Compounds and methods for selectively forming metal-containing films - Patents.com

Abstract

Compounds for selectively forming metal-containing films are provided. Methods for forming metal-containing films are also provided. The methods include, for example, forming a blocking layer on a first substrate surface by a first deposition process and forming the metal-containing film on a second substrate surface by a second deposition process.

Description

Detailed Description of the Invention

[0001] Field of the Invention The present technology relates generally to compounds and deposition methods, and more particularly to compounds and methods for selective metal-containing film growth on substrate surfaces.

[0002] 〔background〕 Thin films, especially metal-containing thin films, have a variety of important applications, such as in nanotechnology and semiconductor device manufacturing. Examples of such applications include high refractive index optical coatings, anticorrosion coatings, photocatalytic self-cleaning glass coatings, biocompatible coatings, dielectric capacitor layers and gate dielectric insulating films in field effect transistors (FETs), capacitor electrodes, gate electrodes, adhesive diffusion barriers, and integrated circuits. Metal and dielectric thin films are also used in microelectronic applications, such as high-κ dielectric oxides for dynamic random access memory (DRAM) applications, and ferroelectric perovskites used in infrared detectors and non-volatile ferroelectric random access memory (NV-FeRAM).

[0003] A variety of precursors can be used to form metal-containing thin films, and a variety of deposition techniques can be used. Such techniques include reactive sputtering, ion-assisted deposition, sol-gel deposition, chemical vapor deposition (CVD) (also known as metal-organic CVD or MOCVD), and atomic layer deposition (ALD) (also known as atomic layer epitaxy). CVD and ALD processes are increasingly being used because they have the advantages of enhanced compositional control, high film uniformity, and effective control of doping.

[0004] CVD is a chemical process in which precursors are used to form a thin film on a substrate surface. In a typical CVD process, precursors are passed over the surface of a substrate (e.g., a wafer) in a reaction chamber at low or atmospheric pressure. The precursors react and / or decompose on the substrate surface to produce a thin film of the deposited material. Volatile by-products are removed by gas flow through the reaction chamber. The thickness of the deposited film can be difficult to control because it depends on the adjustment of many parameters, such as temperature, pressure, volume and uniformity of the gas flow, chemical depletion effects, and time.

[0005] ALD is also a method for the deposition of thin films. ALD is a self-limiting, sequential, unique film growth technique based on surface reactions that provides precise thickness control and allows the deposition of conformal thin films of materials provided by precursors onto surfaces of various compositions. In ALD, the precursors are separated during the reaction. The first precursor is passed over the substrate surface and produces a monolayer on the substrate surface. Any excess unreacted precursor is vented from the reaction chamber. Then, the second precursor is passed over the substrate surface and reacts with the first precursor, forming a second monolayer of film on the first formed monolayer of film on the substrate surface. The cycle is repeated to produce a film of the desired thickness.

[0006] However, with the continued reduction in size of microelectronic components, such as semiconductor devices, several technical challenges remain, thereby increasing the need for improved thin film technology. In particular, microelectronic components may include patterning, for example, to form conductive paths or to form interconnects. Typically, patterning is achieved through etching and lithography techniques, but such techniques can become challenging as the demand for patterning complexity increases. Thus, there is significant interest in developing compounds and thin film deposition methods that can selectively grow films on one or more substrates and achieve improved patterning on the substrate.

[0007] 〔overview〕 According to one embodiment, a compound for selectively forming a metal-containing film is provided, the compound having the structural formula I

[0008] [ka]

[0009] (In the formula, R 1 and R 2 are C1 to C 20 X may be alkyl, each of which may be optionally substituted with one or more of a trifluoromethyl group, a hydroxyl group, a nitrile group, an alkoxy group, and an amino group. 1 can be O or S, and X 2 is R 3 , N.R. 4 R 5 , -SR 6 , and -OR 7 where R 3 , R 4 , R 5 , R 6 , and R 7 are C1 to C 20 alkyl, each of which may be optionally substituted with one or more of trifluoromethyl, hydroxyl, nitrile, alkoxy, and amino groups.

[0010] According to another aspect, a method of forming a metal-containing film is provided. The method includes forming a blocking layer on a first substrate surface by a first deposition process and forming a metal-containing film on a second substrate surface by a second deposition process. The first deposition process includes vaporizing a compound corresponding to structural formula (I) described herein. The second deposition process includes vaporizing at least one metal complex. The first substrate surface can include a metal material and the second substrate surface can include a dielectric material or a metal oxide.

[0011] According to another aspect, another method of forming a metal-containing film is provided. The method includes forming a blocking layer on a first portion of a substrate by a first deposition process and forming a metal-containing film on a second portion of the substrate by a second deposition process. The first deposition process includes exposing the substrate to a compound corresponding to structural formula (I) described herein. The second deposition process includes exposing the substrate to at least one metal complex. The first portion of the substrate can include a metal material and the second portion of the substrate can include a dielectric material or a metal oxide.

[0012] According to another aspect, another method of forming a metal-containing film is provided. The method includes forming a blocking layer on a surface of a first substrate by a first deposition process. The first deposition process comprises depositing a metal-containing film having the formula II

[0013] [ka]

[0014] (In the formula, X 3 is R 8 , N.R. 9 R 10 , -SR 11 , and -OR 12 R 8 , R 9 , R 10 , R 11 , and R 12 are C1 to C 20 alkyl, each of which may be optionally substituted with one or more of trifluoromethyl, hydroxyl, nitrile, alkoxy, and amino groups; X 4 The method further includes forming a metal-containing film on the second substrate surface by a second deposition process. The second deposition process includes vaporizing at least one metal complex. The first substrate surface may include a metallic material and the second substrate surface may include a dielectric material or a metal oxide.

[0015] According to another aspect, another method of forming a metal-containing film is provided. The method includes forming a blocking layer on a first portion of a substrate by a first deposition process. The first deposition process comprises depositing a metal-containing film having the formula II

[0016] [ka]

[0017] (In the formula, X 3 is R 8 , N.R. 9 R 10 , -SR 11 , and -OR 12 may be selected from the group consisting of do. R 8 , R 9 , R 10 , R 11 , and R 12 are independent of each other, C1~C 20 alkyl, each of which may be optionally substituted with one or more of trifluoromethyl, hydroxyl, nitrile, alkoxy, and amino groups; X 4 The method further includes forming a metal-containing film on a second portion of the substrate by a second deposition process. The second deposition process includes exposing the substrate to at least one metal complex. The first portion of the substrate can include a metal material and the second portion of the substrate can include a dielectric material or a metal oxide.

[0018] Other embodiments, including particular aspects of the embodiments summarized above, will become apparent from the following detailed description.

[0019] BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1A shows details of a blocking layer and a metal-containing film according to certain embodiments of the present disclosure.

[0020] FIG. 1B shows details of a blocking layer and a metal-containing film according to a particular alternative embodiment of the present disclosure.

[0021] FIG. 2 shows X-ray photoelectron spectroscopy (XPS) analysis of SiO2, W, Co, and Cu substrates after exposure to N-dodecyl-N-methylcarbamodithioic acid.

