High purity alkynylamines for selective deposition

Abstract

The disclosed and claimed subject matter relates to high purity alkynylamines substantially free of residual halides and / or water and their use for enhancing passivation of metal substrates (e.g., in formulations).

Description

Background Field of the Invention

[0002] The disclosed and claimed subject matter relates to high purity alkynylamines that can be used for the selective deposition of dielectric films on non-metallic substrates. In particular, the disclosed and claimed subject matter relates to high purity alkynylamines and their use for enhanced passivation of metal substrates.

[0003] Related Art

[0004] Transition metal-containing films are used in semiconductor and electronic applications. Chemical vapor deposition (CVD) and atomic layer deposition (ALD) have been used as the main deposition techniques for producing thin films for semiconductor devices. These methods enable conformal films (metals, metal oxides, metal nitrides, metal silicides, etc.) to be obtained through chemical reactions of metal-containing compounds (precursors). The chemical reactions occur on surfaces that can include metals, metal oxides, metal nitrides, metal silicides, and other surfaces. In CVD and ALD, the precursor molecules play a key role in obtaining high-quality films with high conformality and low impurities. The substrate temperature in CVD and ALD processes is an important consideration in the selection of precursor molecules. Higher substrate temperatures in the range of 150 to 500 degrees Celsius (°C) promote higher film growth rates. Preferred precursor molecules must be stable within this temperature range. Preferred precursors can be delivered to the reaction vessel in the liquid phase. Liquid phase delivery of precursors generally provides more uniform precursor delivery to the reaction vessel than solid phase precursors.

[0005] CVD and ALD processes are increasingly being used because they have the advantages of enhanced compositional control, high film uniformity, and effective doping control. In addition, CVD and ALD processes provide excellent conformal step coverage on the highly non-planar geometries associated with modern microelectronic devices. CVD and ALD are particularly attractive for fabricating conformal metal-containing films on substrates such as silicon, silicon oxide, metal nitride, metal oxide, and other metal-containing layers using these metal-containing precursors. In these techniques, the vapor of a volatile metal complex is introduced into the processing chamber, where it contacts the surface of the silicon wafer, and a chemical reaction occurs to deposit a thin film of pure metal or metal compound.

[0006] CVD is a chemical process in which a precursor is used to form a thin film on a substrate surface. In a typical CVD process, a precursor passes through the surface of a substrate (e.g., a wafer) in a low pressure or ambient pressure reaction chamber. The precursor reacts and / or decomposes on the substrate surface to produce a thin film of deposited material. Plasma can be used to help the reaction of the precursor or to improve material properties. Volatile byproducts are removed by a gas stream passing through the reaction chamber. The film thickness of the deposit may be difficult to control because it depends on the coordination of many parameters, such as temperature, pressure, gas flow and uniformity, chemical depletion effects, and time. Therefore, CVD occurs where the precursor reacts thermally at the wafer surface or reacts with a reagent added to the processing chamber at the same time, and film growth occurs in a steady-state deposition. CVD can be applied in a continuous or pulsed mode to obtain a desired film thickness.

[0007] ALD is a chemical method for depositing thin films. It is a self-limiting, sequential, unique film growth technology based on surface reactions, which can provide precise thickness control and deposit conformal material films provided by precursors onto substrate surfaces of different compositions. In ALD, the precursors are separated during the reaction. The first precursor passes through the substrate surface, thereby producing a monolayer on the substrate surface. Any excess unreacted precursor is pumped out of the reaction chamber. Then the second precursor or co-reactant is passed through the substrate surface and reacts with the first precursor, thereby forming a second film monolayer on the film monolayer first formed on the substrate surface. Plasma can be used to help the reaction of the precursor or co-reactant or to improve the quality of the material. Repeat the cycle to produce a film of the desired thickness. ALD provides ultra-thin but continuous deposition of metal-containing films with precise film thickness control, excellent film thickness uniformity, and exceptionally conformal film growth to uniformly coat deeply etched and highly complex structures, such as interconnected vias and trenches. Therefore, ALD is generally preferred for depositing thin films on features with high aspect ratios.

[0008] Thin films, and in particular metal-containing thin films, have a variety of important applications, such as in nanotechnology and semiconductor device manufacturing. Examples of such applications include capacitor electrodes, gate electrodes, adhesion diffusion barriers, and integrated circuits. However, the continuous reduction in the size of microelectronic components such as semiconductor devices has presented several technical challenges and has increased the need for improved thin film technology. In particular, microelectronic components may include features on or in a substrate that need to be filled, for example, to form conductive paths or to form interconnects. Filling such features, especially in increasingly smaller microelectronic components, can be challenging because these features can become thinner or narrower. Thus, as the thickness of the feature approaches zero, complete filling of the feature, for example, by ALD, requires extremely long cycle times. In addition, once the thickness of the feature becomes narrower than the size of the precursor molecules, the feature cannot be completely filled. As a result, when ALD is performed, a hollow seam may remain in the middle portion of the feature. The presence of such hollow seams within the feature is undesirable because they can lead to device failures. Therefore, there is great interest in the development of thin film deposition methods, particularly ALD methods, that can selectively grow a film on one or more substrates and achieve improved filling of features on or in the substrate, including depositing metal-containing films in a manner that substantially fills the feature without any voids.

[0009] As described above, in conventional semiconductor device manufacturing, patterning is a “top-down” process mainly based on lithography and etching, which is the main bottleneck for device size reduction. In contrast, area-selective deposition (e.g., CVD and ALD) provides an alternative “bottom-up” patterning method for advanced semiconductor manufacturing, where a metal layer (e.g., Ru) grows on the bottom metal surface (e.g., Ru and TiN) close to a passivated dielectric substrate, rather than on the sidewalls of the dielectric (e.g., SiO2). See, for example, Figure 1 . It is also desirable that these processes are oxygen-free and / or have a low resistivity.

[0010] In another application, it is desirable to deposit a dielectric film only on another dielectric film, rather than on a metal surface. See, for example, Figure 2 . One potential application of such a process is self-aligned manufacturing. The most common strategy for achieving selective growth is based on the selective passivation of non-growing surfaces. Small volatile molecules are highly desirable for passivation because they can be supplied through the gas phase. Selective passivation of non-metal surfaces with a high hydroxyl concentration is widely used and includes reactions with various silylation reagents, such as R x SiCl y 、R x Si(NR2) yetc. On the other hand, the selective passivation of metal surfaces is much more challenging, and the selectivity through this route is easily lost due to desorption of the passivating agent and incomplete passivation due to impurities remaining on the surface of the metal film, etc. Generally, single-component reagents are used to passivate non-growing surfaces. However, due to the presence of different sites on the metal surface, such as, for example, "bare" metal, metal terminated with hydrogen atoms, metal terminated with oxygen atoms or hydroxyl groups, etc., single-component reagents may not provide complete surface coverage of the metal surface.

