Gas phase delivery of non-volatile metal halide compound precursors

Abstract

The present disclosure relates to a composition for depositing a metal on a substrate. The composition includes a chemical precursor comprising a metal halide compound and a carrier agent for delivering the chemical precursor in a gas phase, the carrier agent comprising a Group 13 halide having a volatilization temperature lower than the volatilization temperature of the metal halide compound at a pressure within a precursor vessel. The present disclosure also relates to a precursor vessel comprising the composition, and to a chemical vapor deposition system and method for depositing a metal using the composition.

Description

[0001] Cross-references to related applications

[0002] This application claims the benefit of U.S. Provisional Application 63 / 726,100, filed November 27, 2024, the entire contents of which are incorporated herein by reference. Technical Field

[0003] This invention relates to the field of chemical vapor deposition, and more specifically, to the gas-phase delivery of metal halide compound precursors for chemical vapor deposition. Background Technology

[0004] Deposition techniques, such as chemical vapor deposition (CVD), and especially atomic layer deposition (ALD), are essential technologies in semiconductor device fabrication, enabling controlled deposition of thin films at the atomic level. These processes rely on delivering chemical precursors in the gas phase to react on a substrate surface, thereby forming materials with the precise composition and properties required for advanced electronic applications.

[0005] Organometallic precursors are commonly used in CVD due to their volatility and thermal stability, which facilitates efficient vapor transport and deposition. These precursors consist of metal centers coordinated with organic ligands, allowing them to evaporate at relatively low temperatures. However, incorporation of carbon-containing ligands can introduce impurities such as carbon, nitrogen, or oxygen into the deposited film. Such impurities can adversely affect the electrical, optical, or structural properties of the film, posing a challenge to achieving the desired material properties.

[0006] In contrast, inorganic metal halides, composed solely of metals and halogens, offer the advantage of being free of potential contaminants associated with organic ligands. Volatile halides such as titanium tetrachloride (TiCl4), tantalum pentachloride (TaCl5), molybdenum pentachloride (MoCl5), and silicon tetrachloride (SiCl4) have been successfully used as precursors in CVD processes. These compounds are commercial chemicals that do not require complex synthesis, making them economically viable for large-scale manufacturing.

[0007] Despite these advantages, the applicability of inorganic metal halides is limited by the volatility of a wide range of inorganic metal halides. Many metals (including cobalt, ruthenium, manganese, nickel, scandium, yttrium, and the lanthanides) form halides that are non-volatile under typical processing conditions. These metal halides typically exist as crystalline solids with strong intermolecular forces, requiring high thermal energy to evaporate. The temperatures required to achieve sufficient vapor pressures in these materials may be impractically high, potentially leading to thermal decomposition or undesirable reactions that compromise film quality.

[0008] The inability to effectively evaporate and transport non-volatile metal halides has hindered the incorporation of a wider range of metals into thin-film technologies. With advancements in the semiconductor industry, the demand for diverse materials with specialized functions is increasing. The development of processes that can transport these metals in vapor form is crucial for expanding the capabilities of CVD technologies, enabling the production of next-generation devices with improved performance and novel features.

[0009] Research is underway on methods to facilitate vapor transport of these materials without introducing impurities or compromising the integrity of the deposited film. Continued progress in this field is needed to address at least some of these challenges. Summary of the Invention

[0010] The purpose of embodiments of the present invention is to achieve vapor transport of metal halide compounds.

[0011] The above objectives are achieved by the method and apparatus according to the present invention.

[0012] An advantage of embodiments of the present invention is that, typically, non-volatile metal halide compounds can be transported in the gas phase. Another advantage of embodiments of the present invention is that metal halide compounds that do not naturally provide volatile forms can be effectively used in chemical vapor deposition processes, such as atomic layer deposition processes.

[0013] An advantage of embodiments of the present invention is that a wide range of metals can be used for deposition without introducing potential contaminants typically generated by organic ligands.

[0014] The advantage of embodiments of the present invention is that the method enables the deposition of thin films for semiconductor manufacturing in a more economical and efficient manner by reducing the need for fine ligand design to achieve volatility.

[0015] In a first aspect, the present invention relates to a precursor container, comprising:

[0016] a. Chemical precursors containing metal halide compounds, and

[0017] b. A carrier for gas-phase delivery of the chemical precursor, the carrier comprising a Group 13 halide, wherein the Group 13 halide has a lower volatilization temperature than the metal halide compound under pressure within the precursor container.

[0018] The precursor container is configured to supply vapors, including chemical precursors and carrier agents, to the reaction chamber of the chemical vapor deposition system.

[0019] In a second aspect, the present invention relates to a method for chemical vapor deposition of a metal-containing material on a substrate, the method comprising:

[0020] a. Provide a substrate in the reaction chamber, and then,

[0021] b. A gas-phase composition comprising a polynuclear complex is supplied from a first source to a reaction chamber, the polynuclear complex comprising:

[0022] i. A chemical precursor comprising a halide compound of the metal, the metal halide compound having a volatilization temperature higher than the temperature at a location along the flow path of the composition from the first source to the reaction chamber, and coordinating with the following...

[0023] ii. A carrier for gas-phase delivery of the metal halide compound, the carrier comprising a Group 13 halide having a volatilization temperature below the stated temperature at the stated pressure.

[0024] This allows a thin film containing metal to be formed on a portion of the substrate surface.

[0025] In a third aspect, the present invention relates to a system for chemical vapor deposition of a metal-containing material, the system comprising:

[0026] a. A reaction chamber for receiving the substrate.

[0027] b. A first source, connected via a first valve to a reaction chamber, for providing a gas-phase composition comprising a polynuclear complex, the polynuclear complex comprising:

[0028] i. A chemical precursor comprising a halide compound of said metal, coordinated with the following,

[0029] ii. A carrier agent for gas-phase delivery of the chemical precursor, the carrier agent comprising a group 13 halide, and

[0030] c. A controller operably connected to the first valve, wherein the controller is configured and programmed to open the first valve to provide flow of the composition into the reaction chamber, and to close the first valve to stop flow of the composition into the reaction chamber.

[0031] The system is configured to provide temperature and pressure at a location along the flow path of the composition from the first source to the reaction chamber when the first valve is opened, wherein the volatilization temperature of the metal halide compound is higher than the temperature at the pressure, and the volatilization temperature of the group 13 halide is lower than the temperature at the pressure.

[0032] In a fourth aspect, the present invention relates to a composition configured for depositing a thin film by chemical vapor deposition, preferably by atomic layer deposition, the composition comprising:

[0033] a. Chemical precursors containing metal halide compounds, and

[0034] b. A carrier for transporting the chemical precursor in the gas phase, the carrier comprising a group 13 halide and having a volatilization temperature below that of the metal halide compound at pressures in the range of 10 to 1000 Pa.

[0035] In a fifth aspect, the present invention relates to a precursor container, comprising:

[0036] The shell, which defines the internal volume of the precursor container.

[0037] An inlet conduit, disposed within the housing and in fluid communication with the internal volume of the precursor container, includes at least one valve positioned thereon.

[0038] An outlet conduit, disposed within the housing and in fluid communication with the internal volume of the precursor container, includes at least one valve positioned thereon.

[0039] Metal halide compounds, which accumulate within the internal volume of a precursor container, wherein the metal halide compounds include:

[0040] (i) Metals selected from the following: cobalt, ruthenium, manganese, nickel, Group 3 metals, and lanthanides; and

[0041] (ii) One or more halogen atoms.

[0042] Specific and preferred aspects of the invention are set forth in the appended independent and dependent claims. Features from the dependent claims may be suitably combined with features from the independent claims and other dependent claims, and not merely those expressly set forth in the claims.

[0043] Despite the ongoing improvements, changes, and evolutions in equipment in this field, this concept is considered to represent fundamentally new and novel improvements, including deviations from existing practices, resulting in more efficient, stable, and reliable equipment with these properties.

[0044] The above and other features, characteristics, and advantages of the present invention will become apparent from the following detailed description taken in conjunction with the accompanying drawings, which illustrate the principles of the invention by way of example. This description is given for illustrative purposes only and does not limit the scope of the invention. The references to the drawings cited below refer to the accompanying drawings. Attached Figure Description

[0045] Figure 1 This is a schematic diagram of a system according to an embodiment of the present invention.

[0046] Figure 2 This is a schematic diagram of the reaction chamber of a system after depositing a thin film containing a metal halide compound and a Group 13 halide on a substrate, according to an embodiment of the present invention.

[0047] Figure 3 This is a schematic diagram of the reaction chamber of a system according to an embodiment of the present invention, wherein Group 13 halides are selectively removed from a thin film.

[0048] Figure 4 This is a schematic diagram of the reaction chamber of the system after the removal of Group 13 halides according to an embodiment of the present invention.

[0049] Figure 5 This is a schematic diagram of a precursor container according to an embodiment of the present invention, which includes separate chambers for metal halide compounds and Group 13 halides according to an embodiment of the present invention.

[0050] Figure 6 The coordination of the carrier aluminum chloride with the metal chloride is schematically shown.

[0051] In different figures, the same reference numerals denote the same or similar elements. Detailed Implementation

[0052] The invention will be described with reference to specific embodiments and certain accompanying drawings, but is not limited thereto; rather, it is limited only by the claims. The described drawings are illustrative only and not restrictive. In the drawings, the dimensions of some elements may be exaggerated and not drawn to scale for illustrative purposes. Dimensions and relative dimensions do not correspond to actual reductions in practice of the invention.

[0053] Furthermore, the terms first, second, third, etc., used in the specification and claims are used to distinguish similar elements and are not necessarily used to describe a sequence in time, space, order, or any other way. It should be understood that the terms thus used are interchangeable where appropriate, and the embodiments of the invention described herein can operate in orders other than those described or shown herein.

