TW201708235A - Diisopropylaminopentachlorodisilane - Google Patents

Abstract

Disclosed is a Silicon Precursor Compound for deposition, the Silicon Precursor Compound comprising diisopropylamino-pentachlorodisilane, which is of formula (A): [(CH3)2CH]2NSiCl2SiCl3 (A); a composition for film forming, the composition comprising the Silicon Precursor Compound and at least one of an inert gas, molecular hydrogen, a carbon precursor, nitrogen precursor, and oxygen precursor; a method of forming a silicon-containing film on a substrate using the Silicon Precursor Compound, and the silicon-containing film formed thereby.

Description

Diisopropylaminopentachlorodioxane

The present invention generally relates to a precursor compound and a composition for forming a film, to a method for forming a film by the deposition device using the precursor compound or composition, and to a film formed by the method.

Elemental cerium, and other cerium materials such as cerium oxide, cerium carbide, cerium nitride, cerium carbonitride, and cerium oxycarbonitride have various known uses. For example, in the fabrication of electronic circuits for electronic or photovoltaic components, germanium films can be used as semiconductors, insulating layers or sacrificial layers.

It is known that a method of preparing a ruthenium material can use one or more ruthenium precursors. The use of these germanium precursors is not limited to the fabrication of germanium for electronic or photovoltaic semiconductor applications. For example, ruthenium precursors can be used to prepare ruthenium based lubricants, elastomers, and resins.

We have seen a long-standing need for improved niobium precursors in the electronics and photovoltaic industries. We believe that improved precursors will achieve lower deposition temperatures and/or finer semiconductor features for better performance electronic and photovoltaic components.

[Summary of the Invention]

We have discovered an improved ruthenium precursor. The present invention provides the following various examples: a precursor compound for depositing, the precursor compound comprising diisopropylamino-pentachlorodioxane having the formula (A): [(CH ₃ ) ₂ CH] ₂ NSiCl ₂ SiCl ₃ (A) (hereinafter referred to as "ruthenium precursor compound").

A composition for forming a film, the composition comprising the ruthenium precursor compound, and at least one of the following: an inert gas, a molecular hydrogen, a carbon precursor, a nitrogen precursor, and an oxygen precursor.

A method of forming a ruthenium-containing film on a substrate, the method comprising subjecting a vapor of a ruthenium precursor comprising the ruthenium precursor compound to a deposition condition in the presence of a substrate to form a ruthenium-containing film on the substrate.

A film formed according to the method.

[Detailed Description of the Invention]

The Summary and Abstract are hereby incorporated by reference. The embodiments, uses, and advantages of the invention outlined above are further described below.

Aspects of the invention are described herein using various common conventions. For example, all material conditions are measured at 25 ° C and 101.3 kPa unless otherwise indicated. All % are by weight unless otherwise stated or indicated. All % values are based on the total amount of all ingredients used to synthesize or manufacture the composition, and all ingredients used to synthesize or manufacture the composition add up to 100%, unless otherwise indicated. Any group of Makusi containing a genus and its subordinates includes a subgenus of the genus, for example, in "R is hydrocarbyl or alkenyl", R may be alkenyl, or R may be A hydrocarbyl group, which includes an alkenyl group in addition to other subordinates. For U.S. patent practice, all U.S. patent applications and patents cited herein are hereby incorporated by reference. A part or a part thereof, if only the referenced part, is not incorporated herein by reference to the present disclosure, and any such singularity is subject to the present embodiment.

Aspects of the invention are described herein using various patent terms. For example, "alternatively" indicates a different and distinct embodiment. "Comparative example" means a non-inventive experiment. "comprise" and its variants (comprising/comprised of) are open-ended. "Consist of" and its constraining of are closed. "Contacting" means making physical contact. "may" represents selectivity, not necessity. "optionally" means that there may or may not exist.

Aspects of the invention are described herein using a variety of chemical terms. The meaning of these terms corresponds to their definition by IUPAC unless otherwise defined herein. For the sake of convenience, certain chemical terms are defined.

The term "deposition" is a process of producing a condensed matter at a specific location. Condensed materials may be limited or unrestricted in size. Examples of deposition are film formation, rod formation, and deposition of formed particles.

The term "film" means a material that is restricted in one dimension. The constrained dimension can be characterized as "thickness" and is the dimension that increases with the length of time that the process of depositing the material to form the film increases, under all other conditions.

The term "halogen" means fluoro, chloro, bromo or iodo unless otherwise defined.

The term "IUPAC" refers to the International Federation of Pure and Applied Chemistry.

The term "lack" means not containing or not at all.

"Periodic Table of the Elements" means IUPAC The version released in 2011.

The term "precursor" means a substance or molecule which contains an atom of the indicated element and which can be used as a source of the element in a film formed by a deposition method.

The term "seperate" means to cause physical separation and therefore no longer be in direct contact.

The term "substrate" means a physical support having at least one surface on which another material may be disposed.

The present invention provides a ruthenium precursor compound and a composition for forming a film. The ruthenium precursor compound is particularly suitable for use in the formation of a ruthenium-containing deposition process, but the ruthenium precursor compound is not limited to such applications. For example, ruthenium precursor compounds can be utilized in other applications, such as as reactants for the preparation of oxoxane or decazane materials. The invention further provides a method of forming a film, and a film formed according to the method.

The chemical name of the ruthenium precursor compound is diisopropylamino-pentachlorodioxane having the formula (A): [(CH ₃ ) ₂ CH] ₂ NSiCl ₂ SiCl ₃ (A). When a ruthenium precursor compound is used in the compositions and methods of the present invention, the ruthenium precursor compound may have a purity from 99 area% (GC) to 99.9999999 area% (GC).

