Gallium precursors for depositing gallium-containing oxide films

Abstract

A method for depositing a gallium-containing oxide film on a substrate, the method comprising: a) simultaneously or sequentially exposing the substrate to a vapor of a gallium precursor, one or more other metal precursors, and an oxidant; b) depositing at least a portion of the gallium precursor and at least a portion of the one or more other metal precursors onto the substrate by a vapor deposition process to form the gallium-containing oxide film on the substrate, wherein the gallium precursor has the following 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 To R 9 Independently selected from H, Me, Et, nPr, iPr, nBu, iBu, sBu, or tBu; R 1 To R 9 They can be the same or different; x = 2, 3, 4, preferably x = 2; Cy-N refers to either saturated N-ring or unsaturated N-ring.

Description

[0001] Cross-reference to related applications

[0002] This application claims the benefit of priority to U.S. Provisional Patent Application No. 63 / 212,184, filed June 18, 2021, pursuant to 35 U.S. SC §119(a) and (b), the entire contents of which are incorporated herein by reference. Technical Field

[0003] This 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 precursor is a liquid, volatile, non-flammable, halogen-free molecule. Background Technology

[0004] The use of gallium oxide (Ga2O3) is of interest for several applications in microdevices, and therefore the development of cost-effective and safe gallium molecules for depositing thin films in chemical vapor deposition (CVD) or atomic layer deposition (ALD), or any vapor-phase growth method, is of great interest. Intriguing applications include: gas sensors, transparent conductive oxides (TCOs), photocatalytic materials, oxide semiconductors, etc.

[0005] 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 very well-defined, uniform thin-film layers to better control their performance and optimize their dimensions. IGZO's advantage lies in its ability to be deposited as a uniform amorphous phase while maintaining the high carrier mobility common to oxide semiconductors. IGZO is also being considered for next-generation semiconductor devices, whether for memory applications or logic applications (n-type BEOL transistors).

[0006] The current obstacle to large-scale IGZO fabrication is the synthesis method. The most widely used technique for synthesizing transparent conductive oxides (TCOs) is pulsed laser deposition (PLD). In PLD, a laser is focused onto nanoscale points on a solid elemental target. The laser pulse frequency is varied proportionally between targets to control the film composition. Due to the low-temperature deposition capability of IGZO, it can be deposited on substrates such as quartz, single-crystal silicon, or even plastics. The substrate is placed in a PLD vacuum chamber, where oxygen pressure is controlled to ensure favorable electrical properties. After synthesis, the film is annealed or gradually exposed to air to acclimatize.

[0007] While PLD is a useful and versatile synthesis technique, it requires expensive equipment and a significant amount of time to acclimatize each sample to typical atmospheric conditions. This is undesirable for industrial manufacturing.

[0008] Solution treatment is a more cost-effective alternative. Specifically, combustion synthesis techniques can be used. One example is the use of an oxidant to generate an exothermic reaction in a metal nitrate solution. A common type of combustion synthesis is spin coating, which involves depositing an In and Ga solution layer onto a hot plate and annealing it at a temperature between approximately 200°C and 400°C, depending on the target composition. The film can be annealed in air, a significant advantage compared to PLD (Plastic Processing Deposition). Combustion treatment shows promise as a novel synthesis method, but further research is needed to assess its feasibility.

[0009] Such optoelectronic devices require very well-defined, uniform thin film layers to better control their performance and optimize their dimensions. Conventional film formation methods, such as chemical vapor deposition (CVD), atomic layer deposition (ALD), or plasma-enhanced atomic layer deposition (PEALD), can fabricate thin films with the desired properties. A key parameter for industrial applications is the development of liquid gallium-containing precursors, as it is more practical and therefore cost-effective to fill them in storage tanks for delivery to the reactor via feed and discharge lines. Using solid precursors requires sublimators for vapor formation, which presents several problems. First, the filling amount in the tank (sublimator) will be limited to a few hundred grams, and the sublimator cannot be refilled while on the tool, thus typically requiring frequent sublimator replacements. Second, solid precursors very often have low vapor pressures, leading to fluctuations in the feed rate. Additionally, some variation in grain size can cause differences in product evaporation. Finally, for safety reasons, gallium-containing precursors will preferably not spontaneously combust (ignite) upon exposure to air.

[0010] For example, a non-self-igniting liquid Ga precursor, trimethyl[N-(2-methoxyethyl)-2-methylprop-2-amine]gallium, namely GaMe3·(CH3OCH2CH2NH ... t Bu), and applied it to ALD GaO x In application. GaO x The thin film can operate within a temperature range of 100℃ to 250℃. / Cyclic growth rate deposition (Ceramics International, Vol. 47, No. 2, January 15, 2021, pp. 1588-1593).

[0011] Another example of a non-self-igniting liquid gallium precursor is gallium dimethylisopropoxy, Me₂Ga(OiPr). It is liquid at room temperature and possesses sufficiently high vapor pressures (0.55 Torr / 25°C; 0.75 Torr / 30°C; 1.0 Torr / 35°C; 1.3 Torr / 40°C) for atomic layer deposition and / or metal-organic chemical vapor deposition. In ALD processes, when water is used as the oxygen source, an apparent ALD temperature window between 300°C and 325°C is obtained, where the growth rate is approximately [missing value]. / Cycle. MOCVD was performed using oxygen as the reactant gas in a temperature range of 450℃–625℃. The Ga₂O₃ films deposited in both processes were found to be stoichiometric and amorphous. Using this precursor, conductive Ga-doped ZnO films could be successfully deposited. Electrical, structural, and optical properties as a function of Ga doping concentration and deposition temperature were systematically investigated. Low resistivity (approximately 3.5 × 10⁻⁶) was observed at a 5 atomic % Ga doping concentration deposited at 250℃. -3 The optimal carrier concentration and transmittance (7.2 × 10⁻⁶ Ωcm) are as follows: 20 cm -3 (and 83.5%)(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 generally limited to very small aspect ratio structures, and to solve this problem, amine-containing molecules are generally preferred.

[0012] Deposition of indium gallium oxide (IGO) and indium gallium zinc oxide (IGZO) films via CVD and ALD methods has been reported. For example, the paper “Atomic Layer Deposition of an Indium Gallium Oxide Thin Film for Thin-Film Transistor Applications” (Appl. Mater. Interfaces, 2017, 9, 23934-23940) investigated the deposition of IGO films via atomic layer deposition (ALD) using [1,1,1-trimethyl-N-(trimethylsilyl)-silaneamine]indium (InCA-1) and trimethylgallium (TMGa) as indium and gallium precursors, respectively.

[0013] 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). Gallium isopropoxy(III) and diethylzinc were used as precursors in this study.

[0014] The research report on the nucleation and growth of InGaZnO thin films using diethylzinc (DEZn), trimethylindium (TMIn), and triethylgallium (TEGa) as Zn, In, and Ga precursors via spatial atmospheric atomic layer deposition is published in the paper "Spatial Atmospheric Atomic Layer Deposition of In x Ga y Zn z O for Thin Film Transistors [In for Thin Film Transistors] x Ga y Zn z [Spatial isolation of atmospheric atomic layer deposition] (ACS Appl. Mater. Interfaces, 2015, 7, 6, 3671-3675).

[0015] In these studies, Ga, Zn, and In precursors were primarily auto-ignition materials, which is why this invention seeks to avoid them and uses comparable materials with similar physical properties.

[0016] Gallium complexes (NMe2)2Ga(MeNCH2CH2NMe2) and (NMe2)2Ga(EtNCH2CH2NMe2) have been reported to be liquid and volatile (MRS proceedings, 1999, ST. Barry et al.). These molecules are reportedly thermally stable and can evaporate without leaving residue (no TGA data). These molecules are non-flammable and therefore safer to handle. Although these gallium molecules are not used for film deposition, their aluminum form has been used for AlN deposition with ammonia in CVD mode. Deposition of AlN from (NMe2)2Al(EtNCH2CH2NMe2) at 200 °C has been reported.

[0017] For the deposition of gallium oxide films, the gallium precursor should not contain halides that could reduce the conductivity of the film produced by its processing. Furthermore, the gallium precursor should be compatible with indium and zinc co-precursors used in IGZO applications, such as having similar volatility and comparable thermal stability. Several studies have been reported on the ALD of Ga2O3 films using precursors including trimethylgallium (GaMe3), hexa(dimethylamino)digallium [(Ga2(NMe2)6], and Ga(acac)3 (acac = pentyl-2,4-diketone). All of these precursors are flammable materials or primarily solid at room temperature and are inconvenient to use, although some of them readily volatilize upon mild heating.

[0018] For depositing gallium-containing binary or ternary oxide films, precursors with similar properties are preferred. The most frequently mentioned indium and zinc molecules are trimethylindium and diethylzinc. These two compounds are flammable, posing a significant safety concern and increasing costs. Furthermore, trimethylindium is a solid at room temperature with a melting point of 88°C. The use of a solid form is not preferred as it also increases costs.

[0019] Several teams have developed new and promising indium or zinc compounds. For example, WO 2020179748A1 discloses the use of isopentyl-cyclopentadienyl indium for indium-containing deposition. The molecule is liquid, non-flammable, and exhibits a vapor pressure of 1 Torr at 65 °C. It also discloses the deposition of indium oxide or indium in ALD mode at 250 °C.

