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 produce 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 relative to the second surface portion of the substrate. In one embodiment, an apparatus includes a substrate having a first surface portion and a second surface portion adjacent to the first surface portion; and a ruthenium layer on the first surface portion of the substrate, where the ruthenium layer has a thickness of at least 25 on the first surface portion of the substrate; wherein the second surface portion of the substrate does not include ruthenium.

Description

TECHNICAL FIELD

[0001] The present disclosure relates to selective deposition of ruthenium and related systems and methods.

[0002] CROSS-REFERENCE TO RELATED APPLICATIONS

[0003] This application claims the benefit under 35 USC 119 of U.S. Provisional Patent Application No. 63 / 472,158, filed June 9, 2023, the disclosure of which is hereby incorporated by reference in its entirety. BACKGROUND

[0004] Conventional processes for depositing ruthenium films require multiple steps. Additionally, conventional processes use O2 as a co-reactant to deposit ruthenium, which is undesirable because O2 can oxidize the substrate during the deposition process. Depositing ruthenium with high selectivity remains a continuing challenge. SUMMARY

[0005] Some embodiments relate to a method for selectively depositing ruthenium. In some embodiments, the method for selectively depositing ruthenium includes vaporizing at least a portion of a ruthenium precursor to produce a vaporized ruthenium precursor. In some embodiments, the method for selectively depositing 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 selectively depositing ruthenium includes depositing ruthenium on the first surface portion of the substrate with a selectivity of at least 25 A relative to the second surface portion of the substrate.

[0006] Some embodiments relate to an apparatus. In some embodiments, the apparatus 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 apparatus includes a ruthenium layer on the first surface portion of the substrate. In some embodiments, the ruthenium layer has a thickness of at least 25 A on the first surface portion of the substrate. In some embodiments, the second surface portion of the substrate does not include ruthenium. BRIEF DESCRIPTION OF DRAWINGS

[0007] Some embodiments of the disclosure are described herein with reference to the accompanying drawings, which are merely for illustration. Specifically referring to the drawings in detail, it should be appreciated that the embodiments are illustrated by way of example only. As such, the descriptions herein should not be deemed as limiting the scope of the embodiments of the disclosure.

[0008] Figure 1 Flowchart for a method for preparing a ruthenium-containing film 100 according to some embodiments.

[0009] Figure 2Graphical view of ruthenium film thickness versus atomic layer deposition cycles according to some embodiments.

[0010] Figure 3 Graphical view of ruthenium film thickness versus atomic layer deposition cycles according to some embodiments.

[0011] Figure 4 Graphical view of ruthenium film thickness versus atomic layer deposition cycles according to some embodiments. DETAILED DESCRIPTION

[0012] Among the benefits and improvements disclosed are that other objects and advantages of the present disclosure will be apparent from the following description and the appended claims, taken in conjunction with the accompanying drawings. Detailed embodiments of the present disclosure are disclosed herein; however, it is to be understood that the disclosed embodiments are merely illustrative of the present disclosure, which can take various and alternative forms. Further, each of the examples given in connection with the various embodiments of the present disclosure are intended to be illustrative, and not restrictive. The scope of the disclosure is not intended to be limited to the embodiments presented herein.

[0013] Any prior patents and publications referred to herein are incorporated by reference in their entirety.

[0014] Throughout the specification and claims, the following terms take the meanings explicitly associated herein, unless the context clearly dictates otherwise. The words "in one embodiment," "in an embodiment," and "in some embodiments" as used herein do not necessarily refer to the same embodiment, but can, but not necessarily, refer to different embodiments unless the context clearly indicates otherwise. All embodiments of the present disclosure can be combined in any permutation or combination, without departing from the scope or spirit of the present disclosure.

[0015] As used herein, unless the context clearly dictates otherwise, the term "based on" is not exclusive and allows for additional factors to be included. Also, throughout the specification, the meaning of "a," "an," and "the" include plural references. The meaning of "in" includes "in" and "on."

[0016] As used herein, the term "alkyl" refers to a hydrocarbon compound having 1 to 30 carbon atoms. Alkyl groups having n carbon atoms can be represented as "C n alkyl." For example, "C3 alkyl" can include n-propyl and iso-propyl. Alkyl groups having a range of carbon atoms, such as 1 to 30 carbon atoms, can be represented as C1-C 30alkyl. In some embodiments, the alkyl is linear. In some embodiments, the alkyl is branched. In some embodiments, the alkyl is substituted. In some embodiments, the alkyl is unsubstituted. In some embodiments, the alkyl comprises at least one of, or consists of a group including at least one of, 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 any combination thereof. In some embodiments, the alkyl comprises at least one of, or consists of a group including at least one of, methyl, ethyl, n-propyl, 1-methylethyl (iso-propyl), 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.

[0017] Some embodiments are directed to depositing ruthenium on a substrate with high selectivity. In some embodiments, ruthenium is selectively deposited in the form of a thin film on a surface of a substrate via an atomic layer deposition process such as, for example, but not limited to, plasma enhanced atomic layer deposition, thermal atomic layer deposition, etc. At least one advantage of the embodiments disclosed herein is that ruthenium can be selectively deposited on a desired surface up to 80 A. At least another advantage of the embodiments disclosed herein is that the deposition process is free or substantially free of oxygen. At least another advantage of the embodiments disclosed herein is that ruthenium is deposited at a temperature of 450 °C or less. At least an additional advantage of the embodiments disclosed herein is that ruthenium is selectively deposited on a surface other than, for example, but not limited to, silicon oxide, thermal oxide, silicon nitride, SiCOH, low-k dielectrics, porous low-k dielectrics, and / or polysilicon. These should not be limiting as other advantages of the embodiments disclosed herein will become apparent upon review of this disclosure.

[0018] As used herein, when described relative to thickness (e.g., thickness in Å), the term "selectivity" refers to the maximum thickness of material on the first surface before it is deposited on a surface other than the first surface. For example, depositing ruthenium on the first surface of a substrate with a selectivity of 80 Å means that when the thickness of ruthenium on the first surface of the substrate exceeds 80 Å, ruthenium will begin to deposit on a surface other than the first surface (e.g., the second surface).

[0019] As used herein, the term "substantially free of" means an amount not exceeding 5% by weight or volume of the substance. In some embodiments, the term "substantially free of" means a substance not exceeding 4%, 3%, 2%, 1%, 0.9%, 0.8%, 0.7%, 0.6%, 0.5%, 0.4%, 0.3%, 0.2%, or 0.1% by weight or volume. In some embodiments, the term "substantially free of" means an amount that cannot be detected using standard equipment (e.g., an undetectable amount). As used herein, the term "free of" means an amount of substance in which the substance is not present.

[0020] Figure 1 This is a flowchart of a method for preparing a ruthenium-containing film 100 according to some embodiments. Figure 1 As shown, a method for preparing a ruthenium-containing film 100 includes one or more of the following steps: vaporizing at least a portion of a ruthenium precursor (102) to produce 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 (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 preparing the ruthenium-containing film 100 is an atomic layer deposition (ALD) process. In some embodiments, the method for preparing the ruthenium-containing film 100 is a plasma-enhanced atomic layer deposition (PEALD) process. In some embodiments, the method for preparing the ruthenium-containing film 100 is a thermal atomic layer deposition (thermal ALD) process.

[0021] A method for preparing a ruthenium-containing film 100 may include vaporizing at least a portion of a ruthenium precursor (102) to produce a vaporized ruthenium precursor.