The ruthenium precursor compound can be provided in any manner. For example, a ruthenium precursor compound can be synthesized or otherwise obtained for use in the process. In one embodiment, the ruthenium precursor compound is synthesized by the following formal process: HN(i-Pr) ₂ +SiCl ₃ SiCl ₃ ->[(CH ₃ ) ₂ CH] ₂ NSiCl ₂ SiCl ₃ + "HCl", Wherein i-Pr is isopropyl and "HCl" means a by-product of the reaction which is typically reacted with an acid scavenger (as described below) to produce a salt. An example of a formal process is: 2 HN(i-Pr) ₂ +SiCl ₃ SiCl ₃ ->[(CH ₃ ) ₂ CH] ₂ NSiCl ₂ SiCl ₃ +H ₂ N(i-Pr) ₂ Cl. The H ₃ N(i-Pr) ₂ Cl salt can be precipitated in the reaction and can be separated from the reaction, such as by filtration or decantation. Process may be included in the hydrocarbon vehicle in the hexachlorodisilane Silane (SiCl ₃ SiCl ₃₎ in contact with the source diisopropylamide, to give a silicon precursor compounds; wherein the source of relatively diisopropylamide The metal diisopropyl aminate [(i-Pr) ₂ N] _m M ^A in the hexachlorodioxane is 0.50 to 1.19 mol equivalent, wherein the subscript m is 1 or 2, wherein when m is 1, M ^A is a group I element of the periodic table, and when m is 2, M ^A is a group II element of the periodic table, or the source of the diisopropylamino group is 1.0 to 2.39 molar equivalent of diisopropyl. The amine, or the source of the diisopropylamino group, is from 0.50 to 1.19 mole equivalents of diisopropylamine ((i-Pr) ₂ NH) and from 0.50 to 1.19 mole equivalents of a pyridine compound or a trialkylamine ( A mixture of alkyl ₃ N) wherein each alkyl group is independently (C ₂ -C ₁₀ )alkyl. Examples of pyridine compounds are pyridine and 2,6-lutidine.

The process for synthesizing the ruthenium precursor compound can be carried out in a hydrocarbon vehicle or an ether vehicle. The ether vehicle may comprise a dimethyl ether, a dialkyl ether, or an alkylene glycol dialkyl ether, or a mixture of two or more thereof. The dihydrocarbyl ether may be a linear ether, a cyclic ether, or a diaryl ether, or a mixture of two or more thereof. Examples of ether vehicles are diethyl ether, dimethyl ether, tetrahydrofuran, 1,2-dimethoxyethane, tetraethylene glycol dimethyl ether. The alkanediol dialkyl ether may be a butanediol di(C ₁ -C ₄ )alkyl ether, a propylene glycol di(C ₂ -C ₄ )alkyl ether, an ethylene glycol di(C ₃ or C ₄ ) alkane. a mixture of ethers, or any two or more thereof. The hydrocarbon vehicle may comprise an alkane having at least 5 carbon atoms, a cycloalkane having at least 5 carbon atoms, an aromatic hydrocarbon having at least 6 carbon atoms, or a mixture of any two or more thereof. The hydrocarbon vehicle may comprise pentane, hexane, hexane, cyclohexane, heptane, benzene, toluene, xylene, or a mixture of any two or more thereof.

The composition of the hydrocarbon vehicle can be envisaged to optimize the contacting step (e.g., selecting a hydrocarbon vehicle having a boiling point for achieving the desired reaction temperature or a hydrocarbon lacking the ability to dissolve reaction by-products) Vehicle). Additionally or alternatively, the composition of the hydrocarbon vehicle can be envisaged to optimize an optional separation step (eg, selecting a hydrocarbon vehicle having the desired boiling point such that it can be achieved without evaporating the ruthenium precursor compound) It evaporates). The hydrocarbon vehicle may be composed of carbon and hydrogen atoms or may be a halogenated hydrocarbon vehicle composed of carbon, hydrogen and halogen atoms. The hydrocarbon vehicle composed of C and H atoms may be an alkane, an aromatic hydrocarbon, and a mixture of two or more thereof. The alkane can be hexane, cyclohexane, heptane, isoalkane, or a mixture of two or more thereof. The aromatic hydrocarbon can be toluene, xylene, or a mixture of two or more thereof. The halogenated hydrocarbon vehicle can be dichloromethane. Processes having different hydrocarbon vehicle compositions can differ from each other in at least one of the results, properties, functions, and/or uses. The different compositions of the hydrocarbon vehicle can provide different solubility for the ruthenium precursor compound, the source of the diisopropylamine group, the reaction by-product, or a combination of any two or more thereof.

As described above, the composition for forming a film comprises a ruthenium precursor compound, and at least one of the following: an inert gas, a molecular hydrogen, a carbon precursor, a nitrogen precursor, and an oxygen precursor; or an inert gas, a nitrogen precursor And oxygen precursors. Molecular hydrogen can be used in the composition together with the ruthenium precursor compound for forming an elemental ruthenium film including an amorphous ruthenium film, a polycrystalline ruthenium film, and a single crystal film. As used herein, the vapor or gas state of a molecular hydrogen, carbon precursor, nitrogen precursor, or oxygen precursor is often referred to as an additional reactant gas.

