Gallium precursors for the deposition of gallium-containing oxide films.

Abstract

A method of depositing a gallium-containing oxide film on a substrate includes: a) simultaneously or sequentially exposing the substrate to vapors of a gallium precursor, an additional metal precursor, and an oxidizing agent; b) depositing at least a portion of the gallium precursor and at least a portion of the additional metal precursor on the substrate to form a gallium-containing oxide film on the substrate via a vapor deposition process, wherein the gallium precursor has the formula: (NR 8 R 9 )(NR 1 R 2 )Ga[(R 3 R 4 N)C x (R 5 R 6 )(NR 7 )](I)(Cy-N)2Ga[(R 3 R 4 N)C x (R 5 R 6 )(NR 7 )](II)(wherein, R 1 ~R 9 is independently selected from H, Me, Et, nPr, iPr, nBu, iBu, sBu, or tBu; R 1 ~R 9 may be the same or different; x=2, 3, 4, preferably x=2; and Cy-N represents a saturated or unsaturated N-containing ring.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of priority under 35 U.S.C. §119(a) and (b) to U.S. Provisional Patent Application No. 63 / 212,184, filed June 18, 2021, the entire contents of which are incorporated herein by reference.

[0002] The present invention relates to gallium precursors for depositing gallium-containing oxide films, such as binary, ternary, or quaternary gallium-containing oxide films. In particular, the gallium precursors are liquid, volatile, non-pyrophoric, and halide-free molecules. [Background technology]

[0003] The use of gallium oxide (Ga2O3) is of interest for several applications in microdevices, and therefore there is growing interest in developing cost-effective and safe gallium molecules that can be used to deposit thin films by chemical vapor deposition (CVD) or atomic layer deposition (ALD), or any vapor deposition method. Applications of interest include gas sensors, transparent conductive oxides (TCOs), photocatalytic materials, and oxide semiconductors.

[0004] Indium gallium zinc oxide (IGZO) is a semiconductor material composed of indium (In), gallium (Ga), zinc (Zn), and oxygen (O). IGZO thin-film transistors (TFTs) are used in optoelectronic devices due to their high electron mobility. Such optoelectronic devices require highly defined, uniform thin film layers to better control their performance and optimize their size. The advantage of IGZO is that it can be deposited as a uniform amorphous phase while maintaining the high carrier mobility common to oxide semiconductors. IGZO is also expected to be used in next-generation semiconductor devices, whether for memory or logic applications (n-type back-end transistors).

[0005] A current obstacle to large-scale IGZO production is the synthesis method. The most widely used technique for transparent conductive oxide (TCO) synthesis is pulsed laser deposition (PLD). In PLD, a laser is used to focus a nanosized spot on a solid elemental target. The frequency of the laser pulse is varied between targets to control the film's composition. IGZO's low-temperature deposition capability allows it to be deposited on substrates such as quartz, single-crystal silicon, and even plastic. The substrate is placed in a PLD vacuum chamber, which controls the oxygen pressure to ensure favorable electrical properties. After synthesis, the film is annealed, or adapted to the atmosphere, by gradually exposing it to air.

[0006] Although PLD is a useful and versatile synthesis technique, it requires expensive equipment and sufficient time for each sample to adapt to normal atmospheric conditions, which is not ideal for industrial production.

[0007] Solution processing is a more cost-effective alternative. Specifically, combustion synthesis techniques can be used. One example is a metal nitrate solution containing an oxidizing agent, which creates an exothermic reaction. One common type of combustion synthesis is spin-coating, which involves depositing a solution layer of In and Ga on a hotplate and annealing it at temperatures of approximately 200–400 °C, depending on the target composition. The films can be annealed in air, which is a major advantage compared to PLD. Combustion processing has potential as a new synthesis method, but further research is needed to evaluate its feasibility.

[0008] Such optoelectronic devices require well-defined, uniform thin film layers to better control their performance and optimize their size. Thin films with the desired properties can be formed by conventional film formation methods, such as chemical vapor deposition (CVD), atomic layer deposition (ALD), or plasma-enhanced atomic layer deposition (PEALD). A key parameter for industrial applications is the development of a liquid gallium-containing precursor. This is because it is more practical and therefore cost-effective to fill a storage canister and deliver it to the reactor via a supply line and exhaust line. The use of a solid precursor requires a sublimator for vapor formation, which presents several challenges. First, the loading capacity in the canister (sublimator) is limited to a few hundred grams, and the sublimator cannot be refilled while on the tool, so it typically requires frequent replacement. Second, solid precursors often have low vapor pressures, which leads to variable delivery rates. Additionally, particle size variations can lead to differences in product evaporation. Finally, for safety reasons, it would be preferable for the gallium-containing precursor to not spontaneously ignite (pyrophoric) when exposed to air.

[0009] For example, the non-pyrophoric liquid type Ga precursor, trimethyl[N-(2-methoxyethyl)-2-methylpropan-2-amine]gallium, GaMe3·(CH3OCH2CH2NH t Bu) was developed, and ALD GaO x It was used for the purpose of GaO x Thin films can be deposited at a growth rate of 1.0 Å / cycle in the temperature range of 100°C to 250°C (Ceramics International, Volume 47, Issue 2, 15 January 2021, Pages 1588-1593).

[0010] Another example of a non-pyrophoric liquid gallium precursor is dimethylgallium isopropoxide (Me2Ga(OiPr)). It is liquid at room temperature and has a fairly high vapor pressure (0.55 Torr / 25°C; 0.75 Torr / 30°C; 1.0 Torr / 35°C; 1.3 Torr / 40°C), sufficiently high for atomic layer deposition and / or metalorganic chemical vapor deposition. In the ALD process, when water is used as the oxygen source, the apparent ALD temperature window is 300-325°C, and a growth rate of approximately 1.5 Å / cycle is achieved. MOCVD is performed in the temperature range of 450-625°C using oxygen as the reactant gas. Ga2O3 films deposited by both processes were found to be stoichiometric and amorphous. Using this precursor, conductive Ga-doped ZnO thin films can be successfully deposited. The electrical, structural, and optical properties are systematically investigated as a function of Ga doping content and deposition temperature. Low resistivity (approximately 3.5×10 -3 Ωcm) and the best carrier concentration and transmittance (7.2×10 20 cm -3 and 83.5%) are observed at a Ga doping concentration of 5 at.% deposited at 250 °C (ECS Transactions, 25(8), 587-592, 2009 and Chem. Vap. Deposition, 17, 191-197, 2011). The problem with alkoxy-containing molecules is that their ALD behavior is often limited to structures with very small aspect ratios, and amine-containing molecules are often preferred to solve this problem.

[0011] The deposition of indium gallium oxide and indium gallium zinc oxide thin films by CVD and ALD techniques has been reported. For example, in the paper “Atomic Layer Deposition of an Indium Gallium Oxide Thin Film for Thin-Film Transistor Applications” (Appl. Mater. Interfaces, 2017, 9, 23934-23940), the deposition of indium gallium oxide (IGO) thin films by atomic layer deposition (ALD) was investigated using [1,1,1-trimethyl-N-(trimethylsilyl)-silanaminato]indium (InCA-1) and trimethylgallium (TMGa) as the indium and gallium precursors, respectively.

[0012] Gallium-doped zinc oxide was reported in the paper “Growth characteristics and film properties of gallium-doped zinc oxide prepared by atomic layer deposition” (J Electroceram (2013) 31:338-344). In this study, gallium(III) isopropoxide and diethylzinc were used as precursors.

[0013] The study on the nucleation and growth of InGaZnO thin films by spatial atmospheric atomic layer deposition using diethylzinc (DEZn), trimethylindium (TMIn), and triethylgallium (TEGa) as Zn, In, and Ga precursors is published in the paper "Spatial Atmospheric Atomic Layer Deposition of In x Ga y Zn z O for Thin Film Transistors” (ACS Appl. Mater. Interfaces 2015, 7, 6, 3671-3675).

[0014] In these studies, the Ga, Zn, and In precursors are mostly pyrophoric materials, which the present invention seeks to avoid and take advantage of the physical properties of comparable materials.

[0015] The gallium complexes (NMe2)2Ga(MeNCH2CH2NMe2) and (NMe2)2Ga(EtNCH2CH2NMe2) have been reported to be liquid and volatile (MRS proceedings by ST Barry et al., 1999). These molecules are reported to be thermally stable and can be evaporated without leaving any residue (TGA data not available). The molecules are not pyrophoric, making them safe to handle. While the gallium molecule was not used for film deposition, its aluminum version was used to deposit AlN in CVD mode using ammonia. Deposition of AlN from (NMe2)2Al(EtNCH2CH2NMe2) was reported at 200 °C.

[0016] For the deposition of gallium oxide-containing films, gallium-containing precursors should be free of halides, which could reduce the electrical conductivity of the resulting film. Furthermore, gallium precursors must be compatible with the indium and zinc co-precursors in IGZO applications, with similar volatility and thermal stability. Several studies have been reported on the ALD of Ga2O3 thin films using precursors including trimethylgallium (GaMe3), hexakis(dimethylamino)digallium [Ga2(NMe2)6], and Ga(acac)3 (acac = pentane-2,4-dionate). All of these precursors are either pyrophoric or mostly solid at room temperature, making them inconvenient to use, although some of them readily volatilize upon gentle heating.

[0017] For depositing binary or ternary oxide films containing gallium, precursors with similar properties are preferred. The most commonly referenced indium and zinc molecules are trimethylindium and diethylzinc. These two compounds are pyrophoric, which poses significant safety concerns and increases costs. In addition, trimethylindium is a solid at room temperature with a melting point of 88°C. The use of solids is not preferred because it also increases costs.

[0018] Several teams have developed interesting new indium or zinc compounds. For example, WO2020179748A1 discloses the use of isopentylcyclopentadienyl indium for indium-containing depositions. This molecule is liquid, non-pyrophoric, and exhibits a vapor pressure of 1 torr at 65°C. ALD deposition of indium oxide or indium at 250°C is disclosed.

