High-purity alkynylamines for selective deposition

Abstract

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

Description

[Technical Field]

[0001] The disclosed and claimed subject matter relates to high-purity alkynylamines useful for selectively depositing dielectric films on non-metallic substrates. Specifically, the disclosed and claimed subject matter relates to high-purity alkynylamines and their use for enhanced passivation of metal substrates. [Background technology]

[0002] Related technologies Transition metal-containing films are used in semiconductor and electronic device applications. Chemical vapor deposition (CVD) and atomic layer deposition (ALD) are the primary deposition techniques used to fabricate thin films for semiconductor devices. These methods allow for the achievement of conformal films (metals, metal oxides, metal nitrides, metal silicides, and the like) through the chemical reaction of metal-containing compounds (precursors). The chemical reaction occurs on surfaces that may include metals, metal oxides, metal nitrides, metal silicides, and other surfaces. In CVD and ALD, precursor molecules play a critical role in achieving high-quality films with high conformality and low impurity content. The temperature in CVD and ALD processes is an important consideration in selecting precursor molecules. Higher substrate temperatures within the 150-500 degrees Celsius (°C) range 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 allows for more uniform delivery of precursors to the reaction vessel than solid-phase precursors.

[0003] CVD and ALD processes are increasingly being used because these techniques offer the advantages of enhanced composition control, high film uniformity, and effective doping control. Furthermore, CVD and ALD processes enable excellent conformal step coverage on the highly nonplanar 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 nitrides, metal oxides, and other metal-containing layers, using these metal-containing precursors. In these techniques, vapors of volatile metal complexes are introduced into a process chamber. When the vapors contact the surface of a silicon wafer in the process chamber, a chemical reaction occurs, depositing a thin film of a pure metal or metal compound.

[0004] CVD is a chemical process that uses precursors to form thin films on a substrate surface. In a typical CVD process, precursors are delivered to the surface of a substrate (e.g., a wafer) in a low-pressure or ambient-pressure reaction chamber. The precursors react and / or decompose on the substrate surface to form a thin film of the deposited material. Plasma can be used to support the precursor reaction or to improve material properties. Volatile byproducts are removed by gas flow through the reaction chamber. The deposited film thickness can be difficult to control because it depends on the coordination of many parameters, such as temperature, pressure, gas flow rate and uniformity, chemical depletion effects, and time. Thus, CVD occurs where precursors react thermally at the wafer surface or with reagents simultaneously added to the process chamber, and film growth occurs in steady-state deposition. CVD can be applied in continuous or pulsed modes to achieve the desired film thickness.

[0005] ALD is a chemical method for the deposition of thin films. It is a self-limiting, continuous, and unique film growth technique based on surface reactions that provide precise thickness control and can deposit conformal thin films of materials provided by precursors onto substrate surfaces of various compositions. In ALD, precursors are separated during the reaction. A first precursor is delivered to the substrate surface and produces a monolayer on the substrate surface. Any excess unreacted precursor is removed from the reaction chamber by a pump. A second precursor or co-reactant is then delivered to the substrate surface and reacts with the first precursor, forming a second monolayer of film on the first monolayer on the substrate surface. Plasma may be used to support the precursor or co-reactant reaction or to improve material quality. This cycle is repeated to produce a film of the desired thickness. ALD offers the deposition of ultra-thin yet continuous metal-containing films with precise control of film thickness, excellent film thickness uniformity, and highly conformal film growth for uniform coverage of deeply etched and highly intricate structures, such as interconnect vias and trenches. Thus, ALD is typically preferred for depositing thin films over features with high aspect ratios.

[0006] Thin films, and specifically thin metal-containing films, have a wide variety of important applications, such as in nanotechnology and semiconductor device fabrication. Examples of such applications include capacitor electrodes, gate electrodes, adhesion diffusion barriers, and integrated circuits. However, the continuing shrinking size of microelectronic components, e.g., semiconductor devices, presents several technological challenges and drives the need for improved thin film technologies. Specifically, microelectronic components may include features on or above a substrate. These features require filling to form conductive paths or to form interconnects. Filling such features, especially in increasingly smaller microelectronic components, can be challenging because the features can become increasingly thin or narrow. As a result, completely filling a feature, for example, via ALD, requires infinitely long cycle times as the feature thickness approaches zero. Furthermore, when the feature thickness becomes narrower than the molecular size of the precursor, the feature cannot be completely filled. As a result, when ALD is performed, hollow seams can remain in the center of the feature. The presence of such hollow seams within the feature is undesirable. Because these hollow seams can lead to device defects, there has been considerable interest in developing thin film deposition methods, particularly ALD methods, that can selectively grow films on one or more substrates to improve the filling of features on or within the substrates, including depositing metal-containing films in a manner that substantially fills the features without any voids.

[0007] As alluded to above, in conventional semiconductor device fabrication, patterning is largely a "top-down" process based on photolithography and etching. This process is a major bottleneck for device miniaturization. In contrast, area-selective deposition (e.g., CVD and ALD) offers a "bottom-up" approach to patterning in advanced semiconductor manufacturing, where a metal layer (e.g., Ru) is grown not on the dielectric (e.g., SiO2) sidewalls but on the bottom metal surface (e.g., Ru and TiN) adjacent to a passivated dielectric substrate. See, e.g., FIG. 1. It is also desirable that these processes be oxygen-free and / or have lower resistivity.