A carbon precursor can be used in the composition with a ruthenium precursor compound for forming a ruthenium carbon film in accordance with an embodiment of the method. The tantalum carbon film contains Si and C atoms and may contain niobium carbide. The carbon precursor may comprise, instead consist essentially of, consisting of, but alternatively consisting of: C, H, and optionally Si atoms. When a carbon precursor comprising C, H, and optionally Si atoms is used in a method for forming a hafnium carbonitride film or a niobium oxycarbide film, the carbon precursor may further comprise N or O atoms, respectively. Or when the carbon precursor is used to form a yttrium oxycarbonitride film When used in the method, the carbon precursor may further comprise N and O atoms. A carbon precursor consisting essentially of C, H, and optionally Si atoms lacks N and O atoms, but may alternatively have one or more halogen atoms (e.g., Cl). Examples of carbon precursors composed of C and H atoms are hydrocarbons such as alkanes. Examples of carbon precursors composed of C, H, and Si atoms are hydrocarbyl decanes such as butyl dioxane or tetramethyl decane.

A nitrogen precursor can be used in the composition with the ruthenium precursor compound for forming a ruthenium nitride film in accordance with an embodiment of the method. The niobium nitride film contains Si and N atoms and optionally C and/or O atoms, and may include tantalum nitride, hafnium oxynitride, or hafnium oxycarbonitride. The nitrogen precursor is different from the ruthenium precursor compound. The niobium nitride film contains Si and N atoms and optionally C and/or O atoms, and may include tantalum nitride, hafnium oxynitride, or hafnium oxycarbonitride. The tantalum nitride may be Si _x N _y , wherein the subscript x is 1, 2, or 3, and the subscript y is an integer from 1 to 5. The nitrogen precursor may comprise an N atom and optionally a H atom; alternatively, the nitrogen precursor may consist essentially of an N atom and optionally a H atom; alternatively, the nitrogen precursor may consist of N and optionally H atoms. When a nitrogen precursor comprising N and optionally a H atom is used in a method for forming a hafnium carbonitride film or a hafnium oxynitride film, the nitrogen precursor may further comprise a C or O atom, respectively, or When the nitrogen precursor is used in a method for forming a hafnium carbonitride film, the nitrogen precursor may further comprise C and O atoms. A nitrogen precursor consisting essentially of N atoms and optionally H atoms lacks C and O atoms, but may alternatively have one or more halogen atoms (e.g., Cl). An example of a nitrogen precursor consisting of N atoms is molecular nitrogen. Examples of nitrogen precursors consisting of N and H atoms are ammonia and hydrazine. An example of a nitrogen precursor consisting of O and N atoms is nitric oxide (N ₂ O) and nitrogen dioxide (NO ₂ ).

An oxygen precursor can be used in the composition with the ruthenium precursor compound for forming a ruthenium oxide film in accordance with an embodiment of the method. The ruthenium oxide film contains Si and O atoms and optionally C and/or N atoms, and may include ruthenium oxide, ruthenium oxycarbide, ruthenium oxynitride, or bismuth oxycarbonitride. The cerium oxide may be SiO or SiO ₂ . The oxygen precursor may comprise an O atom and optionally a H atom; or it may consist essentially of an O atom and optionally a H atom; or it may consist of an O atom and optionally a H atom. When an oxygen precursor comprising an O atom and optionally an H atom is used in a method for forming a ruthenium oxycarbide film or a ruthenium oxynitride film, the oxygen precursor may further comprise a C or N atom, respectively, or When the oxygen precursor is used in a method for forming a hafnium carbonitride film, the oxygen precursor may further contain C and N atoms. Examples of oxygen precursors composed of O atoms are molecular oxygen and ozone. Ozone can be delivered in air at up to 5% v/v or in molecular oxygen up to 14% v/v. Examples of oxygen precursors composed of O and H atoms are water and hydrogen peroxide. An example of an oxygen precursor consisting of O and N atoms is nitric oxide and nitrogen dioxide.

The inert gas can be used in combination with any of the foregoing precursors and any of the embodiments of the compositions or methods. Examples of inert gases are helium, argon, and mixtures thereof. For example, ruthenium can be used in combination with a ruthenium precursor compound and molecular hydrogen or HCl in an embodiment of a method of forming a ruthenium-containing element ruthenium film formed therein. Alternatively, the ruthenium-containing film may be used together with any of the ruthenium precursor compound and the carbon precursor, the nitrogen precursor, and the oxygen precursor to form a ruthenium film, a ruthenium nitride film, or a ruthenium oxide. In an embodiment of the method of film.

The film formed by the method contains a material that is Si and is limited in one dimension, and the dimension may be referred to as the thickness of the material. The ruthenium-containing film may be an elemental ruthenium film, a ruthenium carbon film, a ruthenium nitride film, or an osmium oxide film (for example, a tantalum nitride, a carbonitride, a oxynitride, or a oxynitride film), or a niobium nitride. Membrane, or silicon oxide film (such as tantalum nitride, tantalum oxide). The elemental ruthenium film formed by the method lacks C, N, and O atoms, and may be an amorphous or crystalline Si material. The tantalum carbon film formed by the method contains Si and C atoms and optionally N and/or O atoms. Niobium nitride film formed by the method Contains Si and N atoms and optionally C and/or O atoms. The silicon oxide film formed by the method contains Si and O atoms and optionally C and/or N atoms.

The film can be used in electronic or photovoltaic applications. For example, the tantalum nitride film can form a dielectric layer as an insulating layer, a passivation layer, or a polysilicon layer in a capacitor.

The method of forming a film uses a deposition apparatus. The deposition apparatus utilized in the present method is generally selected based on the desired method of forming the film, and may be any deposition apparatus known to those skilled in the art.

