Method for selectively forming a metal-containing film

Abstract

Methods of forming metal-containing films are provided. These methods include forming a barrier layer, for example, on a first substrate surface by a first deposition process, and forming the metal-containing film, for example, on a second substrate surface by a second deposition process.

Description

Technical Field

[0001] The present technology relates generally to deposition methods, and more particularly to methods for selectively growing metal-containing films on substrate surfaces. Background Art

[0002] Thin films, and in particular metal-containing films, have a variety of important applications, such as in nanotechnology and the manufacture of semiconductor devices. Examples of such applications include high refractive index optical coatings, anti-corrosion 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. Metallic and dielectric films are also used in microelectronics applications, such as high-κ dielectric oxides for dynamic random access memory (DRAM) applications and ferroelectric perovskites for infrared detectors and non-volatile ferroelectric random access memory (NV-FeRAM).

[0003] Various precursors can be used to form metal-containing 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 methods are increasingly being used because they have the advantages of enhanced composition control, high film uniformity, and effective doping control.

[0004] CVD is a chemical process in which a precursor is used to form a thin film on a substrate surface. In a typical CVD method, a precursor is passed through a substrate (e.g., a wafer) surface in a low pressure or ambient pressure reaction chamber. The precursor reacts and / or decomposes on the substrate surface to produce a thin film of deposited material. Volatile byproducts are removed by passing an airflow through the reaction chamber. It may be difficult to control the thickness of the deposited film because it depends on the coordination of many parameters (such as temperature, pressure, airflow volume and uniformity, chemical consumption effects, and time).

[0005] ALD is also a method for thin film deposition. It is a self-limiting, sequential, unique film growth technology based on surface reactions that can provide precise thickness control and deposit conformal thin films of materials provided by precursors onto surface substrates of different compositions. In ALD, the precursors are separated during the reaction. The first precursor is passed over the substrate surface, thereby producing a monolayer on the substrate surface. Any excess unreacted precursor is pumped out of the reaction chamber. The second precursor is then passed over the substrate surface and reacts with the first precursor, thereby forming a second film monolayer on the first formed film monolayer on the substrate surface. This cycle is repeated to produce a film of desired thickness.

[0006] However, as the size of microelectronic components (such as semiconductor devices) continues to decrease, several technical challenges remain, thereby increasing the need for improved thin film technologies. In particular, microelectronic components may include patterning, for example to form conductive paths or to form interconnects. Typically, patterning is achieved via etching and photolithography techniques, but as the demand for patterning complexity increases, such techniques can be challenging. Therefore, there is significant interest in the development of thin film deposition methods that can selectively grow films on one or more substrates and achieve improved patterning on the substrates. Summary of the invention

[0007] According to one aspect, a method for forming a metal-containing film is provided. The method includes forming a barrier layer on a first substrate surface by a first vapor deposition process or a first liquid deposition process. The first vapor deposition process includes vaporizing a compound corresponding to formula (I):

[0008]

[0009] Where X 1 YesR 1 or R 2 R 3 , where R 1 is C optionally substituted by one or more trichlorosilyl groups 1 -C 20 -alkyl, R 2 is C optionally substituted by one or more halogens 1 -C 20 -alkylene, and R 3 Selected from the group consisting of: nitrile, vinyl, halogen, trifluoromethyl, acetoxy, methoxyethoxy, and phenoxy. The first liquid phase deposition process includes contacting the first substrate surface with a solution containing a compound corresponding to formula (I) in structure. 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 dielectric material or a metal oxide and the second substrate surface may include a metallic material.

[0010] According to another aspect, another method of forming a metal-containing film is provided. The method includes forming a barrier layer on a first portion of a substrate by a first vapor deposition process or a first liquid deposition process. The first vapor deposition process includes vaporizing a compound corresponding to formula (I):

[0011]

[0012] Where X 1 YesR 1 or R 2 R 3, where R 1 is C optionally substituted by one or more trichlorosilyl groups 1 -C 20 -alkyl, R 2 is C optionally substituted by one or more halogens 1 -C 20 -alkylene, and R 3 Selected from the group consisting of: nitrile, vinyl, halogen, trifluoromethyl, acetoxy, methoxyethoxy, and phenoxy. The first liquid phase deposition process includes contacting a first portion of the substrate with a solution containing a compound corresponding to formula (I) in structure. 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 vaporizing at least one metal complex. The first portion of the substrate may include a dielectric material or a metal oxide and the second portion of the substrate may include a metallic material.

[0013]

[0011] Other embodiments incorporating specific aspects of the embodiments outlined above will be apparent from the following detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1A Details of barrier layers and metal-containing films according to certain aspects of the present disclosure are described.

[0015] Figure 1B Details of barrier layers and metal-containing films according to certain alternative aspects of the present disclosure are described. DETAILED DESCRIPTION

[0016] Before describing several exemplary embodiments of the present invention technology, it should be understood that the present technology is not limited to the details of the construction or method steps set forth in the following description. The present invention technology can have other embodiments and can be practiced or implemented in different ways. It should also be understood that metal complexes and other compounds can be described herein using structural formulas with specific stereochemistry. These descriptions are intended only as examples and should not be interpreted as limiting the disclosed structures to any specific stereochemistry. On the contrary, the structures shown are intended to cover all such metal complexes and compounds with the chemical formula shown.