[0022] In some embodiments, vaporization may include heating the ruthenium precursor to a level sufficient to obtain vaporized ruthenium precursor. In some embodiments, vaporization may include heating a container containing the ruthenium precursor. In some embodiments, the ruthenium precursor is present in at least one of a liquid phase, a gas phase, a vapor phase, a solid phase, or any combination thereof. In some embodiments, vaporization may include heating the ruthenium precursor in a deposition chamber in which a vapor deposition process is performed. In some embodiments, vaporization may include heating a conduit for delivering the ruthenium precursor, vaporized ruthenium precursor, or any combination thereof to, for example, a deposition chamber. In some embodiments, vaporization may include operating a vapor delivery system comprising the ruthenium precursor. In some embodiments, vaporization may include heating to a temperature sufficient to vaporize the ruthenium precursor to obtain 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, vaporized ruthenium precursor, or any combination thereof. In some embodiments, the ruthenium precursor may be present in a gas phase, in which case step 102 is optional and not required. For example, ruthenium precursors may include vaporized ruthenium precursors.

[0023] In some embodiments, the ruthenium precursor is a precursor of the following formula:

[0024] R 1 R 2 Ru(0),

[0025] Where R 1 It is a benzene or an aryl-containing ligand, and R 2 It is a dienyl ligand.

[0026] As used herein, an "aryl-containing ligand" comprises at least one aromatic ring wherein one or more hydrocarbon substituents are attached to the aromatic ring. For example, in some embodiments, the aryl-containing ligand may be a monoalkylbenzene, dialkylbenzene, or trialkylbenzene, or a fused ring structure such as indane and / or tetrahydronaphthalene (e.g., benzocyclohexane, tetrahydronaphthalene).

[0027] As used herein, a “dienyl-containing ligand” is a compound comprising at least two carbon-carbon double bonds separated by at least one carbon-carbon single bond, and may comprise conjugated dienes and non-conjugated dienes. Dienyl-containing ligands may optionally comprise more than two carbon-carbon double bonds, such as trienes, etc. Dienyl-containing ligands comprise straight-chain compounds and cyclic compounds. Cyclic dienyl-containing ligands may have a monocyclic structure, such as cyclohexadiene, cyclohexadiene or its alkylated derivatives, or may have a fused-ring structure, such as hexahydronaphthalene, thetrahydroindene, dicyclopentadiene, or norbornene.

[0028] For example, in some embodiments, R 1Includes at least one of toluene, xylene, ethylbenzene, isopropylbenzene, methyl isopropylbenzene, or any combination thereof. In the examples, R 2 Includes cyclic non-conjugated dienes or linear non-conjugated dienes. In some embodiments, R 2 It is cyclohexadiene or alkylcyclohexadiene. In some embodiments, R 2 It includes at least one of cyclohexadiene, methylcyclohexadiene, ethylcyclohexadiene, propylcyclohexadiene, or any combination thereof.

[0029] In some embodiments, the ruthenium precursor comprises compounds of formula II:

[0030]

[0031] in:

[0032] R 3 To R 8 Each is independently hydrogen or C1-C6 alkyl;

[0033] R 9 It is a covalent bond or a divalent olefinic group having 1 to 4 carbon atoms; and

[0034] R 10 and R 11 It forms one or more ring structures or is each independently hydrogen or C1-C6 alkyl. In some embodiments, R 3 To R 8 One, two, or three of them are selected from C1-C6 alkyl or C1-C3 alkyl, wherein the remaining R 3 To R 8 It is hydrogen. In some embodiments, R is... 9 It is a covalent bond, and R 10 and R 11 It forms one or more ring structures.

[0035] In some embodiments, formula R 1 and R 2 The ruthenium precursor does not contain any 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 Compounds of Ru(0) can also be described in terms of their degree of unsaturation, their total carbon content, their total hydrogen content, or combinations thereof.

[0036] In some embodiments, formula R 1 R 2The ruthenium precursor of Ru(0) may have a total carbon atomic weight in the range of (a1) 12 to 20, (a2) 14 to 18, or (a3) ​​15 to 17. In some embodiments, the total carbon atomic weight of the ruthenium precursor is (a4) 16. Formula R 1 R 2 The ruthenium precursor of Ru(0) may also have a total hydrogen atomic mass in the range of (b1) 16 to 28, (b2) 19 to 25, or (b3) 20 to 24. In some embodiments, the total hydrogen atomic mass of the ruthenium precursor is 22. In some embodiments, the ruthenium precursor may have a combination of carbon and hydrogen amounts of (a1) and (b1), (a2) and (b2), or (a3) ​​and (b3).

[0037] In some embodiments, the ruthenium precursor comprises at least one of the following: (methylisopropylbenzene)(1,3-cyclohexadiene)Ru(0), (methylisopropylbenzene)(1,4-cyclohexadiene)Ru(0), (methylisopropylbenzene)(1-methylcyclohex-1,3-diene)Ru(0), (methylisopropylbenzene)(2-methylcyclohex-1,3-diene)Ru(0), (methylisopropylbenzene)(3-methylcyclohex-1,3-diene)Ru(0), (methylisopropylbenzene)(4-methylcyclohex-1,3-diene)Ru(0), (methylisopropylbenzene)(5-methylcyclohex-1,3-diene)Ru(0). 0), (methylisopropylbenzene)(6-methylcyclohexyl-1,3-diene)Ru(0), (methylisopropylbenzene)(1-methylcyclohexyl-1,4-diene)Ru(0), (methylisopropylbenzene)(2-methylcyclohexyl-1,4-diene)Ru(0), (methylisopropylbenzene)(3-methylcyclohexyl-1,4-diene)Ru(0), (methylisopropylbenzene)(4-methylcyclohexyl-1,4-diene)Ru(0), (methylisopropylbenzene)(5-methylcyclohexyl-1,4-diene)Ru(0), (methylisopropylbenzene)(6-methylcyclohexyl-1,4-diene)Ru(0), or any combination thereof. Methylisopropylbenzene is also known as 1-methyl-4-(propyl-2-yl)benzene or 1-isopropyl-4-toluene.

[0038] In some embodiments, the ruthenium precursor comprises at least one of the following: (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), and (1,4-xylene)(1,3-cyclohexadiene)Ru(0). , (p-methylisopropylbenzene)(1,3-cyclohexadiene)Ru(0), (o-methylisopropylbenzene)(1,3-cyclohexadiene)Ru(0), (m-methylisopropylbenzene)(1,3-cyclohexadiene)Ru(0), (isopropylbenzene)(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) (hexadiene)Ru(0), (o-ethyltoluene)(1,3-cyclohexadiene)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), (indene) (1,3-cyclohexadiene)Ru(0), (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.

[0039] In some embodiments, the ruthenium precursor includes at least one of the following:

[0040]

[0041] or

[0042] Any combination thereof.

[0043] In some embodiments, the ruthenium precursor may also be described with reference to the melting point and / or boiling point of the compound. In some embodiments, the ruthenium precursor is a liquid at room temperature (25°C). In some embodiments, the ruthenium precursor may also have a boiling point in the temperature range of about 100°C to about 175°C, or about 120°C to about 150°C.

[0044] In some embodiments, if the ruthenium precursor of Formula I is in liquid form at room temperature (25°C), then the ruthenium precursor may be described in terms of its vapor pressure. The vapor pressure of a liquid is higher than the equilibrium pressure of its vapor. Measured in a closed container at a certain temperature, the vapor pressure is generated by the evaporation of the liquid. For example, the precursor may have a vapor pressure of at least about 0.01 Torr or at least about 0.05 Torr at 100°C, such as 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.

