion. In some embodiments, at least one of the first surface portion, the second surface portion, or any combination thereof is a vertical surface portion. In some embodiments, at least one of the first surface portion, the second surface portion, or any combination thereof is a horizontal surface portion. In some embodiments, at least one of the first surface portion, the second surface portion, or any combination thereof is an angled surface portion (e.g., not a vertical surface portion and / or a horizontal surface portion). In some embodiments, the first surface portion of the substrate is the first surface portion of the gate-all-around transistor, and the second surface portion of the substrate is the second surface portion of the gate-all-around transistor.

[0045]

[0053] The first and second surface portions of the substrate may be formed from different substances and / or different materials. In some embodiments, a ruthenium-containing film is deposited on the first surface portion. In some embodiments, the ruthenium-containing film is not deposited on the second surface portion. In some embodiments, the first surface portion of the substrate contains or is formed from at least one of TaN, WCN, WN, TiN, Cu, W, Co, TaN, TiN, Mo, MoN, MoC, MoCN, DHF SiGe, SiGe, or any combination thereof. In some embodiments, the second surface portion of the substrate contains or is formed from SiO2 (e.g., natural silicon oxide), SiN, silicon, DHF silicon, SiCOH, low dielectric constant dielectric, porous low dielectric constant dielectric, or any combination thereof. In some embodiments, the first surface portion of the substrate contains or is formed from TaN, and the second surface portion of the substrate contains or is formed from SiN. In some embodiments, the first surface portion of the substrate includes or is formed from WCN, and the second surface portion of the substrate includes or is formed from SiN. In some embodiments, the first surface portion of the substrate includes or is formed from WN, and the second surface portion of the substrate includes or is formed from SiN. In some embodiments, the first surface portion of the substrate includes or is formed from TiN, and the second surface portion of the substrate includes or is formed from SiN.

[0046]

[0054] In some embodiments, the first surface portion of the substrate contains or is formed from TaN, and the second surface portion of the substrate contains or is formed from SiO2. In some embodiments, the first surface portion of the substrate contains or is formed from WCN, and the second surface portion of the substrate contains or is formed from SiO2. In some embodiments, the first surface portion of the substrate contains or is formed from WN, and the second surface portion of the substrate contains or is formed from SiO2. In some embodiments, the first surface portion of the substrate contains or is formed from TiN, and the second surface portion of the substrate contains or is formed from SiO2.

[0047]

[0055] In some embodiments, the first surface portion of the substrate contains or is formed from Cu, and the second surface portion of the substrate contains or is formed from SiN. In some embodiments, the first surface portion of the substrate contains or is formed from W, and the second surface portion of the substrate contains or is formed from SiN. In some embodiments, the first surface portion of the substrate contains or is formed from Co, and the second surface portion of the substrate contains or is formed from SiN. In some embodiments, the first surface portion of the substrate contains or is formed from TaN, and the second surface portion of the substrate contains or is formed from SiN. In some embodiments, the first surface portion of the substrate contains or is formed from WCN, and the second surface portion of the substrate contains or is formed from SiN. In some embodiments, the first surface portion of the substrate contains or is formed from TiN, and the second surface portion of the substrate contains or is formed from SiN. In some embodiments, the first surface portion of the substrate contains or is formed from Mo, and the second surface portion of the substrate contains or is formed from SiN.

[0048]

[0056] In some embodiments, the first surface portion of the substrate contains or is formed from Cu, and the second surface portion of the substrate contains or is formed from SiO2. In some embodiments, the first surface portion of the substrate contains or is formed from W, and the second surface portion of the substrate contains or is formed from SiO2. In some embodiments, the first surface portion of the substrate contains or is formed from Co, and the second surface portion of the substrate contains or is formed from SiO2. In some embodiments, the first surface portion of the substrate contains or is formed from TaN, and the second surface portion of the substrate contains or is formed from SiO2. In some embodiments, the first surface portion of the substrate contains or is formed from WCN, and the second surface portion of the substrate contains or is formed from SiO2. In some embodiments, the first surface portion of the substrate contains or is formed from TiN, and the second surface portion of the substrate contains or is formed from SiO2. In some embodiments, the first surface portion of the substrate contains or is formed from Mo, and the second surface portion of the substrate contains or is formed from SiO2. In some embodiments, the first surface portion of the substrate is conductive to the second surface portion of the substrate.

[0049]

[0057] In some embodiments, the first surface portion of the substrate contains or is formed from DHF SiGe or SiGe, and the second surface portion of the substrate contains or is formed from polysilicon (e.g., p-doped polysilicon). In some embodiments, the first surface portion of the substrate contains or is formed from DHF SiGe or SiGe, and the second surface portion of the substrate contains or is formed from SiN. In some embodiments, the first surface portion of the substrate contains or is formed from DHF SiGe or SiGe, and the second surface portion of the substrate contains or is formed from SiO2. In some embodiments, the first surface portion of the substrate contains or is formed from DHF SiGe or SiGe, and the second surface portion of the substrate contains or is formed from a thermal oxide. In some embodiments, the thermal oxide is TO xThe formula includes, where x is between 1 and 100. In some embodiments, at least one of the first surface portion, the second surface portion, or any combination thereof is a surface cleaned with dilute hydrofluoric acid (DHF), for example, a 100:1 water:HF solution. For example, in some embodiments, the first surface portion of the substrate contains or is formed from DHF-cleaned SiGe. In some embodiments, the first surface portion of the substrate contains or is formed from DHF-cleaned silicon. In some embodiments, the first surface portion of the substrate contains or is formed from DHF-cleaned polysilicon (e.g., p-doped polysilicon).