[0017] Applicants have discovered methods for depositing that can selectively form metal-containing films. In particular, the methods described herein can form a barrier layer on a first substrate surface or a first portion of a surface by a first deposition process (e.g., a first vapor deposition or a first liquid deposition) and form a metal-containing film on a second substrate surface or a second portion of a surface by a second deposition process. It has been found that a barrier layer can be deposited on a metal-containing substrate, and this barrier layer can substantially block or inhibit the growth of a metal-containing film on the barrier layer while allowing the deposition of a metal-containing film on a substrate containing a dielectric material and / or a substrate containing a metal oxide. Advantageously, the methods described herein can allow for selective dielectric-on-dielectric deposition. In addition, the methods described herein can allow for the delivery of a barrier layer via a vapor phase method that can use the same equipment used to deliver a metal complex.

[0018] I. Definitions

[0019] For purposes of this invention and the claims thereto, the numbering scheme for the Periodic Table Groups is according to the IUPAC Periodic Table of the Elements.

[0020] The term "and / or" as used in phrases such as "A and / or B" is intended herein to include "A and B", "A or B", "A" and "B".

[0021] The terms "substituent," "radical," "group," and "moiety" may be used interchangeably.

[0022] 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, such as by vapor deposition processes such as ALD or CVD. The metal-containing complex can be deposited on, adsorbed to, decomposed on, delivered to and / or through a substrate or surface thereof to form a metal-containing film.

[0023] As used herein, the term "metal-containing film" includes not only elemental metal films as more fully defined below, but also films that contain metal together 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 films consisting of pure metal or consisting essentially of pure metal. For example, the elemental metal film may include 100% pure metal, or the elemental metal film may include 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% pure metal together with one or more impurities. Unless the context dictates otherwise, the term "metal film" should be interpreted as meaning an elemental metal film.

[0024] 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 may take the form of conventional (i.e., continuous flow) CVD, liquid injection CVD, or light-assisted CVD. CVD may 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 over a substrate surface. For conventional ALD processes, see, for example, George S.M. et al., J. Phys. Chem. [Journal of Physical Chemistry], 1996, 100, 13121-13131. In other embodiments, ALD may take the form of conventional (i.e., pulsed injection) ALD, liquid injection ALD, light-assisted ALD, plasma-assisted ALD, or plasma-enhanced ALD. The term "vapor deposition process" further includes the 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.

[0025] As used herein, the term "liquid deposition process" refers to any type of liquid deposition technique in which materials and / or compounds are deposited on a substrate via a liquid phase, wherein the liquid is a solution or dispersion. Exemplary liquid deposition processes include spin coating, knife coating, spray coating, roller coating, extrusion coating, rod coating, dip coating, and the like.

[0026] As used herein, the terms "selectively grow", "selectively grown and selectively grows" may be used synonymously and refer to growing a film on at least a portion of a second substrate surface (or a second portion of a substrate) and substantially no film growing on a first substrate surface (or a first portion of a substrate) and / or on a barrier layer, and growing more film on at least a portion of a second substrate surface (or a second portion of a substrate) than growing a film on the first substrate surface (or a first portion of a substrate) and / or on a barrier layer. With respect to more than one substrate, the terms "selectively grow", "selectively grows" also encompass growing a film on a first substrate and substantially no film growing on a second substrate (or a third substrate, or a fourth substrate, or a fifth substrate, etc.), and growing more film on the first substrate than on the second substrate (or a third substrate, or a fourth substrate, or a fifth substrate, etc.).

[0027] The term "alkyl" (alone or in combination with one or more other terms) refers to a saturated hydrocarbon chain of 1 to about 25 carbon atoms in length, such as, but not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, and the like. Alkyl groups may be straight or branched. "Alkyl" is intended to include 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. Further, 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, alkyl is C 1 -C 5 -alkyl or C 1 -C 4 -alkyl.

[0028] The term "alkylene" refers to a divalent alkyl moiety containing from 1 to 20 carbon atoms in length (i.e., C 1 -C 20 Alkylene) and means that the alkylene moiety is attached to the rest of the molecule at both ends of the alkyl unit. For example, alkylene includes but is not limited to -CH 2 -、-CH 2 CH 2 -、-CH(CH 3 )CH 2 -、-CH 2 CH 2 CH 2 - etc. The alkylene group may be linear or branched.

[0029] The term "alkoxy" refers to an -O-alkyl group containing from 1 to about 8 carbon atoms. The alkoxy group can be straight or branched. Non-limiting examples include methoxy, ethoxy, propoxy, butoxy, isobutoxy, tert-butoxy, pentyloxy, and hexyloxy.

[0030] II. Method for Forming Metal-Containing Film

[0031] Provided herein are methods of forming a metal-containing film, for example, wherein the metal-containing film is selectively grown. In various aspects, such as Figure 1A As described in the foregoing, the method may include forming a barrier layer 20 on the first substrate surface 15 by a first deposition process. The method may further include forming a metal-containing film 23 on the second substrate surface 17 by a second deposition process. Figure 1AAs shown in , 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 the first portion 15 of the substrate 19 and the second substrate surface 17 may be considered as the second portion 17 of the substrate 19. Alternatively, as Figure 1B It is described in the figure that the first substrate surface 15 and the second substrate surface 17 may exist on different substrates (for example, the first substrate 25 and the second substrate 30, respectively).