[0045] In some embodiments, the ruthenium precursor is prepared by reacting a ruthenium-containing reactant, such as a ruthenium hydrate, with a first hydrocarbon-containing ligand (R1) to form an intermediate, and then reacting the intermediate with a second hydrocarbon-containing ligand (R2) to form the final product. For example, (6-1-isopropyl-4-toluene)-(4-cyclohexyl-1,3-diene)Ru(0) (IMBCHRu) can be prepared 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-toluene)ruthenium(II)), then drying the microcrystalline product and then adding it to an ethanol solution containing Na2CO3 and 1,3-cyclohexadiene, and then refluxing for 4.5 hours.

[0046] A method for preparing a ruthenium-containing film 100 may include vaporizing at least a portion of at least one reducing agent to generate at least one reducing gas.

[0047] In some embodiments, vaporization may include sufficiently heating at least one reducing agent 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 in a deposition chamber performing a vapor deposition process. In some embodiments, vaporization may include heating a conduit for delivering at least one reducing agent, at least one reducing gas, or any combination thereof to, for example, a deposition chamber. In some embodiments, vaporization may include operating a vapor delivery system comprising at least one reducing agent. In some embodiments, vaporization may include heating to a temperature sufficient to vaporize at least one reducing agent to obtain at least one reducing gas. In some embodiments, vaporization may include heating to a temperature below the decomposition temperature of at least one of the at least one reducing agent, at least one reducing gas, or any combination thereof. In some embodiments, at least one reducing agent may be present in the gaseous phase, in which case the steps are optional rather than required. For example, at least one reducing agent may include at least one reducing gas.

[0048] At least one reducing agent, at least one reducing gas, or any combination thereof may be selected to obtain the desired ruthenium-containing film. In some embodiments, the at least one reducing agent, at least one reducing gas, or any combination thereof may include 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, their free radicals, or any combination thereof. In some embodiments, the method for preparing 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 include oxygen. For example, in some embodiments, the at least one reducing agent, at least one reducing gas, or any combination thereof does not include at least one of the following: H2, O2, O3, H2O, H2O2, NO, N2O, NO2, CO, CO2, carboxylic acids, alcohols, diols, their free radicals, or any combination thereof. In some embodiments, at least one reducing agent, at least one reducing gas, or any combination thereof are present in a container or other vessel. The at least one reducing agent, at least one reducing gas, or any combination thereof may be in the form of a solid, liquid, gas, vapor, or any combination thereof.

[0049] A method for preparing 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).

[0050] In some embodiments, contacting includes contacting a substrate with at least one of a vaporized ruthenium precursor, at least one reducing gas, or any combination thereof, under vapor deposition conditions to form a ruthenium-containing film on a selected surface of the substrate. Contacting can be performed in any system, apparatus, device, assembly, chamber thereof, or component thereof suitable for a vapor deposition process (including, but not limited to, deposition chambers and other devices). In some embodiments, the method further includes contacting the substrate with at least one inert gas. In some embodiments, the at least one inert gas includes at least one of argon, helium, nitrogen, or any combination thereof.

[0051] In some embodiments, contact includes bringing at least one of a vaporized ruthenium precursor, at least one reducing gas, at least one inert gas, or any combination thereof into close proximity or adjacency to a first surface portion and a second surface portion of the substrate. In some embodiments, contact includes bringing at least one of a vaporized ruthenium precursor, at least one reducing gas, at least one inert gas, or any combination thereof into direct contact with the first surface portion and the second surface portion of the substrate. In some embodiments, contact includes flowing 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. In some embodiments, contact includes pumping 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. In some embodiments, contact includes injecting 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. In some embodiments, contact includes 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.

[0052] In some embodiments, contact includes mixing at least one of a 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 a 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, when one of a vaporized ruthenium precursor, at least one reducing gas, or at least one inert gas is not mixed, an unmixed gas and / or vapor species is 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.

[0053] A vaporized ruthenium precursor and at least one reducing gas may be contacted 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 having the substrate at different times. That is, in some embodiments, contact does not include simultaneous or synchronous contact of the vaporized ruthenium precursor and at least one reducing gas with the substrate. In some embodiments, contact may include alternating and / or sequential contact of the vaporized ruthenium precursor with the substrate in one or more cycles, followed by contact of at least one reducing gas with the substrate. 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 flowing at least one inert gas through the deposition chamber); contacting the substrate with at least one reducing gas in the deposition chamber; and purging the deposition chamber (e.g., by flowing at least one inert gas through the deposition chamber). In some embodiments, the vaporized ruthenium precursor and at least one reducing gas are simultaneously contacted with the substrate in the form of a gas / vapor mixture or via separate gas lines.

[0054] Contact can be performed at the deposition temperature. The deposition temperature can be a temperature below 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 can 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 can be heated to the deposition temperature. In some embodiments, the substrate is heated to the deposition temperature in a chamber or other container in which it is in contact with the vaporized ruthenium precursor and at least one reducing gas. 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 can be from 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.

[0055] Contact can be performed under deposition pressure. In some embodiments, the deposition pressure may include the vapor pressure of at least one of a vaporized ruthenium precursor, at least one reducing gas, or any combination thereof. In some embodiments, the deposition pressure may include chamber pressure. The deposition pressure may be from 0.5 Torr to 100 Torr. For example, in some embodiments, the deposition pressure may be 1 Torr to 100 Torr, 5 Torr to 100 Torr, 10 Torr to 100 Torr, 15 Torr to 100 Torr, 20 Torr to 100 Torr, 25 Torr to 100 Torr, 30 Torr to 100 Torr, 35 Torr to 100 Torr, 40 Torr to 100 Torr, 45 Torr to 100 Torr, 50 Torr to 100 Torr, 55 Torr to 100 Torr, 60 Torr to 100 Torr, 65 Torr to 100 Torr, 70 Torr to 100 Torr, 75 Torr to 100 Torr, 80 Torr to 100 Torr, 85 Torr to 100 Torr, 90 Torr to 100 Torr, 9 Pressures from 5 to 100 tonnage, 0.5 to 95 tonnage, 0.5 to 90 tonnage, 0.5 to 85 tonnage, 0.5 to 80 tonnage, 0.5 to 75 tonnage, 0.5 to 70 tonnage, 0.5 to 65 tonnage, 0.5 to 60 tonnage, 0.5 to 55 tonnage, 0.5 to 50 tonnage, 0.5 to 45 tonnage, 0.5 to 40 tonnage, 0.5 to 35 tonnage, 0.5 to 30 tonnage, 0.5 to 25 tonnage, 0.5 to 20 tonnage, 0.5 to 15 tonnage, 0.5 to 10 tonnage, 0.5 to 5 tonnage, or 0.5 to 1 tonnage.

[0056] 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., the manufacture / fabrication of the electronic device has begun but is not yet complete). In some embodiments, the electronic device is a completed electronic device (e.g., the manufacture / fabrication of the electronic device is completed or at least substantially completed). In some embodiments, the first and second surface portions are surface portions of a gate-all-around transistor. In some embodiments, because the ruthenium-containing film is deposited during the fabrication and / or manufacturing of the gate-all-around transistor, the first and second surface portions of the gate-all-around transistor may be surface portions of an unfinished 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, both partially and fully manufactured gate-all-around transistors have multiple exposed surfaces (e.g., two exposed surfaces, up to hundreds of exposed surfaces), wherein at least two of the exposed surfaces are formed of different chemical compositions. Therefore, it should be understood that the substrate may have more than just a first surface portion and a second surface portion; that is, the substrate may have multiple surface portions (e.g., exposed surface portions).