[0050]

[0058] In some embodiments, the first and second surface portions are the surface portions of the gate of the gate-all-around transistor. In some embodiments, the first surface portion of the gate includes at least one of TaN, WCN, WN, TiN, or any combination thereof. In some embodiments, the second surface portion of the gate includes at least one of SiO2, SiN, or any combination thereof. In some embodiments, the first and second surface portions are the surface portions of the vias of the gate-all-around transistor. In some embodiments, the first surface portion of the via includes at least one of Cu, W, Co, TaN, WCN, TiN, Mo, MoN, MoC, MoCN, or any combination thereof. In some embodiments, the second surface portion of the via includes at least one of SiN, SiO2, or any combination thereof. In some embodiments, the first and second surface portions are the surface portions of the source and / or drain of the gate-all-around transistor. In some embodiments, the first surface portion of the source and / or drain includes SiGe or DHF SiGe. In some embodiments, the second surface portion of the source and / or drain includes at least one of SiO2, SiN, polysilicon, silicon, polysilicon / silicon, natural silicon oxide, SiCOH, low dielectric constant dielectric, porous low dielectric constant dielectric, or any combination thereof.

[0051]

[0059] In some embodiments, ruthenium is deposited on the first surface portion of the substrate with a selectivity of at least 40 Å relative to the second surface portion of the substrate. In some embodiments, ruthenium is deposited on the first surface portion of the substrate with a selectivity of 25 Å to 80 Å, 25 Å to 75 Å, 25 Å to 70 Å, 25 Å to 65 Å, 25 Å to 60 Å, 25 Å to 55 Å, 25 Å to 50 Å, 25 Å to 45 Å, 40 Å to 80 Å, 40 Å to 75 Å, 40 Å to 70 Å, 40 Å to 65 Å, 40 Å to 60 Å, 40 Å to 55 Å, 40 Å to 50 Å, 40 Å to 45 Å, 45 Å to 80 Å, 50 Å to 80 Å, 55 Å to 80 Å, 60 Å to 80 Å, 65 Å to 80 Å, 70 Å to 80 Å, or 75 Å to 80 Å relative to the second surface portion of the substrate. In some embodiments, ruthenium is deposited on the first surface portion of the substrate with a selectivity of up to 80 Å relative to the second surface portion of the substrate.

[0052]

[0060] Some embodiments relate to devices. In some embodiments, the device includes a ruthenium-containing film on the surface of a substrate. In some embodiments, the ruthenium-containing film includes any film formed according to the methods disclosed herein. In some embodiments, the ruthenium-containing film includes any film prepared from a ruthenium precursor disclosed herein. In some embodiments, for example, but not limited to them, the device includes a substrate having a first surface portion and a second surface portion adjacent to the first surface portion. In some embodiments, the ruthenium layer is located on the first surface portion of the substrate. In some embodiments, the ruthenium layer has a thickness of at least 25 Å on the first surface portion of the substrate. In some embodiments, the second surface portion of the substrate does not contain ruthenium.

[0053] Example 1

[0061] Examples 1 to 6 relate to the PEALD deposition of p-cymene(1,3-cyclohexadiene)Ru on the gate of a gate-all-around transistor using NH3 pulses (plasma power 400W, cycle pulse sequence: (5-5-10-5)). Figure 2 is a graph showing the relationship between ruthenium film thickness and atomic layer deposition cycle in several embodiments. As shown in Figure 2, ruthenium was selectively deposited on TaN, WCN, WN, and TiN compared to SiO2 and SiN.

[0054]

[0062] P-cymene(1,3-cyclohexadiene)Ru (P-cymeneCHDRu) was used. TaN was used as the substrate for Ru deposition. The following PEALD deposition cycle was used: 5-second Ru precursor pulse, 5-second argon purge, 10-second ammonia (NH3) plasma pulse, 5-second argon purge (5-5-10-5). The coupon temperature was 330°C and the chamber pressure was 1 Torr. For the Ru precursor supply, an argon carrier flow rate of 250 sccm and an ampoule temperature of 100°C were used. Throughout the entire cycle, argon was introduced into the chamber at 610 sccm. The results are shown in Figure 2, which is a graph showing the relationship between ruthenium film thickness and atomic layer deposition cycles in several embodiments.