[0054] Furthermore, the terms top, bottom, above, below, etc., used in the specification and claims are for descriptive purposes and are not necessarily used to describe relative positions. It should be understood that such terms are interchangeable where appropriate, and the embodiments of the invention described herein can operate in orientations other than those described or shown herein.

[0055] It should be noted that the term "comprising" should not be construed as limited to the devices listed thereafter; it does not exclude other elements or steps. Therefore, it should be interpreted as specifying the presence of the stated feature, integer, step, or component, but not excluding the presence or addition of one or more other features, integers, steps, or components, or groups thereof. Thus, the term "comprising" covers both the presence of only the stated feature and the presence of these features plus one or more other features. Therefore, the term "comprising" according to the invention also includes the absence of other components as an example. Therefore, the scope of the expression "device comprising devices A and B" should not be construed as limited to a device consisting only of components A and B. This means that, with respect to the invention, the only relevant components of the device are A and B. In some embodiments, the term "comprising" includes "consisting of...".

[0056] Similarly, it should be noted that the term "connection" should not be interpreted as limited to direct connection. The terms "connection" and "linkage" and their derivatives may be used. It should be understood that these terms are not intended to be synonyms with each other. Therefore, the scope of the expression "device A connected to device B" should not be limited to devices or systems where the output of device A is directly connected to the input of device B. This implies that there is a path between the output of A and the input of B, which may include other devices or apparatuses. "Connection" can mean two or more elements in direct physical or electrical contact, or two or more elements that are not in direct contact with each other but still cooperate or interact with each other.

[0057] Throughout this specification, the reference to "an embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with that embodiment is included in at least one embodiment of the invention. Therefore, the phrases "in an embodiment" or "in one embodiment" appearing in various places throughout this specification do not necessarily refer to the same embodiment, but may refer to the same embodiment. Furthermore, in one or more embodiments, particular features, structures, or characteristics may be combined in any suitable manner as will be apparent to those skilled in the art based on this disclosure.

[0058] Similarly, it should be understood that in the description of exemplary embodiments of the invention, various features of the invention are sometimes grouped together in a single embodiment, drawing, or description therein in order to simplify the disclosure and aid in understanding one or more of the various aspects of the invention. However, this method of disclosure should not be construed as reflecting an intention that the claimed invention requires more features than are expressly recited in each claim. Rather, as reflected in the following claims, inventive aspects lie in fewer than all features of a single foregoing disclosed embodiment. Therefore, the claims following the detailed description are expressly incorporated herein, wherein each claim is independently a separate embodiment of the invention.

[0059] Furthermore, while some embodiments described herein include features that are not included in other embodiments, combinations of features from different embodiments are intended to be within the scope of the invention and form different embodiments, as will be understood by those skilled in the art. For example, in the following claims, any claimed embodiment may be used in any combination.

[0060] Furthermore, some of the embodiments described herein are methods or combinations of method elements that can be implemented by a processor of a computer system or by other means of performing functions. Therefore, a processor having the necessary instructions for performing such methods or method elements forms means for performing such methods or method elements. Moreover, the elements of the apparatus embodiments described herein are examples of means for performing the functions performed by the elements, for the purposes of this invention.

[0061] Numerous specific details are set forth in the description provided herein. However, it should be understood that embodiments of the invention can be practiced without these specific details. In other instances, well-known methods, structures, and techniques have not been shown in detail so as not to obscure the understanding of this specification.

[0062] The following terms are provided only to aid in understanding the invention.

[0063] As used herein, unless otherwise stated, the term "evaporation temperature" for a substance refers to the temperature at which a substance (i.e., a pure substance, and therefore not a mixture, but its pure form) changes from a condensed phase (solid or liquid) to a gaseous phase under a specified pressure. Evaporation temperature can be the sublimation temperature, boiling temperature, or evaporation temperature. Evaporation temperature depends on pressure, and as elsewhere in the specification, unless otherwise stated, the evaporation temperature of a material refers to the evaporation temperature at the location of the material, i.e., under the ambient pressure of the material.

[0064] As used herein, unless otherwise stated, the term "basic" when applied to a composition, method, or system generally refers to a proportion of a value, property, characteristic, etc., or conversely, a lack thereof, being at least about 70%, at least about 80%, at least about 90%, at least about 95%, at least about 97%, at least about 98%, at least about 99%, at least about 99.5%, at least about 99.9% or more, or any proportion between about 70% and about 100%. In some embodiments, the term "basic" means a proportion of about 90%, about 95%, about 97%, about 98%, about 99%, about 99.5%, or about 99.9%.

[0065] As used herein, unless otherwise stated, the term "chemical vapor deposition" refers to a process in which material is deposited from the vapor phase onto a substrate and in which a reaction occurs between the material and the substrate. The reaction can occur directly while the material is still in the vapor phase, but this is not necessary. Rather, prior to the reaction, a non-reactive deposition, such as condensation or physisorption, can first occur without initially chemically altering the material.

[0066] As used herein, unless otherwise stated, the terms "layer" and / or "film" can refer to any continuous or discontinuous material, such as materials deposited by the methods disclosed herein. For example, layers and / or films can include two-dimensional materials, three-dimensional materials, nanoparticles, or even partially or entirely molecular layers or partially or entirely atomic layers or atomic and / or molecular clusters. Films or layers can include materials or layers with pinholes, which can be at least partially continuous. In some embodiments, layers according to this disclosure are substantially continuous.

[0067] As used herein, "substrate" refers to one or more underlying materials on which devices, circuits, materials, or material layers can be formed or on which they are formed. Substrates can be continuous or discontinuous; rigid or flexible; solid or porous; and combinations thereof. Substrates can be in any form, such as powder, sheet, plate, or workpiece. Sheet-form substrates can extend beyond the boundaries of the reaction space or processing / reaction chamber where the deposition process occurs, and in some cases, move through the chamber so that the process continues until the end of the substrate is reached. Plate-form substrates can include wafers of various shapes and sizes. Substrates can be made of semiconductor materials, including, for example, Mo, Mo germanium, Mo oxide, gallium arsenide, gallium nitride, and Mo carbide. Substrates can include one or more layers covering a bulk material, such as nitrides (e.g., TiN), oxides, insulating materials, dielectric materials, conductive materials, metals (e.g., tungsten, ruthenium, Group 6 metals, cobalt, aluminum, or copper) or other metallic materials, crystalline materials, epitaxial, heteroepitaxial, and / or single-crystal materials. The substrate may include various topologies, such as gaps, grooves, lines, trenches, vias, holes, or spaces between protrusions (e.g., fins) formed in or on at least a portion of the layers of the substrate.

[0068] The present invention will now be described in detail through several embodiments thereof. It is clear that other embodiments of the invention can be configured based on the knowledge of those skilled in the art without departing from the technical teachings of the invention, which is limited only by the terms of the appended claims.

[0069] In a first aspect, the present invention relates to a precursor container, comprising:

[0070] a. Chemical precursors containing metal halide compounds, and

[0071] b. A carrier for gas-phase delivery of the chemical precursor, the carrier comprising a Group 13 halide, wherein the Group 13 halide has a lower volatilization temperature than the metal halide compound under pressure within the precursor container.

[0072] The precursor container is configured to supply vapors comprising a chemical precursor and a carrier agent to the reaction chamber of the chemical vapor deposition system, preferably to the reaction chamber of a semiconductor processing apparatus. The reaction chamber of the chemical vapor deposition system, i.e., the chemical vapor deposition system reaction chamber, can be the reaction chamber of an atomic layer deposition system.

[0073] A wide range of metal halide compounds have volatilization temperatures that are too high for metal halide compounds to be used in chemical vapor deposition techniques, such as atomic layer deposition, under typical processing conditions. In some embodiments, the metal halide compounds may have volatilization temperatures of at least 250°C, at least 300°C, at least 400°C, or even at least 500°C at the pressure within the precursor container.

[0074] This invention allows the delivery of metal halide compounds into the gas phase, thereby enabling the use of typically non-volatile metal halide compounds in chemical vapor deposition processes. The carrier has a low volatilization temperature and can therefore be in the gas phase at a lower temperature than the chemical precursor. At the stated pressure, the volatilization temperature of the Group 13 halides can be at least 20°C lower than the volatilization temperature of the metal halide compound, preferably at least 50°C lower, more preferably at least 100°C lower, and even more preferably at least 200°C lower.

[0075] If Group 13 halides are in the gas phase, they can interact with metal halide compounds, which are typically condensed, thus also transporting the latter into the gas phase. In particular, exposing metal halide compounds to the vapor of a carrier can produce discrete gas-phase polynuclear complexes (such as...). Figure 6 The diagram illustrates an example of three molecules of aluminum trichloride coordinated with a metal (M) trichloride carrier. The metal halide contained in the polynuclear complex can then be transported in the gas phase, even at ambient temperatures below the volatilization temperature of the metal halide.

[0076] Metal halide compounds and Group 13 halides can be present in a precursor container, coordinated with each other, to form the polynuclear complex. The polynuclear complex may comprise one or more molecules of a metal halide compound coordinated with one or more molecules of a Group 13 halide. Polynuclear complexes can generally be described by the following chemical formula: (MX x ) w (M'X' y ) zIn this expression, M is the metal of the metal halide compound, each X is independently an oxygen or nitrogen atom of a halogen and optionally a metal halide compound, M' is a Group 13 element, and each X' is independently an oxygen or nitrogen atom of a halogen and optionally a Group 13 halide. The subscript x can be 1 to 6, such as 3 to 5. The subscript y can be 1 or 3, but is usually 3. The subscript w is usually 1, but values ​​greater than 1 are not strictly excluded. The subscript z can be 2 or 3, or equal to x, but this is not strictly required. Alternatively, for example, if x = z and w = 1, it can be expressed as (M)(XM'X') y ) z Describing multinuclear complexes, for the purposes of this invention, it is considered that (M)(XM'X') y ) z Equivalent to (MX) x ) w (M'X' y ) z .

