Novel sterically hindered chelate ligands for metal-containing film deposition and their corresponding organometallic complexes

Abstract

A ligand L capable of forming a coordination complex with at least one metal atom, having the general formula: N(R1R2)-C(R3R4)-C(R5R6)-N(R7)-CH2-C(CR8R9R 10 A ligand L having a ═O. The present disclosure describes the use of L to form a coordination metal complex ML with a metal M. The present disclosure describes the use of ML for vapor deposition processes.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims priority to U.S. Patent Application No. 63 / 407,325, filed on 16 September 2022, the entire contents of which are incorporated herein by reference.

[0002] Organometallic complexes for depositing metal-containing films, particularly for use in the manufacture of semiconductors and battery electrodes. [Background technology]

[0003] Lithium-containing thin films are well known for their use as surface coating layers for electrode materials in lithium-ion batteries. Examples of lithium-containing thin films include lithium phosphate (LiPO), lithium oxynitride phosphate (LiPON), lithium borate, lithium borate, lithium fluoride, lithium fluoride metal, lithium metal oxides such as lithium niobate, lithium titanate, and lithium zirconate. For some of these materials, particularly lithium niobate, lithium titanate, and lithium zirconate, the absence of silicon is preferable.

[0004] During the first cycle of a lithium-ion battery, the decomposition of the electrolyte at the electrolyte / electrode interface leads to the formation of a solid electrolyte interface (SEI) on the anode and / or cathode. Capacity loss in the lithium-ion battery occurs due to the consumption of lithium. Furthermore, the formed SEI layer is non-uniform and unstable, potentially causing cracking and dendrite formation, leading to thermal runaway. In addition, the SEI layer also forms a barrier potential, making intercalation to the electrodes more difficult.

[0005] Surface coating of electrodes using deposition techniques such as ALD or CVD is the first-choice method for forming a intended solid electrolyte interface thin film, thereby avoiding the formation of unstable layers. As a result, the decomposition of some electrolyte components is significantly reduced, and the dissolution of transition elements from the cathode material, such as manganese, is also avoided. Deposition techniques are suitable for depositing very thin, conformal films with the above advantages without the drawbacks of reduced ionic conductivity and electrical conductivity. Lithium-containing thin films are very promising candidates as protective electrode coatings due to their excellent conductivity and high electrochemical stability.

[0006] Another important application of lithium-containing thin films is the formation of solid electrolyte materials used in solid-state batteries. Solid-state batteries are solvent-free systems with longer lifespans, shorter charging times, and higher energy density than conventional lithium-ion batteries. Preventing the loss of elements in the solid electrolyte, particularly sulfur, is crucial for long-term performance. Solid electrolyte materials are highly sensitive to air and moisture, requiring protective layers to improve performance and scalability. These are considered the next technological stage in battery development. By the same logic, solid microbatteries are being implemented in electronic circuits. Lithium-containing thin-film solid electrolytes such as lithium phosphate, lithium borate, and lithium borate are deposited by ALD / CVD technology. Even in complex structures like 3D batteries, uniform and conformal lithium-containing thin films can be obtained.

[0007] The deposition of a film / coating containing a metal (e.g., Li) requires that the chemical precursor is a) thermally stable enough and b) volatile enough, i.e., c) capable of depositing the metal by a deposition mechanism. The deposition mechanism can be thermal, chemical, surface-catalyzed, or other routes. For the deposition of an alloy or composite film, often two or more chemical precursors that can be used in compatible conditions are required. Co-reactants such as oxidizing or reducing agents are also often needed, which significantly improve the deposition process. Identifying metal-containing chemical precursors that meet these and other processing / application requirements is an ongoing challenge. Deposition onto semiconductor and electrode materials can have significantly different process limitations and criteria, such as temperature and total thermal exposure limits (“thermal budget”).

[0008] N,N,O-tridentate ligands for metals such as lithium have been characterized in the field of catalysis. See, for example, Lu, Wei-Yi, et al. “Synthesis, characterization, and catalytic activity of lithium complexes bearing NNO-tridentate Schiff base ligands toward ring-opening polymerization of L-lactide.” Polymer 139 (2018): 1-10. These molecules are designed for use in catalytic reactions and are not suitable for deposition.

[0009] U.S. Patent Application Publication No. 20090136677A1 describes a group of tridentate β-ketoiminato molecules suitable for use as deposition precursors. [Chemical formula]

[0010] R4 is a C3-10 branched alkylene bridge having at least one chiral carbon atom. This ligand is limited to use with metals having two or more valences and thus cannot be used with alkali metals such as Na, K, or Li.