[0008] In other applications, it is desirable to deposit a dielectric film only on another dielectric film and not on a metal surface. See, for example, FIG. 2. One potential application for such a process is self-aligned fabrication. The most common strategy to achieve selective growth is based on the selective passivation of the non-growth surface. For passivation, small volatile molecules are highly desirable because they can be delivered via the vapor phase. Selective passivation of non-metal surfaces with a high concentration of hydroxyl groups has been widely utilized, and such passivation can be achieved using various silylating agents, e.g., R x SiCl y , R x Si(NR2) y On the other hand, selective passivation of metal surfaces is more challenging, and the selectivity of such approaches can easily be lost due to incomplete passivation caused by desorption of the passivating agent and residual impurities on the surface of the metal film. Typically, single-component reagents are used to passivate non-growth surfaces. However, single-component reagents may not provide complete surface coverage of the metal surface due to the presence of different sites on the metal surface, such as "naked" metal, metal terminated with hydrogen atoms, metal terminated with oxygen atoms or hydroxyl groups, etc.

[0009] Alkynes have been used to passivate metal surfaces, depositing films on growing dielectric surfaces while substantially inhibiting film growth on non-growing metal surfaces. However, the passivation provided by these unfunctionalized alkynes on metal sites is insufficient due to contamination with traces of moisture, halides, and carboxylic acids. Typically, alkyl-substituted alkynes are prepared by reacting metal acetylides with alkyl halides, followed by aqueous workup. 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.

[0010] For example, U.S. Patent Application Publication No. 2020 / 0347493 discloses a method for selectively depositing a dielectric film on a non-metallic surface. The disclosed method requires passivating or blocking the metal surface prior to deposition of 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 the application, the unsaturated hydrocarbon is believed to inhibit nucleation and growth on the metal substrate. While the application provides a method for blocking the metal surface, it does not teach or suggest a process for passivating residual metal oxide sites present on the metal surface.

[0011] Reproducible selective passivation of metal surfaces requires careful design of precursors and deposition processes. In practice, it is highly desirable to enhance passivation of metal surfaces while reducing and / or eliminating passivation of dielectric surfaces. The disclosed and claimed subject matter provides compositions and methods for enhancing passivation and / or blocking of metal surfaces and for enhancing the selective deposition of non-metallic surfaces relative to metal surfaces.

[0012] To achieve selective surface growth (i.e., simultaneous or substantially simultaneous growth and non-growth on different surfaces) during semiconductor manufacturing, it is typically preferred to utilize (i) a metal surface that is expected to be free or substantially free of hydroxyl groups and (ii) a non-metallic surface that contains a high concentration of hydroxyl groups. Examples of suitable metal surfaces include copper, cobalt, tungsten, molybdenum, nickel, ruthenium, and the like. Examples of non-metallic surfaces include silicon oxide, low-K carbon-doped silicon oxide, silicon nitride, silicon carbonitride, and metal oxides such as aluminum oxide, tantalum oxide, hafnium oxide, and zirconium oxide. Examples of films deposited on non-metallic surfaces include silicon oxide, aluminum oxide, tantalum oxide, titanium oxide, hafnium oxide, zirconium oxide, tantalum nitride, and titanium nitride. Films are deposited on non-metallic surfaces by the chemical vapor deposition and atomic layer deposition processes described above. Precursors useful for depositing films include, but are not limited to, trimethylaluminum, tetrakis(dimethylamido)titanium, pentakis(dimethylamido)tantalum, tert-butylimido-tris(dimethylamido)tantalum, tert-butylimido-tris(dimethylamido)niobium, etc. Co-reactants include, but are not limited to, water and ammonia.

[0013] To achieve selective deposition, the metal surface must be passivated and free or substantially free of chemical groups reactive with precursors and co-reactants, such as ammonia, used in subsequent film deposition process steps. On the other hand, the reactants used to passivate the metal surface should not passivate the intended growth on non-metallic surfaces. The disclosed and claimed alkynylamine-containing formulations are uniquely designed to balance these requirements in selective deposition processes. Summary of the Invention [Means for solving the problem]

[0014] The disclosed and claimed subject matter relates to high purity alkynylamines that are substantially free of impurities, including residual halides and / or water, and their use (e.g., in formulations) to enhance passivation of metal substrates. [Effects of the Invention]

[0015] In another embodiment, the disclosed and claimed subject matter includes the use of the above formulations in selective CVD deposition processes.

[0016] In another embodiment, the disclosed and claimed subject matter includes the use of the above formulations in a selective ALD deposition process.

[0017] The accompanying 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 description, serve to explain the principles of the disclosed subject matter. [Brief explanation of the drawings]

[0018] [Figure 1] FIG. 1 illustrates an exemplary target for a selective deposition process in which a metal film is selectively deposited on a conductive film while a dielectric film is passivated. [Figure 2] FIG. 2 illustrates an exemplary target for a selective deposition process in which a dielectric film is selectively deposited on a dielectric film while a metal surface is passivated. [Figure 3] FIG. 3 shows the adsorption of 1,4-bis(dimethylamino)-2-butyne (a) and 1,4-bis(n-propylamino)-2-butyne (b) on a Cu(100) surface. [Figure 4] FIG. 1 shows thermogravimetric analysis (TGA) of 1,4-bis(dimethylamino)-2-butyne under flowing nitrogen. [Figure 5] FIG. 1 shows thermogravimetric analysis (TGA) of low concentration 1,4-bis(dimethylamino)-2-butyne under flowing nitrogen. DETAILED DESCRIPTION OF THE INVENTION

[0019] All references cited in this application, including publications, patent applications, and patents, are herein incorporated by reference to the same extent as if each reference was individually and specifically indicated to be incorporated by reference and was set forth in its entirety herein.