In certain embodiments, the deposition apparatus comprises a physical vapor deposition apparatus. In these embodiments, the deposition apparatus is generally selected from the group consisting of a sputtering apparatus, an atomic layer deposition apparatus (including a plasma enhancement and thermal atomic layer deposition apparatus), and a direct current (DC) magnetron sputtering apparatus; alternatively, the deposition apparatus It is an atomic layer deposition device. The optimum operating parameters for each of these physical vapor deposition devices are based on the desired application of the ruthenium precursor compound utilized in the process and the film formed by the deposition apparatus. In certain embodiments, the deposition apparatus includes a sputtering apparatus. The sputtering device can be, for example, an ion beam sputtering device, a reactive sputtering device, or an ion assisted sputtering device.

More generally, however, the deposition apparatus comprises an atomic layer deposition apparatus or a chemical vapor deposition apparatus. In an embodiment using an atomic layer deposition apparatus, a method of forming a film may be referred to as an atomic layer deposition method, and includes plasma enhanced atomic layer deposition (PEALD), space atomic layer deposition (SALD), and thermal atomic layer deposition. Law (TALD). Also, in the embodiment using the chemical vapor deposition apparatus, the method of forming a film may be referred to as a chemical vapor deposition method. Apparatus and methods for atomic layer deposition and chemical vapor deposition are generally well known in the art. The method is exemplified hereinafter by reference to the use of a chemical vapor deposition apparatus, however the method can be easily adapted to use an atomic layer apparatus.

In an embodiment of the method of using a chemical vapor deposition apparatus, the chemical vapor deposition apparatus may be selected from, for example, a flowable chemical vapor phase apparatus, a thermal chemical vapor deposition apparatus, a plasma enhanced chemical vapor deposition apparatus, and a photochemical gas. A phase deposition device, an electron cyclotron resonance device, an inductively coupled plasma device, a magnetic confinement plasma device, a low pressure chemical vapor deposition device, and a jet vapor deposition device. The optimum operating parameters for each of these chemical vapor deposition apparatus are based on the desired application of the ruthenium precursor compound utilized in the process and the membrane formed by the deposition apparatus. In certain embodiments, the deposition apparatus comprises a plasma enhanced chemical vapor deposition apparatus. In other embodiments, the deposition apparatus comprises a low pressure chemical vapor deposition apparatus.

In chemical vapor deposition, the gas used to form the membrane is typically mixed and reacted in a deposition chamber. The reaction forms a suitable membrane element or molecule in a vapor state. Elements or molecules are then deposited on the substrate (or wafer) and accumulated to form a film. Chemical vapor deposition typically requires the addition of energy to the system, such as heating the deposition chamber and substrate.

The reaction of the gas species is generally well known in the art and any conventional chemical vapor deposition (CVD) technique can be practiced by the method of the present invention. For example, methods such as simple thermal vapor deposition, plasma enhanced chemical vapor deposition (PECVD), electron cyclotron resonance (ECRCVD), atmospheric pressure chemical vapor deposition (APCVD), low pressure chemical vapor deposition (LPCVD), and ultra can be used. High vacuum chemical vapor deposition (UHVCVD), aerosol assisted chemical vapor deposition (AACVD), direct liquid injection chemical vapor deposition (DLICVD), microwave plasma assisted chemical vapor deposition (MPCVD), remote plasma enhanced chemistry Vapor deposition (RPECVD), atomic layer chemical vapor deposition (ALCVD), hot wire chemical vapor deposition (HWCVD), mixed chemical vapor deposition (HPCVD), rapid thermal chemical vapor deposition (RTCVD), and gas phase Vapor phase chemical vapor deposition (VPECVD), photo-assisted chemical vapor deposition (photo-assisted chemical vapor) Displacement, PACVD), flame assisted chemical vapor deposition (FACVD), or any similar technique.

In the case of plasma enhanced atomic layer deposition, the plasma comprises a forming gas, a nitrogen plasma, or an ammonia plasma, or an oxygen plasma, in a nitrogen or argon gas as a carrier. The forming gas contains nitrogen and hydrogen. Those of ordinary skill in the art will understand the composition of the forming gas.

Chemical vapor deposition can be utilized to form films having a variety of thicknesses that will depend on the desired end use of the film. For example, the film can have a thickness of a few nanometers or a thickness of a few microns, or a greater or lesser thickness (or a thickness that falls between these values). These films may optionally be covered by a coating such as a SiO ₂ coating, a SiO ₂ /modified ceramic oxide layer, a ruthenium-containing coating, a ruthenium-containing carbon coating, a ruthenium carbide-containing coating, a ruthenium-nitrogen-containing coating, Contains a tantalum nitride coating, a niobium-nitrogen-containing carbon coating, a niobium-nitrogen-containing coating, and/or a diamond-like carbon coating. Such coatings and methods of depositing them are generally known in the art.

The substrate utilized in the method is not limited. In certain embodiments, the substrate is limited only by the temperature of the deposition chamber and the thermal and chemical stability requirements of the environment. Thus, the substrate can be, for example, glass, metal, plastic, ceramic, semiconductor, including but not limited to germanium (eg, single crystal germanium, polycrystalline germanium, amorphous germanium, etc.). The substrate can have a flat or patterned surface. The patterned surface has an aspect ratio feature of the following range: from 1 to 500, alternatively from 1 to 50, alternatively from 10 to 50. CVD or ALD films can conform to the surface of both planar or patterned substrates.

Embodiments of the method of the invention can include a reactive environment comprising nitric oxide (N ₂ O). Such reactive environments are generally known in the art. In these embodiments, the method generally involves decomposing the ruthenium precursor compound in the presence of nitric oxide. An example of such a method is described in U.S. Patent No. 5,310,583. The composition of the resulting film formed in the chemical vapor deposition method can be modified by using nitric oxide.

