Deposition of noble metal islets or thin films for use in electrochemical catalysts with improved catalytic activity

Abstract

Platinum group metal-containing chemical precursors suitable for vapor deposition are disclosed. Methods for using these precursors for platinum deposition are also disclosed. The chemical precursors and methods are particularly suitable for the deposition of catalytic materials on electrodes.

Description

[Technical Field]

[0001] Deposition of noble metal islets or thin films for use in electrochemical catalysts with improved catalytic activity. [Background technology]

[0002] Pt-containing membranes are well known for use in fuel cell applications to form surface coating layers or membranes of catalytic materials, and examples of Pt-containing membranes include platinum metal, platinum oxide, platinum-ruthenium alloys and compounds, and platinum-titanium alloys and compounds.

[0003] Polymer electrolyte membrane fuel cells (PEMFCs) have great potential as a power source for applications such as zero-emission vehicles. However, current commercialized or prior-art PEMFCs suffer from a variety of problems. One of the most technically and economically significant drawbacks is the amount of expensive platinum and / or other platinum group metals (PGMs)—ruthenium, rhodium, palladium, osmium, and iridium—used as catalysts in the membrane electrode assembly (MEA) of the fuel cell in the form of islets, clusters, or nanoparticles. While the amount of PGM catalyst is primarily determined by the power output specifications per unit cell in the fuel cell stack, adding significant amounts of PGM catalyst can lead to degradation processes that compromise the reliability of the fuel cell over its lifetime. Typical degradation processes involve the loss of platinum or PGM material or catalytically active surface area, such as dissolution and corrosion of platinum or PGM particles, agglomeration of platinum or PGM particles, peeling of platinum or PGM particles from the carbon support, and other issues. At the same time, using larger platinum or PGM particles requires the use of larger amounts of platinum or PGM, increasing the cost of the fuel cell.

[0004] To reduce the amount of Pt or PGM used, it may be preferred to use platinum or PGM nanoparticles, islets, or nanodots (e.g., preferably less than 20 nm, more preferably less than 10 nm, and most preferably 2-5 nm in size). Such platinum or PGM nanoparticles, islets, or nanodots preferably consist of one or more Pt monolayers to maintain a high surface area to volume ratio, thereby enabling high catalytic and / or electrochemical activity.

[0005] Proposed solutions for reducing the amount of PGM include blending PGM with non-precious metals, coating Pt or PGM-containing metals or alloys on non-precious metal core materials, or forming nanostructured thin films. Although alloyed catalysts can improve catalytic activity, alloyed catalysts can result in detrimental degradation. Additionally, the wet deposition techniques typically used to prepare current and prior art catalysts have limited scalability and control over nanoparticle morphology (size, shape), making the nanoparticles highly susceptible to degradation, dissolution, corrosion, and other issues. When Pt or PGM is deposited by physical vapor deposition or sputtering, it results in uneven and non-conformal coatings, which inevitably affect fuel cell performance.

[0006] As a result, to prepare cost-effective quantities of materials incorporating Pt or PGM-containing nanoparticles, the industry has developed batch furnaces to process large quantities of substrates, typically carbon-based, typically in powder form, by vapor deposition, so that the large aggregate surface area provided allows for uniform particle distribution on the substrate or support. Significant efforts have been made to increase the number and variety of vaporizable precursors available in such systems. However, significant challenges remain in delivering significant quantities of some of these materials in a reliable manner.

[0007] The deposition process can be carried out in reactors that process flat or nearly flat surfaces, such as single-substrate, batch, roll-to-roll, or space ALD reactors, as known to those skilled in the art. The use of powder reactors combined with ALD or CVD techniques to produce uniform coatings on battery electrode active materials is also increasingly being explored. A vertical reaction chamber can be used to create a fluidized zone in which the coating reaction occurs. It has been observed that powder particles in a fluidized bed tend to adhere to each other and form larger particle blocks, or agglomerates. To prevent agglomerate formation, an oscillating gas flow is used, whereby a carefully selected oscillating gas flow is supplied to the reaction chamber. Due to the principle of Helmholtz resonance, the incoming gas flow sweeps over and into the cavity, causing oscillations in the outgoing gas flow. The outgoing oscillating gas flow is directed into the reaction chamber to prevent agglomerate formation.

[0008] Therefore, particularly for powder reactor coatings, the industry needs platinum or platinum group metal (PGM) precursors that have high vapor pressures, high stability, and can be prepared cost-effectively. Currently, the platinum precursors that offer the highest vapor pressures and sufficient stability are Pt(MeCp)Me3 and closely related molecules. Pt(MeCp)Me3 has a vapor pressure of 0.053 Torr at 23 °C. The synthesis of these molecules is complex, requiring at least six steps, making chemical preparation a significant economic challenge. Other proposed precursors with higher stability are platinum bis-β-diketonates, such as Pt(tmhd)2 and Pt(acac)2. Summary of the Invention [Means for solving the problem]

[0009] Novel platinum or PGM precursors, their synthesis, and methods of use for depositing platinum or PGM-containing films or islets are disclosed. In particular, the disclosed precursors exhibit good volatility and high thermal stability. The disclosed precursors are liquid below 100°C, preferably below 50°C, and most preferably below 20°C, making them suitable for deposition techniques such as ALD and CVD applications on high surface area surfaces such as powder batch reactors.

[0010] The precursors are suitable for use in depositing catalysts by vapor-phase deposition to form islets, clusters, or nanoparticles, or thin films of PGMs that coat part or all of a substrate, after optional prior surface functionalization. Gas-phase reactions may involve the use of PGM precursors in combination with H, O, N, or F-containing sources. The platinum- or PGM-containing nanoparticles, islets, or nanodots are preferably less than 20 nm, more preferably less than 10 nm, and most preferably between 2 nm and 5 nm in size. Such platinum or PGM nanoparticles, islets, or nanodots preferably consist of one or more monolayers of Pt or PGM-containing material.

[0011] For a better understanding of the nature and objects of the present invention, reference should be made to the following detailed description taken in conjunction with the accompanying drawings, in which like elements are designated with the same or similar reference numerals, and in which: [Brief explanation of the drawings]

[0012] [Figure 1] FIG. 1 shows the vacuum TGA of Pt(allyl)(iPr-amd). [Figure 2] FIG. 2 shows the vacuum TGA of Pt(allyl) (iPr2,Et-amd). [Figure 3] FIG. 3 shows the vacuum TGA of Pt(allyl)(iPr2,nBu-amd). [Figure 4] FIG. 4 shows the vacuum TGA of Pt(allyl)(tBu,Et,Me-amd).

[0013] Notation and Nomenclature The following detailed description and claims utilize numerous abbreviations, symbols, and terms that are commonly known in the art. Certain abbreviations, symbols, and terms are used throughout the following description and claims, including the following:

[0014] As used herein, the indefinite article "a" or "an" means one or more.

[0015] As used herein, "about" or "approximately" or "approximately" in the text or claims means ±10% of the stated value.

[0016] As used herein, "room temperature" in the text and claims means about 20°C to about 25°C.

[0017] The term "ambient temperature" refers to an environmental temperature of about 20°C to about 25°C.

[0018] The term "substrate" refers to the material on which a process is performed. A substrate may refer to a wafer having the material on which a process is performed. A substrate may be any suitable wafer used in the manufacture of semiconductors, solar cells, flat panels, or LCD-TFT devices. A substrate may also have one or more layers of different materials already deposited thereon from a previous manufacturing step. For example, a wafer may include a silicon layer (e.g., crystalline, amorphous, porous, etc.), a silicon-containing layer (e.g., SiO2, SiN, SiON, SiCOH, etc.), a metal-containing layer (e.g., copper, cobalt, tungsten, platinum, palladium, nickel, ruthenium, gold, etc.), or a combination thereof. Furthermore, a substrate may be flat or patterned. A substrate may be an organic patterned photoresist film. The substrate may include an oxide layer (e.g., ZrO2-based materials, HfO2-based materials, TiO2-based materials, rare earth oxide-based materials, ternary oxide-based materials, etc.) used as a dielectric material in MEMS, 3D NAND, MIM, DRAM, or FeRAM device applications, or a nitride-based film (e.g., TaN, TiN, NbN) used as an electrode. Those skilled in the art will recognize that the terms "film" or "layer" as used herein refer to a thickness of any material disposed on or extending over a surface, which may be a trench or line. Throughout this specification and claims, the wafer and any associated layers thereon are referred to as the substrate.