[0055] Example 2

[0063] PEALD deposition of p-cymene(1,3-cyclohexadiene)Ru by NH3 pulse at 400W plasma power, cycle pulse sequence: (5-5-10-5). P-cymene(1,3-cyclohexadiene)Ru (p-cymeneCHDRu) was used. WCN was used as the substrate for Ru deposition. The following PEALD deposition cycle was used: 5-second Ru precursor pulse, 5-second argon purge, 10-second ammonia (NH3) plasma pulse, 5-second argon purge (5-5-10-5). Coupon temperature was 330°C and chamber pressure was 1 Torr. For Ru precursor supply, an argon carrier flow rate of 250 sccm and ampoule temperature of 100°C were used. Throughout the entire cycle, argon was introduced into the chamber at 610 sccm. The results are shown in Figure 2, which is a graph showing the relationship between ruthenium film thickness and atomic layer deposition cycle in several embodiments.

[0056] Example 3

[0064] PEALD deposition of p-cymene(1,3-cyclohexadiene)Ru by NH3 pulse at 400W plasma power, cycle pulse sequence: (5-5-10-5). P-cymene(1,3-cyclohexadiene)Ru (p-cymeneCHDRu) was used. WN was used as the substrate for Ru deposition. The following PEALD deposition cycle was used: 5-second Ru precursor pulse, 5-second argon purge, 10-second ammonia (NH3) plasma pulse, 5-second argon purge (5-5-10-5). Coupon temperature was 330°C and chamber pressure was 1 Torr. For Ru precursor supply, an argon carrier flow rate of 250 sccm and ampoule temperature of 100°C were used. Throughout the entire cycle, argon was introduced into the chamber at 610 sccm. The results are shown in Figure 2, which is a graph showing the relationship between ruthenium film thickness and atomic layer deposition cycle in several embodiments.

[0057] Example 4

[0065] PEALD deposition of p-cymene(1,3-cyclohexadiene)Ru by NH3 pulse at 400W plasma power, cycle pulse sequence: (5-5-10-5). P-cymene(1,3-cyclohexadiene)Ru (p-cymeneCHDRu) was used. TiN was used as the substrate for Ru deposition. The following PEALD deposition cycle was used: 5-second Ru precursor pulse, 5-second argon purge, 10-second ammonia (NH3) plasma pulse, 5-second argon purge (5-5-10-5). Coupon temperature was 330°C and chamber pressure was 1 Torr. For Ru precursor supply, an argon carrier flow rate of 250 sccm and ampoule temperature of 100°C were used. Throughout the entire cycle, argon was introduced into the chamber at 610 sccm. The results are shown in Figure 2, which is a graph showing the relationship between ruthenium film thickness and atomic layer deposition cycle in several embodiments.

[0058] Example 5

[0066] PEALD deposition of p-cymene(1,3-cyclohexadiene)Ru by NH3 pulse at 400W plasma power, cycle pulse sequence: (5-5-10-5). P-cymene(1,3-cyclohexadiene)Ru (p-cymeneCHDRu) was used. SiO2 was used as the substrate for Ru deposition. The following PEALD deposition cycle was used: 5-second Ru precursor pulse, 5-second argon purge, 10-second ammonia (NH3) plasma pulse, 5-second argon purge (5-5-10-5). Coupon temperature was 330°C and chamber pressure was 1 Torr. For Ru precursor supply, an argon carrier flow rate of 250 sccm and ampoule temperature of 100°C were used. Throughout the entire cycle, argon was introduced into the chamber at 610 sccm. The results are shown in Figure 2, which is a graph showing the relationship between ruthenium film thickness and atomic layer deposition cycle in several embodiments.

[0059] Example 6

[0067] PEALD deposition of p-cymene(1,3-cyclohexadiene)Ru by NH3 pulse at 400W plasma power, cycle pulse sequence: (5-5-10-5). P-cymene(1,3-cyclohexadiene)Ru (p-cymeneCHDRu) was used. SiN was used as the substrate for Ru deposition. The following PEALD deposition cycle was used: 5-second Ru precursor pulse, 5-second argon purge, 10-second ammonia (NH3) plasma pulse, 5-second argon purge (5-5-10-5). Coupon temperature was 330°C and chamber pressure was 1 Torr. For Ru precursor supply, an argon carrier flow rate of 250 sccm and ampoule temperature of 100°C were used. Throughout the entire cycle, argon was introduced into the chamber at 610 sccm. The results are shown in Figure 2, which is a graph showing the relationship between ruthenium film thickness and atomic layer deposition cycle for several embodiments.

[0060] Example 7

[0068] Examples 7 to 15 relate to the PEALD deposition of p-cymene(1,3-cyclohexadiene)Ru on vias of a gate-all-around transistor using NH3 pulses (plasma power 400W, cycle pulse sequence: (5-5-10-5)). Figure 3 is a graph showing the relationship between ruthenium film thickness and atomic layer deposition cycles in several embodiments. As shown in Figure 3, ruthenium was selectively deposited on Cu, W, Co, TaN, WCN, TiN, and Mo compared to SiO2 and SiN.