[0022] FIG. 3A shows the atomic percentage of Hf present on SiO, W, Co, and Cu substrates after exposure to N-dodecyl-N-methylcarbamodithioic acid and (MeCp)Hf(OMe)(Me).

[0023] FIG. 3B shows the atomic percentage of Hf present on SiO, W, Co, and Cu substrates after exposure to (MeCp)Hf(OMe)(Me) but not to N-dodecyl-N-methylcarbamodithioic acid.

[0024] 4A-4D provide scanning electron microscope (SEM) images of SiO, W, Co, and Cu substrates, respectively, after exposure to N-dodecyl-N-methylcarbamodithioic acid and (MeCp)Hf(OMe)(Me).

[0025] FIG. 5A is a graphical representation of thermogravimetric analysis (TGA) data showing the % weight loss versus temperature for N-dodecyl-N-methylcarbamodithioic acid N-dodecyl-N-methylammonium salt (Compound I).

[0026] FIG. 5B is a graphical representation of a differential scanning calorimetry (DSC) analysis of Compound I.

[0027] FIG. 6A shows the structure of Compound I. 1 H nuclear magnetic resonance ( 1 1 H NMR spectrum is shown.

[0028] FIG. 6B shows the structure of Compound I. 13 The C NMR spectrum is shown.

[0029] FIG. 7 shows the infrared (IR) spectrum of Compound I.

[0030] FIG. 8 shows the single crystal X-ray structure of Compound I.

[0031] Detailed Description Before presenting some exemplary embodiments of the present technology, it should be understood that the present technology is not limited to the details of the configuration or process steps described in the following presentation. The present technology is capable of other embodiments and can be practiced or carried out in various ways. It should also be understood that metal complexes and other chemical compounds may be described herein using structural formulas having specific stereochemistry. These descriptions are intended as examples only and should not be construed as limiting the disclosed structures to a specific stereochemistry. Rather, the described structures are intended to encompass all metal complexes and chemical compounds having the indicated chemical formulas.

[0032] Applicants have discovered compounds and methods of deposition that can selectively form metal-containing films. In particular, the compounds and methods described herein can form a blocking layer on a first substrate surface or a first portion of the surface by a first deposition process, and a metal-containing film on a second substrate surface or a second portion of the surface by a second deposition process. It has been discovered that a blocking layer can be deposited on a metal-containing substrate, and the blocking layer can substantially block or inhibit the growth of a metal-containing film on the blocking layer while allowing deposition of the metal-containing film on a dielectric material-containing substrate and / or a metal oxide-containing substrate. Advantageously, the methods described herein can allow selective deposition of a dielectric on a dielectric. Additionally, the methods described herein can allow delivery of the blocking layer via a vapor phase process, and can use the same equipment as that utilized for delivery of the metal complex. Also, delivery of the blocking layer can be achieved at lower temperature sources, e.g., below 150°C.

[0033] [I. Definition] For purposes of this invention and the claims, the numbering scheme for the Periodic Table Groups follows the IUPAC Periodic Table of the Elements.

[0034] The term "and / or" as used herein in phrases such as "A and / or B" is intended to include "A and B," "A or B," "A," and "B."

[0035] The terms "substituents," "radicals," "groups," and "moieties" may be used interchangeably.

[0036] As used herein, the terms "metal-containing complex" (or, more simply, "complex") and "precursor" are used interchangeably and refer to metal-containing molecules or compounds that can be used to prepare metal-containing films, for example, by vapor deposition methods such as ALD or CVD. The metal-containing complex may be deposited, adsorbed, decomposed, delivered and / or passed onto a substrate or surface thereof to form the metal-containing film.

[0037] As used herein, the term "metal-containing film" includes elemental metal films, as more fully defined below, as well as films that include metals with one or more elements, such as metal oxide films, metal nitride films, metal silicide films, metal carbide films, etc. As used herein, the terms "elemental metal film" and "pure metal film" are used interchangeably and refer to a film that is made of pure metal or is substantially made of pure metal. For example, an elemental metal film may include a metal with 100% purity, or an elemental metal film may include a metal with one or more impurities with a purity of at least about 70%, at least about 80%, at least about 90%, at least about 95%, at least about 96%, at least about 97%, at least about 98%, at least about 99%, at least about 99.9%, or at least about 99.99%. Unless the context indicates otherwise, the term "metal film" shall be interpreted to mean an elemental metal film.

[0038] As used herein, the term "vapor deposition process" is used to refer to any type of vapor deposition technique, including, but not limited to, CVD and ALD. In various embodiments, CVD can take the form of conventional (i.e., continuous flow) CVD, liquid injection CVD, or photoassisted CVD. CVD can also take the form of a pulsed technique, i.e., pulsed CVD. ALD is used to form a metal-containing film by vaporizing and / or passing at least one metal complex disclosed herein onto a substrate surface. For conventional ALD processes, see, for example, George SM, et al. J. Phys. Chem., 1996, 100, 13121-13131. In other embodiments, ALD can take the form of conventional (i.e., pulsed injection) ALD, liquid injection ALD, photoassisted ALD, plasma-assisted ALD, or plasma-enhanced ALD. The term "vapor deposition processing" further includes various vapor deposition techniques described in Chemical Vapour Deposition: Precursors, Processes, and Applications; Jones, AC; Hitchman, ML, Eds. The Royal Society of Chemistry: Cambridge, 2009; Chapter 1, pp 1-36.

[0039] As used herein, the terms "selective growth," "selectively grown," and "selectively grown" are used synonymously and refer to film growth on a portion of a second substrate surface (or second portion of the substrate) and substantially no film growth on a first substrate surface (or first portion of the substrate), a blocking layer, or a combination thereof. The terms "selective growth," "selectively grown," and "selectively grown" also encompass film growth over at least a portion of a second substrate surface (or second portion of the substrate) compared to film growth on a first substrate surface (or first portion of the substrate), a blocking layer, or a combination thereof. In the context of multiple substrates, the terms "selective growth," "selectively grown," and "selectively grown" encompass not only the growth of a film on a first substrate and substantially no growth of a film on a second substrate (or a third substrate, or a fourth substrate or a fifth substrate, etc.), but also the growth of a film on the first substrate relative to a film on the second substrate (or a third substrate, or a fourth substrate or a fifth substrate, etc.).

[0040] The term "alkyl" (used alone or in combination with another term) refers to a saturated hydrocarbon chain of 1 to about 25 carbon atoms in length, including, but not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, and the like. The alkyl group may be straight or branched chain. "Alkyl" is intended to encompass all structural isomeric forms of alkyl groups. For example, as used herein, propyl encompasses both n-propyl and isopropyl; butyl encompasses n-butyl, sec-butyl, isobutyl, and tert-butyl; pentyl encompasses n-pentyl, tert-pentyl, neopentyl, isopentyl, sec-pentyl, and 3-pentyl. Additionally, as used herein, "Me" refers to methyl, "Et" refers to ethyl, "Pr" refers to propyl, "i-Pr" refers to isopropyl, "Bu" refers to butyl, "t-Bu" refers to tert-butyl, and "Np" refers to neopentyl. In some embodiments, the alkyl group is a C1-C5 or C1-C4 alkyl group.