[0019] The term "wafer" or "patterned wafer" refers to a wafer having a stack of films on a substrate, where at least the topmost film has topographical features formed in a step prior to the deposition of the indium-containing film.

[0020] The term "nanodot" refers to non-continuous deposits, such as Pt, having a maximum cross-sectional dimension of 1 nanometer to 100 nanometers. Nanodots are most often approximately hemispherical or approximately circular, but may be of any shape, including irregularly shaped structures.

[0021] It should be noted that the terms "film" and "layer" may be used interchangeably herein. It is understood that a film may correspond to or relate to a layer, and a layer may refer to a film. Furthermore, those skilled in the art will recognize that the terms "film" or "layer" as used herein refer to a thickness of some material disposed or extending over a surface, which may range in size from as large as an entire wafer to as small as a trench or line.

[0022] The "cathode" in a lithium-ion battery refers to the positive electrode of an electrochemical cell (battery) where the reduction of the cathode material occurs by the insertion of electrons and lithium ions during charging. During discharge, the cathode material is oxidized by the release of electrons and lithium ions. Lithium ions move from the cathode to the anode or vice versa through the electrolyte within the electrochemical cell, while electrons move through an external circuit. The cathode typically consists of a cathode active material (i.e., a lithiated metal layered oxide), a conductive carbon black agent (acetylene black Super C65, Super P), and a binder (PVDF, CMC).

[0023] The "cathode active material" is the major component of the cathode (positive electrode) composition of a battery cell. Cathode materials, such as cobalt, nickel, and manganese in a crystalline structure, e.g., a layered structure, form a complex metal oxide material with lithium intercalated therein. Examples of cathode active materials are layered lithium nickel manganese cobalt oxide (LiNixMnyCozO2), spinel-type lithium manganese oxide (LiMn2O4), and olivine-type lithium iron phosphate (LiFePO4).

[0024] Also, the terms "deposition temperature" and "substrate temperature" may be used interchangeably herein, with the understanding that substrate temperature may correspond to or be related to deposition temperature, and deposition temperature may refer to substrate temperature.

[0025] Also, herein, the terms "precursor" and "deposition compound" and "deposition gas" may be used interchangeably when the precursor is in a gaseous state at room temperature and ambient pressure. It is understood that a precursor may correspond to or be related to a deposition compound or gas, and a deposition compound or gas may refer to a precursor.

[0026] Standard abbreviations for elements from the periodic table of the elements are used herein. It should be understood that elements may be referred to by these abbreviations (e.g., Si refers to silicon, N refers to nitrogen, O refers to oxygen, C refers to carbon, H refers to hydrogen, F refers to fluorine, etc.).

[0027] As used herein, the term "hydrocarbon" refers to a saturated or unsaturated functional group containing only carbon and hydrogen atoms. As used herein, the term "alkyl group" refers to a saturated functional group containing only carbon and hydrogen atoms. An alkyl group is a type of hydrocarbon. Furthermore, the term "alkyl group" refers to a straight-chain, branched, or cyclic alkyl group. Examples of straight-chain alkyl groups include, but are not limited to, methyl, ethyl, propyl, and butyl groups. Examples of branched alkyl groups include, but are not limited to, t-butyl. Examples of cyclic alkyl groups include, but are not limited to, cyclopropyl, cyclopentyl, and cyclohexyl groups.

[0028] As used herein, the abbreviation "Me" represents a methyl group; the abbreviation "Et" represents an ethyl group; the abbreviation "Pr" represents any propyl group (i.e., n-propyl or isopropyl); the abbreviation "iPr" represents an isopropyl group; the abbreviation "Bu" represents any butyl group (i.e., n-butyl, iso-butyl, tert-butyl, sec-butyl); the abbreviation "tBu" represents a tert-butyl group; and the abbreviation "sBu" represents sec-butyl. The abbreviation "iBu" represents an isobutyl group; the abbreviation "Ph" represents a phenyl group; the abbreviation "Am" represents any amyl group (isoamyl, sec-amyl, tert-amyl); the abbreviation "Cy" represents a cyclic hydrocarbon group (cyclobutyl, cyclopentyl, cyclohexyl, etc.); the abbreviation "Ar" represents an aromatic hydrocarbon group (phenyl, xylyl, mesityl, etc.); and the abbreviation "amd" represents an amidinate structure.

[0029] Ranges may be expressed herein as from about one particular value and / or to about another particular value. When such a range is expressed, it is to be understood that another embodiment is from the one particular value and / or to the other particular value, along with all combinations within said range. All ranges described herein are inclusive of the limits (i.e., x=1 to 4 or x ranges from 1 to 4 includes x=1, x=4, and any number therebetween).

[0030] References herein to "one embodiment" or "an embodiment" mean that a particular feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment of the invention. The appearances of the phrase "in one embodiment" in various places throughout the specification do not necessarily all refer to the same embodiment, and different or alternative embodiments are not necessarily mutually exclusive of other embodiments. The same applies to the term "implementation."

[0031] As used herein, the term "independently," when used in the context of describing an R group, should be understood to mean that the R group in question is independently selected not only from another R group having the same or different subscript or superscript, but also from any further species of that same R group. For example, a group of the formula MR 1 x (NR 2 R 3 ) (4-x) (wherein x is 2 or 3), wherein two or three R 1 The groups may be the same as each other, but R 2 Even if it is the same as R 3 It should be understood that unless otherwise stated, the values ​​of the R groups are independent of each other when used in different formulas.

[0032] As used herein, the term "exemplary" is used herein to mean serving as an example, instance, or illustration. Any aspect or design described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other aspects or designs. Rather, use of the word exemplary is intended to present concepts in a concrete form.

[0033] Furthermore, the term "or" is intended to mean an inclusive "or," rather than an exclusive "or." That is, unless expressly stated otherwise or clear from the context, "X uses A or B" is intended to mean any of the natural inclusive permutations. That is, if X uses A, if X uses B, or if X uses both A and B; in any of the foregoing cases, "X uses A or B" is satisfied. Furthermore, the articles "a" and "an," as used in this application and the appended claims, should generally be construed to mean "one or more," unless otherwise specified or clear from the context to refer to the singular form.

[0034] "Comprising" in the claims is an open transitional phrase, meaning that the subsequently identified claim elements are a non-exclusive recitation (i.e., one could additionally include something else and still remain within the scope of "comprising"). "Comprising" is defined herein as necessarily including the more restrictive transitional phrases "consisting essentially of" and "consisting of." Thus, "comprising" could be replaced with "consisting essentially of" or "consisting of" and still remain within the expressly defined scope of "comprising."

[0035] "Providing" in the claims is defined to mean providing, supplying, making available, or preparing something. This step may be performed by any actor, unless there is express language to the contrary in the claims.

[0036] Polydentate is when two or more consecutive atoms in a chemical structure form a ligand with a metal. Polydentate ligands are represented by the Greek symbol eta, followed by the number of atoms involved in the ligand. For example, η5- means a five-atom ligand, and η3- means a three-atom ligand.

