Intramolecularly stabilized group 13 metal complexes with improved thermal stability for vapor thin film deposition techniques

Abstract

The disclosed and claimed subject matter provides Group 13 (i.e., B, Al, Ga, and In) compounds and methods for using the compounds as precursors for the deposition of metal-containing films.

Description

[Technical Field]

[0001] Field

[0002] The disclosed and claimed subject matter relates to Group 13 (i.e., B, Al, Ga, and In) compounds and methods of using the compounds as precursors for the deposition of metal-containing films. [Background technology]

[0003] Related technologies

[0004] Transition metal-containing films are used in semiconductor and electronics applications. Chemical vapor deposition (CVD) and atomic layer deposition (ALD) have been adopted as the primary deposition techniques for producing thin films for semiconductor devices. These methods enable conformal films (metals, metal oxides, metal nitrides, metal silicides, and the like) to be produced through the chemical reaction of metal-containing compounds (precursors). The chemical reaction occurs on surfaces that may include metals, metal oxides, metal nitrides, metal silicides, and other surfaces. In CVD and ALD, precursor molecules play a crucial role in achieving high-quality films with high conformality and low impurities. The substrate temperature in CVD and ALD processes is an important consideration in selecting precursor molecules. Higher substrate temperatures, in the range of 150–500 degrees Celsius (°C), promote faster film growth rates. Preferred precursor molecules must be stable within this temperature range. Preferred precursors can be delivered to the reaction vessel in the liquid phase. Liquid phase delivery of precursors generally results in a more uniform delivery of precursors to the reaction vessel than solid phase precursors.

[0005] In ALD, thin films can be deposited by the reaction of organometallic precursors and co-reactants separated by an inert gas purge. This unique mechanism allows ALD to coat three-dimensional (3D) surfaces with atomic precision, making it essential to the semiconductor industry.

[0006] Precursors for Group 13 metal-containing thin films using ALD are largely dominated by alkyl precursors such as trimethylindium, trimethylgallium, or trimethylaluminum. These precursors share the commonality of being highly volatile and reactive, thereby enabling a wide variety of ALD processes for the corresponding metals, metal oxides, metal nitrides, metal sulfides, and some inorganic-organic hybrid materials. However, their greatest drawback is their high pyrophoricity, which hinders ease of handling and makes them dangerous in the event of an accident. Furthermore, thermal stability is an issue in the case of trimethylindium, which can only be used at deposition temperatures below 250 °C.

[0007] Attempts to increase the thermal stability of trimethylmetal complexes and overcome their pyrophoric nature have resulted in the use of the alkylaminoalkyl ligand 3-(N,N-dimethylamino)propyl (DMP), which is bound to the electron-deficient Group 13 metal center in the complex via its terminal carbon atom and a dative bond through the nitrogen atom. This chelating ligand can therefore stabilize the complex by donating electrons to the metal.

[0008] Examples of such complexes are 3-(N,N-dimethylamino)propyl-dimethylaluminum (DMAD) or 3-(N,N-dimethylamino)propyl-dimethylindium (DADI). L. Mai et al., Chem-Eur. J., 23, 10768-10772 (2017) and L. Mai et al., Chem.-Eur. J., 25, 7489-7500 (2019) describe the synthesis of Al(DMP)R2, where R = Me, NMe2, NEt2, and N(i-Pr)2, and the respective ALD processes using O2 plasma or water. See also DE 4213292 A1. EP 3256478 A1 discloses the synthetic preparation of DADI. T. Hong et al., ACS Appl. Electron. Mater., 4, 3010-3017 (2022) describes a plasma-assisted ALD process using DADI with oxygen. W. J. Maeng et al., Ceram. Int., 41, 10782-10787 (2015) and W. J. Maeng et al., J. Alloys Compd., 649, 216-221 (2015) describe ALD processes using DADI with water and ozone, respectively. Korean Patent No. 102043296 discloses a general synthetic route to Group 13 metal complexes using alkylaminoalkyl ligands with different substituents, where each carbon in the alkyl chain must be identically substituted. WO2022190877(A1) describes alkylaminoalkyl complexes with In and Zn as metal centers, but does not explicitly disclose branched alkyl chains, and therefore the benefits of branched chains compared to linear alkyl chains are not expected or predictable. EP0690748, EP0260534, and U.S. Pat. No. 3,154,528 also disclose metal compounds with alkylaminoalkyl ligands, but only disclose partially substituted alkyl chains with at least one hydrogen atom at the β-position as branched alkyl chains.

[0009] Surprisingly, it was found that modifying the chelating ligands could further significantly improve / increase the thermal stability of the resulting metal complexes. In contrast, the β-positions in the propyl chains were fully substituted with alkyl groups. Without being bound by theory, this substitution may block the precursor decomposition pathway via β-hydrogen elimination, which is predicted for other known precursors (e.g., those described in WO 2022190877). Furthermore, substituting only the β-positions of the chains introduces asymmetry into the chains, which lowers the melting point and increases the volatility of the compounds compared to heavier, fully substituted systems, such as those described in Korean Patent No. 102043296. Summary of the Invention [Problem to be solved by the invention]

[0010] The disclosed and claimed subject matter includes Group 13 (i.e., boron (B); aluminum (Al); gallium (Ga); and indium (In)) organometallic compounds and methods of using the compounds as precursors for the deposition of metal-containing films. The disclosed and claimed subject matter further includes compositions comprising the compounds, methods of using the compounds as precursors for the deposition of metal-containing films, and films derived from the precursors. [Means for solving the problem]

[0011] In one embodiment, the Group 13 compound / precursor has Formula I: [ka] During the ceremony, (a)R 1 and R 2 are (i) each independently one of a C1 to C6 linear alkyl group, a C3 to C6 branched alkyl group, and a C3 to C6 cyclic alkyl group, or (ii) linked to form one of a 3-membered ring, a 4-membered ring, a 5-membered ring, and a 6-membered ring; (b)R 3 and R 4are each independently one of a C1 to C6 linear alkyl group, a C3 to C6 branched alkyl group, and a C3 to C6 cyclic alkyl group; (c) n = 1 to 3; (d) M is one of B, Al, Ga, and In; and (e)L 1 represents a C1-C6 linear alkyl group, a C3-C6 branched alkyl group, and a group of the formula -NR 5 R 6 an amino group of the formula: 5 and R 6 are each independently one of an amino group, which is one of a C1 to C6 linear alkyl group and a C3 to C6 branched alkyl group.

[0012] In one embodiment, the Group 13 compound / precursor has Formula II: [ka] During the ceremony, (a)R 1 and R 2 are (i) each independently one of a C1 to C6 linear alkyl group, a C3 to C6 branched alkyl group, and a C3 to C6 cyclic alkyl group, or (ii) linked to form one of a 3-membered ring, a 4-membered ring, a 5-membered ring, and a 6-membered ring; (b)R 3 and R 4 are each independently one of a C1 to C6 linear alkyl group, a C3 to C6 branched alkyl group, and a C3 to C6 cyclic alkyl group; (c) n = 1 to 3; (d) M is one of B, Al, and Ga; and (e)L 1 represents a C1-C6 linear alkyl group, a C3-C6 branched alkyl group, and a group of the formula -NR 5 R 6 an amino group of the formula: 5 and R 6 are each independently one of an amino group, which is one of a C1 to C6 linear alkyl group and a C3 to C6 branched alkyl group.

[0013] In one embodiment, the Group 13 compound / precursor has Formula III: [ka] During the ceremony, (a)R 1 and R 2 are (i) each independently one of a C1 to C6 linear alkyl group, a C3 to C6 branched alkyl group, and a C3 to C6 cyclic alkyl group, or (ii) linked to form one of a 3-membered ring, a 4-membered ring, a 5-membered ring, and a 6-membered ring; (b)R 3 and R 4 are each independently one of a C1 to C6 linear alkyl group, a C3 to C6 branched alkyl group, and a C3 to C6 cyclic alkyl group; (c) n = 1 to 3; (d)L 1 represents a C1-C6 linear alkyl group, a C3-C6 branched alkyl group, and a group of the formula -NR 5 R 6 an amino group of the formula: 5 and R 6 are each independently one of an amino group, which is one of a C1 to C6 linear alkyl group and a C3 to C6 branched alkyl group.

[0014] The disclosed and claimed subject matter further includes (i) compositions and formulations comprising the disclosed and claimed compounds and / or precursors, (ii) methods of using the disclosed and claimed compounds and / or precursors in deposition processes, and (iii) metal-containing films derived from the disclosed and claimed compounds and / or precursors produced in deposition processes.