[0011] Alkynes have been used for the passivation of metal surfaces to sufficiently inhibit film growth on non-growing metal surfaces while depositing a film on the growing dielectric surface. However, due to contamination by trace amounts of moisture, halides, and carboxylic acids, the non-functionalized alkynes described previously provide insufficient passivation at metal sites. Typically, alkyl-substituted alkynes are prepared by reacting metal acetylides with alkyl halides followed by aqueous treatment. See, for example, Morrison and Boyd, Organic Chemistry, 558-560 (1983). Thus, the alkynes are contaminated with traces of residual alkyl halides, moisture, and carboxylic acids.

[0012] For example, U.S. Patent Application Publication No. 2020 / 0347493 discloses a method for selectively depositing a dielectric film on a non-metal surface. The disclosed method requires passivating or blocking the metal surface before depositing the dielectric film. In some embodiments, the method includes treating the metal surface with an unsaturated hydrocarbon having at least one carbon-carbon triple bond (e.g., 3-hexyne, 4-octyne, 5-decyne, 6-dodecyne, and 7-tetradecyne). According to this application, it is believed that the unsaturated hydrocarbon inhibits nucleation and growth on the metal substrate. While this application provides a method for closing the metal surface, it does not teach or suggest a method for passivating residual metal oxide sites present on the metal surface.

[0013] Renewable selective passivation of metal surfaces requires careful design of precursors and deposition processes. In fact, it is highly desirable to reduce and / or eliminate passivation of the dielectric surface while enhancing passivation of the metal surface. The disclosed and claimed subject matter provides compositions and methods for enhancing passivation and / or blocking of metal surfaces and for enhancing selective deposition on non-metal surfaces relative to metal surfaces.

[0014] In order to achieve selective surface growth in semiconductor manufacturing processes (i.e., growth and non-growth simultaneously or substantially simultaneously on different surfaces), it is generally necessary to utilize (i) a metal surface assumed to be free or substantially free of hydroxyl groups, and (ii) a non-metal surface containing a high concentration of hydroxyl groups. Examples of suitable metal surfaces include, but are not limited to, copper, cobalt, tungsten, molybdenum, nickel, ruthenium, etc. Examples of non-metal surfaces include, but are not limited to, silicon oxide, low-K carbon-doped silicon oxide, silicon nitride, silicon carbonitride, and metal oxides such as aluminum oxide, tantalum oxide, hafnium oxide, zirconium oxide, etc. Examples of films deposited on non-metal surfaces include, but are not limited to, silicon oxide, aluminum oxide, tantalum oxide, titanium oxide, hafnium oxide, zirconium oxide, tantalum nitride, titanium nitride, etc. These films are deposited on non-metal surfaces by the above chemical vapor deposition and atomic layer deposition processes. Precursors for depositing films include, but are not limited to, trimethylaluminum, tetra(dimethylamino)titanium, penta(dimethylamino)tantalum, tert-butylimino-tris(dimethylamino)tantalum, tert-butylimino-tris(dimethylamino)niobium, etc. Co-reactants include, but are not limited to, water, ammonia.

[0015] To achieve selective deposition, the metal surface must be passivated and be free or substantially free of chemical groups reactive to the precursors and co-reactants used for film deposition in the next process step, such as, for example, ammonia. On the other hand, the reactants used for passivating the metal surface should not passivate the desired growth on the non-metal surface. The disclosed and claimed formulations containing alkynylamines are uniquely designed to balance these requirements in the selective deposition process. Summary of the Invention

[0017] The disclosed and claimed subject matter relates to high-purity alkynylamines substantially free of impurities (including residual halides and / or water) and their use for enhancing the passivation of metal substrates (e.g., in formulations).

[0018] In another embodiment, the disclosed and claimed subject matter includes using the above formulations in a selective CVD deposition process.

[0019] In another embodiment, the disclosed and claimed subject matter includes using the above formulations in a selective ALD deposition process. Brief Description of the Drawings

[0021] The drawings, which are included to provide a further understanding of the disclosed subject matter and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosed subject matter and, together with the specification, are used to explain the principles of the disclosed subject matter. In the drawings:

[0022] Figure 1 An exemplary target of a selective deposition process is shown, where a metal film is selectively deposited on a conductive film while the dielectric film is passivated;

[0023] Figure 2 Shows an exemplary target for a selective deposition process, where a dielectric film is selectively deposited on a dielectric film while the metal surface is passivated;

[0024] Figure 3 Shows the adsorption of 1,4 - bis(dimethylamino)-2-butyne (a) and 1,4 - bis(n-propylamino)-2-butyne (b) on the Cu(100) surface;

[0025] Figure 4 Shows the thermogravimetric analysis (TGA) of 1,4 - bis(dimethylamino)-2-butyne under flowing nitrogen; and

[0026] Figure 5 Shows the thermogravimetric analysis (TGA) of low - purity 1,4 - bis(dimethylamino)-2-butyne under flowing nitrogen. Detailed Description of the Invention

[0028] All references cited herein, including published publications, patent applications, and patents, are hereby incorporated by reference as if each reference were individually and specifically indicated to be incorporated by reference and were set forth in full herein.

[0029] In the context of describing the disclosed and claimed subject matter (especially in the context of the following claims), the use of the terms "a" and "an" and "the" and similar referents should be construed to cover the singular and the plural unless otherwise indicated herein or clearly contradicted by the context. Unless otherwise indicated, the terms "comprising," "having," "including," and "containing" should be construed as open - ended terms (i.e., meaning "including, but not limited to"). Unless otherwise indicated herein, the recitation of numerical ranges herein is merely intended to be a shorthand method for individually referring to each separate value falling within the range, and each separate value is incorporated into the specification as if it were individually recited herein. Unless otherwise indicated herein or clearly contradicted by the context, all methods described herein can be performed in any suitable order. The use of any and all examples or exemplary language (e.g., "such as") provided herein is merely intended to better illuminate the disclosed and claimed subject matter and, unless otherwise required, does not limit the scope of the disclosed and claimed subject matter. No language in the specification should be construed as indicating any non - claimed element as essential to the practice of the disclosed and claimed subject matter. The use of the term "comprising" or "including" in the specification and claims includes the narrower language of "consisting essentially of" and "consisting of."

[0030] This document describes embodiments of the disclosed and claimed subject matter, including the best mode known to the inventors for practicing the disclosed and claimed subject matter. Variations of those embodiments will be apparent to one of ordinary skill in the art after reading the foregoing description. The inventors expect skilled artisans to employ such variations appropriately, and the inventors intend for the disclosed and claimed subject matter to be practiced otherwise than as specifically described herein. Accordingly, the disclosed and claimed subject matter includes all modifications and equivalents of the subject matter recited in the appended claims as permitted by applicable law. In addition, any combination of the above-described elements in all possible variations thereof is included in the disclosed and claimed subject matter unless otherwise stated herein or the context clearly dictates otherwise.