[0011] Several lithium precursors are known, and their deposition properties have been evaluated. Haemaelaeinen, Jani, et al. “Lithium phosphate thin films grown by atomic layer deposition.” Journal of The Electrochemical Society 159.3(2012):A259. https: / / iopscience.iop.org / article / 10.1149 / 2.052203jes. The two lithium precursors whose properties have been most clearly defined are lithium tert-butoxide (LiO2). t Bu) and lithium hexamethyldisilazide [LiHMDS, also known as lithium bis(trimethylsilyl)amide]. LiO t In Bu, the formation of high-quality films stops at 200°C, and in LiHMDS, it stops at 250°C.

[0012] LiO t Bu has a very low vapor pressure even at the highest possible temperatures, and it cannot achieve the desirable vapor pressure of 1 torr or higher. Sonsteby, Henrik H., et al. "tert-butoxides as precursors for atomic layer deposition of alkali metal containing thin films." Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films 38.6 (2020): 060804.

[0013] LiHMDS produces deposit materials with both silicon and carbon contamination well above 1%. Haemaelaeinen, Jani, et al. “Lithium phosphate thin films grown by atomic layer deposition.” Journal of The Electrochemical Society 159.3(2012):A259. [Overview of the project] [Problems that the invention aims to solve]

[0014] Ligands capable of forming lithium precursors that are more volatile and have a deposition temperature of less than 200°C are particularly needed. These lithium precursors are preferably capable of producing conformal, high-quality deposited films with good step coverage and low carbon and silicon content. [Means for solving the problem]

[0015] The present invention may be understood in relation to the following embodiments, which are presented in the form of numbered sentences: 1. A ligand L capable of forming a coordination complex with at least one metal atom, wherein the general formula is: N(R1R2)-C(R3R4)-C(R5R6)-N(R7)-CH2-C(CR8R9R 10 ) = O (Equation A), or N(R1R2)-C(R3R4)-C(R5R6)--C(R 11 R 12 )-N(R7)-CH2-C(CR8R9R 10 )=O (formula B) It has, Regarding formula A, SMILES formula: [R2]N(C([R3])([R4])C([R5])([R6])N(CC(C([R8])([R9])[R10])=O)[R7])[R1] has [ka] Structurally represented by, Regarding formula B, SMILES formula: [R2]N([R1])C([R4])(C([R6])(C([R11])([R12])N([R7])CC(C([R9])([R10])[R8])=O)[R5])[R3] has [ka] structurally represented by wherein R1 to R 12 are each independently selected from H, C1 - C4 alkyl (linear or branched when C3 or C4), or C1 - C4 alkylamino C1 - C4NR2, and R is each independently selected from H, C1 - C4 alkyl (linear or branched when C3 or C4), ligand L. 2.

Chemical formula

Chemical formula

[0016] To further understand the nature and purpose of the present invention, please refer to the following detailed description in conjunction with the accompanying drawings. In the drawings, similar elements are given the same or similar reference numerals. [Brief explanation of the drawing]

[0017] [Figure 1] Figure 1 shows the TGA results for Example 1. [Figure 2] Figure 2 shows the TGA results for Example 6. [Figure 3] Figure 3 shows the effect of temperature on the deposition rate in Example 7. [Figure 4] Figure 4 shows the effect of temperature on the refractive index of the deposited material in Example 7. [Figure 5] Figure 5 shows the effect of temperature on the atomic composition of the deposited material in Example 7. [Modes for carrying out the invention]

[0018] The inventors synthesized and tested novel tridentate N,N,O ligands for metals that form low-melting-point solids and possess excellent evaporability due to thermal stability and high volatility. These ligands make the metals to which they are coordinated suitable for vapor deposition. The ligand structure in one group of embodiments is represented by the following formula and structural expression. Formula A: N(R1R2)-C(R3R4)-C(R5R6)-N(R7)-CH2-C(CR8R9R 10 )=O [ka] SMILES expression: [R2]N(C([R3])([R4])C([R5])([R6])N(CC(C([R8])([R9])[R10])=O)[R7])[R1] Formula B: N(R1R2)-C(R3R4)-C(R5R6)--C(R 11 R 12 )-N(R7)-CH2-C(CR8R9R 10 )=O [ka] SMILES expression: [R2]N([R1])C([R4])(C([R6])(C([R11])([R12])N([R7])CC(C([R9])([R10])[R8])=O)[R5])[R3] R1~R 12 Each of the following is independently selected from H, C1-C4 alkyl (linear or branched in the case of C3 or C4), or C1-C4 alkylamino C1-C4NR2, and each of the following is independently selected from H, C1-C4 alkyl (linear or branched in the case of C3 or C4).