[0032] The first substrate surface 15 (or first portion 15) may include a dielectric material, a metal oxide material, or a combination 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, SiO 2 , SiN and combinations thereof. Examples of suitable metal oxide materials include, but are not limited to, HfO 2 、ZrO 2 、SiO 2 、Al 2 O 3 and combinations thereof. The second substrate surface 17 (or second portion 17) may include a metal material. Examples of suitable metal materials include, but are not limited to, tungsten (W), cobalt (Co), copper (Cu), and combinations thereof. In some embodiments, the metal material may include Co, Cu, or a combination thereof. In a specific embodiment, the metal material may include Cu.

[0033] In any embodiment, the first deposition process may include a first vapor deposition process, a first liquid deposition process, or a combination thereof. The first vapor deposition process may include vaporizing a compound corresponding in structure to Formula I:

[0034]

[0035] Where X 1 It can be R 1 or R 2 R 3 . R 1 may be optionally replaced by one or more (Trichlorosilyl) substituted C 1 -C 20 -alkyl. 2 It may be C optionally substituted by one or more halogens (eg, F, Cl, Br, etc.). 1 -C 20 -alkylene. 3 You can choose from the group consisting of: (nitrile group), (vinyl), halogen (e.g., F, Cl, Br, etc.), (trifluoromethyl), (acetoxy), (methoxyethoxy), and (phenoxy).

[0036] The compound structurally corresponding to Formula I can be vaporized in the presence of a substrate (e.g., first substrate surface 15, second substrate surface 17, substrate 19, first substrate 25, second substrate 30) and / or the vaporized compound structurally corresponding to Formula I can be exposed to a substrate (e.g., first substrate surface 15, second substrate surface 17, substrate 19, first substrate 25, second substrate 30). In any embodiment, the first liquid deposition process can include contacting the substrate surface (e.g., first substrate surface 15, second substrate surface 17, substrate 19, first substrate 25, second substrate 30) with a solution comprising a compound structurally corresponding to Formula (I).

[0037] In some embodiments, X 1 It can be R 1 , where R 1 It may be C optionally substituted with one or more trichlorosilyl groups (e.g., 1 to 12 trichlorosilyl groups, 1 to 8 trichlorosilyl groups, 1 to 4 trichlorosilyl groups, or 1 to 2 trichlorosilyl groups). 1 -C 20 -alkyl. In some embodiments, R 1 Can be C 1 -C 15 -alkyl, C 1 -C 12 -alkyl, C 1 -C 10 -alkyl, C 1 -C 8 -alkyl, C 1 -C 4 -alkyl or C 1 -C 2 -alkyl, each optionally substituted by one or more trichlorosilyl groups. The alkyl group may be straight-chain or branched. In particular, the alkyl group is straight-chain.

[0038] In some embodiments, X 1 It can be R 2 R 3 , where R 2 Can be C 1 -C 20 -alkylene, C 1 -C 15 -alkylene, C 1 -C 12 -alkylene, C 1 -C 10 -alkylene, C 1 -C8 -alkylene or C 1 -C 4 -alkylene, each optionally substituted with one or more halogens (eg, F, Cl, Br, etc.).

[0039] In some embodiments, X 1 It can be R 2 R 3 , where R 2 Can be C 1 -C 12 -alkylene, optionally substituted by 1 to 10 halogens (eg, F, Cl, Br, etc.), and R 3 The group may be selected from the group consisting of nitrile, vinyl, halogen, trifluoromethyl, acetoxy, methoxyethoxy, and phenoxy.

[0040] In either embodiment, compounds structurally corresponding to Formula (I) are shown in Table 1 below.

[0041] Table 1

[0042]

[0043]

[0044] In any embodiment, the compound corresponding to formula (I) in structure can be delivered or exposed to the 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 a temperature can be less than or equal to about 185°C, less than or equal to about 175°C, less than or equal to about 150°C, less than or equal to about 140°C, less than or equal to about 130°C, less than or equal to about 120°C, less than or equal to about 110°C, or about 100°C; or from about 100°C to about 185°C, about 100°C to about 175°C, about 100°C to about 150°C, or about 100°C to about 130°C.

[0045] In any embodiment, the second deposition process can include exposing the substrate (eg, first substrate surface 15, second substrate surface 17, substrate 19, first substrate 25, second substrate 30) to at least one metal complex.

[0046] The metal complex may include a suitable metal center and one or more suitable ligands. Examples of suitable metal centers include, but are not limited to, titanium (Ti), zirconium (Zr), and hafnium (Hf). Examples of suitable ligands include, but are not limited to, C 1 -C 10 -alkyl, C 1 -C 10 -alkoxy, optionally substituted with one or more C1 -C 10 -alkyl substituted cyclopentadienyl (Cp), and combinations thereof. For example, each ligand can independently be methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, butoxy, Cp group, methyl substituted Cp (MeCp) group, ethyl substituted Cp (EtCp) group, and combinations thereof.