[0020] RG Gordon et al. disclosed the synthesis of diethylzinc by adduct with tetramethylethylenediamine (TMEDA) and its use in CVD mode for zinc oxide deposition (Optimization of Transparent and Reflective Electrodes for Amorphous Silicon Solar Cells, National Renewable Energy Laboratory, 1998). This molecule is non-flammable, while diethylzinc is. These authors reported that the corresponding fluorine-doped ZnO2 CVD process is more controllable and reproducible, and the film exhibits better uniformity (compared to diethylzinc). This molecule is solid, but other adducts of diethylzinc are liquids, such as diethylzinc-tetraethylethylenediamine (diethylzinc-TEEDA). Internally, the authors of this disclosure measured the vapor pressure of diethylzinc-tetraethylethylenediamine to be 1 Torr at 69 °C.

[0021] In summary, there is a need to develop a gallium compound for depositing binary, ternary, or quaternary oxide films that is liquid at room temperature, halide-free, non-flammable, thermally stable, and has a high vapor pressure. Furthermore, it is valuable for identifying other metallic precursors with similar properties in order to develop optimal deposition processes. Summary of the Invention

[0022] A method for depositing a gallium-containing oxide film on a substrate is disclosed, the method comprising the following steps:

[0023] a) Simultaneously or sequentially exposing the substrate to the vapor and oxidant of a gallium-containing film-forming composition containing a gallium precursor; and

[0024] b) Deposit at least a portion of the gallium precursor onto the substrate using a vapor deposition process to form the gallium-containing oxide film on the substrate.

[0025] The gallium precursor has the following formula:

[0026] (NR 8 R 9 (NR) 1 R 2 )Ga[(R 3 R 4 N)C x (R 5 R 6 (NR) 7 )](I)

[0027] (Cy-N)2Ga[(R 3 R 4 N)C x (R 5 R 6 (NR) 7 (II)

[0028] And the following corresponding structures:

[0029]

[0030] Among them, R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 Independently selected from H, Me, Et, nPr, iPr, nBu, iBu, sBu, or tBu; R 1 R 2 R 3 R 4R 5 R 6 R 7 R 8 R 9 They can be the same or different; x = 2, 3, 4, preferably x = 2; Cy-N refers to saturated or unsaturated N-containing rings; these N-containing rings contain at least one nitrogen atom and 4-6 carbon atoms in the chain.

[0031] The disclosed methods may include one or more of the following aspects:

[0032] Cy-NH includes pyrrolidine, pyrrole, and piperidine, as shown in the following formula:

[0033]

[0034] 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);

[0035] The gallium precursor is (NMe2)2Ga(EtNCH2CH2NMe2);

[0036] The gallium precursor is (NMe2)2Ga(EtNCH2CH2NEt2);

[0037] The gallium precursor is (NEtMe)₂Ga(EtNCH₂CH₂NMe₂);

[0038] The gallium precursor is (NEtMe)2Ga(EtNCH2CH2NEt2);

[0039] The gallium precursor is (NEt2)2Ga(EtNCH2CH2NMe2);

[0040] The gallium precursor is (NEt2)2Ga(EtNCH2CH2NEt2);

[0041] The gallium precursor is (NMe2)2Ga(MeNCH2CH2NMe2);

[0042] Further steps include:

[0043] a1) In step a), simultaneously or sequentially, the surface is exposed to the first metal (M). 1 The vapor of the precursor causes the first metal (M) to...1 At least a portion of the precursor and at least a portion of the gallium precursor are deposited onto the substrate by the vapor deposition process to form a gallium-containing oxide film on the substrate, wherein the gallium-containing oxide film is M 1 GaO film;

[0044] Further steps include:

[0045] a2) In step a1), simultaneously or sequentially, the surface is exposed to the second metal (M). 2 The vapor of the precursor causes the second metal (M) to... 2 At least a portion of the gallium precursor, at least a portion of the gallium precursor, and the first metal (M) 1 At least a portion of the precursor is deposited onto the substrate by the vapor deposition process to form a gallium-containing oxide film on the substrate, wherein the gallium-containing oxide film is M 1 M 2 GaO film;

[0046] Further steps include:

[0047] Each time the film-forming composition is exposed, the first metal (M) 1 Precursor, the second metal (M) 2 The precursor, the oxidant, and their mixture are purged with an inert gas.

[0048] The inert gas is selected from N2, He, Ar, Kr, or Xe;

[0049] The inert gas is N2;

[0050] The inert gas is Ar;

[0051] The first metal (M) 1 The precursor is an indium precursor;

[0052] The first metal (M) 1 The precursor is a zinc precursor;

[0053] The second metal (M) 2 The precursor is an indium precursor;

[0054] The second metal (M) 2 The precursor is a zinc precursor;

[0055] • The indium precursor is selected from trialkylindium, sec-pentyl-cyclopentadienylindium, or isopentyl-cyclopentadienylindium;

[0056] The indium precursor is trialkylindium;

[0057] The indium precursor is isopentyl-cyclopentadienyl indium;

[0058] The indium precursor is sec-pentyl-cyclopentadienyl indium;

[0059] The zinc precursor is selected from the following diethylzinc derivatives: 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;

[0060] The zinc precursor is diethylzinc-tetramethylethylenediamine adduct (TMEDA);

[0061] The zinc precursor is a diethylzinc-tetraethylethylenediamine adduct (TEEDA);

[0062] The zinc precursor is a diethylzinc-N,N'-diethyl-N,N'-diethyl-ethylenediamine adduct;

[0063] The zinc precursor is a diethylzinc-N,N-dimethyl-N',N'-diethylethylenediamine adduct;

[0064] The zinc precursor is a diethylzinc-N,N,N'-trimethyl-N'-ethylethylenediamine adduct;

[0065] ·The M 1 GaO film is InGaO film;

[0066] ·The M 1 GaO film is ZnGaO film;

[0067] ·The M 1 M 2 GaO film is IGZO film;

[0068] • This gallium oxide film is an InGaO film;

[0069] • This gallium oxide film is a ZnGaO film;

[0070] • This gallium oxide film is an IGZO film;

[0071] The oxidizing agent is O2, O3, H2O, H2O2, NO, N2O, NO2, or oxygen-containing free radicals such as O· or OH·.

[0072] The oxidizing agent is O3;

[0073] The oxidizing agent is O2;

[0074] The oxidant was treated with plasma;

[0075] The gallium-containing film-forming composition includes an inert carrier gas;

[0076] • The inert carrier gas is selected from N2, He, Ne, Ar, Kr, Xe, or combinations thereof;

[0077] • The inert carrier gas is N2 or Ar;

[0078] The melting point of this gallium precursor is below approximately 60°C;

[0079] The melting point of this gallium precursor is below approximately 20°C;

[0080] • This gallium precursor is non-flammable;

[0081] • This gallium precursor is liquid at room temperature;

[0082] • The gallium precursor is liquid at temperatures ranging from room temperature to approximately 60°C;

[0083] • The vapor deposition process is ALD, CVD, or a combination thereof;

[0084] • This vapor deposition process is an ALD process;

[0085] • This vapor deposition process is a CVD process;

[0086] • This vapor deposition process is the PEALD process;

[0087] • Deposition pressure remains at approximately 10 -3 Between approximately 100 and 100 tots;

[0088] • Deposition pressure remains at approximately 10 -2 Between 10 and 10 tots;

[0089] The deposition temperature was maintained between approximately 100°C and approximately 600°C.

[0090] The deposition temperature was maintained between approximately 150°C and approximately 500°C.

[0091] • The gallium precursor has a purity ranging from approximately 93% w / w to approximately 100% w / w;

[0092] The gallium precursor has a purity ranging from approximately 99% w / w to approximately 99.999% w / w;

[0093] The indium precursor has a purity ranging from approximately 93% w / w to approximately 100% w / w;

[0094] The indium precursor has a purity ranging from approximately 99% w / w to approximately 99.999% w / w;

[0095] The zinc precursor has a purity ranging from approximately 93% w / w to approximately 100% w / w;

[0096] The zinc precursor has a purity ranging from approximately 99% w / w to approximately 99.999% w / w;

[0097] The gallium-containing film-forming composition has a purity ranging from approximately 93% w / w to approximately 100% w / w; and

[0098] The gallium-containing film-forming composition has a purity ranging from about 99% w / w to about 99.999% w / w.

[0099] It also discloses a method for depositing gallium-containing quaternary oxides (M) on a substrate. 1 M 2 A method for producing GaO films, the method comprising the following steps:

[0100] a) Simultaneously or sequentially exposing the substrate to the vapor of a gallium-containing film-forming composition containing a gallium precursor, a first metal (M... 1 The vapor of the precursor, the second metal (M) 2 The vapor of the precursor, and the oxidant; and

[0101] b) At least a portion of the gallium precursor and the first metal (M) are deposited using a vapor deposition process. 1 At least a portion of the precursor and the second metal (M) 2 At least a portion of the precursor is deposited onto the substrate to form the gallium-containing quaternary oxide film (M) on the substrate. 1 M 2 GaO),

[0102] The gallium precursor has the following formula:

[0103] (NR 8 R 9 (NR) 1 R 2 )Ga[(R 3 R 4 N)C x (R 5 R 6 (NR) 7 )] (I)

[0104] (Cy-N)2Ga[(R 3 R 4 N)C x (R 5 R 6 (NR) 7 (II)

[0105] And the following corresponding structures:

[0106]

[0107] Among them, R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 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 They can be the same or different; x = 2, 3, 4, preferably x = 2; Cy-N refers to saturated or unsaturated N-containing rings; these N-containing rings contain at least one nitrogen atom and 4-6 carbon atoms.