[0077] In the embodiments, the metal halide compound is a metal atom bonded to one or more halogen atoms. In the embodiments, the metal halide compound may be a metal halide, a metal nitride halide, or a metal oxyhalide. In the embodiments, the metal halide compound is a metal halide. The metal halide consists of metal atoms bonded to one or more halogen atoms.

[0078] In these embodiments, the metal may be selected from transition metals, lanthanides, and combinations thereof. In some embodiments, the metal may be selected from cobalt, ruthenium, manganese, nickel, Group 3 metals, lanthanides, and combinations thereof. Group 3 metals include scandium, yttrium, lutetium, and lanthanum. In some embodiments, the Group 3 metal is scandium and / or yttrium. Lanthanides include lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. These metals are considered important for semiconductor applications, but their halide compounds typically have very high volatilization temperatures.

[0079] In some embodiments, the metal halide compound is selected from LaCl3, YCl3, ScCl3, or combinations thereof. In these embodiments, the support agent preferably comprises or is composed of AlCl3. In these embodiments, the polynuclear complex comprising a Group 13 halide coordinated with the metal halide compound may have the formula M''Cl3(AlCl3)3, wherein the metal M'' is selected from La, Y, and Sc. In some of these embodiments, the deposition method may be atomic layer deposition, wherein the composition is alternately introduced into the reaction chamber, alternating with co-reactants to provide a thin film of the metal M'' as an oxide, nitride, carbide, boride, or (pure, i.e., metallic) metal.

[0080] In some embodiments, one or more halogen atoms in the metal halide compound may be selected from fluorine, chlorine, bromine, iodine, and combinations thereof. In some embodiments, each of the one or more halogen atoms in the metal halide compound is bromine or chlorine, preferably chlorine.

[0081] In some embodiments, the Group 13 halide is a Group 13 element bonded to one or more halogen atoms. In some embodiments, under the pressure within the precursor container, the carrier agent, particularly the Group 13 halide, may have a volatilization temperature of up to 400°C, preferably up to 300°C, more preferably up to 250°C, and even more preferably up to 200°C.

[0082] In some embodiments, the group 13 element may be selected from boron, aluminum, gallium, and combinations thereof. In some embodiments, the group 13 element is aluminum.

[0083] In some embodiments, one or more halogen atoms of the Group 13 halide may be selected from fluorine, chlorine, bromine, iodine, and combinations thereof. In some embodiments, each of the one or more halogen atoms of the Group 13 halide is bromine or chlorine, preferably chlorine. In some embodiments, the Group 13 halide is selected from aluminum trichloride, aluminum tribromide, aluminum triiodide, gallium trichloride, gallium tribromide, boron trichloride, boron tribromide, boron trifluoride, indium trichloride, and combinations thereof. In some embodiments, the Group 13 halide is aluminum trichloride. An advantage of these embodiments is that these carriers can be effective carriers with volatilization temperatures entirely within the typical temperature range of normal chemical vapor deposition processing conditions.

[0084] In some embodiments, the halogen atoms of the Group 13 halides have the same type (i.e., the same type of element) as the halogen atoms of the metal halide compound. For example, both the metal halide compound and the Group 13 halides can be chlorides. Due to the spatial similarity between the metal halide compound and the Group 13 halides, good interactions are resulting, which can lead to good transport of the metal halide compound by the Group 13 halides.

[0085] In some embodiments, the precursor container contains a metal halide compound in a condensed phase. During chemical vapor deposition, the metal halide compound may also be at least partially in a condensed phase. In some embodiments, the precursor container may contain a polymeric, amorphous (e.g., non-crystalline), crystalline, or liquid metal halide compound. In some embodiments, the precursor container may contain a metal halide compound in a polymeric or crystalline state. Most metal halide compounds form a polymeric or crystalline phase in a condensed phase.

[0086] In some embodiments, the precursor container may comprise a metal halide compound dispersed in a liquid matrix, preferably in an ionic liquid. An ionic liquid is a salt whose melting point is typically below 100°C at standard pressure (i.e., 1 atm., equivalent to 101325 Pa). For example, the precursor container may comprise polymer, amorphous (e.g., non-crystalline), or crystalline metal halide compound particles dispersed in a liquid matrix. During chemical vapor deposition, while in the gas phase, a carrier containing a Group 13 halide can be bubbled through the liquid matrix, thereby transferring at least a portion of the metal halide compound into the gas phase.

[0087] Group 13 halides can be present in the precursor container during storage. Alternatively, during storage, the precursor container may contain only metal halide compounds, in which case the Group 13 halides can be introduced into the precursor container when it is used in a chemical vapor deposition (CVD) process. Group 13 halides can be condensed or present in the precursor container in a gaseous state. During CVD, Group 13 halides are typically present in the precursor container in a gaseous state.

[0088] The precursor container can be made of a suitable container material, such as stainless steel, aluminum, copper, nickel, silver, alloys thereof, graphite, boron nitride, ceramic materials, or combinations or mixtures of said materials. The container material can be a thermally conductive material. The container material can be a coating or covering material.

[0089] The precursor container includes a shell defining an internal volume of the precursor container. According to embodiments of the invention, the internal volume is adapted to contain the precursor and the carrier agent. In some embodiments, the internal volume has a generally circular cylindrical shape, such that the internal volume has a generally circular base plate. However, the internal volume of the precursor container can have any shape that promotes uniform flow of the carrier gas and the carrier agent through the internal volume. In some embodiments, the precursor container can have a height-to-width ratio in the range of about 0.5 to 4, for example, 1 to 2 or 1 to 3. The height of the precursor container is the dimension of the portion of the shell furthest from the cap at the exterior of the precursor container. The width of the precursor container is the maximum dimension spanning the precursor container perpendicular to its height.

[0090] In some embodiments, the internal volume includes a single chamber for storing a metal halide compound and optionally a Group 13 halide. In some embodiments, the internal volume may be divided into multiple chambers. In some embodiments, the precursor container includes at least one first chamber comprising a chemical precursor containing a metal halide compound; and at least one second chamber comprising a carrier containing a Group 13 halide. The chambers may be connected to each other via valves. The valves may be closed, for example, during storage and transport of the precursor container to prevent materials in different chambers from mixing or coming into contact with each other. For example, when the precursor container is used in a chemical vapor deposition method, the valves may be opened to allow the carrier containing the Group 13 halide to flow in the gas phase from at least one second chamber to at least one first chamber for delivering the metal halide compound into the gas phase. Each first chamber may be connected via a valve to one of one or more second chambers such that the Group 13 halide passes through the first chamber from the second chamber before leaving the precursor container via an outlet of the precursor container. One or more first chambers and one or more second chambers may be connected in series via valves, or pairs of first chambers and second chambers may be connected in series within each pair, and these pairs may be connected in parallel with each other.

[0091] In some embodiments, the pressure within the precursor container (the volatilization temperature of the metal halide compound and the Group 13 halide depends on this pressure) may refer to the pressure within the internal volume of the precursor container, such as the pressure in the first chamber where the metal halide compound is present.

[0092] In some embodiments, the precursor container includes a cap for isolating the internal volume from the surrounding atmosphere. In some embodiments, the cap may include an inlet for feeding a carrier gas (e.g., N2, He, or Ar) into the internal volume of the precursor container. In some embodiments, the precursor container may include an inlet for feeding a Group 13 halide into the internal volume of the precursor container. In some embodiments, the inlet for feeding the Group 13 halide may also provide a carrier gas. The inlet for feeding the carrier gas and / or the carrier agent may include an inlet valve for introducing the carrier gas and / or the carrier agent when the inlet valve is open, and for preventing the carrier gas and / or the carrier agent from being fed into the precursor container when the inlet valve is closed. The cap may include an outlet for feeding the carrier agent, along with the chemical precursor and optionally the carrier gas, into the reaction chamber. The outlet may include an outlet valve for providing the carrier agent, along with the chemical precursor and optionally the carrier gas, into the reaction chamber when the outlet valve is open, and for preventing the carrier agent, along with the chemical precursor and optionally the carrier gas, from being fed into the reaction chamber when the outlet valve is closed.

[0093] The precursor container may be equipped with gas lines extending from the inlet and outlet, isolation valves on the lines, and fittings on the valves, the fittings being configured to connect to gas flow lines of other components of the chemical vapor deposition system. The isolation valves isolate the contents of the precursor container from external fluids. One isolation valve may be located upstream of the precursor container inlet, and another isolation valve may be located downstream of the precursor container outlet.

[0094] A deposition system in which a precursor container or precursor container may be a part may include a heater, such as a radiant heat lamp or a resistance heater. In some embodiments, the heater may be adapted to heat the precursor container to a temperature of 40°C to 200°C, for example, to 70°C, 85°C, 90°C, 110°C, or 120°C. In particular, during the use of a precursor container in a chemical vapor deposition method, the heater may be configured to heat the precursor container to a temperature above the volatilization temperature of the group 13 halides under pressure within the precursor container. More specifically, the heater may be configured to heat the precursor container to a temperature wherein, under pressure within the precursor container, the gas phase may include a polynuclear complex comprising a group 13 halide coordinated to a metal halide compound. That is, the temperature is preferably high enough to allow the polynuclear complex to be in the gas phase, and preferably low enough to prevent the polynuclear complex from decomposing into metal halide compounds, for example, dissociated from the group 13 halide.

[0095] In embodiments, the pressure within the precursor container can be from 10 to 1000 Pa, but the invention is not limited thereto. In particular, the precursor container is typically subjected to such low pressures during use in chemical vapor deposition methods. The precursor container may include, or may be coupled to, a pressure control system for monitoring the pressure within the precursor container. The precursor container may include a valve for coupling the precursor container to a vacuum pump.