[0047] In some embodiments, the metal complex may correspond in structure to Formula II:

[0048]

[0049] wherein M may be Ti, Zr or Hf, especially Hf; and L 1 , L 2 , L 3 and L 4 Each independently may be selected from the group consisting of: C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy and optionally with at least one C 1 -C 8 -alkyl substituted Cp group. In some embodiments, L 1 , L 2 , L 3 and L 4 Can all be the same.

[0050] In some embodiments, M may be Hf and L 1 , L 2 , L 3 and L 4 Each independently may be selected from the group consisting of: C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy and optionally with at least one C 1 -C 4 - Alkyl substituted Cp group.

[0051] In some embodiments, M may be Hf and L 1 , L 2 , L 3 and L 4 Each independently may be selected from the group consisting of: C 1 -C 2 -alkyl, C 1 -C 2 -alkoxy and optionally substituted by at least one C 1 -C 2 - Alkyl substituted Cp group.

[0052] In some embodiments, the metal complex may be (MeCp) 2 Hf(OMe)(Me).

[0053] Advantageously, the metal of the metal-containing film may be substantially present in a small amount on the barrier layer or substantially absent on the barrier layer. For example, the metal of the metal-containing film may be present on the barrier layer in an amount less than or equal to about 25 at.%, less than or equal to about 20 at.%, less than or equal to about 15 at.%, less than or equal to about 10 at.%, less than or equal to about 5 at.%, less than or equal to about 1 at.%, less than or equal to about 0.5 at.%, or about 0 at.%; or from about 0 at.% to about 25 at.%, about 0.5 at.% to about 25 at.%, about 0.5 at.% to about 20 at.%, about 0.5 at.% to about 15 at.%, about 0.5 at.% to about 10 at.%, or about 1 at.% to about 5 at.%.

[0054] Additionally or alternatively, the barrier layer may be present in small amounts or substantially absent on the second substrate surface (or second portion of the substrate, with a 100:1 selectivity).

[0055] As discussed above, the substrate can be exposed to a compound structurally corresponding to Formula I, a metal complex as described herein, or a combination thereof by any suitable deposition technique. For example, a first vapor deposition process can include vaporizing a compound structurally corresponding to Formula I. Additionally or alternatively, a second deposition process can include vaporizing at least one metal complex as described herein.

[0056] For example, this may include (1) vaporizing a compound structurally corresponding to Formula I and / or vaporizing at least one metal complex and (2) delivering a compound structurally corresponding to Formula I and / or delivering at least one metal complex to a substrate surface (e.g., first substrate surface 15, second substrate surface 17, substrate 19, first substrate 25, second substrate 30), or passing a compound structurally corresponding to Formula I and / or passing at least one metal complex through a substrate (and / or decomposing a compound structurally corresponding to Formula I and / or decomposing at least one complex on a substrate surface).

[0057] Alternatively, the first liquid deposition process may include contacting the substrate surface (e.g., first substrate surface 15, second substrate surface 17, substrate 19, first substrate 25, second substrate 30) with a solution containing a compound corresponding to formula (I) in structure. The solution may contain any suitable solvent, such as a hydrocarbon or 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 ethers and cyclic ethers, such as diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether. Examples of suitable amine solvents include, but are not limited to, octylamine and N, N-dimethyldodecylamine. For example, the compound corresponding to formula I in structure may be dissolved in toluene to obtain a solution having a concentration from about 0.01M to about 1M. In any embodiment, the first liquid deposition can include dipping or immersing the substrate (e.g., first substrate surface 15, second substrate surface 17, substrate 19, first substrate 25, second substrate 30) in the solution at least once for a suitable amount of time, for example, from about 1 hour to about 36 hours, from about 6 hours to about 30 hours, or from about 12 hours to about 24 hours. After contacting with the solution, the coated substrate can then be dried.

[0058] In either embodiment, the first vapor deposition process and the second deposition process independently may be chemical vapor deposition (CVD) or atomic layer deposition (ALD).

[0059] ALD and CVD methods encompass various types of ALD and CVD processes, such as, but not limited to, continuous or pulsed injection processes, liquid injection processes, light-assisted processes, plasma-assisted and plasma-enhanced processes. For clarity, the methods of the present technology particularly include direct liquid injection processes. For example, in direct liquid injection CVD ("DLI-CVD"), a solid or liquid compound and / or metal complex corresponding in structure to Formula I may be dissolved in a suitable solvent and the solution thus formed may be injected into a vaporization chamber, which serves as a device for vaporizing the compound and / or metal complex corresponding in structure to Formula I. The vaporized compound and / or metal complex corresponding in structure to Formula I is then transported / delivered to the surface of the substrate. In general, DLI-CVD may be particularly useful in those situations where the metal complex exhibits relatively low volatility or is otherwise difficult to vaporize.

[0060] In one embodiment, conventional or pulsed CVD is used to form a metal-containing film by vaporizing and / or passing at least one metal complex through a substrate surface. Additionally or alternatively, conventional or pulsed CVD is used to deliver a compound structurally corresponding to Formula I by vaporizing and / or passing a compound structurally corresponding to Formula I through a substrate surface. For conventional CVD processes, see, e.g., Smith, Donald (1995). Thin-Film Deposition: Principles and Practice. McGraw-Hill.