[0031] It should be understood that the term "silicon" as a material deposited on a microelectronic device will include polysilicon.

[0032] For purposes of reference, a "microelectronic device" or "semiconductor device" corresponds to a semiconductor wafer on which integrated circuits, memories, and other electronic structures are fabricated, as well as flat panel displays, phase change memory devices, solar panels, and other products, including solar substrates, photovoltaic devices, and microelectromechanical systems (MEMS), which are fabricated for microelectronic, integrated circuit, or computer chip applications. Solar substrates include, but are not limited to, silicon, amorphous silicon, polysilicon, monocrystalline silicon, CdTe, copper indium selenide, copper indium sulfide, and gallium arsenide on gallium. Solar substrates can be doped or undoped. It should be understood that the terms "microelectronic device" or "semiconductor device" are not meant to be limiting in any way, but include any substrate that will ultimately become a microelectronic device or microelectronic component.

[0033] As defined herein, the term "barrier material" corresponds to any material used in the art to seal metal lines (e.g., copper interconnects) to minimize the diffusion of the metal (e.g., copper) into a dielectric material. Preferred barrier layer materials include tantalum, titanium, ruthenium, hafnium, and other refractory metals and their nitrides and silicides.

[0034] "Substantially free of" is defined herein as less than 0.001 weight %. "Substantially free of" also includes 0.000 weight %. The term "free of" means 0.000 weight %. As used herein, "about" or "approximate" is intended to correspond to within ±5% of the stated value.

[0035] Unless otherwise specified, "alkylene" refers to a straight-chain saturated divalent hydrocarbon group having 1 to 6 carbon atoms or a branched-chain saturated divalent hydrocarbon group having 3 to 6 carbon atoms (e.g., methylene, ethylene, propylene, 1-methylpropylene, 2-methylpropylene, butylene, pentylene, etc.).

[0036] "Heteroalkylene" means a -(alkylene)- group as defined above, wherein one, two or three carbons in the alkylene chain are replaced by -O-, N(H, alkyl or substituted alkyl), S, SO, SO2 or CO. In some preferred embodiments, the carbon is replaced by O or N.

[0037] In all such compositions where the specific components of the composition are discussed with reference to weight percentage (or "wt%") ranges that include a zero lower limit, it should be understood that such components may or may not be present in various specific embodiments of the composition, and where such components are present, they may be present at a concentration as low as 0.001 wt% based on the total weight of the composition in which they are used. Note that all component percentages are weight percentages and are based on the total weight of the composition, i.e., 100%. Any reference to "one or more" or "at least one" includes "two or more" and "three or more" and so on.

[0038] Where applicable, unless otherwise stated, all weight percentages are "net", meaning they do not include the aqueous solution in which they are present when added to the composition. For example, "net" refers to the amount of the weight % of an undiluted acid or other substance (i.e., 85% phosphoric acid containing 100 grams constitutes 85 grams of acid and 15 grams of diluent).

[0039] Furthermore, when referring to the compositions described herein in terms of wt%, it should be understood that in any case the weight % of all components (including non-essential components such as impurities) add up to no more than 100 wt%. In a composition "consisting essentially of the said components", these components may add up to 100 wt% of the composition or may add up to less than 100 wt%. When the components add up to less than 100 wt%, such a composition may contain some minor non-essential contaminants or impurities. For example, in one such embodiment, the formulation may contain 2 wt% or less of impurities. In another embodiment, the formulation may contain 1 wt% or less of impurities. In a further embodiment, the formulation may contain 0.05 wt% or less of impurities. In other such embodiments, the ingredients may constitute at least 90 wt%, more preferably at least 95 wt%, more preferably at least 99 wt%, more preferably at least 99.5 wt%, most preferably at least 99.9 wt%, and may include other ingredients that do not substantially affect the performance. Otherwise, if there are no significant non-essential impurity components, it should be understood that the composition of all essential components essentially adds up to 100 wt%.

[0040] The headings used herein are not restrictive; rather, they are for organizational purposes only.

[0041] As described above, the disclosed and claimed subject matter relates to high purity alkynylamines that are substantially free of halides, water, and other related impurities, and their use for enhanced passivation of metal substrates (e.g., in formulations). In particular, it has been found that high purity alkynylamines can readily passivate metal surfaces that are free or substantially free of hydroxyl groups through strong adsorption on the "bare" metal surface. For example, it has been demonstrated that alkynylamines strongly adsorb on the "bare" copper surface with an adsorption energy of -60 to -65 kcal / mol. On the other hand, this behavior is at most inconsistent on partially hydroxylated metal surfaces; for example, it has also been observed that unsubstituted alkynylamines do not adsorb well on hydroxylated metal surfaces such as cuprous oxide (I). Thus, although it is possible to use alkynylamines on "bare" metal surfaces, most metal surfaces contain residual oxides that require further treatment to make them freely reactive. Therefore, it is crucial to eliminate impurities that can form hydroxylated metal surfaces. It has also been found that the adsorption of halides on metal surfaces is very thermodynamically favorable. Residual halides on the metal surface react with the precursors and reactants used in selective deposition and inhibit process selectivity. Therefore, it is crucial to eliminate halogen-containing impurities that can form halide-containing substances on the metal substrate.

[0042] The disclosed and claimed formulations

[0043] In view of the foregoing, in one embodiment, the disclosed and claimed subject matter relates to high purity alkynylamines that are substantially free of residual halides and / or water. Preferred high purity alkynylamines include those exemplified in Tables 1 and 2. However, it should be understood that the high purity alkynylamines of the disclosed and claimed subject matter are not limited to those exemplified in Tables 1 and 2.

[0044]

[0045]

[0046] Table 1

[0047]

[0048] Table 2

[0049] A preferred high purity alkynylamine is N,N-(1-diisopropylamino)-2-butyne (1F).

[0050] Another preferred high purity alkynylamine is 1,4-bis(dimethylamino)-2-butyne (2A).

[0051] In one embodiment, the high-purity alkynylamine is substantially free of water. In one aspect of this embodiment, the high-purity alkynylamine has a residual water concentration of less than about 500 ppm. In one aspect of this embodiment, the high-purity alkynylamine has a residual water concentration of less than about 100 ppm. In one aspect of this embodiment, the high-purity alkynylamine has a residual water concentration of less than about 50 ppm. In one aspect of this embodiment, the high-purity alkynylamine has a residual water concentration of less than about 25 ppm. In one aspect of this embodiment, the high-purity alkynylamine has a residual water concentration of less than about 10 ppm. In one aspect of this embodiment, the high-purity alkynylamine is free of detectable water. In one aspect of this embodiment, the high-purity alkynylamine is free of water.