[0061]

[0069] PEALD deposition of p-cymene(1,3-cyclohexadiene)Ru by NH3 pulse at 400W plasma power, cycle pulse sequence: (5-5-10-5). P-cymene(1,3-cyclohexadiene)Ru (p-cymeneCHDRu) was used. Cu was used as the substrate for Ru deposition. The following PEALD deposition cycle was used: 5-second Ru precursor pulse, 5-second argon purge, 10-second ammonia (NH3) plasma pulse, 5-second argon purge (5-5-10-5). Coupon temperature was 330°C and chamber pressure was 1 Torr. For Ru precursor supply, an argon carrier flow rate of 250 sccm and ampoule temperature of 100°C were used. Throughout the entire cycle, argon was introduced into the chamber at 610 sccm. The results are shown in Figure 3, which is a graph showing the relationship between ruthenium film thickness and atomic layer deposition cycle in several embodiments.

[0062] Example 8

[0070] PEALD deposition of p-cymene(1,3-cyclohexadiene)Ru by NH3 pulse at 400W plasma power, cycle pulse sequence: (5-5-10-5). P-cymene(1,3-cyclohexadiene)Ru (p-cymeneCHDRu) was used. W was used as the substrate for Ru deposition. The following PEALD deposition cycle was used: 5-second Ru precursor pulse, 5-second argon purge, 10-second ammonia (NH3) plasma pulse, 5-second argon purge (5-5-10-5). Coupon temperature was 330°C and chamber pressure was 1 Torr. For Ru precursor supply, an argon carrier flow rate of 250 sccm and ampoule temperature of 100°C were used. Throughout the entire cycle, argon was introduced into the chamber at 610 sccm. The results are shown in Figure 3, which is a graph showing the relationship between ruthenium film thickness and atomic layer deposition cycle in several embodiments.

[0063] Example 9

[0071] PEALD deposition of p-cymene(1,3-cyclohexadiene)Ru by NH3 pulse at 400W plasma power, cycle pulse sequence: (5-5-10-5). P-cymene(1,3-cyclohexadiene)Ru (p-cymeneCHDRu) was used. Co was used as the substrate for Ru deposition. The following PEALD deposition cycle was used: 5-second Ru precursor pulse, 5-second argon purge, 10-second ammonia (NH3) plasma pulse, 5-second argon purge (5-5-10-5). Coupon temperature was 330°C and chamber pressure was 1 Torr. For Ru precursor supply, an argon carrier flow rate of 250 sccm and ampoule temperature of 100°C were used. Throughout the entire cycle, argon was introduced into the chamber at 610 sccm. The results are shown in Figure 3, which is a graph showing the relationship between ruthenium film thickness and atomic layer deposition cycle in several embodiments.

[0064] Example 10

[0072] PEALD deposition of p-cymene(1,3-cyclohexadiene)Ru by NH3 pulse at 400W plasma power, cycle pulse sequence: (5-5-10-5). P-cymene(1,3-cyclohexadiene)Ru (p-cymeneCHDRu) was used. TaN was used as the substrate for Ru deposition. The following PEALD deposition cycle was used: 5-second Ru precursor pulse, 5-second argon purge, 10-second ammonia (NH3) plasma pulse, 5-second argon purge (5-5-10-5). Coupon temperature was 330°C and chamber pressure was 1 Torr. For Ru precursor supply, an argon carrier flow rate of 250 sccm and ampoule temperature of 100°C were used. Throughout the entire cycle, argon was introduced into the chamber at 610 sccm. The results are shown in Figure 3, which is a graph showing the relationship between ruthenium film thickness and atomic layer deposition cycle in several embodiments.

[0065] Example 11

[0073] PEALD deposition of p-cymene(1,3-cyclohexadiene)Ru by NH3 pulse at 400W plasma power, cycle pulse sequence: (5-5-10-5). P-cymene(1,3-cyclohexadiene)Ru (p-cymeneCHDRu) was used. WCN was used as the substrate for Ru deposition. The following PEALD deposition cycle was used: 5-second Ru precursor pulse, 5-second argon purge, 10-second ammonia (NH3) plasma pulse, 5-second argon purge (5-5-10-5). Coupon temperature was 330°C and chamber pressure was 1 Torr. For Ru precursor supply, an argon carrier flow rate of 250 sccm and ampoule temperature of 100°C were used. Throughout the entire cycle, argon was introduced into the chamber at 610 sccm. The results are shown in Figure 3, which is a graph showing the relationship between ruthenium film thickness and atomic layer deposition cycle in several embodiments.

[0066] Example 12

[0074] PEALD deposition of p-cymene(1,3-cyclohexadiene)Ru by NH3 pulse at 400W plasma power, cycle pulse sequence: (5-5-10-5). P-cymene(1,3-cyclohexadiene)Ru (p-cymeneCHDRu) was used. TiN was used as the substrate for Ru deposition. The following PEALD deposition cycle was used: 5-second Ru precursor pulse, 5-second argon purge, 10-second ammonia (NH3) plasma pulse, 5-second argon purge (5-5-10-5). Coupon temperature was 330°C and chamber pressure was 1 Torr. For Ru precursor supply, an argon carrier flow rate of 250 sccm and ampoule temperature of 100°C were used. Throughout the entire cycle, argon was introduced into the chamber at 610 sccm. The results are shown in Figure 3, which is a graph showing the relationship between ruthenium film thickness and atomic layer deposition cycle in several embodiments.