Chemical vapor deposition apparatus, and thus chemical vapor deposition methods, are typically selected by balancing a number of factors including, but not limited to, a ruthenium precursor compound, a desired membrane purity, a geometric configuration of the substrate, And economic considerations.

The main operational variables controlled in chemical vapor deposition and atomic layer deposition include, but are not limited to, reactor temperature, substrate temperature, pressure, gas phase concentration of the ruthenium precursor compound, any additional reactant gas concentration (eg, any carbon). The concentration of the precursor, nitrogen precursor, and/or oxygen precursor gas, total gas flow, and substrate. Chemical vapor deposition and atomic layer deposition are produced by chemical reactions including, but not limited to, pyrolysis, oxidation, reduction, hydrolysis, and combinations thereof. The optimum temperature for chemical vapor deposition and atomic layer deposition requires knowledge of the kinetics and thermodynamics of the ruthenium precursor compound and the selected chemical reaction.

Conventional chemical vapor deposition and atomic layer deposition methods typically require significant elevated temperatures, such as greater than 600 °C, such as from 600 °C to 1000 °C. However, the salty ruthenium precursor compound can be utilized in chemical vapor deposition and atomic layer deposition at significantly lower temperatures. For example, the method can be substituted from 100 ° C to 700 ° C, alternatively from 200 ° C to 700 ° C, alternatively from 200 ° C to 600 ° C, alternatively from 200 ° C to 500 ° C, alternatively from 200 ° C to 400 ° C, The ground is carried out at a temperature of from 100 ° C to 300 ° C. The temperature at which the method is practiced can be constant temperature or dynamic.

The chemical vapor and atomic layer deposition processes are typically carried out at pressures from 0.01 Torr to 100 Torr, alternatively from 0.01 Torr to 10 Torr, alternatively from 0.1 to 10 Torr, alternatively from 1 to 10 Torr.

Chemical vapor and atomic layer deposition processes typically involve the production of precursors, transport of precursors into the reaction chamber, and absorption of the precursor onto the heated substrate, or chemical reaction of the precursor and subsequent absorption onto the substrate. The following is a summary survey of chemical vapor deposition methods. Some of the many options available.

The chemical vapor and atomic layer deposition processes deposit films of the following thickness: from 0.01 nm to 1 micron, alternatively from 0.1 to 100 nm, alternatively from 1 to 100 nm.

In thermal CVD, the film is deposited by passing a vaporous form of a ruthenium precursor compound through a heated substrate. When the vapor form of the ruthenium precursor compound contacts the heated substrate, the ruthenium precursor compound typically reacts and/or decomposes to form a film.

In PECVD, the vapor form of the ruthenium precursor compound is reacted by a plasma domain to form a reactive species. The reactive species are then concentrated and deposited on the substrate to form a film. In general, the advantage of PECVD over thermal CVD is that lower substrate temperatures can be used. The plasma utilized in PECVD contains energy derived from various sources, such as electrical discharges, electromagnetic fields in the radio frequency or microwave range, lasers, or particle beams. In general, PECVD utilizes radio frequencies (10 kHz to 102 megahertz (MHz)) or microwave energy (0.1 to 10 thousand) at medium power density (0.1 to 5 watts per square centimeter (W/cm ² )). Megahertz (GHz), but any of these variables can be modified. However, specific frequencies, powers, and pressures are typically tailored to the deposition apparatus.

In AACVD, a ruthenium precursor compound is dissolved in a chemical medium to form a mixture. A mixture comprising a ruthenium precursor compound and a chemical medium is encapsulated in a conventional aerosol. The aerosol atomizes the ruthenium precursor compound and introduces it into a heated chamber in which the ruthenium precursor compound undergoes decomposition and/or chemical reactions. One advantage of AACVD is the ability to form a film without the need for a vacuum.

The selected deposition process and operating parameters will have an impact on the structure and properties of the film. Generally, the orientation of the membrane structure, the manner in which the membrane coalesces, the uniformity of the membrane, and the knot of the membrane are controlled. Crystalline/non-crystalline structures are possible.

It should be noted that an environment that promotes the desired deposition can also be used in the deposition chamber. For example, in this document, reactive or inert environments such as air, oxygen, oxygen plasma, ammonia, amines, hydrazine, etc. can be used.

Additionally, the present invention provides a film formed in accordance with the present method. The composition and structure of the membrane varies not only with the deposition apparatus and its parameters, but also with the ruthenium precursor compound utilized and the presence or absence of any reactive environment during the process. The ruthenium precursor compound can be utilized in combination with any other known precursor compound or can be utilized in the present method without any other precursor compound.

Since the ruthenium precursor compound contains a Si-N bond, the ruthenium precursor compound can be used to form a tantalum nitride film without using a nitrogen precursor, but a nitrogen precursor can also be used if necessary. That is, it may not be necessary to add a nitrogen precursor (eg, a second vapor) to form a tantalum nitride film. The deposition conditions can be optimized to control the method of the present invention to form an elemental Si film or a SiN film. If desired, a nitrogen precursor can be used in the second vapor to enrich the nitrogen content of the SiN film.

Alternatively, the ruthenium precursor compound can be used with other ruthenium-based precursor compounds that have traditionally been used to form ruthenium films comprising crystalline ruthenium or tantalum nitride. In such embodiments, the film can be, for example, crystalline or epitaxial. Depending on the presence of the reactive environment during the process, the membrane may further comprise oxygen and/or carbon in addition to helium and nitrogen.