[0019] This new group of ligands can form tridentate chelate ligands ("L") with metal ions. In one preferred embodiment, the metal ("M") is an alkali metal (e.g., Na) that forms the chelate chemical ML. + and Li +These are monovalent metal ions such as ). Formula A1: [ka] SMILES expression: [R2][N@@]1([R1])C([R4])(C([R6])([N@]2([R7])C=C(O[M]12)C([R9])([R10])[R8])[R5])[R3] Formula B1: [ka] SMILES expression: [R2][N@]1([R1])[C@]([R4])([C@@]([R6])([C@@]([R11])([R12])[N@]2([R7])CC(C([R9])([R10])[R8])=[O][M]12)[R5])[R3]

[0020] However, the tridentate ligand L can isolate a metal with a higher valence on its own (M +x L x ) It can also be chelated, or combined with other metal ligands (D) to form heteroreptic coordinating metals (M +x L y D z ) can also form. For example, M is Ca +2 It can be chelated by two ligands L and Ca +2 It forms L2 (see Example X below), or is chelated with a different ligand to form D-Ca +2 -L can be formed.

[0021] Chemicals (ML) formed from monovalent metals and ligand L typically have a melting point below 150°C and are therefore low-melting-point solids. Preferred species have a melting point below 70°C. Liquid chemicals or low-melting-point solids that form liquids upon heating are preferred as chemical precursors in vapor deposition processes. Although sublimable solids are also used, handling and managing sublimable precursors are more complex and are often associated with greater loss of chemicals due to thermal decomposition.

[0022] Similarly, highly relevant to its use in the deposition process is the vapor pressure achievable with the chemical precursor. This parameter correlates with the rate and quality of the M-containing material being deposited. Vapor pressure generally shows an inverse trend to thermal stability. It is important to avoid using chemical precursors that cannot achieve sufficient vapor pressure without using temperatures that also cause significant thermal decomposition of the chemical precursor. These conflicting parameters are generally evaluated using thermogravimetric analysis ("TGA"). See, for example, ASTM E2008-17 (2021), Standard Test Methods for Volatility Rate by Thermogravimetry. In TGA evaluation of deposition precursors, the 50% point (T) where half of the chemical has evaporated is used. 50 ) and the perfect evaporation temperature (T) at which the weight of residual material does not decrease even when the temperature is further increased. full To define volatility, the temperature profile of the volatilization curve is evaluated. This is often done at both atmospheric pressure and vacuum (e.g., 15 torr) to represent two common deposition process conditions. TGA also allows for a simple assessment of thermal stability by the weight of the residual material that does not evaporate further as the temperature rises. Finally, by plotting the resulting vapor pressure against the temperature / weight curve, volatility, TGA, can be determined. 50 Furthermore, it is possible to evaluate the effects of the three parameters of thermal stability.

[0023] In the deposition process, T 50 Keep it as low as possible, and the temperature at which the vapor pressure of the chemical precursor reaches 1 torr ("T" 1torr It is preferable to keep the following as low as possible. In particular, a vapor pressure of 1 torr must be reached at the temperature at which thermal decomposition is least likely to occur (balancing this parameter is more difficult in sublimable solids).

[0024] Chemical substances formed from a monovalent metal and ligand L(ML) typically have a temperature of 150°C or lower and a temperature higher than their melting point. 1torr These same chemicals typically have a) a temperature of 250°C or less and a temperature higher than their melting point.50 , and b) exhibit excellent evaporation with TGA residue of less than 1% by weight.

[0025] Due to the above properties, the metal M that forms a complex with ligand L is particularly suitable for use in coating cathode electrode materials containing catalytic carbon support structures. Examples of catalytic carbon support structures include single-walled fullerenes (Ceo and C72), multi-walled fullerenes, single-walled or multi-walled nanotubes, nanohorns, and / or carbon support structures with densities of approximately 0.2 g / cm³ to approximately 1.9 g / cm³, such as special carbons like VULCAN or Imerys' SUPER C65.