[0057] In some embodiments, the first surface portion and the second surface portion may be any two surfaces of a partially or fully constructed gate-around transistor. In some embodiments, the substrate is at least a portion of the gate-around transistor. The first surface portion and the second surface portion may have any spatial arrangement having any two surfaces of the gate-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 a sloping surface portion (e.g., not a vertical surface portion and / or not a horizontal surface portion). In some embodiments, the first surface portion of the substrate is the first surface portion of the gate-around transistor; and the second surface portion of the substrate is the second surface portion of the gate-around transistor.

[0058] The first and second surface portions of the substrate may be formed of 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 comprises or is formed of at least one of the following: 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 comprises or is formed of the following: SiO2 (e.g., native silicon oxide), SiN, silicon, DHF silicon, SiCOH, low-k dielectric, porous low-k dielectric, or any combination thereof. In some embodiments, the first surface portion of the substrate comprises or is formed of TaN, and the second surface portion of the substrate comprises or is formed of SiN. In some embodiments, the first surface portion of the substrate comprises or is formed of WCN, and the second surface portion of the substrate comprises or is formed of SiN. In some embodiments, the first surface portion of the substrate comprises or is formed of WN, and the second surface portion of the substrate comprises or is formed of SiN. In some embodiments, a first surface portion of the substrate comprises or is formed of TiN, and a second surface portion of the substrate comprises or is formed of SiN.

[0059] In some embodiments, a first surface portion of the substrate comprises or is formed of TaN, and a second surface portion of the substrate comprises or is formed of SiO2. In some embodiments, a first surface portion of the substrate comprises or is formed of WCN, and a second surface portion of the substrate comprises or is formed of SiO2. In some embodiments, a first surface portion of the substrate comprises or is formed of WN, and a second surface portion of the substrate comprises or is formed of SiO2. In some embodiments, a first surface portion of the substrate comprises or is formed of TiN, and a second surface portion of the substrate comprises or is formed of SiO2.

[0060] In some embodiments, a first surface portion of the substrate comprises or is formed of Cu, and a second surface portion of the substrate comprises or is formed of SiN. In some embodiments, a first surface portion of the substrate comprises or is formed of W, and a second surface portion of the substrate comprises or is formed of SiN. In some embodiments, a first surface portion of the substrate comprises or is formed of Co, and a second surface portion of the substrate comprises or is formed of SiN. In some embodiments, a first surface portion of the substrate comprises or is formed of TaN, and a second surface portion of the substrate comprises or is formed of SiN. In some embodiments, a first surface portion of the substrate comprises or is formed of WCN, and a second surface portion of the substrate comprises or is formed of SiN. In some embodiments, a first surface portion of the substrate comprises or is formed of TiN, and a second surface portion of the substrate comprises or is formed of SiN. In some embodiments, a first surface portion of the substrate comprises or is formed of Mo, and a second surface portion of the substrate comprises or is formed of SiN.

[0061] In some embodiments, a first surface portion of the substrate comprises or is formed of Cu, and a second surface portion of the substrate comprises or is formed of SiO2. In some embodiments, a first surface portion of the substrate comprises or is formed of W, and a second surface portion of the substrate comprises or is formed of SiO2. In some embodiments, a first surface portion of the substrate comprises or is formed of Co, and a second surface portion of the substrate comprises or is formed of SiO2. In some embodiments, a first surface portion of the substrate comprises or is formed of TaN, and a second surface portion of the substrate comprises or is formed of SiO2. In some embodiments, a first surface portion of the substrate comprises or is formed of WCN, and a second surface portion of the substrate comprises or is formed of SiO2. In some embodiments, a first surface portion of the substrate comprises or is formed of TiN, and a second surface portion of the substrate comprises or is formed of SiO2. In some embodiments, a first surface portion of the substrate comprises or is formed of Mo, and a second surface portion of the substrate comprises or is formed of SiO2. In some embodiments, the first surface portion of the substrate is conductive relative to the second surface portion of the substrate.

[0062] In some embodiments, a first surface portion of the substrate comprises, or is formed of, DHF SiGe or SiGe, and a second surface portion of the substrate comprises, or is formed of, polycrystalline silicon (e.g., p-doped polycrystalline silicon). In some embodiments, a first surface portion of the substrate comprises, or is formed of, DHF SiGe or SiGe, and a second surface portion of the substrate comprises, or is formed of, SiN. In some embodiments, a first surface portion of the substrate comprises, or is formed of, DHF SiGe or SiGe, and a second surface portion of the substrate comprises, or is formed of, SiO2. In some embodiments, a first surface portion of the substrate comprises, or is formed of, DHF SiGe or SiGe, and a second surface portion of the substrate comprises, or is formed of, a thermal oxide. In some embodiments, the thermal oxide comprises TO. x Where x is 1 to 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) (e.g., a 100:1 water:HF solution). For example, in some embodiments, the first surface portion of the substrate comprises or is formed of DHF-cleaned SiGe. In some embodiments, the first surface portion of the substrate comprises or is formed of DHF-cleaned silicon. In some embodiments, the first surface portion of the substrate comprises or is formed of DHF-cleaned polycrystalline silicon (e.g., p-doped polycrystalline silicon).

[0063] In some embodiments, the first surface portion and the second surface portion are surface portions of the gate of a 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 surface portion and the second surface portion are surface portions of a via of a 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 surface portion and the second surface portion are surface portions of the source and / or drain of a 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 the following: SiO2, SiN, polysilicon, silicon, polysilicon / silicon, native silicon oxide, SiCOH, low-k dielectric, porous low-k dielectric, or any combination thereof.

[0064] In some embodiments, ruthenium is selectively deposited on a first surface portion of the substrate with a minimum of 40 Å relative to a second surface portion of the substrate. In some embodiments, ruthenium is positioned relative to the second surface portion of the substrate at 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. Ruthenium is selectively deposited on a first surface portion of the substrate at a rate of up to 80 Å relative to a second surface portion of the substrate.

[0065] Some embodiments relate to an apparatus. In some embodiments, the apparatus includes a ruthenium-containing film on a substrate surface. 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, such as, but not limited to, the apparatus includes a substrate having a first surface portion and a second surface portion adjacent to the first surface portion. In some embodiments, a 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 include ruthenium.

[0066] Example 1

[0067] Examples 1 to 6 involve depositing p-methylisopropylbenzene (1,3-cyclohexadiene) Ru PEALD onto the gate of a gate-all-around transistor using NH3 pulses at a plasma power of 400 W and a cyclic pulse sequence of (5-5-10-5). Figure 2 This is a graphical view of the ruthenium film thickness relative to an atomic layer deposition cycle according to some embodiments. Figure 2 As shown, ruthenium is selectively deposited on TaN, WCN, WN, and TiN, relative to SiO2 and SiN.

[0068] p-Methylisopropylbenzene (1,3-cyclohexadiene)Ru (p-methylisopropylbenzene CHD Ru) was used. TaN was used as the substrate for Ru deposition. The following PEALD deposition cycle was used: 5 sec Ru precursor pulse; 5 sec argon purge; 10 sec ammonia (NH3) plasma pulse; 5 sec argon purge (5-5-10-5). The sample temperature was 330 °C, and a chamber pressure of 1 Torr was used. For Ru precursor delivery, an argon carrier flow rate of 250 sccm and an ampoule temperature of 100 °C were used. Argon flowed into the chamber at 610 sccm throughout the cycle. The results are presented in... Figure 2 In the figure, the diagram is a graphical view of the ruthenium film thickness relative to an atomic layer deposition cycle according to some embodiments.