[0015] The accompanying drawings, which are included to provide a further understanding of the disclosed subject matter, and which are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosed subject matter and, together with the description, serve to explain the principles of the disclosed subject matter. [Brief explanation of the drawings]

[0016] [Figure 1] FIG. 1 shows the 1H NMR of the compound from Synthesis Example 1. [Figure 2] FIG. 2 shows the TGA of the compound from Synthesis Example 1. [Figure 3] FIG. 3 shows the differential scanning calorimetry (DSC) analysis of the compound from Synthesis Example 1. [Figure 4] FIG. 4 shows the 1H NMR of the compound from Synthesis Example 2. [Figure 5] FIG. 5 shows the TGA of the compound from Synthesis Example 2. DETAILED DESCRIPTION OF THE INVENTION

[0017] All references, including publications, patent applications, and patents, cited in this specification are herein incorporated by reference to the same extent as if each reference was individually and specifically indicated to be incorporated by reference and was set forth in its entirety herein.

[0018] The use of the terms "a," "an," and "the," and similar referents in the context of describing the disclosed and claimed subject matter (particularly in the context of the claims below) should be construed to encompass both the singular and the plural, unless otherwise stated herein or otherwise clearly contradicted by context. The terms "comprising," "having," "including," and "containing" should be construed as open-ended terms (i.e., meaning "including, but not limited to"), unless otherwise indicated. The recitation of ranges of values ​​herein is merely intended to be used as a shorthand method of separately referring to each individual value falling within the range, unless otherwise stated herein, and each individual value is incorporated herein by reference as if it were separately recited herein. All methods described herein may be performed in any suitable order unless otherwise stated herein or otherwise clearly contradicted by context. The use of any examples or exemplary language (e.g., "such as") provided herein is intended merely to better illustrate the disclosed and claimed subject matter and does not impose limitations on the scope of the disclosed and claimed subject matter unless specifically asserted otherwise. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the disclosed and claimed subject matter. The use of the terms "comprising" or "including" in the specification and claims includes the narrower language of "consisting essentially of" and "consisting of."

[0019] Embodiments of the disclosed and claimed subject matter are described herein, including the best mode known to the inventors for carrying out the disclosed and claimed subject matter. Variations on these embodiments will become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors anticipate that such variations will occur to those of ordinary skill in the art, and the inventors intend that the disclosed and claimed subject matter may be practiced otherwise than as specifically described herein. Accordingly, the disclosed and claimed subject matter includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Furthermore, any combination of the above-described elements in all possible variations thereof is encompassed by the disclosed and claimed subject matter unless otherwise indicated herein or otherwise clearly contradicted by context.

[0020] It is understood that the term "silicon" deposited as a material on a microelectronic device includes polysilicon.

[0021] For ease of reference, "microelectronic device" or "semiconductor device" refers to semiconductor wafers with integrated circuits, memory, and other electronic structures fabricated thereon, manufactured for use in microelectronics, integrated circuit, or computer chip applications, as well as flat panel displays, phase change memory devices, solar panels and other products including solar cell substrates, photovoltaic devices, and microelectromechanical systems (MEMS). Solar cell substrates include, but are not limited to, silicon, amorphous silicon, polycrystalline silicon, single crystal silicon, CdTe, copper indium selenide, copper indium sulfide, and gallium arsenide on gallium. Solar cell substrates may be doped or undoped. It should be understood that the terms "microelectronic device" or "semiconductor device" are not intended to be limiting and include any substrate that ultimately becomes a microelectronic device or microelectronic assembly.

[0022] As defined herein, the term "barrier material" refers to any material used in the art to encapsulate metal lines, e.g., copper interconnects, and to minimize the diffusion of said metals, e.g., copper, into dielectric materials. Preferred barrier layer materials include tantalum, titanium, ruthenium, hafnium, and other refractory metals, as well as their nitrides and silicides.

[0023] As used herein, "C x-y " indicates the number of carbon atoms in the chain. For example, C 1-6 Alkyl means an alkyl chain having a chain of 1 to 6 carbon atoms (e.g., methyl, ethyl, propyl, butyl, pentyl, and hexyl). Unless otherwise specified, the chain may be straight or branched.

[0024] Unless otherwise specified, "alkyl" refers to a hydrocarbon group that may be straight-chained, branched (e.g., methyl, ethyl, propyl, isopropyl, tert-butyl, and the like), cyclic (e.g., cyclohexyl, cyclopropyl, cyclopentyl, and the like), or polycyclic (e.g., norbornyl, adamantyl, and the like). Suitable acyclic groups can be methyl, ethyl, n- or iso-propyl, n-, iso-, or tert-butyl, straight- or branched-chain pentyl, hexyl, heptyl, octyl, decyl, dodecyl, tetradecyl, and hexadecyl. Unless otherwise specified, alkyl refers to a moiety containing 1 to 10 carbon atoms. Cyclic alkyl groups can be monocyclic or polycyclic. Suitable examples of monocyclic alkyl groups include substituted cyclopentyl, cyclohexyl, and cycloheptyl groups. The substituents can be any of the acyclic alkyl groups described herein. Suitable bicyclic alkyl groups include substituted bicyclo[2.2.1]heptane, bicyclo[2.2.2]octane, bicyclo[3.2.1]octane, bicyclo[3.2.2]nonane, and bicyclo[3.3.2]decane, and the like. Examples of tricyclic alkyl groups include tricyclo[5.4.0.0. 2,9 ]Undecane, Tricyclo[4.2.1.2. 7,9]Undecane, Tricyclo[5.3.2.0. 4, 9]dodecane, and tricyclo[5.2.1.0. 2,6 ]decane. As mentioned herein, cyclic alkyl groups may have any of the acyclic alkyl groups as a substituent. These alkyl moieties may be substituted or unsubstituted.

[0025] "Halogenated alkyl" refers to a linear, cyclic, or branched saturated alkyl group, as defined above, in which one or more of the hydrogens have been replaced with a halogen (e.g., F, Cl, Br, and I). Thus, for example, a fluorinated alkyl (also referred to as a "fluoroalkyl") refers to a linear, cyclic, or branched saturated alkyl group, as defined above, in which one or more of the hydrogens have been replaced with a fluorine (e.g., trifluoromethyl, pefluoroethyl, 2,2,2-trifluoroethyl, prefluoroisopropyl, perfluorocyclohexyl, and the like). Such haloalkyl moieties (e.g., fluoroalkyl moieties), when not perhalogenated / polyhalogenated, can be unsubstituted or further substituted.

[0026] "Alkoxy" (also referred to as "alkyloxy") means an alkyl group, as defined above, attached through an oxy (-O-) moiety (e.g., methoxy, ethoxy, propoxy, butoxy, 1,2-isopropoxy, cyclopentyloxy, cyclohexyloxy, and the like). These alkoxy moieties may be substituted or unsubstituted.

[0027] "Alkylcarbonyl" means an alkyl group, as defined above, attached through a carbonyl (-C(=O-)) moiety (e.g., methylcarbonyl, ethylcarbonyl, propylcarbonyl, butylcarbonyl, cyclopentylcarbonyl, and the like). These alkylcarbonyl moieties may be substituted or unsubstituted.

[0028] "Halo" or "halide" means halogen (e.g., F, Cl, Br, and I).

[0029] "Hydroxy" or "hydroxyl" refers to the group --OH.

[0030] Unless otherwise noted, the term "substituted" when referring to alkyl, alkoxy, fluorinated alkyl, and the like means one of these moieties that also contains one or more of the following substituents, including, but not limited to, alkyl, substituted alkyl, unsubstituted aryl, substituted aryl, alkyloxy, alkylaryl, haloalkyl, halide, hydroxy, amino, and aminoalkyl. Similarly, the term "unsubstituted" refers to these same moieties in which there are no substituents other than hydrogen.

[0031] Alkylene groups are divalent alkyl groups derived from any of the alkyl groups described herein above. When referring to alkylene groups, these include those having (C1-C6) in the main carbon chain of the alkylene group. 18 ) alkylene chains substituted with alkyl groups. The alkylene group may also contain one or more alkyne groups in the alkylene portion, where alkyne refers to a triple bond. Essentially, alkylenes are based on divalent hydrocarbon groups. Thus, divalent acyclic groups can be methylene, 1,1- or 1,2-ethylene, 1,1-, 1,2-, or 1,3-propylene, 2,5-dimethyl-hexene, 2,5-dimethyl-hex-3-yne, and the like. Similarly, divalent cyclic alkyl groups can be 1,2- or 1,3-cyclopentylene, 1,2-, 1,3-, or 1,4-cyclohexylene, and the like. Divalent tricycloalkyl groups can be any of the tricyclic alkyl groups described herein above. An example of a tricyclic alkyl group is 4,8-bis(methylene)-tricyclo[5.2.1.0. 2,6]decane. When perfluoroalkylenes are mentioned, these include those alkylene groups described above but in which hydrogen atoms have been replaced by fluorine. Similarly, when a partially fluorinated alkylene group is mentioned, this is an alkylene group in which some of the hydrogen atoms have been replaced by fluorine.