[0108] A method for depositing an indium gallium zinc oxide (IGZO) film on a substrate is also disclosed, the method comprising the following steps:

[0109] a) Simultaneously or sequentially exposing the substrate to vapors of a gallium-containing film-forming composition containing a gallium precursor, vapors of an indium precursor, vapors of a zinc precursor, and O3; and

[0110] b) Deposit 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 onto the substrate using a vapor deposition process to form an IGZO film on the substrate.

[0111] The gallium precursor has the following formula:

[0112] (NR 8 R 9 (NR) 1 R 2 )Ga[(R 3 R 4 N)C x (R 5 R 6 (NR) 7 )](I)

[0113] (Cy-N)2Ga[(R 3 R 4 N)C x (R 5 R6 (NR) 7 (II)

[0114] And the following corresponding structures:

[0115]

[0116] Among them, R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 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 They can be the same or different; x = 2, 3, 4, preferably x = 2; Cy-N refers to saturated or unsaturated N-containing rings; these N-containing rings contain at least one nitrogen atom and 4-6 carbon atoms.

[0117] Notation and naming conventions

[0118] The following detailed description and claims utilize many abbreviations, symbols, and terms commonly known in the art. Specific abbreviations, symbols, and terms are used throughout the following description and claims, and include:

[0119] As used in this article, the indefinite article “a or an” means one or more species.

[0120] As used herein, “about” or “around / approximately” in the text or claims means ±10% of the value.

[0121] As used herein, “room temperature” in the text or claims means from about 20°C to about 25°C.

[0122] The term "high thermal stability" refers to the characteristic that a product evaporates smoothly in thermogravimetric analysis, exhibits no "tail" or produces no residue at temperatures above 200°C, more preferably with a residue of less than about 5% at 300°C, and even more preferably with a residue of less than about 2% at 300°C, or that the product's DSC analysis shows an initial decomposition temperature higher than that of commercially available products, and more preferably higher than 235°C.

[0123] The term "substrate" refers to one or more materials on which processes are performed. A substrate can refer to a wafer having one or more materials on which processes are performed. A substrate can be any suitable wafer used in the manufacture of semiconductor, photovoltaic, flat panel, or LCD-TFT devices. A substrate can also have one or more different material layers deposited thereon from previous manufacturing steps. For example, a wafer can include silicon layers (e.g., crystalline, amorphous, porous, etc.), silicon-containing layers (e.g., SiO2, SiN, SiON, SiCOH, etc.), metal-containing layers (e.g., copper, cobalt, ruthenium, tungsten, platinum, palladium, nickel, ruthenium, gold, etc.), or combinations thereof. Furthermore, a substrate can be planar or patterned. A substrate can be an organically patterned photoresist film. The substrate may include an oxide layer used as a dielectric material in MEMS, 3D NAND, MIM, DRAM, or FeRam device applications (e.g., ZrO2-based materials, HfO2-based materials, TiO2-based materials, rare earth oxide-based materials, ternary oxide-based materials, etc.) or a nitride-based film (e.g., TaN, TiN, NbN) used as an electrode. The substrate may also be a powder, such as powder used in rechargeable battery technology. An unlimited 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.

[0124] The term “wafer” or “patterned wafer” refers to a wafer having a stack of films on a substrate, and at least the topmost film having morphological features that have been generated in a step prior to the deposition of an indium-containing film.

[0125] The term "aspect ratio" refers to the ratio of the height of a groove (or hole) to the width of the groove (or the diameter of the hole).

[0126] It should be noted herein that the terms "film" and "layer" are used interchangeably. It should be 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 recognize that, as used herein, the terms "film" or "layer" refer to a material of a certain thickness laid or spread on a surface, and that surface can range from as large as an entire wafer to as small as a trench or line. Throughout the specification and claims, the wafer and any associated layers thereon are referred to as a substrate.

[0127] It should be noted in this article that the terms “aperture,” “via,” “hole,” and “trench” are used interchangeably to refer to openings formed in semiconductor structures.

[0128] As used herein, the abbreviation “NAND” refers to a “Negative AND or Not AND” gate; the abbreviation “2D” refers to a 2D gate structure on a planar substrate; and the abbreviation “3D” refers to a 3D or vertical gate structure in which the gate structures are stacked in the vertical direction.

[0129] It should be noted in this document that the terms "deposition temperature" and "substrate temperature" are used interchangeably. It should be understood that substrate temperature can correspond to or be related to deposition temperature, and deposition temperature can refer to substrate temperature.

[0130] It should be noted in this document that when the precursor is in a gaseous state at room temperature and ambient pressure, the terms "precursor," "deposited compound," and "deposited gas" are used interchangeably. It should be understood that a precursor can correspond to, or be associated with, a deposited compound or deposited gas, and a deposited compound or deposited gas can refer to a precursor.

[0131] This article uses standard abbreviations of elements from the periodic table. It should be understood that elements may be referred to by these abbreviations (e.g., Si for silicon, N for nitrogen, O for oxygen, C for carbon, H for hydrogen, F for fluorine, etc.).

[0132] A unique CAS registry number (i.e., "CAS") assigned by the Chemical Abstracts Service is provided to identify the specific molecule disclosed.

[0133] As used herein, the term "alkyl" refers to a saturated functional group containing only carbon and hydrogen atoms. An alkyl group is a type of hydrocarbon. Additionally, the term "alkyl" can refer to a straight-chain, branched, or cyclic alkyl group. Examples of straight-chain alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, etc. Examples of branched alkyl groups include, but are not limited to, tert-butyl. Examples of cyclic alkyl groups include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, etc.

[0134] As used in this article, the abbreviation "Me" refers to methyl; the abbreviation "Et" refers to ethyl; the abbreviation "Pr" refers to any propyl (i.e., n-propyl or isopropyl); the abbreviation "iPr" refers to isopropyl; the abbreviation "Bu" refers to any butyl (n-butyl, isobutyl, tert-butyl, sec-butyl); the abbreviation "tBu" refers to tert-butyl; the abbreviation "sBu" refers to sec-butyl; the abbreviation "iBu" refers to isobutyl; the abbreviation "Ph" refers to phenyl; the abbreviation "Amy" refers to any pentyl (isopentyl, sec-pentyl, tert-pentyl); the abbreviation "Cy" refers to cyclic hydrocarbons (cyclobutyl, cyclopentyl, cyclohexyl, etc.); and the abbreviation "Ar" refers to aromatic hydrocarbons (phenyl, xylyl, mesityl, etc.). As used in the disclosed embodiments, the term "independently" when used in the context of describing an R group should be understood to mean that the subject R group is chosen independently not only relative to other R groups with the same or different subscripts or superscripts, but also independently relative to any other kind of the same R group. For example, in the formula MR 1 x (NR 2 R 3 ) (4-x) In the case where x is 2 or 3, two or three R 1 Groups may (but need not) be identical to each other or with R 2 Or R 3 The same. Furthermore, it should be understood that, unless otherwise specified, the values ​​of the R group are independent of each other when used in different formulas.

[0135] In this document, a range may be expressed as from about one specific value and / or to about another specific value. When such a range is expressed, it should be understood that another embodiment is from one specific value and / or to another specific value, together with all combinations within the range. Any and all ranges listed in the disclosed embodiments include their endpoints (i.e., x = 1 to 4 or x in the range from 1 to 4 includes x = 1, x = 4, and x = any value therebetween), whether or not the term "including endpoints" is used.

[0136] In this document, references to "an embodiment" or "embodiment" mean that a particular feature, structure, or characteristic described with respect to that embodiment may be included in at least one embodiment of the invention. The phrase "in an embodiment" appearing in different places in the specification does not necessarily refer to the same embodiment in all instances, and individual or alternative embodiments are not necessarily mutually exclusive with other embodiments. The foregoing also applies to the term "implementation".

[0137] As used herein, the term “exemplary” is used to mean serving as an instance, example, 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, the use of the term “exemplary” is intended to present the concept in a specific manner.

[0138] The term "comprising" in the claims is an open-ended transitional term, meaning that the subsequently defined claim elements are a non-exclusive list, i.e., anything else may be additionally included and remain within the scope of "comprising". "Comprising" is defined herein to necessarily encompass the more restrictive transitional terms "substantially consists of" and "consisting of"; therefore, "comprising" can be replaced by "substantially consists of" or "consisting of" and remain within the clearly defined scope of "comprising".