[0019] R.G. Gordon et al. disclose the synthesis of diethylzinc adducted with tetramethylethylenediamine (TMEDA) and its use in zinc oxide deposition in CVD mode (Optimization of Transparent and Reflective Electrodes for Amorphous Silicon Solar Cells, National Renewable Energy Laboratory, 1998). This molecule is not pyrophoric, whereas diethylzinc is. The authors report that the corresponding fluorine-doped ZnO CVD process is more controllable and reproducible, with superior film uniformity (compared to diethylzinc). While this molecule is a solid, other adducted diethylzinc compounds, such as diethylzinc-tetraethylethylenediamine and diethylzinc-TEEDA, are liquids. The authors of this disclosure measured the vapor pressure of diethylzinc-tetraethylethylenediamine in-house to be 1 torr at 69 °C. Summary of the Invention [Problem to be solved by the invention]

[0020] In conclusion, there is a need to develop gallium compounds for the deposition of binary, ternary, or quaternary oxide films that are liquid at room temperature, halide-free, non-pyrophoric, thermally stable, and have high vapor pressures; in addition, it is also important to identify additional metal precursors with similar properties to develop the best deposition processes. [Means for solving the problem]

[0021] A method for depositing a gallium-containing oxide film on a substrate is disclosed, the method comprising: a) simultaneously or sequentially exposing a substrate to vapor of a gallium-containing film-forming composition containing a gallium precursor and an oxidizing agent; b) depositing at least a portion of the gallium precursor on a substrate to form a gallium-containing oxide film on the substrate via a vapor deposition process; Including, The gallium precursor has the formula: (NR 8 R 9 )(NR 1 R 2 )Ga[(R 3 R 4 N)C x (R 5 R 6 )(NR 7 )] (I) (Cy-N)2Ga[(R 3 R 4 N)C x (R 5 R 6 )(NR 7 )] (II) and the corresponding structure: [ka] (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R9 are independently selected from H, Me, Et, nPr, iPr, nBu, iBu, sBu, or tBu; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 may be the same or different; x=2, 3, or 4, preferably x=2; Cy-N represents a saturated or unsaturated N-containing ring; the N-containing ring contains at least one nitrogen atom and 4 to 6 carbon atoms in the chain. It has.

[0022] The methods of the present disclosure may include one or more of the following aspects: Cy-NH includes the following pyrrolines, pyrroles, and piperidines: [ka] ; Gallium precursors include (NMe2)2Ga(EtNCH2CH2NMe2), (NMe2)2Ga(EtNCH2CH2NEt2), (NEtMe)2Ga(EtNCH2CH2NMe2), (NEtMe)2Ga(EtNCH2CH2NEt2), (NEt2)2Ga(EtNCH2CH2NMe2), (NEt2)2Ga(EtNCH2CH2NEt2), and (NMe2)2Ga(MeNCH2CH2NMe2); · The gallium precursor is (NMe2)2Ga(EtNCH2CH2NMe2); · The gallium precursor is (NMe2)2Ga(EtNCH2CH2NEt2); · The gallium precursor is (NEtMe)2Ga(EtNCH2CH2NMe2); · The gallium precursor is (NEtMe)2Ga(EtNCH2CH2NEt2); · The gallium precursor is (NEt2)2Ga(EtNCH2CH2NMe2); · The gallium precursor is (NEt2)2Ga(EtNCH2CH2NEt2); · The gallium precursor is (NMe2)2Ga(MeNCH2CH2NMe2); a1) In step a), simultaneously or sequentially, the surface is treated with a first metal (M 1 ) precursor vapor to form a first metal (M 1 ) depositing at least a portion of the precursor and at least a portion of the gallium precursor on a substrate to form a gallium-containing oxide film on the substrate via a vapor deposition process, wherein the gallium-containing oxide film is 1 The GaO film is further included; a2) In step a1), simultaneously or sequentially, the surface is treated with a second metal (M 2 ) precursor vapor to form a second metal (M 2 ) precursor, at least a portion of a gallium precursor, and a first metal (M 1 ) depositing at least a portion of the precursor on a substrate to form a gallium-containing oxide film on the substrate via a vapor deposition process, wherein the gallium-containing oxide film is M 1 M 2 The GaO film is further included; a film-forming composition, a first metal (M 1 ) precursor, a second metal (M 2 ) further comprising purging with an inert gas between each exposure to the precursor, the oxidizer, and the mixture thereof; The inert gas is selected from N2, He, Ar, Kr, or Xe; · The inert gas is N2; · The inert gas is Ar; First metal (M 1 ) precursor is an indium precursor; First metal (M 1 ) precursor is a zinc precursor; Second metal (M 2 ) precursor is an indium precursor; the second metal (M 2 ) precursor is a zinc precursor; the indium precursor is selected from trialkylindium, sec-pentylcyclopentadienylindium, or isopentylcyclopentadienylindium; The indium precursor is a trialkylindium; · The indium precursor is isopentylcyclopentadienyl indium; The indium precursor is sec-pentylcyclopentadienyl indium; The zinc precursor is diethylzinc-tetramethylethylenediamine adduct (TMEDA), diethylzinc-tetraethylethylenediamine adduct (TEEDA), diethylzinc-N,N'-diethyl-N,N'-diethylethylenediamine adduct, diethylzinc-N,N-dimethyl-N',N'-diethylethylenediamine adduct, or diethylzinc-N,N,N'-trimethyl-N'-ethylethylenediamine adduct; · The zinc precursor is diethylzinc-tetramethylethylenediamine adduct (TMEDA); · The zinc precursor is diethylzinc-tetraethylethylenediamine adduct (TEEDA); The zinc precursor is diethylzinc-N,N-diethyl-N',N'-diethylethylenediamine adduct; The zinc precursor is diethylzinc-N,N-dimethyl-N',N'-diethylethylenediamine adduct; The zinc precursor is diethylzinc-N,N,N'-trimethyl-N'-ethylethylenediamine adduct; M 1 The GaO film is an InGaO film; M 1 The GaO film is a ZnGaO film; M 1 M 2 The GaO film is an IGZO film; The gallium-containing oxide film is an InGaO film; The gallium-containing oxide film is a ZnGaO film; · Gallium-containing oxide film is IGZO film; Oxidizing agents include O2, O3, H2O, H2O2, NO, N2O, NO2, oxygen-containing radicals, e.g., O · or OH · is; · The oxidizing agent is O3; · The oxidizing agent is O2; · The oxidizer is plasma treated; The gallium-containing film-forming composition comprises an inert carrier gas; The inert carrier gas is selected from N2, He, Ne, Ar, Kr, Xe, or a combination thereof. The inert carrier gas is N2 or Ar; The melting point of the gallium precursor is approximately 60°C or less; The melting point of the gallium precursor is approximately 20°C or less; · Gallium precursors are not pyrophoric; · The gallium precursor is liquid at room temperature; The gallium precursor is liquid at temperatures ranging from room temperature to approximately 60°C; The vapor deposition process is an ALD process, a CVD process, or a combination thereof; · The vapor deposition process is an ALD process; · The vapor deposition process is a CVD process; · The vapor deposition process is a PEALD process; The deposition pressure is about 10 -3 Torr to approximately 100 Torr; The deposition pressure is about 10 -2 held at Torr~10 Torr; · The deposition temperature is kept between about 100°C and about 600°C; · The deposition temperature is kept between about 150°C and about 500°C; The gallium precursor has a purity ranging from approximately 93% w / w to approximately 100% w / w; The gallium precursor has a purity ranging from approximately 99% w / w to approximately 99.999% w / w; The indium precursor has a purity ranging from approximately 93% w / w to approximately 100% w / w; The indium precursor has a purity ranging from approximately 99% w / w to approximately 99.999% w / w; The zinc precursor has a purity ranging from approximately 93% w / w to approximately 100% w / w; The zinc precursor has a purity ranging from approximately 99% w / w to approximately 99.999% w / w; the gallium-containing film-forming composition has a purity in the range of approximately 93% w / w to approximately 100% w / w; The gallium-containing film-forming composition has a purity ranging from approximately 99% w / w to approximately 99.999% w / w.

[0023] In addition, a gallium-containing quaternary oxide (M 1 M 2 A method for depositing a GaO film is also disclosed, the method comprising: a) simultaneously or sequentially reacting a gallium precursor with a first metal (M 1 ) precursor vapor and a second metal (M 2 ) exposing the substrate to vapors of a gallium-containing film-forming composition containing vapors of a precursor and an oxidizer; and b) at least a portion of the gallium precursor, a first metal (M 1 ) precursor, and a second metal (M 2 ) precursor onto a substrate via a vapor deposition process to form the gallium-containing quaternary oxide film (M 1 M 2 forming GaO); Including, The gallium precursor has the formula: (NR 8 R 9 )(NR 1 R 2 )Ga[(R 3 R 4 N)C x (R 5 R 6 )(NR 7 )] (I) (Cy-N)2Ga[(R 3 R 4 N)C x (R 5 R 6 )(NR 7 )] (II) and the corresponding structure: [ka] (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 are independently selected from H, Me, Et, nPr, iPr, nBu, iBu, sBu, or tBu; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 may be the same or different; x=2, 3, or 4, preferably x=2; Cy-N represents a saturated or unsaturated N-containing ring; the N-containing ring contains at least one nitrogen atom and 4 to 6 carbon atoms. It has.

[0024] Also disclosed is a method for depositing an indium gallium zinc oxide (IGZO) film on a substrate, the method comprising: a) simultaneously or sequentially exposing a substrate to vapor of a gallium-containing film-forming composition containing a gallium precursor, vapor of an indium precursor, vapor of a zinc precursor, and O3; and b) depositing at least a portion of the gallium precursor, at least a portion of the indium precursor, and at least a portion of the zinc precursor on the substrate to form an IGZO film on the substrate via a vapor deposition process; Including, The gallium precursor has the formula: (NR 8 R9 )(NR 1 R 2 )Ga[(R 3 R 4 N)C x (R 5 R 6 )(NR 7 )] (I) (Cy-N)2Ga[(R 3 R 4 N)C x (R 5 R 6 )(NR 7 )] (II) and the corresponding structure: [ka] (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 are independently selected from H, Me, Et, nPr, iPr, nBu, iBu, sBu, or tBu; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 may be the same or different; x=2, 3, or 4, preferably x=2; Cy-N represents a saturated or unsaturated N-containing ring; the N-containing ring contains at least one nitrogen atom and 4 to 6 carbon atoms. It has.

[0025] Notation and Nomenclature The following detailed description and claims utilize several abbreviations, symbols, and terminology that are commonly known in the art. The following specific abbreviations, symbols, and terminology are used throughout the following description and claims:

[0026] As used herein, the indefinite article "a" or "an" means one or more.