The purity of the ruthenium precursor compound can be determined by ²⁹ Si-NMR, reverse phase liquid chromatography, or more preferably by gas chromatography (GC) as described later. For example, the purity measured by GC can range from 60 area% to 100 area% (GC), alternatively from 70 area% to 100 area% (GC), alternatively from 80 area% to 100 area% (GC), alternatively from 90 area% to 100 area% (GC), alternatively from 93 area% to 100 area% (GC), alternatively from 95 area% to 100 area% (GC), alternatively from 97 area% to 100 area% (GC), alternatively from 99.0 area% to 100 area% (GC). each 100 area% (GC) can be independently as previously defined.

The invention is further illustrated by the following non-limiting examples, and the embodiments of the invention may include any combination of the features and limitations of the following limiting examples. The ambient temperature is about 23 ° C unless otherwise indicated.

Gas Chromatography-Flame Ionization Detector (GC-FID) conditions: a capillary column with a length of 30 meters and an inner diameter of 0.32 mm, and a 0.25 μm thick fixed coating on the inner surface of the capillary column Phase wherein the stationary phase consists of phenylmethyl decane. The carrier gas is helium used at a flow rate of 105 mL per minute. The GC instrument was an Agilent Model 7890A Gas Chromatograph. The inlet temperature was 150 °C. The GC experimental temperature profile consisted of holding (maintaining) at 50 ° C for 2 minutes, raising the temperature to 250 ° C at a rate of 15 ° C / minute, and then holding (holding) at 250 ° C for 10 minutes.

GC-MS instruments and conditions: Samples were analyzed by electron impact ionization and chemical ionization gas chromatography-mass spectrometry (EI GC-MS and CI GC-MS). The Agilent 6890 GC conditions include a DB-1 column with a 30 meter (m) x 0.25 mm (mm) x 0.50 micron (μm) membrane configuration. The oven program was held at 50 ° C for 2 minutes, at 15 ° C / minute to 250 ° C, and then at 250 ° C for 10 minutes. The helium carrier gas flow rate was a constant flow rate of 70 mL/min and a 50:1 separation spray. MS Agilent 5973 MSD conditions include a scan range from 15 to 800 Daltons of, EI ionization, ionization and CI (using custom 5% NH ₃ and 95% CH ₄ mixed gas of CI).

²⁹ Si-NMR instrument and solvent: A Varian 400 MHz mercury spectrometer was used. C ₆ D _{6 was used} as a solvent.

¹ H-NMR instrument and solvent: A Varian 400 MHz mercury spectrometer was used. C ₆ D _{6 was used} as a solvent.

Example (Ex.) A: Synthesis of diisopropylamino-pentachlorodioxane using 2.21 molar equivalent of diisopropylamine: hexachlorodioxane (HCDS; 20.0 ml (mL), 0.116 mol) Anhydrous hexane (200 mL) was mixed in a 1 liter (L) round bottom flask. The mixture was cooled to -20 ° C with dry ice. A solution of diisopropylamine (DiPA; 35.8 mL, 0.256 mol) in hexanes (100 mL) was added at -20 ° C over 35 min with stirring with a mechanical stirrer. After the addition, the slurry was allowed to warm to 23 ° C and stirred (thick) overnight. Another 100 mL portion of hexane was added to dilute the slurry, and the diluted slurry was filtered through a D-type glass filled with 1 inch thick celite (CELITE). The resulting filter cake was rinsed with 100 mL of hexane. The clear filtrate (about 400 mL) was collected. The filtrate (<1 Torr) was distilled under vacuum to remove volatile organics. 28.43 g (73.5% yield) of crude diisopropylamino-pentachlorodioxane as a clear, slightly yellow liquid was recovered.

Example B: Synthesis of diisopropylamino-pentachlorodioxane using 1.10 molar equivalents of diisopropylamine and 1.10 mole equivalents of triethylamine: Procedure for replicating Example A, except that 35.8 mL of DiPA was used A solution of DiPA (17.9 mL, 0.128 mol) and triethylamine (17.8 mL, 0.128 mol) in hexane (100 mL) was used in hexane (100 mL). The amount of clear filtrate was about 450 mL. After removal of the volatile organics by distillation, 29.2 g (75.5% yield) of crude diisopropylamino-pentachlorodioxane as a clear, slightly yellow liquid was recovered.

Example C: Synthesis of diisopropylamino-pentachlorodioxane using 1.10 molar equivalent of lithium diisopropylamide: a solution of 10.0 M n-BuLi in hexane (92.0 mL; 0.920 mol) Anhydrous hexane (828 mL) was mixed in a 2 L round bottom flask. DiPA (129.0 mL, 0.920 mol) was added over 15 minutes with stirring under a magnetic stirrer up to 40 °C. Stir at 23 ° C The resulting lithium diisopropylamide solution was mixed for 1 hour. To another 2L round bottom flask was added HCDS (144.0 mL, 0.836 mol) and 93.1 mL hexane. The second flask was cooled with some dry ice at approximately 0 °C. The lithium diisopropylamide solution was fed under a constant feed rate with a feed rate through a 1⁄4 吋 (0.635 cm (cm)) inner diameter poly(tetrafluoroethylene) tube into the second flask. . A white precipitate formed immediately. The feed rate was controlled to keep the reaction temperature below 40 °C. This addition takes 1 hour and 15 minutes. After the addition, the slurry was stirred (thickened) overnight. The slurry was then filtered and the volatile organics removed (using a procedure similar to Example 1) to give 199.8 g (71.6% yield) of crude diisopropylamino-pentachlorodioxane as a clear yellow liquid.