[0020] The use of the terms "a," "an," and "the," and similar referents in the context of describing the disclosed and claimed subject matter (particularly in the context of the claims below) should be construed to cover both the singular and the plural unless otherwise indicated or clearly contradicted by context. The terms "comprising," "having," "including," and "containing" should be construed as open-ended terms (i.e., meaning "including, but not limited to") unless otherwise noted. The recitation of ranges of values ​​herein is merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated, and each separate value is incorporated herein as if it were individually set forth. All methods described herein can be performed in any suitable order unless otherwise indicated herein or clearly contradicted by context. Any and all examples provided herein, or the use of example language (e.g., "such as"), are intended merely to better describe the disclosed and claimed subject matter and do not limit the scope of the disclosed and claimed subject matter unless otherwise asserted. No language in the specification should be construed as implying any non-claimed element as essential to the practice of the disclosed and claimed subject matter. The use of the terms "comprising" or "including" in the specification and claims includes the narrower language of "consisting essentially of" and "consisting of."

[0021] Embodiments of the disclosed and claimed subject matter are described herein, including the best mode known to the inventors for carrying out the disclosed and claimed subject matter. Variations of these preferred embodiments may become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors anticipate that skilled artisans will adopt such variations as necessary, 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 claims appended hereto as permitted by applicable law. Furthermore, any combination of the above-described elements in all possible variations thereof is encompassed by the disclosed and claimed subject matter unless otherwise indicated herein or otherwise clearly contradicted by context.

[0022] Of course, the term "silicon" as deposited as a material on a microelectronic device includes polysilicon.

[0023] For ease of reference, "microelectronic device" or "semiconductor device" refers to a semiconductor wafer having integrated circuits, memory, and other electronic structures fabricated thereon, and to flat panel displays, phase-change memory devices, solar panels, and other products including solar substrates, photovoltaic power generators, and microelectromechanical systems (MEMS) fabricated for use in microelectronic, integrated circuit, or computer chip applications. Examples of solar substrates include silicon, amorphous silicon, polycrystalline silicon, single-crystalline silicon, CdTe, copper indium selenide, copper indium sulfide, and gallium arsenide on gallium. Solar substrates may be doped or undoped. Of course, the terms "microelectronic device" or "semiconductor device" are not meant to be limiting in any way and include any substrate that will ultimately become a microelectronic device or microelectronic assembly.

[0024] As defined herein, the term "barrier material" refers to any material used in the art to seal metal lines, e.g., copper interconnects, thereby minimizing the diffusion of said metal, e.g., copper, into dielectric materials. Preferred barrier layer materials include tantalum, titanium, ruthenium, hafnium, and other refractory metals, and their nitrides and silicides.

[0025] "Substantially free" is defined herein as less than 0.001% by weight. "Substantially free" also includes 0.000% by weight. The term "free of" means 0.000% by weight. As used herein, "about" or "approximately" shall correspond to within ±5% of the stated value.

[0026] "Alkylene," unless otherwise specified, means a linear saturated divalent hydrocarbon radical of one to six carbon atoms or a branched saturated divalent hydrocarbon radical of three to six carbon atoms (e.g., methylene, ethylene, propylene, 1-methylpropylene, 2-methylpropylene, butylene, pentylene, and the like).

[0027] "Heteroalkylene" refers to an -(alkylene)- radical, as defined above, in which one, two, or three carbons within the alkylene chain are replaced by -O-, N(H, alkyl, or substituted alkyl), S, SO, SO, or CO. In some preferred embodiments, carbons are replaced by O or N.

[0028] In all such compositions, when a particular component of the composition is discussed in terms of a weight percentage (or "wt %") range including a zero lower limit, it will be understood that such component may be present or absent in various specific embodiments of the composition, and in instances where such component is present, it may be present in concentrations as low as 0.001 wt %, based on the total weight of the composition in which such component is employed. Furthermore, all percentages of components are weight percentages and are based on the total weight of the composition, i.e., 100%. References to "one or more" or "at least one" include "two or more," "two or more," and "three or more," etc.

[0029] Where applicable, unless otherwise indicated, all weight percentages are "neat." "Neat" means that they do not include the aqueous solution present when added to the composition. For example, "neat" refers to the weight percent amount of undiluted acid or other material (i.e., the inclusion of 100 g of 85% phosphoric acid constitutes 85 g of acid and 15 grams of diluent).

[0030] Furthermore, when referring to compositions described herein in terms of weight percent, it is understood that in no event will the weight percent of all components, including non-essential components, exceed 100 weight percent. In a composition "consisting essentially of" listed components, such components may total 100 weight percent of the composition, or may total less than 100 weight percent. Where the components total less than 100 weight percent, such compositions may contain some minor amounts of non-essential contaminants or impurities. For example, in one such embodiment, the formulation may contain 2 weight percent or less of impurities. In another embodiment, the formulation may contain 1 weight percent or less of impurities. In a further embodiment, the formulation may contain 0.05 weight percent or less of impurities. In other such embodiments, the components may form at least 90 weight percent, more preferably at least 95 weight percent, more preferably at least 99 weight percent, more preferably at least 99.5 weight percent, and most preferably at least 99.9 weight percent, and may include other ingredients that do not affect the performance of the material. Otherwise, it goes without saying that the composition of all essential components will essentially total 100% by weight, provided that there are no significant non-essential impurity components.