[0037] Some ligands can form different polydentates: for example, cyclopentadienyl ligands can be η-, η-, or η-, often separating them as a special subcategory of metal ligands. DETAILED DESCRIPTION OF THE INVENTION

[0038] precursor The disclosed precursors are liquid below 100°C, preferably below 50°C, and most preferably below 20°C, which is suitable for deposition techniques such as ALD and CVD applications on high surface area surfaces such as powder batch reactors.

[0039] The precursors disclosed herein are defined by the following chemical genus definitions: M(L1)(L2)x (In the formula, M represents Pt or another PGM element, L1 may be an η5-ligand other than cyclopentadienyl, such as pentadienyl, cyclohexadienyl, cycloheptadienyl, pyrrolyl, or a heterocyclic ligand; L2 may be H, an alkyl group, an aryl group, NO, a halide, an alkoxide, an amide, an alkoxycarbyl, an aminocarbyl, a β-diketonate, a β-diketoiminate, a ketoiminate, a formamidinate, an amidinate, a guanidinate, a carbon chain, or a carbyl; x represents the number of L2 ligands, Each L2 can be the same or different, Each L2 may independently be an ionic or neutral ligand. M(L3)(L4)x (In the formula, M represents Pt or another PGM element, L3 may be a η-ligand, such as a cyclopentadienyl ligand; L4 may be H, a C2-C6 alkyl group, NO, a halide, an alkoxide, an amide, an alkoxycarbyl, an aminocarbyl, a β-diketonate, a β-diketoimide, a formamidinate, an amidinate, or a guanidinate; x represents the number of L4 ligands, Each L4 may be the same or different, Each L4 may independently be an ionic or neutral ligand. M(L5)(L6)x (In the formula, M represents Pt or another PGM element, L5 may be a η3-ligand, such as an allyl ligand; L6 may be H, a C2-C6 alkyl group, NO, a halide, an alkoxide, an amide, an alkoxycarbyl, an aminocarbyl, a pentadienyl, a cyclohexadienyl, a cycloheptadienyl, a pyrrolyl, a heterocyclic ligand, a β-diketonate, a β-diketoimide, a formamidinate, an amidinate, or a guanidinate; x represents the number of L6 ligands, Each L6 may be the same or different, Each L6 may independently be an ionic or neutral ligand).

[0040] In one preferred subgenus of M(L5)(L6)x, L5 is an allyl ligand and L6 is an amidinate ligand: [ka] (In the formula, R1, R2, R3, R4, R5, R6, R7, and R8 are each independently selected from H; a C1 to C6 linear, branched, or cyclic alkyl group; a C1 to C6 linear, branched, or cyclic alkylsilyl group (mono-, bis-, or tris-alkyl); a C1 to C6 linear, branched, or cyclic alkylamino group; or a C1 to C6 linear, branched, or cyclic fluoroalkyl group).

[0041] The disclosed PGM precursors exhibit good volatility and thermal stability. Furthermore, the disclosed PGM precursors can be liquids or low-melting solids. The low melting point of the disclosed phosphorus-containing platinum or PGM precursors can be <100°C, preferably less than 50°C, and more preferably about 20°C. The disclosed PGM precursors are convenient for use in ALD and CVD applications.

[0042] The disclosed PGM precursors may have chelating functional groups to lower their melting points and increase their volatility. More specifically, nitrogen or oxygen chelating functional groups, for example, are introduced as neutral donors for the electronic and steric properties of the PGMs. Therefore, the coordination spheres of the disclosed PGM precursors are more saturated and less prone to oligomerization. Therefore, when ALD or CVD processes are targeted, the vapors of the disclosed PGM precursors can be more efficiently delivered into the deposition reactor, thereby shortening deposition times and producing highly uniform and conformal deposited films or islets.

[0043] The disclosed PGM precursors can be synthesized by unknown or known synthesis methods and can be used in chemical vapor deposition processes such as ALD and CVD, either alone or in mixtures with different platinum and metal precursors, in solution or not, to form Pt-containing films or islets, such as Pt metal, platinum-ruthenium alloys, platinum-titanium alloys, platinum-ruthenium compounds, and platinum-titanium compounds.

[0044] Preferably, the disclosed PGM precursors have properties suitable for vapor deposition processes, such as a vapor pressure ranging from about 0.1 Torr at 23°C to about 1,000 Torr at 23°C, a melting point below 20°C (preferably in liquid form at room temperature), more preferably below -20°C to prevent freeze / thaw problems, and exhibit 0% by volume or v / v to 1% v / v decomposition per week at the temperatures required to achieve a usable vapor pressure (1-100 Torr).

[0045] The disclosed PGM precursors are ideally liquid and vaporized using a bubbler or direct liquid injection system, although solid precursors can also be used for ALD / CVD precursor vaporization using a sublimator such as that disclosed in Xu et al., International Publication No. WO 2009 / 087609. Alternatively, solid precursors can be mixed or dissolved in a solvent to reach a melting point and viscosity usable for use in a direct liquid injection system. While the disclosed PGM precursors are ideally liquid, solid precursors for liquid deposition techniques such as spray coating, slit coating, and spin-on deposition can be mixed or dissolved in a solvent to reach a melting point and viscosity usable for flowing the precursor solution into a reactor.

[0046] To ensure process reliability, the disclosed PGM precursors can be purified by continuous or fractional batch distillation or sublimation prior to use to a purity ranging from about 93% weight or w / w to about 100% w / w, preferably from about 99% w / w to about 99.999% w / w, and more preferably from about 99% w / w to about 100% w / w. Those skilled in the art will appreciate that purity can be achieved by 1It will be appreciated that the purity of the Pt-containing film or islet-forming composition may be determined by H NMR or gas or liquid chromatography followed by mass spectrometry. The Pt-containing film or islet-forming composition may contain any of the following impurities: oxygen, hydroxide, fluorine, nitrogen, hydrogen, phosphorus, metal halide compounds. Preferably, the total amount of these impurities is less than 0.1% w / w. Purified compositions can be produced by recrystallization, sublimation, distillation, and / or by passing the gas or liquid through a suitable adsorbent such as a 4 Å molecular sieve.

[0047] The disclosed Pt-containing membrane or islet-forming compositions preferably contain less than 5% v / v, preferably less than 1% v / v, more preferably less than 0.1% v / v, and even more preferably less than 0.01% v / v of any of its analogs or other reaction products. This embodiment may provide better process reproducibility. This embodiment can be manufactured by distillation or other purification techniques known in the art.

[0048] The concentrations of trace metals and metalloids in the purified PGM membrane or islet-forming composition may each independently range from about 0 ppbw to about 100 ppbw, more preferably from about 0 ppbw to about 10 ppbw. These metal or metalloid impurities include, but are not limited to, aluminum (Al), arsenic (As), barium (Ba), beryllium (Be), bismuth (Bi), cadmium (Cd), calcium (Ca), chromium (Cr), cobalt (Co), copper (Cu), gallium (Ga), germanium (Ge), hafnium (Hf), zirconium (Zr), indium (In), iron (Fe), lead (Pb), magnesium (Mg), manganese (Mn), tungsten (W), nickel (Ni), potassium (K), sodium (Na), strontium (Sr), thorium (Th), tin (Sn), titanium (Ti), uranium (U), vanadium (V), and zinc (Zn). The concentration of X (X=Cl, Br) in the purified PGM membrane or islet-forming composition may range from about 0 ppmw to about 100 ppmw, more preferably from about 0 ppmw to about 10 ppmw.

[0049] Deposition Process Also disclosed are methods of using the disclosed PGM film- or islet-forming compositions for vapor deposition, such as ALD or CVD techniques. The disclosed methods provide for the use of the PGM film- or islet-forming compositions for the deposition of PGM-containing films or islets. The disclosed methods may be useful for the production of electrochemical catalyst materials in the fuel cell industry.

[0050] The disclosed methods for forming a PGM-containing layer on a substrate include placing the substrate in a reactor, providing a vapor of the disclosed PGM-containing film or islet-forming composition to the reactor, and contacting the vapor with the substrate (and typically directing the vapor toward the substrate) to form a PGM-containing layer, islet, or nanodot on the surface of the substrate.