Example D: Diisopropylamino-pentachlorodioxane was distilled from the crude diisopropylamino-pentachlorodioxane of Example A to give the purified diisopropylamino-pentachlorodioxane. Distillate.

Example E: Instrumentation and standard conditions for differential scanning calorimetry (DSC): A sample material of known weight is loaded into a 20 microliter (μL) high pressure DSC crucible, sealed with a press and loaded into a Mettler Toledo TGA/ The heating furnace of the DSC 1 instrument. The furnace was allowed to equilibrate at 35 ° C for 20 minutes and then warmed from 35 ° C to a specific temperature (for example 400 ° C) at a rate of 10 ° C per minute. When a specific temperature (for example, 400 ° C) is reached, the furnace is maintained at this temperature for 20 minutes, and then cooled to ambient temperature (23 ° C ± 1 ° C) at a cooling rate of 10 ° C per minute. The sample is then reheated to this temperature (e.g., 400 ° C) at a heating rate of 10 ° C per minute. Next, the crucible is removed from the furnace, allowed to cool, and the sample is reweighed to determine if the sample loses mass during the test method. This method was applied to diisopropylaminopentachlorodioxane to determine the thermal decomposition onset temperature of diisopropylaminopentachlorodioxane was 352 °C.

Example (Ex) 1 (forecast): use of ruthenium precursor compounds and atomic layer deposition (ALD) to form a tantalum nitride film: using a ALD reactor, and a bubbler containing a ruthenium precursor compound and in fluid communication with the ALD reactor, heating the bubbler containing the ruthenium precursor compound to 100 ° C to increase the ruthenium The vapor pressure of the precursor compound. The ALD reactor was purged with nitrogen, which contained a plurality of horizontally oriented and spaced tantalum wafers heated to 500 °C. The nitrogen is then passed through a bubbler to carry the vapor of the ruthenium precursor compound into the ALD reactor for 10 seconds. The ALD reactor was again purged with nitrogen to remove any residual ruthenium precursor compound vapor. Ammonia was then flowed into the ALD reactor for 10 seconds. The foregoing sequence of steps is repeated until a conformal tantalum nitride film having a desired thickness is formed on the wafer. One cycle equals ten seconds of precursor usage, followed by ten seconds of nitrogen purge, followed by ten seconds of ammonia usage, and then ten seconds of nitrogen purge.

Example 2 (hypothesis): Formation of a tantalum nitride film using a ruthenium precursor compound with ammonia (NH ₃ ) and LPCVD: heating using a LPCVD reactor, and a bubbler containing a ruthenium precursor compound in fluid communication with the LPCVD reactor A bubbler containing a ruthenium precursor compound is brought to 100 ° C to increase the vapor pressure of the ruthenium precursor compound. The nitrogen is then passed through a bubbler to carry the vapor of the ruthenium precursor compound into the LPCVD reactor, wherein the LPCVD reactor contains vaporous ammonia and a plurality of vertically oriented and spaced tantalum wafers heated to 500 ° C to A conformal tantalum nitride film is formed on the wafer.

Example 3 (hypothesis): A tantalum nitride film was formed using a ruthenium precursor compound with ammonia and PEALD, using a PEALD reactor, and a bubbler containing a ruthenium precursor compound in fluid communication with the PEALD reactor. The bubbler containing the ruthenium precursor compound was heated to 100 ° C to increase the vapor pressure of the ruthenium precursor compound. The PEALD reactor was purged with nitrogen. (The PEALD reactor contains a plurality of horizontally oriented and spaced tantalum wafers heated to 500 ° C.) The nitrogen carrier gas is then passed through a bubbler to carry the vapor of the rhodium precursor compound into the ALD reactor. Blowing again with nitrogen The ALD reactor was swept to remove any residual ruthenium precursor compound vapor. The ammonia is then passed to an ALD reactor where the plasma power is turned on. The ALD reactor is then purged with nitrogen again to remove any reactive species produced by the remaining plasma. The foregoing sequence of steps is repeated until a conformal tantalum nitride film having a desired thickness is formed on the wafer. A sequence of equal seconds of precursor charge, followed by a 30 second nitrogen purge followed by a fifteen second plasma treatment, followed by a 30 second nitrogen purge.

Example 4 (hypothesis): Formation of a tantalum nitride film using a ruthenium precursor compound with ammonia and PECVD: using a PECVD reactor, and a bubbler in fluid communication with the PECVD reactor, heating the bubbler containing the ruthenium precursor compound to 70 ° C to increase the vapor pressure of the ruthenium precursor compound. The He carrier is then passed through a bubbler to carry the vapor of the ruthenium precursor compound into the PECVD reactor, wherein the PECVD reactor has a plasma derived from ammonia and contains a plurality of horizontally oriented and spaced apart heated to 500 °C. Wafer wafers to form a conformal tantalum nitride film on the wafer.

Example 5 (hypothesis): A ruthenium oxide film was formed using a ruthenium precursor compound with ozone and ALD, wherein an ALD reactor, and a bubbler containing a ruthenium precursor compound and in fluid communication with the ALD reactor were used. The bubbler containing the ruthenium precursor compound was heated to 100 ° C to increase the vapor pressure of the ruthenium precursor compound. The ALD reactor was purged with argon containing a plurality of horizontally oriented and spaced tantalum wafers heated to 500 °C. An argon carrier gas stream is then passed through the bubbler to carry the vapor of the ruthenium precursor compound into the ALD reactor. The ALD reactor was again purged with argon to remove any residual ruthenium precursor compound vapor. Ozone (in oxygen) is then passed to the ALD reactor. The foregoing sequence of steps is repeated until a conformal yttrium oxide film of the desired thickness is formed on the wafer. One cycle is equivalent to a three second precursor amount, followed by a 10 second argon purge followed by a 10 second ozone treatment, followed by a 10 second argon purge.