[0032] Aryl groups contain 6 to 24 carbon atoms and include phenyl, tolyl, xylyl, naphthyl, anthracyl, biphenyl, bis-phenyl, tris-phenyl, and the like. These aryl groups may be further substituted with any suitable substituent, e.g., alkyl, alkoxy, acyl, or aryl groups, as described hereinabove. Similarly, suitable polyvalent aryl groups may be used in the present invention, if desired. Representative examples of arylene, a divalent aryl group, include phenylene, xylylene, naphthylene, biphenylene, and the like. As used herein, unless otherwise specified, the term "aromatic" refers to an unsaturated cyclic hydrocarbon having a delocalized conjugated π-system and having 4 to 20 carbon atoms (aromatic C4-C6). 20"Aromatic" refers to a hydrocarbon. Exemplary aromatics include, but are not limited to, benzene, toluene, xylene, mesitylene, ethylbenzene, cumene, naphthalene, methylnaphthalene, dimethylnaphthalene, ethylnaphthalene, acenaphthalene, anthracene, phenanthrene, tetraphene, naphthacene, benzanthracene, fluoranthrene, pyrene, chrysene, triphenylene, and the like, and combinations thereof. Aromatics may be optionally substituted, for example, with one or more alkyl groups, alkoxy groups, halogens, and the like. For example, aromatics may include anisole. Additionally, aromatics may include one or more heteroatoms. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, phosphorus, boron, and / or sulfur. Aromatics having one or more heteroatoms include, but are not limited to, furan, benzofuran, thiophene, benzothiophene, oxazole, thiazole, and the like, and combinations thereof. The aromatic may include monocyclic, bicyclic, tricyclic, and / or polycyclic rings (in some embodiments, at least monocyclic rings, only monocyclic and bicyclic rings, or only monocyclic rings), and may be fused rings.

[0033] As used herein, the term "arene" means a cyclic hydrocarbon having alternating double and single bonds between carbon atoms (i.e., aromatic rings), and also includes heteroarenes in which one or more of the carbon atoms forming such an aromatic ring are replaced with a heteroatom (e.g., oxygen, sulfur, nitrogen, silicon, germarium, phosphorus). Examples of arenes include, for example, benzene, substituted benzene, naphthalene, anthracene, and the like. Examples of heteroarenes include, for example, pyridine, furan, indole, benzimidazole, thiophene, benzthiazole, and the like.

[0034] The term "non-aromatic" means that four or more carbon atoms are bonded in at least one ring structure, and at least one of the four or more carbon atoms in the ring structure is not an aromatic carbon atom.

[0035] As used herein, "substantially free" is defined as less than 0.001% by weight. "Substantially free" also includes 0.000% by weight. The term "free" means 0.000% by weight. As used herein, "about" or "approximately" is intended to correspond to within ±5% of the stated value.

[0036] In all compositions where particular components of a composition are discussed with reference to a weight percent (or weight %) range that includes a lower limit of zero, it is understood that such components may or may not be present in various specific embodiments of the composition, and that when such components are present, they may be present in concentrations as low as 0.001 weight percent, based on the total weight of the composition in which such component is used. Note that all component percentages are weight percents and are based on the total weight of the composition, i.e., 100%. Any reference to "one or more" or "at least one" includes "two or more" and "three or more," etc.

[0037] Where applicable, unless otherwise specified, all weight percentages are "neat," meaning that they do not include the aqueous solution they are in when added to the composition. For example, "neat" refers to the amount by weight of an acid or other material that is not diluted (i.e., 100 grams of 85% phosphoric acid contains 85 grams of acid and 15 grams of diluent).

[0038] Furthermore, when compositions described herein are referred to in terms of weight percent, it is understood that the weight percent of all components, including non-essential components such as impurities, may not in any event total more than 100 weight percent. In a composition "consisting essentially of" listed components, such components may total 100 weight percent of the composition, or may total less than 100 weight percent. Where components total less than 100 weight percent, such compositions may contain certain minor amounts of non-essential contaminants or impurities. For example, in one such embodiment, the formulation may contain 2 weight percent or less of impurities. In another embodiment, the formulation may contain 1 weight percent or less of impurities. In a further embodiment, the formulation may contain 0.05 weight percent or less of impurities. In other such embodiments, the components may form at least 90 weight percent, more preferably at least 95 weight percent, more preferably at least 99 weight percent, more preferably at least 99.5 weight percent, and most preferably at least 99.9 weight percent, and may include other raw material components that do not substantially affect the performance of the wet etchant. Otherwise, it is understood that the composition of all essential components will add up to essentially 100% by weight in the absence of significant non-essential impurity components.

[0039] The headings used herein are not intended to be limiting; rather, they are included for organizational purposes only.

[0040] Illustrative Embodiments

[0041] One aspect of the disclosed and claimed subject matter relates to Group 13 (i.e., B, Al, Ga, and In) compounds and methods of using the same as precursors for the deposition of metal-containing films.

[0042] In one embodiment, the Group 13 compound / precursor has Formula I: [ka] During the ceremony, (a)R 1 and R 2are (i) each independently one of a C1 to C6 linear alkyl group, a C3 to C6 branched alkyl group, and a C3 to C6 cyclic alkyl group, or (ii) linked to form one of a 3-membered ring, a 4-membered ring, a 5-membered ring, and a 6-membered ring; (b)R 3 and R 4 are each independently one of a C1 to C6 linear alkyl group, a C3 to C6 branched alkyl group, and a C3 to C6 cyclic alkyl group; (c) n = 1 to 3; (d) M is one of B, Al, Ga, and In; and (e)L 1 represents a C1-C6 linear alkyl group, a C3-C6 branched alkyl group, and a group of the formula -NR 5 R 6 an amino group of the formula: 5 and R 6 are each independently one of an amino group, which is one of a C1 to C6 linear alkyl group and a C3 to C6 branched alkyl group.

[0043] In one aspect of this embodiment, M is B. In another aspect of this embodiment, M is Al. In another aspect of this embodiment, M is Ga. In another aspect of this embodiment, M is In.

[0044] In one aspect of this embodiment, n=1. In another aspect of this embodiment, n=2. In another aspect of this embodiment, n=3.

[0045] In one aspect of this embodiment, R 1 and R 2 are each independently one of a C1 to C6 straight chain alkyl group, a C3 to C6 branched chain alkyl group, and a C3 to C6 cyclic alkyl group. In one aspect of this embodiment, R 3 and R 4 are each independently one of a C1 to C6 straight chain alkyl group, a C3 to C6 branched chain alkyl group, and a C3 to C6 cyclic alkyl group. In one aspect of this embodiment, R 1 , R2 , R 3 , and R 4 are each independently one of a C1 to C6 linear alkyl group, a C3 to C6 branched alkyl group, and a C3 to C6 cyclic alkyl group.

[0046] In one aspect of this embodiment, R 1 and R 2 are linked to form one of a 3-membered ring, a 4-membered ring, a 5-membered ring, and a 6-membered ring.

[0047] In one aspect of this embodiment, R 1 and R 2 are linked to form a three-membered ring. In one aspect of this embodiment, R 1 and R 2 are linked to form a cyclopropyl ring.

[0048] In one aspect of this embodiment, R 1 and R 2 are linked to form a four-membered ring. In one aspect of this embodiment, R 1 and R 2 are linked to form a cyclobutyl ring.

[0049] In one aspect of this embodiment, R 1 and R 2 are linked to form a five-membered ring. In one aspect of this embodiment, R 1 and R 2 are linked to form a cyclopentyl ring.

[0050] In one aspect of this embodiment, R 1 and R 2 are linked to form a six-membered ring. In one aspect of this embodiment, R 1 and R 2 are linked to form a cyclohexyl ring.

[0051] In one aspect of this embodiment, L 1 , R 1 , R2 , R 3 , R 4 , R 5 , and R 6 In one aspect of this embodiment, three or more of L 1 , R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 In one aspect of this embodiment, two or more of L 1 , R 1 , R 2 , R 3 , and R 4 are each a methyl group (“Me” or “—CH”). In one aspect of this embodiment, n=1 and L 1 , R 1 , R 2 , R 3 , and R 4 are each a methyl group (“Me” or “—CH”). In one aspect of this embodiment, n=2 and L 1 , R 1 , R 2 , R 3 , and R 4 are each a methyl group (“Me” or “—CH”). In one aspect of this embodiment, R 5 and R 6 are present, each a methyl group (“Me” or “—CH3”).

[0052] In one aspect of this embodiment, L 1 , R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 Three of L are ethyl groups (“Et” or “—CH2CH3”). In one aspect of this embodiment, L 1 , R 1 , R 2 , R 3 , R 4 , R 5 , and R6 Two of L are ethyl groups (“Et” or “—CH2CH3”). In one aspect of this embodiment, L 1 , R 1 , R 2 , R 3 , and R 4 are each an ethyl group (“Et” or “—CH2CH3”). In one aspect of this embodiment, n=1 and L 1 , R 1 , R 2 , R 3 , and R 4 are each an ethyl group (“Et” or “—CH2CH3”). In one aspect of this embodiment, n=2 and L 1 , R 1 , R 2 , R 3 , and R 4 are each an ethyl group (“Et” or “—CH2CH3”). In one aspect of this embodiment, R 5 and R 6 are present, each an ethyl group (“Et” or “—CH2CH3”).