[0027] As used herein, in the text or claims, "about" or "around" or "approximately" means ±10% of the stated value.

[0028] As used herein, "room temperature" in the text and claims means approximately 20°C to approximately 25°C.

[0029] The term "high thermal stability" refers to the property of a product that, in thermogravimetric analysis, evaporates smoothly without exhibiting a "tail" or residue above 200°C, more preferably with a residue of less than about 5% at 300°C, more preferably less than about 2% at 300°C, or that, in DSC analysis, exhibits a higher onset of decomposition temperature than commercially available products, more preferably greater than 235°C.

[0030] The term "substrate" refers to one or more materials on which a process is performed. A substrate can refer to a wafer having one or more materials on which a process is performed. A substrate can be any suitable wafer used in semiconductor, photovoltaic, flat panel, or LCD-TFT device manufacturing. A substrate can also have one or more layers of different materials already deposited thereon from a previous manufacturing step. For example, a wafer can include a silicon layer (e.g., crystalline, amorphous, porous, etc.), a silicon-containing layer (e.g., SiO2, SiN, SiON, SiCOH, etc.), a metal-containing layer (e.g., copper, cobalt, ruthenium, tungsten, platinum, palladium, nickel, ruthenium, gold, etc.), or a combination thereof. Furthermore, a substrate can be planar or patterned. A substrate can be an organic patterned photoresist film. The substrate can include a layer of oxide (e.g., ZrO2-based materials, HfO2-based materials, TiO2-based materials, rare earth oxide-based materials, ternary oxide-based materials, etc.) used as a dielectric material in MEMS, 3D NAND, MIM, DRAM, or FeRam device applications, or a nitride-based film (e.g., TaN, TiN, NbN) used as an electrode. The substrate can also be a powder, such as powders used in battery technology. A non-limiting number of powder materials include NMC (lithium nickel manganese cobalt oxide), LCO (lithium cobalt oxide), LFP (lithium iron phosphate), and other battery cathode materials. Exemplary powder substrates also include activated carbon.

[0031] The term "wafer" or "patterned wafer" means a wafer having a stack of films on a substrate, with at least a top film having topographical features formed in a step prior to the deposition of the indium-containing film.

[0032] The term "aspect ratio" refers to the ratio of the height of a trench (or aperture) to the width of the trench (or diameter of the aperture).

[0033] It should be noted that the terms "film" and "layer" can be used interchangeably herein. It is understood that a film can correspond to or be associated with a layer, and a layer can refer to a film. Furthermore, those skilled in the art will understand that the terms "film" or "layer" as used herein refer to a thickness of material disposed on or spread across a surface, which may range in surface area from as large as an entire wafer to as small as a trench or line. Throughout this specification and claims, the wafer and any associated layers thereon are referred to as the substrate.

[0034] It should be noted that the terms "aperture," "via," "hole," and "trench" may be used interchangeably herein to refer to an opening formed in a semiconductor structure.

[0035] As used herein, the abbreviation "NAND" refers to a "Negative AND" or "Not AND" gate, the abbreviation "2D" refers to a two-dimensional gate structure on a planar substrate, and the abbreviation "3D" refers to a three-dimensional or vertical gate structure in which the gate structures are stacked vertically.

[0036] It should be noted that the terms "deposition temperature" and "substrate temperature" may be used interchangeably herein. It is understood that substrate temperature may correspond to or be related to deposition temperature, and deposition temperature may refer to substrate temperature.

[0037] It should be noted that, as used herein, the terms "precursor" and "deposition compound" and "deposition gas" may be used interchangeably when the precursor is in a gaseous state at room temperature and ambient pressure. It is understood that a precursor may correspond to or be associated with a deposition compound or deposition gas, and a deposition compound or deposition gas may refer to a precursor.

[0038] Standard abbreviations for elements from the Periodic Table of the Elements are used herein, and it should be understood that elements may be referred to by such abbreviations (e.g., Si means silicon, N means nitrogen, O means oxygen, C means carbon, H means hydrogen, F means fluorine, etc.).

[0039] Unique CAS Registry Numbers (ie, "CAS") assigned by the Chemical Abstract Service are provided to identify the particular molecules disclosed.

[0040] As used herein, the term "alkyl group" refers to a saturated functional group containing exclusively carbon and hydrogen atoms. Alkyl groups are a group of hydrocarbons. Furthermore, the term "alkyl group" refers to linear, branched, or cyclic alkyl groups. Examples of linear alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, and the like. Examples of branched alkyl groups include, but are not limited to, t-butyl. Examples of cyclic alkyl groups include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, and the like.

[0041] As used herein, the abbreviation "Me" means a methyl group, "Et" means an ethyl group, "Pr" means any propyl group (i.e., n-propyl or isopropyl), "iPr" means an isopropyl group, "Bu" means any butyl group (n-butyl, iso-butyl, tert-butyl, sec-butyl), "tBu" means a tert-butyl group, "sBu" means a sec-butyl group, "iBu" means an isobutyl group, "Ph" means a phenyl group, "Amy" means any amyl group (iso-amyl, sec-amyl, tert-amyl), "Cy" means a cyclic hydrocarbon group (e.g., cyclobutyl, cyclopentyl, cyclohexyl), and "Ar" means an aromatic hydrocarbon group (e.g., phenyl, xylyl, mesityl). As used in the embodiments of the present disclosure, the term "independently," when used in the context of describing an R group, should be understood to mean that the subject R group is independently selected not only from other R groups having the same or different subscripts or superscripts, but also from any further species of that same R group. For example, 1 x (NR 2 R 3 ) (4-x) (wherein x is 2 or 3), two or three R 1 The groups may be spaced apart relative to each other or R 2 For or R 3 Furthermore, it should be understood that unless otherwise specified, the values ​​of the R groups are independent of each other when used in different formulas.

[0042] Ranges may be expressed herein as from about one particular value and / or to about another particular value. When such ranges are expressed, another embodiment should be understood to be from the one particular value and / or to the other particular value, along with all combinations within said ranges. All ranges recited in the embodiments of this disclosure are inclusive of their endpoints (i.e., x=1 to 4 or x is in the range of 1 to 4 includes x=1, x=4, and any number therebetween), regardless of whether the term "inclusive" is used.

[0043] References herein to "one embodiment" or "an embodiment" mean that a particular feature, structure, or characteristic described in connection with that embodiment may be included in at least one embodiment of the invention. The appearances of the phrase "in one embodiment" in various places throughout this specification do not necessarily all refer to that embodiment, nor do separate or alternative embodiments necessarily mutually exclude other embodiments. The same applies to the term "implementation."

[0044] As used herein, the word "exemplary" is used herein to mean serving as an example, instance, or illustration. Any aspect or design described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other aspects or designs. Rather, use of the word exemplary is intended to present a concept in concrete terms.

[0045] "Comprising" in a claim is an open transitional term meaning that the subsequently identified claim element is a non-exclusive listing, i.e., anything else may additionally be included and still fall within the scope of "comprising." "Comprising" is defined herein as necessarily including the more narrow transitional terms "consisting essentially of" and "consisting of," such that "comprising" could be replaced with "consisting essentially of" or "consisting of" and still fall within the expressly defined scope of "comprising."

[0046] Additionally, the term "or" is intended to mean an inclusive "or" rather than an exclusive "or." That is, unless otherwise specified or clear from the context, "X employs A or B" is intended to mean any of the reasonable inclusive permutations. That is, if X employs A, X employs B, or X employs both A and B, then "X employs A or B" is satisfied under any of the above cases. Additionally, the articles "a" and "an," as used in this application and the appended claims, should generally be construed to mean "one or more" unless otherwise specified or clear from the context to the singular.

[0047] "Providing" in the claims is defined to mean giving, supplying, making available, or preparing something. In the absence of clear language to the contrary in the claims, this step may be performed by any actor.

[0048] For a better understanding of the nature and objects of the present invention, reference should be made to the following detailed description taken in conjunction with the accompanying drawings, in which like elements are given the same or similar reference numerals, and in which: [Brief explanation of the drawings]

[0049] [Figure 1] FIG. 1 is a comparison of TGA performed on tris(dimethylamino)gallium (TDMAGa) and (NMe2)2Ga(EtNCH2CH2NMe2). [Figure 2] Figure 2 is a comparison of DSC performed on TDMAGa and (NMe2)2Ga(EtNCH2CH2NMe2). DETAILED DESCRIPTION OF THE INVENTION

[0050] A gallium-containing film-forming composition comprising a gallium precursor containing an aminoamide ligand and a method for using the same to deposit a gallium-containing oxide film, such as an indium gallium zinc oxide (IGZO) film, for manufacturing a semiconductor device is disclosed. The gallium-containing oxide film may be a binary, ternary, or quaternary gallium oxide film. The gallium precursor of the present disclosure is a gallium amino compound that is liquid, volatile, non-pyrophoric, and halogen-free at temperatures ranging from room temperature to approximately 60°C. The gallium precursor of the present disclosure is preferably liquid at about 20°C. The melting point of the gallium precursor is less than approximately 60°C, and preferably the melting point of the gallium precursor is less than approximately 20°C. The volatility and thermal stability of the gallium precursor of the present disclosure are higher than those of existing gallium precursors, such as tris(dimethylamino)gallium (Ga(NMe2)3, TDMAGa), which is a solid that melts at about 110°C and has been used as the primary Ga source for gallium oxide-containing films such as IGZO. The gallium precursors of the present disclosure are liquids at room temperature, allowing for easy manipulation of their preparation, synthesis, purification, storage in canisters, and delivery to liquid delivery systems. These properties are beneficial to industry for reducing costs when the precursors are used in high volume manufacturing (HVM).

[0051] The gallium precursors of the present disclosure are not pyrophoric, thereby reducing safety-related costs. It is known that pyrophoric chemicals cannot be transported by air and must be shipped by sea. The need to use ships for international shipping significantly increases costs, depending on the volume, during development, start-up, and even mass production. Additionally, the shipping and storage of pyrophoric products, as well as the shipping time and container quality requirements associated with certain regulations, result in increased production costs.