[0061] In one embodiment, the CVD growth conditions for the compounds and / or metal complexes structurally corresponding to Formula I disclosed herein include, but are not limited to:

[0062] a) Substrate temperature: 50℃-600℃

[0063] b) Evaporator temperature (metal precursor temperature): 0℃-200℃

[0064] c) Reactor pressure: 0-100 Torr

[0065] d) Argon or nitrogen carrier gas flow rate: 0-500sccm

[0066] e) Oxygen flow rate: 0-500sccm

[0067] f) Hydrogen flow rate: 0-500sccm

[0068] g) Run time: will vary depending on desired film thickness

[0069] In another embodiment, light-assisted CVD is used to form a metal-containing film by vaporizing and / or passing at least one metal complex disclosed herein over a substrate surface. Additionally or alternatively, light-assisted CVD is used to deliver a compound structurally corresponding to Formula I by vaporizing and / or passing the compound structurally corresponding to Formula I over a substrate surface.

[0070] In another embodiment, conventional (i.e., pulsed injection) ALD is used to form a metal-containing film by vaporizing and / or passing at least one metal complex disclosed herein over a substrate surface. Additionally or alternatively, conventional (i.e., pulsed injection) ALD is used to deliver a compound structurally corresponding to Formula I by vaporizing and / or passing the compound structurally corresponding to Formula I over a substrate surface. For conventional ALD processes, see, e.g., George SM et al., J. Phys. Chem., 1996, 100, 13121-13131.

[0071] 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 through a substrate surface, wherein the at least one metal complex is delivered to the reaction chamber by direct liquid injection, as opposed to pumping the vapor through a bubbler. Additionally or alternatively, liquid injection ALD is used to deliver a compound structurally corresponding to Formula I by vaporizing and / or passing the compound structurally corresponding to Formula I through a substrate surface, wherein the compound structurally corresponding to Formula I is delivered to the reaction chamber by direct liquid injection, as opposed to pumping the vapor through a bubbler. For liquid injection ALD processes, see, e.g., Potter R.J. et al., Chem. Vap. Deposition, 2005, 11(3), 159-169.

[0072] Examples of ALD growth conditions for the metal complexes disclosed herein include, but are not limited to:

[0073] a) Substrate temperature: 0℃-400℃

[0074] b) Evaporator temperature (metal precursor temperature): 0℃-200℃

[0075] c) Reactor pressure: 0-100 Torr

[0076] d) Argon or nitrogen carrier gas flow rate: 0-500sccm

[0077] e) Reactive gas flow rate: 0-500sccm

[0078] f) Pulse sequence (metal complex / purge / reactive gas / purge): will vary depending on optimized process conditions and chamber dimensions

[0079] g) Number of cycles: will vary depending on desired film thickness

[0080] In another embodiment, light-assisted ALD is used to form a metal-containing film by vaporizing and / or passing at least one metal complex disclosed herein over a substrate surface. Additionally or alternatively, light-assisted ALD is used to deliver a compound structurally corresponding to Formula I by vaporizing and / or passing the compound structurally corresponding to Formula I over a substrate surface. For light-assisted ALD processes, see, e.g., U.S. Pat. No. 4,581,249.

[0081] 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 over a substrate surface. Additionally or alternatively, plasma-assisted or plasma-enhanced ALD is used to deliver a compound structurally corresponding to Formula I by vaporizing and / or passing the compound structurally corresponding to Formula I over a substrate surface.

[0082] In another embodiment, a method of forming a metal-containing film on a surface of a substrate comprises: during an ALD process, exposing the substrate to a vapor-phase metal complex according to one or more embodiments described herein, such that a layer comprising the metal complex is formed on the surface, the metal complex being bound to the surface via a metal center (e.g., hafnium); during the ALD process, exposing the substrate with the bound metal complex to a co-reactant 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 surface of the substrate; and repeating the ALD process and treatment in sequence.

[0083] The reaction time, temperature and pressure are selected to produce metal-surface interactions and obtain a layer on the substrate surface. The reaction conditions of the ALD reaction will be selected based on the characteristics of the metal complex. Deposition can be carried out at atmospheric pressure, but is more usually carried out under reduced pressure. The vapor pressure of the metal complex should be low enough to be practiced in such applications. The substrate temperature should be high enough to keep the bonds between the metal atoms at the surface intact and prevent thermal decomposition of the gaseous reactants. However, the substrate temperature should also be high enough to keep the source material (i.e., reactants) in the gas phase and provide enough activation energy for the surface reaction. The appropriate temperature depends on various parameters, including the specific metal complex and pressure used. The characteristics of the specific metal complex used for the ALD deposition method 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, the presence of a lower molecular weight and a functional group that increases the rotational entropy of the ligand sphere results in a melting point of a liquid at a typical delivery temperature and an increased vapor pressure.

[0084] The metal complex used in the deposition method will have all the requirements for sufficient vapor pressure, sufficient thermal stability at the selected substrate temperature, and sufficient reactivity to produce a reaction on the substrate surface without unwanted impurities in the film. Sufficient vapor pressure ensures that the source compound molecules are present at the substrate surface in sufficient concentration to enable a complete self-saturation reaction. Sufficient thermal stability ensures that the source compound will not undergo thermal decomposition that produces impurities in the film.