[0067] Example 13

[0075] PEALD deposition of p-cymene(1,3-cyclohexadiene)Ru by NH3 pulse at 400W plasma power, cycle pulse sequence: (5-5-10-5). P-cymene(1,3-cyclohexadiene)Ru (p-cymeneCHDRu) was used. Mo was used as the substrate for Ru deposition. The following PEALD deposition cycle was used: 5-second Ru precursor pulse, 5-second argon purge, 10-second ammonia (NH3) plasma pulse, 5-second argon purge (5-5-10-5). Coupon temperature was 330°C and chamber pressure was 1 Torr. For Ru precursor supply, an argon carrier flow rate of 250 sccm and ampoule temperature of 100°C were used. Throughout the entire cycle, argon was introduced into the chamber at 610 sccm. The results are shown in Figure 3, which is a graph showing the relationship between ruthenium film thickness and atomic layer deposition cycle in several embodiments.

[0068] Example 14

[0076] PEALD deposition of p-cymene(1,3-cyclohexadiene)Ru by NH3 pulse at 400W plasma power, cycle pulse sequence: (5-5-10-5). P-cymene(1,3-cyclohexadiene)Ru (p-cymeneCHDRu) was used. SiN was used as the substrate for Ru deposition. The following PEALD deposition cycle was used: 5-second Ru precursor pulse, 5-second argon purge, 10-second ammonia (NH3) plasma pulse, 5-second argon purge (5-5-10-5). Coupon temperature was 330°C and chamber pressure was 1 Torr. For Ru precursor supply, an argon carrier flow rate of 250 sccm and ampoule temperature of 100°C were used. Throughout the entire cycle, argon was introduced into the chamber at 610 sccm. The results are shown in Figure 3, which is a graph showing the relationship between ruthenium film thickness and atomic layer deposition cycle in several embodiments.

[0069] Example 15

[0077] PEALD deposition of p-cymene(1,3-cyclohexadiene)Ru by NH3 pulse at 400W plasma power, cycle pulse sequence: (5-5-10-5). P-cymene(1,3-cyclohexadiene)Ru (p-cymeneCHDRu) was used. SiO2 was used as the substrate for Ru deposition. The following PEALD deposition cycle was used: 5-second Ru precursor pulse, 5-second argon purge, 10-second ammonia (NH3) plasma pulse, 5-second argon purge (5-5-10-5). Coupon temperature was 330°C and chamber pressure was 1 Torr. For Ru precursor supply, an argon carrier flow rate of 250 sccm and ampoule temperature of 100°C were used. Throughout the entire cycle, argon was introduced into the chamber at 610 sccm. The results are shown in Figure 3, which is a graph showing the relationship between ruthenium film thickness and atomic layer deposition cycle in several embodiments.

[0070] Example 16

[0078] Examples 16 to 21 relate to the PEALD deposition of p-cymene(1,3-cyclohexadiene)Ru on vias of a gate-all-around transistor by NH3 pulses (plasma power 400W, cycle pulse sequence: (5-5-10-5)). Figure 4 is a graph showing the relationship between ruthenium film thickness and atomic layer deposition cycle in several embodiments. As shown in Figure 4, ruthenium is used with DHF polysilicon, SiN, SiO2, and TO x (where x is 1 to 100 in the formula) was selectively deposited on DHF SiGe.

[0071]

[0079] PEALD deposition of p-cymene(1,3-cyclohexadiene)Ru using NH3 pulses at 400W plasma power, cycle pulse sequence: (5-5-10-5). P-cymene(1,3-cyclohexadiene)Ru (p-cymeneCHDRu) was used. DHF SiGe was used as the substrate for Ru deposition. Before deposition, the SiGe was washed with DHF (diluted hydrofluoric acid, 100:1) for 1 minute. The following PEALD deposition cycle was used: 5-second Ru precursor pulse, 5-second argon purge, 10-second ammonia (NH3) plasma pulse, 5-second argon purge (5-5-10-5). Coupon temperature was 330°C and chamber pressure was 1 Torr. For Ru precursor supply, an argon carrier flow rate of 250 sccm and ampoule temperature of 100°C were used. Throughout the entire cycle, argon was introduced into the chamber at 610 sccm. The results are shown in Figure 4, which is a graph illustrating the relationship between ruthenium film thickness and atomic layer deposition cycles in several embodiments.

