Gallium precursor for deposition of gallium-containing oxide films

Abstract

A method for depositing a gallium-containing oxide film on a substrate comprises: a) exposing the substrate to vapors of a gallium precursor, additional metal precursor(s), and an oxidizing agent, either simultaneously or sequentially; b) forming a gallium-containing oxide film on the substrate by depositing at least a portion of the gallium precursor and at least a portion of the additional metal precursor(s) onto the substrate through a vapor deposition process, wherein the gallium precursor has the following chemical formula: [Chemical Formula I] (NR8R9)(NR1R2)Ga[(R3R4N)Cx(R5R6)(NR7)] [Chemical Formula II] (Cy-N)2Ga[(R3R4N)Cx(R5R6)(NR7)] In the formula, R1 to R9 are independently selected from H, Me, Et, nPr, iPr, nBu, iBu, sBu, or tBu; R1 to R9 may be the same or different; x = 2, 3, 4, preferably x = 2; and Cy-N refers to a saturated N-containing ring or an unsaturated N-containing ring.

Description

Technology Field

[0001] Cross-reference of related applications

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

[0003] Technology field

[0004] The present invention relates to a gallium precursor for the deposition of gallium-containing oxide films, such as binary, ternary, or quaternary gallium-containing oxide films. In particular, the gallium precursor is a liquid, volatile, non-spontaneous, halide-free molecule. Background Technology

[0005] The use of gallium oxide (Ga2O3) is attracting interest in various microdevice applications; therefore, there is interest in developing cost-effective and safe gallium molecules that can be used to deposit thin films via chemical vapor deposition (CVD), atomic layer deposition (ALD), or any gas-phase growth method. Areas of interest include gas sensors, transparent conductive oxides (TCOs), photocatalytic materials, and oxide semiconductors.

[0006] 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, homogeneous thin-film layers to better control their performance and optimize their size. An advantage of IGZO is that it can be deposited as a uniform amorphous phase while maintaining the high carrier mobility typical of oxide semiconductors. IGZO is also considered for use in next-generation semiconductor devices, whether for memory applications or logic applications (n-type BEOL transistors).

[0007] Currently, the obstacle to large-scale IGZO manufacturing is the synthesis method. The most widely used technique for the synthesis of transparent conductive oxides (TCOs) is pulsed laser deposition (PLD). In PLD, a laser is used to focus on nano-sized spots on a solid elemental target. The laser pulse frequency varies the ratio between targets to control the composition of the film. Due to its ability for low-temperature deposition, IGZO can be deposited onto substrates such as quartz, single-crystal silicon, or even plastic. The substrate is placed inside a PLD vacuum chamber with controlled oxygen pressure to ensure favorable electrical properties. After synthesis, the film is annealed or gradually exposed to air to adapt to the atmosphere.

[0008] PLD is a useful and versatile synthesis technique, but adapting each sample to normal atmospheric conditions requires expensive equipment and a significant amount of time. This makes it unsuitable for industrial manufacturing.

[0009] Solution processing is a more cost-effective alternative. Specifically, combustion synthesis techniques can be used. One example is a metal nitrate solution using an oxidizing agent that induces an exothermic reaction. One common type of combustion synthesis is spin coating, which involves depositing layers of In and Ga solutions onto a hot plate and annealing them at a temperature of approximately 200 to 400°C, depending on the target composition. The films can be annealed in air, which is a significant advantage over PLDs. While combustion processing holds potential as a novel synthesis method, further research is required to evaluate its feasibility.

[0010] Such optoelectronic devices require highly defined, homogeneous thin film layers to better control their performance and optimize their size. Thin films with desired properties can be fabricated 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 liquid gallium-containing precursors because they are more practical and therefore cost-effective for filling into storage vessels and transporting them to reactors via feed and exhaust lines. The use of solid precursors requires a sublimator for vapor formation, which presents several challenges. First, the capacity of the vessel (sublimator) is limited to a few hundred grams, and since the sublimator cannot be refilled while in the apparatus, it typically requires frequent replacement. Second, solid precursors often have very low vapor pressures, causing fluctuations in the feed rate. Additionally, slight variations in grain size can lead to differences in product evaporation. Finally, for safety reasons, it is desirable that the gallium-containing precursor does not spontaneously ignite (spontaneous combustion) when exposed to air.

[0011] For example, non-spontaneous liquid type Ga precursor, trimethyl[N-(2-methoxyethyl)-2-methylpropane-2-amine]gallium, GaMe3·(CH3OCH2CH2NH t Bu) was developed and ALD GaO x It was applied to applications. GaO x Thin films can be deposited at a growth rate of 1.0 Å / cycle in a temperature range of 100°C and 250°C (Literature[ Ceramics International, Volume 47, Issue 2, 15 January 2021, Pages 1588-1593]).

[0012] Another example of a non-spontaneous liquid gallium precursor is dimethyl gallium isopropoxide, Me2Ga(OiPr). It is liquid at room temperature and has a significantly high vapor pressure (0.55 Torr / 25°C; 0.75 Torr / 30°C; 1.0 Torr / 35°C; 1.3 Torr / 40°C), which is sufficiently high for atomic layer deposition and / or metal-organic chemical vapor deposition. In the ALD process, when water is used as the oxygen source, an apparent ALD temperature window of 300 to 325°C is achieved with a growth rate of about 1.5 Å / cycle. MOCVD is performed in a temperature range of 450 to 625°C using oxygen as the reaction gas. The Ga2O3 films deposited in both processes were found to be stoichiometric and amorphous. Using these precursors, conductive Ga-doped ZnO thin films can be successfully deposited. Electrical, structural, and optical properties are systematically investigated as a function of Ga doping content and deposition temperature. When a Ga doping concentration of 5 at.% is deposited at 250°C, low resistivity (approx. 3.5 x 10⁻⁶) -3 Optimal carrier concentration and transmittance (7.2x10⁻⁶) along with Ωcm) 20 cm -3 and 83.5%) is observed (literature[ ECS Transactions , 25 (8), 587-592, 2009 and Chem. Vapor 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 to solve this problem, amine-containing molecules are often preferred.

[0013] The deposition of indium gallium oxide and indium gallium zinc oxide thin films by CVD and ALD methods 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 an indium gallium oxide (IGO) thin film via atomic layer deposition (ALD) was studied using [1,1,1-trimethyl-N-(trimethylsilyl)-silaneaminato]indium (InCA-1) and trimethylgallium (TMGa), respectively, as indium and gallium precursors.

[0014] 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(III) isopropoxide and diethyl zinc were used as precursors in the above study.

[0015] Paper ["Spatial Atmospheric Atomic Layer Deposition of In x Ga y Zn zIn "O for Thin Film Transistors" (ACS Appl. Mater. Interfaces 2015, 7, 6, 3671-3675), a study was reported on the nucleation and growth of InGaZnO thin films by space-atmosphere atomic layer deposition using diethyl zinc (DEZn), trimethyl indium (TMIn), and triethyl gallium (TEGa) as Zn, In, and Ga precursors.

[0016] In this study, Ga, Zn, and In precursors are mostly spontaneously combustible materials, and the present invention attempts to avoid this and use the physical properties of similar materials.

[0017] Gallium complexes (NMe2)2Ga(MeNCH2CH2NMe2) and (NMe2)2Ga(EtNCH2CH2NMe2) have been reported to be liquid and volatile (Reference [MRS proceedings, 1999 by ST. Barry, et al]). These molecules have been reported to be thermally stable and can vaporize without leaving residues (no TGA data available). Since these molecules are not spontaneously combustible, they are safer to handle. Gallium molecules are not used to deposit films, but their aluminum versions have been used to deposit AlN via CVD using ammonia. Deposition of AlN from (NMe2)2Al(EtNCH2CH2NMe2) at 200°C has been reported.

[0018] To deposit gallium oxide-containing films, gallium-containing precursors must not contain halides that could degrade the electrical conductivity of the film produced from the process. Additionally, gallium precursors should be compatible with indium and zinc precursors in IGZO applications, such as having nearly similar volatility and comparable 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 spontaneously combustible materials or are mostly solid at room temperature; although some of them volatilize immediately upon slight heating, they are not convenient to use.

[0019] To deposit a gallium-containing binary or ternary oxide film, precursors with similar properties are preferred. The most commonly mentioned indium and zinc molecules are trimethylindium and diethylzinc. These two compounds are spontaneously combustible, which raises significant safety concerns and adds to costs. Additionally, trimethylindium has a melting point of 88°C and is a solid at room temperature. The use of solids is also undesirable as it increases costs.

[0020] Several organizations have developed new indium or zinc compounds of interest. For example, WO 2020179748A1 discloses the use of iso-pentyl-cyclopentadienyl indium for indium-containing deposition. The molecule is a liquid, is non-spontaneous, and exhibits a vapor pressure of 1 torr at 65°C. Deposition of indium oxide or indium by an ALD method at 250°C is disclosed.

[0021] RG Gordon et al. disclose the synthesis of diethyl zinc with tetramethylethylenediamine and TMEDA added, as well as its use in the deposition of zinc oxide via CVD (Reference [Optimization of Transparent and Reflective Electrodes for Amorphous Silicon Solar Cells, National Renewable Energy Laboratory, 1998]). Unlike diethyl zinc, the molecule is not spontaneously combustible. The authors report that the corresponding fluorine-doped ZnO2 CVD process is more controllable and reproducible, and that the film uniformity is superior (compared to using diethyl zinc). The molecule is a solid, but other added diethyl zinc compounds, such as diethyl zinc-tetraethylethylenediamine and diethyl zinc-TEEDA, are liquids. Intuitively, the authors of this disclosure measured the vapor pressure of diethyl zinc-tetraethylethylenediamine to be 1 torr at 69°C.