[0041] The term "alkoxy" refers to an -O-alkyl containing 1 to about 8 carbon atoms. The alkoxy may be straight or branched chain. Non-limiting examples include methoxy, ethoxy, propoxy, butoxy, isobutoxy, tert-butoxy, pentoxy, and hexoxy.

[0042] As used herein, the term "amino" refers to an optionally substituted monovalent nitrogen atom (i.e., -NR c R d , where R c and R d may be the same or different). For example, R C and R d Regarding each, C1~C 10 Examples of amino groups encompassed by the present invention include, but are not limited to, the following:

[0043] [ka]

[0044] II. Compounds for forming blocking layer According to various embodiments, a compound of formula I

[0045] [ka]

[0046] (In the formula, R 1 and R 2 are C1 to C 20 alkyl, each of which is optionally substituted with one or more of trifluoromethyl, hydroxyl, nitrile, alkoxy, and amino groups; X 1 is O or S; X 2 is R 3 , N.R. 4 R 5 , -SR 6 , and -OR 7 wherein R 3 , R 4 , R 5 , R 6 , and R 7 are C1 to C 20 alkyl, each of which may be optionally substituted with one or more of a trifluoromethyl group, a hydroxyl group, a nitrile group, an alkoxy group, and an amino group, are provided.

[0047] In some embodiments, X 2 is R 3 where R 3 is C1~C 20 It can be an alkyl group and can be optionally substituted with one or more of a trifluoromethyl group, a hydroxyl group, a nitrile group, an alkoxy group, and an amino group.

[0048] In some embodiments, X 2 is NR 4 R5 where R 4 and R 5 are C1 to C 20 It can be an alkyl group and can be optionally substituted with one or more of a trifluoromethyl group, a hydroxyl group, a nitrile group, an alkoxy group, and an amino group.

[0049] In some embodiments, X 2 Ha-SR 6 where R 6 is C1~C 20 It can be an alkyl group and can be optionally substituted with one or more of a trifluoromethyl group, a hydroxyl group, a nitrile group, an alkoxy group, and an amino group.

[0050] In some embodiments, X 2 -OR 7 where R 7 is C1~C 20 It can be an alkyl group and can be optionally substituted with one or more of a trifluoromethyl group, a hydroxyl group, a nitrile group, an alkoxy group, and an amino group.

[0051] In any of the above-described embodiments, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are independent of each other, C1~C 20 Alkyl, C1-C 15 Alkyl, C1-C 12 Alkyl, C1-C 10 In some embodiments, R may be alkyl, C1-C8 alkyl, C1-C4 alkyl, or C1-C2 alkyl, each of which may be optionally substituted with one or more of a trifluoromethyl group, a hydroxyl group, a nitrile group, an alkoxy group, and an amino group. 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R7 One or more (e.g., two, three, four, five, six, or all) of R may be a methyl group. 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 One or more (e.g., two, three, four, five, six, or all) of the alkyl groups may be dodecyl groups. The alkyl groups may be straight-chain or branched-chain. In particular, the alkyl groups are straight-chain.

[0052] In some embodiments, X 1 can be S, and X 2 is NR 4 R 5 where R 4 is C1~C 15 Alkyl or C1-C 12 may be alkyl, R 5 can be C1-C4 alkyl or C1-C2 alkyl, where R 4 and R 5 may each be optionally substituted with one or more of a trifluoromethyl group, a hydroxyl group, a nitrile group, an alkoxy group, and an amino group. Additionally or alternatively, R 1 is C1~C 15 Alkyl or C1-C 12 may be alkyl, R 2 can be C1-C4 alkyl or C1-C2 alkyl, where R 1 and R 2 each may be optionally substituted with one or more of trifluoromethyl groups, hydroxyl groups, nitrile groups, alkoxy groups, and amino groups.

[0053] In any embodiment, the compound corresponding to structural formula (I) can be described as an addition complex or a salt complex.

[0054] In some embodiments, the compound corresponding to structural formula (I) is N-dodecyl-N-methylcarbamodithioic acid N-dodecyl-N-methylammonium salt (Compound I).

[0055] III. METHOD FOR FORMING METAL-CONTAINING FILMS Provided herein is a method of forming a metal-containing film, e.g., a selectively grown metal-containing film. In various embodiments, as shown in FIG. 1A, the method may include forming a blocking layer 20 on a first substrate surface 15 by a first deposition process. The method may further include forming a metal-containing film 23 on a second substrate surface 17 by a second deposition process. As shown in FIG. 1A, the first substrate surface 15 and the second substrate surface 17 may be present on a single substrate 19, i.e., the same substrate. For example, when a single substrate 19 is used, the first substrate surface 15 may be considered as a first portion 15 of the substrate 19, and the second substrate surface 17 may be considered as a second portion 17 of the substrate 19. Alternatively, as shown in FIG. 1B, the first substrate surface 15 and the second substrate surface 17 may be present on different substrates, e.g., a first substrate 25 and a second substrate 30, respectively.

[0056] The first substrate surface 15 (or first portion 15) may include a metallic material. Examples of suitable metallic materials include, but are not limited to, tungsten (W), cobalt (Co), copper (Cu), and combinations thereof. In some embodiments, the metallic material may include Co, Cu, or combinations thereof. In certain embodiments, the metallic material may include Cu. The second substrate surface 17 (or second portion 17) may include a dielectric material, a metal oxide material, or combinations thereof. The dielectric material may be a low-κ dielectric or a high-κ dielectric. Examples of suitable dielectric materials include, but are not limited to, SiO2, SiN, and combinations thereof. Examples of suitable metal oxide materials include, but are not limited to, HfO2, ZrO2, SiO2, Al2O3, and combinations thereof.

[0057] In any embodiment, the first deposition process may include exposing a substrate (e.g., first substrate surface 15, second substrate surface 17, substrate 19, first substrate 25, second substrate 30) to a compound corresponding to structural formula I and / or a compound of formula II described herein.

[0058] [ka]

[0059] (In the formula, X 3 is R 8 , N.R. 9 R 10 , -SR 11 , and -OR 12 where R 8 , R 9 , R 10 , R 11 , and R 12 are C1 to C 20 alkyl, each of which may be optionally substituted with one or more of trifluoromethyl, hydroxyl, nitrile, alkoxy, and amino groups; X 4 can be O or S).

[0060] In some embodiments, X 3 is R 8 where R 8 is C1~C 20 It can be an alkyl group and can be optionally substituted with one or more of a trifluoromethyl group, a hydroxyl group, a nitrile group, an alkoxy group, and an amino group.

[0061] In some embodiments, X 3 is NR 9 R 10 where R 9 and R 10 are C1 to C 20 It can be an alkyl group and can be optionally substituted with one or more of a trifluoromethyl group, a hydroxyl group, a nitrile group, an alkoxy group, and an amino group.

[0062] In some embodiments, X 3 Ha-SR 11 where R 11 is C1~C 20 It can be an alkyl group and can be optionally substituted with one or more of a trifluoromethyl group, a hydroxyl group, a nitrile group, an alkoxy group, and an amino group.

[0063] In some embodiments, X 3 -OR 12 where R 12 is C1~C 20 It can be an alkyl group and can be optionally substituted with one or more of a trifluoromethyl group, a hydroxyl group, a nitrile group, an alkoxy group, and an amino group.