[0053] In one aspect of this embodiment, L 1 , R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are propyl groups (“Pr” or “—CH2CH2CH3”). In one aspect of this embodiment, L 1 , R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 In one aspect of this embodiment, two or more of L 1 , R 1 , R 2 , R 3 , and R 4are each a propyl group (“Pr” or “—CH2CH2CH3”). In one aspect of this embodiment, n=1 and L 1 , R 1 , R 2 , R 3 , and R 4 are each a propyl group (“Pr” or “—CH2CH2CH3”). In one aspect of this embodiment, n=2 and L 1 , R 1 , R 2 , R 3 , and R 4 are each a propyl group (“Pr” or “—CHCHCH”). In one aspect of this embodiment, R 5 and R 6 are present and are each a propyl group (“Pr” or “—CH2CH2CH3”).

[0054] In one aspect of this embodiment, L 1 , R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 In one aspect of this embodiment, two or more of L 1 , R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 At least one of the isopropyl groups ("iPr").

[0055] In one embodiment, the Group 13 compound / precursor has Formula II: [ka] During the ceremony, (a)R 1 and R 2are (i) each independently one of a C1 to C6 linear alkyl group, a C3 to C6 branched alkyl group, and a C3 to C6 cyclic alkyl group, or (ii) linked to form one of a 3-membered ring, a 4-membered ring, a 5-membered ring, and a 6-membered ring; (b)R 3 and R 4 are each independently one of a C1 to C6 linear alkyl group, a C1 to C6 branched alkyl group, and a C3 to C6 cyclic alkyl group; (c) n = 1 to 3; (d) M is one of B, Al, and Ga; and (e)L 1 represents a C1-C6 linear alkyl group, a C3-C6 branched alkyl group, and a group of the formula -NR 5 R 6 an amino group of the formula: 5 and R 6 are each independently one of an amino group, which is one of a C1 to C6 linear alkyl group and a C1 to C6 branched alkyl group.

[0056] In one aspect of this embodiment, M is B. In another aspect of this embodiment, M is Al. In another aspect of this embodiment, M is Ga.

[0057] In one aspect of this embodiment, n=1. In another aspect of this embodiment, n=2. In another aspect of this embodiment, n=3.

[0058] In one aspect of this embodiment, R 1 and R 2 are each independently one of a C1 to C6 straight chain alkyl group, a C3 to C6 branched chain alkyl group, and a C3 to C6 cyclic alkyl group. In one aspect of this embodiment, R 3 and R 4 are each independently one of a C1 to C6 straight chain alkyl group, a C3 to C6 branched chain alkyl group, and a C3 to C6 cyclic alkyl group. In one aspect of this embodiment, R 1 , R 2 , R 3, and R 4 are each independently one of a C1 to C6 linear alkyl group, a C3 to C6 branched alkyl group, and a C3 to C6 cyclic alkyl group.

[0059] In one aspect of this embodiment, R 1 and R 2 are linked to form one of a 3-membered ring, a 4-membered ring, a 5-membered ring, and a 6-membered ring.

[0060] In one aspect of this embodiment, R 1 and R 2 are linked to form a three-membered ring. In one aspect of this embodiment, R 1 and R 2 are linked to form a cyclopropyl ring.

[0061] In one aspect of this embodiment, R 1 and R 2 are linked to form a four-membered ring. In one aspect of this embodiment, R 1 and R 2 are linked to form a cyclobutyl ring.

[0062] In one aspect of this embodiment, R 1 and R 2 are linked to form a five-membered ring. In one aspect of this embodiment, R 1 and R 2 are linked to form a cyclopentyl ring.

[0063] In one aspect of this embodiment, R 1 and R 2 are linked to form a six-membered ring. In one aspect of this embodiment, R 1 and R 2 are linked to form a cyclohexyl ring.

[0064] In one aspect of this embodiment, L 1 , R 1 , R 2 , R 3 , R4 , R 5 , and R 6 In one aspect of this embodiment, three or more of L 1 , R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 In one aspect of this embodiment, two or more of L 1 , R 1 , R 2 , R 3 , and R 4 are each a methyl group (“Me” or “—CH”). In one aspect of this embodiment, at least R 1 and R 2 are each a methyl group (“Me” or “—CH”). In one aspect of this embodiment, n=1 and L 1 , R 1 , R 2 , R 3 , and R 4 are each a methyl group (“Me” or “—CH”). In one aspect of this embodiment, n=2 and L 1 , R 1 , R 2 , R 3 , and R 4 are each a methyl group (“Me” or “—CH”). In one aspect of this embodiment, R 5 and R 6 are present, each a methyl group (“Me” or “—CH3”).

[0065] In one aspect of this embodiment, L 1 , R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 Three of L are ethyl groups (“Et” or “—CH2CH3”). In one aspect of this embodiment, L 1 , R 1 , R 2 , R3 , R 4 , R 5 , and R 6 Two of L are ethyl groups (“Et” or “—CH2CH3”). In one aspect of this embodiment, L 1 , R 1 , R 2 , R 3 , and R 4 is an ethyl group (“Et” or “—CH2CH3”). In one aspect of this embodiment, n=1 and L 1 , R 1 , R 2 , R 3 , and R 4 are each an ethyl group (“Et” or “—CH2CH3”). In one aspect of this embodiment, n=2 and L 1 , R 1 , R 2 , R 3 , and R 4 are each an ethyl group (“Et” or “—CH2CH3”). In one aspect of this embodiment, R 5 and R 6 are present, each an ethyl group (“Et” or “—CH2CH3”).

[0066] In one aspect of this embodiment, L 1 , R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are propyl groups (“Pr” or “—CH2CH2CH3”). In one aspect of this embodiment, L 1 , R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 In one aspect of this embodiment, two or more of L 1 , R 1 , R 2 , R 3 , and R 4are each a propyl group (“Pr” or “—CH2CH2CH3”). In one aspect of this embodiment, n=1 and L 1 , R 1 , R 2 , R 3 , and R 4 are each a propyl group (“Pr” or “—CH2CH2CH3”). In one aspect of this embodiment, n=2 and L 1 , R 1 , R 2 , R 3 , and R 4 are each a propyl group (“Pr” or “—CHCHCH”). In one aspect of this embodiment, R 5 and R 6 are present and are each a propyl group (“Pr” or “—CH2CH2CH3”).

[0067] In one aspect of this embodiment, L 1 , R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 In one aspect of this embodiment, two or more of L 1 , R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 At least one of the isopropyl groups ("iPr").

[0068] In one embodiment, the Group 13 compound / precursor has Formula III: [ka] During the ceremony, (a)R 1 and R 2are (i) each independently one of a C1 to C6 linear alkyl group, a C3 to C6 branched alkyl group, and a C3 to C6 cyclic alkyl group, or (ii) linked to form one of a 3-membered ring, a 4-membered ring, a 5-membered ring, and a 6-membered ring; (b)R 3 and R 4 are each independently one of a C1 to C6 linear alkyl group, a C3 to C6 branched alkyl group, and a C3 to C6 cyclic alkyl group; (c) n = 1 to 3; (d)L 1 represents a C1-C6 linear alkyl group, a C3-C6 branched alkyl group, and a group of the formula -NR 5 R 6 an amino group of the formula: 5 and R 6 are each independently one of an amino group, which is one of a C1 to C6 linear alkyl group and a C1 to C6 branched alkyl group.

[0069] In one aspect of this embodiment, n=1. In another aspect of this embodiment, n=2. In another aspect of this embodiment, n=3.

[0070] In one aspect of this embodiment, R 1 and R 2 are each independently one of a C1 to C6 straight chain alkyl group, a C3 to C6 branched chain alkyl group, and a C3 to C6 cyclic alkyl group. In one aspect of this embodiment, R 3 and R 4 are each independently one of a C1 to C6 straight chain alkyl group, a C3 to C6 branched chain alkyl group, and a C3 to C6 cyclic alkyl group. In one aspect of this embodiment, R 1 , R 2 , R 3 , and R 4 are each independently one of a C1 to C6 linear alkyl group, a C3 to C6 branched alkyl group, and a C3 to C6 cyclic alkyl group.

[0071] In one aspect of this embodiment, R 1and R 2 are linked to form one of a 3-membered ring, a 4-membered ring, a 5-membered ring, and a 6-membered ring.

[0072] In one aspect of this embodiment, R 1 and R 2 are linked to form a three-membered ring. In one aspect of this embodiment, R 1 and R 2 are linked to form a cyclopropyl ring.

[0073] In one aspect of this embodiment, R 1 and R 2 are linked to form a four-membered ring. In one aspect of this embodiment, R 1 and R 2 are linked to form a cyclobutyl ring.