[0022] 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, halogen-free, non-spontaneous, thermally stable, and have high vapor pressure, and it is also worth identifying additional metallic precursors with similar properties to develop the best deposition process. means of solving the problem

[0023] A method for depositing a gallium-containing oxide film on a substrate is disclosed, and the method

[0024] a) simultaneously or sequentially exposing the substrate to the vapor of a gallium-containing film-forming composition containing a gallium precursor and an oxidizing agent; and

[0025] b) forming a gallium-containing oxide film on the substrate by depositing at least a portion of the gallium precursor onto the substrate through a vapor deposition process.

[0026] Includes,

[0027] The above gallium precursor

[0028] [Chemical Formula I]

[0029] (NR 8 R 9 )(NR 1 R 2 )Ga[(R 3 R 4 N)C x (R 5 R 6 )(NR 7 )]

[0030] [Chemical Formula II]

[0031] (Cy-N)2Ga[(R 3 R 4 N)C x (R 5 R 6 )(NR 7 )]

[0032] and corresponding structure:

[0033] [Chemical Formula I]

[0034]

[0035] [Chemical Formula II]

[0036]

[0037] Having,

[0038] During the meal, 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; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R8 , R 9 may be the same or different; x = 2, 3, 4, preferably x = 2; Cy-N refers to a saturated N-containing ring or an unsaturated N-containing ring; and the N-containing ring comprises at least one nitrogen atom and 4 to 6 carbon atoms within one chain.

[0039] The disclosed method may include one or more of the following embodiments:

[0040] · Cy-NH comprises the following modalities: pyrroline, pyrrole, and piperidine:

[0041] ;

[0042] · A gallium precursor comprises an embodiment including (NMe2)2Ga(EtNCH2CH2NMe2), (NMe2)2Ga(EtNCH2CH2NEt2), (NEtMe)2Ga(EtNCH2CH2NMe2), (NEtMe)2Ga(EtNCH2CH2NEt2), (NEt2)2Ga(EtNCH2CH2NMe2), (NEt2)2Ga(EtNCH2CH2NEt2) and (NMe2)2Ga(MeNCH2CH2NMe2);

[0043] · An embodiment in which the gallium precursor is (NMe2)2Ga(EtNCH2CH2NMe2);

[0044] · An embodiment in which the gallium precursor is (NMe2)2Ga(EtNCH2CH2NEt2);

[0045] · An embodiment in which the gallium precursor is (NEtMe)2Ga(EtNCH2CH2NMe2);

[0046] · An embodiment in which the gallium precursor is (NEtMe)2Ga(EtNCH2CH2NEt2);

[0047] · An embodiment in which the gallium precursor is (NEt2)2Ga(EtNCH2CH2NMe2);

[0048] · An embodiment in which the gallium precursor is (NEt2)2Ga(EtNCH2CH2NEt2);

[0049] · The gallium precursor is (NMe2)2Ga(MeNCH2CH2NMe2);

[0050] · A mode that additionally includes the following steps:

[0051] a1) In step a), simultaneously or sequentially, the surface of the first metal (M 1 ) by exposing to the vapor of a precursor, the first metal (M) is formed through a vapor deposition process. 1 A step of forming a gallium-containing oxide film on a substrate by depositing at least a portion of a precursor and at least a portion of a gallium precursor onto a substrate, wherein the gallium-containing oxide film is M 1 Step, which is a GaO film;

[0052] · A mode that additionally includes the following steps:

[0053] a2) In step a1), simultaneously or sequentially, the surface of the second metal (M 2 ) by exposing to the vapor of the precursor, a second metal (M) is produced through a vapor deposition process. 2 ) at least a portion of the precursor, at least a portion of the gallium precursor, and the first metal (M 1 A step of forming a gallium-containing oxide film on a substrate by depositing at least a portion of a precursor onto a substrate, wherein the gallium-containing oxide film is M 1 M 2 Step, which is a GaO film;

[0054] · A mode that additionally includes the following steps:

[0055] Film-forming composition, first metal (M 1 ) precursor, second metal (M 2 ) A step of purging with an inert gas between each exposure to the precursor, the oxidizer, and the mixture thereof;

[0056] · The inert gas is selected from N2, He, Ar, Kr, or Xe;

[0057] · An embodiment where the inert gas is N2;

[0058] · An embodiment where the inert gas is Ar;

[0059] · First metal (M 1 ) The precursor is an indium precursor mode;

[0060] · First metal (M 1 The precursor is a zinc precursor;

[0061] · Second metal (M 2 ) The precursor is an indium precursor mode;

[0062] · Second metal (M 2 The precursor is a zinc precursor;

[0063] · An embodiment in which the indium precursor is selected from trialkyl indium, sec-pentyl-cyclopentadienyl indium, or iso-pentyl-cyclopentadienyl indium;

[0064] · An embodiment in which the indium precursor is trialkyl indium;

[0065] · An embodiment in which the indium precursor is iso-pentyl-cyclopentadienyl indium;

[0066] · An embodiment in which the indium precursor is sec-pentyl-cyclopentadienyl indium;

[0067] · An embodiment in which the zinc precursor is a diethyl zinc derivative selected from diethyl zinc-tetramethylethylenediamine adduct (TMEDA), diethyl zinc-tetraethylethylenediamine adduct (TEEDA), diethyl zinc-N,N'-diethyl-N,N'-diethyl-ethylenediamine adduct, diethyl zinc-N,N-dimethyl-N',N'-diethylethylenediamine adduct, or diethyl zinc-N,N,N'-trimethyl-N'ethylethylenediamine adduct;

[0068] · An embodiment in which the zinc precursor is a diethyl zinc-tetramethylethylenediamine adduct (TMEDA);

[0069] · An embodiment in which the zinc precursor is a diethyl zinc-tetraethylethylenediamine adduct (TEEDA);

[0070] · An embodiment in which the zinc precursor is a diethyl zinc-N,N'-diethyl-N,N'-diethyl-ethylenediamine adduct;

[0071] · An embodiment in which the zinc precursor is a diethyl zinc-N,N-dimethyl-N',N'-diethylethylenediamine adduct;

[0072] · An embodiment in which the zinc precursor is a diethyl zinc - N,N,N'-trimethyl-N'ethylethylenediamine adduct;

[0073] · M 1 The GaO film is an InGaO film;

[0074] · M 1 An embodiment in which the GaO film is a ZnGaO film;

[0075] · M 1 M 2 The GaO film is an IGZO film in the form of a GaO film;

[0076] · A mode in which the gallium-containing oxide film is an InGaO film;

[0077] · A mode in which the gallium-containing oxide film is a ZnGaO film;

[0078] · A mode in which the gallium-containing oxide film is an IGZO film;

[0079] · An oxidizing agent is O2, O3, H2O, H2O2, NO, N2O, NO2, an oxygen-containing radical, such as O· or OH·;

[0080] · An embodiment where the oxidizing agent is O3;

[0081] · An embodiment where the oxidizing agent is O2;

[0082] · The oxidizing agent is plasma-treated;

[0083] · A gallium-containing film-forming composition in an embodiment comprising an inert carrier gas;

[0084] · The inert carrier gas is selected from N2, He, Ne, Ar, Kr, Xe, or a combination thereof;

[0085] · An embodiment in which the inert carrier gas is N2 or Ar;

[0086] · An embodiment in which the melting point of the gallium precursor is approximately less than 60°C;

[0087] · An embodiment in which the melting point of the gallium precursor is approximately less than 20℃;

[0088] · Gallium precursor in a non-spontaneous mode;

[0089] · Gallium precursor in a liquid form at room temperature;

[0090] · A mode in which the gallium precursor is liquid at a temperature ranging from room temperature to approximately 60°C;

[0091] · The vapor deposition process is an ALD process, a CVD process, or a combination thereof;

[0092] · The vapor deposition process is an ALD process mode;

[0093] · The vapor deposition process is a CVD process;

[0094] · The vapor deposition process is an embodiment of the PEALD process;

[0095] · The deposition pressure is approximately 10 -3 A mode maintained at Torr to about 100 Torr;

[0096] · The deposition pressure is approximately 10 -2 A mode maintained at Torr to 10 Torr;

[0097] · An embodiment in which the deposition temperature is maintained at approximately 100°C to approximately 600°C;

[0098] · An embodiment in which the deposition temperature is maintained at approximately 150℃ to approximately 500℃;

[0099] · An embodiment in which the purity of the gallium precursor is in the range of approximately 93% w / w to approximately 100% w / w;

[0100] · An embodiment in which the purity of the gallium precursor is in the range of approximately 99% w / w to approximately 99.999% w / w;

[0101] · An embodiment in which the purity of the indium precursor is in the range of approximately 93% w / w to approximately 100% w / w;

[0102] · An embodiment in which the purity of the indium precursor is in the range of approximately 99% w / w to approximately 99.999% w / w;

[0103] · An embodiment in which the purity of the zinc precursor is in the range of approximately 93% w / w to approximately 100% w / w;

[0104] · An embodiment in which the purity of the zinc precursor is in the range of approximately 99% w / w to approximately 99.999% w / w;

[0105] · An embodiment in which the purity of the gallium-containing film-forming composition is in the range of approximately 93% w / w to approximately 100% w / w; and

[0106] · An embodiment in which the purity of the gallium-containing film-forming composition is in the range of approximately 99% w / w to approximately 99.999% w / w.