[0064] In any of the above-described embodiments, R 8 , R 9 , R 10 , R 11 , and R 12 are independent of each other, C1~C 20 Alkyl, C1-C 15 Alkyl, C1-C 10 In some embodiments, R may be alkyl, C1-C8 alkyl, C1-C4 alkyl, or C1-C2 alkyl, each of which may be optionally substituted with one or more of a trifluoromethyl group, a hydroxyl group, a nitrile group, an alkoxy group, and an amino group. 8 , R 9 , R 10 , R 11 , and R 12 One or more (e.g., two, three, four, or all) of the may be a methyl group. The alkyl group may be straight-chain or branched-chain. In particular, the alkyl is straight-chain.

[0065] In some embodiments, X 3 is NR 9 R 10 X 4 can be S, where R 9can be C1-C4 alkyl or C1-C2 alkyl, R 10 is C1~C 15 Alkyl or C1-C 12 may be alkyl, R 9 and R 10 is optionally substituted with one or more of a trifluoromethyl group, a hydroxyl group, a nitrile group, an alkoxy group, and an amino group.

[0066] In some embodiments, the compound corresponding to structural formula (II) is N-dodecyl-N-methylcarbamodithioic acid (Compound II).

[0067] In any embodiment, the compound corresponding to structural formula (I), the compound corresponding to structural formula (II), or both, can be delivered or exposed to a substrate (e.g., first substrate surface 15, second substrate surface 17, substrate 19, first substrate 25, second substrate 30) at a lower temperature. For example, such temperatures can be about 175°C or less, about 150°C or less, about 140°C or less, about 130°C or less, about 120°C or less, about 110°C or less, or about 100°C; about 100°C to about 175°C, about 100°C to about 150°C, or about 100°C to about 130°C.

[0068] In any embodiment, the second deposition treatment can include exposing a substrate (e.g., first substrate surface 15, second substrate surface 17, substrate 19, first substrate 25, second substrate 30) to at least one metal complex.

[0069] The metal complexes may include a suitable metal center, or more preferably a ligand. Examples of suitable metal centers include, but are not limited to, titanium (Ti), zirconium (Zr) and hafnium (Hf). Examples of suitable ligands include C1-C 10 Alkyl groups, C1-C 10 Alkoxy groups, optionally one or more C1-C 10Examples of suitable ligands include, but are not limited to, cyclopentadienyl groups (Cp) substituted with alkyl groups, and combinations thereof. For example, each ligand can independently be a methyl group, an ethyl group, a propyl group, a butyl group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a Cp group, a methyl-substituted Cp (MeCp) group, an ethyl-substituted Cp (EtCp) group, and combinations thereof.

[0070] In some embodiments, the metal complex has formula III

[0071] [ka]

[0072] (wherein M can be Ti, Zr or Hf, in particular Hf; L 1 , L 2 , L 3 and L 4 may each independently be selected from a C1-C8 alkyl group, a C1-C8 alkoxy group, and a Cp group optionally substituted with at least one C1-C8 alkyl group. 1 , L 2 , L 3 and L 4 may all correspond to the same

[0073] In some embodiments, M can be Hf, and L 1 , L 2 , L 3 and L 4 may each be independently selected from the group consisting of a C1-C4 alkyl group, a C1-C4 alkoxy group, and a Cp group optionally substituted with at least one C1-C4 alkyl group.

[0074] In some embodiments, M can be Hf, and L 1 , L 2 , L 3 and L 4may each independently be selected from the group consisting of a C1-C2 alkyl group, a C1-C2 alkoxy group, and a Cp group optionally substituted with at least one C1-C2 alkyl group.

[0075] In some embodiments, the metal complex can be (MeCp)2Hf(OMe)(Me).

[0076] Advantageously, the metal of the metal-containing film may be present on the blocking layer in a small amount or may be substantially absent, for example, the metal of the metal-containing film may be present on the blocking layer in an amount of about 25 atomic % or less, about 20 atomic % or less, about 15 atomic % or less, about 10 atomic % or less, about 5 atomic % or less, about 1 atomic % or less, about 0.5 atomic % or less, or about 0 atomic %, or between about 0 atomic % and about 25 atomic %, between about 0.5 atomic % and about 25 atomic %, between about 0.5 atomic % and about 20 atomic %, between about 0.5 atomic % and about 15 atomic %, between about 0.5 atomic % and about 10 atomic %, or between about 1 atomic % and about 5 atomic %.

[0077] Additionally or alternatively, the blocking layer may be present in small amounts or may be substantially absent on the second substrate surface (or the second portion of the substrate with a selectivity of 100:1).

[0078] In any embodiment, the substrate can be exposed to a compound corresponding to structural formula (I), a compound corresponding to structural formula (II), a metal complex described herein, or a combination thereof, by any suitable deposition technique. For example, the first deposition process can include vaporizing a compound corresponding to structural formula (I), a compound corresponding to structural formula (II), or both. Alternatively, the substrate can be immersed or submerged in a solution containing a compound corresponding to structural formula (I), a compound corresponding to structural formula (II), or both. Additionally or alternatively, the second deposition process can include vaporizing at least one metal complex described herein.

[0079] For example, this can include: (1) vaporizing a compound corresponding to structural formula (I), vaporizing a compound corresponding to structural formula (II), vaporizing at least one metal complex (e.g., one corresponding to structural formula (III)), or a combination thereof; and (2) delivering a compound corresponding to structural formula (I), delivering a compound corresponding to structural formula (II), at least one metal complex (e.g., one corresponding to structural formula (III)) to a substrate surface (e.g., first substrate surface 15, second substrate surface 17, substrate 19, first substrate 25, second substrate 30). or a combination thereof, or passing a compound corresponding to structural formula (I), passing a compound corresponding to structural formula (II), passing at least one metal complex (e.g., one corresponding to structural formula (III)) over the substrate, or a combination thereof (and / or decomposing a compound corresponding to structural formula (I), decomposing a compound corresponding to structural formula (II), and / or decomposing at least one metal complex (e.g., one corresponding to structural formula (III)) on the substrate surface, or a combination thereof).

[0080] In any embodiment, the first deposition process and the second deposition process can independently be chemical vapor deposition (CVD) or atomic layer deposition (ALD).

[0081] ALD and CVD methods encompass various types of ALD and CVD processes, including, but not limited to, continuous or pulsed injection processes, liquid injection processes, light-assisted processes, plasma-assisted processes, and plasma-enhanced processes. For clarity, the methods of the present technology specifically include direct liquid injection processes. For example, in direct liquid injection CVD ("DLI-CVD"), a solid or liquid compound corresponding to structural formula (I), a solid or liquid compound corresponding to structural formula (II), a solid or liquid metal complex (e.g., corresponding to structural formula (III)), or a combination thereof can be dissolved in a suitable solvent, and the solution formed therefrom can be injected into a vaporization chamber as a means for vaporizing the compound corresponding to structural formula (I), the compound corresponding to structural formula (II), the metal complex (e.g., corresponding to structural formula (III)), or a combination thereof. The vaporized compound corresponding to structural formula (I), the vaporized compound corresponding to structural formula (II), the vaporized metal complex (e.g., corresponding to structural formula (III)), or a combination thereof is then transported / delivered to a substrate surface. In general, DLI-CVD can be particularly useful when the metal complex exhibits relatively low volatility or is otherwise difficult to vaporize.