[0051] The method can include forming a bimetal-containing layer on a substrate using a vapor deposition process, more specifically for depositing a PtRu, PtTi layer. The disclosed method can be useful in manufacturing fuel cells.

[0052] The disclosed PGM-containing film or islet-forming compositions can be used to deposit PGM-containing films, nanodots, or islets using any deposition method known to those skilled in the art. Examples of suitable deposition methods include chemical vapor deposition (CVD) or atomic layer deposition (ALD) with or without plasma treatment, or liquid-based deposition. Exemplary CVD methods include thermal CVD, pulsed CVD (PCVD), low-pressure CVD (LPCVD), subatmospheric pressure CVD (SACVD) or atmospheric pressure CVD (APCVD), hot-wire CVD or hot-filament CVD (also known as cat-CVD, in which a hot wire serves as the energy source for the deposition process), hot-wall CVD, cold-wall CVD, aerosol-assisted CVD, direct liquid injection CVD, combustion CVD, hybrid physical CVD, metalorganic CVD, rapid thermal CVD, photoinitiated CVD, laser CVD, radical-incorporated CVD, plasma-enhanced CVD (PECVD, including, but not limited to, flowable PECVD), and combinations thereof. Exemplary ALD methods include thermal ALD, plasma-enhanced ALD (PEALD), spatially resolved ALD, temporal ALD, selective or non-selective ALD, hot wire ALD (HWALD), radical-incorporated ALD, and combinations thereof. Supercritical fluid deposition can also be used. The deposition method is preferably ALD, PE-ALD, or spatial ALD to provide adequate step coverage and film thickness control. Liquid-based deposition is exemplified by spin-on deposition (SOD), spray deposition, dip coating, and slit coating.

[0053] A vapor of the PGM-containing film- or islet-forming composition is generated and then introduced into a reaction chamber containing a substrate. The temperature and pressure within the reaction chamber, as well as the temperature of the substrate, are maintained at conditions suitable for depositing at least a portion of the PGM-containing precursor onto the substrate. In other words, after the vaporized composition is introduced into the reaction chamber, conditions within the reaction chamber are adjusted so that at least a portion of the precursor deposits on the substrate to form a PGM-containing layer, islet, or nanodot. Those skilled in the art will recognize that "at least a portion of the precursor is deposited" means that some or all of the precursor reacts with or adheres to the substrate.

[0054] The reaction chamber or reactor may be any enclosure or chamber of a device in which a deposition method is performed, such as, but not limited to, a parallel-plate reactor, a cold-wall reactor, a hot-wall reactor, a single-wafer reactor, a multi-wafer reactor, or other such types of deposition systems. All of these exemplary reaction chambers can function as ALD or CVD reaction chambers. The reaction chamber can be maintained at a pressure ranging from about 0.5 mTorr to about 20 Torr for all ALD and subatmospheric CVD processes. The pressure for subatmospheric CVD and atmospheric CVD processes can range up to 760 Torr (atmospheric pressure). Furthermore, the temperature within the reaction chamber can range from below room temperature, such as about 0°C, to about 600°C. Preferably, the temperature within the reaction chamber can range from about 15°C to about 400°C. More preferably, the temperature within the reaction chamber can range from about 20°C to about 300°C. Those skilled in the art will recognize that temperatures can be optimized by simple experimentation to achieve desired results.

[0055] The reactor temperature can be controlled by controlling the temperature of the substrate holder or by controlling the temperature of the reactor walls. Devices used to cool or heat substrates are known in the art. The reactor walls are heated to a temperature sufficient to obtain the desired film or islet at a sufficient growth rate and with the desired physical state and composition. Non-limiting exemplary temperature ranges to which the reactor walls can be heated include about 20°C to about 600°C. If a plasma deposition process is utilized, the deposition temperature can range from about 20°C to about 550°C. Alternatively, if a thermal process is performed, the deposition temperature can range from about 50°C to about 600°C.

[0056] Alternatively, the substrate can be heated to a sufficient temperature to obtain the desired PGM-containing film, islet, or nanodot with the desired physical state and composition at a sufficient growth rate. Non-limiting exemplary temperature ranges to which the substrate can be heated include room temperature to about 600° C. Preferably, the temperature of the substrate remains below 500° C.

[0057] The reactor contains one or more substrates onto which the film, nanodots, or islets are deposited. A substrate is generally defined as the material on which the process is performed. The substrate may be any suitable substrate used in the semiconductor or lithium battery industry. Examples of suitable substrates include wafers or supports, such as silicon, silica, or glass substrates. The support may have one or more layers of different materials deposited thereon from a previous manufacturing step. For example, the support may include a silicon layer (crystalline, amorphous, porous, etc.), a silicon oxide layer, a silicon nitride layer, a silicon oxynitride layer, a carbon-doped silicon oxide (SiCOH) layer, or a combination thereof. The PGM precursors of the present disclosure used in the fuel cell industry can be deposited on powders made from graphite, doped graphite, particularly Si-doped graphite, silicon and silicon alloys, or graphite made from metal oxides. The base material may include graphene, nanotubes, glassy carbon, graphite, or amorphous carbon, etc. The substrate may be planar, spherical, rounded, patterned, or may not have a regular structure (see above). For example, the layer may be a hydrogenated carbon, e.g., CH x (x is greater than zero) Preferred substrate materials are graphite or amorphous carbon, graphene, nanotubes, or glassy carbon.

[0058] The disclosed methods can deposit a PGM-containing layer directly onto a substrate or onto one or more layers on a substrate. The substrate may be patterned and may contain complex three-dimensional structures. For example, conformal PGM-containing films, such as Pt metal, can be deposited using any ALD / CVD technique on substrates having aspect ratios ranging from about 20:1 to about 1000:1. Furthermore, those skilled in the art will recognize that the terms "film" or "layer" as used herein refer to a thickness of any material disposed on or extending over a surface, which may be a trench or line. Throughout this specification and claims, the wafer and associated layers thereon are referred to as the substrate. However, in many cases, the preferred substrate utilized can be selected from hydrogenated carbon, silicon-based carbon, or Si-type substrates.

[0059] The disclosed PGM-containing film-forming compositions can be supplied either neat or blended with a suitable solvent, such as toluene, ethylbenzene, xylene, mesitylene, decane, dodecane, octane, hexane, pentane, tertiary amines, acetone, tetrahydrofuran, ethanol, ethyl methyl ketone, 1,4-dioxane, or others. The disclosed compositions can be present in various concentrations in the solvent. For example, the resulting concentration can range from about 0.05 M to about 2 M.

[0060] The neat or blended PGM-containing film-forming composition is delivered to the reactor in vapor form via conventional means, such as tubing and / or flow meters. Vaporized compositions can be produced by vaporizing the neat or blended composition via conventional vaporization processes, such as direct vaporization or distillation, by bubbling, or by using a sublimator, such as that disclosed in WO 2009 / 087609 to Xu et al. The neat or blended composition can be delivered in liquid form to a vaporizer, where it is vaporized and then introduced into the reactor. Alternatively, the neat or blended composition can be vaporized by passing a carrier gas through a vessel containing the composition or by bubbling the carrier gas into the composition. Carrier gases include, but are not limited to, Ar, He, or N2, and mixtures thereof. Bubbling with a carrier gas can also remove dissolved oxygen present in the neat or blended composition. The carrier gas and composition are then introduced into the reactor as a vapor.

[0061] If necessary, the vessel can be heated to a temperature that allows the PGM-containing film-forming composition to be in its liquid phase and have sufficient vapor pressure. The vessel can be maintained at a temperature ranging, for example, from 0 to 150° C. Those skilled in the art will recognize that the temperature of the vessel can be adjusted in known ways to control the amount of PGM-containing film-forming composition that vaporizes.