[0052] In one embodiment, the high-purity alkynylamine is substantially free of impurities that can react with the metal surface during the passivation process. In one embodiment, the high-purity alkynylamine is substantially free of impurities that react with the precursor during the deposition process.

[0053] In one embodiment, the high-purity alkynylamine is substantially free of impurities that passivate non-metal surfaces and inhibit growth on non-metal surfaces.

[0054] In one embodiment, the high-purity alkynylamine is substantially free of halogen-containing impurities. In one aspect of this embodiment, the halogen-containing impurity is one or more of fluorohydrocarbons, chlorohydrocarbons, bromohydrocarbons, and iodohydrocarbons. In another aspect of this embodiment, the halogen-containing impurity is an ammonium halide salt. In one aspect of this embodiment, the high-purity alkynylamine has a residual concentration of halogen-containing impurities of less than about 1000 ppm. In one aspect of this embodiment, the high-purity alkynylamine has a residual concentration of halogen-containing impurities of less than about 500 ppm. In one aspect of this embodiment, the high-purity alkynylamine has a residual concentration of halogen-containing impurities of less than about 100 ppm. In one aspect of this embodiment, the high-purity alkynylamine has a residual concentration of halogen-containing impurities of less than about 50 ppm. In one aspect of this embodiment, the high-purity alkynylamine has a residual concentration of halogen-containing impurities of less than about 10 ppm. In one aspect of this embodiment, the high-purity alkynylamine is free of halogen-containing impurities. In the above aspects, the residual concentration of halogen-containing impurities is detected by one or more of GC-ICP-OES, FC-FID, GC-ECD, HPLC, and UV / Vis.

[0055] In one embodiment, high-purity alkynylamine is purified by adsorption on alumina. In one aspect of this embodiment, the alkynylamine passes through an adsorption bed filled with acidic alumina. In another aspect of this embodiment, the alkynylamine passes through an adsorption bed filled with neutral alumina. In another aspect of this embodiment, the alkynylamine passes through an adsorption bed filled with basic alumina. In another aspect of this embodiment, the alkynylamine passes through an adsorption bed comprising a combination of acidic, basic, and neutral alumina.

[0056] In one embodiment, high-purity alkynylamine is purified by exposure to molecular sieves. In one embodiment, high-purity alkynylamine is purified by exposure to silica gel. In one embodiment, high-purity alkynylamine is purified by exposure to one or more adsorbent materials.

[0057] In another embodiment, the high-purity alkynylamine is a high-purity alkynylamine purified by exposure to one or more metal salts. In one embodiment, the alkynylamine is purified by exposure to one or more silver salts. In one embodiment, the alkynylamine is purified by exposure to silver carbonate. In one embodiment, the alkynylamine is purified by exposure to supported silver carbonate.

[0058] In one embodiment, high-purity alkynylamine is purified by exposure to activated carbon. In one aspect of this embodiment, the alkynylamine is separated by filtration and the non-volatile products are removed by distillation after treatment with activated carbon.

[0059] In another aspect of this embodiment, (i) one or more alkynylamines are high-purity alkynylamines.

[0060] In another embodiment, (i) one or more alkynylamines are alkynyl diamines. In another embodiment, (i) one or more alkynylamines are high-purity alkynyl diamines.

[0061] Method of Use

[0062] The disclosed and claimed subject matter also includes using one or more of the disclosed and claimed high-purity alkynylamines in chemical vapor deposition processes known to those skilled in the art. As used herein, the term "chemical vapor deposition process" refers to any process in which a substrate is exposed to one or more volatile precursors that react and / or decompose on the surface of the substrate to produce the desired deposition.

[0063] In one embodiment, the method includes passivating a metal surface of a substrate using one or more of the disclosed and claimed high-purity alkynylamines and inhibiting the growth of an oxide or nitride film on the metal surface during a film deposition step that follows the surface passivation. The metal surface can include, but is not limited to, Au, Pd, Rh, Ru, W, Mo, Al, Ni, Cu, Ti, Co, Pt, and metal silicides (e.g., TiSi2, CoSi2, and NiSi2). Metal nitride films deposited on the pre-passivated metal substrate can include, but are not limited to, TaN, TiN, WN, MoN, TaCN, TiCN, TaSiN, and TiSiN, as well as silicon nitride. Metal oxide films deposited on the pre-passivated metal substrate can include, but are not limited to, SiO2, SiON, HfO2, Ta2O5, ZrO2, TiO2, Al2O3, barium strontium titanate, and combinations thereof.

[0064] When used in such deposition methods and processes, the high-purity alkynylamines can be delivered to the reaction chamber, such as an ALD reactor, in a variety of ways. In some cases, a liquid delivery system can be used. In other cases, a combined liquid delivery and flash evaporation process unit, such as, for example, a turbo evaporator manufactured by MSP Corporation of Shoreview, MN, can be used to enable the quantitative delivery of low volatility materials, which results in reproducible delivery and deposition without thermal decomposition of the precursor. The claimed formulations described herein can be effectively used as source reagents by direct liquid injection (DLI) to provide a vapor stream of these metal precursors into an ALD reactor.

[0065] When used in these processes, the high-purity alkynylamines can be combined with, and include, a hydrocarbon solvent, which is particularly desirable due to its ability to be dried to a water content of sub-ppm. Exemplary hydrocarbon solvents that can be used for the precursor include, but are not limited to, toluene, mesitylene, cumene (isopropylbenzene), p-cymene (4-isopropyltoluene), 1,3-diisopropylbenzene, octane, dodecane, 1,2,4-trimethylcyclohexane, n-butylcyclohexane, and decalin (naphthane). In certain embodiments, the hydrocarbon solvent is a high-boiling solvent or has a boiling point of 100 °C or higher.

[0066] A flow of argon and / or other gases can be used as a carrier gas to assist in delivering the vapor containing the formulation to the reaction chamber during a formulation pulse. When delivering the high-purity alkynylamine, the reaction chamber process pressure is between 1 and 100 Torr, preferably between 5 and 20 Torr.

[0067] The substrate temperature can be an important process variable in the passivation of the metal-containing film. The typical substrate temperature range is from about 150 °C to about 350 °C.

[0068] In one embodiment, the disclosed and claimed subject matter includes a method for treating a metal surface in the presence of at least one other surface, the method comprising the steps of:

[0069] a. providing the at least one surface of the substrate in a reaction vessel;

[0070] b. forming at least one passivated surface by exposing the at least one surface to one or more of the disclosed and claimed high-purity alkynylamines.