[0074] In one aspect of this embodiment, R 1 and R 2 are linked to form a five-membered ring. In one aspect of this embodiment, R 1 and R 2 are linked to form a cyclopentyl ring.

[0075] In one aspect of this embodiment, R 1 and R 2 are linked to form a six-membered ring. In one aspect of this embodiment, R 1 and R 2 are linked to form a cyclohexyl ring.

[0076] In one aspect of this embodiment, L 1 , R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 In one aspect of this embodiment, three or more of L 1 , R 1 , R 2 , R 3 , R4 , R 5 , and R 6 In one aspect of this embodiment, two or more of L 1 , R 1 , R 2 , R 3 , and R 4 are each a methyl group (“Me” or “—CH”). In one aspect of this embodiment, at least R 1 and R 2 are each a methyl group (“Me” or “—CH”). In one aspect of this embodiment, n=1 and L 1 , R 1 , R 2 , R 3 , and R 4 are each a methyl group (“Me” or “—CH”). In one aspect of this embodiment, n=2 and L 1 , R 1 , R 2 , R 3 , and R 4 are each a methyl group (“Me” or “—CH”). In one aspect of this embodiment, R 5 and R 6 are present, each a methyl group (“Me” or “—CH3”).

[0077] In one aspect of this embodiment, L 1 , R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 Three of L are ethyl groups (“Et” or “—CH2CH3”). In one aspect of this embodiment, L 1 , R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 Two of L are ethyl groups (“Et” or “—CH2CH3”). In one aspect of this embodiment, L 1 , R 1 , R 2 , R3 , and R 4 are each an ethyl group (“Et” or “—CH2CH3”). In one aspect of this embodiment, n=1 and L 1 , R 1 , R 2 , R 3 , and R 4 are each an ethyl group (“Et” or “—CH2CH3”). In one aspect of this embodiment, n=2 and L 1 , R 1 , R 2 , R 3 , and R 4 are each an ethyl group (“Et” or “—CH2CH3”). In one aspect of this embodiment, R 5 and R 6 are present, each an ethyl group (“Et” or “—CH2CH3”).

[0078] In one aspect of this embodiment, L 1 , R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are propyl groups (“Pr” or “—CH2CH2CH3”). In one aspect of this embodiment, L 1 , R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 In one aspect of this embodiment, two or more of L 1 , R 1 , R 2 , R 3 , and R 4 are each a propyl group (“Pr” or “—CH2CH2CH3”). In one aspect of this embodiment, n=1 and L 1 , R 1 , R 2 , R 3 , and R 4are each a propyl group (“Pr” or “—CH2CH2CH3”). In one aspect of this embodiment, n=2 and L 1 , R 1 , R 2 , R 3 , and R 4 are each a propyl group (“Pr” or “—CHCHCH”). In one aspect of this embodiment, R 5 and R 6 are present and are each a propyl group (“Pr” or “—CH2CH2CH3”).

[0079] In one aspect of this embodiment, L 1 , R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 In one aspect of this embodiment, two or more of L 1 , R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 At least one of the isopropyl groups ("iPr").

[0080] Specific Exemplary Embodiments

[0081] In one embodiment, M=In, n=1, and L 1 = Me and R 1 , R 2 , R 3 , and R 4 Each of these is = Me. [ka]

[0082] In one embodiment, M=In, n=2, and L 1 = Me and R 1 , R 2 , R3 , and R 4 Each of these is = Me. [ka]

[0083] In one embodiment, M=Ga, n=1, and L 1 = Me and R 1 , R 2 , R 3 , and R 4 Each of these is = Me. [ka]

[0084] In one embodiment, M=Ga, n=2, and L 1 = Me and R 1 , R 2 , R 3 , and R 4 Each of these is = Me. [ka]

[0085] In one embodiment, M=Al, n=1, and L 1 = Me and R 1 , R 2 , R 3 , and R 4 Each of these is = Me. [ka]

[0086] In one embodiment, M=Al, n=2, and L 1 = Me and R 1 , R 2 , R 3 , and R 4 Each of these is = Me. [ka]

[0087] In one embodiment, M=In, n=1, and L 1 =-NR 5 R 6 In the formula, R 5 and R 6 = Et, and R 1 , R 2 , R 3 , and R 4 Each of these is = Me. [ka]

[0088] In one embodiment, M=Al, n=1, and L 1 =-NR 5 R 6 In the formula, R 5 and R 6 = Et, and R 1 , R 2 , R 3 , and R 4 Each of these is = Me. [ka]

[0089] In one embodiment, M=Ga, n=1, and L 1 =-NR 5 R 6 In the formula, R 5 and R 6 = Et, and R 1 , R 2 , R 3 , and R 4 Each of these is = Me. [ka]

[0090] In one embodiment, M=In, n=1, and L 1 =Me and R 1 , R 2 , and R 3 Each of these is Me, and R 4 =Et. [ka]

[0091] In one embodiment, M=In, n=1, and L 1 =Me and R 1 and R 2 is linked to form a cyclopropyl group (" cy Pr"), and R 3 and R 4 Each of these is = Me. [ka]

[0092] In one embodiment, M=In, n=1, L1=Me, R1 and R2 join to form a cyclopentyl group ("cyPent"), and each of R3 and R4=Me, as follows: [ka]

[0093] How to use

[0094] The disclosed precursors can be deposited to form lanthanide-containing films using any chemical vapor deposition process known to those skilled in the art. As used herein, the term "chemical vapor deposition process" refers to any process in which a substrate is exposed to one or more volatile precursors, which react and / or decompose on the substrate surface to produce the desired deposit. As used herein, the term "atomic layer deposition process" refers to a self-limiting (e.g., the amount of film material deposited in each reaction cycle is constant) sequential surface chemistry that deposits films of materials on substrates of various compositions. While precursors, reagents, and sources used herein are sometimes described as "gases," it is understood that precursors may be liquids or solids transported into a reactor via direct vaporization, bubbling, or sublimation, with or without an inert gas. In some cases, vaporized precursors may be passed through a plasma generator. As used herein, the term "reactor" includes, but is not limited to, a reaction chamber, a reaction vessel, or a deposition chamber.

[0095] Chemical vapor deposition processes in which the disclosed and claimed precursors can be used include, but are not limited to, those used in the fabrication of semiconductor-type microelectronic devices, such as ALD, CVD, pulsed CVD, plasma-enhanced ALD (PEALD), and / or plasma-enhanced CVD (PECVD). Examples of suitable deposition processes for the methods disclosed herein include, but are not limited to, cyclic CVD (CCVD), MOCVD (metal-organic CVD), thermal chemical vapor deposition, plasma-enhanced chemical vapor deposition ("PECVD"), high-density PECVD, photo-CVD, plasma-enhanced photo-CVD ("PPECVD"), low-temperature chemical vapor deposition, chemical vapor deposition, hot-filament chemical vapor deposition, CVD of liquid polymer precursors, deposition from supercritical fluids, and low-energy CVD (LECVD). In certain embodiments, metal-containing films are deposited via atomic layer deposition (ALD), plasma-enhanced ALD (PEALD), or plasma-enhanced cyclic CVD (PECCVD) processes.

[0096] In one embodiment, for example, the metal-containing film is deposited using an ALD process. In another embodiment, the metal-containing film is deposited using a CCVD process. In a further embodiment, the metal-containing film is deposited using a thermal CVD process.

[0097] Suitable substrates onto which the disclosed and claimed precursors can be deposited are not particularly limited and will vary depending on the intended end use. For example, the substrate can be selected from oxide or nitride based films, such as HfO2-based materials, TiO2-based materials, ZrO2-based materials, rare earth oxide-based materials, ternary oxide-based materials, etc. Other substrates may include solid substrates such as metal substrates (e.g., Au, Pd, Rh, Ru, W, Al, Ni, Ti, Co, Pt, and metal silicides (e.g., TiSi2, CoSi2, and NiSi2); metal nitride-containing substrates (e.g., TaN, TiN, WN, TaCN, TiCN, TaSiN, and TiSiN); semiconductor materials (e.g., Si, SiGe, GaAs, InP, diamond, GaN, and SiC); insulators (e.g., SiO2, Si3N4, SiON, HfO2, Ta2O5, ZrO2, TiO2, Al2O3, and barium strontium titanate); combinations thereof, and the like. Preferred substrates include TiN, Ru, and Si type substrates.

[0098] Such deposition methods and processes may employ an oxidizing agent, which is typically introduced in gaseous form. Examples of suitable oxidizing agents include, but are not limited to, oxygen gas, water vapor, ozone, oxygen plasma, or mixtures thereof.

[0099] Deposition methods and processes may also involve one or more purge gases. Purge gases, used to purge unconsumed reactants and / or reaction by-products, are inert gases that do not react with the precursors. Exemplary purge gases include, but are not limited to, argon (Ar), nitrogen (N), helium (He), neon, and mixtures thereof. For example, a purge gas such as Ar may be used at a flow rate of about 10 to about 2000 sccm (about 0.0169 to about 3.38 Pa m).3 / sec) for about 0.1 to 10,000 seconds, thereby purging the reactor of unreacted materials and any by-products that may remain.