[0139] Furthermore, the term "or" is intended to mean an inclusive "or" rather than an exclusive "or". That is, unless otherwise stated or clear from the context, "X adopts A or B" is intended to mean any natural inclusive arrangement. That is, if X adopts A; X adopts B; or X adopts both A and B, then "X adopts A or B" is satisfied in any of the foregoing cases. Additionally, the article "a / an" as used in this application and the appended claims should generally be interpreted as meaning "one or more" unless otherwise stated or clearly indicated from the context to the singular form.

[0140] In the claims, "provide" is defined as supplying, providing, making available, or preparing something. The steps can, conversely, be performed by any actor even if not explicitly stated in the claims. Attached Figure Description

[0141] To further understand the nature and purpose of the present invention, reference should be made to the following detailed description in conjunction with the accompanying drawings, in which similar elements are given the same or similar reference numerals, and in the drawings:

[0142] Figure 1 A comparison of TGA results for tris(dimethylamino)gallium (TDMAGa) and (NMe2)2Ga (EtNCH2CH2NMe2); and

[0143] Figure 2 This is a DSC comparison of TDMAGa and (NMe2)2Ga(EtNCH2CH2NMe2). Detailed Implementation

[0144] This paper discloses a gallium-containing film-forming composition comprising a gallium precursor containing an aminoamide ligand, and a method for depositing gallium-containing oxide films (such as indium gallium zinc oxide (IGZO) films) using the composition for manufacturing semiconductor devices. The gallium-containing oxide film can be a binary, ternary, or quaternary gallium oxide film. The disclosed gallium precursor is a liquid, volatile, non-flammable, halogen-free gallium amino compound that is liquid at temperatures ranging from room temperature to about 60°C. The disclosed gallium precursor is preferably liquid at about 20°C. The melting point of the gallium precursor is below about 60°C, preferably below about 20°C. The disclosed gallium precursor exhibits higher volatility and thermal stability than 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 a primary Ga source in gallium-containing oxide films (such as IGZO). The fact that the disclosed gallium precursor is liquid at room temperature simplifies its preparation, synthesis, purification, storage in containers, and delivery to liquid delivery systems. When the current body is used in high-volume manufacturing (HVM), these properties are beneficial for industrial cost savings.

[0145] The disclosed gallium precursor is non-flammable, which reduces safety-related costs. Flammable chemicals are known to be unsuitable for air transport and must be transported by sea. The necessity of international shipping by vessel during the development, commissioning, and even large-scale manufacturing phases represents a significant cost increase, depending on the volume. Furthermore, transit time and container quality requirements, along with shipping, storage, and individual regulations for flammable products, contribute to increased production costs.

[0146] The disclosed gallium precursor is halogen-free and compatible with the two molecules used in the disclosed process, such as indium and zinc precursors. Therefore, there is no corrosion effect throughout the system, which will also reduce process costs because it eliminates the need for special structural corrosion-resistant materials, special O-rings, or special and expensive pumps, reducing maintenance requirements, etc.

[0147] The higher volatility of the disclosed gallium precursors compared to TDMAGa (see Table 1) allows users to provide a greater flow rate of the disclosed gallium precursors compared to TDMAGa when heating the vessel in the reactor at the same temperature. The higher partial pressure of Ga compared to TDMAGa can lead to a faster deposition rate. A faster deposition rate can reduce manufacturing costs. A faster deposition rate also allows for increased Ga content in the film, which can lead to flexibility in adjusting the film composition. The higher stability of the disclosed gallium precursors compared to TDMAGa (as demonstrated by thermogravimetric analysis measurements) allows for the adjustment of the deposition process window. Due to the greater stability of the disclosed molecules, they can allow for deposition of films in ALD mode at higher temperatures than current molecules (such as TDMAGa). The ability to deposit films at higher temperatures generally results in films of higher quality, 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 for the deposition of films with different crystalline phases, which can exhibit better properties than films deposited at lower temperatures due to higher mobility, etc.

[0148] The disclosed gallium precursors have the following general formula:

[0149] (NR 8 R 9 (NR) 1 R 2 )Ga[(R 3 R 4 N)C x (R 5 R 6 (NR) 7 )] (I)

[0150] (Cy-N)2Ga[(R 3 R 4 N)C x (R 5 R 6 (NR) 7 (II)

[0151] And the following corresponding structures:

[0152]

[0153] In (I), R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9Independently 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 They can be the same or different; x = 2, 3, 4, preferably x = 2;

[0154] In (II), R 3 R 4 R 5 R 6 R 7 Independently selected from H, Me, Et, nPr, iPr, nBu, iBu, sBu, or tBu; R 3 R 4 R 5 R 6 R 7 They can be the same or different; x = 2, 3, 4, preferably x = 2; Cy-N refers to saturated or unsaturated N-containing rings; these N-containing rings contain at least one nitrogen atom and 4-6 carbon atoms in the chain; examples of Cy-NH include pyrroline, pyrrole, and piperidine, as shown in the following formula:

[0155]

[0156] Exemplary disclosed gallium precursors include

[0157]

[0158]

[0159] The disclosed gallium precursors are (NMe2)2Ga(EtNCH2CH2NMe2), (NMe2)2Ga(EtNCH2CH2NEt2), (NEtMe)2Ga(EtNCH2CH2NMe2), (NEtMe)2Ga(EtNCH2CH2NEt2), (NEt2)2Ga(EtNCH2CH2NMe2), (NEt2)2Ga(EtNCH2CH2NEt2), and (NMe2)2Ga(MeNCH2CH2NMe2).

[0160] The disclosed gallium precursor possesses the following characteristics that make it suitable for the deposition of gallium oxide and multi-metal gallium-containing oxide films. On one hand, the disclosed gallium precursor is liquid at room temperature, which makes it more volatile and thermally stable than the reference Ga compound (TDMAGa), exhibiting sufficient vapor pressure at lower temperatures. On the other hand, the disclosed gallium precursor is a non-flammable compound, making it easy to prepare, synthesize, purify, store, and transport for use in the semiconductor industry. The disclosed gallium precursor is suitable for use as a deposition precursor in the formation of gallium oxide films and multi-metal gallium-containing oxide films (including IGZO films).

[0161] The disclosed gallium precursor is suitable for use as a precursor for the deposition of gallium oxide films, gallium indium oxide films, gallium zinc oxide films, and IGZO films. Furthermore, the disclosed gallium precursor is a non-flammable and volatile liquid compound at room temperature, exhibiting excellent vapor pressure and superior thermal stability. The key properties (vapor pressure, melting point) of the disclosed gallium precursor are closer to those of standard indium and zinc precursors (such as trimethylindium or diethylzinc) than those of currently used gallium precursors (such as TDMAGa).

[0162] The disclosed gallium precursor exhibits high thermal stability and can be used to form high-speed, high-sensitivity semiconductor layers, such as in CMOS systems, 3D NAND channels, or photodetectors. The disclosed gallium precursor is suitable for depositing films containing the corresponding element and for related applications in depositing layers containing the corresponding element.

[0163] The disclosed film-forming composition may include the disclosed gallium precursor, co-reactants, carrier gas, etc. The co-reactants may include one or more other precursors and oxidants such as O2 or O3. The disclosed gallium precursor and the disclosed film-forming composition are suitable for forming gallium oxide thin films, such as Ga2O3, for use in the electronics field. The disclosed gallium precursor and the disclosed film-forming composition are suitable for manufacturing indium gallium oxide films, zinc gallium oxide films, and indium gallium zinc oxide (IGZO) films for use in the display, semiconductor, logic, and memory industries.

[0164] This disclosure also includes methods for forming gallium oxide films, indium gallium oxide films, zinc gallium oxide films, and indium gallium zinc oxide (IGZO) films using the disclosed gallium precursor via vapor deposition methods (such as ALD or CVD). The disclosed deposition process involves using the disclosed gallium precursor and introducing it into a reaction chamber to deposit films to form films via ALD, CVD, spin coating, spraying, dip coating, slot coating, or any other deposition technique, with or without co-reactants, i.e., one or more oxidants (e.g., O2 and O3, or H2O and H2O2). The disclosed deposition methods using the disclosed gallium precursor can be assisted by heating, light, direct or remote plasma, or combinations thereof.

[0165] The co-reactant can be one or more precursors other than the disclosed gallium precursor. The co-reactant can be an indium precursor, a zinc precursor, or a combination thereof. The additional precursor can be selected from any non-flammable, liquid, halogen-free indium or zinc molecule having a vapor pressure of 1 Torr at a temperature below 100°C, preferably 1 Torr at a temperature below 80°C.

[0166] Furthermore, the co-reactants can be oxidizing gases, such as one of the following: O2, O3, H2O, H2O2, NO, N2O, NO2, oxygen-containing free radicals such as O· or OH·, alcohols, silanols, amino alcohols, carboxylic acids such as formic acid, acetic acid, propionic acid, paraformaldehyde, other oxidizing compounds, and mixtures thereof. Preferably, the oxidizing gas is selected from the group consisting of O2, O3, H2O2, and H2O. Preferably, when performing the ALD method, the co-reactants are plasma-treated oxygen, ozone, or a combination thereof. The resulting gallium-containing oxide film will be a gallium oxide film.