[0071] In step (b), the at least one surface is passivated by exposing the at least one surface to one or more of the disclosed and claimed high-purity alkynylamines to form a passivation film on the at least one surface. In another aspect of this embodiment, the method includes depositing a nitride film on at least one passivated surface. In a further aspect of this embodiment, the method includes depositing an oxide film on at least one passivated surface.

[0072] In one embodiment, the method includes using an atomic layer deposition process (ALD), including plasma-enhanced ALD (PEALD), to deposit one or more precursors known in the art to form a film on the passivation film. As used herein, the term "atomic layer deposition process" or ALD refers to a self-limiting (e.g., the amount of film material deposited in each reaction cycle is constant), sequential surface chemistry for depositing a film of material onto a substrate of a different composition. Although the precursors, reagents, and sources used herein may sometimes be described as "gaseous," it should be understood that the precursors can be liquids or solids that are transported to the reactor by direct evaporation, bubbling, or sublimation with or without an inert gas. In some cases, the evaporated precursor can pass through a plasma generator. The term "reactor" as used herein includes, but is not limited to, a reaction chamber, a reaction vessel, or a deposition chamber.

[0073] In a further aspect of this embodiment, the method includes introducing at least one reactant into the reaction vessel, wherein the at least one reactant is selected from water, diatomic oxygen, oxygen plasma, ozone, NO, N2O, NO2, carbon monoxide, carbon dioxide, and combinations thereof. In another aspect of this embodiment, the method includes introducing at least one reactant into the reaction vessel, wherein the at least one reactant is selected from ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen / hydrogen, ammonia plasma, nitrogen plasma, nitrogen / hydrogen plasma, and combinations thereof. In another aspect of this embodiment, the method includes introducing at least one reactant into the reaction vessel, wherein the at least one reactant is selected from hydrogen, hydrogen plasma, a mixture of hydrogen and helium, a mixture of hydrogen and argon, hydrogen / helium plasma, hydrogen / argon plasma, boron-containing compounds, silicon-containing compounds, and combinations thereof.

[0074] The deposition methods and processes may also involve one or more purge gases. The purge gas used to purge away unconsumed reactants and / or reaction by-products is an inert gas that does not react with the precursors. Exemplary purge gases include, but are not limited to, argon (Ar), nitrogen (N2), helium (He), neon, and mixtures thereof. For example, a purge gas such as Ar is supplied to the reactor at a flow rate of about 10 to about 2000 sccm for about 0.1 to 10,000 seconds to purge unreacted materials and any by-products that may remain in the reactor.

[0075] The deposition methods and processes require applying energy to at least one of the precursors, oxidants, other precursors, or combinations thereof to induce a reaction and form a metal-containing film or coating on the substrate. This energy can be provided by, but not limited to, heat, plasma, pulsed plasma, helicon wave plasma, high density plasma, inductively coupled plasma, X-rays, electron beam, photons, remote plasma methods, and combinations thereof. In some processes, a second RF frequency source can be used to modify the plasma characteristics at the substrate surface. When using plasma, the plasma generation process can include a direct plasma generation process where the plasma is generated directly in the reactor, or alternatively, a remote plasma generation process where the plasma is generated outside the reactor and supplied to the reactor.

[0076] When used in such deposition methods and processes, suitable precursors can be delivered to the reaction chamber, such as an ALD reactor, in a variety of ways. In some cases, a liquid delivery system can be used. In other cases, a combined liquid delivery and flash evaporation process unit, such as, for example, a turbo evaporator manufactured by MSP Corporation of Shoreview, MN, can be used to enable the quantitative delivery of low volatility materials, which results in reproducible delivery and deposition without thermal decomposition of the precursors. The precursor compositions described herein can be effectively used as source reagents by direct liquid injection (DLI) to provide vapor streams of these metal precursors into the ALD reactor.

[0077] When used in these deposition methods and processes, the precursors can be combined with and include hydrocarbon solvents, which are particularly desirable due to their ability to be dried to sub-ppm water content. Exemplary hydrocarbon solvents that can be used for the precursors include, but are not limited to, toluene, mesitylene, cumene (isopropylbenzene), p-cymene (4-isopropyltoluene), 1,3-diisopropylbenzene, octane, dodecane, 1,2,4-trimethylcyclohexane, n-butylcyclohexane, and decalin (naphthane). In certain embodiments, the hydrocarbon solvent is a high boiling point solvent or has a boiling point of 100 °C or higher. The precursors can also be mixed with other suitable metal precursors, and the mixture is used to simultaneously deliver two metals for the growth of binary metal-containing films.

[0078] A flow of argon and / or other gases can be used as a carrier gas to assist in delivering the precursor-containing vapor to the reaction chamber during precursor pulses. When delivering the precursor, the reaction chamber process pressure is between 1 and 50 Torr, preferably between 5 and 20 Torr.

[0079] In the deposition of high-quality metal-containing films, the substrate temperature can be an important process variable. The typical substrate temperature range is from about 150 °C to about 550 °C. Higher temperatures can promote higher film growth rates.

[0080] In view of the foregoing, those skilled in the art will recognize that the disclosed and claimed subject matter also includes the use of the disclosed and claimed formulations in chemical vapor deposition (CVD) processes as described below.

[0081] In one embodiment, the disclosed and claimed subject matter includes a method of forming a metal-containing film on at least one surface of a substrate, the method comprising the steps of:

[0082] a. Providing at least one surface of a substrate in a reaction vessel;

[0083] b. Forming at least one passivated surface by exposing the at least one surface to one or more of the disclosed and claimed high-purity alkynylamines; and

[0084] c. Forming a transition metal-containing film on at least one pre-passivated surface during a deposition process by chemical vapor deposition (CVD) using one or more precursors.

[0085] In step (b), the at least one surface is passivated by exposing the at least one surface to one or more of the disclosed and claimed high-purity alkynylamines to form a passivation film on the at least one surface. In a further aspect of this embodiment, the method includes introducing at least one reactant into the reaction vessel. In another aspect of this embodiment, the method includes introducing at least one reactant into the reaction vessel, wherein the at least one reactant is selected from water, diatomic oxygen, oxygen plasma, ozone, NO, N2O, NO2, carbon monoxide, carbon dioxide, and combinations thereof. In another aspect of this embodiment, the method includes introducing at least one reactant into the reaction vessel, wherein the at least one reactant is selected from ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen / hydrogen, ammonia plasma, nitrogen plasma, nitrogen / hydrogen plasma, and combinations thereof. In another aspect of this embodiment, the method includes introducing at least one reactant into the reaction vessel, wherein the at least one reactant is selected from hydrogen, hydrogen plasma, a mixture of hydrogen and helium, a mixture of hydrogen and argon, hydrogen / helium plasma, hydrogen / argon plasma, boron-containing compounds, silicon-containing compounds, and combinations thereof.