[0052] The disclosed gallium precursor is halogen-free and compatible with the two molecules, such as the indium and zinc precursors, used in the disclosed method, which means the entire system is believed to be corrosion-free, eliminating the need for special anti-corrosion materials of construction, special O-rings, or specialized and expensive pumps, and reducing the cost of the process by reducing the need for maintenance, etc.

[0053] Due to the higher volatility of the disclosed gallium precursor compared to TDMAGa (see Table 1), a higher flow rate of the disclosed gallium precursor can be delivered into the reactor compared to TDMAGa while heating the vessel at the same temperature. A higher Ga partial pressure can potentially result in a faster deposition rate compared to TDMAGa. A faster deposition rate can potentially reduce production costs. It may also be possible to increase the Ga content in the film, potentially resulting in greater flexibility in tailoring the film composition. The higher stability of the disclosed gallium precursor compared to TDMAGa, as demonstrated by thermogravimetry, allows the disclosed gallium precursor to tailor the deposition process window. Because the disclosed molecule is more stable, it may be possible to deposit films in ALD mode at higher temperatures than current molecules, such as TDMAGa. The ability to deposit films at higher temperatures generally allows for improved quality of the deposited film, i.e., lower impurity content, carbon, or nitrogen. In some cases, the possibility of depositing films at high temperatures while still in ALD mode allows films to be deposited in different crystalline phases, which can give them better properties than films deposited at lower temperatures, for example due to higher mobility.

[0054] Gallium precursors of the present disclosure have the following general formula: (NR 8 R 9 )(NR 1 R 2 )Ga[(R 3 R 4 N)C x (R 5 R 6 )(NR 7 )] (I) (Cy-N)2Ga[(R 3 R 4 N)C x (R 5 R 6 )(NR 7 )] (II) and the corresponding structure: [ka]

[0055] In formula (I), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 are independently selected from H, Me, Et, nPr, iPr, nBu, iBu, sBu, or tBu; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 may be the same or different; x=2, 3, 4, preferably x=2.

[0056] In formula (II), R 3 , R 4 , R 5 , R 6 , R 7are independently selected from H, Me, Et, nPr, iPr, nBu, iBu, sBu, or tBu; R 3 , R 4 , R 5 , R 6 , R 7 may be the same or different; x=2, 3, or 4, preferably x=2; Cy-N represents a saturated or unsaturated N-containing ring; the N-containing ring contains at least one nitrogen atom and 4 to 6 carbon atoms in the chain. Examples of Cy-NH include: [ka] Examples of suitable aryl groups include pyrroline, pyrrole, and piperidine.

[0057] Exemplary gallium precursors of the present disclosure include: [ka]

[0058] Gallium precursors of the present disclosure are (NMe2)2Ga(EtNCH2CH2NMe2), (NMe2)2Ga(EtNCH2CH2NEt2), (NEtMe)2Ga(EtNCH2CH2NMe2), (NEtMe)2Ga(EtNCH2CH2NEt2), (NEt2)2Ga(EtNCH2CH2NMe2), (NEt2)2Ga(EtNCH2CH2NEt2), and (NMe2)2Ga(MeNCH2CH2NMe2).

[0059] The gallium precursors of the present disclosure may have the following characteristics that make them suitable for depositing gallium oxide and multimetallic gallium-containing oxide films: In one aspect, the gallium precursors of the present disclosure are liquid at room temperature, making them much more volatile, more thermally stable, and have sufficient vapor pressure at low temperatures than the reference Ga compound, TDMAGa; In another aspect, the gallium precursors of the present disclosure are non-pyrophoric compounds, allowing for easy preparation, synthesis, purification, storage, and delivery for semiconductor industry applications; The gallium precursors of the present disclosure may be suitable for use as deposition precursors in the formation of gallium oxide and multimetallic gallium-containing oxide films, including IGZO films.

[0060] The gallium precursors of the present disclosure are suitable for use as precursors for the deposition of gallium oxide films, gallium indium oxide films, gallium zinc oxide films, and IGZO films. Again, the gallium precursors of the present disclosure are non-pyrophoric and volatile liquid compounds at room temperature, with excellent vapor pressure and excellent thermal stability. The key properties of the gallium precursors of the present disclosure (vapor pressure, melting point) are closer to those of standard indium and zinc precursors, such as trimethylindium or diethylzinc, than to those of currently used gallium precursors, such as TDMAGa.

[0061] The gallium precursors of the present disclosure have high thermal stability and can be used to form high-speed, high-sensitivity semiconductor layers, for example, in CMOS systems, 3D NAND channels, or photodetectors. The gallium precursors of the present disclosure are suitable for the deposition of corresponding element-containing films and their related uses for the deposition of corresponding element-containing layers.

[0062] The film-forming composition of the present disclosure may include a gallium precursor of the present disclosure, a co-reactant, a carrier gas, etc. The co-reactant may include one or more additional precursors and an oxidizer such as O2 or O3. The gallium precursor of the present disclosure and the film-forming composition of the present disclosure are suitable for forming gallium oxide thin films such as Ga2O3 used in the electronics field. The gallium precursor of the present disclosure and the film-forming composition of the present disclosure are suitable for producing indium gallium oxide films, zinc gallium oxide films, and indium gallium zinc oxide (IGZO) films used in the display, semiconductor, logic, and memory industries, etc.

[0063] The present disclosure also includes processes for forming gallium oxide films, indium gallium oxide films, zinc gallium oxide films, and indium gallium zinc oxide (IGZO) films using the gallium precursors of the present disclosure by vapor deposition methods such as ALD or CVD. The present disclosure also includes deposition processes in which the gallium precursors of the present disclosure, with or without co-reactants that are one or more oxidizers (e.g., O and O, or HO and HO), are simultaneously and / or sequentially introduced into a reaction chamber for film deposition by ALD, CVD, spin-on, spray, dip coating, slit coating, or any other deposition technique. The deposition processes of the present disclosure using the gallium precursors of the present disclosure can be assisted by heat, light, direct or remote plasma, or a combination thereof.

[0064] The co-reactant may be one or more additional precursors other than the gallium precursor of the present disclosure. The co-reactant may be an indium precursor, a zinc precursor, or a combination thereof. The additional precursor may be selected from non-pyrophoric, liquid, and halide-free indium or zinc molecules with a vapor pressure of 1 torr at temperatures below 100°C, preferably 1 torr at temperatures below 80°C.

[0065] Additionally, the co-reactant may be O, O, H, H, O, NO, N, O, NO, oxygen-containing radicals, e.g., O ·or OH · The oxidizing gas may be one of the following: alcohols, silanols, amino alcohols, carboxylic acids, such as formic acid, acetic acid, propionic acid, para-formaldehyde, other oxidizing compounds, and mixtures thereof. Preferably, the oxidizing gas is selected from the group consisting of O2, O3, HO2, and HO. Preferably, when an ALD process is performed, the co-reactant is plasma-treated oxygen, ozone, or a combination thereof. The resulting gallium-containing oxide film is a gallium oxide film.

[0066] The co-reactant may be treated with plasma, and O3 and O2 can be used as oxygen source gases when treated with plasma to decompose the reactant into its radical form. The plasma source may be He plasma, Ar plasma, or a mixture thereof. For example, the plasma can be generated at a power ranging from about 10 W to about 1000 W, preferably from about 50 W to about 500 W. The plasma can be generated and exist within the reactor itself. Alternatively, the plasma can generally exist at a location remote from the reactor, e.g., in a remotely located plasma system. Those skilled in the art will recognize suitable methods and apparatus for such plasma treatment.

[0067] For example, to produce plasma-treated reactants within the reaction chamber, the co-reactant can be introduced into a direct plasma reactor where plasma is generated within the reaction chamber. The co-reactant can be introduced and maintained within the reaction chamber prior to plasma treatment. Alternatively, plasma treatment can occur simultaneously with the introduction of the reactants.

[0068] Alternatively, plasma-treated co-reactants can be generated outside the reaction chamber, for example, in a remote plasma, to treat the co-reactant before passing it into the reaction chamber.

[0069] Also disclosed is a method for forming a gallium-containing oxide layer on a substrate using a vapor deposition process. Applicants believe that the film-forming compositions of the present disclosure are suitable for ALD. More specifically, the film-forming compositions of the present disclosure are capable of surface saturation, cycle-by-cycle self-limiting growth, and greater than 90% complete step coverage with aspect ratios of holes, trenches, and the like ranging from approximately 2:1 to approximately 200:1, preferably from approximately 20:1 to approximately 150:1, and more preferably from approximately 50:1 to approximately 100:1. Additionally, the film-forming compositions of the present disclosure have high decomposition temperatures, demonstrating good thermal stability that enables ALD. The high decomposition temperatures allow ALD at higher temperatures, resulting in films with higher purity. The methods of the present disclosure may be useful in the manufacture of semiconductor, photovoltaic, LCD-TFT, and flat-panel devices.

[0070] The gallium-containing film-forming composition of the present disclosure can be used to deposit a gallium-containing oxide film using any deposition method known to those skilled in the art. Examples of suitable deposition methods include chemical vapor deposition (CVD) with or without plasma assistance or atomic layer deposition (ALD). Exemplary ALD methods include thermal ALD with or without the use of inhibitors, plasma-enhanced ALD (PEALD), spatially isolated ALD, temporal ALD, selective or non-selective ALD, hot wire ALD (HWALD), radical-introduced ALD, flowable ALD (thermal or plasma), and combinations thereof. To obtain suitable step coverage and film thickness control, the deposition method is preferably ALD, PE-ALD, or spatial ALD. Exemplary CVD methods include metal-organic CVD (MOCVD), thermal CVD, pulsed CVD (PCVD), low-pressure CVD (LPCVD), subatmospheric pressure CVD (SACVD) or atmospheric pressure CVD (APCVD), hot-wire CVD or hot-filament CVD (also known as cat-CVD, where a hot wire serves as the energy source for the deposition process), hot-wall CVD, cold-wall CVD, aerosol-assisted CVD, direct liquid injection CVD, combustion CVD, hybrid physical CVD, metal-organic CVD, rapid thermal CVD, photoinitiated CVD, laser CVD, radical-introduced CVD, plasma-enhanced CVD (PECVD), such as, but not limited to, flowable PECVD, and combinations thereof.