[0167] Co-reactants can be treated with plasma to decompose them into their free radical forms. When treated with plasma, O3 and O2 can be used as the oxygen source gases. The plasma source can be He plasma, Ar plasma, or mixtures thereof. For example, 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 or present within the reactor itself. Alternatively, the plasma can typically be located remotely from the reactor, such as in a remotely positioned plasma system. Those skilled in the art will recognize methods and apparatus suitable for such plasma treatment.

[0168] For example, co-reactants can be introduced into a direct plasma reactor (which generates plasma in a reaction chamber) to produce plasma-treated reactants within the reaction chamber. The co-reactants can be introduced and held in the reaction chamber prior to plasma processing. Alternatively, plasma processing can occur simultaneously with the introduction of the reactants.

[0169] Alternatively, plasma-treated co-reactants can be generated outside the reaction chamber, for example, by remotely plasma-treating the co-reactants before they are introduced into the reaction chamber.

[0170] A method for forming a gallium oxide layer on a substrate using a vapor deposition process is also disclosed. The applicants believe the disclosed film-forming composition is suitable for ALD (Alternating Current Deposition). More specifically, the disclosed film-forming composition is capable of surface saturation, self-limiting growth per cycle, and perfect step coverage of over 90% in aspect ratios of pores, trenches, etc., ranging from about 2:1 to about 200:1, and preferably from about 20:1 to about 150:1, and more preferably from about 50:1 to about 100:1. Furthermore, the disclosed film-forming composition has a high decomposition temperature, indicating good thermal stability that enables ALD. The high decomposition temperature allows for ALD at higher temperatures, resulting in films with higher purity. The disclosed method can be used to manufacture semiconductors, photovoltaics, LCD-TFTs, and flat panel devices.

[0171] The disclosed gallium-containing film-forming compositions can be used to deposit gallium-containing oxide films using any deposition method known to those skilled in the art. Examples of suitable deposition methods include plasma-enhanced chemical vapor deposition (CVD) or atomic layer deposition (ALD), with or without plasma. Exemplary ALD methods include thermal ALD, plasma-enhanced ALD (PEALD), spatially isolated ALD, time-isolated ALD, selective or non-selective ALD, hot-wire ALD (HWALD), radical-binding ALD, flowable ALD (thermal or plasma) with or without one or more inhibitors, and combinations thereof. The deposition method is preferably ALD, PE-ALD, or spatial ALD to provide suitable stepped coverage and film thickness control. 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 the hot wire is used as the energy source for the deposition method), hot-wall CVD, cold-wall CVD, aerosol-assisted CVD, direct liquid jet CVD, combustion CVD, hybrid physical CVD, metal-organic CVD, rapid thermal CVD, photo-initiated CVD, laser CVD, radical-binding CVD, plasma-enhanced CVD (PECVD) including but not limited to flowable PECVD, and combinations thereof.

[0172] The disclosed gallium-containing film-forming composition contains any one of its analogues or other reaction products at 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. This embodiment provides better process reproducibility. This embodiment can be produced by purifying (e.g., distillation, sublimation, chromatography, etc.) the gallium-containing film-forming composition.

[0173] The disclosed film-forming composition has a purity 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 about 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 combined with mass spectrometry. The disclosed film-forming composition may contain any of the following impurities: pyrazole; pyridine; alkylamine; alkylimine; THF; ether; pentane; cyclohexane; heptane; benzene; toluene; chlorinated metal compounds; lithium pyrazolium, sodium pyrazolium, potassium pyrazolium. 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 disclosed film-forming composition can be obtained by recrystallization, sublimation, distillation, and / or by passing the gas or liquid through a suitable adsorbent (e.g., Molecular sieve purification.

[0174] Purification of the disclosed film-forming composition may also result in metallic impurities, each independently ranging from 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 metallic 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).

[0175] Care should be taken to prevent the disclosed gallium-containing film-forming composition from being exposed to water, as this may cause the disclosed gallium precursor to decompose into Ga(OH)3.

[0176] The disclosed film-forming compositions may be supplied in pure form or as blends with suitable solvents such as ethylbenzene, xylene, mesitylene, naphthane, decane, and dodecane. The disclosed precursors may be present in solvents at different concentrations.

[0177] The pure, blended film-forming composition is introduced into the reactor in vapor form using conventional means such as piping systems and / or flow meters. Vapor form can be generated by vaporizing the pure or blended composition via conventional vaporization steps (such as direct vaporization, distillation, bubbling, or using a sublimator). The pure or blended composition can be fed as a liquid into a vaporizer before being introduced into the reactor, where it is vaporized. Alternatively, the pure or blended composition can be vaporized by bubbling a carrier gas into the composition, which is then passed to a container containing the composition. The carrier gas can include, but is not limited to, Ar, He, N2, and mixtures thereof. Bubbling with a carrier gas also removes any dissolved oxygen present in the pure or blended composition. The carrier gas and composition are then introduced into the reactor as vapor.

[0178] If necessary, the container holding the disclosed film-forming composition may be heated to a temperature that allows the composition to have sufficient vapor pressure. The container may be maintained at a temperature, for example, in the range of about 0°C to about 200°C. Those skilled in the art will recognize that the temperature of the container can be adjusted in known ways to control the amount of the vaporized precursor.

[0179] The reactor can be any accessory chamber within the apparatus in which the deposition method takes place, such as, but not limited to: parallel plate reactors, cold-wall reactors, hot-wall reactors, single-wafer reactors, multi-wafer reactors, and other types of deposition systems under conditions suitable for inducing the reaction of the compounds and the formation of a layer. Those skilled in the art will recognize that any of these reactors can be used for ALD or CVD deposition processes.

[0180] The reactor contains one or more substrates on which a film will be deposited. A substrate is generally defined as the material on which the method is performed. The substrate can be any suitable substrate used in the manufacture of semiconductor, photovoltaic, flat panel, and LCD-TFT devices. Examples of suitable substrates include wafers such as silicon, silicon dioxide, glass, and GaAs wafers. The wafer can 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 silicon layers (crystalline, amorphous, porous, etc.), silicon oxide layers, silicon nitride layers, silicon oxynitride layers, carbon-doped silicon oxide (SiCOH) layers, metals, metal oxides, metal nitride layers (Ti, Ru, Ta, etc.), and combinations thereof. Additionally, the wafer can include copper layers and noble metal layers (e.g., platinum, palladium, rhodium, gold). The wafer can include barrier layers such as manganese, manganese oxide, etc. Plastic layers, such as poly(3,4-ethylenedioxythiophene) poly(styrene sulfonate) [PEDOT:PSS], can also be used. These layers can be planar or patterned. When a patterned layer is formed on a substrate, the disclosed process can deposit the layer directly onto the wafer, or directly onto one or more layers on top of the wafer. The patterned layer can be an alternating layer 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 a material of a certain thickness laid or spread on a surface, and the surface can be trenches or lines. Throughout the 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 an HfO2 layer).

[0181] The final applications of the substrate are not limited to this invention, but this technology can be particularly beneficial for substrates such as silicon wafers, glass wafers and glass panels, beads, powders and nanopowders, monolithic porous media, printed circuit boards, plastic sheets, etc. Exemplary powder substrates include powders used in rechargeable battery technology. An unlimited number of powder materials include NMC (lithium nickel manganese cobalt oxide), LCO (lithium cobalt oxide), LFP (lithium iron phosphate), and other battery cathode materials.

[0182] The temperature and pressure within the reactor are maintained under conditions suitable for vapor deposition (such as ALD and CVD). In other words, after the vaporized, disclosed film-forming composition is introduced into the chamber, the conditions within the chamber are such that at least a portion of the precursor is deposited onto the substrate to form a layer. For example, the pressure in the reactor, or the deposition pressure, can be maintained at approximately 10 °C, as required by the deposition parameters. -3 Between 100 and approximately 100, more preferably between 10 -2The temperature is between 10 Torr and 10 Torr. Similarly, the temperature in the reactor or the 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 "deposition of at least a portion of the precursor" means that some or all of the precursor reacts with the substrate and adheres to the substrate.

[0183] The optimal temperature for film growth can be controlled by adjusting the temperature of the substrate support. Apparatus for heating the substrate is known in the art. The substrate is heated to a sufficient temperature to obtain the desired film at a sufficient growth rate and with the desired physical state and composition. Non-limiting exemplary temperature ranges to which the substrate can be heated include from about 100°C to about 600°C. When using plasma deposition methods, the deposition temperature is preferably less than 400°C. Alternatively, when performing thermal processes, the deposition temperature can be in the range of about 100°C to about 600°C.

[0184] Alternatively, the substrate can be heated to a sufficient temperature to obtain the desired gallium-containing oxide film at a sufficient growth rate and with the desired physical state and composition. Non-limiting exemplary temperature ranges to which the substrate can be heated include from room temperature to approximately 600°C. Preferably, the temperature of the substrate is maintained at less than or equal to 500°C.

[0185] The ALD conditions within the chamber allow the disclosed film-forming composition, adsorbed or chemisorbed onto the substrate surface, to react and form a film on the substrate. In some embodiments, the applicants believe that plasma treatment of the co-reactants can provide the co-reactants with the energy required to react with the disclosed film-forming composition. When the co-reactants in this exemplary ALD process are treated with plasma, the exemplary ALD process becomes an exemplary PEALD process. The co-reactants may be treated with plasma before or after introduction into the chamber.