[0069] Example 2

[0070] PEALD deposition of p-methylisopropylbenzene (1,3-cyclohexadiene)Ru was performed using NH3 pulses at a plasma power of 400 W and a cyclic pulse sequence of (5-5-10-5). p-Methylisopropylbenzene (1,3-cyclohexadiene)Ru (p-methylisopropylbenzene CHD Ru) was used. WCN was used as the substrate for Ru deposition. The following PEALD deposition cycle was employed: 5 sec Ru precursor pulse; 5 sec argon purge; 10 sec ammonia (NH3) plasma pulse; 5 sec argon purge (5-5-10-5). The sample temperature was 330 °C, and a chamber pressure of 1 Torr was used. For Ru precursor delivery, an argon carrier flow rate of 250 sccm and an ampoule temperature of 100 °C were used. Argon flow into the chamber was 610 sccm throughout the cycle. The results are presented in… Figure 2 In the figure, the diagram is a graphical view of the ruthenium film thickness relative to an atomic layer deposition cycle according to some embodiments.

[0071] Example 3

[0072] PEALD deposition of p-methylisopropylbenzene (1,3-cyclohexadiene)Ru was performed using NH3 pulses at a plasma power of 400 W and a cyclic pulse sequence of (5-5-10-5). p-Methylisopropylbenzene (1,3-cyclohexadiene)Ru (p-methylisopropylbenzene CHD Ru) was used. WN was used as the substrate for Ru deposition. The following PEALD deposition cycle was used: 5 sec Ru precursor pulse; 5 sec argon purge; 10 sec ammonia (NH3) plasma pulse; 5 sec argon purge (5-5-10-5). The sample temperature was 330 °C, and a chamber pressure of 1 Torr was used. For Ru precursor delivery, an argon carrier flow rate of 250 sccm and an ampoule temperature of 100 °C were used. Argon flow into the chamber was 610 sccm throughout the cycle. The results are presented in… Figure 2In the figure, the diagram is a graphical view of the ruthenium film thickness relative to an atomic layer deposition cycle according to some embodiments.

[0073] Example 4

[0074] PEALD deposition of p-methylisopropylbenzene (1,3-cyclohexadiene)Ru was performed using NH3 pulses at a plasma power of 400 W and a cyclic pulse sequence of (5-5-10-5). p-Methylisopropylbenzene (1,3-cyclohexadiene)Ru (p-methylisopropylbenzene CHD Ru) was used. TiN was used as the substrate for Ru deposition. The following PEALD deposition cycle was used: 5 sec Ru precursor pulse; 5 sec argon purge; 10 sec ammonia (NH3) plasma pulse; 5 sec argon purge (5-5-10-5). The sample temperature was 330 °C, and a chamber pressure of 1 Torr was used. For Ru precursor delivery, an argon carrier flow rate of 250 sccm and an ampoule temperature of 100 °C were used. Argon flow into the chamber was 610 sccm throughout the cycle. The results are presented in… Figure 2 In the figure, the diagram is a graphical view of the ruthenium film thickness relative to an atomic layer deposition cycle according to some embodiments.

[0075] Example 5

[0076] PEALD deposition of p-methylisopropylbenzene (1,3-cyclohexadiene)Ru was performed using an NH3 pulse at a plasma power of 400 W and a cyclic pulse sequence of (5-5-10-5). p-Methylisopropylbenzene (1,3-cyclohexadiene)Ru (p-methylisopropylbenzene CHD Ru) was used. SiO2 was used as the substrate for Ru deposition. The following PEALD deposition cycle was used: 5 sec Ru precursor pulse; 5 sec argon purge; 10 sec ammonia (NH3) plasma pulse; 5 sec argon purge (5-5-10-5). The sample temperature was 330 °C, and a chamber pressure of 1 Torr was used. For Ru precursor delivery, an argon carrier flow rate of 250 sccm and an ampoule temperature of 100 °C were used. Argon flow into the chamber was 610 sccm throughout the cycle. The results are presented in… Figure 2 In the figure, the diagram is a graphical view of the ruthenium film thickness relative to an atomic layer deposition cycle according to some embodiments.

[0077] Example 6

[0078] PEALD deposition of p-methylisopropylbenzene (1,3-cyclohexadiene)Ru was performed using an NH3 pulse at a plasma power of 400 W and a cyclic pulse sequence of (5-5-10-5). p-Methylisopropylbenzene (1,3-cyclohexadiene)Ru (p-methylisopropylbenzene CHD Ru) was used. SiN was used as the substrate for Ru deposition. The following PEALD deposition cycle was employed: 5 sec Ru precursor pulse; 5 sec argon purge; 10 sec ammonia (NH3) plasma pulse; 5 sec argon purge (5-5-10-5). The sample temperature was 330 °C, and a chamber pressure of 1 Torr was used. For Ru precursor delivery, an argon carrier flow rate of 250 sccm and an ampoule temperature of 100 °C were used. Argon flow into the chamber was 610 sccm throughout the cycle. The results are presented in… Figure 2 In the figure, the diagram is a graphical view of the ruthenium film thickness relative to an atomic layer deposition cycle according to some embodiments.

[0079] Example 7

[0080] Examples 7 to 15 involve depositing p-methylisopropylbenzene (1,3-cyclohexadiene) Ru PEALD onto the via of a gate-all-around transistor using an NH3 pulse at a plasma power of 400 W and a cyclic pulse sequence of (5-5-10-5). Figure 3 This is a graphical view of the ruthenium film thickness relative to an atomic layer deposition cycle according to some embodiments. Figure 3 As shown, ruthenium is selectively deposited on Cu, W, Co, TaN, WCN, TiN, and Mo, relative to SiO2 and SiN.

[0081] PEALD deposition of p-methylisopropylbenzene (1,3-cyclohexadiene)Ru was performed using NH3 pulses at a plasma power of 400 W and a cyclic pulse sequence of (5-5-10-5). p-Methylisopropylbenzene (1,3-cyclohexadiene)Ru (p-methylisopropylbenzene CHD Ru) was used. Cu was used as the substrate for Ru deposition. The following PEALD deposition cycle was used: 5 sec Ru precursor pulse; 5 sec argon purge; 10 sec ammonia (NH3) plasma pulse; 5 sec argon purge (5-5-10-5). The sample temperature was 330 °C, and a chamber pressure of 1 Torr was used. For Ru precursor delivery, an argon carrier flow rate of 250 sccm and an ampoule temperature of 100 °C were used. Argon flowed into the chamber at 610 sccm throughout the cycle. The results are presented in… Figure 3 In the figure, the diagram is a graphical view of the ruthenium film thickness relative to an atomic layer deposition cycle according to some embodiments.

[0082] Example 8

[0083] PEALD deposition of p-methylisopropylbenzene (1,3-cyclohexadiene)Ru was performed using an NH3 pulse at a plasma power of 400 W and a cyclic pulse sequence of (5-5-10-5). p-Methylisopropylbenzene (1,3-cyclohexadiene)Ru (p-methylisopropylbenzene CHD Ru) was used. W was used as the substrate for Ru deposition. The following PEALD deposition cycle was used: 5 sec Ru precursor pulse; 5 sec argon purge; 10 sec ammonia (NH3) plasma pulse; 5 sec argon purge (5-5-10-5). The sample temperature was 330 °C, and a chamber pressure of 1 Torr was used. For Ru precursor delivery, an argon carrier flow rate of 250 sccm and an ampoule temperature of 100 °C were used. Argon flow into the chamber was 610 sccm throughout the cycle. The results are presented in… Figure 3 In the figure, the diagram is a graphical view of the ruthenium film thickness relative to an atomic layer deposition cycle according to some embodiments.