[0072] Example 17

[0080] PEALD deposition of p-cymene(1,3-cyclohexadiene)Ru using NH3 pulses at 400W plasma power, cycle pulse sequence: (5-5-10-5). P-cymene(1,3-cyclohexadiene)Ru (P-cymeneCHDRu) was used. Polysilicon was used as the substrate for Ru deposition. Prior to deposition, the p-doped polysilicon substrate was washed with DHF (diluted hydrofluoric acid, 100:1) for 1 minute. The following PEALD deposition cycle was used: 5-second Ru precursor pulse, 5-second argon purge, 10-second ammonia (NH3) plasma pulse, 5-second argon purge (5-5-10-5). Coupon temperature was 330°C and chamber pressure was 1 Torr. For Ru precursor supply, an argon carrier flow rate of 250 sccm and ampoule temperature of 100°C were used. Throughout the entire cycle, argon was introduced into the chamber at 610 sccm. The results are shown in Figure 4, which is a graph illustrating the relationship between ruthenium film thickness and atomic layer deposition cycles in several embodiments.

[0073] Example 18

[0081] PEALD deposition of p-cymene(1,3-cyclohexadiene)Ru by NH3 pulse at 400W plasma power, cycle pulse sequence: (5-5-10-5). P-cymene(1,3-cyclohexadiene)Ru (p-cymeneCHDRu) was used. SiN was used as the substrate for Ru deposition. The following PEALD deposition cycle was used: 5-second Ru precursor pulse, 5-second argon purge, 10-second ammonia (NH3) plasma pulse, 5-second argon purge (5-5-10-5). Coupon temperature was 330°C and chamber pressure was 1 Torr. For Ru precursor supply, an argon carrier flow rate of 250 sccm and ampoule temperature of 100°C were used. Throughout the entire cycle, argon was introduced into the chamber at 610 sccm. The results are shown in Figure 4, which is a graph showing the relationship between ruthenium film thickness and atomic layer deposition cycle in several embodiments.

[0074] Example 19

[0082] PEALD deposition of p-cymene(1,3-cyclohexadiene)Ru by NH3 pulse at 400W plasma power, cycle pulse sequence: (5-5-10-5). P-cymene(1,3-cyclohexadiene)Ru (p-cymeneCHDRu) was used. SiO2 (e.g., SiO2 natural oxide) was used as the substrate for Ru deposition. The following PEALD deposition cycle was used: 5-second Ru precursor pulse, 5-second argon purge, 10-second ammonia (NH3) plasma pulse, 5-second argon purge (5-5-10-5). Coupon temperature was 330°C and chamber pressure was 1 Torr. For Ru precursor supply, an argon carrier flow rate of 250 sccm and ampoule temperature of 100°C were used. Throughout the entire cycle, argon was introduced into the chamber at 610 sccm. The results are shown in Figure 4, which is a graph showing the relationship between ruthenium film thickness and atomic layer deposition cycle in several embodiments.

[0075] Example 20

[0083] PEALD deposition of p-cymene(1,3-cyclohexadiene)Ru using NH3 pulses at 400W plasma power, cycle pulse sequence: (5-5-10-5). P-cymene(1,3-cyclohexadiene)Ru (p-cymeneCHDRu) was used. Thermo-oxide (TO) was used as the substrate for Ru deposition. x The following PEALD deposition cycle was used: 5-second Ru precursor pulse, 5-second argon purge, 10-second ammonia (NH3) plasma pulse, 5-second argon purge (5-5-10-5). The coupon temperature was 330°C and the chamber pressure was 1 Torr. For the Ru precursor supply, an argon carrier flow rate of 250 sccm and an ampoule temperature of 100°C were used. Throughout the entire cycle, argon was introduced into the chamber at 610 sccm. The results are shown in Figure 4, which is a graph showing the relationship between ruthenium film thickness and atomic layer deposition cycles in several embodiments.

[0076] Example 21

[0084] PEALD deposition of p-cymene(1,3-cyclohexadiene)Ru by NH3 pulse at 400W plasma power, cycle pulse sequence: (5-5-10-5). P-cymene(1,3-cyclohexadiene)Ru (p-cymeneCHDRu) was used. Silicon / polysilicon was used as the substrate for Ru deposition. The following PEALD deposition cycle was used: 5-second Ru precursor pulse, 5-second argon purge, 10-second ammonia (NH3) plasma pulse, 5-second argon purge (5-5-10-5). Coupon temperature was 330°C and chamber pressure was 1 Torr. For Ru precursor supply, an argon carrier flow rate of 250 sccm and ampoule temperature of 100°C were used. Throughout the entire cycle, argon was introduced into the chamber at 610 sccm. The results are shown in Figure 4, which is a graph showing the relationship between ruthenium film thickness and atomic layer deposition cycle in several embodiments.