[0071] The gallium-containing film-forming composition of the present disclosure contains less than 5% v / v, preferably less than 1% v / v, more preferably less than 0.1% v / v, and even more preferably less than 0.01% v / v of any analogs or other reaction products. This embodiment can provide better process reproducibility. This embodiment can be produced by purification (e.g., distillation, sublimation, chromatography, etc.) of the gallium-containing film-forming composition.

[0072] The purity of the film-forming compositions of the present disclosure is greater than 93% w / w (i.e., 95.0% w / w to 100.0% w / w), preferably greater than 98% w / w (i.e., 98.0% w / w to 100.0% w / w), and more preferably greater than 99% w / w (i.e., 99.0% w / w to approximately 99.999% w / w or 99.0% w / w to 100.0% w / w). Those skilled in the art will recognize that purity can be determined by NMR spectroscopy and gas or liquid chromatography coupled with mass spectrometry. The film-forming compositions of the present disclosure may contain any of the following impurities: pyrazole, pyridine, alkylamines, alkylimines, THF, ethers, pentane, cyclohexane, heptane, benzene, toluene, chlorinated metal compounds, lithium, sodium, and potassium pyrazolyl. The total amount of these impurities is preferably less than 5% w / w (i.e., 0.0% w / w to 5.0% w / w), preferably less than 2% w / w (i.e., 0.0% w / w to 2.0% w / w), and more preferably less than 1% w / w (i.e., 0.0% w / w to 1.0% w / w). The film-forming compositions of the present disclosure can be purified by recrystallization, sublimation, distillation, and / or gas-liquid passage through a suitable adsorbent such as a 4 Å molecular sieve.

[0073] The film-forming compositions of the present disclosure can also be purified to metal impurities, each independently, at levels of 0 ppbw to 1 ppmw, preferably from about 0 to about 500 ppbw (parts per billion by weight), more preferably from about 0 ppbw to about 100 ppbw, and even more preferably from about 0 ppbw to about 10 ppbw. These metal or metalloid impurities include, but are not limited to, aluminum (Al), arsenic (As), barium (Ba), beryllium (Be), bismuth (Bi), cadmium (Cd), calcium (Ca), chromium (Cr), cobalt (Co), copper (Cu), germanium (Ge), hafnium (Hf), zirconium (Zr), iron (Fe), lead (Pb), lithium (Li), magnesium (Mg), manganese (Mn), tungsten (W), nickel (Ni), potassium (K), sodium (Na), strontium (Sr), thorium (Th), tin (Sn), titanium (Ti), uranium (U), and vanadium (V).

[0074] Care should be taken to avoid contact of the gallium-containing film-forming composition of the present disclosure with water, as this may cause the gallium precursor of the present disclosure to decompose into Ga(OH)3.

[0075] The film-forming compositions of the present disclosure can be supplied either neat or blended with a suitable solvent such as ethylbenzene, xylene, mesitylene, decane, dodecane, etc. The precursors of the present disclosure can be present in the solvent at various concentrations.

[0076] The neat blend film-forming composition is introduced into the reactor in vapor form by conventional means, such as tubing and / or a flow meter. The vapor form can be produced by vaporizing the neat blend composition through conventional vaporization steps, such as direct vaporization, distillation, bubbling, or using a sublimator. The neat blend composition can be fed in liquid form to a vaporizer, where it is vaporized prior to introduction into the reactor. Alternatively, the neat blend composition can be vaporized by passing a carrier gas through a vessel containing the composition, thereby bubbling the carrier gas through the composition. Carrier gases can include, but are not limited to, Ar, He, N2, and mixtures thereof. Bubbling with a carrier gas can also remove any dissolved oxygen present in the neat blend composition. The carrier gas and composition are then introduced into the reactor as a vapor.

[0077] If necessary, the vessel containing the film-forming composition of the present disclosure can be heated to a temperature that allows the composition to have sufficient vapor pressure. The vessel can be maintained at a temperature, for example, within the range of approximately 0° C. to approximately 200° C. Those skilled in the art will recognize that the temperature of the vessel can be adjusted as known to control the amount of precursor vaporized.

[0078] The reactor can be any enclosure chamber within the device in which the deposition method takes place, such as, but not limited to, a parallel plate reactor, a cold-wall reactor, a hot-wall reactor, a single-wafer reactor, a multi-wafer reactor, or any other type of deposition system under conditions suitable to cause the compounds to react and form a layer. Those skilled in the art will recognize that any of these reactors can be used in either ALD or CVD deposition processes.

[0079] The reactor contains one or more substrates onto which the film is deposited. A substrate is generally defined as the material on which the process is performed. The substrate can be any suitable substrate used in semiconductor, photovoltaic, flat panel, or LCD-TFT device manufacturing. Examples of suitable substrates include wafers such as silicon, silica, glass, and GaAs wafers. The wafer can also have one or more layers of different materials deposited thereon from previous manufacturing steps. For example, the wafer can include a dielectric layer. Furthermore, the wafer can include a silicon layer (crystalline, amorphous, porous, etc.), a silicon oxide layer, a silicon nitride layer, a silicon oxynitride layer, a carbon-doped silicon oxide (SiCOH) layer, a metal, a metal oxide, a metal nitride layer (Ti, Ru, Ta, etc.), and combinations thereof. In addition, the wafer can include a copper layer, a noble metal layer (e.g., platinum, palladium, rhodium, gold), or a barrier layer such as manganese or manganese oxide. Plastic layers such as poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) [PEDOT:PSS] can also be used. The layers can be planar or patterned. The process of the present disclosure can deposit a layer directly onto a wafer or onto one or more layers on a wafer, with the patterned layer being formed on a substrate. The patterned layer can be alternating layers of two specific layers, such as SiO and SiN, used in 3D NAND. Furthermore, those skilled in the art will recognize that the terms "film" and "layer" as used herein refer to the thickness of any material laid down or spread on a surface, whether the surface is a trench or a line. Throughout this specification and claims, the wafer and any associated layers thereon are referred to as the substrate. For example, a gallium oxide film can be deposited on a metal oxide layer, such as a HfO layer.

[0080] While the end use of the substrate is not limited to the present invention, this technology may find particular advantage for substrate types such as silicon wafers, glass wafers and panels, beads, powders and nanopowders, monolithic porous media, printed circuit boards, plastic sheets, etc. Exemplary powder substrates include powders used in rechargeable battery technology. A non-limiting number of powder materials include NMC (lithium nickel manganese cobalt oxide), LCO (lithium cobalt oxide), LFP (lithium iron phosphate), and other battery cathode materials.

[0081] The temperature and pressure in the reactor are maintained at conditions suitable for vapor deposition, such as ALD or CVD. In other words, after the vaporized film-forming composition of the present disclosure is introduced into the chamber, the conditions in the chamber are such that at least a portion of the precursor deposits on the substrate to form a layer. For example, the pressure in the reactor or deposition pressure can be adjusted to about 10°C or higher, as needed for each deposition parameter. -3 torr to about 100 torr, more preferably about 10 -2 The pressure in the reactor or deposition temperature can be maintained between about 100°C and about 600°C, preferably between about 150°C and about 500°C. Those skilled in the art will recognize that "at least a portion of the precursor is deposited" means that some or all of the precursor reacts with and adheres to the substrate.

[0082] The temperature to achieve optimal film growth can be controlled by controlling the temperature of the substrate holder. Equipment used to heat the substrate is known in the art. The substrate is heated to a temperature sufficient to obtain the desired film having the desired physical state and composition at a sufficient growth rate. Non-limiting exemplary temperature ranges to which the substrate can be heated include approximately 100°C to approximately 600°C. If a plasma deposition process is utilized, the deposition temperature is preferably less than 400°C. Alternatively, if a thermal process is performed, the deposition temperature can range from approximately 100°C to approximately 600°C.

[0083] Alternatively, the substrate can be heated to a temperature sufficient to obtain the desired gallium-containing oxide film having the desired physical state and composition at a sufficient growth rate. Non-limiting exemplary temperature ranges to which the substrate can be heated include room temperature to approximately 600° C. Preferably, the substrate temperature is maintained at or below 500° C.

[0084] The ALD conditions in the chamber allow the film-forming composition of the present disclosure, adsorbed or chemisorbed onto the substrate surface, to react and form a film on the substrate. In some embodiments, Applicants believe that plasma-treating the co-reactant can provide the co-reactant with the energy necessary to react with the film-forming composition of the present disclosure. When the co-reactant in this exemplary ALD process is treated with plasma, the exemplary ALD process becomes an exemplary PEALD process. The co-reactant may be treated with plasma prior to or subsequent to introduction into the chamber.

[0085] The film-forming composition and co-reactant may be introduced into the reactor sequentially (ALD). The reactor may be purged with an inert gas between each introduction of the film-forming composition, any additional precursors, and co-reactant. Another example is to introduce the co-reactant continuously and pulse the film-forming composition while continuously activating the co-reactant with a plasma, provided that the film-forming composition and the unactivated co-reactant do not substantially react under the temperature and pressure conditions of the chamber (CW PEALD).

[0086] Each pulse of the film-forming composition of the present disclosure can last for a time ranging from about 0.001 seconds to about 120 seconds, alternatively from about 1 second to about 80 seconds, and alternatively from about 5 seconds to about 30 seconds. A co-reactant may also be pulsed into the reactor. In such embodiments, each pulse can last for a time ranging from about 0.01 seconds to about 120 seconds, alternatively from about 1 second to about 30 seconds, and alternatively from about 2 seconds to about 20 seconds. In another alternative, the vaporized film-forming composition and co-reactant can be sprayed simultaneously (without mixing of the composition and the reactants) from different sectors of a showerhead while a susceptor holding multiple wafers rotates beneath it (spatial ALD).

[0087] Depending on the specific process parameters, deposition can be carried out for a variety of times. Generally, deposition can continue for as long as necessary to produce a film with the desired properties. Typical film thicknesses can vary from a few angstroms to hundreds of microns, typically between 1 and 100 nm, depending on the specific deposition process. The deposition process can also be carried out as many times as necessary to obtain the desired film.

[0088] The disclosed method for forming a gallium-containing oxide layer on a substrate includes placing the substrate in a reactor, supplying vapor of the disclosed gallium-containing film-forming composition into the reactor, and contacting / adsorbing the substrate with the vapor (typically by directing the vapor onto the substrate) to form a gallium-containing oxide layer on the substrate surface. Alternatively, the disclosed method for forming a gallium-containing oxide layer on a substrate includes placing the substrate in a reactor, exposing the substrate to vapor of the disclosed gallium-containing film-forming composition, and depositing a gallium-containing oxide layer on the substrate surface.