[0096] In some embodiments, the precursor container may include precursor distribution means for achieving efficient precursor evaporation, such as a precursor holding structure or carrier gas guiding means within the internal volume of the precursor container. The precursor container may include features for filtering solid particles to prevent their presence in the gas phase flow, such as filters or other interception structures. Additionally, the inlet and outlet of the precursor container and the gas lines extending therefrom may include heaters for heating the valves and gas lines between the precursor container and the reaction chamber to prevent reactant vapors from condensing and depositing on any components.

[0097] Any feature of any embodiment of the first aspect may be independently described as in any embodiment of any other aspect of the invention.

[0098] In a second aspect, the present invention relates to a method for chemical vapor deposition of a metal-containing material on a substrate, the method comprising:

[0099] a. Provide a substrate in the reaction chamber, and then,

[0100] b. A gas-phase composition comprising a polynuclear complex is supplied from a first source to a reaction chamber, the polynuclear complex comprising:

[0101] i. A chemical precursor comprising a halide compound of the metal, the metal halide compound having a volatilization temperature higher than the temperature at a location along the flow path of the composition from the first source to the reaction chamber, and coordinating with the following...

[0102] ii. A carrier for gas-phase delivery of the metal halide compound, the carrier comprising a Group 13 halide having a volatilization temperature below the stated temperature at the stated pressure.

[0103] This allows a thin film containing metal to be formed on a portion of the substrate surface.

[0104] Compositions and polynuclear complexes are described in the first aspect of this disclosure.

[0105] The flow path of the composition from the first source to the reaction chamber is understood to include the flow path of the composition within the first source, the flow path of the composition within the reaction chamber, and the flow path of the composition between the first source and the reaction chamber (if the first source and the reaction chamber are not directly connected to each other). In some embodiments, this location may include the first source, such as the internal volume or chamber of a precursor container according to an embodiment of the first aspect of the invention, in which a metal halide compound may be present or stored. In some embodiments, this location may include a reaction chamber, particularly the environment within the reaction chamber. In some embodiments, this location may include a flow path between the first source and the reaction chamber, for example, via a gas line and / or valve. In some embodiments, this location substantially includes the complete flow path of the composition from the first source to the reaction chamber. In some embodiments, this location includes a substantially complete first source, a substantially complete reaction chamber, and a substantially complete flow path of the composition between the first source and the reaction chamber. Thus, although the metal halide compound is typically in a condensed phase in at least a portion of the flow path from the first source where it is stored to the substrate, it can be transported along said flow path by a Group 13 halide.

[0106] The temperature at this location or along the substantially complete flow path is adjusted such that the polynuclear complex (comprising a metal halide compound coordinated with a Group 13 halide) is in the gas phase. Typically, a polynuclear complex can form when it encounters or contacts a Group 13 halide in the gas phase. That is, the presence of a Group 13 halide in the gas phase is usually sufficient to keep the polynuclear complex in the gas phase. The temperature at this location is typically higher than the volatilization temperature of the polynuclear complex at the pressure at that location. The temperature along the substantially complete flow path can be higher than the volatilization temperature of the polynuclear complex (depending on the pressure).

[0107] In embodiments according to a first aspect of the invention, the first source includes a precursor container containing a metal halide compound and a Group 13 halide (either alone or contained in the polynuclear complex). In some embodiments, the first source includes a carrier container containing the Group 13 halide and a precursor container for storing the metal halide compound. In these embodiments, providing the gaseous composition may include providing the Group 13 halide into the gas phase of the carrier container (e.g., by heating with a heater) and inducing the gaseous Group 13 halide to flow from the carrier container into the precursor container. The gaseous Group 13 halide may coordinate with the metal halide compound and deliver the metal halide compound into the gas phase, thereby forming the gaseous composition. Subsequently, the gaseous composition may be transferred from the precursor container to a reaction chamber.

[0108] The provision of a substrate in a reaction chamber typically means that the substrate is in a space where deposition conditions can be controlled. The reaction chamber can be a single-wafer reactor. Alternatively, the reaction chamber can be a batch reactor. The reaction chamber can form part of a vapor phase processing assembly for fabricating semiconductor devices. The processing assembly can include one or more multi-station processing chambers. In some embodiments, the substrate moves between processing stations within a multi-station processing chamber. The reaction chamber can be part of a cluster tool where different processes are performed to form integrated circuits. The various stages of a chemical vapor deposition method can be performed in a single reaction chamber, or they can be performed in multiple reaction chambers, such as the reaction chambers of a cluster tool, or the deposition stations of a multi-station processing chamber.

[0109] In some embodiments, the reaction chamber is a reaction chamber of a semiconductor processing apparatus. In some embodiments, the reaction chamber may be a flow reactor, such as a crossflow reactor. In some embodiments, the reaction chamber may be a spray head reactor. In some embodiments, the reaction chamber may be a spatially partitioned reactor. In some embodiments, the reaction chamber may be a single-wafer atomic layer deposition reactor. In some embodiments, the reaction chamber may be a high-capacity manufacturing single-wafer atomic layer deposition reactor. In some embodiments, the reaction chamber may be a batch reactor for simultaneously manufacturing multiple substrates.

[0110] The reaction chamber may be part of a chemical vapor deposition system. In some embodiments, the chemical vapor deposition is atomic layer deposition. The reaction chamber may be part of an atomic layer deposition system. In some embodiments, the system or reaction chamber may be equipped with a heater to activate the reaction by raising the temperature of one or more of the substrate and / or precursors and / or co-reactants.

[0111] The substrate may be a semiconductor wafer, such as a silicon wafer, gallium arsenide wafer, silicon carbide wafer, germanium wafer, or indium phosphide wafer, but the invention is not limited thereto. In embodiments, portions of the substrate surface are reactive to metal halide compounds or to polynuclear complexes comprising metal halide compounds and Group 13 halides. In some embodiments, portions of the substrate surface may be functionalized to promote the chemisorption of metal halide compounds or said polynuclear complexes on said portions of the surface. In some embodiments, portions of the surface may be functionalized with functional groups selected from: hydroxyl, amino, carboxyl, thiol, silyl groups, or combinations thereof.

[0112] The following describes in detail different types of chemical vapor deposition, which can be performed according to embodiments of the present invention, but the invention is not limited thereto.

[0113] In some embodiments, the substrate temperature of a portion of the surface can be adjusted to induce chemisorption of metal halide compounds on the substrate. The chemisorption reaction is typically a reaction between the metal halide compound and a surface (e.g., with surface functional groups). The chemisorption reaction can occur directly, with the composition in the gas phase. In some embodiments, the substrate temperature can be adjusted such that the adsorption of the metal halide compound occurs selectively with respect to the adsorption of Group 13 halides. In these embodiments, the substrate temperature can be adjusted such that when a polynuclear complex contacts a portion of the surface, the Group 13 halides dissociate from the metal halide compound, such that the film contains only the chemisorbed metal halide compound. In different embodiments, the substrate temperature is adjusted such that the chemisorption of the polynuclear complex occurs on a portion of the substrate surface, such that the film can contain the chemisorbed polynuclear complex.

[0114] Chemisorbed metal halide compounds may comprise a portion of the metal halide compound bonded to the substrate surface, wherein one or more halogen atoms of the metal halide compound may remain bonded to the metal atom. If the metal halide compound is a metal oxohalide, the chemisorbed metal halide compound may further comprise an oxygen atom bonded to said metal. If the metal halide compound is a metal nitride halide, the chemisorbed metal halide compound may further comprise a nitrogen atom bonded to said metal. Surface-bonded chemisorbed polynuclear complexes may comprise the metal of the metal halide compound and a Group 13 element, and optionally one or more halogen atoms and / or oxygen atoms and / or nitrogen atoms of the metal halide compound and / or Group 13 halide.

[0115] If the film contains chemisorbed polynuclear complexes, but it is undesirable for Group 13 elements to remain incorporating into the material to be deposited, the method may include an additional step: inducing the selective release of Group 13 halides from the film. This portion of the surface may be heated, and / or the ambient pressure within the reaction chamber may be adjusted to selectively release the Group 13 halides from the chemisorbed polynuclear complexes, where the chemisorbed metal halides remain on the surface. Prior to and / or during the heating, the Group 13 halides in the reaction chamber may be purged, which may facilitate the release.

[0116] In some embodiments, the chemisorption process can be self-limiting, for example, if the chemisorbed metal halide compound does not readily react with the gas-phase polynuclear complex. In these embodiments, the chemisorption process can be limited, for example, by the size of the reactive region on the surface, or by the number of functional groups present on a portion of the substrate surface. These embodiments may involve atomic layer deposition. In these embodiments, the thin film can comprise a monolayer of chemisorbed metal halide compound or chemisorbed polynuclear complex, the thickness of which is substantially equal to the size of the single chemisorbed metal halide compound or the single chemisorbed polynuclear complex.

[0117] However, in some embodiments, the chemisorption process is not self-limiting. For example, a vapor-phase polynuclear complex may be adapted to react with a metal halide compound or polynuclear complex chemisorbed on the surface, in which case chemical vapor deposition can be performed to form multiple atomic layers on a portion of the surface. In these embodiments, the time the surface portion is exposed to the composition during this period can be adjusted to form a thin layer with a particularly preferred thickness.