[0084] Example 9

[0085] PEALD deposition of p-methylisopropylbenzene (1,3-cyclohexadiene)Ru was performed using an NH3 pulse at a plasma power of 400 W and a cyclic pulse sequence of (5-5-10-5). p-Methylisopropylbenzene (1,3-cyclohexadiene)Ru (p-methylisopropylbenzene CHD Ru) was used. Co was used as the substrate for Ru deposition. The following PEALD deposition cycle was used: 5 sec Ru precursor pulse; 5 sec argon purge; 10 sec ammonia (NH3) plasma pulse; 5 sec argon purge (5-5-10-5). The sample temperature was 330 °C, and a chamber pressure of 1 Torr was used. For Ru precursor delivery, an argon carrier flow rate of 250 sccm and an ampoule temperature of 100 °C were used. Argon flow into the chamber was 610 sccm throughout the cycle. The results are presented in… Figure 3 In the figure, the diagram is a graphical view of the ruthenium film thickness relative to an atomic layer deposition cycle according to some embodiments.

[0086] Example 10

[0087] PEALD deposition of p-methylisopropylbenzene (1,3-cyclohexadiene)Ru was performed using NH3 pulses at a plasma power of 400 W and a cyclic pulse sequence of (5-5-10-5). p-Methylisopropylbenzene (1,3-cyclohexadiene)Ru (p-methylisopropylbenzene CHD Ru) was used. TaN was used as the substrate for Ru deposition. The following PEALD deposition cycle was employed: 5 sec Ru precursor pulse; 5 sec argon purge; 10 sec ammonia (NH3) plasma pulse; 5 sec argon purge (5-5-10-5). The sample temperature was 330 °C, and a chamber pressure of 1 Torr was used. For Ru precursor delivery, an argon carrier flow rate of 250 sccm and an ampoule temperature of 100 °C were used. Argon flow into the chamber was 610 sccm throughout the cycle. The results are presented in… Figure 3 In the figure, the diagram is a graphical view of the ruthenium film thickness relative to an atomic layer deposition cycle according to some embodiments.

[0088] Example 11

[0089] PEALD deposition of p-methylisopropylbenzene (1,3-cyclohexadiene)Ru was performed using NH3 pulses at a plasma power of 400 W and a cyclic pulse sequence of (5-5-10-5). p-Methylisopropylbenzene (1,3-cyclohexadiene)Ru (p-methylisopropylbenzene CHD Ru) was used. WCN was used as the substrate for Ru deposition. The following PEALD deposition cycle was employed: 5 sec Ru precursor pulse; 5 sec argon purge; 10 sec ammonia (NH3) plasma pulse; 5 sec argon purge (5-5-10-5). The sample temperature was 330 °C, and a chamber pressure of 1 Torr was used. For Ru precursor delivery, an argon carrier flow rate of 250 sccm and an ampoule temperature of 100 °C were used. Argon flow into the chamber was 610 sccm throughout the cycle. The results are presented in… Figure 3 In the figure, the diagram is a graphical view of the ruthenium film thickness relative to an atomic layer deposition cycle according to some embodiments.

[0090] Example 12

[0091] PEALD deposition of p-methylisopropylbenzene (1,3-cyclohexadiene)Ru was performed using NH3 pulses at a plasma power of 400 W and a cyclic pulse sequence of (5-5-10-5). p-Methylisopropylbenzene (1,3-cyclohexadiene)Ru (p-methylisopropylbenzene CHD Ru) was used. TiN was used as the substrate for Ru deposition. The following PEALD deposition cycle was used: 5 sec Ru precursor pulse; 5 sec argon purge; 10 sec ammonia (NH3) plasma pulse; 5 sec argon purge (5-5-10-5). The sample temperature was 330 °C, and a chamber pressure of 1 Torr was used. For Ru precursor delivery, an argon carrier flow rate of 250 sccm and an ampoule temperature of 100 °C were used. Argon flow into the chamber was 610 sccm throughout the cycle. The results are presented in… Figure 3 In the figure, the diagram is a graphical view of the ruthenium film thickness relative to an atomic layer deposition cycle according to some embodiments.

[0092] Example 13

[0093] PEALD deposition of p-methylisopropylbenzene (1,3-cyclohexadiene)Ru was performed using an NH3 pulse at a plasma power of 400 W and a cyclic pulse sequence of (5-5-10-5). p-Methylisopropylbenzene (1,3-cyclohexadiene)Ru (p-methylisopropylbenzene CHD Ru) was used. Mo was used as the substrate for Ru deposition. The following PEALD deposition cycle was employed: 5 sec Ru precursor pulse; 5 sec argon purge; 10 sec ammonia (NH3) plasma pulse; 5 sec argon purge (5-5-10-5). The sample temperature was 330 °C, and a chamber pressure of 1 Torr was used. For Ru precursor delivery, an argon carrier flow rate of 250 sccm and an ampoule temperature of 100 °C were used. Argon flow into the chamber was 610 sccm throughout the cycle. The results are presented in… Figure 3 In the figure, the diagram is a graphical view of the ruthenium film thickness relative to an atomic layer deposition cycle according to some embodiments.

[0094] Example 14

[0095] PEALD deposition of p-methylisopropylbenzene (1,3-cyclohexadiene)Ru was performed using an NH3 pulse at a plasma power of 400 W and a cyclic pulse sequence of (5-5-10-5). p-Methylisopropylbenzene (1,3-cyclohexadiene)Ru (p-methylisopropylbenzene CHD Ru) was used. SiN was used as the substrate for Ru deposition. The following PEALD deposition cycle was employed: 5 sec Ru precursor pulse; 5 sec argon purge; 10 sec ammonia (NH3) plasma pulse; 5 sec argon purge (5-5-10-5). The sample temperature was 330 °C, and a chamber pressure of 1 Torr was used. For Ru precursor delivery, an argon carrier flow rate of 250 sccm and an ampoule temperature of 100 °C were used. Argon flow into the chamber was 610 sccm throughout the cycle. The results are presented in… Figure 3 In the figure, the diagram is a graphical view of the ruthenium film thickness relative to an atomic layer deposition cycle according to some embodiments.

[0096] Example 15

[0097] PEALD deposition of p-methylisopropylbenzene (1,3-cyclohexadiene)Ru was performed using NH3 pulses at a plasma power of 400 W and a cyclic pulse sequence of (5-5-10-5). p-Methylisopropylbenzene (1,3-cyclohexadiene)Ru (p-methylisopropylbenzene CHD Ru) was used. SiO2 was used as the substrate for Ru deposition. The following PEALD deposition cycle was used: 5 sec Ru precursor pulse; 5 sec argon purge; 10 sec ammonia (NH3) plasma pulse; 5 sec argon purge (5-5-10-5). The sample temperature was 330 °C, and a chamber pressure of 1 Torr was used. For Ru precursor delivery, an argon carrier flow rate of 250 sccm and an ampoule temperature of 100 °C were used. Argon flow into the chamber was 610 sccm throughout the cycle. The results are presented in… Figure 4 In the figure, the diagram is a graphical view of the ruthenium film thickness relative to an atomic layer deposition cycle according to some embodiments.

[0098] Example 16

[0099] Examples 16 to 21 involve depositing p-methylisopropylbenzene (1,3-cyclohexadiene) Ru PEALD onto the source-drain of a gate-all-around transistor using NH3 pulses at a plasma power of 400 W and a cyclic pulse sequence of (5-5-10-5). Figure 4 This is a graphical view of the ruthenium film thickness relative to an atomic layer deposition cycle according to some embodiments. Figure 4 As shown in the figure, ruthenium is superior to DHF polycrystalline silicon, SiN, SiO2 and TO. x Selectively deposited on DHF SiGe, where x is 1 to 100.