[0031] The headings employed herein are not intended to be limiting; rather, they are included for organizational purposes only.

[0032] As noted above, the disclosed and claimed subject matter relates to high-purity alkynylamines substantially free of halides, water, and other related impurities, and their use (in formulations) to enhance the passivation of metal substrates. Specifically, it has been found that high-purity alkynylamines can readily passivate metal surfaces that are free or substantially free of hydroxyl groups due to their strong adsorption on "naked" metal surfaces. For example, alkynylamines have been shown to adsorb strongly on "bare" copper surfaces with adsorption energies of -60 to -65 kcal / mol. On the other hand, this behavior has been inconsistent at best 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 copper(I) oxide. Thus, while it is possible to utilize alkynylamines on "bare" metal surfaces, most metal surfaces contain residual oxides that require further treatment to free them for reaction. Thus, it is important to eliminate impurities that can form hydroxylated metal surfaces. It has also been found that the adsorption of halides on metal surfaces is kinetically highly favorable. Residual halides on metal surfaces react with precursors and reactants used during selective deposition and suppress process selectivity. Thus, it is important to eliminate halogen-containing impurities that can form halide-containing species on metal substrates.

[0033] Disclosed and Claimed Formulations 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. It should be understood, however, that the high-purity alkynylamines of the disclosed and claimed subject matter are not limited to those exemplified in Tables 1 and 2. [Table 1] [Table 2]

[0034] A preferred high purity alkynylamine is N,N-(1-di-isopropylamino)-2-butyne (1F).

[0035] Another preferred high purity alkynylamine is 1,4-bis(dimethylamino)-2-butyne (2A).

[0036] In one embodiment, the high-purity alkynylamine is substantially free of water. In an aspect of this embodiment, the residual concentration of water in the high-purity alkynylamine is less than about 500 ppm. In an aspect of this embodiment, the residual concentration of water in the high-purity alkynylamine is less than about 100 ppm. In an aspect of this embodiment, the residual concentration of water in the high-purity alkynylamine is less than about 50 ppm. In an aspect of this embodiment, the residual concentration of water in the high-purity alkynylamine is less than about 25 ppm. In an aspect of this embodiment, the residual concentration of water in the high-purity alkynylamine is less than about 10 ppm. In an aspect of this embodiment, the high-purity alkynylamine does not contain detectable water. In an aspect of this embodiment, the high-purity alkynylamine does not contain water.

[0037] 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 can react with the precursor during the deposition process.

[0038] In one embodiment, the high purity alkynylamine is substantially free of impurities that passivate and inhibit growth on non-metallic surfaces.

[0039] 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 fluorocarbons, chlorinated hydrocarbons, brominated hydrocarbons, and iodinated hydrocarbons. In another aspect of this embodiment, the halogen-containing impurity is an ammonium halide salt. In one aspect of this embodiment, the residual concentration of the halogen-containing impurity in the high-purity alkynylamine is less than about 1000 ppm. In one aspect of this embodiment, the residual concentration of the halogen-containing impurity in the high-purity alkynylamine is less than about 500 ppm. In one aspect of this embodiment, the residual concentration of the halogen-containing impurity in the high-purity alkynylamine is less than about 100 ppm. In one aspect of this embodiment, the residual concentration of the halogen-containing impurity in the high-purity alkynylamine is less than about 50 ppm. In one aspect of this embodiment, the residual concentration of the halogen-containing impurity in the high-purity alkynylamine is less than about 10 ppm. In one aspect of this embodiment, the residual concentration of the halogen-containing impurity in the high-purity alkynylamine is less than about 10 ppm. In one aspect of this embodiment, the high-purity alkynylamine is free of halogen-containing impurities. In the foregoing embodiments, 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.

[0040] In one embodiment, the high purity alkynylamine is purified by adsorption on alumina. In one aspect of this embodiment, the alkynylamine is delivered through an adsorbent bed packed with acidic alumina. In one aspect of this embodiment, the alkynylamine is delivered through an adsorbent bed packed with neutral alumina. In one aspect of this embodiment, the alkynylamine is delivered through an adsorbent bed packed with basic alumina. In one aspect of this embodiment, the alkynylamine is delivered through an adsorbent bed comprising a combination of acidic, basic, and neutral aluminas.

[0041] In one embodiment, the high purity alkynylamine is purified by exposure to molecular sieves. In one embodiment, the high purity alkynylamine is purified by exposure to silica gel. In one embodiment, the high purity alkynylamine is purified by exposure to one or more adsorbent materials.

[0042] 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 silver carbonate supported on Celite®.

[0043] In one embodiment, the high purity alkynylamine is purified by exposure to activated carbon. In one aspect of this embodiment, the alkynylamine is isolated by filtration and distilled to remove non-volatile products after treatment with activated carbon.

[0044] In another aspect of this embodiment, the (i) one or more alkynylamines are high purity alkynylamines.

[0045] In another embodiment, the (i) one or more alkynylamines are alkynyldiamines. In another embodiment, the (i) one or more alkynylamines are high-purity alkynyldiamines.

[0046] How to use The disclosed and claimed subject matter further includes the use of one or more of the disclosed and claimed high purity alkynylamines in chemical vapor deposition processes well 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 substrate surface to produce a desired deposit.