[0085] Thus, the metal complexes disclosed herein for use in these methods can be liquid, solid, or gaseous. Typically, the metal complex is liquid or solid at ambient temperature and a vapor pressure sufficient to allow consistent vapor transport to the processing chamber.

[0086] In certain embodiments, the metal-containing complex and / or the compound corresponding to Formula I in structure can be dissolved in a suitable solvent such as a hydrocarbon or amine solvent to facilitate the vapor deposition process. 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 ethers and cyclic ethers such as diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether. 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 from about 0.05M to about 1M.

[0087] In another embodiment, at least one metal complex and / or compound corresponding in structure to Formula I may be delivered to the substrate surface "neat" (undiluted by a carrier gas).

[0088] In another embodiment, a mixed metal film can be formed by methods described herein that vaporize at least a first metal complex as disclosed herein, which is combined with a second metal complex (and / or with a third metal complex and / or with a fourth metal complex, etc.) containing a metal other than the metal of the first metal complex disclosed herein, but not necessarily simultaneously. For example, the first metal complex can contain Hf and the second metal-containing complex can contain Zr to form a mixed metal Hf-Zr film. In some embodiments, the mixed metal film can be a mixed metal oxide, a mixed metal nitride, or a mixed metal oxynitride.

[0089] In one embodiment, an elemental metal, metal nitride, metal oxide, or metal silicide film may be formed by delivering at least one metal complex as disclosed herein, either alone or in combination with a co-reactant, for deposition. In this regard, the co-reactant may be deposited or delivered to or through the substrate surface, either alone or in combination with at least one metal complex. As will be readily appreciated, the specific 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, H 2 O 2 、N 2 O, 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-butyl alcohol, etc. Examples of suitable boranes include, but are not limited to, hydrogenated (i.e., reduced) boranes such as borane, diborane, triborane, etc. Examples of suitable silanes include, but are not limited to, hydrogenated silanes such as monosilane, disilane, trisilane, etc. Examples of suitable hydrazines include, but are not limited to, hydrazine (N 2 H 4), such as methylhydrazine, tert-butylhydrazine, N,N- or N,N′-dimethylhydrazine, etc., hydrazines optionally substituted by one or more alkyl groups (i.e., alkyl-substituted hydrazines), such as phenylhydrazine, etc., hydrazines optionally substituted by one or more aryl groups (i.e., aryl-substituted hydrazines), etc.

[0090] In one embodiment, the metal complex disclosed herein is delivered to the substrate surface in pulses alternating with pulses of an oxygen-containing co-reactant to provide a metal oxide film. Examples of such oxygen-containing co-reactants include, but are not limited to, H 2 O, H 2 O 2 , O 2 , ozone, air, i-PrOH, t-BuOH or N 2 O.

[0091] In other embodiments, the co-reactant comprises a reducing agent such as hydrogen. In such embodiments, an elemental metal film is obtained. In particular embodiments, the elemental metal film consists of or consists essentially of pure metal. Such pure metal films may contain more than about 80%, 85%, 90%, 95%, or 98% of the metal. In even more particular embodiments, the elemental metal film is a hafnium film.

[0092] In other embodiments, a co-reactant is used to form a metal nitride film by delivering at least one metal complex as disclosed herein, alone or in combination with a co-reactant such as, but not limited to, ammonia, hydrazine, and / or other nitrogen-containing compounds (e.g., amines) to a reaction chamber for deposition. A variety of such co-reactants may be used. In further embodiments, the metal nitride film is a hafnium nitride film.

[0093] In certain embodiments, the methods of the present technology are used 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.

[0094] 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 be used as oxidation catalysts, anode materials (e.g., SOFC or LIB anodes), conductive layers, sensors, diffusion barriers / coatings, superconducting and non-superconducting materials / coatings, friction coatings and / or protective coatings. It will be understood by those of ordinary skill in the art that film properties (e.g., conductivity) will depend on many factors such as the one or more metals used for deposition, the presence or absence of co-reactants and / or co-complexes, the thickness of the resulting film, the parameters used during growth and subsequent processing, and the substrate.

[0095] References throughout this specification to "one embodiment," "certain embodiments," "one or more embodiments," or "an embodiment" mean that the particular features, structures, materials, or characteristics described in conjunction with the embodiment are included in at least one embodiment of the present technology. Thus, the appearance of phrases such as "in one or more embodiments," "in certain embodiments," "in one embodiment," or "in an embodiment" in various places throughout this specification are not necessarily referring to the same embodiment of the present technology. Furthermore, the particular features, structures, materials, or characteristics may be combined in any suitable manner in one or more embodiments.

[0096] Although the present invention technology has been described herein with reference to specific embodiments, it should be understood that these embodiments only illustrate the principles and applications of the present invention technology. It will be apparent to those skilled in the art that various modifications and changes may be made to the methods and devices of the present invention technology without departing from the spirit and scope of the present invention technology. Therefore, the present invention technology is intended to include modifications and changes within the scope of the appended claims and their equivalents. The present invention technology described so generally will be more easily understood by reference to the following examples, which are provided by way of illustration and are not intended to be limiting.