[0086] In one embodiment, the disclosed and claimed subject matter includes a method of forming a metal-containing film by a thermal atomic layer deposition (ALD) process or a thermal ALD-like process, the method comprising the steps of:

[0087] a. Providing a substrate in a reaction vessel;

[0088] b. Forming at least one passivated surface by exposing at least one surface to one or more of the disclosed and claimed high-purity alkynylamines;

[0089] c. Purging the reaction vessel with a first purge gas;

[0090] d. Introducing one or more precursors into the reaction vessel;

[0091] e. Introducing a source gas into the reaction vessel;

[0092] f. Purging the reaction vessel with a second purge gas; and

[0093] g. Sequentially repeating steps c to f until a transition metal-containing film of a desired thickness is obtained.

[0094] In step (b), the at least one surface is passivated by exposing the at least one surface to one or more of the disclosed and claimed high-purity alkynylamines to form a passivation film on the at least one surface. In a further aspect of this embodiment, the source gas is one or more oxygen-containing source gases selected from water, diatomic oxygen, ozone, NO, N2O, NO2, carbon monoxide, carbon dioxide, and combinations thereof. In another aspect of this embodiment, the source gas is one or more nitrogen-containing source gases selected from ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen / hydrogen, ammonia plasma, nitrogen plasma, nitrogen / hydrogen plasma, and mixtures thereof. In a further aspect of this embodiment, the first and second purge gases of the method are each independently selected from one or more of argon, nitrogen, helium, neon, and combinations thereof. In a further aspect of this embodiment, the method further comprises applying energy to one or more precursors, source gases, substrates, and combinations thereof, wherein the energy is one or more of heat, plasma, pulsed plasma, helicon wave plasma, high-density plasma, inductively coupled plasma, X-ray, electron beam, photon, remote plasma method, and combinations thereof. In a further aspect of this embodiment, step b of the method further comprises using a carrier gas stream to transport the vapor of one or more of the disclosed and claimed formulations to the reaction vessel, thereby introducing one or more of the disclosed and claimed formulations into the reaction vessel. In a further aspect of this embodiment, step b of the method further comprises using a solvent medium comprising one or more of toluene, mesitylene, cumene, p-cymene (4-isopropyltoluene), 1,3-diisopropylbenzene, octane, dodecane, 1,2,4-trimethylcyclohexane, n-butylcyclohexane, and decalin (naphthane) and combinations thereof.

[0095] In one aspect of the present disclosure, the precursor can be used for co-depositing a multi-component oxide film. The multi-component oxide film can include oxides of two or more elements selected from magnesium, calcium, strontium, barium, aluminum, gallium, indium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, molybdenum, tungsten, tellurium, and antimony.

[0096] Examples of precursors and co-precursors include, but are not limited to, trimethylaluminum, tetrakis(dimethylamino)titanium, tetrakis(ethylmethylamino)zirconium, tetrakis(ethylmethylamino)hafnium, pentakis(dimethylamino)tantalum, and tris(isopropylcyclopentadienyl)lanthanum. Examples

[0097] Reference will now be made to more specific embodiments of the present disclosure and the experimental results supporting these embodiments. The examples given below more fully illustrate the disclosed and claimed subject matter and should not be construed as limiting the disclosed subject matter in any way.

[0098] It will be apparent to those skilled in the art that various modifications and variations can be made to the disclosed subject matter and the specific embodiments provided herein without departing from the spirit or scope of the disclosed subject matter. Accordingly, it is intended that the disclosed subject matter, including the description provided by the following examples, cover modifications and variations of the disclosed subject matter within the scope of any claim and its equivalents.

[0099] Materials and Methods:

[0100] All reactions and operations described in the examples were carried out using an inert atmosphere glove box or standard Schlenk techniques under a nitrogen atmosphere. Unless otherwise stated, all reagents were purchased from Sigma-Aldrich and used "as is" without further purification. The adsorption properties of the disclosed and claimed subject matter were calculated and studied using the computer simulation program Dmol3 from Biovia with the M11-L / DNP density functional method. The alkynylamines were characterized by NMR, GC-MS, GC-FID, TGA, and DSC. TGA and DSC analyses confirmed that the formulations were thermally stable for delivery to the deposition equipment. Specific Embodiments

[0102] Example 1: Adsorption of alkyne [5-decyne] and alkynylamine [1,4-bis(dimethylamino)-2-butyne (2A)] on alumina and copper surfaces.

[0103] This example illustrates a comparison of the adsorption of alkyne [5-decyne] and alkynylamine [1,4-bis(dimethylamino)-2-butyne (2A)] on aluminum oxide (alumina) and metallic copper substrates. The results show that the alkynylamine adsorbs more strongly on both substrates than the alkyne, especially on metallic copper. Thus, formulations containing an alkynylamine (e.g., bis(dimethylamino)-2-butyne (2A)) provide stronger passivation of the copper surface relative to alkynes without an alkynylamine. Figure 3 Illustrates the adsorption of 1,4-bis(dimethylamino)-2-butyne (a) and 1,4-bis(n-propylamino)-2-butyne (b) on the Cu(100) surface. The alkynylamine shows strong coordination with the copper surface. Thus, alkynylamines can be used to passivate copper surfaces.

[0104]

[0105] Table 3: Adsorption energies of alkynes and alkynylamines on alumina and copper surfaces.

[0106] Example 2: Adsorption of alkynylamines and non-alkynylamines on alumina and tungsten surfaces

[0107] This example illustrates the comparison of the adsorption of acetylenic amines and non-acetylenic amines on aluminum oxide (alumina) and metal tungsten substrates. Without being bound by theory, it is believed that the tungsten-based substrate may contain "bare" W sites terminated directly with W atoms and sites with partially oxidized W atoms terminated with OH groups. Therefore, two different surfaces were modeled to measure the adsorption of amines on the W film: "bare W" and "OH-terminated WO2". Two different alumina structures were also selected to simulate the alumina substrate: boehmite and gibbsite. The results are summarized in Table 4. The results show that the adsorption energy of acetylenic amines on "bare" W is unexpectedly high, >2 - 3 times higher than that of non-acetylenic amines with similar structures. Therefore, acetylenic amines can be used to passivate tungsten films with a high concentration of "bare" W sites.

[0108]

[0109]

[0110] Table 4: Adsorption energies of various amines on alumina and tungsten surfaces.

[0111] Example 3: Synthesis of 1,4-bis(dimethylamino)-2-butyne (2A)

[0112] A 20% aqueous solution of dimethylamine (500 g) was placed in a 1 L round-bottom flask equipped with an internal thermocouple. Neat 1,4-dichloro-2-butyne (50 g) was added dropwise. The internal temperature rose to approximately 50 °C, and the addition rate was adjusted to maintain the temperature at approximately 50 °C for the remainder of the addition. The dark yellow solution was allowed to cool to room temperature and stirred overnight. A 2M sodium hydroxide solution was added dropwise until the pH was measured to be 10 - 11, as determined by analysis using pH test paper. Once the resulting brown solution had cooled to room temperature, the aqueous solution was extracted repeatedly with diethyl ether (5 × 200 mL), and the organic extracts were combined. The diethyl ether was evaporated under vacuum to give a brown liquid containing a small amount of suspended solids.