[0089] A vapor of a gallium-containing film-forming composition is generated and then introduced into a reaction chamber containing a substrate. The temperature and pressure in the reaction chamber, as well as the temperature of the substrate, are maintained at conditions suitable for vapor-phase deposition of at least a portion of the gallium precursor of the present disclosure onto the substrate. In other words, after the vaporized composition is introduced into the reaction chamber, conditions in the reaction chamber are adjusted so that at least a portion of the gallium precursor deposits on the substrate to form a gallium-containing oxide layer. Those skilled in the art will recognize that "at least a portion of the gallium precursor is deposited" means that some or all of the precursor reacts with or adheres to the substrate. Here, a co-reactant may also be used to assist in the formation of the gallium-containing oxide layer.

[0090] The film-forming composition and co-reactant of the present disclosure can be introduced into the reactor either simultaneously (CVD), sequentially (ALD), or in different combinations thereof. The reactor can be purged with an inert gas (e.g., N, He, Ar, Kr, or Xe) between the introduction of the film-forming composition and the introduction of the co-reactant. Alternatively, the co-reactant and the film-forming composition can be mixed together to form a co-reactant / compound mixture and then introduced into the reactor in the form of a mixture. Another example is to introduce the co-reactant sequentially and the film-forming composition of the present disclosure in pulses (pulsed CVD).

[0091] In a non-limiting exemplary ALD process for forming a gallium oxide film, a binary film, the vapor phase of a film-forming composition of the present disclosure, such as (NMe2)2Ga(EtNCH2CH2NMe2), is introduced into a reactor, where it contacts a suitable substrate by either chemisorption or physisorption. Excess composition can then be removed from the reactor by purging and / or evacuating the reactor, i.e., by purging the reactor with an inert gas (e.g., N2, He, Ar, Kr, or Xe) or by passing the substrate through a sector under high vacuum and / or a carrier gas curtain. A co-reactant, such as O3, is introduced into the reactor, where it reacts with the adsorbed film-forming composition in a self-limiting manner. Excess co-reactant is removed from the reactor by purging and / or evacuating the reactor. The desired film is gallium oxide. This two-step process can be repeated until a film having the desired thickness is obtained to provide the desired film thickness. By alternately supplying the gallium film-forming composition and the co-reactant, a film of desired composition and thickness can be deposited.

[0092] Alternatively, if the desired indium-containing film contains three elements, such as ternary films such as InGaO or ZnGaO, the above two-step process (e.g., the formation of a gallium oxide film) can be inserted by introducing the vapor of an additional precursor compound into the reactor (a three-step process). The additional precursor compound is selected based on the properties of the film to be deposited. Additional elements can include nitrogen (N), sulfur (S), phosphorus (P), tin (Sn), arsenic (As), antimony (Sb), indium (In), zinc (Zn), and mixtures thereof. When an additional precursor compound is utilized, the resulting film deposited on the substrate contains gallium and a co-reactant in combination with the additional element. When the additional precursor and gallium precursor are used in multiple ALD supercycle sequences, a nanolaminate film can be obtained. After introduction into the reactor, the additional precursor compound contacts or adsorbs onto the substrate. Excess precursor compound is then removed from the reactor by purging and / or evacuating the reactor. Depending on the process requirements, a co-reactant, such as O2, or additional precursors may be introduced into the reactor to react with the gallium precursor compound. Excess co-reactant or precursor is removed from the reactor by purging and / or evacuating the reactor. In the final step of the cycle, the remaining co-reactant or precursor is introduced into the reactor, and the excess is removed by purging and / or evacuating the reactor. The entire three-step process can be repeated until the desired film thickness is achieved. By alternating the supply of the gallium film-forming composition, additional precursor compound, and co-reactant, a film of the desired composition and thickness can be deposited.

[0093] In one embodiment, the additional precursor may be an indium precursor. The indium precursor may be selected from non-pyrophoric, liquid, and halide-free indium molecules having a vapor pressure of 1 torr at temperatures below 100°C, preferably 1 torr at temperatures below 80°C. The indium precursor may be selected from trialkylindium, sec-pentylcyclopentadienylindium, and isopentylcyclopentadienylindium. Preferably, the indium precursor is isopentylcyclopentadienylindium.

[0094] In an alternative embodiment, the additional precursor may be a zinc precursor. The zinc precursor may be selected from non-pyrophoric, liquid, and halide-free zinc molecules having a vapor pressure of 1 torr at temperatures below 100°C, preferably 1 torr at temperatures below 80°C. The zinc precursor may be selected from diethylzinc-tetramethylethylenediamine adduct (TMEDA), diethylzinc-tetraethylethylenediamine adduct (TEEDA), diethylzinc-N,N'-diethyl-N,N'-diethyl-ethylenediamine adduct, diethylzinc-N,N-dimethyl-N',N'-diethylethylenediamine adduct, and diethylzinc-N,N,N'-trimethyl-N'-ethylethylenediamine adduct. Preferably, the zinc precursor is diethylzinc-tetraethylethylenediamine adduct (TEEDA).

[0095] The gallium precursors of the present disclosure have vapor pressures closer to those of indium and zinc precursors than existing gallium precursors such as TDMAGa and Ga(NMe2)3.

[0096] Alternatively, if the desired gallium-containing oxide film contains four elements, such as a quaternary film, InGaZnO (IGZO), the above three-step process can be inserted by introducing the vapor of another additional precursor compound into the reactor (four-step process). The additional precursor compound is selected based on the properties of the film to be deposited. Additional elements can include N, S, P, Sn, As, Sb, In, Zn, and mixtures thereof. When another additional precursor compound is utilized, the resulting film deposited on the substrate contains gallium combined with the three additional elements. When two additional precursors and a gallium precursor are used in multiple ALD supercycle sequences, a nanolaminate film is obtained. When an IGZO film is formed, the precursors can include a gallium precursor such as (NMe2)2Ga(EtNCH2CH2NMe2), an indium precursor such as In(isopentylcyclopentadienyl), and a Zn precursor such as diethylzinc-TEEDA, combined with the co-reactant O3. By alternately supplying the gallium film-forming composition, the additional precursor, another additional precursor, and the co-reactant, a film of the desired composition and thickness can be deposited. Similarly, excess of each composition or precursor can be removed from the reactor after exposure by purging and / or evacuating the reactor, i.e., by either purging the reactor with an inert gas (e.g., N, He, Ar, Kr, or Xe) or by passing the substrate through a sector under a high vacuum and / or a carrier gas curtain.

[0097] The gallium oxide film obtained from the above process is Ga x O yThe gallium-containing oxide film may comprise a gallium-containing oxide layer, such as InZnO (IZO), InGaZnO (IGZO), or a combination thereof, or a pure gallium oxide layer. The gallium-containing oxide film may contain a second element selected from P, N, S, Ga, As, B, Ta, Hf, Nb, Mg, Al, Sr, Y, Ba, Ca, As, Sb, Bi, Sn, Pb, Co, one or more lanthanides, or a combination thereof. Those skilled in the art will recognize that a desired film composition can be obtained by appropriately selecting the film-forming composition and co-reactants. The methods of the present disclosure are useful for producing semiconductor materials; for example, the gallium-containing oxide can function as a semiconductor material to form heterojunctions with p-InP, n-GaAs, n-Si, and other materials.

[0098] The gallium precursor of the present disclosure has a vapor pressure closer to the vapor pressure of the additional precursor and another additional precursor than existing gallium precursors such as TDMAGa, Ga(NMe2)3.

[0099] Once the desired film thickness is achieved, further processing of the film may be performed, such as thermal annealing, furnace annealing, rapid thermal annealing, UVe beam curing, and / or plasma gas exposure. Those skilled in the art will recognize the systems and methods utilized to perform these additional processing steps. For example, IGZO films may be exposed to temperatures ranging from approximately 100°C to approximately 1000°C for times ranging from approximately 0.1 seconds to approximately 7200 seconds in an inert atmosphere, an O-containing atmosphere, or a combination thereof. Most preferably, the temperature range is 350-450°C for 3600-7200 seconds in an inert or O-containing atmosphere. The resulting film may contain fewer impurities, thereby improving density and leakage current. The annealing step may be performed in the same reaction chamber as the deposition. Alternatively, the substrate may be removed from the reaction chamber and the annealing / flash annealing process may be performed in a separate apparatus. Any of the above post-treatment methods, particularly thermal annealing, have been found to be effective in reducing carbon and nitrogen contamination in IGZO films. This in turn tends to improve the resistivity of the film.

[0100] After annealing, films deposited by any of the processes of the present disclosure may have bulk resistivities of approximately 50 μΩ·cm to approximately 1,000 μΩ·cm at room temperature, which is approximately 20°C to approximately 25°C depending on the season. Bulk resistivity is also referred to as volume resistivity. Those skilled in the art will recognize that bulk resistivity is typically measured at room temperature for films approximately 50 nm thick. Bulk resistivity typically increases as the film becomes thinner due to changes in electron transport mechanisms. Bulk resistivity also increases at elevated temperatures. [Example]

[0101] The following non-limiting examples are provided to further illustrate embodiments of the present invention, however, the examples are not intended to be exhaustive and are not intended to limit the scope of the invention described herein.

[0102] Thermogravimetric (TG) analyses were performed in an open aluminum cup at 25°C to 500°C under atmospheric pressure (1000 mBar, N2 220 sccm) or vacuum (20 mBar, N2 20 sccm). Vapor pressure (VP) was determined by TG analysis. Bisalkylamino(trialkyldiamino)gallium complexes can be prepared by varying the required diamine ligands using a reported method ("Monomeric Chelated Amides of Aluminum and Gallium: Volatile, Miscible Liquid Precursors for CVD", ST Barry, RG Gordon, and VA Agner, MRS Proceedings, 606, 1999, 83). (NMe2)2Ga(EtNCH2CH2NMe2) is a liquid at room temperature. In contrast, TDMAGa, as a reference, is a solid at room temperature (melting at approximately 110°C).