[0047] In one embodiment, a method includes passivating a metal surface of a substrate and using one or more of the disclosed and claimed high-purity alkynylamines to inhibit the growth of oxide or nitride films on the metal surface during a film deposition process performed after surface passivation. Examples of metal surfaces include Au, Pd, Rh, Ru, W, Mo, Al, Ni, Cu, Ti, Co, Pt, and metal silicides (e.g., TiSi2, CoSi2, and NiSi2). Examples of metal nitride films deposited on pre-passivated metal substrates include TaN, TiN, WN, MoN, TaCN, TiCN, TaSiN, and TiSiN, and silicon nitride. Examples of metal oxide films deposited on pre-passivated metal substrates include SiO2, SiON, HfO2, Ta2O5, ZrO2, TiO2, Al2O3, barium strontium titanate, and combinations thereof.

[0048] When utilized in such deposition methods and processes, high-purity alkynylamines can be delivered to a reaction chamber, such as an ALD reactor, in a variety of ways. In some cases, a liquid delivery system may be utilized. In other cases, a combined liquid delivery and flash evaporation process unit, such as a turbo evaporator manufactured by MSP Corporation of Shoreview, Minnesota, can be employed to allow low-volatility materials to be delivered volumetrically. This results in reproducible transport and deposition without thermal decomposition of the precursor. The claimed formulations described herein can be effectively used as source reagents via direct liquid injection (DLI) to provide vapor streams of these metal precursors into an ALD reactor.

[0049] When used in these processes, high-purity alkynylamines can be combined with and include hydrocarbon solvents. Hydrocarbon solvents are particularly desirable based on their ability to dry to water levels below 1 ppm. Exemplary hydrocarbon solvents that can be used in 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 decahydronaphthalene (decalin). In certain embodiments, the hydrocarbon solvent is a high-boiling solvent, or has a boiling point of 100°C or higher.

[0050] A flow of argon and / or other gas may be employed as a carrier gas to aid in the delivery of vapor containing the claimed formulations to the reaction chamber during formulation pulse delivery. When delivering high purity alkynylamines, the reaction chamber process pressure is 1-100 Torr, preferably 5-20 Torr.

[0051] Substrate temperature can be an important process variable in passivating metal-containing films. Typical substrate temperatures are from about 150°C to about 350°C.

[0052] In one embodiment, the disclosed and claimed subject matter includes a method of treating a metal surface in the presence of at least one other surface, the method comprising: a. providing said at least one surface of said substrate in a reaction vessel; b. forming at least one passivated surface by exposing said at least one surface to one or more of the disclosed and claimed high purity alkynylamines; The process includes: 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, thereby forming a passivating film on the at least one surface. In a further aspect of this embodiment, the method comprises depositing a nitride film on the at least one passivated surface. In a further aspect of this embodiment, the method comprises depositing an oxide film on the at least one passivated surface.

[0053] In one embodiment, the method includes depositing one or more precursors known to those skilled in the art as a film on a passivating film using an atomic layer deposition process (ALD), including plasma-enhanced ALD (PEALD). As used herein, the term "atomic layer deposition process" or ALD refers to a self-limiting (e.g., constant amount of film material deposited in each reaction cycle), sequential surface chemistry that deposits a material film on a substrate of varying composition. While the precursors, reagents, and sources used herein are sometimes described as "gaseous," it should be understood that precursors can also be liquids or solids that are transported into a reactor via direct evaporation, effervescence, or sublimation, with or without an inert gas. In some cases, the evaporated precursor can be passed through a plasma generator. The term "reactor" includes, by way of example, a reaction chamber, reaction vessel, or deposition chamber.

[0054] In a further aspect of this embodiment, the method includes introducing at least one reactant into a reaction vessel, wherein the at least one reactant is selected from the group consisting of water, diatomic oxygen, oxygen plasma, ozone, NO, NO, NO, carbon monoxide, carbon dioxide, and combinations thereof. In another aspect of this embodiment, the method includes introducing at least one reactant into a reaction vessel, wherein the at least one reactant is selected from the group consisting of 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 a reaction vessel, wherein the at least one reactant is selected from the group consisting of hydrogen, hydrogen plasma, a mixture of hydrogen and helium, a mixture of hydrogen and argon, hydrogen / helium plasma, hydrogen / argon plasma, a boron-containing compound, a silicon-containing compound, and combinations thereof.

[0055] Deposition methods and processes may involve the use of one or more purge gases. Purge gases, used to purge away unconsumed reactants and / or reaction by-products, are inert gases that do not react with the precursors. Exemplary purge gases include argon (Ar), nitrogen (N), helium (He), neon, and mixtures thereof. For example, a purge gas, such as Ar, is supplied into 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 remaining in the reactor.

[0056] Deposition methods and processes require the application of energy to at least one of a precursor, an oxidizer, another precursor, or a combination thereof to induce a reaction and form a metal-containing film or coating on a substrate. Such energy can be provided by, for example, heat, plasma, pulsed plasma, helicon plasma, high-density plasma, inductively coupled plasma, x-ray, electron beam, photon, remote plasma, and combinations thereof. In some processes, a secondary RF frequency source can be used to modify the plasma characteristics at the substrate surface. When utilizing plasma, plasma-generated processes can include direct plasma-generated processes, in which the plasma is generated directly within the reactor, or remote plasma-generated processes, in which the plasma is generated outside the reactor and fed into the reactor.