[0062] In addition to the disclosed PGM precursors, reactants or co-reactants can also be introduced into the reactor. The co-reactant can be an oxygen-containing gas for Pt-containing film deposition. Oxygen-containing gases include, but are not limited to, oxidizers such as O3, O2, HO, trimethyl phosphate, alkyl phosphates, alkyl phosphinimines, RuO4, NO, NO, HO, HO2, O radicals, or combinations thereof, preferably O3 or O2. Typically, O3 / O2 mixtures are used for high-temperature (e.g., above about 500°C) oxide deposition. Furthermore, the co-reactant can also be F2, NF3, N2F4, FNO, ClF, ClF3, or other interhalogen compounds.

[0063] The disclosed deposition processes (e.g., ALD, CVD) typically include a step of removing excess co-reactant from the deposition surface by purging the reactor with an inert gas or by providing a purge step in which the substrate is passed through a sector under high vacuum and / or a carrier gas curtain. The co-reactant can be treated with a plasma to decompose the co-reactant into its radical form. N2 can also be utilized as a reducing agent when treating with a plasma. For example, the plasma can be generated at a power ranging from about 50 W to about 500 W, preferably from about 100 W to about 200 W. The plasma can be generated or present within the reactor itself. Alternatively, the plasma can be located away from the reactor, typically in a remotely located plasma system, for example. Those skilled in the art will recognize methods and apparatus suitable for such plasma treatment.

[0064] The disclosed PGM-containing film-, nanodot-, or islet-forming compositions and one or more co-reactants can be introduced into the reaction chamber simultaneously (e.g., CVD), sequentially (e.g., ALD), or in other combinations. For example, the PGM-containing film- or islet-forming composition can be introduced in one pulse, and two additional reactants can be introduced together in separate pulses (e.g., advanced ALD). Alternatively, the reaction chamber may already contain the co-reactant before the disclosed PGM-containing film- or islet-forming composition is introduced. The co-reactant can be passed through a localized or separate plasma system from the reaction chamber and decomposed into radicals. Alternatively, the PGM-containing film-, nanodot-, or islet-forming composition can be introduced sequentially into the reaction chamber while the other reactants are being introduced in pulses (e.g., pulsed CVD). In each case, the pulse may be followed by a purge or evacuation step to remove excess introduced components. In each instance, the pulse may last for a time ranging from about 0.01 seconds to about 10 seconds, alternatively from about 0.3 seconds to about 3 seconds, or alternatively from about 0.5 seconds to about 2 seconds. In another alternative, the PGM-containing film-, nanodot-, or islet-forming composition and one or more co-reactants may be sprayed simultaneously from a showerhead beneath which a susceptor holding several substrates rotates (e.g., spatial ALD).

[0065] In one non-limiting exemplary ALD-type process, the vapor phase of a PGM-containing film-, nanodot-, or islet-forming composition is introduced into a reaction chamber, where at least a portion of the PGM-containing precursor reacts with a suitable substrate, such as C, Si, SiO2, or Al2O3, to form an adsorbed PGM-containing layer, nanodot, or islet. Excess composition can then be removed from the reaction chamber by purging and / or evacuating the reaction chamber. H2 or NH3 is introduced into the reaction chamber, where it reacts with the adsorbed PGM-containing layer in a self-limiting manner. Excess H2 or NH3 is removed from the reaction chamber by purging and / or evacuating the reaction chamber. This two-step process can be repeated until the desired film thickness is achieved or a film having the required thickness is obtained.

[0066] Alternatively, if the desired PGM-containing film, nanodot, or islet contains a second element (e.g., PtM, where M is P, Ru, Ti, Ga, Ge, As, B, Ta, Hf, Nb, Mg, Al, Sr, Y, Ba, Ca, As, Sb, Bi, Sn, Pb, Co, a lanthanide, or a combination thereof), the two-step process can be followed by introducing vapor of a second precursor into the reaction chamber. The second precursor is selected based on the properties of the PGM-M film or islet to be deposited. After introduction into the reaction chamber, the second precursor is contacted with the substrate. Excess second precursor is removed from the reaction chamber by purging and / or evacuating the reaction chamber. Again, H2 or NH3 can be introduced into the reaction chamber to react with the second precursor. Excess H2 or NH3 is removed from the reaction chamber by purging and / or evacuating the reaction chamber. When the desired film or islet thickness is achieved, the process can be terminated. However, if a thicker film or islet is desired, the entire four-step process can be repeated, alternating between the PGM precursor, the second precursor, and H or NH feeds to deposit a film of the desired composition and thickness.

[0067] The disclosed PGM-containing film-, nanodot-, or islet-forming compositions may contain impurities that are any of the following: undesired co-produced species; solvents; chlorinated metal compounds; or other reaction products. In one alternative, the total amount of these impurities is less than 0.1% w / w.

[0068] Solvents such as hexane, pentane, dimethyl ether, or anisole may be used in the synthesis of the precursor. The concentration of the solvent in the disclosed Si-containing precursor may range from about 0% w / w to about 5% w / w, preferably from about 0% w / w to about 0.1% w / w. Separation of the solvent from the precursor may be difficult if both have similar boiling points. Cooling the mixture may produce a solid precursor in the liquid solvent, which can be separated by filtration. Vacuum distillation can also be used, as long as the precursor product is not heated above its decomposition point.

[0069] In one alternative, the disclosed PGM-containing film-, nanodot-, or islet-forming compositions contain less than 5% v / v, preferably less than 1% v / v, more preferably less than 0.1% v / v, and even more preferably less than 0.01% v / v of any of their undesired congeners, reactants, or other reaction products. This alternative may provide greater process reliability. This alternative can be produced by distillation of the disclosed PGM precursors.

[0070] In another alternative, the disclosed PGM-containing film-, nanodot-, or islet-forming compositions can contain 5% v / v to 50% v / v of one or more of the same PGM-containing precursors, reactants, or other reaction products, particularly if the mixture provides improved process parameters or if isolation of the desired compounds is too difficult or expensive. For example, a mixture of two PGM-containing precursors can produce a stable liquid mixture suitable for vapor deposition.

[0071] Also disclosed are methods or processes for forming PGM-containing layers, islets, or nanodots on a substrate using ALD or CVD processes in a reaction chamber. The disclosed PGM precursors can be used to deposit Pt-containing films or islets using ALD or CVD methods known to those skilled in the art.

[0072] The disclosed vapor deposition processes using the disclosed PGM-containing precursors can be carried out on substrates having temperatures ranging from about 20°C to about 750°C, more preferably from 50°C to about 300°C.

[0073] Substrate exposure times in the disclosed vapor deposition processes (e.g., ALD, CVD) using the disclosed precursors can range from 1 millisecond to 5 minutes, preferably from 1 second to 60 seconds. Co-reactant exposure times in the disclosed ALD processes using the disclosed precursors can range from 1 millisecond to 1 minute, preferably from 100 milliseconds to 30 seconds.

[0074] The pressure in the reaction chamber is maintained at a suitable condition for the PGM-containing precursor to react with the surface, for example, the pressure in the chamber can be maintained at about 0.1 mTorr to about 1000 Torr, preferably about 0.1 Torr to about 400 Torr, more preferably about 1 Torr to about 100 Torr, and even more preferably about 1 Torr to about 10 Torr.

[0075] The temperature of the reaction chamber can be controlled by controlling the temperature of the substrate holder or by controlling the temperature of the reactor walls. Devices used to heat the substrate are known in the art. The reactor walls are heated to a temperature sufficient to obtain the desired film at a sufficient growth rate and with the desired physical state and composition. Non-limiting exemplary temperature ranges to which the reactor walls can be heated include about 20°C to about 1000°C, preferably about 50°C to about 400°C. Alternatively, non-limiting exemplary temperatures to which the reactor walls can be heated include about 50°C or higher. When a thermal process is performed, the deposition temperature can range from about 20°C to about 800°C, preferably about 50°C to about 350°C, and more preferably about 100°C to about 300°C.