[0100] Deposition methods and processes require the application of energy to at least one of a precursor, an oxidizer, another precursor, or a combination thereof to induce a reaction and form a metal-containing film or coating on the substrate. Such energy can be provided by, but is not limited to, thermal, plasma, pulsed plasma, helicon plasma, high-density plasma, inductively coupled plasma, x-ray, electron beam, photon, remote plasma, and combinations thereof. In some processes, a secondary RF frequency source can be used to modify the plasma characteristics at the substrate surface. When using plasma, the plasma generation process can include a direct plasma generation process in which the plasma is generated directly in the reactor, or alternatively, a remote plasma generation process in which the plasma is generated outside the reactor and fed into the reactor.

[0101] When used in such deposition methods and processes, suitable precursors, such as those disclosed and claimed in the present invention, can be delivered to a reaction chamber, such as a CVD or ALD reactor, in a variety of ways. In some cases, a liquid delivery system can be used. In other cases, a process unit combining liquid delivery and flash vaporization, such as a turbo vaporizer manufactured by MSP Corporation of Shoreview, MN, can be employed to provide a metered delivery of low-volatility materials, thereby providing reproducible transport and deposition without thermal decomposition of the precursor. The precursor compositions described herein can be effectively used as source reagents via direct liquid injection (DLI) to deliver vapor streams of these metal precursors to an ALD or CVD reactor.

[0102] When used in these deposition methods and processes, the disclosed and claimed precursors contain hydrocarbon solvents, which are particularly desirable because they can be dried to sub-ppm levels of moisture. Exemplary hydrocarbon solvents that can be used in the precursors include, but are not limited to, toluene, mesitylene, cumene (isopropylbenzene), p-cymene (4-isopropyltoluene), 1,3-diisopropylbenzene, octane, dodecane, 1,2,4-trimethylcyclohexane, n-butylcyclohexane, and decahydronaphthalene (decalin). The disclosed and claimed precursors can also be stored and used in stainless steel containers. In certain embodiments, the hydrocarbon solvent is a high-boiling solvent, or has a boiling point of 100 degrees Celsius or higher. The disclosed and claimed precursors can also be mixed with other suitable metal precursors, and the mixture can be used to simultaneously deliver both metals for the growth of bimetallic films.

[0103] A flow of argon and / or other gases may be used as a carrier gas to assist in delivering a vapor containing at least one of the disclosed and claimed precursors to the reaction chamber during the precursor pulse delivery. During precursor delivery, the process pressure in the reaction chamber is maintained at 1-50 Torr (approximately 1.3×10 2 ~Approx. 6.7×10 3 Pa), preferably 5 to 20 Torr (approximately 6.7 × 10 2 ~Approx. 2.7×10 3 Pa).

[0104] Substrate temperature can be an important process variable in the deposition of high-quality metal-containing films. Typical substrate temperatures are in the range of about 150°C to about 550°C. Higher temperatures can promote faster film growth rates.

[0105] In light of the foregoing, one skilled in the art will recognize that the disclosed and claimed subject matter further includes the use of the disclosed and claimed precursors in chemical vapor deposition processes, as follows:

[0106] In one embodiment, the disclosed and claimed subject matter includes a method of forming a Group 13 metal-containing film on at least one side of a substrate, comprising the steps of: a. providing at least one surface of a substrate in a reaction vessel; b. Forming a Group 13 metal-containing film on at least one surface by a deposition process selected from a chemical vapor deposition (CVD) process and an atomic layer deposition (ALD) process using one of the disclosed and claimed precursors as a metal source compound for the deposition process. In a further aspect of this embodiment, the method includes introducing at least one reactant into the reaction vessel. In a further aspect of this embodiment, the method includes introducing at least one reactant into the reaction vessel, wherein the at least one reactant is selected from the group consisting of water, diatomic oxygen, oxygen plasma, ozone, NO, NO, NO, NO, carbon monoxide, carbon dioxide, and combinations thereof. In another aspect of this embodiment, the method includes introducing at least one reactant into the reaction vessel, wherein the at least one reactant is selected from the group consisting of ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen / hydrogen, ammonia plasma, nitrogen plasma, nitrogen / hydrogen plasma, and combinations thereof. In another aspect of this embodiment, the method includes introducing at least one reactant into the reaction vessel, wherein the at least one reactant is selected from the group consisting of hydrogen, hydrogen plasma, a mixture of hydrogen and helium, a mixture of hydrogen and argon, hydrogen / helium plasma, hydrogen / argon plasma, a boron-containing compound, a silicon-containing compound, and combinations thereof.

[0107] In one embodiment, the disclosed and claimed subject matter includes a method of forming a Group 13 metal-containing film via an atomic layer deposition (ALD) process or an ALD-like process, comprising the steps of: a. providing a substrate into a reaction vessel; b. introducing one or more of the disclosed and claimed precursors into a reaction vessel; c. purging the reaction vessel with a first purge gas; d. introducing a feed gas into the reaction vessel; e. purging the reaction vessel with a second purge gas; f. sequentially repeating steps b through e until a desired thickness of the Group 13 metal-containing film is obtained. In a further aspect of this embodiment, the source gas is one or more of an oxygen-containing source gas selected from water, diatomic oxygen, oxygen plasma, ozone, NO, NO, NO, carbon monoxide, carbon dioxide, and combinations thereof. In another aspect of this embodiment, the source gas is one or more of a nitrogen-containing source gas selected from ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen / hydrogen, ammonia plasma, nitrogen plasma, nitrogen / hydrogen plasma, and mixtures thereof. In a further aspect of this embodiment, the first and second purge gases are each independently selected from one or more of argon, nitrogen, helium, neon, and combinations thereof. In a further aspect of this embodiment, the method further includes applying energy to at least one of the precursor, the source gas, the substrate, and combinations thereof, wherein the energy is one or more of thermal, plasma, pulsed plasma, helicon plasma, high-density plasma, inductively coupled plasma, x-ray, electron beam, photon, remote plasma, and combinations thereof. In a further aspect of this embodiment, step b of the method further comprises introducing the precursor into the reaction vessel using a carrier gas flow to provide vapor of the precursor into the reaction vessel. In a further aspect of this embodiment, step b of the method further comprises using a solvent medium comprising one or more of toluene, mesitylene, isopropylbenzene, 4-isopropyltoluene, 1,3-diisopropylbenzene, octane, dodecane, 1,2,4-trimethylcyclohexane, n-butylcyclohexane, and decahydronaphthalene, and combinations thereof. [Example]

[0108] Example

[0109] Reference will now be made to more specific embodiments of the present disclosure and experimental results that provide support for such embodiments. These examples are presented below in order to more fully illustrate the disclosed subject matter, and should not be construed as limiting the disclosed subject matter in any way.

[0110] It will be apparent to those skilled in the art that various modifications and variations can be made in the subject matter disclosed herein and in the specific examples provided without departing from the spirit or scope of the disclosed subject matter. Accordingly, the disclosed subject matter, including the description provided by way of example below, is intended to cover modifications and variations of the disclosed subject matter that come within the scope of any claims and their equivalents.

[0111] Materials and Methods:

[0112] All solvents and starting materials were purchased from Sigma-Aldrich unless otherwise noted.

[0113] Example 1 [ka]

[0114] Dimethylindium chloride (1 equivalent) was dissolved in dry THF. The solution was cooled to 0°C, and 1 equivalent of a Grignard solution prepared from 3-(N,N-dimethylamino)-2,2-dimethyl-1-propyl chloride and Mg turnings was added dropwise. The mixture was allowed to warm to room temperature and stirred overnight. The solvent was removed from the mixture under reduced pressure, and the crude residue was suspended in 50 mL of pentane. After stirring for 1 hour, the suspension was filtered. The solvent was removed from the filtrate under reduced pressure, and the crude product was distilled and recovered (50°C oil bath, 20 cm column, 2 x 10 -2 mbar (2 Pa), cooled collection flask; 60% yield.

[0115] Characterization of In(DMDMP)Me2: 1H NMR(500MHz,C6D6)δ1.82(s,6H),1.73(s,1H),0.98(s,6H),0.63(s,2H),-0.06(s,6H), see Figure 1;TGA:T 50% = 137°C, see Figure 2; DSC: melting point -34°C; DSC decomposition temperature 330.4°C, see Figure 3.

[0116] Example 2 [ka]

[0117] Dimethylaluminum chloride (1 equivalent) was dissolved in dry THF. This solution was cooled to 0°C, and 1 equivalent of a Grignard solution prepared from 3-(N,N-dimethylamino)-2,2-dimethyl-1-propyl chloride and Mg turnings was added dropwise. The mixture was allowed to warm to room temperature and stirred overnight. The solvent was removed from the mixture under reduced pressure, and the crude residue was suspended in 50 mL of pentane. After stirring overnight, the suspension was filtered. The solvent was removed from the filtrate under reduced pressure, and the crude liquid product was distilled and collected (oil bath at 25°C, 2 x 10 -2 mbar (2 Pa), cooled collection flask; 60% yield.