[0107] In addition, a gallium-containing quaternary oxide (M) on a substrate 1 M 2 A method for depositing a GaO film is disclosed, and the method

[0108] a) Simultaneously or sequentially, the substrate is a gallium precursor, a first metal (M 1 ) Vapor of the precursor, second metal (M 2 ) a step of exposing to the vapor of a precursor and the vapor of a gallium-containing film-forming composition containing an oxidizing agent; and

[0109] b) at least a portion of the gallium precursor through a vapor deposition process, the first metal (M 1 ) At least a portion of the precursor and the second metal (M 2 ) At least a portion of the precursor is deposited onto a substrate to form a gallium-containing quaternary oxide film (M) on the substrate. 1 M 2 Step of forming GaO

[0110] Includes,

[0111] The above gallium precursor

[0112] [Chemical Formula I]

[0113] (NR 8 R 9)(NR 1 R 2 )Ga[(R 3 R 4 N)C x (R 5 R 6 )(NR 7 )]

[0114] [Chemical Formula II]

[0115] (Cy-N)2Ga[(R 3 R 4 N)C x (R 5 R 6 )(NR 7 )]

[0116] and corresponding structure:

[0117] [Chemical Formula I]

[0118]

[0119] [Chemical Formula II]

[0120]

[0121] Having,

[0122] During the meal, 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; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9may be the same or different; x = 2, 3, 4, preferably x = 2; Cy-N refers to a saturated N-containing ring or an unsaturated N-containing ring; and the N-containing ring comprises at least one nitrogen atom and 4 to 6 carbon atoms.

[0123] In addition, a method for depositing an indium gallium zinc oxide (IGZO) film on a substrate is disclosed, and the method

[0124] a) simultaneously or sequentially exposing the substrate to vapor of a gallium precursor, vapor of an indium precursor, vapor of a zinc precursor, and vapor of a gallium-containing film-forming composition containing O3; and

[0125] b) A step of forming an IGZO film on a substrate by depositing at least a portion of a gallium precursor, at least a portion of an indium precursor, and at least a portion of a zinc precursor onto a substrate through a vapor deposition process.

[0126] Includes,

[0127] The above gallium precursor

[0128] [Chemical Formula I]

[0129] (NR 8 R 9 )(NR 1 R 2 )Ga[(R 3 R 4 N)C x (R 5 R 6 )(NR 7 )]

[0130] [Chemical Formula II]

[0131] (Cy-N)2Ga[(R 3 R 4 N)C x (R 5 R 6 )(NR 7 )]

[0132] and corresponding structure:

[0133] [Chemical Formula I]

[0134]

[0135] [Chemical Formula II]

[0136]

[0137] Having,

[0138] During the meal, 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; 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; Cy-N refers to a saturated N-containing ring or an unsaturated N-containing ring; and the N-containing ring comprises at least one nitrogen atom and 4 to 6 carbon atoms.

[0139] Notation and Naming

[0140] The following detailed description and claims use many abbreviations, symbols, and terms generally well known in the art. Specific abbreviations, symbols, and terms are used throughout the following description and claims and include the following:

[0141] As used herein, the singular form means one or more.

[0142] As used herein, "about, around" or "approximately" in the text or claims means ±10% of the stated value.

[0143] As used herein, "room temperature" in the text or claims means approximately 20°C to approximately 25°C.

[0144] The term “high thermal stability” refers to the characteristics of a product that does not produce a residue above 200°C (more preferably, the residue is less than about 5% at 300°C and more preferably less than about 2% at 300°C), evaporates smoothly in thermogravimetric analysis without exhibiting a “tail,” or exhibits a decomposition temperature starting point higher than that of commercially available products by DSC analysis, more preferably above 235°C.

[0145] The term "substrate" refers to the material or materials on which the process is performed. The substrate may refer to a wafer having the material or materials on which the process is performed. The substrate may be any suitable wafer used in the manufacture of semiconductors, photovoltaics, flat panel panels, or LCD-TFT devices. The substrate may also have one or more layers of different materials already deposited on the substrate in a previous manufacturing step. For example, the wafer may comprise 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. Additionally, the substrate may be planar or patterned. The substrate may be a patterned organic photoresist film. The substrate may comprise a layer of oxide used as a dielectric material (e.g., ZrO2-based materials, HfO2-based materials, TiO2-based materials, rare earth oxide-based materials, ternary oxide-based materials, etc.) 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 may also be a powder, e.g., a powder 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. Exemplary powder substrates also include activated carbon.

[0146] The term "wafer" or "patterned wafer" refers to a wafer having a stack of films on a substrate, wherein at least the topmost film has topographic features generated in the pre-deposition steps of an indium-containing film.

[0147] The term "aspect ratio" refers to the ratio of the height of a trench (or opening) to the width (or diameter) of a trench.

[0148] It should be noted that the terms “film” and “layer” may be used interchangeably herein. It is understood that a film may correspond to or be associated with a layer, and that a layer may refer to a film. Furthermore, those skilled in the art will recognize that as used herein, the terms “film” or “layer” refer to a portion of material of a certain thickness placed on or diffused over a surface, and that said surface may range from large enough to be an entire wafer to small enough to be a trench or a line. Throughout the entire specification and claims, a wafer and any associated layer on the wafer are referred to as a substrate.

[0149] It should be noted that in this document, the terms "opening," "via," "hole," and "trench" may be used interchangeably to refer to openings formed in a semiconductor structure.

[0150] 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, wherein the gate structure is stacked in a vertical direction.

[0151] It is noted herein that the terms "deposition temperature" and "substrate temperature" may be used interchangeably. It is understood that the substrate temperature may correspond to or be related to the deposition temperature, and that the deposition temperature may refer to the substrate temperature.

[0152] It is noted herein that the terms "precursor," "deposited compound," and "deposited gas" may be used interchangeably when the precursor is in a gaseous state at room temperature and ambient pressure. It is understood that the precursor may correspond to or be related to the deposited compound or deposited gas, and that the deposited compound or deposited gas may refer to the precursor.

[0153] Standard abbreviations for elements from the periodic table are used herein. It should be understood that an element may be referred to by its abbreviation (e.g., Si refers to silicon, N refers to nitrogen, O refers to oxygen, C refers to carbon, H refers to hydrogen, F refers to fluorine, etc.).

[0154] A unique CAS registration number (i.e., "CAS") designated by the Chemical Identification Service is provided to identify a specific disclosed molecule.

[0155] As used herein, the term "alkyl group" refers to a saturated functional group containing only carbon and hydrogen atoms. An alkyl group is a type of hydrocarbon. Additionally, the term "alkyl group" refers to a linear, branched, or cyclic alkyl group. Examples of linear alkyl groups include, without limitation, methyl groups, ethyl groups, propyl groups, butyl groups, etc. Examples of branched alkyl groups include, without limitation, t-butyl. Examples of cyclic alkyl groups include, without limitation, cyclopropyl groups, cyclopentyl groups, cyclohexyl groups, etc.

[0156] As used herein, the abbreviation "Me" refers to a methyl group; the abbreviation "Et" refers to an ethyl group; the abbreviation "Pr" refers to any propyl group (i.e., n-propyl or isopropyl); and the abbreviation " i "Pr" refers to the isopropyl group; the abbreviation "Bu" refers to any butyl group ( n -butyl, Iso -butyl, tert -butyl, sec Refers to -butyl; abbreviation " t Bu" is tert -Referring to the butyl group; abbreviation " s Bu" is sec -Referring to the butyl group; abbreviation " i Bu" is Iso - Refers to a butyl group; the abbreviation "Ph" refers to a phenyl group; the abbreviation "Amy" refers to any amyl group ( Iso -Amil, sec -Amil, tert -Amyl) refers to; the abbreviation "Cy" refers to a cyclic hydrocarbon group (cyclobutyl, cyclopentyl, cyclohexyl, etc.); and the abbreviation "Ar" refers to an aromatic hydrocarbon group (phenyl, xylyl, mesithyl, etc.). As used in the disclosed embodiments, the term "independently" should be understood to indicate that, when used in a context describing an R group, the subject R group is selected independently of other R groups having the same or different subscripts or superscripts, as well as independently of any additional species of the same R group. For example, the chemical formula MR where x is 2 or 3 1 x (NR 2 R 3 ) (4-x) In, 2 or 3 R 1 The energies are identical to each other or R 2 or R 3 It may be identical to, but not necessarily. Also, unless specifically stated otherwise, the values ​​of the R groups should be understood as independent of each other when used in different chemical formulas.

[0157] A range may be expressed herein as approximately from one specific value and / or approximately from another specific value. When such a range is expressed, another embodiment should be understood as being from one specific value and / or another specific value, together with all combinations within said range. Any and all ranges mentioned in the disclosed embodiments include their endpoints, regardless of whether the term "inclusively" is used (i.e., x = 1 to 4 or the x range of 1 to 4 includes x = 1, x = 4, and x = any number in between).

[0158] References to “one embodiment” or “an embodiment” herein mean that a specific feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment of the present invention. Throughout this specification, the appearance of the phrase “in one embodiment” does not necessarily refer to the same embodiment, nor are separate or alternative embodiments necessarily mutually exclusive from other embodiments. The same applies to the term “an embodiment.”

[0159] As used in this application, the word “exemplary” is used to mean that it functions as an example, case, or illustration. Any embodiment or design described herein as “exemplary” is not to be interpreted as being more desirable or advantageous than any other embodiment or design. Rather, the use of the word “exemplary” is intended to provide the concept in a concrete manner.