[0082] In one embodiment, at least one metal complex (e.g., corresponding to structural formula (III)) is vaporized and / or passed over a substrate surface using conventional or pulsed CVD to form a metal-containing film. Additionally or alternatively, a compound corresponding to structural formula (I), a compound corresponding to structural formula (II), or a combination thereof is delivered by vaporizing and / or passing the compound corresponding to structural formula (I), a compound corresponding to structural formula (II), or a combination thereof over a substrate surface using conventional or pulsed CVD. For conventional CVD processing, see, for example, Smith, Donald (1995). Thin-Film Deposition: Principles and Practice. McGraw-Hill.

[0083] In one embodiment, the CVD growth conditions for a compound corresponding to structural formula (I), a compound corresponding to structural formula (II), a metal complex (e.g., corresponding to structural formula (III)), or a combination thereof, include: a) Base material temperature: 50~600℃ b) Evaporator temperature (metal precursor temperature): 0 to 200°C c) Reactor pressure: 0 to 100 Torr d) Argon or nitrogen carrier gas flow rate: 0 to 500 sccm e) Oxygen flow rate: 0~500sccm f) Hydrogen flow rate: 0 to 500 sccm g) Run time: Varies depending on desired film thickness These include, but are not limited to:

[0084] In another embodiment, photo-assisted CVD is used to form a metal-containing film by vaporizing and / or passing at least one metal complex disclosed herein (e.g., corresponding to structural formula (III)) over a substrate surface. Additionally or alternatively, photo-assisted CVD is used to deliver a compound corresponding to structural formula (I), a compound corresponding to structural formula (II), or a combination thereof, by vaporizing and / or passing the compound corresponding to structural formula (I), a compound corresponding to structural formula (II), or a combination thereof over a substrate surface.

[0085] In a further embodiment, conventional (i.e., pulsed) ALD is used to form a metal-containing film by vaporizing and / or passing at least one metal complex disclosed herein (e.g., corresponding to structural formula (III)) over a substrate surface. Additionally or alternatively, conventional (i.e., pulsed) ALD can be used to deliver a compound corresponding to structural formula (I), a compound corresponding to structural formula (II), or a combination thereof, by vaporizing and / or passing the compound corresponding to structural formula (I), a compound corresponding to structural formula (II), or a combination thereof over a substrate surface. For conventional ALD processing, see, for example, George SM, et al. J. Phys. Chem., 1996, 100, 13121-13131.

[0086] In another embodiment, liquid injection ALD is used to form a metal-containing film by vaporizing and / or passing at least one metal complex disclosed herein (e.g., corresponding to structural formula (III)) onto a substrate surface, where the at least one metal complex is delivered to a reaction chamber by direct liquid injection, as opposed to vapor drawing by a bubbler. Additionally or alternatively, liquid injection ALD is used to deliver a compound corresponding to structural formula (I), a compound corresponding to structural formula (II), or a combination thereof, by vaporizing and / or passing the compound corresponding to structural formula (I), a compound corresponding to structural formula (II), or a combination thereof onto a substrate surface, where the compound corresponding to structural formula (I), a compound corresponding to structural formula (II), or a combination thereof, is delivered to a reaction chamber by direct liquid injection, as opposed to vapor drawing by a bubbler. For liquid injection ALD processing, see, for example, Potter RJ, et al., Chem. Vap. Deposition, 2005, 11(3), 159-169.

[0087] Exemplary ALD growth conditions for a compound corresponding to structural formula (I), a compound corresponding to structural formula (II), a metal complex (e.g., corresponding to structural formula (III)), or a combination thereof include: a) Base material temperature: 0~400℃ b) Evaporator temperature (metal precursor temperature): 0 to 200°C c) Reactor pressure: 0 to 100 Torr d) Argon or nitrogen carrier gas flow rate: 0 to 500 sccm e) Reactive gas flow rate: 0 to 500 sccm f) Pulse sequence (metal complex / purge / reactive gas / purge): Varies depending on optimized process conditions and chamber size g) Number of cycles: Varies depending on desired film thickness but Included But not limited to these.

[0088] In another embodiment, photo-assisted ALD is used to form a metal-containing film by vaporizing and / or passing at least one metal complex disclosed herein (e.g., corresponding to structural formula (III)) over a substrate surface. Additionally or alternatively, photo-assisted ALD is used to deliver a compound corresponding to structural formula (I), a compound corresponding to structural formula (II), or a combination thereof, by vaporizing and / or passing the compound corresponding to structural formula (I), a compound corresponding to structural formula (II), or a combination thereof over a substrate surface. For a photo-assisted ALD process, see, for example, U.S. Pat. No. 4,581,249.

[0089] In another embodiment, plasma-assisted or plasma-enhanced ALD is used to form a metal-containing film by vaporizing and / or passing at least one metal complex disclosed herein (e.g., corresponding to structural formula (III)) over a substrate surface. Additionally or alternatively, plasma-assisted or plasma-enhanced ALD is used to deliver a compound corresponding to structural formula (I), a compound corresponding to structural formula (II), or a combination thereof, by vaporizing and / or passing the compound corresponding to structural formula (I), a compound corresponding to structural formula (II), or a combination thereof over a substrate surface.

[0090] In another embodiment, a method of forming a metal-containing film on a substrate surface includes: exposing the substrate to a gas-phase metal complex according to one or more of the embodiments described herein (e.g., one corresponding to Structural Formula (III)) during an ALD process to form a layer on the surface including a metal complex bound to the surface by a metal center (e.g., hafnium); exposing the substrate having the bound metal complex to a co-reactant during an ALD process such that an exchange reaction occurs between the bound metal complex and the co-reactant, thereby dissociating the bound metal complex and producing a first layer of elemental metal on the substrate surface; and continuously repeating the ALD process and treatment.

[0091] The reaction time, temperature and pressure are selected to effect metal-surface interactions and achieve a layer on the surface of the substrate. The reaction conditions for the ALD reaction may be selected based on the properties of the metal complex. Deposition can be carried out at atmospheric pressure, but is more commonly carried out under reduced pressure. The vapor pressure of the metal complex should be low enough to be practical in such applications. The substrate temperature should be low enough to keep the bonds between the metal atoms at the surface intact and to prevent thermal decomposition of the gaseous reactants. lowHowever, the substrate temperature should also be high enough to keep the raw materials (i.e., reactants) in the gas phase and provide sufficient activation energy for the surface reaction. The suitable temperature depends on a variety of parameters, including the particular metal complex and pressure used. The properties of a particular metal complex for use in the ALD deposition methods disclosed herein can be evaluated using methods known in the art, allowing the selection of a suitable temperature and pressure for the reaction. In general, low molecular weight and the presence of functional groups that increase the rotational entropy of the ligand sphere result in a melting point that results in a liquid under typical delivery temperatures and enhanced vapor pressures.