[0097] Example

[0098] Example 1: Barrier layer formation by liquid deposition and barrier layer inhibition of hafnium-containing films

[0099] The compound of formula (I) was mixed with toluene to form solutions 1 to 10 as shown in Table 2 below.

[0100] Table 2

[0101]

[0102] The barrier layer was prepared by a liquid phase delivery method (i.e., an immersion method), which involved immersing Si samples in solutions 1-10 for 24 hours in a glove box to form coated samples 1-10. After 24 hours, the coated samples 1-10 were rinsed with toluene in the glove box and with acetone and dichloromethane in the chemical fume hood. The coated samples 1-10 were treated with N 2 Dry and characterize by ellipsometry and water contact angle measurements.

[0103] The barrier layer formed on the coated samples 1-10 was then tested for its ability to inhibit the growth of Hf-containing films. Each of the coated samples 1-10 was loaded into an ALD chamber and tested in a separate experiment (MeCp) 2 Hf(OMe)(Me) and H 2O for 50, 100, 200 and 300 cycles. For the control, the Si specimens were exposed only to (MeCp) 2 Hf(OMe)(Me). HfO ALD process conditions are as follows: 2 second pulse (MeCp) 2 Hf(OMe)(Me), 10 sec pulse N 2 , 2 second pulse H 2 O, and 10 second pulse N 2 , at 350 °C. For 200 cycles, solution 3 containing 11-cyanoundecyltrichlorosilane showed the highest barrier. Coated sample 3 treated with solution 3 showed the lowest HfO after exposure to 200 cycles. 2 thickness.

[0104] Example 2: Formation of barrier layer by vapor deposition and barrier layer inhibition of hafnium-containing film

[0105] Compound 1 (n-octyltrichlorosilane), Compound 2 (dodecyltrichlorosilane) and Compound 3 (11-cyanoundecyltrichlorosilane) were delivered to the silicon substrate via vapor extraction to form coated substrates 1 to 3. The ampoule temperature of Compound 1 was 120°C, Compound 2 was 160°C, and Compound 3 was 185°C.

[0106] The barrier layers formed on coated substrates 1-3 were then tested for their ability to inhibit the growth of Hf-containing films. Each of the coated substrates 1-3 was loaded into an ALD chamber and tested in a separate experiment (MeCp) 2 Hf(OMe)(Me) and H 2 O for 50, 100, 200, 300 and 400 cycles. For the control, the Si specimens were exposed only to (MeCp) 2 Hf(OMe)(Me). HfO ALD process conditions are as follows: 2 second pulse (MeCp) 2 Hf(OMe)(Me), 10 sec pulse N 2 , 2 second pulse H 2 O, and 10 second pulse N 2 , at 350°C.

[0107] All publications, patent applications, issued patents, and other documents mentioned in this specification are incorporated herein by reference 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 text incorporated by reference are excluded to the extent they conflict with definitions in this disclosure.

[0108] The words "comprise", "comprises" and "comprising" are to be construed as being inclusive rather than exclusive.

Claims

1. A method for forming a metal-containing film, the method comprising: forming a barrier layer on the surface of the first substrate by a first vapor deposition process or a first liquid deposition process, The first vapor deposition process is to vaporize a compound corresponding to formula (I): in X 1 YesR 1 or R 2 R 3 ; where R 1 is a C8-C 20 -alkyl; R 2 is a C8-C 20 -alkylene; and R 3 is selected from the group consisting of nitrile, vinyl, halogen, trifluoromethyl, acetoxy, methoxyethoxy, and phenoxy; and The first liquid deposition process is to contact the surface of the first substrate with a solution containing the compound having a structure corresponding to formula (I); as well as The metal-containing film is formed on the surface of the second substrate by a second deposition process, the second deposition process comprising vaporizing at least one metal complex corresponding in structure to Formula II: wherein M is Hf; and L 1 , L 2 , L 3 and L 4 each independently selected from the group consisting of C1-C8-alkyl, C1-C8-alkoxy and a Cp group optionally substituted by at least one C1-C8-alkyl; The first substrate surface comprises a dielectric material and the second substrate surface comprises a metal material.

2. A method for forming a metal-containing film, the method comprising: forming a barrier layer on the surface of the first substrate by a first vapor deposition process or a first liquid deposition process, The first vapor deposition process is to vaporize a compound corresponding to formula (I): in X 1 YesR 1 or R 2 R 3 ; where R 1 is a C8-C 20 -alkyl; R 2 is a C8-C 20 -alkylene; and R 3 is selected from the group consisting of nitrile, vinyl, halogen, trifluoromethyl, acetoxy, methoxyethoxy, and phenoxy; and The first liquid deposition process is to contact the surface of the first substrate with a solution containing the compound having a structure corresponding to formula (I); as well as The metal-containing film is formed on the surface of the second substrate by a second deposition process, the second deposition process comprising vaporizing at least one metal complex corresponding in structure to Formula II: wherein M is Hf; and L 1 , L 2 , L 3 and L 4 each independently selected from the group consisting of C1-C8-alkyl, C1-C8-alkoxy and a Cp group optionally substituted by at least one C1-C8-alkyl; The first substrate surface comprises a metal oxide material and the second substrate surface comprises a metal material.