[0103] Thermogravimetric analyses of the two identical compounds can be seen in Figure 1. It can be observed that (NMe2)2Ga(EtNCH2CH2NMe2) evaporates fastest, before TDMAGa, indicating the highest volatility of this product. Furthermore, the amount of residue remaining after evaporation is smaller for (NMe2)2Ga(EtNCH2CH2NMe2), which is considered to be an indication of its higher thermal stability. Such characteristics are crucial not only when considering the potential for extending the ALD window, but also when considering the need to heat molecules for extended periods of time without observing decomposition during use. The TGA results indicate that (NMe2)2Ga(EtNCH2CH2NMe2) may behave better than TDMAGa in this respect. Figure 2 shows a comparison of the DSC spectra of TDMAGa and (NMe2)2Ga(EtNCH2CH2NMe2).

[0104] Example 1 Table 1 summarizes the properties of some of the main molecules used in IGZO vapor deposition, including TDMAGa, triethylgallium (TEGa), (NMe2)2Ga(EtNCH2CH2NMe2), trimethylindium (TMIn), and diethylzinc (DEZn). TDMAGa has a much lower vapor pressure than the other precursors, but has the advantage of not being pyrophoric. (NMe2)2Ga(EtNCH2CH2NMe2) is also non-pyrophoric, but its vapor pressure is much higher than TDMAGa, and it is a liquid, making the molecule easier to use and reducing the costs associated with its use.

[0105] [Table 1]

[0106] Hypothetical Example 1. Deposition of Gallium Oxide Films Using (NMe2)2Ga(EtNCH2CH2NMe2) by CVD The vessel filled with (NMe2)2Ga(EtNCH2CH2NMe2) can be heated to increase and adjust its vapor pressure. The selected temperature is often close to 1 torr, although any other temperature may be used. The vapor of the gallium precursor (NMe2)2Ga(EtNCH2CH2NMe2) is transported to the reaction chamber using, but not necessarily, an inert carrier gas, such as N2, Ar, or any other gas. An oxygen source, in this case ozone, is simultaneously introduced into the reaction chamber. Any other oxygen source or mixture of oxygen sources, such as oxygen or water, is also contemplated. The wafer or wafer piece, or any substrate, is placed in the reaction chamber, which is heated to 200-300°C, although any other temperature is also contemplated. The pressure in the reaction chamber is set to 0.1 torr to 10 torr, although any other pressure is also contemplated. The (NMe2)2Ga(EtNCH2CH2NMe2) vapor and ozone react on the heated substrate surface to form a gallium oxide film. The purity of this film is very high, with carbon and nitrogen levels below the detection limit of measurement tools (XPS). If ozone is replaced by another oxidant, such as O2 or H2O, or even if either of the two oxidants is supplied together, high-purity gallium oxide films can be obtained.

[0107] Hypothetical Example 2. Deposition of Gallium Oxide Films Using (NMe2)2Ga(EtNCH2CH2NMe2) by ALD The vessel filled with (NMe2)2Ga(EtNCH2CH2NMe2) can be heated to increase and adjust its vapor pressure. The temperature chosen is often close to 1 torr, but any other temperature may be used. The gallium precursor vapor is transported to the reaction chamber using an inert carrier gas, such as N2, Ar, or any other gas, although this is not required. Ozone is used as the oxygen source. A wafer or wafer fragment, or any substrate, is placed in the reaction chamber, which is heated to 250°C. The deposition cycle is divided into four distinct steps. First, only (NMe2)2Ga(EtNCH2CH2NMe2) vapor is introduced into the reaction chamber and adsorbed on the wafer or substrate surface (precursor pulse). Then, the (NMe2)2Ga(EtNCH2CH2NMe2) vapor is purged from the reaction chamber using an inert gas, such as N2 or Ar (precursor purge pulse). Next, ozone, an oxygen source, is introduced into the reaction chamber and reacts with (NMe2)2Ga(EtNCH2CH2NMe2) on the wafer or substrate surface. Finally, the oxygen source is purged from the reaction chamber with an inert gas. Each of the four steps can last for tens of seconds or even a few seconds, depending on the tool configuration, deposition pressure, deposition temperature, and other conditions. In this case, the precursor pulse was set to 4 seconds, the precursor purge pulse step was set to 20 seconds, the ozone pulse was set to 2 seconds, and the ozone purge step was set to 20 seconds. It is expected that shorter pulse times will be obtained with better tools. This four-step cycle is then repeated until a gallium oxide film of the desired thickness is obtained. Gallium oxide growth with each deposition cycle ranges from 0.5 to 1 Å. The resulting gallium oxide film has low impurity levels, and deposition on patterned substrates provides step coverage exceeding 90% for holes or trenches with aspect ratios up to 50:1. Similar film properties can be obtained by using oxygen or water instead of ozone, but the respective pulse and purge times must be adjusted accordingly.

[0108] Hypothetical Example 3. Deposition of indium gallium zinc oxide (IGZO) films using (NMe2)2Ga(EtNCH2CH2NMe2) by ALD Deposition is performed in a similar manner to Hypothetical Example 2, except that two additional four-step cycles are added to allow for the deposition of indium oxide and zinc oxide to form an InGaZnO film (IGZO). Any indium or zinc precursor can be used, such as trimethylindium, triethylindium, or diethylzinc. In one exemplary embodiment, trimethylindium and diethylzinc are used. Gallium, indium, and zinc precursor vapors are introduced repeatedly, starting with gallium, followed by indium and zinc, although any other order can be used. To adjust the film composition, cycles using the same metal can be repeated several times before switching to the next metal cycle. Ozone, oxygen, and water (HO) are the most common oxygen sources and are used in this embodiment, but any type of oxidizer can be used instead. For example, different oxidizers can be used to react with each metal, such as ozone with the gallium precursor, water with the indium precursor, and mixtures thereof, such as a mixture of ozone and water with the indium precursor and water alone with the gallium precursor. IGZO films are obtained in ALD mode at temperatures between 200 and 250 °C, although different temperature windows can be achieved using different tools or deposition conditions. Deposition rates are expected to be in the range of 1 to 2 Å per cycle (including full cycles and subcycles of gallium indium and zinc precursors). The resulting IGZO films have low impurity levels, with carbon and nitrogen levels below the detection limit of analytical tools (XPS). Deposition on patterned substrates exhibits step coverage greater than 90% for holes or trenches with aspect ratios up to 50:1.

[0109] Hypothetical Example 4. Deposition of indium gallium oxide films using (NMe2)2Ga(EtNCH2CH2NMe2) and In(isopentylcyclopentadienyl) by ALD Deposition is performed in a similar manner to Hypothetical Example 3, except that indium(isopentylcyclopentadienyl) is used instead of trimethylindium or other indium precursors. No zinc precursor is used. (NMe2)2Ga(EtNCH2CH2NMe2) and indium(sec-pentylcyclopentadienyl) vapors can be introduced in any order. To adjust the film composition, cycles using the same metal may be repeated several times before switching to the next metal cycle. Water was used as the oxygen source. It is possible to use a different oxygen source or a mixture of two different oxygen sources for each of the two precursors. In this case, the gallium precursor pulse time was set to 4 seconds, the indium precursor pulse time was set to 4 seconds, the water pulse time was set to 2 seconds, and both water purge times were set to 30 seconds. Indium gallium oxide films were obtained in ALD mode at temperatures up to 250 °C, with deposition rates ranging from 0.5 to 1.5 Å per cycle. The resulting films have low impurity levels (below the detection limit of XPS), and deposition on patterned substrates exhibits step coverage greater than 90% for holes or trenches with aspect ratios up to 50:1. Similar film properties can be obtained by using oxygen instead of ozone, although the respective pulse and purge times must be adjusted.

[0110] Hypothetical Example 5. Deposition of IGZO Films Using (NMe2)2Ga(EtNCH2CH2NMe2), In(Isopentylcyclopentadienyl), and Diethylzinc-TEEDA by CVD The vessel containing (NMe2)2Ga(EtNCH2CH2NMe2), In(isopentylcyclopentadienyl), and diethylzinc-TEEDA can be heated to increase and adjust the vapor pressure of the precursors. The temperature chosen is often close to 1 torr, but any other temperature may be used. Because these three precursors have similar vapor pressures, they can be heated to the same temperature and therefore placed together in the same oven. The precursor vapors and water are then simultaneously delivered to the reaction chamber using, although not necessarily, an inert carrier gas such as N2, Ar, or any other gas (e.g., O2 for water). The wafer or wafer fragment, or any substrate, is placed in the reaction chamber, which is heated to 200-400°C, although any other temperature is also contemplated. The pressure in the reaction chamber is set to 0.1-10 torr, although any other pressure is also contemplated. The three precursor vapors and water react on the surface of the heated substrate to form an IGZO film. The purity of the IGZO film is very high, with carbon and nitrogen levels below the detection limit of analytical tools (XPS). High-purity IGZO films can also be obtained if water is replaced with another oxygen source, such as ozone (O3) or oxygen (O2), or if either of the two oxygen sources is supplied together.

[0111] Hypothetical Example 6. Deposition of IGZO Films Using (NMe2)2Ga(EtNCH2CH2NMe2), In(Isopentylcyclopentadienyl), and Diethylzinc-TEEDA by ALD Deposition is performed in a similar manner to Hypothetical Example 3, except that indium(isopentylcyclopentadienyl) and diethylzinc-TEEDA are used as the indium and zinc precursors instead of trimethylindium and diethylzinc. Vapors of (NMe2)2Ga(EtNCH2CH2NMe2), indium(isopentylcyclopentadienyl), and diethylzinc-TEEDA can be introduced in any order. To adjust the film composition, cycles using the same metal may be repeated several times before switching to the next metal cycle. Water is used as the oxygen source. Finally, different oxygen sources can be used to react with each metal. In this case, the pulse times for the gallium precursor, indium precursor, and zinc precursor were set to 4 seconds, and the water pulse time was set to 2 seconds for the three pulses of metal precursors. The three water purge times were set to 30 seconds. IGZO films were obtained in ALD mode at temperatures up to 250 °C or higher, with deposition rates ranging from 1 to 2 Å per cycle. The resulting films have low impurity levels (below the detection limit of XPS), and deposition on patterned substrates exhibits step coverage of greater than 90% in holes or trenches with aspect ratios up to 50:1. IGZO films of excellent purity are obtained when water is replaced with another oxygen source, such as ozone or oxygen, or even when either of the two oxygen sources is supplied together.