[0160] The term “comprising” within the claim is an open transitional term, meaning that the elements of the claim identified prior to it are a non-exclusive list, that is, any other may additionally be included and maintained within the scope of “comprising”. “Comprising” is defined herein as essentially including the more restrictive transitional terms “essentially composed of” and “composed of”; “comprising” may, accordingly, be replaced by “essentially composed of” or “composed of” and is maintained within the scope of the explicitly defined “comprising”.

[0161] Furthermore, the term "or" is intended to mean an inclusive "or" rather than an exclusive "or." That is, unless otherwise specified or is not evident from the context, "X uses A or B" is intended to mean any natural inclusive permutation. In other words, if X uses A; if X uses B; or if X uses both A and B, "X uses A or B" is satisfied in any of these cases. Additionally, the singular form used in this application and the appended claims should generally be deemed to mean "one or more" unless otherwise specified or clearly indicated by the context.

[0162] "Provides" within the scope of the claim is defined as meaning to equip, supply, make available, or prepare something. A step may be carried out by any act unless otherwise clearly stated in the scope of the claim. Brief explanation of the drawing

[0163] To better understand the features and purposes of the present invention, reference will be made to the following detailed description in conjunction with the accompanying drawings, in which similar components are given the same or similar reference numbers: Fig. 1 is a comparison of TGAs performed on tris(dimethylamino)gallium (TDMAGa) and (NMe2)2Ga (EtNCH2CH2NMe2); Fig. 2 This is a comparison of DSCs performed on TDMAGa and (NMe2)2Ga(EtNCH2CH2NMe2). Specific details for implementing the invention

[0164] A gallium-containing film-forming composition comprising a gallium precursor containing an aminoamide ligand is disclosed, and a method for using the same to deposit a gallium-containing oxide film, such as an indium gallium zinc oxide (IGZO) film, in the manufacture of a semiconductor device is disclosed. The gallium-containing oxide film may be a binary, ternary, or quaternary gallium oxide film. The disclosed gallium precursor is liquid at a temperature in the range of room temperature to approximately 60°C and is a volatile, non-spontaneous, halogen-free, gallium amino compound. The disclosed gallium precursor is preferably liquid at approximately 20°C. The melting point of the gallium precursor is approximately less than 60°C, and preferably the melting point of the gallium precursor is approximately less than 20°C. The volatility and thermal stability of the disclosed gallium precursor are higher than those of conventional gallium precursors, such as tris(dimethylamino)gallium (Ga(NMe2)3, TDMAGa), which are solids that melt at approximately 110°C and have been used as the primary Ga source in gallium oxide-containing films, such as IGZO. The disclosed gallium precursor is liquid at room temperature, so its manufacture, synthesis, purification, storage in containers, and transfer to liquid delivery systems operate simply. These characteristics are industrially beneficial in terms of cost reduction when the precursor is used in high-volume manufacturing (HVM).

[0165] The disclosed gallium precursor is non-spontaneous, which reduces safety-related costs. Spontaneous chemical substances are known to be unsuitable for air transport and must be shipped via sea freight. The inevitable use of boats for international transport clearly adds costs depending on volume during the development, ramp, and even mass production phases. Furthermore, boat transport, storage, and transit times and container quality requirements in accordance with specific regulations for spontaneously combustible products increase production costs.

[0166] The disclosed gallium precursor is halogen-free and is suitable for two molecules, such as the indium and zinc precursors used in the disclosed process. Therefore, there may be no corrosive effects on the entire system, which can also reduce process costs because the need for maintenance is reduced by eliminating the need for special construction corrosion-resistant materials, special O-rings, or expensive special pumps.

[0167] Higher volatility of the gallium precursor disclosed compared to TDMAGa ( Table 1 (Reference) allows the user to provide a larger flow of the initiated gallium precursor within the reactor compared to TDMAGa while the vessel is heated at the same temperature. The higher partial pressure of Ga can lead to a faster deposition rate compared to TDMAGa. A faster rate can reduce manufacturing costs. Additionally, the Ga content within the film can be increased, thereby providing flexibility in adjusting the film composition. The higher stability of the initiated gallium precursor compared to TDMAGa, as indicated by thermogravimetric measurements, enables adjustment of the deposition process window. Because the initiated molecules are more stable, they can deposit films via ALD at higher temperatures than current molecules such as TDMAGa. The ability to deposit films at higher temperatures typically improves the quality of the deposited film, meaning it can reduce the content of impurities, carbon, or nitrogen. In some cases, the possibility of depositing films at high temperatures while still using the ALD method allows for the deposition of films with different crystal phases that may possess superior properties compared to films deposited at lower temperatures due to factors such as higher mobility.

[0168] The disclosed gallium precursor has the following general chemical formula:

[0169] [Chemical Formula I]

[0170] (NR 8 R 9 )(NR 1R 2 )Ga[(R 3 R 4 N)C x (R 5 R 6 )(NR 7 )]

[0171] [Chemical Formula II]

[0172] (Cy-N)2Ga[(R 3 R 4 N)C x (R 5 R 6 )(NR 7 )]

[0173] and the corresponding structure below:

[0174] [Chemical Formula I]

[0175]

[0176] [Chemical Formula II]

[0177]

[0178] has

[0179] In chemical formula I, 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; 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;

[0180] In chemical formula II, R 3 , R 4 , R 5 , R6 , R 7 is 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, 4, preferably x = 2; Cy-N refers to a saturated N-containing ring or an unsaturated N-containing ring; the N-containing ring comprises at least one nitrogen atom and 4 to 6 carbon atoms within a single chain; examples of Cy-NH include pyrroline, pyrrole, and piperidine, etc., as described below:

[0181] .

[0182] In the exemplary disclosed gallium precursor

[0183]

[0184] and is included.

[0185] 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).

[0186] The disclosed gallium precursor may have the following characteristics that make them suitable for the deposition of gallium oxide and multimetal gallium-containing oxide films. In one embodiment, the disclosed gallium precursor is liquid at room temperature, which has sufficient vapor pressure at low temperatures, and makes the disclosed gallium precursor much more volatile and thermally stable than the reference Ga compound, TDMAGa. In another embodiment, the disclosed gallium precursor is a non-spontaneous compound that allows for easy manufacturing, synthesis, purification, storage, and delivery for applications in the semiconductor industry. The disclosed gallium precursor may be suitable for use as a deposition precursor in the formation of multimetal gallium-containing oxide films, including gallium oxide films and IGZO films.

[0187] The disclosed gallium precursor is suitable for use as a precursor for depositing gallium oxide films, gallium indium oxide films, gallium zinc oxide films, and IGZO films. Again, the disclosed gallium precursor is a non-spontaneous and volatile liquid compound at room temperature with excellent vapor pressure and excellent thermal stability. Unlike currently used gallium precursors such as TDMAGa, the key characteristics (vapor pressure, melting point) of the disclosed gallium precursor are more similar to those of standard indium and zinc precursors, such as trimethylindium or diethyl zinc.

[0188] The disclosed gallium precursor has 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 disclosed gallium precursor is suitable for depositing corresponding element-containing films and is suitable for its related applications for depositing corresponding element-containing layers.

[0189] The disclosed film-forming composition may comprise the disclosed gallium precursor, a co-reactant, a carrier gas, etc. The co-reactant may comprise one or more additional precursors and an oxidizing agent, 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, used 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 applied in the display, semiconductor, logic, and memory industries, etc.

[0190] Additionally, the present disclosure includes a method for forming gallium oxide films, indium gallium oxide films, zinc gallium oxide films, and indium gallium zinc oxide (IGZO) films using a gallium precursor disclosed by a vapor deposition method such as ALD or CVD. A deposition process for forming a film is disclosed by using the disclosed gallium precursor, with or without co-reactants which are one or more oxidizing agents (e.g., O2 and O3, or H2O and H2O2), simultaneously and / or sequentially, and introducing the gallium precursor into a reaction chamber to deposit the film by ALD, CVD, spin-on, spray, dip coating, slit coating, or any other deposition technique. The disclosed deposition process using the disclosed gallium precursor may be assisted by heating, light, direct or remote plasma, or a combination thereof.

[0191] The co-reactant may be one or more additional precursors in addition to the disclosed gallium precursor. The co-reactant may be an indium precursor, a zinc precursor, or a combination thereof. The additional precursor may be selected from any non-spontaneous, liquid, halide-free indium or zinc molecule having a vapor pressure of 1 torr at less than 100°C, preferably 1 torr at less than 80°C.

[0192] In addition, the co-reactant may be an oxidizing gas such as O2, O3, H2O, H2O2, NO, N2O, NO2, oxygen-containing radicals, e.g., O· or OH·, alcohols, silanols, amino alcohols, carboxylic acids, e.g., 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, H2O2, and H2O. 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 will be a gallium oxide film.

[0193] Co-reactants may be treated by plasma to decompose the reactants into radicals, and O3 and O2 may be used as oxygen source gases when treated by plasma. The plasma source may be He plasma, Ar plasma, or a mixture thereof. For example, the plasma may be generated at a power range of about 10 W to about 1000 W, preferably about 50 W to about 500 W. The plasma may be generated and present within the reactor itself. Alternatively, the plasma may generally be located at a location away from the reactor, for example, in a remotely located plasma system. Those skilled in the art will recognize methods and apparatus suitable for such plasma treatment.