[0092] Metal complexes for use in deposition methods require all of the following: sufficient vapor pressure, sufficient thermal stability at the selected substrate temperature, and sufficient reactivity to cause a reaction on the surface of the substrate without introducing undesirable impurities into the thin film. Sufficient vapor pressure ensures that the source compound molecules are present at the substrate surface in sufficient concentration to allow a complete self-saturating reaction. Sufficient thermal stability ensures that the source compound does not undergo thermal decomposition that would produce impurities in the thin film.

[0093] Thus, the metal complexes disclosed herein utilized in these methods can be liquid, solid, or gaseous. Typically, the metal complexes are liquid or solid at environmental temperatures that have sufficient vapor pressure to allow consistent transport of the vapor to the processing chamber.

[0094] In certain embodiments, to facilitate the deposition process, the metal-containing complex (e.g., corresponding to structural formula (III)), the compound corresponding to structural formula (I), the compound corresponding to structural formula (II), or a combination thereof may be dissolved in a suitable solvent, such as a hydrocarbon solvent or an amine solvent. Suitable hydrocarbon solvents include, but are not limited to, aliphatic hydrocarbons, such as hexane, heptane, and nonane; aromatic hydrocarbons, such as toluene and xylene; and aliphatic and cyclic ethers, such as diglyme, triglyme, and tetraglyme. Examples of suitable amine solvents include, but are not limited to, octylamine and N,N-dimethyldodecylamine. For example, the metal-containing complex can be dissolved in toluene to obtain a solution having a concentration of about 0.05 M to about 1 M.

[0095] In another embodiment, at least one metal complex (e.g., one corresponding to structural formula (III)), a compound corresponding to structural formula (I), a compound corresponding to structural formula (II), or combinations thereof may be delivered "neat" (undiluted by a carrier gas) to the substrate surface.

[0096] In another embodiment, a mixed metal film can be formed by the method described herein. The method includes vaporizing at least a first metal complex (e.g., corresponding to structural formula (III)) disclosed herein in combination (but not necessarily simultaneously) with a second metal complex (and / or a third metal complex and / or a fourth metal complex, etc.) that includes a metal other than the metal of the first metal complex disclosed herein. For example, to form a mixed metal Hf-Zr film, the first metal complex can include Hf and the second metal-containing complex can include Zr. In some embodiments, the mixed metal film can be a mixed metal oxide, mixed metal nitride, or mixed metal oxynitride.

[0097] In one embodiment, an elemental metal, metal nitride, metal oxide, or metal silicide film can be formed by delivering at least one metal complex disclosed herein (e.g., corresponding to structural formula (III)) for deposition, alone or in combination with a co-reactant. In this regard, the co-reactant can be deposited on, delivered to, or passed over the substrate surface, alone or in combination with at least one or more metal complexes. As will be readily understood, the particular co-reactant used will determine the type of metal-containing film obtained. Examples of such co-reactants include, but are not limited to, hydrogen, hydrogen plasma, oxygen, air, water, alcohol, H2O2, N2O, ammonia, hydrazine, borane, silane, ozone, or any combination of two or more thereof. Examples of suitable alcohols include, but are not limited to, methanol, ethanol, propanol, isopropanol, tert-butanol, and the like. Examples of suitable boranes include, but are not limited to, hydridic (i.e., reducible) boranes, such as borane, diborane, triborane, and the like. Examples of suitable silanes include, but are not limited to, hydridic silanes such as silane, disilane, trisilane, etc. Examples of suitable hydrazines include, but are not limited to, hydrazine (NH), methylhydrazine, tert-butylhydrazine, hydrazines optionally substituted with one or more alkyl groups such as N,N- or N,N'-dimethylhydrazine (i.e., alkyl-substituted hydrazines), and hydrazines optionally substituted with one or more aryl groups such as phenylhydrazine (i.e., aryl-substituted hydrazines).

[0098] In one embodiment, to provide a metal oxide film, the metal complexes disclosed herein are delivered to a substrate surface in pulses alternating with pulses of an oxygen-containing co-reactant. Examples of such co-reactants include, but are not limited to, HO, HO, O, ozone, air, i-PrOH, t-BuOH, or N2O.

[0099] In other embodiments, the co-reactant includes a reducing agent, such as hydrogen. In such embodiments, an elemental metal film is obtained. In particular embodiments, the elemental metal film consists of pure metal or consists essentially of pure metal. Such pure metal films may include greater than about 80, 85, 90, 95, or 98% purity of metal. In even more particular embodiments, the elemental metal film is a hafnium film.

[0100] In other embodiments, a co-reactant is used to form a metal nitride film by delivering at least one metal complex disclosed herein (e.g., corresponding to structural formula (III)) alone or in combination with a co-reactant such as ammonia, hydrazine, and / or other nitrogen-containing compounds (e.g., amines) to a reaction chamber for deposition. Multiple such co-reactants can be used. In a further embodiment, the metal nitride film is a hafnium nitride film.

[0101] In certain embodiments, the methods of the present technology are utilized in applications such as dynamic random access memory (DRAM) and complementary metal oxide semiconductor (CMOS) for memory and logic applications on substrates such as silicon chips.

[0102] Any of the metal complexes disclosed herein can be used to prepare thin films of elemental metals, metal oxides, metal nitrides, and / or metal silicides. Such films can find applications as oxidation catalysts, anode materials (e.g., SOFC or LIB anodes), conductive layers, sensors, diffusion barriers / coatings, superconducting and non-superconducting materials / coatings, tribological coatings, and / or protective coatings. Those skilled in the art will understand that film properties (e.g., electrical conductivity) depend on many factors, such as the metal used in deposition, the presence or absence of co-reactants and / or co-complexes, the thickness of the film produced, the parameters and substrates employed during growth and subsequent processing.

[0103] Throughout this specification, reference to "one embodiment," "a particular embodiment," "one or more embodiments," or "an embodiment" means that a particular feature, structure, material, or characteristic described in connection with that embodiment is included in at least one embodiment of the technology. Thus, the appearances of phrases such as "in one or more embodiments," "a particular embodiment," or "in an embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment of the technology. Furthermore, the particular features, structures, materials, or characteristics may be combined in any suitable manner in one or more embodiments.

[0104] Although the present technology has been described with reference to specific embodiments, it should be understood that these embodiments are merely illustrative of the principles and applications of the present technology. It will be apparent to those skilled in the art that various modifications and variations can be made to the method and apparatus of the present technology without departing from the spirit and scope of the present technology. Therefore, the present technology is intended to include modifications and variations that are within the scope of the appended claims and their equivalents. Having thus generally described, the present technology will be more readily understood by reference to the following examples, which are provided for illustration and are not intended to be limiting.

[0105] [Example] Example 1: Formation of a blocking layer by exposing various substrates to N-dodecyl-N-methylcarbamodithioic acid The blocking layers were prepared by a vapor-phase delivery method using N-dodecyl-N-methylcarbamodithioic acid in a cross-flow atomic layer deposition (ALD) reactor. N-dodecyl-N-methylcarbamodithioic acid was kept in an ampoule at 130 °C. A stainless steel cylinder kept at 150 °C connected the N-dodecyl-N-methylcarbamodithioic acid ampoule to a delivery manifold. First, the cylinder was filled with N-dodecyl-N-methylcarbamodithioic acid vapor, and then the N-dodecyl-N-methylcarbamodithioic acid vapor was pulsed for 60 s at 130 °C into the ALD chamber containing the following substrates: W, Co, Cu on Si, and SiO2 as a control, and trapped for 1 h. X-ray photoelectron spectroscopy (XPS) analysis was performed on the substrates, and the S2p region of the XPS was used to confirm the grafting of N-dodecyl-N-methylcarbamodithioic acid as a blocking layer on the substrates, as shown in Figure 2.