[0076] The disclosed PGM precursors and co-reactants can be introduced into the reactor either sequentially (ALD) or simultaneously (CVD). The reactor can be purged with an inert gas between the introduction of precursors and the introduction of co-reactants. Alternatively, the substrate can be moved from one region for precursor exposure to another region for co-reactant exposure (spatial ALD).

[0077] Depending on the specific process parameters, deposition can occur for various lengths of time. Generally, deposition can continue as long as desired or necessary to produce a film of the required thickness. Typical film thicknesses can vary from an atomic monolayer to hundreds of microns, preferably 0.5-100 nm, more preferably 1-50 nm, depending on the specific deposition process. The deposition process can also be performed as many times as necessary to obtain the desired film.

[0078] In one non-limiting exemplary ALD-type process, the vapor phase of the disclosed PGM-containing precursor is introduced into a reactor, where it is physically or chemically adsorbed onto the substrate. Excess composition can then be removed from the reactor by purging and / or evacuating the reactor. A desired gas (e.g., O) is introduced into the reactor, where it reacts with the physically or chemically adsorbed precursor in a self-limiting manner. Any excess reducing gas is removed from the reactor by purging and / or evacuating the reactor. If the desired film is a PGM-containing film, this two-step process can provide the desired film thickness, or it can be repeated until a film having the required thickness is obtained. Pt-containing films, nanodots, or islets formed by the disclosed PGM-containing precursors via a vapor deposition process include Pt, PtOx, PtRuy, PtRuyOz, PtTiyOz, etc. [Example]

[0079] Selected Embodiments and Examples Examples of M(L1)(L2)x include: ·Pt(dmpd)Me3, Pt(chd)Me3, Pt(Me2-chd)Me3, Pt(Me2-chd)EtMe2, Pt(pyr)Me3, Pd(dmpd)Me3, Pd(chd)Me3, Pd(Me2-chd)Me3, Pd(Me2-chd)EtMe2, Pd(pyr)Me3; ·Pt(dmpd)(NO), Pt(chd)(NO), Pt(Me2-chd)(NO), Pt(pyr)(NO), Pd(dmpd)(NO), Pd(chd)(NO), Pd(Me2-chd)(NO), Pd(pyr)(NO); ·Pt(dmpd)(iPr-amd), Pt(chd)(iPr-amd), Pt(Me2-chd)(iPr-amd), Pt(pyr)(iPr-amd) , Pd(dmpd)(iPr-amd), Pd(chd)(iPr-amd), Pd(Me2-chd)(iPr-amd), Pd(pyr)(iPr-amd); ·Pt(dmpd)(tmhd), Pt(chd)(tmhd), Pt(Me2-chd)(tmhd), Pt(pyr)(tmhd), Pd(dmpd)(tmhd), Pd(chd)(tmhd), Pd(Me2-chd)(tmhd), Pd(pyr)(tmhd); ·Pt(dmpd)(hfac), Pt(chd)(hfac), Pt(Me2-chd)(hfac), Pt(pyr)(hfac), Pd(dmpd)(hfac), Pd(chd)(hfac), Pd(Me2-chd)(hfac), and Pd(pyr)(hfac). 〇 "dmpd" = 2,4-dimethylpentadienyl

[0080] Example 1: Synthesis of Pt(2,4-dimethylpentadienyl)Me3 To a Schlenk flask containing [PtMe3I]4 (2.9 g, 2 mmol) in THF (20 mL) was added K(dmpd) (1.0 g, 8 mmol) dissolved in THF (10 mL). The reaction mixture was stirred at room temperature for 30 min. Evaporation of the volatiles gave an oily, viscous solid. After extraction with hexane (30 mL) to remove insoluble salts, the volatiles were removed under reduced pressure to give a brownish oily solid, which was purified by sublimation to give a pale yellow solid.

[0081] 1 H NMR (400 MHz, CD): 5.22 (s, 1H, CH on dmpd), 2.65 (br s, 2H, CHH on dmpd), 2.21 (t, 2H, J Pt-H = 15.7 Hz, CHH on dmpd), 1.8 (br, 3H, Pt-CH3), 1.73 (t, 6H, JPt-H = 4.5 Hz, CH3 on dmpd), 0.71 (br t, 6H, Pt-CH3).

[0082] Hypothetical Example of the Use of Pt(dmpd)Me3 (Deposition conditions) By using the Pt(dmpd)Me3 synthesized in this way in combination with H2O and / or O3 as reactive gases, platinum nanodots can be formed on a substrate by the ALD method under the following conditions.

[0083] A cylinder filled with Pt(dmpd)Me3 is heated to 90 °C and introduced into a reaction chamber by bubbling 100 sccm of N2 gas (Pulse A) and supplying H2 along with 50 sccm of N2 gas (Pulse B introduction into the reaction chamber is alternated with a 4-second purge step using 200 sccm of N2 as purge gas). At a pressure of approximately 20 torr, 12 cycles are performed on carbon powder with a substrate temperature of 150 °C in the ALD chamber. The result is platinum nanodots at 150 °C.

[0084] Examples of M(L3)(L4)x include: Pt(EtCp)(allyl), Pt(EtCp)(1-Me-allyl), Pt(EtCp(2-Me-allyl), Pd(EtCp)(allyl), Pd(EtCp)(1-Me-allyl), Pd(EtCp(2-Me-allyl), Pt(EtCp)(NO), Pd(EtCp)(NO), Pt(EtCp)(iPr-amd), Pd(EtCp)(iPr-amd), P(EtCp)(tmhd), Pd(EtCp)(thmd), P(EtCp)(hfac), and Pd(EtCp)(hfac).

[0085] Hypothetical Example of the Synthesis of Pt(EtCp)(Allyl) To a Schlenk flask containing [Pt(allyl)Cl]4 in THF, K(EtCp) dissolved in THF is added. The reaction mixture is stirred at room temperature for 30 minutes. Evaporation of the volatiles gives an oily solid. After extraction with hexane to remove insoluble salts, the volatiles are removed under reduced pressure to give an oil. This is purified by vacuum distillation to give a pale yellow liquid.

[0086] 1H NMR(400MHz,C6D6):5.75-5.60(m,4H,Cp-H),4.05-3.80(m,1H,CH on allyl),3.53(td,2H,J Pt-H = 29.7 Hz, CHH on the aryl), 2.35 (q, 2H, J H-H =7.5Hz,CH2CH3),2.04(td,2H,J Pt-H = 54.2Hz, CHH on aryl), 1.10(t, 3H, J H-H =7.5Hz,CH2CH3)

[0087] Hypothetical Example of the Use of Pt(EtCp)(Allyl) (Deposition conditions) By using the Pt(EtCp)(allyl) synthesized in this way in combination with H2O and / or O3 as reactive gases, platinum nanodots can be formed on a substrate by the ALD method under the following conditions.

[0088] A cylinder filled with Pt(EtCp)(allyl) was heated to 90 °C and introduced into a reaction chamber by bubbling 100 sccm of N2 gas (Pulse A) and supplying H2 along with 50 sccm of N2 gas (Pulse B introduction into the reaction chamber was alternated with a 4-second purge step using 200 sccm of N2 as purge gas). At a pressure of approximately 20 torr, 12 cycles were performed on carbon powder with a substrate temperature of 150 °C in the ALD chamber. The result was platinum nanodots at 150 °C.

[0089] Examples of M(L5)(L6)x include: Pt(allyl)(iPr-amd), Pt(allyl)(iPr2,Et-amd), Pt(allyl)(iPr2,nBu-amd), Pt(NO)(allyl), Pt(allyl)(hfac), Pt(allyl)(tmhd), Pd(allyl)(iPr-amd), Pd(allyl)(NO), Pd(allyl)(hfac), and Pd(allyl)(tmhd).