[0194] For example, a co-reactant can be introduced into a direct plasma reactor that generates plasma in the reaction chamber to produce a plasma-treated reactant in the reaction chamber. The co-reactant can be introduced and maintained in the reaction chamber prior to plasma treatment. Alternatively, plasma treatment can occur simultaneously with the introduction of the reactant.

[0195] Alternatively, plasma-treated co-reactants can be generated outside the reaction chamber, for example, with a remote plasma to treat the co-reactants before they enter the reaction chamber.

[0196] A method for forming a gallium-containing oxide layer on a substrate using a vapor deposition process is also disclosed. The applicant believes that the disclosed film-forming composition is suitable for ALD. More specifically, the disclosed film-forming composition enables surface saturation, self-limiting growth per cycle, and perfect step coverage exceeding 90% for aspect ratios such as holes and trenches in the range of approximately 2:1 to approximately 200:1, preferably approximately 20:1 to approximately 150:1, more preferably approximately 50:1 to approximately 100:1. Additionally, the disclosed film-forming composition has a high decomposition temperature, which indicates excellent thermal stability and makes ALD possible. The high decomposition temperature enables ALD at higher temperatures, thereby producing films of higher purity. The disclosed method may be useful for manufacturing semiconductors, photovoltaic cells, LCD-TFTs, and flat panel type devices.

[0197] The disclosed gallium-containing film-forming composition may 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 enhancement or atomic layer deposition (ALD). Exemplary ALD methods include thermal ALD, plasma-enhanced ALD (PEALD), spatially divided ALD, temporal ALD, selective or non-selective ALD, hot wire ALD (HWALD), radical-entrained ALD, fluid ALD (thermal or plasma) with or without inhibitor(s), and combinations thereof. To provide 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), near-atmospheric CVD (SACVD) or atmospheric CVD (APCVD), hot wire CVD or thermal filament CVD (also known as cat-CVD, where a hot wire is used as an 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, photo-initiated CVD, laser CVD, radical-incorporated CVD, plasma-enhanced CVD (including but not limited to fluid PECVD), and combinations thereof.

[0198] The disclosed gallium-containing film-forming composition contains any analogue thereof or other reaction product in an amount of 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 may provide better process repeatability. This embodiment may be produced by purification of the gallium-containing film-forming composition (e.g., distillation, sublimation, chromatography, etc.).

[0199] The purity of the disclosed film-forming composition 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), 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 may be determined by gas or liquid chromatography and NMR spectroscopy in combination 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; metal chloride compounds; lithium, sodium, 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), 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 purified by recrystallization, sublimation, distillation, and / or by passing the gas-liquid through a suitable adsorbent such as a 4 Å molecular sieve.

[0200] Purification of the disclosed film-forming composition may also independently produce metal impurities in the range of 0 ppbw to 1 ppmw, preferably about 0 to about 500 ppbw (parts per billion weight), more preferably about 0 ppbw to about 100 ppbw, and even more preferably 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).

[0201] Since the disclosed gallium precursor can decompose into Ga(OH)3, care must be taken to ensure that the disclosed gallium-containing film-forming composition is not exposed to water.

[0202] The disclosed film-forming composition may be supplied in a pure (neat) form or as a blend with a suitable solvent such as ethylbenzene, xylene, mesitylene, decalin, decane, and dodecane. The disclosed precursor may be present in the solvent at various concentrations.

[0203] The blended pure 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 pure blended composition through conventional vaporization steps such as direct vaporization or distillation, by bubbling, or by using a sublimator. The pure blended composition can be supplied to the vaporizer in a liquid state, where it is vaporized before being introduced into the reactor. Alternatively, the pure blended composition can be vaporized by passing a carrier gas through a vessel containing the composition, or by bubbling the carrier gas into the composition. The carrier gas may include, but is not limited to, Ar, He, N2, and mixtures thereof. Bubbling with the carrier gas may also remove any dissolved oxygen present in the pure blended composition. Subsequently, the carrier gas and the composition are introduced into the reactor as vapor.

[0204] If necessary, a 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, for example, at a temperature in the range of approximately 0°C to approximately 200°C. Those skilled in the art recognize that the temperature of the container may be adjusted in a known manner to control the amount of vaporized precursor.

[0205] The reactor may be any enclosure chamber within the device where the deposition method is performed, such as a parallel-plate reactor, a low-temperature-wall reactor, a high-temperature-wall reactor, a single-wafer reactor, a multi-wafer reactor, or other types of deposition systems, under suitable conditions that allow the compounds to react and form a layer, without limitation. Those skilled in the art will recognize that any of these reactors may be used in either an ALD or CVD deposition process.

[0206] The reactor accommodates one or more substrates on which a film is to be deposited. A substrate is generally defined as the material on which the process is performed. The substrate may be any suitable substrate used in the manufacture of semiconductors, photovoltaics, flat panel panels, and LCD-TFT devices. Examples of suitable substrates include wafers such as silicon wafers, silica wafers, glass wafers, and GaAs wafers. The wafer may have one or more layers of different materials deposited on the wafer from a previous manufacturing step. For example, the wafer may include a dielectric layer. Additionally, the wafer may 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 layer, a metal nitride layer (Ti, Ru, Ta, etc.), and combinations thereof. Furthermore, the wafer may include a copper layer and a precious metal layer (e.g., platinum, palladium, rhodium, gold). The wafer may include a barrier layer such as manganese, manganese oxide, etc. A plastic layer such as poly(3,4-ethylenedioxythiophene)poly(styrenesulfonate) [PEDOT:PSS] may also be used. The layer may be planar or patterned. The disclosed process may deposit the layer directly onto the wafer or directly onto one or more layers on the wafer when the patterned layer is formed on the substrate. The patterned layer may be an alternating layer of two specific layers, such as SiO and SiN used in 3D NAND. Additionally, those skilled in the art will recognize that as used herein, the terms “film” and “layer” refer to a portion of a certain thickness of material placed on or diffused over a surface, and said surface may be a trench or a line. Throughout this specification and claims, the wafer and any related layer on the wafer are referred to as the substrate. For example, a gallium oxide film may be deposited on a metal oxide layer, such as an HfO2 layer.

[0207] The end applications of the substrate are not limited to the present invention, but the technology may be particularly advantageous for the following types of substrates: 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.

[0208] 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 disclosed vaporized film-forming composition is introduced into the chamber, the conditions within the chamber are set such that at least a portion of the precursor is deposited onto the substrate to form a layer. For example, the pressure within the reactor or the deposition pressure is approximately 10 as required by the deposition parameters. -3 torr to about 100 torr, more preferably about 10 -2 It may be maintained at torr to 10 torr. Likewise, the temperature in the reactor or the deposition temperature may be maintained at about 100°C to about 600°C, preferably about 150°C to 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 and adheres to the substrate.

[0209] The temperature for achieving optimal film growth can be controlled by controlling the temperature of the substrate holder. Devices used to heat the substrate are known in the art. The substrate is heated to a temperature sufficient to obtain a desired film having a desired physical state and composition at a sufficient growth rate. Non-limiting exemplary temperature ranges in which the substrate may be heated include approximately 100°C to approximately 600°C. If a plasma deposition process is used, the deposition temperature is preferably less than 400°C. Alternatively, if a thermal process is performed, the deposition temperature may be in the range of approximately 100°C to approximately 600°C.

[0210] Alternatively, the substrate may be heated to a temperature sufficient to obtain a desired gallium-containing oxide film having a desired physical state and composition at a sufficient growth rate. An exemplary, non-limiting temperature range in which the substrate may be heated includes room temperature to approximately 600°C. Preferably, the temperature of the substrate is maintained at 500°C or lower.

[0211] The ALD conditions within the chamber cause the disclosed film-forming composition, which is adsorbed or chemically adsorbed on the substrate surface, to react and form a film on the substrate. In some embodiments, the applicants believe that the energy required to react with the disclosed film-forming composition can be provided to the co-reactant by plasma treatment. When the co-reactant in such an exemplary ALD process is plasma treated, the exemplary ALD process becomes an exemplary PEALD process. The co-reactant may be plasma treated before or after being introduced into the chamber.

[0212] The film-forming composition and co-reactants may be introduced sequentially into the reactor (ALD). The reactor may be purged with an inert gas between the introduction of each of the film-forming composition, any additional precursor, and co-reactants. Another example is to introduce the co-reactants sequentially and the film-forming composition by pulse while sequentially activating the co-reactants with plasma, provided that the film-forming composition and the unactivated co-reactants do not substantially react under chamber temperature and pressure conditions (CW PEALD).

[0213] Each pulse of the disclosed film-forming composition may be sustained for a period ranging 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 may also be pulsed into the reactor, and in such an embodiment, each pulse may be sustained for a period ranging 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 may be sprayed simultaneously from different sectors of a showerhead (without mixing the composition and the reactants), where a susceptor supporting multiple wafers is rotated below the showerhead (space ALD).

[0214] Depending on specific process parameters, deposition can occur for varying lengths of time. Generally, deposition can be continued as long as needed to produce a film with the required properties. Typical film thicknesses can vary from a few angstroms to hundreds of micrometers, and typically from 1 nm to 100 nm, depending on the specific deposition process. The deposition process can also be performed multiple times as needed to obtain the desired film.

[0215] A disclosed method for forming a gallium-containing oxide layer on a substrate comprises the steps of placing the substrate in a reactor, delivering vapor of the disclosed gallium-containing film-forming composition into the reactor, and contacting / adsorbing the vapor with the substrate (and typically directing the vapor toward the substrate) to form a gallium-containing oxide layer on the surface of the substrate. Alternatively, a disclosed method for forming a gallium-containing oxide layer on a substrate comprises the steps of 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 surface of the substrate.