[0057] When utilized in such deposition methods and processes, appropriate precursors can be delivered to a reaction chamber, e.g., an ALD reactor, in a variety of ways. In some cases, a liquid delivery system may be utilized. In other cases, a combined liquid delivery and flash evaporation process unit, e.g., a turbo evaporator manufactured by MSP Corporation, Shoreview, Minnesota, can be employed to allow low-volatility materials to be delivered volumetrically. This results in reproducible transport and deposition without precursor thermal decomposition. The precursor compositions described herein can be effectively used as source reagents via direct liquid injection (DLI) to provide a vapor flow of these metal precursors into an ALD reactor.

[0058] When used in these deposition methods and processes, the precursors can be combined with and include hydrocarbon solvents. Hydrocarbon solvents are particularly desirable based on their ability to dry to water levels below 1 ppm. Exemplary hydrocarbon solvents that can be used in the precursors include toluene, mesitylene, cumene (isopropylbenzene), p-cymene (4-isopropyltoluene), 1,3-diisopropylbenzene, octane, dodecane, 1,2,4-trimethylcyclohexane, n-butylcyclohexane, and decahydronaphthalene (decalin). In certain embodiments, the hydrocarbon solvent is a high-boiling solvent, or has a boiling point above 100°C. The precursors can also be mixed with other suitable metal precursors, and the mixture can be used to simultaneously deliver both metals for the growth of binary metal-containing films.

[0059] A flow of argon and / or other gases may be employed as a carrier gas to aid in delivering the precursor-containing vapor to the reaction chamber during precursor pulsing. When delivering the precursor, the reaction chamber process pressure is 1-50 Torr, preferably 5-20 Torr.

[0060] Substrate temperature can be an important process variable in the deposition of high-quality metal-containing films. Typical substrate temperatures are from about 150°C to about 550°C. Higher temperatures can promote higher film growth rates.

[0061] In light of the foregoing, it will be apparent to those skilled in the art that the disclosed and claimed subject matter further includes the use of the disclosed and claimed formulations in chemical vapor deposition (CVD) processes.

[0062] 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: a. providing said at least one surface of said substrate in a reaction vessel; b. forming at least one passivated surface by exposing said at least one surface to one or more of the disclosed and claimed high purity alkynylamines; and c. forming a transition metal-containing film on the at least one pre-passivated surface by a chemical vapor deposition (CVD) process using one or more precursors during the deposition process. The process includes: 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, thereby forming a passivating film on the at least one surface. In a further aspect of this embodiment, the method includes introducing at least one reactant into a reaction vessel. In a further aspect of this embodiment, the method includes introducing at least one reactant into a reaction vessel, wherein the at least one reactant is selected from the group consisting of water, dioxygen, oxygen plasma, ozone, NO, NO, NO, carbon monoxide, carbon dioxide, and combinations thereof. In another aspect of this embodiment, the method includes introducing at least one reactant into a reaction vessel, wherein the at least one reactant is selected from the group consisting of 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 a reaction vessel, wherein the at least one reactant is selected from the group consisting of hydrogen, hydrogen plasma, a mixture of hydrogen and helium, a mixture of hydrogen and argon, hydrogen / helium plasma, hydrogen / argon plasma, a boron-containing compound, a silicon-containing compound, and combinations thereof.

[0063] In one embodiment, the disclosed and claimed subject matter includes a method of forming a metal-containing film via a thermal atomic layer deposition (ALD) process or a thermal ALD-like process, the method comprising: a. providing a substrate in a reaction vessel; b. forming at least one passivated surface by exposing said at least one surface to one or more of the disclosed and claimed high purity alkynylamines; 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. Successively repeating steps c through f until the desired thickness of the transition metal-containing film is obtained. The process includes: 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, thereby forming a passivating 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, NO, NO, 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 combinations thereof. In a further aspect of this embodiment, the method further comprises a first purge gas and a second purge gas, 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 the one or more precursors, the source gas, the substrate, and combinations thereof, wherein the energy is one or more of thermal plasma, pulsed plasma, helicon plasma, high density plasma, inductively coupled plasma, x-ray, electron beam, photon, remote plasma, and combinations thereof. In a further aspect of this embodiment, step b of the method further comprises introducing one or more of the disclosed and claimed formulations into the reaction vessel using a carrier gas flow to deliver vapor of 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 comprising one or more of toluene, mesitylene, isopropylbenzene, p-cymene (4-isopropyltoluene), 1,3-diisopropylbenzene, octane, dodecane, 1,2,4-trimethylcyclohexane, n-butylcyclohexane, and decahydronaphthalene (decalin), and combinations thereof.

[0064] In one aspect of this invention, the precursors may be used to co-deposit a multi-component oxide film, which may 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.

[0065] Examples of precursors and co-precursors include trimethylaluminum, tetrakis(dimethylamido)titanium, tetrakis(ethylmethylamino)zirconium, tetrakis(ethylmethylamido)hafnium, pentakis(dimethylamido)tantalum, and tris(isopropylcyclopentadienyl)lanthanum. [Example]

[0066] Reference is now made to more specific embodiments of the present disclosure, and test results supporting such embodiments. The examples are provided below to more fully illustrate the disclosed and claimed subject matter, and should not be construed as limiting the disclosed subject matter in any way.

[0067] 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 examples provided herein without departing from the spirit or scope of the disclosed subject matter. Thus, the disclosed subject matter, including the description provided by the examples below, is intended to cover modifications and variations of the disclosed subject matter that come within the scope of any claims and their equivalents.