[0113] Example 4: Preparation of high-purity 1,4-bis(dimethylamino)-2-butyne (2A)

[0114] 1,4-Bis(dimethylamino)-2-butyne was added dropwise to hexane, resulting in the formation of a light brown solution with suspended solids. The solids were filtered using a 5-μm Teflon membrane filter. The hexane was removed under vacuum to give a light yellow liquid. A small amount of silver carbonate (0.1 g) was added to the liquid with stirring (overnight). The liquid was decanted and distilled under vacuum (approx. 90 °C @ 200 mTorr) to yield a light yellow liquid. 1 1H NMR (d8-THF): 2.20 ppm (s, 6H), 3.22 ppm (s, 6H). 1313C NMR (d8-THF): 44.2 ppm (s), 48.5 ppm (s), 80.5 ppm (s). Figure 4 Figure Figure 4 shows the thermogravimetric analysis (TGA) of high purity 1,4-bis(dimethylamino)-2-butyne under flowing nitrogen. This figure illustrates the very clean evaporation of high purity 1,4-bis(dimethylamino)-2-butyne, with residues well below 1 wt%, indicating its suitability for vapor delivery to semiconductor processing equipment, for example, for passivation of metal surfaces.

[0115] Clean evaporation of the precursor is absolutely crucial for vapor delivery applications. In the case of incomplete evaporation, residual non-volatile solids may be carried into the vapor pipelines and deposition chambers, leading to particle contamination of the equipment. When direct liquid injection is used for precursor delivery, non-volatile residues may clog the syringe and also cause particle contamination of the equipment. For vapor pumping and bubbling applications, the residue after evaporation is preferably less than 2 wt%, more preferably less than 1 wt%, and most preferably less than 0.1 wt%. For direct liquid injection applications, the residue after evaporation is preferably less than 1 wt%, more preferably less than 0.1 wt%, and most preferably less than 0.05 wt%.

[0116] Comparative Example 5: Preparation of Low Purity 1,4-Bis(dimethylamino)-2-butyne (2A)

[0117] A 2 M solution of dimethylamine in THF (200 mL) was diluted by adding 300 mL of anhydrous THF. 0.5 equivalents of neat 1,4-dichloro-2-butyne (24.6 g) was added dropwise to this solution. The solution turned dark brown and a light solid precipitated. The solution was stirred overnight at room temperature. An excess of 2 M aqueous sodium hydroxide solution (300 mL) was added with stirring, resulting in the dissolution of the suspended solid. THF was removed in vacuo and the resulting aqueous solution was extracted with ether (3 x 100 mL). The ether was evaporated in vacuo to give a brown liquid containing some suspended solids. The solid was filtered off to give a brown liquid.

[0118] Figure 5 Figure Figure 5 shows the thermogravimetric analysis (TGA) of 1,4-bis(dimethylamino)-2-butyne under flowing nitrogen. This figure illustrates the evaporation of low purity 1,4-bis(dimethylamino)-2-butyne, with residues exceeding 1 wt%, indicating that the low purity material is not suitable for vapor delivery to semiconductor processing equipment and causes particle contamination of the equipment due to incomplete evaporation.

[0119] It is expected that the disclosed and claimed methods can be used in combination with deposition equipment commonly found in semiconductor manufacturing facilities to produce molybdenum-containing layers for logic applications and other potential functions.

[0120] The foregoing description is primarily intended for illustrative purposes. Although the disclosed and claimed subject matter has been shown and described with reference to its exemplary embodiments, those skilled in the art should understand that various other changes, omissions, and additions to its form and details may be made without departing from the spirit and scope of the disclosed and claimed subject matter.

Claims

1. A high-purity alkynylamine substantially free of alkyl halides and water.

2. The high-purity alkynylamine according to claim 1, wherein the high-purity alkynylamine is one or more of the following:

3. The preparation according to claim 1, wherein the high-purity alkynylamine comprises:

4. The preparation according to claim 1, wherein the high-purity alkynylamine comprises:

5. The high-purity alkynylamine according to any one of claims 1-4, wherein the high-purity alkynylamine is free of detectable halides.

6. The high-purity alkynylamine according to any one of claims 1-4, wherein the high-purity alkynylamine is free of halides.

7. The high-purity alkynylamine according to any one of claims 1-4, wherein the high-purity alkynylamine is free of detectable halogen-containing impurities detected by one or more of GC-ICP-OES, FC-FID, GC-ECD, HPLC, and UV / Vis.

8. The high-purity alkynylamine according to any one of claims 1-4, wherein the high-purity alkynylamine has a concentration of halogen-containing impurities of less than about 1000 ppm.

9. The high-purity alkynylamine according to any one of claims 1-4, wherein the high-purity alkynylamine has a concentration of halogen-containing impurities of less than about 500 ppm.

10. The high-purity alkynylamine according to any one of claims 1-4, wherein the high-purity alkynylamine has a concentration of halogen-containing impurities of less than about 100 ppm.

11. The high-purity alkynylamine according to any one of claims 1-4, wherein the high-purity alkynylamine has a concentration of halogen-containing impurities of less than about 50 ppm.

12. The high-purity alkynylamine according to any one of claims 1-4, wherein the high-purity alkynylamine has a concentration of halogen-containing impurities of less than about 10 ppm.

13. The high-purity alkynylamine according to any one of claims 5-12, wherein the halogen-containing impurities are one or more of fluorohydrocarbons, chlorohydrocarbons, bromohydrocarbons, iodohydrocarbons, and ammonium halides.

14. The high-purity alkynylamine according to any one of claims 1-4, wherein the high-purity alkynylamine is free of detectable water.

15. The high-purity alkynylamine according to any one of claims 1-4, wherein the high-purity alkynylamine is free of water.

16. The high-purity alkynylamine according to any one of claims 1-4, wherein the high-purity alkynylamine has a water concentration of less than about 500 ppm.

17. The high-purity alkynylamine according to any one of claims 1-4, wherein the high-purity alkynylamine has a water concentration of less than about 100 ppm.

18. The high-purity alkynylamine according to any one of claims 1-4, wherein the high-purity alkynylamine has a water concentration of less than about 50 ppm.

19. The high-purity alkynylamine according to any one of claims 1-4, wherein the high-purity alkynylamine has a water concentration of less than about 25 ppm.