[0186] The film-forming composition and co-reactants can be sequentially introduced into the reactor (ALD). Between the introduction of each film-forming composition, any additional precursors, and the co-reactants, the reactor can be purged with an inert gas. Another example is the continuous introduction of co-reactants and the introduction of the film-forming composition via pulsed introduction, while the co-reactants are sequentially activated with plasma, provided that the film-forming composition and the unactivated co-reactants do not substantially react under the chamber temperature and pressure conditions (CW PEALD).

[0187] The duration of each pulse of the disclosed film-forming composition can range from about 0.001 seconds to about 120 seconds, alternatively from about 1 second to about 80 seconds, or alternatively from about 5 seconds to about 30 seconds. Co-reactants can also be pulsed into the reactor; in such embodiments, the pulse of each co-reactant can last from about 0.01 seconds to about 120 seconds, alternatively from about 1 second to about 30 seconds, or alternatively from about 2 seconds to about 20 seconds. In another alternative, the vaporized film-forming composition and co-reactants can be simultaneously sprayed from different portions of a spray head (without mixing of the composition and reactants), while a substrate of several wafers is rotated under the spray head (space ALD).

[0188] Depending on the specific process parameters, deposition can take varying durations. Typically, deposition can continue for the length necessary to produce a film with the desired properties. Depending on the specific deposition process, typical film thicknesses can range from a few angstroms to hundreds of micrometers, and typically vary from 1 to 100 nm. The deposition process can also be performed many times as necessary to obtain the desired film.

[0189] The disclosed method for forming a gallium-containing oxide layer on a substrate includes: placing the substrate in a reactor, introducing vapors of the disclosed gallium-containing film-forming composition into the reactor, and contacting / adsorbing the vapors with the substrate (and typically directing the vapors to the substrate) to form a gallium-containing oxide layer on the surface of the substrate. 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 vapors of the disclosed gallium-containing film-forming composition, and depositing a gallium-containing oxide layer on the surface of the substrate.

[0190] 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 within the reaction chamber, as well as the temperature of the substrate, are maintained under conditions suitable for the vapor-phase deposition of at least a portion of the disclosed gallium precursor onto the substrate. In other words, after the vaporized composition is introduced into the reaction chamber, the conditions within the reaction chamber are adjusted such that at least a portion of the gallium precursor is deposited onto the substrate to form a gallium-containing oxide layer. Those skilled in the art will recognize that "depositing at least a portion of the gallium precursor" means that some or all of the precursor reacts with or adheres to the substrate. Co-reactants may also be used herein to aid in the formation of the gallium-containing oxide layer.

[0191] The disclosed film-forming composition and co-reactants can be introduced into the reactor simultaneously (CVD), sequentially (ALD), or in different combinations thereof. The reactor can be purged with an inert gas (e.g., N2, He, Ar, Kr, or Xe) between the introduction of the film-forming composition and the introduction of the co-reactants. Alternatively, the co-reactants and film-forming composition can be mixed together to form a co-reactant / compound mixture, and then introduced into the reactor as a mixture. Another example is the continuous introduction of the co-reactants and the introduction of the disclosed film-forming composition via pulsed (pulsed CVD).

[0192] In a non-limiting exemplary ALD process for forming gallium oxide films and binary films, the vapor phase of the disclosed film-forming composition (e.g., (NMe2)2Ga(EtNCH2CH2NMe2)) is introduced into a reactor, where it is brought into contact with a suitable substrate and chemically or physically adsorbed thereon. 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 section under a high vacuum and / or carrier gas curtain. A co-reactant (e.g., O3) is introduced into the reactor and reacts with the adsorbed film-forming composition in a self-limiting manner. Any 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 with the desired thickness has been obtained to provide the desired film thickness. By alternately providing the gallium film-forming composition and co-reactant, films with the desired composition and thickness can be deposited.

[0193] Alternatively, if the desired indium-containing film contains three elements (e.g., InGaO and ZnGaO, a ternary film), the above two-step process (e.g., forming 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 deposited film. Additional elements may include nitrogen (N), sulfur (S), phosphorus (P), tin (Sn), arsenic (As), antimony (Sb), indium (In), zinc (Zn), and mixtures thereof. When using an additional precursor compound, the resulting film deposited on the substrate contains gallium and co-reactants in combination with the additional element. When additional precursors and gallium precursors are used in more than one ALD supercycle sequence, nanolayer films are obtained. After introduction into the reactor, the additional precursor compound is brought into contact with or adsorbed onto the substrate. Subsequently, any excess precursor compound is removed from the reactor by purging and / or evacuating the reactor. Depending on process requirements, co-reactants (e.g., O2) or additional precursors may be introduced into the reactor to react with the gallium precursor compound. Excess co-reactants or precursors are removed from the reactor by purging and / or evacuating the reactor. In the final step of the cycle, any remaining co-reactants or precursors can be introduced into the reactor and removed in excess by purging and / or evacuating the reactor. The entire three-step process can be repeated until the desired film thickness is achieved. By alternately providing the gallium film-forming composition, additional precursor compounds, and co-reactants, films with the desired composition and thickness can be deposited.

[0194] In one embodiment, the additional precursor may be an indium precursor. The indium precursor may be selected from any non-flammable, liquid, halogen-free indium molecule 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-pentyl-cyclopentadienylindium, and isopentyl-cyclopentadienylindium. Preferably, the indium precursor is isopentyl-cyclopentadienylindium.

[0195] In an alternative embodiment, the additional precursor may be a zinc precursor. This zinc precursor may be selected from any non-flammable, liquid, halogen-free zinc molecule 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 derivatives, specifically 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).

[0196] The disclosed gallium precursor has a vapor pressure that is closer to that of indium and zinc precursors than that of existing gallium precursors (such as TDMAGa and Ga(NMe2)3).

[0197] Alternatively, if the desired gallium oxide film contains four elements (e.g., InGaZnO (IGZO), a quaternary film), the above three-step (four-step) process can be inserted by introducing the vapor of another precursor compound into the reactor. The other precursor compound will be selected based on the properties of the deposited film. The other elements may include N, S, P, Sn, As, Sb, In, Zn, and mixtures thereof. When another precursor compound is used, the resulting film deposited on the substrate contains gallium in combination with the other three elements. When two additional precursors and a gallium precursor are used in more than one ALD supercycle sequence, a nanolayered film is obtained. In the case of forming an IGZO film, these precursors may include gallium precursors combined with the co-reactant O3, such as ((NMe2)2Ga(EtNCH2CH2NMe2)), indium precursors (e.g., In(isopentyl-cyclopentadienyl)), and Zn precursors (e.g., diethylzinc-TEEDA). By alternately providing gallium film-forming compositions, additional precursors, yet another additional precursor, and co-reactants, films with desired compositions and thicknesses can be deposited. Similarly, each excess composition or precursor can 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 section under a high vacuum and / or carrier gas curtain after exposure.

[0198] The gallium oxide films obtained by the methods discussed above may include Ga x O y (x = 0.5 to 1.5, y = 0.5 to 1.5), InZnO (IZO), InGaZnO (IGZO), or combinations thereof, or pure gallium oxide layers. The gallium oxide film may contain a second element selected from the following: 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 combinations thereof. Those skilled in the art will recognize that desired film compositions can be obtained through appropriate selection of the film-forming composition and co-reactants. The disclosed method can be used to manufacture semiconductor materials; for example, the gallium oxide can be used as a semiconductor material to form heterojunctions with p-InP, n-GaAs, n-Si, and other materials.

[0199] The disclosed gallium precursor has a vapor pressure that is closer to that of other precursors and yet another precursor than that of existing gallium precursors (such as TDMAGa, Ga(NMe2)3).

[0200] Once the desired film thickness is obtained, the film can be subjected to further processing, such as thermal annealing, furnace annealing, rapid thermal annealing, UV curing, electron beam curing, and / or plasma gas exposure. Those skilled in the art will recognize the systems and methods used to perform these additional processing steps. For example, in an inert atmosphere, an O-containing atmosphere, or combinations thereof, the IGZO film can be exposed to temperatures ranging from about 100°C to about 1000°C for durations ranging from about 0.1 seconds to about 7200 seconds. Most preferably, in an inert or O-containing atmosphere, the temperature range is 350°C to 450°C for 3600–7200 seconds. The resulting film may contain fewer impurities and therefore may have improved density, resulting in improved leakage current. The annealing step can be performed in the same reaction chamber in which the deposition process takes place. Alternatively, the substrate can be removed from the reaction chamber, and the annealing / rapid annealing process can be performed in a separate device. Any of the above post-treatment methods, but especially thermal annealing, has been found to effectively reduce carbon and nitrogen contamination of the IGZO film. This, in turn, tends to improve the resistivity of the membrane.

[0201] Following annealing, films deposited by any of the disclosed methods can have a bulk resistivity of approximately 50 μohm·cm to approximately 1,000 μohm·cm at room temperature. Room temperature ranges from approximately 20°C to approximately 25°C, depending on the season. Bulk resistivity is also known as volume resistivity. Those skilled in the art will recognize that bulk resistivity is measured at room temperature on films typically approximately 50 nm thick. For thinner films, bulk resistivity typically increases due to changes in electron transport mechanisms. Bulk resistivity also increases at higher temperatures.