[0100] PEALD deposition of p-methylisopropylbenzene (1,3-cyclohexadiene)Ru was performed using an NH3 pulse at a plasma power of 400 W and a cyclic pulse sequence of (5-5-10-5). p-Methylisopropylbenzene (1,3-cyclohexadiene)Ru (p-methylisopropylbenzene CHD Ru) was used. DHF SiGe was used as the substrate for Ru deposition. Prior to deposition, the SiGe was cleaned with DHF (diluted hydrofluoric acid, 100:1) for one 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). The sample temperature was 330 °C, and a chamber pressure of 1 Torr was used. For Ru precursor delivery, an argon carrier flow rate of 250 sccm and an ampoule temperature of 100 °C were used. Argon flow into the chamber was 610 sccm throughout the cycle. The results are presented in… Figure 4 In the figure, the diagram is a graphical view of the ruthenium film thickness relative to an atomic layer deposition cycle according to some embodiments.

[0101] Example 17

[0102] PEALD deposition of p-methylisopropylbenzene (1,3-cyclohexadiene)Ru was performed using an NH3 pulse at a plasma power of 400 W and a cyclic pulse sequence of (5-5-10-5). p-Methylisopropylbenzene (1,3-cyclohexadiene)Ru (p-methylisopropylbenzene CHD Ru) was used. P-doped polycrystalline silicon was used as the substrate for Ru deposition. Prior to deposition, the P-doped polycrystalline silicon substrate was cleaned with DHF (diluted hydrofluoric acid, 100:1) for one minute. The following PEALD deposition cycle was used: 5-second Ru precursor pulse; 5-second argon purging; 10-second ammonia (NH3) plasma pulse; 5-second argon purging (5-5-10-5). The sample temperature was 330 °C, and a chamber pressure of 1 Torr was used. For Ru precursor delivery, an argon carrier flow rate of 250 sccm and an ampoule temperature of 100 °C were used. Argon flowed into the chamber at 610 sccm throughout the cycle. The results are presented in… Figure 4 In the figure, the diagram is a graphical view of the ruthenium film thickness relative to an atomic layer deposition cycle according to some embodiments.

[0103] Example 18

[0104] PEALD deposition of p-methylisopropylbenzene (1,3-cyclohexadiene)Ru was performed using an NH3 pulse at a plasma power of 400 W and a cyclic pulse sequence of (5-5-10-5). p-Methylisopropylbenzene (1,3-cyclohexadiene)Ru (p-methylisopropylbenzene CHD Ru) was used. SiN was used as the substrate for Ru deposition. The following PEALD deposition cycle was used: 5 sec Ru precursor pulse; 5 sec argon purge; 10 sec ammonia (NH3) plasma pulse; 5 sec argon purge (5-5-10-5). The sample temperature was 330 °C, and a chamber pressure of 1 Torr was used. For Ru precursor delivery, an argon carrier flow rate of 250 sccm and an ampoule temperature of 100 °C were used. Argon flow into the chamber was 610 sccm throughout the cycle. The results are presented in… Figure 4 In the figure, the diagram is a graphical view of the ruthenium film thickness relative to an atomic layer deposition cycle according to some embodiments.

[0105] Example 19

[0106] PEALD deposition of p-methylisopropylbenzene (1,3-cyclohexadiene)Ru was performed using an NH3 pulse at a plasma power of 400 W and a cyclic pulse sequence of (5-5-10-5). p-Methylisopropylbenzene (1,3-cyclohexadiene)Ru (p-methylisopropylbenzene CHD Ru) was used. SiO2 (e.g., SiO2 native oxide) was used as the substrate for Ru deposition. The following PEALD deposition cycle was used: 5 sec Ru precursor pulse; 5 sec argon purge; 10 sec ammonia (NH3) plasma pulse; 5 sec argon purge (5-5-10-5). The sample temperature was 330 °C, and a chamber pressure of 1 Torr was used. For Ru precursor delivery, an argon carrier flow rate of 250 sccm and an ampoule temperature of 100 °C were used. Argon flow into the chamber was 610 sccm throughout the cycle. The results are presented in… Figure 4 In the figure, the diagram is a graphical view of the ruthenium film thickness relative to an atomic layer deposition cycle according to some embodiments.

[0107] Example 20

[0108] PEALD deposition of p-methylisopropylbenzene (1,3-cyclohexadiene)Ru was performed using NH3 pulses at a plasma power of 400W and a cyclic pulse sequence of (5-5-10-5). The p-methylisopropylbenzene (1,3-cyclohexadiene)Ru (p-methylisopropylbenzene CHD Ru) was used. Thermal oxides (TO) xThe substrate was used 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 sample temperature was 330°C, and a chamber pressure of 1 Torr was used. For Ru precursor delivery, an argon carrier flow rate of 250 sccm and an ampoule temperature of 100°C were used. Argon flow into the chamber was 610 sccm throughout the cycle. The results are presented in… Figure 4 In the figure, the diagram is a graphical view of the ruthenium film thickness relative to an atomic layer deposition cycle according to some embodiments.

[0109] Example 21

[0110] PEALD deposition of p-methylisopropylbenzene (1,3-cyclohexadiene)Ru was performed using an NH3 pulse at a plasma power of 400 W and a cyclic pulse sequence of (5-5-10-5). p-Methylisopropylbenzene (1,3-cyclohexadiene)Ru (p-methylisopropylbenzene CHD Ru) was used. Silicon / polycrystalline silicon was used as the substrate for Ru deposition. The following PEALD deposition cycle was used: 5 sec Ru precursor pulse; 5 sec argon purge; 10 sec ammonia (NH3) plasma pulse; 5 sec argon purge (5-5-10-5). The sample temperature was 330 °C, and a chamber pressure of 1 Torr was used. For Ru precursor delivery, an argon carrier flow rate of 250 sccm and an ampoule temperature of 100 °C were used. Argon flow into the chamber was 610 sccm throughout the cycle. The results are presented in… Aspects In the figure, the diagram is a graphical view of the ruthenium film thickness relative to an atomic layer deposition cycle according to some embodiments.

[0111] ​

[0112] Various aspects are described below. It should be understood that any one or more of the features described in one or more of the following aspects may be combined with any one or more of the other aspects.

[0113] Aspect 1. A method comprising:

[0114] At least a portion of the ruthenium precursor is vaporized to produce a vaporized ruthenium precursor;

[0115] The first and second surface portions of the substrate are brought into contact with a vaporized ruthenium precursor and at least one reducing gas; and

[0116] Ruthenium is deposited 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.

[0117] Aspect 2. The method according to aspect 1, wherein the first surface portion of the substrate comprises at least one of the following: TaN, WCN, WN, TiN, Cu, W, Co, TaN, TiN, Mo, MoN, MoCN, DHF, SiGe, SiGe, or any combination thereof.

[0118] Aspect 3. The method according to aspect 1 or 2, wherein the second surface portion of the substrate comprises at least one of the following: SiO2, SiN, silicon, DHF silicon, native silicon oxide, SiCOH, SiOCNH, low-k dielectric, porous low-k dielectric, or any combination thereof.

[0119] Aspect 4. The method described according to any one of aspects 1 to 3,

[0120] The first surface portion includes:

[0121] At least one of TaN, WCN, WN, TiN, or any combination thereof; and

[0122] The second surface portion includes:

[0123] At least one of SiO2, SiN, SiOCNH, or any combination thereof.

[0124] Aspect 5. The method according to aspect 4, wherein the first surface portion contacts the gate of the transistor, and the second surface portion electrically isolates the gate from the other parts of the structure.