20. The high-purity alkynylamine according to any one of claims 1-4, wherein the high-purity alkynylamine has a water concentration of less than about 10 ppm.

21. The high-purity alkynylamine as claimed in claim 1, wherein the high-purity alkynylamine does not contain detectable halides and detectable water.

22. The high-purity alkynylamine as claimed in claim 1, wherein the high-purity alkynylamine does not contain halides and water.

23. A surface passivation preparation, comprising (i) one or more high-purity alkynylamines as claimed in any one of claims 1-22.

24. The surface passivation preparation as claimed in claim 23, wherein the one or more high-purity alkynylamines in (i) comprise two or more high-purity alkynylamines as claimed in any one of claims 1-22.

25. The surface passivation preparation as claimed in claim 23, wherein the one or more high-purity alkynylamines in (i) comprise one or more of N,N-(1-di-isopropylamino)-2-butyne (1F) and 1,4-bis(dimethylamino)-2-butyne (2A).

26. The surface passivation preparation as claimed in claim 23, wherein the one or more high-purity alkynylamines in (i) comprise N,N-(1-di-isopropylamino)-2-butyne (1F) and 1,4-bis(dimethylamino)-2-butyne (2A).

27. The surface passivation preparation as claimed in claim 23, wherein the one or more high-purity alkynylamines in (i) comprise N,N-(1-di-isopropylamino)-2-butyne (1F).

28. The surface passivation preparation as claimed in claim 23, wherein the one or more high-purity alkynylamines in (i) comprise 1,4-bis(dimethylamino)-2-butyne (2A).

29. A method of forming a film on at least one surface of a substrate, comprising: a. providing the at least one surface of the substrate in a reaction vessel; b. forming at least one passivated surface by exposing the at least one surface to one or more high-purity alkynylamines as claimed in any one of claims 1-22.

30. The method as claimed in claim 29, wherein the method comprises an atomic layer deposition process (ALD).

31. The method as claimed in claim 29, wherein the method comprises plasma-enhanced ALD (PEALD).

32. The method as claimed in claim 29, wherein the method comprises a chemical vapor deposition process (CVD).

33. A method of forming a metal-containing film by a chemical vapor deposition (CVD) process, comprising: a. providing at least one surface of a substrate in a reaction vessel; b. forming at least one passivated surface by exposing the at least one surface to one or more high-purity alkynylamines as claimed in any one of claims 1-22; c. forming a transition metal-containing film on the at least one pre-passivated surface during the deposition process by chemical vapor deposition (CVD) using one or more precursors.

34. The method as claimed in claim 33, further comprising introducing at least one reactant into the reaction vessel.

35. The method according to claim 33, further comprising introducing at least one reactant into the reaction vessel, the reactant being selected from water, diatomic oxygen, oxygen plasma, ozone, NO, N2O, NO2, carbon monoxide, carbon dioxide, and combinations thereof.

36. The method according to claim 33, further comprising introducing at least one reactant into the reaction vessel, the reactant being selected from ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen / hydrogen, ammonia plasma, nitrogen plasma, nitrogen / hydrogen plasma, and combinations thereof.

37. The method according to claim 33, further comprising introducing at least one reactant into the reaction vessel, the reactant being selected from hydrogen, hydrogen plasma, a mixture of hydrogen and helium, a mixture of hydrogen and argon, hydrogen / helium plasma, hydrogen / argon plasma, boron-containing compounds, silicon-containing compounds, and combinations thereof.

38. A method of forming a metal-containing film by a thermal atomic layer deposition (ALD) process or a thermal ALD-like process, comprising: a. providing a substrate in a reaction vessel; b. forming at least one passivated surface by exposing at least one surface to one or more high-purity alkynylamines as described in any one of claims 1-22; c. purging the reaction vessel with a first purge gas; d. introducing one or more precursors into the reaction vessel; e. introducing a source gas into the reaction vessel; f. purging the reaction vessel with a second purge gas; and g. sequentially repeating steps c to f until a metal-containing film of a desired thickness is obtained.

39. The method according to claim 38, wherein the source gas is one or more oxygen-containing source gases selected from water, diatomic oxygen, ozone, NO, N2O, NO2, carbon monoxide, carbon dioxide, and combinations thereof.

40. The method according to claim 38, wherein the source gas is one or more nitrogen-containing source gases selected from ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen / hydrogen, ammonia plasma, nitrogen plasma, nitrogen / hydrogen plasma, and mixtures thereof.

41. The method according to claim 38, wherein the first purge gas and the second purge gas are each independently selected from one or more of argon, nitrogen, helium, neon, and combinations thereof.

42. The method according to claim 38, further comprising applying energy to the one or more precursors, the source gas, the substrate, and combinations thereof.

43. The method according to claim 38, further comprising applying energy to the one or more precursors, the source gas, the substrate, and combinations thereof, wherein the energy is one or more of heat, plasma, pulsed plasma, helicon wave plasma, high-density plasma, inductively coupled plasma, X-rays, electron beam, photons, remote plasma methods, and combinations thereof.

44. The method according to claim 38, wherein step b comprises introducing one or more formulations as a vapor into the reaction vessel using a carrier gas stream.

45. The method according to claim 38, wherein step b comprises introducing one or more formulations using a solvent medium comprising one or more of toluene, mesitylene, cumene, p-cymene (4-isopropyltoluene), 1,3-diisopropylbenzene, octane, dodecane, 1,2,4-trimethylcyclohexane, n-butylcyclohexane, and decalin (naphthane) and combinations thereof.

46. The method according to any one of claims 29-45, further comprising depositing a nitride film on the at least one passivated surface.

47. The method according to any one of claims 29-45, further comprising depositing an oxide film on the at least one passivated surface.

48. The method according to any one of claims 29-45, further comprising depositing a multi-component oxide film on the at least one passivated surface.

49. The method according to any one of claims 29-45, further comprising depositing a multi-component oxide film on the at least one passivated surface, wherein the multi-component oxide film comprises oxides of two or more elements selected from magnesium, calcium, strontium, barium, aluminum, gallium, indium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, molybdenum, tungsten, tellurium, and antimony.

50. The method according to any one of claims 29-45, wherein the one or more precursors comprise trimethylaluminum.

51. The method according to any one of claims 29-45, wherein the one or more precursors comprise tetrakis(dimethylamino)titanium.

52. The method according to any one of claims 29-45, wherein the one or more precursors comprise tetrakis(ethylmethylamino)zirconium.

53. The method according to any one of claims 29-45, wherein the one or more precursors comprise tetrakis(ethylmethylamino)hafnium.

54. The method according to any one of claims 29-45, wherein the one or more precursors comprise pentakis(dimethylamino)tantalum.

55. The method according to any one of claims 29-45, wherein the one or more precursors comprise tris(isopropylcyclopentadienyl)lanthanum.

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