[0202] Example

[0203] The following non-limiting examples are provided to further illustrate embodiments of the invention. However, these examples are not intended to be all-encompassing, nor are they intended to limit the scope of the invention described herein.

[0204] Thermogravimetric (TG) analysis was performed using an open aluminum cup at atmospheric pressure (1000 mbar, N2 220 sccm) or vacuum (20 mbar, N2 20 sccm) from 25°C to 500°C. Vapor pressure (VP) was determined by TG analysis. Dialkylamino (trialkyldiamino)gallium complexes can be prepared by the reported method and by changing the desired diamine ligand (“Monomeric Chelated Amides of Aluminum and Gallium: Volatile, Miscible Liquid Precursors for CVD”, ST. Barry, R.G. Gordon, and V.A. Wagner, MRS Proceedings, 606, 1999, 83). (NMe2)2Ga(EtNCH2CH2NMe2) is liquid at room temperature. In contrast, for reference, TDMAGa is solid at room temperature (melting at approximately 110°C).

[0205] Thermogravimetric analysis of two identical compounds in Figure 1 The results are available online. It can be observed that (NMe2)2Ga(EtNCH2CH2NMe2) exhibits the highest volatility, as it evaporates the fastest before TDMAGa. Furthermore, (NMe2)2Ga(EtNCH2CH2NMe2) has a lower residual amount after evaporation, which is likely a sign of higher thermal stability. This characteristic is significant when considering the potential expansion of the ALD window, and also when considering the necessity of prolonged heating of the molecule during its use without observing any decomposition. These TGA results suggest that (NMe2)2Ga(EtNCH2CH2NMe2) may outperform TDMAGa in this respect. Figure 2 This is a DSC comparison of TDMAGa and (NMe2)2Ga(EtNCH2CH2NMe2).

[0206] Example 1

[0207] Table 1 summarizes some properties 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. However, it has the advantage of not being spontaneously combustible. (NMe2)2Ga(EtNCH2CH2NMe2) is also non-spontaneously combustible, but its vapor pressure is much higher than that of TDMAGa and it is a liquid, which will be beneficial for the use of the molecule and reduce the costs associated with its use.

[0208] Table 1. Comparison of characteristics

[0209]

[0210] Predictive Example 1. Deposition of gallium oxide film by CVD using (NMe2)2Ga(EtNCH2CH2NMe2)

[0211] The container filled with (NMe2)2Ga(EtNCH2CH2NMe2) can be heated to increase and regulate its vapor pressure. The chosen temperature is typically close to 1 Torr, but any other temperature can be used. The vapor of the gallium precursor (NMe2)2Ga(EtNCH2CH2NMe2) is transported to the reaction chamber using an inert carrier gas (N2 or Ar or any other gas) (although not always required). An oxygen source, in this case ozone, is simultaneously introduced into the reaction chamber. Any other oxygen source, or mixture of sources, such as oxygen or water, can be considered. The wafer or wafer sheet, or any substrate, is placed in the reaction chamber heated between 200°C and 300°C, but any other temperature can be considered. The pressure within the reaction chamber is set between 0.1 and 10 Torr, but any other pressure can be considered. The vapor of (NMe2)2Ga(EtNCH2CH2NMe2) and ozone react at the surface of the heated substrate to form a gallium oxide film. The film exhibits very high purity, with carbon and nitrogen levels below the detection limit of the measuring instrument (XPS). Gallium oxide films of good purity can also be obtained when ozone is replaced by another oxidant (e.g., O2 or H2O), or even when either of the two oxidants is supplied together.

[0212] Predictive Example 2. Deposition of gallium oxide film using (NMe2)2Ga(EtNCH2CH2NMe2) via ALD

[0213] The container filled with (NMe2)2Ga(EtNCH2CH2NMe2) can be heated to increase and regulate its vapor pressure. The chosen temperature is typically close to 1 Torr, but any other temperature can be used. An inert carrier gas (N2 or Ar or any other gas) (although not always required) is used to transport the gallium precursor vapor to the reaction chamber. Ozone is used as the oxygen source. The wafer or wafer sheet, or any substrate, is placed in the reaction chamber heated to 250°C. The deposition cycle is divided into four distinct steps. First, only the vapor of (NMe2)2Ga(EtNCH2CH2NMe2) is introduced into the reaction chamber and adsorbed onto the surface of the wafer or substrate (precursor pulse). Then, the vapor of (NMe2)2Ga(EtNCH2CH2NMe2) is purged from the reaction chamber with an inert gas (e.g., N2 or Ar) (precursor purging pulse). Then, an oxygen source (ozone) 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 these four steps can last between tens of seconds and a few seconds, depending on the tooling configuration, deposition pressure, deposition temperature, or other conditions. In this case, the precursor pulse is set to 4 seconds, the precursor purge pulse step to 20 seconds, the ozone pulse to 2 seconds, and the ozone purge step to 20 seconds. Shorter pulse times are expected with better tools. The four-step cycle is then repeated until a gallium oxide film of the desired thickness is obtained. Gallium oxide growth per deposition cycle is between 0.5 and... Within the range. The obtained gallium oxide film has low levels of impurities and exhibits over 90% step coverage in holes or trenches with aspect ratios up to 50:1 on the patterned substrate. Similar film properties are obtained when oxygen or water is used instead of ozone, but their respective pulse and purge times need to be adjusted.

[0214] Predictive Example 3. Deposition of Indium Gallium Zinc Oxide (IGZO) Films via ALD using (NMe2)2Ga(EtNCH2CH2NMe2)

[0215] Deposition is performed in a manner similar to that in Predictive Example 2, except that two additional 4-step cycles are added to allow the deposition of indium oxide and zinc oxide, forming an InGaZnO film (IGZO). Any indium or zinc precursor can be used, such as trimethylindium, triethylindium, diethylzinc, etc. In one exemplary embodiment, trimethylindium and diethylzinc can be used. Vapors of gallium, indium, and zinc precursors are introduced in a repetitive sequence, starting with gallium, then indium and zinc, but any other sequence can be used. The cycle of the same metal can be repeated several times to adjust the film composition before switching to the next metal cycle. Ozone, oxygen, and water (H2O) are the most common oxygen sources, and they are used in this embodiment, but any kind of oxidant can be used instead. Different oxidants can be used to react with each metal, such as ozone reacting with a gallium precursor, and water reacting with an indium precursor, as well as mixtures of them, such as a mixture of ozone and water reacting with an indium precursor and water reacting only with a gallium precursor. IGZO films were obtained in ALD mode between 200°C and 250°C, but different temperature windows could be obtained when using different tools or under different deposition conditions. The expected deposition rate was 1 to 100°C per cycle. Within the range (full cycle, including sub-cycles of gallium indium and zinc precursors). The obtained IGZO films exhibit low levels of impurities, with carbon and nitrogen levels below the detection limits of the analytical tool (XPS). Deposition on patterned substrates exhibits over 90% step coverage in pores or trenches with aspect ratios up to 50:1.

[0216] Predictive Example 4. Deposition of Indium Gallium Oxide Films via ALD using (NMe2)2Ga(EtNCH2CH2NMe2) and In (isopentylcyclopentadienyl)

[0217] Deposition was performed in a manner similar to that in predictive example 3, except that indium (isopentyl-cyclopentadienyl) was used instead of trimethylindium or other indium precursors. Zinc precursors were not used. Vapors of (NMe2)2Ga(EtNCH2CH2NMe2) and indium (sec-pentyl-cyclopentadienyl) could be introduced in any order; cycles of the same metal could be repeated several times to adjust the film composition before switching to the next metal cycle. Water was used as the oxygen source. Different oxygen sources or mixtures of two different oxygen sources could be used for each of the two precursors. In this case, the gallium precursor pulse time was set to 4 seconds, the indium precursor pulse time to 4 seconds, the water pulse time to 2 seconds, and both water purge times were set to 30 seconds. Indium gallium oxide films were obtained in ALD mode at up to 250°C, with deposition rates of 0.5 to 1000°C per cycle. Within the acceptable range. The resulting membrane exhibits low levels of impurities (below the detection limit of XPS) and demonstrates over 90% stepped coverage in pores or trenches with aspect ratios up to 50:1 on the patterned substrate. Similar membrane properties are obtained when ozone or oxygen is used instead of ozone, but their respective pulse and purge times need to be adjusted.

[0218] Predictive Example 5. Deposition of IGZO film by CVD using (NMe2)2Ga(EtNCH2CH2NMe2), In (isopentylcyclopentadienyl) and diethylzinc-TEEDA

[0219] A container filled with (NMe2)2Ga(EtNCH2CH2NMe2), In (isopentylcyclopentadienyl), and diethylzinc-TEEDA can be heated to increase and regulate the vapor pressure of the precursors. The chosen temperature is typically close to 1 Torr, but any other temperature can be used. Since the three precursors have similar vapor pressures, they can be heated at the same temperature and thus placed together in the same oven. The vapors of the precursors, along with water, are then simultaneously supplied to the reaction chamber using an inert carrier gas, N2 or Ar, or any other gas (e.g., O2 for water) (although not always necessary). The wafer or wafer sheet, or any substrate, is placed in the reaction chamber heated between 200°C and 400°C, but any other temperature is acceptable. The pressure within the reaction chamber is set between 0.1 Torr and 10 Torr, but any other pressure is acceptable. The vapors of the three precursors and water react at the surface of the heated substrate to form an IGZO film. The IGZO film has very good purity, with carbon and nitrogen levels below the detection limits of the analytical tool (XPS). When water is replaced by another oxygen source (such as ozone (O3) or oxygen (O2)), or even when either of the two oxygen sources is supplied together, a good purity IGZO membrane is obtained.