[0077]

[0085] manner

[0086] Various embodiments are described below. Please understand that one or more of the features described in the following embodiments can be combined with one or more of the features of the other embodiments. Appearance 1 It is a method, To produce a vaporized ruthenium precursor, at least a portion of the ruthenium precursor is vaporized, The first and second surface portions of the substrate are brought into contact with a vaporized ruthenium precursor and at least one reducing gas, Depositing ruthenium on the first surface portion of the substrate with a selectivity of at least 25 Å relative to the second surface portion of the substrate, and A method that includes this. Appearance 2 The method according to embodiment 1, wherein the first surface portion of the substrate includes at least one of TaN, WCN, WN, TiN, Cu, W, Co, TaN, TiN, Mo, MoN, MoCN, DHF SiGe, SiGe, or any combination thereof. Appearance 3 The method according to embodiment 1 or 2, wherein the second surface portion of the substrate includes at least one of SiO2, SiN, silicon, DHF silicon, natural silicon oxide, SiCOH, SiOCNH, low dielectric constant dielectric, porous low dielectric constant dielectric, or any combination thereof. Pattern 4 The first surface portion is It includes at least one of TaN, WCN, WN, TiN, or any combination thereof, The second surface portion is A material comprising at least one of SiO2, SiN, SiOCNH, or any combination thereof, The method according to any one of embodiments 1 to 3. Appearance 5 The method according to embodiment 4, wherein the first surface portion contacts the gate of the transistor, and the second surface portion electrically isolates the gate from the rest of the structure. Appearance 6 The method according to embodiment 4, wherein the first surface portion and the second surface portion are part of a gate-all-around (GAA) transistor. Appearance 7 The first surface portion is It contains at least one of Cu, W, Co, TaN, WCN, TiN, Mo, MoN, MoCN, or any combination thereof. The second surface portion of the via contains SiN, SiO2, or a low dielectric constant dielectric. The method according to any one of embodiments 1 to 3. Appearance 8 The method according to embodiment 7, wherein the first surface portion is located at the bottom of the via structure, and the second surface portion electrically isolates the via from the rest of the structure. Appearance 9 The first surface portion contains DHF SiGe or SiGe, The second surface portion includes at least one of SiO2, SiN, DHF polysilicon / silicon, silicon, natural silicon oxide, SiOCNH, or any combination thereof. The method according to any one of embodiments 1 to 3. Appearance 10 The method according to embodiment 9, wherein the first surface portion and the second surface portion are part of a gate-all-around (GAA) transistor. Appearance 11 The method according to any one of embodiments 1 to 10, wherein the deposition is carried out at a temperature of at least 300°C and a pressure of at least 0.5 Torr. Appearance 12 The method according to any one of embodiments 1 to 11, wherein the deposition is carried out at a temperature of 300°C to 450°C and a pressure of 0.5 Torr to 5 Torr. Appearance 13 The method according to any one of embodiments 1 to 12, wherein at least one reducing gas contains NH3. Appearance 14 The method according to any one of embodiments 1 to 13, wherein at least one reducing gas contains H2. Appearance 15 The method according to any one of embodiments 1 to 14, wherein the deposition is carried out in a substantially oxygen-free chamber. Appearance 16 The method according to any one of embodiments 1 to 15, wherein ruthenium is deposited on the first surface portion of the substrate with a selectivity of at least 40 Å relative to the second surface portion of the substrate. Appearance 17 The method according to any one of embodiments 1 to 16, wherein ruthenium is deposited on the first surface portion of the substrate with a selectivity of 40 Å to 80 Å relative to the second surface portion of the substrate. Aspect 18: A device, A substrate having a first surface portion and a second surface portion adjacent to the first surface portion, A ruthenium layer located on the first surface portion of the substrate and A device including, The ruthenium layer has a thickness of at least 25 Å on the first surface portion of the substrate. The second surface portion of the substrate does not contain ruthenium. device. Appearance 19 The device according to embodiment 18, wherein the first surface portion of the substrate includes at least one of TaN, WCN, WN, TiN, Cu, W, Co, TaN, TiN, Mo, MoN, MoC, MoCN, DHF SiGe, SiGe, or any combination thereof. Appearance 20 The device according to embodiment 18 or 19, wherein the second surface portion of the substrate includes at least one of SiO2, SiN, silicon, DHF silicon, natural silicon oxide, SiCOH, SiOCNH, low dielectric constant dielectric, porous low dielectric constant dielectric, or any combination thereof. Appearance 21 The first surface portion is It includes at least one of TaN, WCN, WN, MoN, TiN, or any combination thereof, The second surface portion is A material comprising at least one of SiO2, SiN, or any combination thereof, A device according to any one of embodiments 18 to 20. Appearance 22 The device according to embodiment 21, wherein the first surface portion and the second surface portion are part of a gate-all-around (GAA) transistor. Appearance 23 The first surface portion is It contains at least one of Cu, W, Co, TaN, WCN, TiN, Mo, MoN, MoC, MoCN, or any combination thereof. The second surface portion contains SiO2. A device according to any one of embodiments 18 to 20. Pattern 24 The device according to embodiment 23, wherein the first surface portion is located at the bottom of the via structure, and the second surface portion electrically isolates the via from the rest of the structure. Appearance 25 The first surface portion includes DHF SiGe, SiGe, or any combination thereof. The second surface portion includes at least one of SiO2, SiN, DHF polysilicon / silicon, silicon, natural silicon oxide, or any combination thereof. A device according to any one of embodiments 18 to 20. Embodiment 26: The device according to Embodiment 25, wherein the first surface portion and the second surface portion are part of a gate-all-around (GAA) transistor.