[0118] Characterization of Al(DMDMP)Me2: 1 H NMR(500MHz,C6D6)δ1.92(s,2H),1.84(s,6H),0.99(s,6H),0.25(s,2H),-0.48(s,6H), see Figure 4;TGA:T 50% = 135°C, see Figure 5; DSC: decomposition temperature 415°C.

[0119] Example 3 [ka]

[0120] Gallium trichloride (1 equivalent) was dissolved in dry THF. The solution was cooled to 0°C, and 1 equivalent of a Grignard solution prepared from 3-(N,N-dimethylamino)-2,2-dimethyl-1-propyl chloride and Mg turnings was added dropwise. Two equivalents of methyllithium solution (1.6 M in diethyl ether) were then added dropwise. The mixture was allowed to warm to room temperature and stirred overnight. The solvent was removed from the mixture under reduced pressure, and the crude residue was suspended in 50 mL of pentane. After stirring overnight, the suspension was filtered. The solvent was removed from the filtrate under reduced pressure, and the crude liquid product was distilled and collected (oil bath 25°C, 7 x 10 -3 mbar (0.7 Pa), cooled collection flask; 30% yield.

[0121] Characterization of Ga(DMDMP)Me2: 1 H NMR(500MHz,C6D6)δ1.86(s,6H),1.83(s,2H),0.98(s,6H),0.52(s,2H),-0.14(s,6H),TGA:T 50% = 125°C; DSC: melting point -27°C, decomposition temperature 417°C.

[0122] Example 4 [ka]

[0123] Indium trichloride (1 equivalent) was dissolved in dry THF. The solution was cooled to 0°C, and 2 equivalents of a Grignard solution prepared from 3-(N,N-dimethylamino)-2,2-dimethyl-1-propyl chloride and Mg turnings were added dropwise. Next, 1 equivalent of methyllithium solution (1.6 M in diethyl ether) was added dropwise. The mixture was allowed to warm to room temperature and stirred overnight. The solvent was removed from the mixture under reduced pressure, and the crude residue was suspended in 50 mL of pentane. After stirring overnight, the suspension was filtered. The solvent was removed from the filtrate under reduced pressure, and the crude product was sublimated and recovered (oil bath at 60°C, 2 x 10 -2 mbar (2 Pa), cooled collection flask; 80% yield.

[0124] Characterization of In(DMDMP)2Me: 1 H NMR(500MHz,C6D6)δ2.01(s,12H),1.89(s,4H),1.14(s,12H),0.57(s,4H),-0.02(s,3H),TGA:T 50% = 190°C; DSC: melting point 57°C, decomposition temperature 316°C.

[0125] Example 5 [ka]

[0126] Gallium trichloride (1 equivalent) was dissolved in dry THF. The solution was cooled to 0°C, and 2 equivalents of a Grignard solution prepared from 3-(N,N-dimethylamino)-2,2-dimethyl-1-propyl chloride and Mg turnings were added dropwise. Next, 1 equivalent of methyllithium solution (1.6 M in diethyl ether) was added dropwise. The mixture was allowed to warm to room temperature and stirred overnight. The solvent was removed from the mixture under reduced pressure, and the crude residue was suspended in 50 mL of pentane. After stirring overnight, the suspension was filtered. The solvent was removed from the filtrate under reduced pressure, and the crude liquid product was collected by distillation (oil bath at 60°C, 4 x 10 -3 mbar (0.4 Pa), cooled collection flask; 55% yield.

[0127] Characterization of Ga(DMDMP)2Me: 1 H NMR(500MHz,C6D6)δ2.03(s,12H),1.96(m,4H),1.13(s,12H),0.50(m,4H),-0.06(s,3H),TGA:T 50% = 175°C; DSC: melting point 24°C, decomposition temperature 390°C.

[0128] The foregoing description is intended primarily for purposes of illustration. While the disclosed and claimed subject matter has been shown and described with respect to exemplary embodiments thereof, it should be understood by those skilled in the art that the above and other various changes, omissions, and additions in form and detail thereof can be made therein without departing from the spirit and scope of the disclosed and claimed subject matter.

Claims

1. A precursor having formula I: 【Chemistry 1】 During the ceremony, (a) R １ and R ２ (i) each independently represents C １ ~C ６ Straight-chain alkyl group, C ３ ~C ６ Branched alkyl groups, and C ３ ~C ６ or (ii) linked to form one of a 3-, 4-, 5-, and 6-membered ring; (b) R ３ and R ４ are each independently C １ ~C ６ Straight-chain alkyl group, C ３ ~C ６ Branched alkyl groups, and C ３ ~C ６ is one of the cyclic alkyl groups; (c) n=1 to 3; (d) M is one of B, Al, Ga, and In; and (e) L １ is C １ ~C ６ Straight-chain alkyl group, C ３ ~C ６ Branched alkyl groups and groups of the formula -NR ５ R ６ an amino group of the formula: ５ and R ６ are each independently C １ ~C ６ Straight-chain alkyl groups and C ３ ~C ６ one of a branched alkyl group, an amino group, Precursor.

2. A precursor having formula II: 【Chemistry 2】 During the ceremony, (a) R １ and R ２ (i) each independently represents C １ ~C ６ Straight-chain alkyl group, C ３ ~C ６ Branched alkyl groups, and C ３ ~C ６ or (ii) linked to form one of a 3-, 4-, 5-, and 6-membered ring; (b) R ３ and R ４ are each independently C １ ~C ６ Straight-chain alkyl group, C ３ ~C ６ Branched alkyl groups, and C ３ ~C ６ is one of the cyclic alkyl groups; (c) n=1 to 3; (d) M is one of B, Al, and Ga; and (e) L １ is C １ ~C ６ Straight-chain alkyl group, C ３ ~C ６ Branched alkyl groups and groups of the formula -NR ５ R ６ an amino group of the formula: ５ and R ６ are each independently C １ ~C ６ Straight-chain alkyl groups and C ３ ~C ６ one of a branched alkyl group, an amino group, Precursor.

3. A precursor having formula III: 【Transformation 3】 During the ceremony, (a) R １ and R ２ (i) each independently represents C １ ~C ６ Straight-chain alkyl group, C ３ ~C ６ Branched alkyl groups, and C ３ ~C ６ or (ii) linked to form one of a 3-, 4-, 5-, and 6-membered ring; (b) R ３ and R ４ are each independently C １ ~C ６ Straight-chain alkyl group, C ３ ~C ６ Branched alkyl groups, and C ３ ~C ６ is one of the cyclic alkyl groups; (c) n=1 to 3; (d) L １ is C １ ~C ６ Straight-chain alkyl group, C ３ ~C ６ Branched alkyl groups and groups of the formula -NR ５ R ６ an amino group of the formula: ５ and R ６ are each independently C １ ~C ６ Straight-chain alkyl groups and C ３ ~C ６ one of a branched alkyl group, an amino group, Precursor.

4. 3. The precursor of claim 1, wherein M is B.

5. 3. The precursor of claim 1, wherein M is Al.

6. 3. The precursor according to claim 1, wherein M is Ga.

7. 3. The precursor of claim 1, wherein M is In.

8. Precursor according to any one of claims 1 to 7, wherein n=1.

9. Precursor according to any one of claims 1 to 7, wherein n=2.

10. Precursor according to any one of claims 1 to 7, wherein n=3.

11. R １ and R ２ However, each independently, C １ ~C ６ Straight-chain alkyl group, C ３ ~C ６ Branched alkyl groups, and C ３ ~C ６ The precursor according to any one of claims 1 to 7, which is one of cyclic alkyl groups.

12. R ３ and R ４ However, each independently, C １ ~C ６ The precursor according to any one of claims 1 to 7, which is a linear alkyl group.

13. R １ , R ２ , R ３ , and R ４ However, each independently, C １ ~C ６ Straight-chain alkyl group, C １ ~C ６ Branched alkyl groups, and C ３ ~C ６ The precursor according to any one of claims 1 to 7, which is one of cyclic alkyl groups.

14. R １ and R ２ are linked to form one of a 3-membered ring, a 4-membered ring, a 5-membered ring, and a 6-membered ring.

15. R １ and R ２ The precursor according to any one of claims 1 to 7, wherein: are linked to form a three-membered ring.

16. R １ and R ２ The precursor according to any one of claims 1 to 7, wherein:

17. R １ and R ２ The precursor according to any one of claims 1 to 7, wherein:

18. R １ and R ２ The precursor according to any one of claims 1 to 7, wherein:

19. L １ , R １ , R ２ , R ３ , R ４ , R ５ , and R ６ The precursor according to any one of claims 1 to 7, wherein three or more of the groups are methyl groups.