[0220] Predictive Example 6. Deposition of IGZO film by ALD using (NMe2)2Ga(EtNCH2CH2NMe2), In(isopentyl-cyclopentadienyl) and diethylzinc-TEEDA

[0221] Deposition was performed in a manner similar to that in Predictive Example 3, except that indium (isopentyl-cyclopentadienyl) and diethylzinc-TEEDA were used instead of trimethylindium and diethylzinc as the indium and zinc precursors. Vapors of (NMe2)2Ga(EtNCH2CH2NMe2), indium (isopentyl-cyclopentadienyl), and diethylzinc-TEEDA could be introduced in any order; cycles of the same metal could be repeated several times to adjust the film composition before switching to the next metal cycle. Water was used as the oxygen source. Different oxygen sources could eventually be used with each metal. In this case, the gallium precursor pulse time, as well as the indium and zinc precursor pulse times, were set to 4 seconds; for the three pulses of the metal precursors, the water pulse time was set to 2 seconds; and the three water purging times were set to 30 seconds. IGZO films were obtained in ALD mode at temperatures up to 250°C or higher, with deposition rates of 1 to 1000°C per cycle. Within the acceptable range. The resulting membranes exhibit low levels of impurities (below the detection limit of XPS) and demonstrate over 90% step coverage in pores or trenches with an aspect ratio of up to 50:1 on the patterned substrate. Good purity IGZO membranes are also obtained when water is replaced by another oxygen source (e.g., ozone or oxygen), or even when either of the two oxygen sources is supplied together.

[0222] Table 2

[0223]

[0224] Table 2 compares the expected results between the reference process, Predictive Example 3, and Predictive Example 5, demonstrating the advantages of the disclosed gallium precursor over existing gallium precursors. The disclosed gallium precursor is non-flammable, which will reduce costs by facilitating transportation, storage, and use. It also allows for an increase in the maximum ALD window, which generally allows for higher quality films. Furthermore, the disclosed gallium precursor is liquid at room temperature, which reduces the cost of the method. Note that tris(dimethylamino)gallium is another standard gallium precursor that can also be used with trimethylindium and diethylzinc. While tris(dimethylamino)gallium is non-flammable, 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 benefits of the disclosed gallium precursor are even greater, as the use of low vapor pressure solid compounds is a real disadvantage for any method used in large-scale production. The benefits in terms of safety and method results are even greater when the indium and zinc precursors are replaced by non-flammable compounds with properties similar to gallium molecules, as in Predictive Example 6.

[0225] While the subject matter described herein can be described in the context of illustrative implementations to address one or more computing application features / operations of a computing application with user interaction components, the subject matter is not limited to these specific embodiments. Rather, the techniques described herein can be applied to any suitable type of user interaction component execution management methods, systems, platforms, and / or devices.

[0226] It should be understood that many additional changes in details, materials, steps, and arrangements of parts that have been described and elucidated to explain the nature of the invention can be made by those skilled in the art within the principles and scope of the invention as set forth in the appended claims. Therefore, the invention is not intended to be limited to the specific embodiments given above and / or in the drawings.

[0227] Although embodiments of the invention have been shown and described, those skilled in the art can modify them without departing from the spirit or teachings of the invention. The embodiments described herein are exemplary and not limiting. Many variations and modifications of the compositions and methods are possible and are within the scope of the invention. Therefore, the scope of protection is not limited to the embodiments described herein, but is defined only by the following claims, the scope of which should include all equivalents of the subject matter of the claims.

Claims

1. A method for depositing a gallium-containing oxide film on a substrate, the method comprising the following steps: a) Simultaneously or sequentially exposing the substrate to the vapor and oxidant of a gallium-containing film-forming composition containing a gallium precursor; as well as b) Deposit at least a portion of the gallium precursor onto the substrate using a vapor deposition process to form the gallium-containing oxide film on the substrate. The gallium precursor has the following 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 following corresponding structures: (I)(II) Among them, R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 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 They can be the same or different; x = 2, 3, 4; Cy-N refers to saturated or unsaturated N-containing rings; these N-containing rings contain at least one nitrogen atom and 4-6 carbon atoms in the chain.

2. The method as described in claim 1, wherein, The gallium precursors include (NMe2)2Ga(EtNCH2CH2NEt2), (NEtMe)2Ga(EtNCH2CH2NMe2), (NEtMe)2Ga(EtNCH2CH2NEt2), (NEt2)2Ga(EtNCH2CH2NMe2) and (NEt2)2Ga(EtNCH2CH2NEt2).

3. The method as described in claim 1, wherein, x = 2。 4. The method of claim 1, further comprising the following steps: a1) In step a), simultaneously or sequentially, the surface is exposed to the first metal (M). 1 The vapor of the precursor causes the first metal (M) to... 1 At least a portion of the precursor and the at least a portion of the gallium precursor are deposited onto the substrate by the vapor deposition process to form a gallium-containing oxide film on the substrate, wherein the gallium-containing oxide film is M 1 GaO film.

5. The method of claim 4, further comprising the following steps: a2) In step a1), simultaneously or sequentially, the surface is exposed to the second metal (M). 2 The vapor of the precursor causes the second metal (M) to... 2 At least a portion of the precursor, the at least a portion of the gallium precursor, and the first metal (M) 1 At least a portion of the precursor is deposited onto the substrate by the vapor deposition process to form a gallium-containing oxide film on the substrate, wherein the gallium-containing oxide film is M 1 M 2 GaO film, Among them, the first metal (M) 1 The precursor is an indium precursor, and the second metal (M) 2 The precursor is a zinc precursor, and vice versa.

6. The method of claim 5, wherein, The indium precursor is selected from trialkylindium, sec-pentyl-cyclopentadienylindium, or isopentyl-cyclopentadienylindium.

7. The method of claim 5, wherein, The zinc precursor is selected from the following diethylzinc derivatives: 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.

8. The method according to any one of claims 1 to 7, wherein, The melting point of this gallium precursor is below approximately 60°C.

9. A method for depositing gallium-containing quaternary oxides (M) on a substrate 1 M 2 A method for producing GaO films, the method comprising the following steps: a) Simultaneously or sequentially exposing the substrate to the vapor of a gallium-containing film-forming composition containing a gallium precursor, a first metal (M... 1 Precursor, second metal (M) 2 Precursors and oxidizing agents; as well as b) At least a portion of the gallium precursor and the first metal (M) are deposited using a vapor deposition process. 1 At least a portion of the precursor and the second metal (M) 2 At least a portion of the precursor is deposited onto the substrate to form the gallium-containing quaternary oxide film (M) on the substrate. 1 M 2 GaO). The gallium precursor has the following 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 following corresponding structures: (I)(II) Among them, R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 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 They can be the same or different; x = 2, 3, 4; Cy-N refers to saturated or unsaturated N-containing rings; these N-containing rings contain at least one nitrogen atom and 4-6 carbon atoms in the chain.

10. The method of claim 9, wherein, The gallium precursors include (NMe2)2Ga(EtNCH2CH2NEt2), (NEtMe)2Ga(EtNCH2CH2NMe2), (NEtMe)2Ga(EtNCH2CH2NEt2), (NEt2)2Ga(EtNCH2CH2NMe2), and (NEt2)2Ga(EtNCH2CH2NEt2).

11. The method of claim 9, wherein, x = 2。 12. The method of claim 9, wherein, The first metal (M) 1 The precursor is an indium precursor, and the second metal (M) 2 The precursor is a zinc precursor, and vice versa.

13. The method of claim 12, wherein, The indium precursor is selected from trialkylindium, sec-pentyl-cyclopentadienylindium, or isopentyl-cyclopentadienylindium.

14. The method of claim 12, wherein, The zinc precursor is selected from the following diethylzinc derivatives: 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 this Ga precursor is below 60°C.

16. A method for depositing an indium gallium zinc oxide (IGZO) film on a substrate, the method comprising the steps of: a) Simultaneously or sequentially exposing the substrate to the vapor of a gallium-containing film-forming composition containing a gallium precursor, an indium precursor, a zinc precursor, and O3; as well as b) Deposit 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 onto the substrate using a vapor deposition process to form the IGZO film on the substrate. The gallium precursor has the following 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 following corresponding structures: (I)(II) Among them, R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 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 They can be the same or different; x = 2, 3, 4; Cy-N refers to saturated or unsaturated N-containing rings; these N-containing rings contain at least one nitrogen atom and 4-6 carbon atoms in the chain.

17. The method of claim 16, wherein, x = 2。 18. The method of claim 16, wherein, The indium precursor is isopentyl-cyclopentadienyl indium.

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

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

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