[0216] After the vapor of the gallium-containing film-forming composition is generated, it is introduced into a reaction chamber containing a substrate. The temperature and pressure within the reaction chamber and the temperature of the substrate are maintained under conditions suitable for vapor deposition of at least a portion of the disclosed gallium precursor on the substrate. In other words, after the vaporized composition is introduced into the reaction chamber, the conditions within the reaction chamber are adjusted so 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 "at least a portion of the gallium precursor is deposited" means that some or all of the precursor reacts with the substrate or adheres to the substrate. In this invention, a co-reactant may also be used to aid in the formation of the gallium-containing oxide layer.

[0217] The disclosed film-forming composition and co-reactant may be introduced into the reactor simultaneously (CVD), sequentially (ALD), or in various combinations thereof. The reactor may be purged with an inert gas (e.g., N2He, 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 may be mixed together to form a co-reactant / compound mixture, which is then introduced into the reactor in the form of a mixture. Another example is to introduce the co-reactant sequentially and the disclosed film-forming composition by pulse (pulse CVD).

[0218] In a non-limiting exemplary ALD process for forming a gallium oxide film (binary film), the vapor phase of the disclosed film-forming composition, e.g., (NMe2)2Ga(EtNCH2CH2NMe2), is introduced into a reactor, where it comes into contact with a suitable substrate and is chemically or physically adsorbed thereon. Subsequently, excess composition may be removed from the reactor by purging and / or evacuating the reactor, that is, 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 a high vacuum and / or a carrier gas curtain. A co-reactant, e.g., O3, is introduced into the reactor, where it reacts with the film-forming composition adsorbed in the reactor 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 of the desired thickness is obtained, thereby providing the desired film thickness. By alternately providing a gallium film-forming composition and a co-reactant, a film of a desired composition and thickness can be deposited.

[0219] Alternatively, if the desired indium-containing film contains three elements, such as InGaO and ZnGaO (ternary film), a step of introducing vapor of an additional precursor compound into the reactor may be inserted into the two-step process (e.g., forming a gallium oxide film) (three-step process). The additional precursor compound will be selected based on the properties of the film to be deposited. The additional elements may 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 used, the resulting film deposited on the substrate contains gallium and co-reactants along with the additional elements. If the additional precursor and the gallium precursor are used in more than one ALD supercycle sequence, a nanolaminate film is obtained. After being introduced into the reactor, the additional precursor compound comes into contact with or is adsorbed onto the substrate. Afterward, any excess precursor compound is removed from the reactor by purging and / or evacuating the reactor. Depending on process requirements, a co-reactant, such as O2, or additional precursor 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 stage of the cycle, any remaining co-reactant or precursor may be introduced into the reactor and the excess is removed by purging and / or evacuating the reactor. The entire 3-step process can be repeated until the desired film thickness is achieved. By alternately providing the gallium film-forming composition, additional precursor compound, and co-reactant, a film of the desired composition and thickness can be deposited.

[0220] In one embodiment, the additional precursor may be an indium precursor. The indium precursor may be selected from any non-spontaneous, liquid, halide-free indium molecule having a vapor pressure of 1 torr at less than 100°C, preferably 1 torr at less than 80°C. The indium precursor may be selected from trialkyl indium, sec-pentyl-cyclopentadienyl indium, and iso-pentyl-cyclopentadienyl indium. Preferably, the indium precursor is iso-pentyl-cyclopentadienyl indium.

[0221] In an alternative embodiment, the additional precursor may be a zinc precursor. The zinc precursor may be selected from any non-spontaneous, liquid, halide-free zinc molecule having a vapor pressure of 1 torr at less than 100°C, preferably 1 torr at less than 80°C. The zinc precursor may be selected from diethyl zinc-tetramethylethylenediamine adduct (TMEDA), diethyl zinc-tetraethylethylenediamine adduct (TEEDA), diethyl zinc-N,N'-diethyl-N,N'-diethyl-ethylenediamine adduct, diethyl zinc-N,N-dimethyl-N',N'-diethylethylenediamine adduct, and diethyl zinc-N,N,N'-trimethyl-N'ethylethylenediamine adduct. Preferably, the zinc precursor is diethyl zinc-tetraethylethylenediamine adduct (TEEDA).

[0222] The disclosed gallium precursor has a vapor pressure closer to that of indium and zinc precursors than that of conventional gallium precursors, such as TDMAGa and Ga(NMe2)3.

[0223] Alternatively, if the desired gallium-containing oxide film contains four elements, such as InGaZnO (IGZO) (quaternary film), a step of introducing vapor of another additional precursor compound into the reactor may be inserted into the 3-step process (4-step process). The other additional precursor compound will be selected based on the properties of the film to be deposited. The additional elements may include N, S, P, Sn, As, Sb, In, Zn, and mixtures thereof. When another additional precursor compound is used, the resulting film deposited on the substrate contains gallium along with three additional elements. When two additional precursors and a gallium precursor are used in more than one ALD supercycle sequence, a nanolaminate film is obtained. In the case of an IGZO film, along with the co-reactant O3, the precursor may include a gallium precursor, e.g., (NMe2)2Ga(EtNCH2CH2NMe2), an indium precursor, e.g., In(iso-pentyl-cyclopentadienyl), and a Zn precursor, e.g., diethylzinc-TEEDA. By alternately providing the gallium film-forming composition, additional precursors, another additional precursor, and co-reactant, a film of the desired composition and thickness can be deposited. Likewise, after exposure, the excess composition or precursor can be removed from the reactor by purging and / or evacuating the reactor, that is, 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 a high vacuum and / or a carrier gas curtain.

[0224] The gallium oxide film produced from the process discussed above is Ga x O y(x=0.5 to 1.5, y=0.5 to 1.5), InZnO (IZO), InGaZnO (IGZO), or a combination thereof, or a pure gallium oxide layer may be included. 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 appropriate selection of the film-forming composition and the co-reactant. The disclosed method may be useful for the manufacture of semiconductor materials, for example, the gallium-containing oxide may act as a semiconductor material to form heterojunctions with p-InP, n-GaAs, n-Si, and other materials.

[0225] The disclosed gallium precursor has a vapor pressure closer to that of additional precursors and other additional precursors than that of existing gallium precursors, such as TDMAGa and Ga(NMe2)3.

[0226] Once the desired film thickness is obtained, the film may undergo additional processes such as thermal annealing, furnace-annealing, rapid thermal annealing, UV, e-beam curing, and / or plasma gas exposure. Those skilled in the art recognize the systems and methods used to perform these additional processing steps. For example, the IGZO film may be exposed to a temperature in the range of approximately 100°C to approximately 1000°C for a time in the range of approximately 0.1 seconds to approximately 7200 seconds under an inert atmosphere, an O-containing atmosphere, and a combination thereof. Most preferably, the temperature range is 350°C to 450°C for 3600 to 7200 seconds under an inert atmosphere or an O-containing atmosphere. The resulting film may contain fewer impurities, and thus its density may be improved, which may lead to improved leakage current. The annealing step may be performed in the same reaction chamber where the deposition process is carried out. Alternatively, the substrate can be removed from the reaction chamber, and an annealing / flash annealing process is performed in a separate device. While any of the above post-treatment methods are effective in reducing carbon and nitrogen contamination of the IGZO film, thermal annealing has been found to be particularly effective. This consequently tends to improve the resistivity of the film.

[0227] After annealing, a film deposited by any disclosed process may have a bulk resistivity of approximately 50 μohm·cm to approximately 1,000 μohm·cm at room temperature. Room temperature is 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 typically measured at room temperature for a film with a thickness of approximately 50 nm. Bulk resistivity typically increases as the film becomes thinner due to changes in the electron transport mechanism. Bulk resistivity also increases with higher temperatures.

[0228] Examples

[0229] The following non-limiting embodiments are provided to further illustrate embodiments of the present invention. However, the embodiments are not intended to be all-encompassing, nor are they intended to limit the scope of the invention as described herein.

[0230] Thermogravimetric (TG) analysis was performed in an open aluminum cup at atmospheric pressure (1000 mBar, N2220 sccm) or vacuum (20 mBar, N220 sccm) from 25°C to 500°C. Vapor pressure (VP) was determined by TG analysis. Bisalkylamino(trialkyldiamino)gallium complexes can be prepared by the reported method and by varying the required diamine ligand (see reference ["Monomeric Chelated Amides of Aluminum and Gallium: Volatile, Miscible Liquid Precursors for CVD", ST Barry, RG Gordon and VA Wagner, MRS Proceedings, 606, 1999, 83]). (NMe2)2Ga(EtNCH2CH2NMe2) is liquid at room temperature. In contrast, TDMAGa as a reference material is solid at room temperature (melts at approximately 110°C).

[0231] Thermogravimetric analysis of two identical compounds Fig. 1It is available in. (NMe2)2Ga(EtNCH2CH2NMe2) can be observed to have the highest volatility, as the evaporation of this product is the fastest prior to TDMAGa. Additionally, the residual amount after evaporation was lower for (NMe2)2Ga(EtNCH2CH2NMe2), which may be an indication of higher thermal stability. Such characteristics are very important not only when considering the possible expansion of the ALD window but also when considering the inevitable need to heat the molecule for an extended period during use without any decomposition being observed. These TGA results indicate that (NMe2)2Ga(EtNCH2CH2NMe2) may behave better than TDMAGa in this regard. Fig. 2 This is a DSC comparison of TDMAGa and (NMe2)2Ga(EtNCH2CH2NMe2).