[0078]

[0087] In particular, please understand that the constituent materials, shapes, sizes, and arrangements of components used may be modified in detail without departing from the scope of this disclosure. This specification and the embodiments described herein are examples, and the true scope and spirit of the disclosure are indicated by the subsequent claims.

Claims

1. It is a method, To produce a vaporized ruthenium precursor, at least a portion of the ruthenium precursor is vaporized, The first and second surface portions of the substrate are brought into contact with a vaporized ruthenium precursor and at least one reducing gas, Depositing ruthenium on the first surface portion of the substrate with a selectivity of at least 25 Å relative to the second surface portion of the substrate, and A method that includes this.

2. The method according to claim 1, wherein the first surface portion of the substrate includes at least one of TaN, WCN, WN, TiN, Cu, W, Co, TaN, TiN, Mo, MoN, MoCN, DHF SiGe, SiGe, or any combination thereof.

3. The second surface portion of the substrate is SiO ２ The method according to claim 1, comprising at least one of SiN, silicon, DHF silicon, natural silicon oxide, SiCOH, SiOCNH, low dielectric constant dielectric, porous low dielectric constant dielectric, or any combination thereof.

4. The first surface portion is It includes at least one of TaN, WCN, WN, TiN, or any combination thereof, and The second surface portion is SiO ２ , including at least one of SiN, SiOCNH, or any combination thereof, The method according to claim 1.

5. The method according to claim 4, wherein the first surface portion contacts the gate of the transistor, and the second surface portion electrically isolates the gate from the rest of the structure.

6. The method according to claim 4, wherein the first surface portion and the second surface portion are part of a gate-all-around (GAA) transistor.

7. The first surface portion is It includes at least one of Cu, W, Co, TaN, WCN, TiN, Mo, MoN, MoCN, or any combination thereof. The second surface portion of the via is SiN, SiO ２ , or including low dielectric constant dielectrics The method according to claim 1.

8. The method according to claim 7, wherein the first surface portion is located at the bottom of the via structure, and the second surface portion electrically isolates the via from the rest of the structure.

9. The first surface portion contains DHF SiGe or SiGe, The second surface portion is SiO ２ , containing at least one of SiN, DHF polysilicon / silicon, silicon, natural silicon oxide, SiOCNH or any combination thereof The method according to claim 1.

10. The method according to claim 9, wherein the first surface portion and the second surface portion are part of a gate-all-around (GAA) transistor.

11. The method according to claim 1, wherein the deposition is carried out at a temperature of at least 300°C and a pressure of at least 0.5 Torr.

12. The method according to claim 1, wherein the deposition is carried out at a temperature of 300°C to 450°C and a pressure of 0.5 Torr to 5 Torr.

13. At least one reducing gas is NH ３ The method according to claim 1, including the method described in claim 1.

14. At least one reducing gas is H ２ The method according to claim 1, including the method described in claim 1.

15. The method according to claim 1, wherein the deposition is carried out in a substantially oxygen-free chamber.

16. The method according to claim 1, wherein ruthenium is deposited on the first surface portion of the substrate with a selectivity of at least 40 Å relative to the second surface portion of the substrate.

17. The method according to claim 1, wherein ruthenium is deposited on the first surface portion of the substrate with a selectivity of 40 Å to 80 Å relative to the second surface portion of the substrate.

18. A substrate having a first surface portion and a second surface portion adjacent to the first surface portion, A ruthenium layer located on the first surface portion of the substrate and A device including, The ruthenium layer has a thickness of at least 25 Å on the first surface portion of the substrate. The second surface portion of the substrate does not contain ruthenium. device.

19. The device according to claim 18, wherein the first surface portion of the substrate includes at least one of TaN, WCN, WN, TiN, Cu, W, Co, TaN, TiN, Mo, MoN, MoC, MoCN, DHF SiGe, SiGe, or any combination thereof.

20. The second surface portion of the substrate is SiO ２ The device according to claim 18, comprising at least one of SiN, silicon, DHF silicon, natural silicon oxide, SiCOH, SiOCNH, low dielectric constant dielectric, porous low dielectric constant dielectric, or any combination thereof.

21. The first surface portion is It includes at least one of TaN, WCN, WN, MoN, TiN, or any combination thereof, The second surface portion is SiO ２ , SiN, or at least one of any combination thereof, The device according to claim 18.

22. The device according to claim 21, wherein the first surface portion and the second surface portion are part of a gate-all-around (GAA) transistor.

23. The first surface portion is It includes at least one of Cu, W, Co, TaN, WCN, TiN, Mo, MoN, MoC, MoCN, or any combination thereof. The second surface portion contains SiO ２ and The device according to claim 18.

24. The device according to claim 23, wherein the first surface portion is located at the bottom of the via structure, and the second surface portion electrically isolates the via from the rest of the structure.

25. The first surface portion comprises DHF SiGe, SiGe, or any combination thereof. The second surface portion is SiO ２ , containing at least one of SiN, DHF polysilicon / silicon, silicon, natural silicon oxide, or any combination thereof The device according to claim 18.

26. The device according to claim 25, wherein the first surface portion and the second surface portion are part of a gate-all-around (GAA) transistor.

Images