[0068] Materials and Methods All reactions and manipulations described in the examples were carried out under a nitrogen atmosphere using an inert atmosphere glovebox or standard Schlenk techniques. Unless otherwise indicated, all reagents were purchased from Sigma-Aldrich and used "as is" without further purification. The computer simulation program Dmol3 by Biovia with M11-L / DNP density functional methods was used to calculate and study the adsorption properties of the disclosed and claimed subject matter. The acetylenic amines 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 deposition tools.

[0069] Specific Examples Example 1: Adsorption of the alkyne [5-decyne] and the acetylenic amine [1,4-bis(dimethylamino)-2-butyne (2A)] on aluminum oxide and copper surfaces This example compares the adsorption of an alkyne [5-decyne] and an acetylenic amine [1,4-bis(dimethylamino)-2-butyne (2A)] on aluminum oxide (alumina) and metallic copper substrates. The results show that the acetylenic amine adsorbs more strongly than the alkyne on both substrates, but especially on metallic copper. Thus, formulations containing an acetylenic amine, such as bis(dimethylamino)-2-butyne (2A), provide stronger passivation of the copper surface compared to alkynes without the acetylenic amine. Figure 3 shows the adsorption of 1,4-bis(dimethylamino)-2-butyne (a) and 1,4-bis(n-propylamino)-2-butyne (b) on a Cu(100) surface. The acetylenic amine exhibits strong coordination with the copper surface. Therefore, acetylenic amines can be used to passivate copper surfaces. [Table 3]

[0070] Example 2: Adsorption of acetylenic and non-acetylenic amines on aluminum oxide and tungsten surfaces This example compares the adsorption of acetylenic and nonacetylenic amines on aluminum oxide (alumina) and metallic tungsten substrates. Without being bound by theory, it is believed that tungsten substrates may contain both "bare" W sites terminated directly by W atoms and sites with partially oxidized W atoms terminated by OH groups. Thus, by modeling two different surfaces, we measured the adsorption of amines on W films, namely, "bare W" and "OH-terminated WO." Two different aluminum oxide structures were also chosen to model aluminum oxide substrates, namely, boehmite and gibbsite. The results are summarized in Table 4. The results show that the adsorption energies of acetylenic amines on “bare” W are unexpectedly >2–3 times higher compared to nonacetylenic amines with similar structures. Therefore, acetylenic amines can produce tungsten films with a high concentration of "bare" W sites. may be used to passivate [Table 4]

[0071] Example 3: Synthesis of 1,4-bis(dimethylamino)-2-butyne (2A) A solution of 20% aqueous 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 rate of addition 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 solution of 2 M sodium hydroxide was added dropwise until the pH was measured to be 10-11, as determined by analysis with pH paper. Once the resulting brown solution had cooled to room temperature, the aqueous solution was repeatedly extracted with diethyl ether (5 x 200 mL), and the organic extracts were combined. Evaporation of the ether under vacuum yielded a brown liquid with a small amount of suspended solids.

[0072] Example 4: Preparation of Highly Purified 1,4-Bis(dimethylamino)-2-butyne (2A) 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 micron Teflon membrane filter. Removal of the hexane under vacuum yielded 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 (approximately 90°C at 200 mTorr) to yield a pale yellow liquid. 1 H NMR (d8-THF): 2.20ppm(s,6H), 3.22ppm(s,6H). 13 C NMR (d8-THF): 44.2 ppm(s), 48.5 ppm(s), 80.5 ppm(s). Figure 4 shows the thermogravimetric analysis (TGA) of high-purity 1,4-bis(dimethylamino)-2-butyne under flowing nitrogen. The figure shows extremely clean evaporation of high-purity 1,4-bis(dimethylamino)-2-butyne with residues well below 1 wt%, suggesting its use for vapor delivery to semiconductor processing tools, for example, for passivation of metal surfaces.

[0073] Clean evaporation of precursors is absolutely critical for use in vapor delivery applications. Incomplete evaporation results in residual non-volatile solids being carried over into the vapor lines and deposition chamber, resulting in particulate contamination of the tool. When direct liquid injection is used for precursor delivery, non-volatile residues can clog the injector, ultimately contaminating the tool with particles. For vapor aspirating and foaming applications, the evaporation residue 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 evaporation residue is preferably less than 1 wt%, more preferably less than 0.1 wt%, and most preferably less than 0.05 wt%.

[0074] Comparative Example 5: Preparation of low purity 1,4-bis(dimethylamino)-2-butyne (2A) A solution of 2 M dimethylamine in THF (200 cc) was diluted by adding 300 cc of dry THF. To this solution, 0.5 equivalents of neat 1,4-bis(dimethylamino)-2-butyne (24.6 g) was added dropwise. The solution turned dark brown, and a pale solid precipitated. The solution was stirred overnight at room temperature. Excess aqueous 2 M sodium hydroxide (300 cc) was added with stirring, thereby dissolving the suspended solids. The THF was removed under vacuum, and the resulting aqueous solution was extracted with diethyl ether (3 x 100 cc). Evaporation of the diethyl ether under vacuum yielded a brown liquid with some suspended solids. Filtration of the solids yielded a brown liquid.

[0075] Figure 5 shows a thermogravimetric analysis (TGA) of 1,4-bis(dimethylamino)-2-butyne under flowing nitrogen. The figure shows the evaporation of low-purity 1,4-bis(dimethylamino)-2-butyne with residues greater than 1 wt%, suggesting that the low-purity material cannot be used for vapor delivery to semiconductor processing tools and causes contamination of the tools with particles due to incomplete evaporation.

[0076] It is anticipated that the disclosed and claimed methods may be used in conjunction with deposition tools commonly found in semiconductor manufacturing sites to produce molybdenum-containing layers for logic applications and other potential functions.