[0232] Example 1

[0233] Table 1 This summarizes some of the characteristics of the major molecules used in IGZO gas phase deposition, including TDMAGa, triethyl gallium (TEGa), (NMe2)2Ga (EtNCH2CH2NMe2), trimethyl indium (TMIn), and diethyl zinc (DEZn). TDMAGa has a much lower vapor pressure than other precursors. However, this has the advantage of not being spontaneously combustible. (NMe2)2Ga (EtNCH2CH2NMe2) is also non-spontaneous, but its vapor pressure is much higher than that of TDMAGa, and it is liquid, which will facilitate the use of the molecule and lower the costs associated with its use.

[0234] [Table 1]

[0235]

[0236] Prediction Example 1. Gallium oxide film deposited using (NMe2)2Ga(EtNCH2CH2NMe2) by CVD

[0237] A 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, but any other temperature may be used. Vapor of the gallium precursor (NMe2)2Ga(EtNCH2CH2NMe2) is transported to a reaction chamber using an inert carrier gas, N2 or Ar, or any other gas, although this is not always necessary. An oxygen source, in this case ozone, is simultaneously introduced into the reaction chamber. Any other oxygen source, such as oxygen or water, or a mixture of sources may be considered. A wafer or wafer piece, or any substrate, is placed in the reaction chamber, and the reaction chamber is heated to 200 to 300°C, but any other temperature may be considered. The pressure inside the reaction chamber is set to 0.1 to 10 torr, but any other pressure may be considered. A gallium oxide film is formed by reacting the vapor of (NMe2)2Ga(EtNCH2CH2NMe2) with ozone on the surface of a heated substrate. The film has excellent purity with carbon and nitrogen levels below the detection limits of a measuring instrument (XPS). If ozone is replaced by another oxidizing agent, for example, O2 or H2O, or even if any two oxidizing agents are supplied together, a gallium oxide film of excellent purity can also be obtained.

[0238] Prediction Example 2. Gallium oxide film deposited using (NMe2)2Ga(EtNCH2CH2NMe2) by ALD

[0239] The container filled with (NMe2)2Ga(EtNCH2CH2NMe2) can be heated to increase and adjust its vapor pressure. The selected temperature 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 or Ar, or any other gas, although this is not always necessary. Ozone is used as the oxygen source. A wafer, wafer piece, or any substrate is placed in the reaction chamber and heated to 250°C. The deposition cycle is divided into four distinct stages. 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). Subsequently, the vapor of (NMe2)2Ga(EtNCH2CH2NMe2) is purged from the reaction chamber using an inert gas, such as N2 or Ar (precursor purge pulse). Next, an oxygen source, ozone, is introduced into the reaction chamber and reacted with (NMe2)2Ga(EtNCH2CH2NMe2) on the surface of the wafer or substrate. Finally, the oxygen source is purged from the reaction chamber using an inert gas. Each of the four steps can last for tens of seconds or several seconds, depending on the instrument configuration, deposition pressure, deposition temperature, or other conditions. In this case, the precursor pulse was 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 to be obtained on superior instruments. Subsequently, the four-step cycle is repeated until the desired gallium oxide film thickness is obtained. For each deposition cycle, the gallium oxide growth is in the range of 0.5 to 1 Å. The obtained gallium oxide film has a low level of impurities, and the deposition on the patterned substrate has step coverage exceeding 90% in holes or trenches with an aspect ratio of up to 50:1.When oxygen or water is used instead of ozone, similar film characteristics are obtained, but it is necessary to adjust the respective pulse time and purge time.

[0240] Prediction Example 3. Indium gallium zinc oxide (IGZO) films were deposited using (NMe2)2Ga(EtNCH2CH2NMe2) by ALD.

[0241] Deposition is performed in a manner similar to Predicted Example 2, but two additional four-step cycles are added to deposit indium oxide and zinc oxide to form an InGaZnO film (IGZO). Any indium or zinc precursor, such as trimethylindium, triethylindium, diethylzinc, etc., may be used. In one exemplary embodiment, trimethylindium and diethylzinc may be used. Vapors of gallium, indium, and zinc precursors are introduced in a manner that starts with gallium followed by a repeating sequence of indium and zinc, but any other sequence may be used. To adjust the film composition, cycles using the same metal may be repeated several times before switching to the next metal cycle. Ozone, oxygen, and water (H2O) are the most common oxygen sources and are used in this embodiment, but any type of oxidizing agent may be used instead. Different oxidizing agents can be used to react with each metal (e.g., ozone with the gallium precursor and water with the indium precursor, as well as 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 by the ALD method at 200 to 250°C, but different temperature windows may be obtained depending on the use of different tools or different deposition conditions. The deposition rate is expected to be in the range of 1 to 2 Å per cycle (the entire cycle includes subcycles of gallium, indium, and zinc precursors). The obtained IGZO films have low levels of impurities, with carbon and nitrogen levels below the detection limits of analytical tools (XPS). Deposition on patterned substrates exhibits step coverage exceeding 90% in holes or trenches with an aspect ratio of up to 50:1.

[0242] Prediction Example 4. Indium gallium oxide films were deposited using (NMe2)2Ga(EtNCH2CH2NMe2) and In(iso-pentylcyclopentadienyl) by ALD.

[0243] Deposition is performed in a manner similar to Predicted Example 3, but indium (iso-pentyl-cyclopentadienyl) is used instead of trimethylindium or other indium precursors. Zinc precursors are not used. Vapors of (NMe2)2Ga(EtNCH2CH2NMe2) and indium (sec-pentyl-cyclopentadienyl) can be introduced in any order; to adjust the film composition, cycles using the same metal can be repeated several times before switching to the next metal cycle. Water was used as the oxygen source. It is possible to use different oxygen sources 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 the water purge time for both was set to 30 seconds. An indium-gallium-oxide film is obtained by ALD up to 250°C, and the deposition rate is in the range of 0.5 to 1.5 Å per cycle. The obtained film has a low level of impurities (below the detection limit of XPS), and the deposition on the patterned substrate exhibits step coverage exceeding 90% in holes or trenches with an aspect ratio of up to 50:1. Similar film characteristics are obtained when using ozone or oxygen instead of ozone, but the respective pulse time and purge time need to be adjusted.

[0244] Prediction Example 5. IGZO films were deposited by CVD using (NMe2)2Ga(EtNCH2CH2NMe2), In(isopentylcyclopentadienyl), and diethylzinc-TEEDA.

[0245] The vapor pressure of the precursors can be increased and adjusted by heating a container filled with (NMe2)2Ga(EtNCH2CH2NMe2), In (isopentylcyclopentadienyl), and diethylzinc-TEEDA. The selected temperature is often close to 1 torr, but any other temperature may be used. Since these three precursors have similar vapor pressures, they can be heated at the same temperature, and thus it is possible to place them together in the same oven. Subsequently, the vapors of the precursors as well as water are simultaneously supplied to the reaction chamber using an inert carrier gas, N2 or Ar, or any other gas (e.g., O2 in the case of water), although not always necessary. A wafer, wafer piece, or any substrate is placed in the reaction chamber and heated to 200 to 400°C, but any other temperature may be considered. The pressure inside the reaction chamber is set to 0.1 torr to 10 torr, but any other pressure may be considered. The vapors of the three precursors and water are reacted on the surface of the heated substrate to form an IGZO film. IGZO films have very high purity, with carbon and nitrogen levels below the detection limits of an analytical tool (XPS). When water is replaced by another oxygen source, for example, ozone (O3) or oxygen (O2), or even when any two oxygen sources are supplied together, IGZO films of high purity are also obtained.

[0246] Prediction Example 6. IGZO films were deposited by ALD using (NMe2)2Ga(EtNCH2CH2NMe2), In(iso-pentyl-cyclopentadienyl), and diethylzinc-TEEDA.

[0247] Deposition is performed in a manner similar to that in Predicted Example 3, but indium (iso-pentyl-cyclopentadienyl) and diethyl zinc-TEEDA are used as indium and zinc precursors instead of trimethyl indium and diethyl zinc. Vapors of (NMe2)2Ga(EtNCH2CH2NMe2), indium (iso-pentyl-cyclopentadienyl), and diethyl zinc-TEEDA can be introduced in any order; and to adjust the film composition, cycles using the same metal can 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 indium precursor pulse time and the zinc precursor pulse time, as well as the gallium precursor pulse time, are set to 4 seconds, the water pulse time for the three pulses of the metallic precursor is set to 2 seconds, and the three water purge times are set to 30 seconds. An IGZO film is obtained by an ALD method at a temperature of 250°C or higher, with a deposition rate in the range of 1 to 2 Å per cycle. The obtained film has a low level of impurities (below the detection limit of XPS), and the deposition on the patterned substrate exhibits step coverage exceeding 90% in holes or trenches with an aspect ratio of up to 50:1. When water is replaced by another oxygen source, such as ozone or oxygen, or even when any two oxygen sources are supplied together, an IGZO film of excellent purity is also obtained.