3. A method for forming a metal-containing film, the method comprising: forming a barrier layer on a first portion of the substrate by a first vapor deposition process or a first liquid deposition process, The first vapor deposition process is to vaporize a compound corresponding to formula (I): in X 1 YesR 1 or R 2 R 3 ; where R 1 is a C8-C 20 -alkyl; R 2 is a C8-C 20 -alkylene; and R 3 is selected from the group consisting of nitrile, vinyl, halogen, trifluoromethyl, acetoxy, methoxyethoxy, and phenoxy; and wherein the first liquid deposition process is to contact the first portion of the substrate with a solution comprising the compound having a structure corresponding to formula (I); as well as The metal-containing film is formed on a second portion of the substrate by a second deposition process, the second deposition process comprising vaporizing at least one metal complex corresponding in structure to Formula II: wherein M is Hf; and L 1 , L 2 , L 3 and L 4 each independently selected from the group consisting of C1-C8-alkyl, C1-C8-alkoxy and a Cp group optionally substituted by at least one C1-C8-alkyl; The first portion of the substrate comprises a dielectric material and the second portion of the substrate comprises a metallic material.

4. A method for forming a metal-containing film, the method comprising: forming a barrier layer on a first portion of the substrate by a first vapor deposition process or a first liquid deposition process, The first vapor deposition process is to vaporize a compound corresponding to formula (I): in X 1 YesR 1 or R 2 R 3 ; where R 1 is a C8-C 20 -alkyl; R 2 is a C8-C 20 -alkylene; and R 3 is selected from the group consisting of nitrile, vinyl, halogen, trifluoromethyl, acetoxy, methoxyethoxy, and phenoxy; and wherein the first liquid deposition process is to contact the first portion of the substrate with a solution comprising the compound having a structure corresponding to formula (I); as well as The metal-containing film is formed on a second portion of the substrate by a second deposition process, the second deposition process comprising vaporizing at least one metal complex corresponding in structure to Formula II: wherein M is Hf; and L 1 , L 2 , L 3 and L 4 each independently selected from the group consisting of C1-C8-alkyl, C1-C8-alkoxy and a Cp group optionally substituted by at least one C1-C8-alkyl; The first portion of the substrate comprises a metal oxide material and the second portion of the substrate comprises a metal material.

5. The method according to any one of claims 1 to 4, wherein: R 1 is a C8-C 15 -alkyl.

6. The method according to any one of claims 1 to 4, wherein: R 1 is a C8-C 12 -alkyl.

7. The method according to any one of claims 1 to 4, wherein: R 2 It is C8-C 15 -alkylene.

8. The method according to any one of claims 1 to 4, wherein: R 2 It is C8-C 12 -alkylene.

9. The method according to any one of claims 1 to 4, wherein: The compound corresponding in structure to formula (I) is selected from the group consisting of: n-Octyltrichlorosilane; Dodecyltrichlorosilane; 11-Cyanoundecyltrichlorosilane; 11-Acetoxyundecyltrichlorosilane; (tridecafluoro-1,1,2,2-tetrahydrooctyl)trichlorosilane; 10-Undecenyltrichlorosilane; 11-Bromoundecyltrichlorosilane; 11-(2-Methoxyethoxy)undecyltrichlorosilane; 11-phenoxyundecyltrichlorosilane; and 1,2-Bis(trichlorosilyl)decane.

10. The method according to any one of claims 1 to 4, wherein: The metal complex is (MeCp)2Hf(OMe)(Me).

11. The method according to any one of claims 1 to 4, wherein: The metal of the metal-containing film is present on the barrier layer in an amount less than 15 at. %.

12. The method according to any one of claims 1 to 2, wherein: The first substrate surface and the second substrate surface exist on the same substrate or on different substrates.

13. The method according to any one of claims 1 to 4, wherein: The metal material includes W, Co, Cu or a combination thereof.

14. The method according to claim 1 or 3, wherein: The dielectric material includes SiO2, SiN or a combination thereof.

15. The method according to claim 2 or 4, wherein: The metal oxide material includes HfO2, ZrO2, SiO2, Al2O3 or a combination thereof.

16. The method according to any one of claims 1 to 4, wherein: The first vapor deposition process and the second deposition process are independently chemical vapor deposition or atomic layer deposition.

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

18. The method of claim 16, wherein: The atomic layer deposition is liquid injection atomic layer deposition or plasma enhanced atomic layer deposition.

19. The method according to any one of claims 1 to 4, wherein: The first liquid deposition process comprises immersing the first substrate surface or the first portion of the substrate surface in the solution comprising the compound of formula (I) one or more times.

20. The method of any one of claims 1 to 4, wherein: The metal complex is delivered to the substrate in pulses alternating with pulses of an oxygen source.

21. The method of claim 20, wherein: The oxygen source is selected from the group consisting of H2O, H2O2, O2, ozone, air, i-PrOH, t-BuOH and N2O.

22. The method of any one of claims 1-4, further comprising gasifying 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.

23. The method of any one of claims 1 to 4, wherein: This method is used in DRAM or CMOS applications.

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