[0077] The foregoing description is intended primarily for purposes of illustration. While the disclosed and claimed subject matter has been shown and described with respect to exemplary embodiments thereof, it will be understood by those skilled in the art that the foregoing and various other changes, omissions, and additions in form and detail may be made therein without departing from the spirit and scope of the disclosed and claimed subject matter.

Claims

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

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

3. The high purity alkynylamine 【Chemistry 1】 2. The formulation of claim 1, comprising:

4. The high purity alkynylamine 【Chemistry 2】 2. The formulation of claim 1, comprising:

5. 5. The high-purity alkynylamine of any one of claims 1 to 4, wherein the high-purity alkynylamine contains no detectable halides.

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

7. 5. The high-purity alkynylamine of any one of claims 1 to 4, wherein the high-purity alkynylamine contains no detectable halogen-containing impurities as detected by one or more of GC-ICP-OES, FC-FID, GC-ECD, HPLC, and UV / Vis.

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

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

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

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

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

13. 13. The high-purity alkynylamine of any one of claims 5 to 12, wherein the halogen-containing impurities are one or more of fluorocarbons, chlorocarbons, brominated hydrocarbons, iodinated hydrocarbons, and ammonium halides.

14. 5. The high-purity alkynylamine of any one of claims 1 to 4, wherein the high-purity alkynylamine contains no detectable water.

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

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

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

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

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

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

21. 10. The high-purity alkynylamine of claim 1, wherein the high-purity alkynylamine contains no detectable halides and no detectable water.

22. 10. The high-purity alkynyl amine of claim 1, wherein the high-purity alkynyl amine is halide- and water-free.

23. (i) A surface passivation formulation comprising one or more high-purity alkynylamines according to any one of claims 1 to 22.

24. 24. The surface passivation formulation of claim 23, wherein the (i) one or more high-purity alkynylamines comprises two or more high-purity alkynylamines according to any one of claims 1 to 22.

25. 24. The surface passivation formulation according to claim 23, wherein the (i) one or more high-purity alkynylamines include one or more of N,N-(1-di-isopropylamino)-2-butyne (1F) and 1,4-bis(dimethylamino)-2-butyne (2A).

26. 24. The surface passivation formulation according to claim 23, wherein the (i) one or more high-purity alkynylamines include N,N-(1-di-isopropylamino)-2-butyne (1F) and 1,4-bis(dimethylamino)-2-butyne (2A).

27. 24. The surface passivation formulation of claim 23, wherein the (i) one or more high-purity alkynylamines comprises N,N-(1-di-isopropylamino)-2-butyne (1F).

28. 24. The surface passivation formulation of claim 23, wherein the (i) one or more high-purity alkynylamines comprises 1,4-bis(dimethylamino)-2-butyne (2A).

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

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

31. 30. The method of claim 29, wherein the method comprises plasma-assisted ALD (PEALD).

32. 30. The method of claim 29, wherein the method comprises a chemical vapor deposition process (CVD).

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

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

35. Water, diatomic oxygen, oxygen plasma, ozone, NO, N ２ O, NO ２ 34. The method of claim 33, further comprising introducing into the reaction vessel at least one reactant selected from the group consisting of carbon monoxide, carbon dioxide, and combinations thereof.

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

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

38. 1. A method for forming a metal-containing film via a thermal atomic layer deposition (ALD) or thermal ALD-like process, comprising: a. providing a substrate in a reaction vessel; b. forming at least one passivated surface by exposing said at least one surface to one or more of the high-purity alkynylamines of any one of claims 1 to 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. Successively repeat steps c through f until the desired thickness of the transition metal-containing film is achieved. The method includes:

39. The source gas is water, diatomic oxygen, ozone, NO, N ２ O, NO ２ 39. The method of claim 38, wherein the oxygen-containing source gas is one or more selected from the group consisting of carbon monoxide, carbon dioxide, and combinations thereof.

40. 39. The method of 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 combinations thereof.

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

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

43. 39. The method of 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 a thermal plasma, a pulsed plasma, a helicon plasma, a high density plasma, an inductively coupled plasma, x-ray, an electron beam, a photon, a remote plasma method, and combinations thereof.

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

45. 39. The method of claim 38, wherein step b comprises introducing the one or more agents using a solvent comprising one or more of toluene, mesitylene, isopropylbenzene, p-cymene (4-isopropyltoluene), 1,3-diisopropylbenzene, octane, dodecane, 1,2,4-trimethylcyclohexane, n-butylcyclohexane, and decahydronaphthalene (decalin), and combinations thereof.

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

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

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

49. 46. ​​The method of any one of claims 29 to 45, further comprising depositing a multicomponent oxide film on the at least one passivated surface, the multicomponent oxide film comprising 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. 46. ​​The method of any one of claims 29 to 45, wherein the one or more precursors comprise trimethylaluminum.

51. 46. ​​The method of any one of claims 29 to 45, wherein the one or more precursors comprise tetrakis(dimethylamido)titanium.

52. 46. ​​The method of any one of claims 29 to 45, wherein the one or more precursors comprise tetrakis(ethylmethylamido)zirconium.

53. 46. ​​The method of any one of claims 29 to 45, wherein the one or more precursors comprise tetrakis(ethylmethylamido)hafnium.

54. 46. ​​The method of any one of claims 29 to 45, wherein the one or more precursors comprise pentakis(dimethylamido)tantalum.

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

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