[0248] [Table 2]

[0249]

[0250] Table 2This is a comparison of the expected results of the reference process, Predicted Example 3, and Predicted Example 5, which demonstrates the advantages of the disclosed gallium precursor over existing ones. The disclosed gallium precursor is non-spontaneous, which will reduce costs by facilitating transportation, storage, and use. This also increases the maximum ALD window, thereby generally yielding better quality films. Furthermore, the disclosed gallium precursor is liquid at room temperature, which reduces process costs. It should be noted that tris(dimethylamino)gallium is another standard gallium precursor that can also be used in combination with trimethylindium and diethyl zinc. Although tris(dimethylamino)gallium is non-spontaneous, 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 advantages of the disclosed gallium precursor are much greater, as the use of low vapor pressure solid compounds is a substantial disadvantage in any process used for mass production. When indium and zinc precursors are replaced with non-spontaneous compounds having properties similar to gallium molecules, as in Predicted Example 6, there are much greater advantages in terms of safety and process results.

[0251] The subject matter of the claims described herein may be described in relation to exemplary embodiments for handling one or more computing application features / operations for a computing application having a user-interaction component, but the subject matter of the claims is not limited to these specific embodiments. Rather, the technology described herein may be applicable to any suitable type of user-interaction component execution management method, system, platform and / or device.

[0252] It will be understood that many additional modifications to the details, materials, steps, and arrangements of parts described and illustrated herein to illustrate the essence of the invention may be made by those skilled in the art within the principles and scope of the invention as set forth in the appended claims. Accordingly, the invention is not limited to the foregoing embodiments and / or specific embodiments of the accompanying drawings.

[0253] Although embodiments of the present invention have been presented 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 illustrative and non-limiting. Many variations and modifications of the composition and method are possible and are within the scope of the present invention. Accordingly, the scope of protection is not limited to the embodiments described herein, but is limited only by the following claims, which include all equivalents to the subject matter of the claims.

Claims

Claim 1 A method for depositing a gallium-containing oxide film on a substrate, the method comprising: a) exposing the substrate to vapor of a gallium-containing film-forming composition containing a gallium precursor and an oxidizing agent, either simultaneously or sequentially; and b) forming the gallium-containing oxide film on the substrate by depositing at least a portion of the gallium precursor onto the substrate through a vapor deposition process, wherein the gallium precursor is [Chemical Formula I](NR 8 R 9 )(NR 1 R 2 )Ga[(R 3 R 4 N)C x (R 5 R 6 )(NR 7 )][Chemical Formula II](Cy-N)2Ga[(R 3 R 4 N)C x (R 5 R 6 )(NR 7 )] and corresponding structure: [Chemical Formula I] [Chemical Formula II] Having, among 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; provided that R 1 , R 2 , R 3 , R 4 , R 8 , R 9 If each is Me, R 5 , R 6 is not H, and 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 refers to a saturated N-containing ring or an unsaturated N-containing ring; and the N-containing ring comprises at least one nitrogen atom and 4 to 6 carbon atoms within one chain, method. Claim 2 The method according to claim 1, wherein the gallium precursor comprises (NMe2)2Ga(EtNCH2CH2NEt2), (NEtMe)2Ga(EtNCH2CH2NMe2), (NEtMe)2Ga(EtNCH2CH2NEt2), (NEt2)2Ga(EtNCH2CH2NMe2), and (NEt2)2Ga(EtNCH2CH2NEt2). Claim 3 In paragraph 1, x is 2, method. Claim 4 In claim 1, a1) in step a), simultaneously or sequentially, the substrate is a first metal (M 1 ) by exposing to the vapor of the precursor, the first metal (M) through a vapor deposition process 1 A step of forming a gallium-containing oxide film on a substrate by depositing at least a portion of a precursor and at least a portion of the gallium precursor onto the substrate, wherein the gallium-containing oxide film is M 1 A method further comprising the step of a GaO film. Claim 5 In paragraph 4, a2) in step a1), simultaneously or sequentially, the substrate is a second metal (M 2 ) by exposing to the vapor of the precursor, the second metal (M) through a vapor deposition process 2 At least a portion of the precursor, at least a portion of the gallium precursor, and the first metal (M 1 ) A step of forming a gallium-containing oxide film on the substrate by depositing at least a portion of the precursor onto the substrate, wherein the gallium-containing oxide film is M 1 M 2 The step of being a GaO film is further included, and the first metal (M 1 The ) precursor is an indium precursor and the second metal (M 2 The ) precursor is a zinc precursor, or the first metal (M 1 The ) precursor is a zinc precursor and the second metal (M 2 ) The precursor is an indium precursor, method. Claim 6 A method according to claim 5, wherein the indium precursor is selected from trialkyl indium, sec-pentyl-cyclopentadienyl indium, or iso-pentyl-cyclopentadienyl indium. Claim 7 The method of claim 5, wherein the zinc precursor is a diethyl zinc derivative selected from diethyl zinc-tetramethylethylenediamine adduct (TMEDA), diethyl zinc-tetraethylethylenediamine adduct (TEEDA), diethyl zinc-N,N'-diethyl-N,N'-diethyl-ethylenediamine adduct, diethyl zinc-N,N-dimethyl-N',N'-diethylethylenediamine adduct, or diethyl zinc-N,N,N'-trimethyl-N'ethylethylenediamine adduct. Claim 8 A method according to any one of claims 1 to 7, wherein the melting point of the gallium precursor is less than 60°C. Claim 9 Gallium-containing quaternary oxide (M) on a substrate 1 M 2 A method for depositing a GaO film, wherein the method a) simultaneously or sequentially deposits the substrate with a gallium precursor, a first metal (M 1 ) precursor, second metal (M 2 ) a step of exposing a gallium-containing film-forming composition containing a precursor and an oxidizing agent to vapor; and b) at least a portion of the gallium precursor, the first metal (M) through 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 The method includes a step of forming GaO), wherein the gallium precursor is [Chemical Formula I](NR 8 R 9 )(NR 1 R 2 )Ga[(R 3 R 4 N)C x (R 5 R 6 )(NR 7 )][Chemical Formula II](Cy-N)2Ga[(R 3 R 4 N)C x (R 5 R 6 )(NR 7 )] and corresponding structure: [Chemical Formula I] [Chemical Formula II] Having, among 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; provided that R 1 , R 2 , R 3 , R 4 , R 8 , R 9 If each is Me, R 5 , R 6 is not H, and 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 refers to a saturated N-containing ring or an unsaturated N-containing ring; and the N-containing ring comprises at least one nitrogen atom and 4 to 6 carbon atoms within one chain, method. Claim 10 In claim 9, the gallium precursor comprises (NMe2)2Ga(EtNCH2CH2NEt2), (NEtMe)2Ga(EtNCH2CH2NMe2), (NEtMe)2Ga(EtNCH2CH2NEt2), (NEt2)2Ga(EtNCH2CH2NMe2) and (NEt2)2Ga(EtNCH2CH2NEt2). Claim 11 In Paragraph 9, x is 2 people, method. Claim 12 In claim 9, the above-mentioned first metal (M 1 The ) precursor is an indium precursor and the second metal (M 2 The ) precursor is a zinc precursor, or the first metal (M 1 The ) precursor is a zinc precursor and the second metal (M 2 ) The precursor is an indium precursor, method. Claim 13 In claim 12, the method wherein the indium precursor is selected from trialkyl indium, sec-pentyl-cyclopentadienyl indium, or iso-pentyl-cyclopentadienyl indium. Claim 14 The method of claim 12, wherein the zinc precursor is a diethyl zinc derivative selected from diethyl zinc-tetramethylethylenediamine adduct (TMEDA), diethyl zinc-tetraethylethylenediamine adduct (TEEDA), diethyl zinc-N,N'-diethyl-N,N'-diethyl-ethylenediamine adduct, diethyl zinc-N,N-dimethyl-N',N'-diethylethylenediamine adduct, or diethyl zinc-N,N,N'-trimethyl-N'ethylethylenediamine adduct. Claim 15 A method according to any one of claims 9 to 14, wherein the melting point of the Ga precursor is less than 60°C. Claim 16 A method for depositing an indium gallium zinc oxide (IGZO) film on a substrate, the method comprising: a) exposing the substrate to a vapor of a gallium-containing film-forming composition containing a gallium precursor, an indium precursor, a zinc precursor, and O3, either simultaneously or sequentially; and b) forming the IGZO film on the substrate by 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 onto the substrate through a vapor deposition process, wherein the gallium precursor is [Chemical Formula I](NR 8 R 9 )(NR 1 R 2 )Ga[(R 3 R 4 N)C x (R 5 R 6 )(NR 7 )][Chemical Formula II](Cy-N)2Ga[(R 3 R 4 N)C x (R 5 R 6 )(NR 7 )] and corresponding structure: [Chemical Formula I] [Chemical Formula II] Having, among 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; provided that R 1 , R 2 , R 3 , R 4 , R 8 , R 9 If each is Me, R 5 , R 6 is not H, and 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 refers to a saturated N-containing ring or an unsaturated N-containing ring; and the N-containing ring comprises at least one nitrogen atom and 4 to 6 carbon atoms within one chain, method. Claim 17 In Paragraph 16, x is 2 people, method. Claim 18 In paragraph 16, the method wherein the indium precursor is iso-pentyl-cyclopentadienyl indium. Claim 19 In paragraph 16, the zinc precursor is a diethyl zinc-tetraethylethylenediamine adduct (TEEDA), method. Claim 20 A method according to any one of claims 16 to 19, wherein the melting point of the Ga precursor is less than 60°C. Claim 21 delete Claim 22 delete Claim 23 delete Claim 24 delete Claim 25 delete Claim 26 delete Claim 27 delete Claim 28 delete Claim 29 delete Claim 30 delete Claim 31 delete Claim 32 delete Claim 33 delete Claim 34 delete Claim 35 delete Claim 36 delete Claim 37 delete

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