[0118] In some embodiments, the substrate temperature can be adjusted to induce non-reactive deposition of vapors, initially without undergoing a reaction, such as physical adsorption or condensation (i.e., a transition from the gas phase to the condensed phase, initially without reaction), followed by a chemical reaction between the deposited material and the surface. In these embodiments, the thin film formed after the deposition but before the reaction can contain metal halide compounds or polynuclear complexes. In some embodiments, the substrate temperature of a portion of the substrate surface can be below the volatilization temperature of the Group 13 halides under pressure in the reaction chamber. In some of these embodiments, the substrate temperature of a portion of the substrate surface can be low enough that non-reactive deposition of polynuclear complexes can be induced initially. However, in some embodiments, the substrate temperature of a portion of the substrate surface can be adjusted to induce selective non-reactive deposition of Group 13 halides (but not polynuclear complexes). In these embodiments, polynuclear complexes can contact portions of the substrate, where the dissociation of the metal halide compound from the Group 13 halides occurs, wherein the metal halide compound is deposited while the Group 13 halides can be retained in the gas phase.

[0119] The non-reactive deposition may or may not be self-limiting. The substrate temperature, the ambient temperature within the reaction chamber, the concentrations of the precursor and carrier agents within the reaction chamber, and the time between providing the composition into and purging the composition from the reaction chamber can be adjusted to achieve a specific amount of metal halide compound or polynuclear complex, such as a single-molecule-thick layer, on a portion of the surface.

[0120] In embodiments where the thin film formed therein comprises a polynuclear complex, the method may include an additional step: inducing the selective release of a Group 13 halide from the thin film. In some embodiments, inducing the selective release may include adjusting (e.g., increasing) the temperature of a portion of the substrate surface such that the Group 13 halide is released from the surface, while the metal halide compound remains on the surface. Specifically, during the selective release, the temperature of the portion of the substrate surface may be higher than the volatilization temperature of the Group 13 halide at the pressure of the environment within the reaction chamber, and lower than the volatilization temperature of the metal halide at the pressure of the environment within the reaction chamber. The temperature may be adjusted such that decomposition of the polynuclear complex occurs, for example, bond breaking between the metal halide compound and the halide of the Group 13 compound, leading to the release. To facilitate the release, the Group 13 halide may be purged from the reaction chamber. The advantage of these embodiments is that thin films comprising metal halide compounds but substantially free of Group 13 halides can be formed.

[0121] The formed thin film containing metal halide compounds or polynuclear complexes can then be induced to react with the surface. Specifically, the temperature of a portion of the substrate surface can be adjusted to induce a reaction between the metal halide compounds or polynuclear complexes on the surface portion and said surface portion (e.g., with functional groups on said surface portion). The reaction can be self-limiting, although this is not necessary, similar to that described above for chemisorption processes. The reaction can result in the chemisorption of metal halide compounds or chemisorption of polynuclear complexes on the surface portion.

[0122] In some embodiments, the present invention relates to a cyclic chemical vapor deposition process, such as atomic layer deposition. In a cyclic chemical vapor deposition process, during each cycle, a composition is introduced into a reaction chamber, and a metal halide compound or polynuclear complex can be chemisorbed (or chemically adsorbed) onto a substrate surface in a self-limiting manner, as described above. Subsequently, a co-reactant can be introduced into the reaction chamber to convert the chemically adsorbed metal halide compound or polynuclear complex into the desired material. The co-reactant can be capable of further reacting with the chemically adsorbed metal halide compound or polynuclear complex. Furthermore, the deposition of the co-reactant can be self-limiting because the co-reactant may not readily react with the co-reactant. A purging step can be used to remove any excess precursor and carrier agent from the processing chamber and / or any excess co-reactant and / or reaction byproducts from the reaction chamber.

[0123] When the gas-phase composition is introduced back into the reaction chamber after the co-reactant deposition, the metal halide compound or polynuclear complex reacts with the deposited co-reactant, or reacts with the chemisorbed metal halide compound or polynuclear complex after reacting with the co-reactant, to which it is chemisorbed, and then reopened to react with the co-reactant. This cycle of providing gas-phase deposition and co-reactant can be repeated multiple times.

[0124] In some embodiments, the cyclic chemical vapor deposition method includes, after providing the vapor composition to the reaction chamber, cyclically:

[0125] Optionally, the reaction chamber of the gaseous composition is purged, and then...

[0126] The gas-phase co-reactant is introduced into the reaction chamber from a second source (e.g., from a co-reactant container), and then...

[0127] Optionally, the co-reactants in the reaction chamber are purged, and then,

[0128] The gaseous composition is supplied from the first source to the reaction chamber, and then,

[0129] Optionally, the selective release of Group 13 halides (if present on the surface) can be induced.

[0130] In some embodiments, at least one cycle of the cyclic chemical vapor deposition process includes:

[0131] The gaseous composition is introduced into the reaction chamber from the first source;

[0132] Optionally, the gaseous composition in the reaction chamber may be purged;

[0133] The gas-phase co-reactant is introduced into the reaction chamber from a second source (e.g., from a co-reactant container);

[0134] Optionally, the co-reactants in the reaction chamber are purged; and

[0135] Optionally, the selective release of Group 13 halides (if present on the surface) can be induced.

[0136] In some embodiments, the co-reactant may be an oxygen precursor, and the material formed by the cyclic chemical vapor deposition process is an oxide of a metal from a metal halide compound and optionally an oxide of a Group 13 element. The oxygen precursor can provide oxygen for forming the oxide. The oxygen precursor may be a gas or a material that can be converted to a gaseous state and can be represented by a chemical formula including oxygen. In some embodiments, the oxygen precursor is selected from water, molecular oxygen, hydrogen peroxide, ozone, and reactive oxygen species. In some embodiments, the oxygen precursor comprises hydrogen and oxygen. In some embodiments, the oxygen precursor does not contain carbon, i.e., it is carbon-free. In some embodiments, the oxygen precursor does not contain silicon, i.e., it is silicon-free. In some embodiments, the oxygen precursor comprises water. In some embodiments, the oxygen precursor is water. In some embodiments, the oxygen precursor is molecular oxygen. In some embodiments, the oxygen precursor includes hydrogen peroxide. In some embodiments, the oxygen precursor is hydrogen peroxide. In some embodiments, the oxygen precursor is ozone. Depending on the selected oxygen precursor, the oxygen precursor may be liquid or gaseous in the co-reactant container. However, the invention is not limited thereto; instead, solid precursors may be used.

[0137] In some embodiments, the co-reactant may be a nitrogen precursor, and the material formed by the cyclic chemical vapor deposition process is a nitride of a metal, a nitride from a metal halide compound, and optionally a nitride of a Group 13 element. The nitrogen precursor can provide nitrogen for the formation of the nitride. The term nitrogen precursor can refer to a gas or a material that can be converted into a gaseous state and can be represented by a chemical formula including nitrogen. In some embodiments, the chemical formula includes nitrogen and hydrogen. In some embodiments, the nitrogen precursor comprises an activated nitrogen substance that can be generated in a plasma (e.g., N2 plasma or N2+H2 plasma). In these embodiments, a gas containing nitrogen, and optionally also containing hydrogen, may be introduced into the reaction chamber and may be converted into plasma, for example, by heating, discharge, or laser ionization. In some embodiments, the nitrogen precursor does not include diatomic nitrogen. In some embodiments, the nitrogen precursor may be selected from ammonia (NH3), hydrazine (N2H4), and one or more other compounds containing nitrogen and hydrogen or composed thereof. For example, a mixture of nitrogen and hydrogen may be used. In some embodiments, the nitrogen precursor does not include diatomic nitrogen, i.e., the nitrogen precursor is a non-diatomic precursor. In some embodiments, the nitrogen precursor is selected from molecular nitrogen (N2), ammonia (NH3), hydrazine (NH2NH2), and hydrazine derivatives (e.g., tert-butylhydrazine). In some embodiments, the nitrogen precursor does not contain carbon, i.e., the nitrogen precursor may be carbon-free. In some embodiments, the nitrogen precursor does not contain silicon, i.e., the nitrogen precursor may be silicon-free. Depending on the nitrogen precursor selected, the nitrogen precursor may be liquid or gaseous in the co-reactant container upon evaporation. However, the invention is not limited thereto, and the nitrogen precursor may be solid. In some embodiments, the nitrogen precursor comprises ammonia. In some embodiments, the nitrogen precursor consists of or is substantially composed of ammonia. In some embodiments, the nitrogen precursor comprises alkylamines. In some embodiments, the nitrogen precursor consists of or is substantially composed of alkylamines. Examples of alkylamines include dimethylamine, n-butylamine, and tert-butylamine. In some embodiments, the nitrogen precursor comprises hydrazine. In some embodiments, the nitrogen precursor consists of or is substantially composed of hydrazine. In some embodiments, the nitrogen precursor comprises hydrazine substituted with one or more alkyl or aryl substituents. In some embodiments, the nitrogen precursor consists of or is substantially composed of hydrazine substituted with one or more alkyl or aryl substituents.In some embodiments, the hydrazine derivative comprises alkyl hydrazine, which includes at least one of the following: tert-butylhydrazine (C4H9N2H3), methylhydrazine (CH3NHNH2), 1,1-dimethylhydrazine ((CH3)2NNH2), 1,2-dimethylhydrazine (CH3NHNHCH3), ethylhydrazine, 1,1-diethylhydrazine, 1-ethyl-1-methylhydrazine, isopropylhydrazine, phenylhydrazine, 1,1-diphenylhydrazine, 1,2-diphenylhydrazine, N-aminopiperidine. N-aminopyrrole, N-aminopyrrolidine, N-methyl-N-phenylhydrazine, 1-amino-1,2,3,4-tetrahydroquinoline, N-aminopiperazine, 1,1-dibenzylhydrazine, 1,2-dibenzylhydrazine, 1-ethyl-1-phenylhydrazine, 1-aminoazacycloheptane, 1-methyl-1-(m-tolyl)hydrazine, 1-ethyl-1-(p-tolyl)hydrazine, 1-aminoimidazolium, 1-amino-2,6-dimethylpiperidine, N-aminoazapyridine, and azo tert-butane.