[0106] Example 2: Blocking Layer Inhibition of Hafnium-Containing Films The blocking layers formed by exposing W, Co, Cu and control SiO2 on Si substrates to N-dodecyl-N-methylcarbamodithioic acid were tested for their ability to inhibit the growth of Hf-containing films. W, Co, Cu and control SiO2 on Si substrates were exposed to N-dodecyl-N-methylcarbamodithioic acid as described above in Example 1, followed by 200 cycles of exposure to (MeCp)2Hf(OMe)(Me) and H2O at 350°C. The metal substrates were pre-cleaned with 2% citric acid for 1 minute before exposure to N-dodecyl-N-methylcarbamodithioic acid. The SiO2 samples were not pre-cleaned. For control purposes, W, Co, Cu and control SiO2 on Si substrates were exposed only to (MeCp)2Hf(OMe)(Me). The deposition conditions were as follows: 2 s pulse Hf (from (MeCp)2Hf(OMe)(Me)), 10 s pulse N2 purge, 2 s pulse H2O, and 10 s pulse N2 purge. The atomic percentages of Hf on SiO2, W, Co, and Cu substrates exposed to N-dodecyl-N-methylcarbamodithioic acid and (MeCp)2Hf(OMe)(Me) were measured by XPS and are shown in Figure 3A. Also, the atomic percentages of Hf on control SiO2, W, Co, and Cu substrates not exposed to N-dodecyl-N-methylcarbamodithioic acid but exposed to (MeCp)2Hf(OMe)(Me) were measured by XPS and are shown in Figure 3B. Scanning electron microscope (SEM) images of the SiO, W, Co, and Cu substrates after exposure to N-dodecyl-N-methylcarbamodithioic acid and (MeCp)Hf(OMe)(Me), respectively, are shown in Figures 4A-4D.

[0107] Example 3: Synthesis of N-dodecyl-N-methylcarbamodithioic acid N-dodecyl-N-methylammonium salt (Compound I) To a solution of N-dodecyl-N'-methylamine (25 mmol) in methanol (50 mL) was added carbon disulfide (188 mmol) at 0°C. The reaction mixture was then stirred at 0°C for 2 h and then at room temperature (15°C-25°C) overnight (8-12 h). The solvent was removed under nitrogen to give an off-white solid (87% yield). The crude product (off-white solid) was purified by crystallization from methanol, 1 H nuclear magnetic resonance ( 1 H NMR), 13 Compound I was characterized by C NMR, thermogravimetric analysis (TGA), liquid chromatography-mass spectrometry (LCMS), elemental analysis, single crystal X-ray and titration analysis. By the above characterization methods, compound I was found to exist in the following complex / salt forms:

[0108] [ka]

[0109] It was confirmed to exist in.

[0110] TGA was performed on Compound I (4.47 mg sample and 10° C. / min heating rate). The results are shown in FIG. 5A. TGA showed a melt at 61° C., 0.2% residue at 180° C., and T 1 / 2 = about 171° C. Differential scanning calorimetry (DSC) was performed on Compound I. The results are shown in FIG. 5B.

[0111] 1 H NMR was performed on compound I. The results are shown in Figure 6A. 13 C NMR was performed on compound I. The results are shown in Figure 6B. 1 H NMR and 13 C NMR showed no free amine starting material.

[0112] Elemental analysis was determined for Compound I, giving the following results: carbon, 68.3%; nitrogen, 5.8%; sulfur, 13.4%.

[0113] Titration analysis was performed on Compound I. The results are shown in Table 1 below.

[0114] [Table 1]

[0115] Infrared (IR) spectroscopy was performed on Compound I. The results are shown in Figure 7. Single crystal X-ray analysis was performed on Compound I. The results are shown in Figure 8.

[0116] All publications, patent applications, issued patents, and other documents mentioned herein are incorporated by reference herein as if each individual publication, patent application, issued patent, or other document was specifically and individually indicated to be incorporated by reference in its entirety. Definitions contained in the texts incorporated by reference are disregarded to the extent they do not contradict definitions in this disclosure.

[0117] The terms "comprise", "comprises" and "comprising" are to be interpreted inclusively rather than exclusively. [Brief description of the drawings]

[0118] [Figure 1A] FIG. 1A shows details of a blocking layer and a metal-containing film according to certain embodiments of the present disclosure. [Figure 1B] FIG. 1B shows details of a blocking layer and a metal-containing film according to a particular alternative embodiment of the present disclosure. [Diagram 2] FIG. 2 shows X-ray photoelectron spectroscopy (XPS) analysis of SiO2, W, Co, and Cu substrates after exposure to N-dodecyl-N-methylcarbamodithioic acid. [Figure 3A] FIG. 3A shows the atomic percentage of Hf present on SiO, W, Co, and Cu substrates after exposure to N-dodecyl-N-methylcarbamodithioic acid and (MeCp)Hf(OMe)(Me). [Figure 3B]FIG. 3B shows the atomic percentage of Hf present on SiO, W, Co, and Cu substrates after exposure to (MeCp)Hf(OMe)(Me) but not to N-dodecyl-N-methylcarbamodithioic acid. [Figure 4A] 4A-4D provide scanning electron microscope (SEM) images of SiO, W, Co, and Cu substrates, respectively, after exposure to N-dodecyl-N-methylcarbamodithioic acid and (MeCp)Hf(OMe)(Me). [Figure 4B] 4A-4D provide scanning electron microscope (SEM) images of SiO, W, Co, and Cu substrates, respectively, after exposure to N-dodecyl-N-methylcarbamodithioic acid and (MeCp)Hf(OMe)(Me). [Figure 4C] 4A-4D provide scanning electron microscope (SEM) images of SiO, W, Co, and Cu substrates, respectively, after exposure to N-dodecyl-N-methylcarbamodithioic acid and (MeCp)Hf(OMe)(Me). [Figure 4D] 4A-4D provide scanning electron microscope (SEM) images of SiO, W, Co, and Cu substrates, respectively, after exposure to N-dodecyl-N-methylcarbamodithioic acid and (MeCp)Hf(OMe)(Me). [Figure 5A] FIG. 5A is a graphical representation of thermogravimetric analysis (TGA) data showing the % weight loss versus temperature for N-dodecyl-N-methylcarbamodithioic acid N-dodecyl-N-methylammonium salt (Compound I). [Figure 5B] FIG. 5B is a graphical representation of a differential scanning calorimetry (DSC) analysis of Compound I. [Figure 6A] FIG. 6A shows the 1H nuclear magnetic resonance (1H NMR) spectrum of compound I. [Figure 6B] FIG. 6B shows the 13C NMR spectrum of compound I. [Figure 7] FIG. 7 shows the infrared (IR) spectrum of Compound I. [Figure 8] FIG. 8 shows the single crystal X-ray structure of Compound I.