Example 6 (hypothesis): formation of oxygen using a ruthenium precursor compound and LPCVD Hydrazine film: A bubbler containing a ruthenium precursor compound was heated to 100 ° C using a LPCVD reactor and a bubbler in fluid communication with the LP CVD reactor to increase the vapor pressure of the ruthenium precursor compound. The argon carrier is then passed through a bubbler to carry the vapor of the ruthenium precursor compound into the LPCVD reactor, wherein the LPCVD reactor has ozone in an oxygen atmosphere and contains a plurality of vertically oriented and spaced apart heated to 500 °C. Wafer wafers to form a conformal hafnium oxide film on the wafer.

Example 7 (hypothesis): Formation of a tantalum nitride film using a ruthenium precursor compound with methane and PECVD: using a PECVD reactor and a bubbler in fluid communication with the PECVD reactor, heating the bubbler containing the ruthenium precursor compound to 100 ° C to increase the vapor pressure of the ruthenium precursor compound. The He carrier is then passed through a bubbler to carry the vapor of the ruthenium precursor compound into the PECVD reactor, wherein the PECVD reactor has a plasma derived from methane and contains a plurality of horizontally oriented and spaced apart heated to 500 °C. Wafer wafers to form a conformal tantalum carbide film on the wafer.

The scope of the following patent application is hereby incorporated by reference in its entirety, and the &quot;claim&quot; can be replaced by the term "aspect". Embodiments of the invention also include these generated numbered aspects.

Claims (13)

A method of forming a ruthenium-containing film on a substrate, the method comprising subjecting a vapor of a ruthenium precursor comprising diisopropylamino-pentachlorodioxane to a deposition condition in the presence of the substrate to form a substrate on the substrate A ruthenium-containing film having a formula (A): [(CH ₃ ) ₂ CH] ₂ NSiCl ₂ SiCl ₃ (A) is formed thereon. The method of claim 1, wherein the ruthenium-containing film element ruthenium film, ruthenium carbon film, ruthenium nitride film, or ruthenium oxide film. The method of claim 1, which comprises subjecting the first vapor of the ruthenium precursor comprising diisopropylamino-pentachlorodioxane to a second vapor comprising helium, hydrogen, or HCI in the presence of the substrate A deposition condition is formed to form a ruthenium-containing film on the substrate, wherein the ruthenium-containing film element ruthenium film. The method of claim 1, which comprises, in the presence of the substrate, the first vapor of the ruthenium precursor comprising diisopropylamino-pentachlorodioxane and comprising a hydrocarbon, a hydrocarbyl decane, or both The second vapor of the combined carbon precursor is subjected to deposition conditions to form a ruthenium containing film on the substrate, wherein the ruthenium containing film is a ruthenium carbon film. The method of claim 1, which comprises, in the presence of the substrate, the first vapor of the ruthenium precursor comprising diisopropylamino-pentachlorodioxane and the molecular nitrogen, ammonia, amine, hydrazine, or The second vapor of the nitrogen precursor of any two or three of the combinations undergoes deposition conditions to form a ruthenium containing film on the substrate, wherein the ruthenium containing film is a ruthenium nitride film. The method of claim 1, which comprises, in the presence of the substrate, the first vapor of the ruthenium precursor comprising diisopropylamino-pentachlorodioxane and comprising molecular oxygen, ozone, nitrogen monoxide, dioxide The second vapor of the oxygen precursor of nitrogen, water, hydrogen peroxide, or a combination of any two or three thereof, is subjected to deposition conditions to form a ruthenium-containing film on the substrate, wherein the ruthenium-containing film is a ruthenium-oxide film. The method of any one of claims 3 to 6, wherein the substrate is heated and disposed in a deposition reactor configured for atomic layer deposition, the method comprising: repeatedly feeding the diisopropylamine The first vapor of the ruthenium precursor of quinone-pentachlorodioxane, purged with an inert gas, fed the second vapor into the deposition reactor, and purged with an inert gas to be heated by the atomic layer deposition The ruthenium-containing film is formed on a substrate, wherein the atomic layer deposition comprises plasma enhanced atomic layer deposition or thermal atomic layer deposition, and wherein the feeds may be the same or different. The method of claim 7, wherein the atomic layer deposition is a plasma enhanced atomic layer deposition, and wherein the plasma is an ammonia plasma in nitrogen or argon, or wherein the plasma is forming gas, nitrogen Or oxygen plasma. The method of any one of claims 3 to 6, wherein the substrate is heated and disposed in a deposition reactor configured for chemical vapor deposition, the method comprising: feeding comprising a diisopropylamino group - the first vapor of the ruthenium precursor of pentachlorodioxane, and feeding the second vapor to the deposition reactor to form the ruthenium containing film on the heated substrate by chemical vapor deposition, wherein The feeds can be the same or different. The method of claim 5, wherein the vapor deposition conditions lack carbon and oxygen, and the niobium nitride film comprises a tantalum nitride film. The method of any of the preceding claims, wherein the substrate is a semiconductor material. A composition for forming a ruthenium nitride film, the composition comprising: a ruthenium precursor comprising diisopropylamino-pentachlorodioxane, and a nitrogen precursor. A use as in the method of claim 11 for forming a ruthenium nitride film.