[0138] In some embodiments, the co-reactant may be a hydrocarbon. In these embodiments, the material formed on the surface portion may be a carbide. The hydrocarbon may be aliphatic or aromatic. The hydrocarbon may be saturated or unsaturated, straight-chain or branched, cyclic or acyclic. The hydrocarbon may include, for example, alkyl halides, alkenes, alkynes, or alkyl metals. In some embodiments, the hydrocarbon is an unsubstituted hydrocarbon, i.e., it contains only carbon and hydrogen. In some embodiments, the hydrocarbon is a substituted or functionalized hydrocarbon. For example, the hydrocarbon may be a haloalkanes, such as chlorinated hydrocarbons, fluorinated hydrocarbons, bromine hydrocarbons, or iodoalkanes. The hydrocarbon may be a hydroxylated hydrocarbon, an alcohol, or a carboxylic acid. The hydrocarbon may be an ester, a ketone, or an aldehyde. The hydrocarbon may include an amine or an imine.

[0139] In some embodiments, the co-reactant may comprise boron. In these embodiments, the material formed on the surface portion may be a metal boride. In these embodiments, the co-reactant may comprise an adduct of B₂H₆, BH₃, or a compound of formula B. x H y More advanced boranes.

[0140] In some embodiments, the co-reactant may be a reducing agent. In these embodiments, the material formed on a portion of the surface by a cyclic chemical vapor deposition method is a metallic material, which may consist substantially of a metal of a metal halide compound and optionally a Group 13 element (if it is metallic, such as Al, Ga, or In). The reducing agent may be a gas or a material that can be gasified and can reduce the deposited or chemisorbed metal halide compound or polynuclear complex to a metal. The reducing agent may be provided to the reaction chamber in a gaseous or fumed phase. The reducing agent may be in contact with the substrate containing the metal halide compound or polynuclear complex chemisorbed onto the substrate. The introduction of the gaseous composition and the reducing agent into the reaction chamber may at least partially overlap. In some embodiments, the introduction of the gaseous composition and the reducing agent into the reaction chamber may be simultaneous. However, in some embodiments, the introduction of the gaseous composition and the reducing agent into the reaction chamber may be at least partially separate. In some embodiments, the reducing agent may contain hydrogen. In some embodiments, the reducing agent may contain molecular hydrogen (H2) or a plasma derived from H2. In some embodiments, the reducing agent may contain boron. In some embodiments, the reducing agent comprises, or is substantially composed of, a neutral ligand adduct of diborane (B2H6) or borane (BH3). In some embodiments, the reducing agent comprises nitrogen. In some embodiments, the reducing agent may comprise, or is substantially composed of, hydrazine or a derivative thereof. In some embodiments, the reducing agent may comprise alkylhydrazine or dialkylhydrazine. In some embodiments, the reducing agent may comprise a diazepine compound. The diazepine compound may be azo tert-butane. In some embodiments, the reducing agent may comprise, consist of, or substantially comprise the following: 1,1-diethylhydrazine, 1-ethyl-1-methylhydrazine, isopropylhydrazine, phenylhydrazine, 1,1-diphenylhydrazine, 1,2-diphenylhydrazine, N-aminopiperidine, N-aminopyrrole, N-aminopyrrolidine, N-methyl-N-phenylhydrazine, 1-amino-1,2,3,4-tetrahydroquinoline, N-aminopiperazine, 1,1-dibenzylhydrazine, 1,2-dibenzylhydrazine, 1-ethyl-1-phenylhydrazine, 1-aminoazacycloheptane, 1-methyl-1-(m-tolyl)hydrazine, 1-ethyl-1-(p-tolyl)hydrazine, 1-aminoimidazolium, 1-amino-2,6-dimethylpiperidine, N-aminoazapyridine, and azo tert-butane. In some embodiments, the reducing agent may comprise, consist of, or substantially comprise one or more hydrocarbon-substituted hydrazine reducing agents. In some embodiments, the substituted hydrazine may comprise one or more alkyl groups. Each alkyl group may contain one or more, such as two, three, four, five, six, seven, or eight carbon atoms. The number of alkyl groups in a substituted hydrazine reducing agent may be one, two, three, or four. For the purposes of this disclosure, the alkyl group may be aryl. Therefore, the reducing agent according to this disclosure may contain, for example, phenylhydrazine or diphenylhydrazine.

[0141] In some embodiments, the gaseous composition and co-reactant are supplied to the reaction chamber in a pulsed manner. In some embodiments, the gaseous composition and the co-reactant are supplied in a pulsed manner, and the reaction chamber is purged between consecutive pulses containing the precursor of the polynuclear complex and the co-reactant. The duration for which the gaseous composition and the co-reactant are provided to the reaction chamber (i.e., the pulse time of the gaseous composition and the pulse time of the co-reactant, respectively) can each be independently, for example, at least 0.01 s, for example, from about 0.01 s to about 60 s, for example, from about 0.01 s to about 5 s, or from about 1 s to about 20 s, or from about 0.5 s to about 10 s, or from about 5 s to about 15 s, or from about 10 s to about 30 s, or from about 10 s to about 60 s, or from about 20 s to about 60 s, for example, 0.03 s, 0.1 s, 0.5 s, 1 s, 1.5 s, 2 s, 2.5 s, 3 s, 4 s, 5 s, 8 s, 10 s, 12 s, 15 s, 25 s, 30 s, 40 s, 50 s, or 60 s. In some embodiments, the pulse time of the gaseous composition can be at least 5 seconds or at least 10 seconds. In some embodiments, the pulse time for the gas phase composition can be up to 5 seconds, or up to 10 seconds, or up to 20 seconds, or up to 30 seconds. In some embodiments, the pulse time for the co-reactant can be at least 5 seconds, or at least 10 seconds, or at least 20 seconds. In some embodiments, the pulse time for the co-reactant can be at most 5 seconds, or at most 10 seconds, or at most 20 seconds, or up to 30 seconds. Pulse times can vary independently of each other and can depend on the process in question. The selection of an appropriate pulse time can depend on the substrate topology. For higher aspect ratio structures, longer pulse times may be required to achieve sufficient surface saturation in different regions of the high aspect ratio structure. Furthermore, the selected precursor and co-reactant chemicals can influence the appropriate pulse time. For process optimization purposes, shorter pulse times may be preferred, provided that appropriate layer properties can be achieved. In some embodiments, the pulse time for the gas phase composition is longer than the pulse time for the co-reactant. In some embodiments, the pulse time for the co-reactant is longer than the pulse time for the gas phase composition. In some embodiments, the pulse time for the gas phase composition is the same as the pulse time for the co-reactant. In some embodiments, the gaseous composition may be pulsed more than once, such as twice, three times, or four times, before the co-reactant is pulsed into the reaction chamber. Similarly, more than one pulse of the co-reactant may be present, such as two, three, or four pulses, before the gaseous composition is pulsed (i.e., provided) into the reaction chamber.

[0142] In some embodiments, one or more purging steps are performed to remove any precursors, carriers, co-reactants, and / or gaseous byproducts from the reaction chamber. Purging may include evacuating the reaction chamber with a vacuum pump and / or replacing the gas in the reaction chamber with an inert or substantially inert gas (e.g., argon or nitrogen). Purging can limit or prevent interactions between precursors and co-reactants, for example, in the gas phase. Purging may be performed temporally, spatially, or both. In some embodiments, the purging step may include supplying a purge gas to the reaction chamber while simultaneously pumping gas from the reaction chamber, wherein the substrate on which the deposited layer is deposited remains stationary. The purging step may be performed for about 0.01 seconds to about 20 seconds, about 0.05 seconds to about 20 seconds, or about 1 second to about 20 seconds, or about 0.5 seconds to about 10 seconds, or between about 1 second and about 7 seconds, such as 5 seconds, 6 seconds, or 8 seconds, but other purging times may be utilized if desired. In some embodiments, the purging step may include moving the substrate from a first position where the gas phase composition is continuously supplied to a second position where the co-reactant is continuously supplied by means of a purging gas curtain or another means of separating the first position from the second position.

[0143] Any feature of any embodiment of the second aspect may be independently described as in any embodiment of any other aspect of the invention.

[0144] In a third aspect, the present invention relates to a system for chemical vapor deposition of a metal-containing material, the system comprising:

[0145] a. A reaction chamber for receiving the substrate.

[0146] b. A first source, connected via a first valve to a reaction chamber, for providing a gas-phase composition comprising a polynuclear complex, the polynuclear complex comprising:

[0147] i. A chemical precursor comprising a halide compound of said metal, coordinated with the following,

[0148] ii. A carrier agent for gas-phase delivery of the chemical precursor, the carrier agent comprising a group 13 halide, and

[0149] c. A controller operably connected to the first valve, wherein the controller is configured and programmed to open the first valve to provide flow of the composition into the reaction chamber, and to close the first valve to stop flow of the composition into the reaction chamber.

[0150] The system is configured to provide temperature and pressure at a location along the flow path of the composition from the first source to the reaction chamber when the first valve is opened, wherein the volatilization temperature of the metal halide compound is higher than the temperature at the pressure, and the volatilization temperature of the group 13 halide is lower than the temperature at the pressure.

[0151] Compositions and polynuclear complexes are described in the first aspect of this disclosure.

[0152] In one embodiment, the system is a semiconductor processing apparatus. In another embodiment, the reaction chamber includes a substrate. The first source may include a precursor container according to an embodiment of a first aspect of the invention.

[0153] The precursor container may have an inlet fluidly connected to a carrier gas source. The carrier gas may be an inert gas, such as N2, He, or Ar. The carrier gas can sweep the vapor of Group 13 halides, along with the metal halide compounds, into the reaction chamber through the precursor container outlet.