[0026] Due to these aforementioned properties, the chemicals formed by the monovalent metal and ligand L(ML) are very suitable for use in deposition processes that require low temperatures due to the substrate's limitations on temperature and / or exposure to co-reactants. LiTHD and LiO t In Bu, a pressure of 1 Torr is obtained above 150°C, resulting in longer pulses and / or higher dep T, which negatively impacts many electrode materials in terms of exposure to absolute temperature and also in terms of the thermal budget of these materials. For example, cathode materials can undergo lattice changes, oxygen loss, compositional changes, etc., at high temperatures above 200°C. In deposited materials adversely affected by silicon contamination, ligand L provides a silicon-free chemical precursor that enables the deposition of M-containing films without Si contamination. This is advantageous over LiTMSO and LiHMDS, both of which produce silicon-contaminated deposits, which is particularly problematic at the lowest ALD temperatures available for these chemicals.

[0027] A metal M chelated with or otherwise coordinated to ligand L as described herein can be used as an M-source gas-phase precursor for vapor deposition of M-containing material on a substrate. Vapor deposition methods such as chemical vapor deposition and atomic layer deposition are well known in the art. The deposited material may also contain other co-reactants or other atoms from the gas-phase precursor. Common co-reactants are oxygen-source reactants, phosphorus-source reactants, and nitrogen-source reactants, which, depending on the vapor deposition process, may provide O, N, or P as dopants, or react with the M-L vapor-phase precursor to form oxides or nitrides of M, such as MOx, MNx, MONx, MPO, MPON, etc. Specific examples herein are LiNbOx and LiPOx, but many other materials are possible with different combinations of precursors and co-reactants. Those skilled in the art can select from a variety of known oxygen-source reactants, phosphorus-source reactants, and nitrogen-source reactants to design a vapor deposition process. Oxygen-source reactants include O2, O3, H2O, H2O2, NO, NO2, carboxylic acids, alcohols, diols, their radicals, and combinations thereof. Nitrogen-source reactants include N2, H2, NH3, hydrazines (N2H4, MeHNNH2, MeHNNHMe, etc.), organic amines (NMeH2, NETH2, NMe2H, NET2H, NMe3, NET3, (SiMe3)2NH, etc.), pyrazolines, pyridines, diamines (ethylenediamine, etc.), their radical species, and mixtures thereof. Phosphorus-source reactants include trimethyl phosphate (TMPO), diethyl phosphoramidate (DEPA), triethyl phosphate (TEPO), TMP, and combinations thereof. [Examples]

[0028] Example 1 - Synthesis [ka] Ligand synthesized by reacting O=C(tBu)CH2NMe(CH2)2NMe2 in a 1:1 ratio with HNMe[(CH2)2NMe2] in THF / ACN at 50-60°C using TEA, NMe2CO3, or NaHCO3. ¹H NMR (CDCl3, 400MHz): 3.412 (2H, br s), 2.488 (2H, t, 3J=7.7Hz), 2.327 (2H, t, 3J=7.7Hz), 2.247 (3H, br s), 2.147 (6H, br s), 1.060 (9H, br s)

[0029] This complex was prepared by reacting O=C(tBu)CH2NMe[(CH2)2NMe2] with BuLi, LiNH2, or LiH in hexane, pentane, or MTBE. Purification of the crude material by distillation yielded a white solid in 85% yield. Melting point = 68°C. 1H NMR (C6D6,400MHz):2.110(6H,br s),1.871(2H,q,3J=10.2Hz),1.625(2H,q,3J=10.2Hz),2.811 (1H,t,3J=11.9Hz),2.460(1H,t,3J=11.9Hz),2.345(3H,s),4.126(1H,s),1.369(9H,s)13C NMR(C6D6,101MHz):57.1,46.9,36.2,57.5,102.6,171.3,30.3,28.9.

[0030] TGA was performed under the following measurement conditions: sample weight 11.4 mg, closed cup in 1 atm of N2 (complete evaporation temperature 305°C); sample weight 10.4 mg, open cup in 1 atm of N2 (complete evaporation temperature T full =254℃); Sample weight 30.1 mg, open cup in 15 torr N2 (complete evaporation temperature T full (=178°C). The heating rate was set to 10.0°C / min. 50% evaporation TGA was performed using the open-cup TGA method in N2 at 1 atmosphere. 50 = 225℃.

[0031] These results are shown in the graph in Figure 1. As shown, Tfull Therefore, the residue is very small (less than 1% by weight).