20. L １ , R １ , R ２ , R ３ , R ４ , R ５ , and R ６ The precursor according to any one of claims 1 to 7, wherein two or more of the groups are methyl groups.

21. At least R １ and R ２ The precursor according to any one of claims 1 to 7, wherein each is a methyl group.

22. L １ , R １ , R ２ , R ３ , and R ４ The precursor according to any one of claims 1 to 7, wherein each is a methyl group.

23. n=1, and L １ , R １ , R ２ , R ３ , and R ４ The precursor according to any one of claims 1 to 7, wherein each is a methyl group.

24. n=2, and L １ , R １ , R ２ , R ３ , and R ４ The precursor according to any one of claims 1 to 7, wherein each is a methyl group.

25. R ５ and R ６ A precursor according to any one of claims 1 to 7, wherein:

26. L １ , R １ , R ２ , R ３ , R ４ , R ５ , and R ６ 8. The precursor according to claim 1, wherein three of the groups are ethyl groups.

27. L １ , R １ , R ２ , R ３ , R ４ , R ５ , and R ６ The precursor according to any one of claims 1 to 7, wherein two of the groups are ethyl groups.

28. L １ , R １ , R ２ , R ３ , and R ４ The precursor according to any one of claims 1 to 7, wherein each is an ethyl group.

29. n=1, and L １ , R １ , R ２ , R ３ , and R ４ The precursor according to any one of claims 1 to 7, wherein each is an ethyl group.

30. n=2, and L １ , R １ , R ２ , R ３ , and R ４ The precursor according to any one of claims 1 to 7, wherein each is an ethyl group.

31. R ５ and R ６ A precursor according to any one of claims 1 to 7, wherein:

32. L １ , R １ , R ２ , R ３ , R ４ , R ５ , and R ６ The precursor according to any one of claims 1 to 7, wherein three or more of the groups are propyl groups.

33. L １ , R １ , R ２ , R ３ , R ４ , R ５ , and R ６ The precursor according to any one of claims 1 to 7, wherein two or more of are propyl groups.

34. L １ , R １ , R ２ , R ３ , and R ４ The precursor according to any one of claims 1 to 7, wherein each is a propyl group.

35. n=1, and L １ , R １ , R ２ , R ３ , and R ４ The precursor according to any one of claims 1 to 7, wherein each is a propyl group.

36. n=2, and L １ , R １ , R ２ , R ３ , and R ４ The precursor according to any one of claims 1 to 7, wherein each is a propyl group.

37. R ５ and R ６ A precursor according to any one of claims 1 to 7, wherein:

38. L １ , R １ , R ２ , R ３ , R ４ , R ５ , and R ６ The precursor according to any one of claims 1 to 7, wherein two or more of the groups are isopropyl groups.

39. L １ , R １ , R ２ , R ３ , R ４ , R ５ , and R ６ The precursor according to any one of claims 1 to 7, wherein at least one of the groups is an isopropyl group.

40. M=In, n=1, and L １ = Me, and R １ , R ２ , R ３ , and R ４ 2. The precursor of claim 1, wherein each of =Me.

41. M=In, n=2, and L １ = Me, and R １ , R ２ , R ３ , and R ４ 2. The precursor of claim 1, wherein each of =Me.

42. M=Ga, n=1, and L １ = Me, and R １ , R ２ , R ３ , and R ４ 2. The precursor of claim 1, wherein each of =Me.

43. M=Ga, n=2, and L １ = Me, and R １ , R ２ , R ３ , and R ４ 2. The precursor of claim 1, wherein each of =Me.

44. M=Al, n=1, and L １ = Me, and R １ , R ２ , R ３ , and R ４ 2. The precursor of claim 1, wherein each of =Me.

45. M=Al, n=2, and L １ = Me, and R １ , R ２ , R ３ , and R ４ 2. The precursor of claim 1, wherein each of =Me.

46. M=In, n=1, and L １ =-NR ５ R ６ In the formula, R ５ and R ６ = Et, and R １ , R ２ , R ３ , and R ４ 2. The precursor of claim 1, wherein each of =Me.

47. M=Al, n=1, and L １ =-NR ５ R ６ In the formula, R ５ and R ６ = Et, and R １ , R ２ , R ３ , and R ４ 2. The precursor of claim 1, wherein each of =Me.

48. M=Ga, n=1, and L １ =-NR ５ R ６ In the formula, R ５ and R ６ = Et, and R １ , R ２ , R ３ , and R ４ 2. The precursor of claim 1, wherein each of =Me.

49. M=In, n=1, and L １ = Me, and R １ , R ２ , and R ３ Each of = Me, and R ４ 2. The precursor of claim 1, wherein = Et.

50. M=In, n=1, and L １ = Me, and R １ and R ２ is linked to form a cyclopropyl group (" ｃｙ Pr"), and R ３ and R ４ 2. The precursor of claim 1, wherein each of =Me.

51. M=In, n=1, and L １ = Me, and R １ and R ２ is linked to form a cyclopentyl group (" ｃｙ Pent"), and R ３ and R ４ 2. The precursor of claim 1, wherein each of =Me.

52. 1. A method for forming a Group 13 metal-containing film on at least one surface of a substrate, comprising: a. providing the at least one side of the substrate in a reaction vessel; b. forming a Group 13 metal-containing film on said at least one surface by a deposition process selected from a chemical vapor deposition (CVD) process and an atomic layer deposition (ALD) process using the precursor of any one of claims 1-51 as a metal source compound for said deposition process; A method comprising:

53. 53. The method of claim 52, further comprising introducing at least one reactant into the reaction vessel.

54. Water, diatomic oxygen, oxygen plasma, ozone, NO, N ２ O, NO ２ 53. The method of claim 52, further comprising introducing at least one reactant selected from the group consisting of carbon monoxide, carbon dioxide, and combinations thereof into the reaction vessel.

55. 53. The method of claim 52, further comprising introducing at least one reactant selected from the group consisting of ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen / hydrogen, ammonia plasma, nitrogen plasma, nitrogen / hydrogen plasma, and combinations thereof into the reaction vessel.

56. 53. The method of claim 52, further comprising introducing into the reaction vessel at least one reactant selected from the group consisting of hydrogen, hydrogen plasma, a mixture of hydrogen and helium, a mixture of hydrogen and argon, hydrogen / helium plasma, hydrogen / argon plasma, a boron-containing compound, a silicon-containing compound, and combinations thereof.

57. 1. A method for forming a Group 13 metal-containing film via an atomic layer deposition (ALD) or ALD-like process, comprising: a. providing a substrate into a reaction vessel; b. introducing the precursor of any one of claims 1 to 51 into the reaction vessel; c. purging the reaction vessel with a first purge gas; d) introducing a raw material gas into the reaction vessel; e. purging the reaction vessel with a second purge gas; f. sequentially repeating steps b through e until a desired thickness of the Group 13 metal-containing film is obtained; A method comprising:

58. The raw material gas is water, diatomic oxygen, oxygen plasma, ozone, NO, N ２ O, NO ２ 58. The method of claim 57, wherein the oxygen-containing feed gas is one or more selected from the group consisting of carbon monoxide, carbon dioxide, and combinations thereof.

59. 58. The method of claim 57, wherein the source gas is one or more of a nitrogen-containing source gas selected from ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen / hydrogen, ammonia plasma, nitrogen plasma, nitrogen / hydrogen plasma, and mixtures thereof.

60. 58. The method of claim 57, wherein the first and second purge gases are each independently selected from one or more of argon, nitrogen, helium, neon, and combinations thereof.

61. 58. The method of claim 57, further comprising applying energy to at least one of the precursor, the feedstock gas, the substrate, and combinations thereof, wherein the energy is one or more of a thermal plasma, a pulsed plasma, a helicon plasma, a high density plasma, an inductively coupled plasma, x-rays, an electron beam, photons, and combinations thereof.

62. 58. The method of claim 57, wherein step b further comprises introducing the precursor into the reaction vessel using a carrier gas flow to provide vapor of the precursor into the reaction vessel.

63. 58. The method of claim 57, wherein step b further comprises using a solvent medium comprising one or more of toluene, mesitylene, isopropylbenzene, 4-isopropyltoluene, 1,3-diisopropylbenzene, octane, dodecane, 1,2,4-trimethylcyclohexane, n-butylcyclohexane, and decahydronaphthalene, and combinations thereof.

64. 1. A method for forming a Group 13 metal-containing film on at least one surface of a substrate, comprising: a. providing the at least one side of the substrate in a reaction vessel; b. forming a Group 13 metal-containing film on said at least one surface by a deposition process selected from a chemical vapor deposition (CVD) process and an atomic layer deposition (ALD) process using a precursor as a metal source compound for said deposition process; and c) using the precursor according to any one of claims 1 to 51 as a dopant material; A method comprising:

65. A precursor supply package comprising a container and a precursor according to any one of claims 1 to 51, said container configured to contain and dispense said precursor.

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