[0090] Hypothetical Example of the Use of Pt(allyl)(hfac) (Deposition conditions) By using Pt(allyl)(hfac) in combination with H2O and / or O3 as reactive gases, platinum nanodots can be formed on a substrate by ALD under the following conditions:

[0091] A cylinder filled with Pt(allyl)(hfac) was heated to 90 °C and introduced into a reaction chamber by bubbling with 100 sccm of N2 gas (Pulse A), followed by H2 gas supply with 50 sccm of N2 gas (Pulse B introduction into the reaction chamber was alternated with a 4-second purge step using 200 sccm of N2 as purge gas). Twelve cycles were performed on carbon powder with a substrate temperature of 150 °C in the ALD chamber at a pressure of approximately 20 torr. Platinum nanodots were obtained at 150 °C.

[0092] Synthesis of Pt(allyl)(iPr-amd) To a Schlenk flask containing N,N'-diisopropylcarbodiimide (0.51 g, 4.0 mmol) and 10 mL of THF, MeLi (1.0 M, 4.0 mL, 4.0 mmol) was added at room temperature, and the resulting mixture was stirred for 3 h to give a Li(iPr-amd) solution. To a separate Schlenk flask containing [Pt(allyl)Cl]4 (1.1 g, 1.0 mmol) in 10 mL of THF, the Li(iPr-amd) solution was added at room temperature, and the resulting mixture was stirred for 30 min to give a cloudy yellow solution. All volatiles were removed under reduced pressure to give a pale yellow solid, which was extracted with 10 mL of pentane. All volatiles were removed from the tan pentane solution under reduced pressure at room temperature to give a crude solid. The flask containing the crude solid was heated to 80 °C under dynamic vacuum (approximately 10 Pa), and a white solid was collected in a Schlenk flask cooled to -196 °C. The yield was 1.2 g (3.1 mmol, 77%). MP: 70-80°C (by DTA).

[0093] 1H NMR(C6D6,400MHz):3.8-3.6(m,3H,CHH'CHCHH' and CH2CHCH2),3.5-3.2(sept,2H, 3 J=6.2Hz,J Pt-H =83.6Hz,CHMe2),2.0-1.7(d,2H,3J=9.4Hz,J Pt-H =77.6Hz,CHH'CHCHH'),1.40(s,3H,Me on amd),1.10(d,6H,J=6.2Hz,CHMe2),0.98(d,6H,J=6.2Hz,CHMe2)

[0094] TG measurements were performed under the following conditions: sample weight: 27.81 mg, atmosphere: N2, 1 atm, heating rate: 10.0°C / min. The temperature at which 50% of the compound mass evaporated was 195°C. Vacuum TG measurements were performed under the following conditions: sample weight: 25.32 mg, atmosphere: N2, 20 mbar, heating rate: 10.0°C / min. TG measurements were performed under reactor supply conditions (approximately 20 mbar). The temperature at which 50% of the compound mass evaporated was 126°C. The results are shown in the chart in Figure 1.

[0095] Hypothetical Example of the Use of Pt(allyl) (iPr-amd) (Deposition conditions) Platinum nanodots can be formed on substrates by ALD using Pt(allyl)(iPr-amd) in combination with H2, O2, and / or O3 as reactive gases under the following conditions: Pt(allyl)(iPr-amd) vapor is introduced into a fluidized powder reactor at a flow rate of 2 sccm for 60 seconds, alternating with 40 seconds of H2 (30 sccm) and N2 gas (Pulse B). These precursor pulses are separated by a 60-second purge step using 30 sccm of N2 as the purge gas. Twelve cycles were performed on carbon powder at substrate temperatures ranging from 50 to 200 °C in an ALD chamber at approximately 20 torr pressure. Platinum nanodots are expected to be obtained at temperatures ranging from 50 to 300 °C.

[0096] Synthesis of Pt(allyl)(iPr2,Et-amd) To a Schlenk flask containing N,N'-diisopropylcarbodiimide (0.51 g, 4.0 mmol) and 10 mL of THF, EtLi (0.5 M, 8.0 mL, 4.0 mmol) was added at room temperature, and the resulting mixture was stirred for 3 h to give a Li(iPr2,Et-amd) solution. To a separate Schlenk flask containing [Pt(allyl)Cl]4 (1.1 g, 1.0 mmol) in 10 mL of THF, the Li(iPr2,Et-amd) solution was added at room temperature, and the resulting mixture was stirred for 1 h to give a cloudy orange-brown solution. All volatiles were removed under reduced pressure to give an ochre solid, which was extracted with a mixture of 10 mL of pentane and 10 mL of toluene. All volatiles were removed from the yellow solution under reduced pressure at room temperature to give a crude oil. The flask containing the crude oil was heated to 90°C under dynamic vacuum (approximately 10 Pa), and a pale yellow solid was collected in a Schlenk flask cooled to -196°C. The yield was 0.65 g (1.7 mmol, 42%). mp: 50-60°C (by DTA).

[0097] 1 H NMR(C6D6,400MHz):3.7-3.5(m,3H,CHH'CHCHH' and CH2CHCH2),3.6-3.2(sept,2H, 3 J=6.2Hz,J Pt-H =89.0Hz,CHMe2),1.95-1.7(m,4H,J Pt-H =77.6Hz,CH2CH3 and CHH'CHCHH'),1.11(d,6H,J=6.2Hz,CHMe2),0.99(d,6H,J=6.2Hz,CHMe2),0.95(t, 3 J=7.7Hz)

[0098] TG measurements were performed under the following conditions: sample weight: 25.10 mg, atmosphere: N2, 1 atm, heating rate: 10.0°C / min. The temperature at which 50% of the compound mass evaporated was 199°C. Vacuum TG measurements were performed under the following conditions: sample weight: 27.64 mg, atmosphere: N2, 20 mbar, heating rate: 10.0°C / min. TG measurements were performed under reactor supply conditions (approximately 20 mbar). The temperature at which 50% of the compound mass evaporated was 135°C. The results are shown in the chart in Figure 2.

[0099] Hypothetical Example of the Use of Pt(allyl) (iPr2,Et-amd) (Deposition conditions) Platinum nanodots can be formed on substrates by ALD using Pt(allyl)(iPr2,Et-amd) in combination with H2, O2, and / or O3 as reactive gases under the following conditions: Pt(allyl)(iPr2,Et-amd) vapor is introduced into a fluidized powder reactor at a flow rate of 2 sccm for 60 seconds, alternating with 40 seconds of H2 (30 sccm) and N2 gas (Pulse B). These precursor pulses are separated by a 60-second purge step using 30 sccm of N2 as the purge gas. Twelve cycles were performed on carbon powder at substrate temperatures ranging from 50 to 200 °C in an ALD chamber at approximately 20 torr pressure. Platinum nanodots are expected to be obtained at temperatures ranging from 50 to 300 °C.

[0100] Synthesis of Pt(allyl)(iPr2,nBu-amd) To a Schlenk flask containing N,N'-diisopropylcarbodiimide (0.51 g, 4.0 mmol) and 10 mL of THF, nBuLi (1.6 M, 2.5 mL, 4.0 mmol) was added at room temperature, and the resulting mixture was stirred for 3 h to give a Li(iPr2,nBu-amd) solution. To a separate Schlenk flask containing [Pt(allyl)Cl]4 (1.1 g, 1.0 mmol) in 10 mL of THF, the Li(iPr2,nBu-amd) solution was added at room temperature, and the resulting mixture was stirred for 30 min to give a cloudy brown solution. All volatiles were removed under reduced pressure to give a brown oil, which was extracted with 10 mL of pentane. All volatiles were removed from the brown solution under reduced pressure at room temperature to give a crude oil. The flask containing the crude oil was heated to 90 °C under dynamic vacuum (approximately 10 Pa), and a pale yellow liquid was collected in a Schlenk flask cooled to -196 °C. The yield was 1.38 g (3.3 mmol, 82%). mp: below room temperature.