[0154] The system may include a heater operable by a controller for maintaining the gaseous composition at or above the volatilization temperature of the Group 13 halide throughout the deposition system, and at a temperature such that the polynuclear complex containing the Group 13 halide coordinated with the metal halide compound is in the gas phase, to prevent unwanted condensation in valves, filters, conduits, and other components associated with delivering the gaseous composition to the reaction chamber. In addition to the heater for heating the precursor container, as described elsewhere in this specification, additional heaters may be provided for heating various valves and gas flow lines between the precursor container and the reaction chamber to prevent condensation and deposition of the gaseous composition on these components. A gas delivery component may be provided between the precursor container and the reaction chamber, wherein the temperature is maintained above the volatilization temperature of the Group 13 compound halide (i.e., the “hot zone”).

[0155] In some embodiments, the system further includes a second source, such as a co-reactant container, coupled to the reaction chamber via a second valve. The second source can be used to provide gaseous co-reactants. The second source can include any source suitable for providing co-reactants, such as a co-reactant container, a compressed gas cylinder (in which the co-reactants can be contained as pressurized gas), or a co-reactant generator (e.g., an ozone generator). In these embodiments, the system may also include a controller operatively connected to the second valve, wherein the controller is configured and programmed to open the second valve to provide co-reactant flow into the reaction chamber and to close the second valve to stop co-reactant flow into the reaction chamber.

[0156] In some embodiments, the system further includes means for purging the reaction chamber, such as means for purging the reaction chamber with an inert gas or means for vacuum pumping the reaction chamber. The system may also include a controller for activating the purging means to purge the reaction chamber. The controller may be configured and programmed to purge the reaction chamber after the first valve is closed and before the second valve is opened, and / or after the second valve is closed and before the first valve is opened.

[0157] Any feature of any embodiment of the third aspect may be independently described as in any embodiment of any other aspect of the invention.

[0158] In a fourth aspect, the present invention relates to a composition configured for depositing a thin film by chemical vapor deposition, preferably by atomic layer deposition, the composition comprising:

[0159] a. Chemical precursors containing metal halide compounds, and

[0160] b. A carrier for transporting the chemical precursor in the gas phase, the carrier comprising a group 13 halide and having a volatilization temperature below that of the metal halide compound at pressures in the range of 10 to 1000 Pa.

[0161] The composition is described in the first aspect of this disclosure. The composition is generally stable enough to allow storage and use over extended periods (e.g., several months). The composition is generally adapted to withstand deposition conditions that allow vapor transfer into the reaction chamber. Additionally, the evaporation rate of the composition under predetermined conditions preferably remains constant. Some compositions may be subject to evaporation of more than one substance (e.g., impurities in chemical precursors and / or carriers). If the substances have different volatility, the composition may become enriched with the less volatile substance over time. This can lead to a phenomenon known as process drift: one or more of the deposition process parameters gradually change over time as the chemical composition of the composition changes. The consequences of process drift can be detrimental in sensitive applications, and adjusting the process to compensate for drift can be costly, difficult, or even impossible.

[0162] In the embodiments, the purity of the composition, such as the purity of the combined metal halide compound and the Group 13 halide, is at least 95 mol-, preferably at least 99 mol-, more preferably at least 99.9 mol-, even more preferably at least 99.99 mol-, even more preferably at least 99.999 mol-, and even more preferably at least 99.9999 mol-. Such high purity is generally strongly preferred for chemical vapor deposition, especially for atomic layer deposition.

[0163] Any feature of any embodiment of the fourth aspect may be independently described as in any embodiment of any other aspect of the invention.

[0164] In a fifth aspect, the present invention relates to a precursor container, comprising:

[0165] The shell, which defines the internal volume of the precursor container.

[0166] An inlet conduit or inlet, disposed within the housing and in fluid communication with the internal volume of the precursor container, the inlet conduit including at least one valve positioned thereon.

[0167] An outlet conduit or outlet, disposed within the housing and in fluid communication with the internal volume of the precursor container, the outlet conduit including at least one valve positioned thereon, and

[0168] Metal halide compounds, which accumulate within the internal volume of a precursor container, wherein the metal halide compounds include:

[0169] (i) Metals selected from the following: cobalt, ruthenium, manganese, nickel, Group 3 metals, and lanthanides; and

[0170] (ii) One or more halogen atoms.

[0171] In an embodiment, the precursor container is configured to receive a vapor stream of the carrier agent into its internal volume and to supply vapor streams of the metal halide compound and the carrier agent from its internal volume.

[0172] In the embodiments, the metal halide compound is an inorganic compound. In the embodiments, the metal halide compound is an inorganic metal halide compound.

[0173] In the embodiments, the metal halide compound has a vapor pressure of less than about 1 Torr or less than about 0.5 Torr at temperatures ranging from 25°C to 200°C.

[0174] In an embodiment, the precursor container further includes a carrier agent comprising a Group 13 halide, which has a volatilization temperature below the volatilization temperature of the metal halide compound under pressure within the precursor container.

[0175] In one embodiment, the precursor container also includes at least one filter coupled to the outlet conduit.

[0176] In an embodiment, at least one valve located on the outlet conduit and at least one valve located on the inlet conduit are rated for temperatures of at least about 100°C, or at least about 150°C, or at least about 200°C.

[0177] In embodiments, the precursor container further includes precursor distribution means for achieving efficient precursor evaporation, such as a precursor holding structure or carrier gas guiding device within the internal volume of the precursor container. The carrier gas guiding device can be used to promote the flow of the carrier agent onto a surface or through a metal halide compound into the precursor container.

[0178] In the embodiments, the metal halide compound has a volatilization temperature of at least about 250°C, at least about 300°C, at least about 400°C, or even at least about 500°C.

[0179] In some embodiments, the purity of the metal halide compound is at least 95 mol-, preferably at least 99 mol-, more preferably at least 99.9 mol-, even more preferably at least 99.99 mol-, even more preferably at least 99.999 mol-, even more preferably at least 99.9999 mol-.

[0180] Any feature of any embodiment of the precursor container of the fifth aspect may be independently described as corresponding to any embodiment of the precursor container of the first aspect of the invention.

[0181] Any feature of any embodiment of the fifth aspect may be independently described as in any embodiment of any other aspect of the invention.

[0182] Example: Deposition of metal halide compounds

[0183] refer to Figure 1 , Figure 1 This is a schematic diagram of a system 7 for depositing material on a substrate 31 according to an embodiment of the present invention.

[0184] System 7 includes a reaction chamber 3. A substrate 31 is located in the reaction chamber 3, and its surface is exposed to the environment 32 within the reaction chamber 3.

[0185] System 7 includes a first source 1 connected to reaction chamber 3 via a first valve (not shown). The first source 1 is used to provide a gaseous composition according to an embodiment of the invention. In this example, the first source 1 includes a carrier container 11 comprising a carrier comprising a group 13 halide; and a precursor container 12 comprising a chemical precursor comprising a metal halide compound. In this example, the outlet of the carrier container 11 is fluidly connected to the inlet of the precursor container 12. The outlet of the precursor container 12 is connected to reaction chamber 3 via the first valve.

[0186] System 7 includes a controller 4 configured to control the temperature and / or pressure of the carrier container 11 for evaporating the Group 13 halides in the carrier container 11. For example, the interior of the carrier container 11, in which the Group 13 halides are stored, can be heated to a temperature above the volatilization temperature of the Group 13 halides under the pressure inside.

[0187] In this embodiment, a carrier gas 10, such as N2, He, or Ar, is introduced into the carrier agent container 11 through the inlet to induce the carrier agent containing the Group 13 halide in the gaseous phase to flow into the precursor container 12 through the outlet of the carrier agent container 11 and the inlet of the precursor container 12. The controller 4 can adjust the temperature and / or pressure of the precursor container 12 so that the Group 13 halide remains in the gaseous phase in the precursor container 12.

[0188] Instead of using carrier gas 10 to induce the flow, or in addition, the flow can be induced by pressure differential, wherein the reaction chamber 32 (where the first valve is open) is at a lower pressure than the first source 1, thereby inducing the carrier agent in the carrier agent container 11 to flow to the precursor container 12 (and subsequently to the reaction chamber 32).

[0189] Under the pressure within precursor container 12, the volatilization temperature of the metal halide compound is higher than the temperature within precursor container 12, causing the metal halide compound to exist in a condensed state within precursor container 12. Group 13 halides can coordinate with the metal halide compound within precursor container 12, so that the metal halide compound coordinated with the gaseous Group 13 halides also enters the gas phase. Therefore, a gaseous composition comprising Group 13 halides and metal halide compounds is obtained.

[0190] When the first valve connecting the first source 1 to the reaction chamber 3 is opened via the controller 4, the carrier gas 10 can induce the gaseous composition to flow from the precursor container 12 through the outlet of the precursor container 12 and through the first valve (not shown) into the reaction chamber 3.

[0191] Therefore, the gas-phase composition has a flow path from the first source 1, more particularly from the precursor container 12 of the first source 1, via a conduit connecting the outlet of the precursor container 12 to the inlet of the reaction chamber 3, and via a first valve into the reaction chamber 3, more particularly reaching the substrate 31. In this embodiment, the temperature along the substantially intact flow path is too low for the metal halide compound to be kept in the gas phase, i.e., below the volatilization temperature of the metal halide compound (depending on pressure). However, the temperature along the substantially intact flow path is high enough to keep the Group 13 halide in the gas phase, i.e., above the volatilization temperature of the Group 13 halide (depending on pressure). Furthermore, the temperature along the substantially intact flow path is high enough to keep the polynuclear complex containing the Group 13 halide coordinated with the metal halide in the gas phase.

[0192] refer to Figure 2 Therefore, Group 13 halides can effectively transport metal halide compounds from precursor container 12 to substrate 31 in reaction chamber 32 to form a thin film of metal comprising at least the metal halide compound on substrate 31.