[0125] Aspect 6. The method according to aspect 4, wherein the first surface portion and the second surface portion are portions of a gate-all-around (GAA) transistor.

[0126] Aspect 7. The method described according to any one of aspects 1 to 3,

[0127] The first surface portion includes:

[0128] At least one of Cu, W, Co, TaN, WCN, TiN, Mo, MoN, MoCN, or any combination thereof; and

[0129] The second surface portion of the through-hole includes SiN, SiO2, or a low-K dielectric.

[0130] Aspect 8. The method according to aspect 7, wherein the first surface portion is located at the bottom of the through-hole structure, and the second surface portion electrically isolates the through-hole from the other parts of the structure.

[0131] Aspect 9. The method described according to any one of aspects 1 to 3,

[0132] The first surface portion includes DHF SiGe or SiGe, and

[0133] The second surface portion includes at least one of SiO2, SiN, DHF polycrystalline silicon / silicon, silicon, native silicon oxide, SiOCNH, or any combination thereof.

[0134] Aspect 10. The method according to aspect 9, wherein the first surface portion and the second surface portion are portions of a gate-all-around (GAA) transistor.

[0135] Aspect 11. The method according to any one of aspects 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.

[0136] Aspect 12. The method according to any one of aspects 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.

[0137] Aspect 13. The method according to any one of aspects 1 to 12, wherein at least one reducing gas comprises NH3.

[0138] Aspect 14. The method according to any one of aspects 1 to 13, wherein at least one reducing gas comprises H2.

[0139] Aspect 15. The method according to any one of aspects 1 to 14, wherein the deposition is carried out in a substantially oxygen-free chamber.

[0140] Aspect 16. The method according to any one of aspects 1 to 15, wherein ruthenium is selectively deposited on a first surface portion of the substrate with a minimum of 40 Å relative to a second surface portion of the substrate.

[0141] Aspect 17. The method according to any one of aspects 1 to 16, wherein ruthenium is selectively deposited on a first surface portion of the substrate with a density of 40 Å to 80 Å relative to a second surface portion of the substrate.

[0142] Aspect 18. An apparatus comprising:

[0143] A substrate having a first surface portion and a second surface portion adjacent to the first surface portion; and

[0144] A ruthenium layer, which is located on the first surface portion of the substrate,

[0145] The ruthenium layer has a thickness of at least 25 Å on the first surface portion of the substrate;

[0146] The second surface portion of the substrate does not include ruthenium.

[0147] Aspect 19. The apparatus according to aspect 18, wherein a first surface portion of the substrate comprises at least one of the following: TaN, WCN, WN, TiN, Cu, W, Co, TaN, TiN, Mo, MoN, MoC, MoCN, DHF, SiGe, SiGe, or any combination thereof.

[0148] Aspect 20. The apparatus according to aspect 18 or 19, wherein the second surface portion of the substrate comprises at least one of the following: SiO2, SiN, silicon, DHF silicon, native silicon oxide, SiCOH, SiOCNH, low-k dielectric, porous low-k dielectric, or any combination thereof.

[0149] Aspect 21. The apparatus according to any one of aspects 18 to 20,

[0150] The first surface portion includes:

[0151] At least one of TaN, WCN, WN, MoN, TiN, or any combination thereof; and

[0152] The second surface portion includes:

[0153] At least one of SiO2, SiN, or any combination thereof.

[0154] Aspect 22. The apparatus according to aspect 21, wherein the first surface portion and the second surface portion are portions of a gate-all-around (GAA) transistor.

[0155] Aspect 23. The apparatus according to any one of aspects 18 to 20,

[0156] The first surface portion includes:

[0157] At least one of Cu, W, Co, TaN, WCN, TiN, Mo, MoN, MoC, MoCN, or any combination thereof;

[0158] The second surface portion includes SiO2.

[0159] Aspect 24. The apparatus according to aspect 23, wherein a first surface portion is located at the bottom of the through-hole structure, and a second surface portion electrically isolates the through-hole from other parts of the structure.

[0160] Aspect 25. The apparatus according to any one of aspects 18 to 20,

[0161] The first surface portion comprises DHF SiGe, SiGe, or any combination thereof; and

[0162] The second surface portion includes at least one of SiO2, SiN, DHF polycrystalline silicon / silicon, silicon, native silicon oxide, or any combination thereof.

[0163] Aspect 26. The apparatus according to aspect 25, wherein the first surface portion and the second surface portion are portions of a gate-all-around (GAA) transistor.

[0164] It should be understood that detailed changes may be made without departing from the scope of this disclosure, particularly in terms of the building materials used, and the shape, size, and arrangement of parts. This specification and the described embodiments are examples, wherein the true scope and spirit of this disclosure are indicated by the appended claims.

Claims

1. A method comprising: At least a portion of the ruthenium precursor is vaporized to produce a vaporized ruthenium precursor; The first and second surface portions of the substrate are brought into contact with the vaporized ruthenium precursor and at least one reducing gas. as well as Ruthenium is deposited 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.

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

3. The method of claim 1, wherein the second surface portion of the substrate comprises at least one of the following: SiO2, SiN, silicon, DHF silicon, native silicon oxide, SiCOH, SiOCNH, low-k dielectric, porous low-k dielectric, or any combination thereof.

4. The method according to claim 1, The first surface portion includes: At least one of TaN, WCN, WN, TiN, or any combination thereof; and The second surface portion includes: At least one of SiO2, SiN, SiOCNH, or any combination thereof.

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

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

7. The method according to claim 1, The first surface portion includes: At least one of Cu, W, Co, TaN, WCN, TiN, Mo, MoN, MoCN, or any combination thereof; and The second surface portion of the through-hole comprises SiN, SiO2, or a low-K dielectric.

8. The method of claim 7, wherein the first surface portion is located at the bottom of the through-hole structure, and the second surface portion electrically isolates the through-hole from other portions of the structure.

9. The method according to claim 1, The first surface portion comprises DHF SiGe or SiGe, and The second surface portion includes at least one of SiO2, SiN, DHF polycrystalline silicon / silicon, silicon, native silicon oxide, SiOCNH, or any combination thereof.

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

11. The method of 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 of 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. The method according to claim 1, wherein the at least one reducing gas comprises NH3.

14. The method according to claim 1, wherein the at least one reducing gas comprises H2.

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

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

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

18. An apparatus comprising: A substrate having a first surface portion and a second surface portion adjacent to the first surface portion; as well as A ruthenium layer, which is located on the first surface portion of the substrate. 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 include ruthenium.

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

20. The apparatus of claim 18, wherein the second surface portion of the substrate comprises at least one of the following: SiO2, SiN, silicon, DHF silicon, native silicon oxide, SiCOH, SiOCNH, low-k dielectric, porous low-k dielectric, or any combination thereof.

21. The apparatus according to claim 18, The first surface portion includes: At least one of TaN, WCN, WN, MoN, TiN, or any combination thereof; and The second surface portion includes: At least one of SiO2, SiN, or any combination thereof.

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

23. The apparatus according to claim 18, The first surface portion includes: At least one of Cu, W, Co, TaN, WCN, TiN, Mo, MoN, MoC, MoCN, or any combination thereof; The second surface portion includes SiO2.

24. The apparatus of claim 23, wherein the first surface portion is located at the bottom of the through-hole structure, and the second surface portion electrically isolates the through-hole from other portions of the structure.

25. The apparatus according to claim 18, The first surface portion comprises DHF SiGe, SiGe, or any combination thereof; and The second surface portion includes at least one of SiO2, SiN, DHF polycrystalline silicon / silicon, silicon, native silicon oxide, or any combination thereof.

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

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