Claims

1. Structural formula I 【Chemistry 1】 (In the formula, R １ and R ２ are each independently C １ ~C ２０ alkyl, each of which is optionally substituted with one or more of trifluoromethyl, hydroxyl, alkoxy, and amino groups; X １ is S; X ２ is NR ４ R ５ where R ４ and R5 are each independently C １ ~C ２０ alkyl, each of which is optionally substituted with one or more of trifluoromethyl, hydroxyl, alkoxy, and amino groups; １ and R ４ at least one of which is dodecyl compound.

2. R １ , R ２ , R ４ and R5 are each independently C １ ~C １５ alkyl, each of which is optionally substituted with one or more of trifluoromethyl, hydroxyl, alkoxy, and amino groups; The compound of claim 1.

3. R １ , R ２ , R ４ and R5 are each independently C １ ~C １２ alkyl, each of which is optionally substituted with one or more of trifluoromethyl, hydroxyl, alkoxy, and amino groups; 3. A compound according to claim 1 or 2.

4. R １ is C １ ~C １５ alkyl, R ２ is C １ ~C ４ alkyl, each of which is optionally substituted with one or more of trifluoromethyl, hydroxyl, alkoxy, and amino groups; R ４ is C １ ~C １５ alkyl, R ５ is C １ ~C ４ alkyl, each of which is optionally substituted with one or more of trifluoromethyl, hydroxyl, alkoxy, and amino groups; The compound according to any one of claims 1 to 3.

5. The compound corresponding to structural formula (I) is N-dodecyl-N-methylcarbamodithioic acid N-dodecyl-N-methylammonium salt. The compound according to any one of claims 1 to 4.

6. 1. A method of forming a metal-containing film, the method comprising: forming a blocking layer on a surface of a first substrate by a first deposition process, the first deposition process comprising depositing a compound represented by the following structural formula I: 【Chemistry 2】 wherein R 1 and R 2 are each independently a C 1 -C 20 alkyl, each of which is optionally substituted with one or more of a trifluoromethyl group, a hydroxyl group, an alkoxy group, a nitrile group, and an amino group; X 1 is S; X 2 is NR 4 R 5 ; where R 4 and R 5 are each independently C 1 -C 20 alkyl, each optionally substituted with one or more of trifluoromethyl, hydroxyl, alkoxy, nitrile, and amino groups; and where at least one of R 1 and R 4 is dodecyl; forming the metal-containing film on a second substrate surface by a second deposition process, the second deposition process comprising vaporizing at least one metal complex; Including, the first substrate surface comprises a metallic material and the second substrate surface comprises a dielectric material or a metal oxide; method.

7. 1. A method of forming a metal-containing film, the method comprising: forming a blocking layer on a first portion of a substrate by a first deposition process, the first deposition process comprising a compound represented by structural formula I 【Chemistry 3】 wherein R 1 and R 2 are each independently a C 1 -C 20 alkyl, each of which is optionally substituted with one or more of a trifluoromethyl group, a hydroxyl group, an alkoxy group, a nitrile group, and an amino group; X 1 is S; X 2 is NR 4 R 5 ; where R 4 and R 5 are each independently C 1 -C 20 alkyl, each optionally substituted with one or more of trifluoromethyl, hydroxyl, alkoxy, nitrile, and amino groups; and where at least one of R 1 and R 4 is dodecyl; forming the metal-containing film on a second portion of the substrate by a second deposition process, the second deposition process comprising exposing the substrate to at least one metal complex; Including, the first portion of the substrate comprises a metallic material and the second portion of the substrate comprises a dielectric material or a metal oxide. method.

8. The metal complex has the formula III 【Chemistry 4】 wherein M is Hf; L １ , L ２ , L ３ and L ４ are each independently C １ ~C ８ Alkyl group, C １ ~C ８ an alkoxy group, and optionally at least one C １ ~C ８ Alkyl-substituted C ｐ (selected from the group consisting of groups): The method according to claim 6 or 7.

9. The metal complex is (MeCp) ２ Hf(OMe)(Me), The method according to any one of claims 6 to 8.

10. the metal of the metal-containing film is present on the blocking layer in an amount of less than 15 atomic %; The method according to any one of claims 6 to 9.

11. The first substrate surface and the second substrate surface are on the same substrate or on different substrates. The method according to any one of claims 6 and 8 to 10.

12. The metallic material includes W, Co, Cu or a combination thereof; The method according to any one of claims 6 to 11.

13. The dielectric material is SiO ２ , SiN, or a combination thereof; or The metal oxide material is HfO ２ , ZrO ２ , SiO ２ , Al ２ O ３ or any combination thereof, The method according to any one of claims 6 to 12.

14. The compound according to structural formula (I) is delivered at a temperature of less than 150° C. The method according to any one of claims 6 to 13.

15. the first deposition process and the second deposition process are independently chemical vapor deposition or atomic layer deposition; The method according to any one of claims 6 to 14.

16. The chemical vapor deposition is pulsed chemical vapor deposition, continuous flow chemical vapor deposition, or liquid injection chemical vapor deposition. The method of claim 15.

17. The atomic layer deposition is liquid injection atomic layer deposition or plasma enhanced atomic layer deposition. The method of claim 15.

18. The metal complex is delivered to the substrate in pulses alternating with pulses of an oxygen source. The method according to any one of claims 6 to 17.

19. The oxygen source is H ２ O, H ２ O ２ , O ２ , ozone, air, i-PrOH, t-BuOH, and N ２ O, 20. The method of claim 18.

20. further comprising vaporizing at least one co-reactant selected from the group consisting of hydrogen, hydrogen plasma, oxygen, air, water, ammonia, hydrazine, borane, silane, ozone, and combinations of any two or more thereof; The method according to any one of claims 6 to 19.

21. The method is used in DRAM or CMOS applications. The method according to any one of claims 6 to 20.

22. R 1 , R 2 , R 4 , and R 5 are each independently C 1 to C 15 alkyl, each of which is optionally substituted with one or more of a trifluoromethyl group, a hydroxyl group, a nitrile group, an alkoxy group, and an amino group; The method according to claim 6 or 7.

23. R 1 , R 2 , R 4 , and R 5 are each independently C 1 to C 12 alkyl, each of which is optionally substituted with one or more of a trifluoromethyl group, a hydroxyl group, a nitrile group, an alkoxy group, and an amino group; The method according to claim 6 or 7.

24. R 1 is C 1 -C 15 alkyl and R 2 is C 1 -C 4 alkyl, each of which is optionally substituted with one or more of trifluoromethyl, hydroxyl, nitrile, alkoxy, and amino groups; R 4 is C 1 -C 15 alkyl and R 5 is C 1 -C 4 alkyl, each of which is optionally substituted with one or more of trifluoromethyl, hydroxyl, nitrile, alkoxy, and amino groups. The method according to claim 6 or 7.

25. The compound corresponding to structural formula (I) is N-dodecyl-N-methylcarbamodithioic acid N-dodecyl-N-methylammonium salt. The method according to claim 6 or 7.

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