[0112] [Table 2]

[0113] Table 2 compares the expected results between the Reference Process, Hypothetical Example 3, and Hypothetical Example 5, demonstrating the advantages of the disclosed gallium precursor over existing processes. The disclosed gallium precursor is not pyrophoric, which simplifies transportation, storage, and use, reducing costs. It also allows for an increase in the maximum ALD window, which typically results in higher-quality films. Furthermore, the disclosed gallium precursor is a liquid at room temperature, reducing process costs. Note that tris(dimethylamino)gallium is another standard gallium precursor that can also be used together with trimethylindium and diethylzinc. While tris(dimethylamino)gallium is not pyrophoric, it is a solid with a melting point of approximately 107°C and a low vapor pressure of 1 torr at 105°C. In this case, the use of a solid compound with a low vapor pressure is an inherent drawback for processes used in mass production, further amplifying the advantages of the disclosed gallium precursor. Replacing the indium and zinc precursors with non-pyrophoric compounds with properties similar to the gallium molecule, as in Hypothetical Example 6, offers further advantages in terms of safety and process results.

[0114] Although the subject matter described herein may be described in the context of an example implementation of processing one or more computing application features / operations for a computing application having a user-interaction component, the subject matter is not limited to such particular implementation. Rather, the techniques described herein may be applied to any suitable type of user-interaction component execution management method, system, platform, and / or device.

[0115] Those skilled in the art will recognize that many additional changes in the details, materials, steps, and arrangements of parts described and illustrated herein to explain the nature of the invention may be made within the principles and scope of the invention as defined in the appended claims, and therefore, it is not intended that the invention be limited to the specific embodiments of the examples given above and / or the accompanying drawings.

[0116] While embodiments of the present invention have been shown and described, modifications thereof may be made by those skilled in the art without departing from the spirit or teachings of the present invention. The embodiments described herein are merely exemplary and not limiting. Many variations and modifications of the compositions and methods are possible and are within the scope of the present invention. Therefore, the scope of protection is not limited to the embodiments described herein, but is limited only by the scope of the claims that follow, which scope is intended to include all equivalents of the subject matter of the claims.

Claims

1. 1. A method for depositing a gallium-containing oxide film on a substrate, comprising: a) simultaneously or sequentially exposing a substrate to vapor of a gallium-containing film-forming composition containing a gallium precursor and an oxidizing agent; b) depositing at least a portion of the gallium precursor on the substrate to form the gallium-containing oxide film on the substrate via a vapor deposition process; Including, The gallium precursor has the formula: (NR ８ R ９ )(NR １ R ２ )Ga[(R ３ R ４ N)C ｘ (R ５ R ６ )(NR ７ )] (I) (?) ２ [() ３ ( ４ ?) ｘ () ５ ( ６ )()) ７ ) ( ) and the corresponding structure: 【Chemical 1】 (In the formula, R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ is independently selected from H, Me, Et, nPr, iPr, nBu, iBu, sBu, or tBu, with R １ , R ２ , R ３ , R ４ , R ８ , R ９ If each is Me, then R ５ , R ６ is not H and is R ７ is not Me or Et; R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ may be the same or different; x=2, 3, 4 Cy-N represents a saturated or unsaturated N-containing ring; said N-containing ring contains at least one nitrogen atom and 4 to 6 carbon atoms in the chain. A method comprising:

2. The gallium precursor is (NMe ２ ) ２ Ga(EtNCH ２ CH ２ NET ２ ), (NEtMe) ２ Ga(EtNCH ２ CH ２ NMe ２ ), (NEtMe) ２ Ga(EtNCH ２ CH ２ NET ２ ), (NEt ２ ) ２ Ga(EtNCH ２ CH ２ NMe ２ ), and (NEt ２ ) ２ Ga(EtNCH ２ CH ２ NET ２ 10. The method of claim 1, comprising:

3. 2. The method of claim 1, wherein x=2.

4. a1) In step a), simultaneously or sequentially, the surface is treated with a first metal (M １ ) precursor vapor to form the first metal (M １ ) depositing at least a portion of the precursor and at least a portion of the gallium precursor on the substrate to form the gallium-containing oxide film on the substrate via the vapor deposition process, wherein the gallium-containing oxide film is M １ The method of claim 1 , further comprising the step of:

5. a2) In step a1), simultaneously or sequentially, the surface is treated with a second metal (M ２ ) precursor vapor to form the second metal (M ２ ) precursor, at least a portion of the gallium precursor, and the first metal (M １ ) depositing at least a portion of a precursor onto the substrate to form the gallium-containing oxide film on the substrate via the vapor deposition process, wherein the gallium-containing oxide film is M １ M ２ The method further comprises the step of: The first metal (M １ ) precursor is an indium precursor and the second metal (M ２ 5. The method of claim 4, wherein the first metal (M 1 ) precursor is a zinc precursor, or the first metal (M 1 ) precursor is a zinc precursor and the second metal (M 2 ) precursor is an indium precursor.

6. The method of claim 5, wherein the indium precursor is selected from trialkylindium, sec-pentylcyclopentadienyl indium, or isopentylcyclopentadienyl indium.

7. 6. The method of claim 5, wherein the zinc precursor is a diethylzinc derivative selected from diethylzinc-tetramethylethylenediamine adduct (TMEDA), diethylzinc-tetraethylethylenediamine adduct (TEEDA), diethylzinc-N,N'-diethyl-N,N'-diethylethylenediamine adduct, diethylzinc-N,N-dimethyl-N',N'-diethylethylenediamine adduct, or diethylzinc-N,N,N'-trimethyl-N'-ethylethylenediamine adduct.

8. The method of any one of claims 1 to 7, wherein the gallium precursor has a melting point below approximately 60°C.

9. A gallium-containing quaternary oxide (M １ M ２ 1. A method for depositing a GaO film comprising: a) simultaneously or sequentially reacting a gallium precursor with a first metal (M １ ) precursor and a second metal (M ２ exposing the substrate to vapor of a gallium-containing film-forming composition containing a gallium precursor and an oxidizing agent; and b) mixing at least a portion of the gallium precursor, the first metal (M １ ) precursor, and the second metal (M ２ ) precursor onto the substrate via a vapor deposition process to form the gallium-containing quaternary oxide film (M １ M ２ forming a GaO layer; Including, The gallium precursor has the formula: (NR ８ R ９ )(NR １ R ２ )Ga[(R ３ R ４ N)C ｘ (R ５ R ６ )(NR ７ )] (I) (?) ２ [() ３ ( ４ ?) ｘ () ５ ( ６ )()) ７ ) ( ) and the corresponding structure: 【Chemistry 2】 (In the formula, R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ is independently selected from H, Me, Et, nPr, iPr, nBu, iBu, sBu, or tBu, with R １ , R ２ , R ３ , R ４ , R ８ , R ９ If each is Me, then R ５ , R ６ is not H and is R ７ is not Me or Et; R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ may be the same or different; x=2, 3, 4; Cy-N represents a saturated or unsaturated N-containing ring; said N-containing ring contains at least one nitrogen atom and 4 to 6 carbon atoms in the chain. A method comprising:

10. The gallium precursor is (NMe ２ ) ２ Ga(EtNCH ２ CH ２ NET ２ ), (NEtMe) ２ Ga(EtNCH ２ CH ２ NMe ２ ), (NEtMe) ２ Ga(EtNCH ２ CH ２ NET ２ ), (NEt ２ ) ２ Ga(EtNCH ２ CH ２ NMe ２ ), and (NEt ２ ) ２ Ga(EtNCH ２ CH ２ NET ２ 10. The method of claim 9, comprising:

11. 10. The method of claim 9, wherein x=2.

12. The first metal (M １ ) precursor is an indium precursor and the second metal (M ２ 10. The method of claim 9, wherein the first metal (M1) precursor is a zinc precursor, or the first metal (M2) precursor is a zinc precursor and the second metal (M2) precursor is an indium precursor.

13. 13. The method of claim 12, wherein the indium precursor is selected from trialkylindium, sec-pentylcyclopentadienyl indium, or isopentylcyclopentadienyl indium.

14. 13. The method of claim 12, wherein the zinc precursor is a diethylzinc derivative selected from diethylzinc-tetramethylethylenediamine adduct (TMEDA), diethylzinc-tetraethylethylenediamine adduct (TEEDA), diethylzinc-N,N'-diethyl-N,N'-diethyl-ethylenediamine adduct, diethylzinc-N,N-dimethyl-N',N'-diethylethylenediamine adduct, or diethylzinc-N,N,N'-trimethyl-N'-ethylethylenediamine adduct.

15. The method according to any one of claims 9 to 14, wherein the melting point of the Ga precursor is below 60°C.

16. 1. A method for depositing an indium gallium zinc oxide (IGZO) film on a substrate, comprising: a) simultaneously or sequentially reacting a gallium precursor, an indium precursor, a zinc precursor, and O ３ exposing the substrate to vapor of a gallium-containing film-forming composition comprising: b) depositing at least a portion of the gallium precursor, at least a portion of the indium precursor, and at least a portion of the zinc precursor on the substrate to form an IGZO film on the substrate via a vapor deposition process; Including, The gallium precursor has the formula: (NR ８ R ９ )(NR １ R ２ )Ga[(R ３ R ４ N)C ｘ (R ５ R ６ )(NR ７ )] (I) (?) ２ [() ３ ( ４ ?) ｘ () ５ ( ６ )()) ７ ) ( ) and the corresponding structure: 【Chemistry 3】 (In the formula, R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ is independently selected from H, Me, Et, nPr, iPr, nBu, iBu, sBu, or tBu, with R １ , R ２ , R ３ , R ４ , R ８ , R ９ If each is Me, then R ５ , R ６ is not H and is R ７ is not Me or Et; R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ may be the same or different; x=2, 3, 4; Cy-N represents a saturated or unsaturated N-containing ring; said N-containing ring contains at least one nitrogen atom and 4 to 6 carbon atoms in the chain. A method comprising:

17. 17. The method of claim 16, wherein x=2.

18. 17. The method of claim 16, wherein the indium precursor is isopentylcyclopentadienyl indium.

19. 17. The method of claim 16, wherein the zinc precursor is diethylzinc-tetraethylethylenediamine adduct (TEEDA).

20. The method according to any one of claims 16 to 19, wherein the melting point of the Ga precursor is below 60°C.

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