[0101] 1 H NMR(C6D6,400MHz):3.7-3.5(m,3H,CHH'CHCHH' and CH2CHCH2),3.6-3.3(sept,2H, 3 J=6.2Hz,J Pt-H =90.1Hz,CHMe2),1.98-1.7(m,4H,CH2CH2CH2CH3 and CHH'CHCHH'),1.5-1.4(m,2H,CH2CH2CH2CH3),1 .3-1.2(m,2H,CH2CH2CH2CH3),1.13(d,6H,J=6.2Hz,CHMe2),1.00(d,6H,J=6.2Hz,CHMe2),0.80(t, 3 J=7.3Hz, CH2CH2CH2CH3)

[0102] TG measurements were performed under the following conditions: sample weight: 25.85 mg, atmosphere: N2, 1 atm, heating rate: 10.0°C / min. The temperature at which 50% of the compound mass evaporated was 205°C. Vacuum TG measurements were performed under the following conditions: sample weight: 26.53 mg, atmosphere: N2, 20 mbar, heating rate: 10.0°C / min. TG measurements were performed under reactor supply conditions (approximately 20 mbar). The temperature at which 50% of the compound mass evaporated was 146°C. The results are shown in the chart in Figure 3.

[0103] Hypothetical Example of the Use of Pt(allyl)(iPr2,nBu-amd) (Deposition conditions) Platinum nanodots can be formed on substrates by ALD using Pt(allyl)(iPr2,nBu-amd) in combination with H2, O2, and / or O3 as reactive gases. Pt(allyl)(iPr2,nBu-amd) vapor is introduced into a fluidized powder reactor at a flow rate of 2 sccm for 60 seconds, alternating with 40 seconds of H2 (30 sccm) and N2 gas (Pulse B). These precursor pulses are separated by a 60-second purge step using 30 sccm of N2 as the purge gas. Twelve cycles were performed on carbon powder at substrate temperatures ranging from 50 to 200 °C in an ALD chamber at approximately 20 torr pressure. Platinum nanodots are expected to be obtained at temperatures ranging from 50 to 300 °C.

[0104] Synthesis of Pt(allyl)(tBu,Et,Me-amd) To a Schlenk flask containing 1-tert-butyl-3-ethylcarbodiimide (0.51 g, 4.0 mmol) and 10 mL of THF, MeLi (1.0 M, 4.0 mL, 4.0 mmol) was added at room temperature, and the resulting mixture was stirred for 3 h to give a Li(tBu,Et,Me-amd) solution. To a separate Schlenk flask containing [Pt(allyl)Cl]4 (1.1 g, 1.0 mmol) in 10 mL of THF, Li(iPr-amd) solution was added at room temperature, and the resulting mixture was stirred for 30 min to give a cloudy brown solution. All volatiles were removed under reduced pressure to give a brown oil, which was extracted with a mixture of 10 mL of pentane and 10 mL of toluene. All volatiles were removed from the yellow solution under reduced pressure at room temperature to give a crude solid. The flask containing the crude solid was heated to 80°C under dynamic vacuum (approximately 10 Pa), and a pale yellow solid was collected in a Schlenk flask cooled to -196°C. The yield was 0.80 g (2.0 mmol, 50%). mp: 70-80°C (by DTA).

[0105] 1 H NMR(C6D6,400MHz):3.8-3.6(m,1H,CH2CHCH2),3.6-3.5(m,2H,CHH'CHCHH'),3.2-2.9(m,2H,CH2CH3),2.0-1.7(m,2H,J Pt-H =79.5Hz,CHH'CHCHH'),1.48(s,3H,CH3 on amd),1.25(s,9H,C(CH3)3),1.08(t, 3 J=7.1Hz, CH2CH3)

[0106] TG measurements were performed under the following conditions: sample weight: 25.76 mg, atmosphere: N2, 1 atm, heating rate: 10.0°C / min. The temperature at which 50% of the compound mass evaporated was 194°C. Vacuum TG measurements were performed under the following conditions: sample weight: 24.93 mg, atmosphere: N2, 20 mbar, heating rate: 10.0°C / min. TG measurements were performed under reactor supply conditions (approximately 20 mbar). The temperature at which 50% of the compound mass evaporated was 135°C. The results are shown in the chart in Figure 4.

[0107] Hypothetical Example of the Use of Pt(allyl)(tBu,Et,Me-amd) (Deposition conditions) Platinum nanodots can be formed on substrates by ALD using Pt(allyl)(tBu,Et,Me-amd) in combination with H2, O2, and / or O3 as reactive gases under the following conditions: Pt(allyl)(tBu,Et,Me-amd) vapor is introduced into a fluidized powder reactor at a flow rate of 2 sccm for 60 seconds, alternating with 40 seconds of H2 (30 sccm) and N2 gas (Pulse B). These precursor pulses are separated by a 60-second purge step using 30 sccm N2 as the purge gas. Twelve cycles were performed on carbon powder at substrate temperatures ranging from 50 to 200 °C in an ALD chamber at approximately 20 torr pressure. Platinum nanodots are expected to be obtained at temperatures ranging from 50 to 300 °C.

Claims

1. Formula M(L5)(L6)x ３ wherein M represents platinum, L5 is an allyl ligand, L6 is an amidinate ligand, x 3 represents the number of L6 ligands, and x ３ A chemical substance represented by the structure of [Chemical Formula 1] below, wherein: 【Chemistry 1】 ([Chemical formula 1], R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , and R ８ are each independently H; C １ ~C ６ a linear, branched, or cyclic alkyl group of the formula C １ ~C ６ a branched or cyclic alkylsilyl group (mono-, bis-, or tris-alkyl) of the formula: １ ~C ６ a linear, branched, or cyclic alkylamino group of the formula: １ ~C ６ (selected from linear, branched, or cyclic fluoroalkyl groups such as

2. Pt(allyl) (iPr-amd) in which R 1 and R 2 are H and R 3 is isopropyl, Pt(allyl) (iPr) in which R 1 and R 2 are isopropyl and R 3 is ethyl ２ , Et-amd), Pt(allyl) (iPr) where R 1 and R 2 are isopropyl and R 3 is n-butyl; ２ 10. The chemical entity of claim 1 having a formula selected from Pt(allyl)(tBu,Et,Me-amd) where R 1 is tert-butyl, R 2 is ethyl, and R 3 is methyl.

3. A composition comprising one or more chemical entities according to claim 1 or 2.

4. 10. A method for depositing films, islets, or nanodots comprising platinum group metals, comprising the steps of: a) providing a gas or vapor phase comprising one or more chemicals according to claim 1 or 2; and b) depositing the film, islet, or nanodot on a substrate; A method comprising:

5. The method of claim 4 , comprising depositing the film, islet, or nanodot by atomic layer deposition or chemical vapor deposition.

6. The method of claim 4 , comprising depositing the film, islet, or nanodot by atomic layer deposition.

7. The method of claim 4, wherein the deposition temperature is between 0°C and 600°C.

8. The method of claim 4 , wherein the substrate is a cathode or a cathode active material.

9. The method of claim 8 , wherein the substrate is a cathode active material.

10. 9. The method of claim 8, wherein the cathode active material, or the cathode active material within the cathode, is selected from the group consisting of: a) layered oxides; b) spinel-type cathode materials; c) olivine-structured cathode materials; and combinations thereof.

11. The method described in claim 4, further comprising the step of providing an oxidizing co-reactant, an oxygen-containing silicon precursor, an oxygen-containing tin precursor, a phosphate, or a sulfate simultaneously with step a).

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