[0193] In this example, the substrate temperature of substrate 31 is adjusted by controller 4 such that the polynuclear complex is deposited as a whole on a portion of the exposed surface of substrate 31 via chemisorption. After the deposition, the first valve can be closed by controller 4. The deposition results in the formation of a thin film 61 on the portion of the exposed surface of substrate 31 containing the chemisorbed polynuclear complex.

[0194] However, as described elsewhere in the specification, the invention is not limited thereto. Instead, firstly, the polynuclear complex can condense and then chemically react with the surface, or selective chemisorption of metal halide compounds on the surface can occur.

[0195] In this example, the carrier is only present to transport the metal halide compound to the substrate 31, but should not bind to the material to be formed on the substrate 31. Therefore, in this embodiment, the chemisorbed Group 13 halides are selectively released from the thin film 61.

[0196] refer to Figure 3 For the selective release, the Group 13 halides in reaction chamber 3 can be purged (e.g., by vacuum pumping via outlet 5 of reaction chamber 3). The substrate 31 can be heated to the temperature at which the bonds of the chemisorbed Group 13 halides with the substrate 31 and with the metal halide compounds break by a heater controlled by controller 4. This may result in the selective release of the chemisorbed Group 13 halides from the film 61 (in... Figure 3 (Schematic representation of Group 13 halide vapor 110). The released Group 13 halide can be removed, for example, by the purging.

[0197] refer to Figure 4 As a result, a thin film 62 containing chemisorbed metal halide compounds can be formed, with virtually no chemisorbed Group 13 halides.

[0198] Also refer to Figure 1 Subsequently, a second valve (not shown) can be opened by controller 4, allowing the co-reactant to be supplied from the co-reactant container 21 included in the second source 2 to the reaction chamber 3, the second source 2 being connected to the reaction chamber 3 via the second valve. The co-reactant can be, for example, an oxygen precursor, a nitrogen precursor, or a reducing agent. The co-reactant can react with a chemisorbed metal halide compound on the thin film 62 on the substrate 31. Subsequently, the second valve can be closed, and the co-reactant can be purged from the reaction chamber 3.

[0199] This can be followed by multiple cycles, including: opening the first valve to supply the gaseous composition to the reaction chamber 3; closing the first valve; purging; opening the second valve to supply the co-reactant to the reaction chamber; closing the second valve; and purging. The cycle can be terminated once a material with preferred dimensions and composition has been formed on the substrate 31.

[0200] Although this example provides a single controller 4 for performing different functions (including controlling the valve, the temperature of the substrate 31, the temperature of the carrier container 11, the temperature of the precursor container 12, and the pressure within the reaction chamber 3), those skilled in the art will recognize that different functions can be performed by different controllers, or some functions can be performed by the first controller while others can be performed by the second controller.

[0201] Example: Precursor container with multiple chambers

[0202] Although in the above example, the first source includes a carrier container for providing Group 13 halides and a precursor container for providing metal halide compounds, the present invention is not limited to this particular configuration.

[0203] refer to Figure 5 This is a schematic diagram of another example of a precursor container 8 according to an embodiment of the present invention. The internal volume of the precursor container 8 in this example includes a first chamber 81 separated from a second chamber 82 by a wall 80. The wall 80 includes a channel 83, which may include a valve (not shown). During storage, the valve can be closed so that the Group 13 halide in the first chamber 81 can be separated from the metal halide compound in the second chamber 82.

[0204] When the current container 8 is used in a chemical deposition method and a metal halide compound is to be provided in the reaction chamber for deposition, the valve separating the first chamber 81 from the second chamber 82 can be opened. The first chamber 81 can be heated so that the Group 13 halide is in the gas phase, and a carrier gas 10 can be introduced into the first chamber 81 through the inlet to induce the Group 13 halide to flow into the second chamber 82 through the channel 83. The second chamber 82 can also be heated to keep the Group 13 halide in the gas phase. The Group 13 halide can also combine with the metal halide compound to allow the metal halide compound to enter the gas phase. Subsequently, a gas-phase composition containing the metal halide compound bonded to the Group 13 halide can be induced to flow through the outlet of the second chamber 82 into the reaction chamber.

[0205] Although this example relates to a precursor container 8 comprising two chambers, the invention is not limited thereto, and the precursor container 8 may comprise multiple chambers interconnected by valves. Alternatively, the metal halide compound and the Group 13 halide may be supplied together and / or stored in a single chamber of the precursor container 8.

[0206] It should be understood that although preferred embodiments, specific constructions and configurations, and materials have been discussed herein with respect to the apparatus according to the invention, various changes or modifications in form and detail may be made without departing from the scope of the invention. Functions may be added or removed from the block diagrams, and operations may be interchanged between functional blocks. Steps may be added or removed from the methods described within the scope of the invention.

Claims

1. A precursor container, comprising: Chemical precursors containing metal halide compounds, and A carrier agent for gas-phase delivery of the chemical precursor, comprising a Group 13 halide, wherein the Group 13 halide has a lower volatilization temperature than the metal halide compound under pressure within the precursor container. The precursor container is configured to supply vapors, including chemical precursors and carrier agents, to the reaction chamber of the chemical vapor deposition system.

2. The precursor container according to claim 1, wherein, The metal halide compound has a volatilization temperature of at least 250°C, at least 300°C, at least 400°C, or at least 500°C under the pressure.

3. The precursor container according to claim 1, wherein, Under the stated pressure, the volatilization temperature of the group 13 halides is at least 20°C lower than that of the metal halide compounds.

4. The precursor container according to claim 1, wherein, The metal halide compound is a metal halide, a metal nitride halide, or a metal oxyhalide.

5. The precursor container according to claim 4, wherein, The metal halide compounds include metals selected from the following: transition metals, lanthanides, and combinations thereof.

6. The precursor container according to claim 4, wherein, The metal halide compound includes one or more halogen atoms selected from the following: fluorine, chlorine, bromine, iodine, and combinations thereof.

7. The precursor container according to claim 6, wherein, Each of one or more halogen atoms in the metal halide compound is chlorine.

8. The precursor container according to claim 1, comprising the metal halide compound in a polymeric, amorphous, crystalline, or liquid state.

9. The precursor container according to claim 8, comprising the metal halide compound in a polymerized or crystalline state.

10. The precursor container according to claim 1, wherein, The Group 13 elements of the Group 13 halides are selected from boron, aluminum, gallium, and combinations thereof.

11. The precursor container according to claim 10, wherein, The Group 13 element of the Group 13 halides is aluminum.

12. The precursor container according to claim 1, wherein, The group 13 halides include one or more halogen atoms selected from the following: fluorine, chlorine, bromine, iodine, and combinations thereof.

13. The precursor container according to claim 12, wherein, Each of one or more halogen atoms in the group 13 halides is chlorine.

14. The precursor container according to claim 1, wherein, The halogen atoms of the group 13 halides are of the same type as the halogen atoms of the metal halide compounds.

15. The precursor container according to claim 1, wherein, The metal halide compound and the group 13 halide form a polynuclear complex.

16. A method for chemically vapor-depositing a metal-containing material on a substrate, the method comprising: A substrate is provided in the reaction chamber, and then, A gas-phase composition comprising a polynuclear complex is provided from a first source into the reaction chamber. The polynuclear complex comprises: A chemical precursor comprising a halide compound of the metal, the metal halide compound having a volatilization temperature higher than the temperature at a location along the flow path of the composition from the first source to the reaction chamber under pressure, and coordinated with the following... A carrier agent for gas-phase delivery of the metal halide compound, the carrier agent comprising a Group 13 halide having a volatilization temperature below the stated temperature at the stated pressure. This allows a thin film containing metal to be formed on a portion of the substrate surface.

17. The method according to claim 16, wherein, The formed thin film contains chemisorbed polynuclear complexes, wherein the method further includes the following steps: Inducing the selective release of the group 13 halides from the membrane.

18. The method according to claim 16, wherein, The location essentially encompasses the entire flow path of the composition.

19. A system for chemical vapor deposition of a material comprising a metal, the system comprising: Reaction chamber for receiving substrate A first source, connected to the reaction chamber via a first valve, is used to provide a gas-phase composition comprising a polynuclear complex, the polynuclear complex comprising: A chemical precursor comprising a halide compound of the said metal, coordinated with the following, A carrier agent for gas-phase delivery of the chemical precursor, the carrier agent comprising a group 13 halide, and A controller, operably connected to a first valve, wherein the controller is configured and programmed to open the first valve to provide a flow of composition into the reaction chamber, and to close the first valve to stop the flow of composition into the reaction chamber. The system is configured to provide temperature and pressure at a location along the flow path of the composition from the first source to the reaction chamber when the first valve is opened, wherein the volatilization temperature of the metal halide compound is higher than the temperature at the pressure, and the volatilization temperature of the group 13 halide is lower than the temperature at the pressure.

20. A composition configured for depositing a thin film by chemical vapor deposition, preferably by atomic layer deposition, the composition comprising: Chemical precursors containing metal halide compounds, and The carrier agent used for gas-phase delivery of the chemical precursor comprises a Group 13 halide and has a volatilization temperature below that of the metal halide compound at pressures ranging from 10 to 1000 Pa.

21. A precursor container, comprising: The shell, which defines the internal volume of the precursor container. An inlet conduit, disposed within the housing and in fluid communication with the internal volume of the precursor container, includes at least one valve positioned thereon. An outlet conduit, disposed within the housing and in fluid communication with the internal volume of the precursor container, includes at least one valve positioned thereon. Metal halide compounds, which accumulate within the internal volume of a precursor container, wherein the metal halide compounds include: (i) Metals selected from the following: cobalt, ruthenium, manganese, nickel, Group 3 metals, and lanthanides; and (ii) One or more halogen atoms.

22. The precursor container according to claim 21, wherein, The precursor container also includes a carrier agent comprising a group 13 halide, which, under pressure within the precursor container, has a volatilization temperature lower than that of the metal halide compound.

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