[0032] Examples 2-5 - Additional Synthesis The same synthesis was performed using the following variations of Example 1. Example 2: The positions of R1, R2, and R7 are changed to ethyl acetate. • Example 3: Change the position of R7 to n-butyl. • Example 3: Change the position of R7 to ethyl. Example 5: M is Na

[0033] The synthesis of ML was carried out in the same manner as in Example 1, except that L had the different alkyl group described above. For M=Na, Na was supplied as NaNH2 for the formation of ML. Similar results were obtained in terms of yield and purity.

[0034] Example 6 - Exemplary M +2 Synthesis of L2 and M=Ca [ka] Synthesis: Na{OC(tBu)=CHN(Me)(CH2CH2NMe2)} was added to 0.5 equivalents of CaI2 in THF, stirred for 16 hours, filtered, and sublimated (120°C / 0.1 Torr). ¹H NMR (C6D6, 400MHz): 3.812 (2H, br s), 2.488 (4H, br dt), 2.327 (4H, br dt), 2.147 (6H, br s), 2.032 (12H, br s), 1.000 (19H, br s).

[0035] TGA measurements were performed under the following conditions: sample weight 6.2 mg, open cup in 1 atm of N2 (complete evaporation temperature 280°C), heating rate set to 10.0°C / min. 50% evaporation using the open cup TGA method in 1 atm of N2: T 50 =230℃ (See Figure 2).

[0036] Example 7 - LiPOx deposition on a substrate For atomic layer deposition (ALD) of a LiPOx film on a blank silicon wafer as a test substrate, the Li-OC(tBu)=CHNMe(CH2)2NMe2 from Example 1 was used as the Li source. Trimethyl phosphate (TMPO) is a standard phosphate source in the art that is used with conventional Li precursors. Therefore, TMPO was selected as the co-reactant.

[0037] Preliminary characterization: Li-OC(tBu)=CHNMe(CH2)2NMe2 undergoes thermal decomposition at 250°C. Therefore, to avoid parasitic CVD, the basic design for experimental parameter evaluation was performed at 200°C. Gradually increasing the pulse duration of both precursors resulted in self-terminating growth at 0.9 angstroms / cycle under the tested conditions (ozone as a co-reactant). This confirmed that the deposition at 200°C was an ALD process. • An oxygen source was necessary for LiPOx formation. Without ozone, ALD did not occur.

[0038] Subsequently, the effect of temperature on ALD of LiPOx was evaluated using experimental parameter design from preliminary tests at 200°C.

[0039] Experimental conditions: Reactor temperature: X℃ Reactor pressure: 1 torr Carrier N2: 80sccm Canister temperature: 110℃ Canister P:30torr Li bubbling FR N2:30 sccm TMPO Canister T: 80℃ TMPO Canister P:15torr P bubbling FR N2:30 sccm Substrate: Si (1% HF) Number of cycles: 150

[0040] Pulse conditions: Li-OC(tBu)=CHNMe(CH2)2NMe2(0.64sccm): 30 seconds Purge: 120 seconds TMPO(30sccm):15 seconds Purge: 30 seconds O3:5 seconds Purge: 30 seconds

[0041] As shown in Figures 3-5, the tested temperatures were 125, 150, 175, and 200°C. LiPOx deposited as a uniform continuous film within this temperature range.

[0042] As shown in Figure 3, the main difference was (as expected) the deposition rate, which was highest at 200°C. However, even at 125°C, a deposit 0.36 angstroms thick was formed in each ALD cycle. This is a commercially viable deposition rate. This is in contrast to the molecules of the conventional technology mentioned earlier, where deposition stops above 200°C.

[0043] Figure 4 shows that the refractive index of the deposited material remains stable across the entire temperature range and is close to that of Li3PO4 (RI 1.59).

[0044] Figure 5 shows atomic percentages, with silicon, N, and C all below the detection limit (less than 1%). Consistent with RI measurements, the composition of the deposited material is Li 2.8 PO 3.8 It is very similar to Li3PO4. This combination of low-temperature ALD, GPC rate, and composition represents a significant advance that enables LiPOx deposition on a variety of substrates where temperature / thermal budget is limited, particularly materials used in lithium-ion battery electrodes.

[0045] Good step coverage on non-uniform substrate surfaces is crucial for good electrode / cathode performance. This is because 1) thicker areas hinder Li ion transport, and 2) thinner areas cause TM losses (e.g., Mn migration from the cathode) and / or dendrite formation. To evaluate the applicability of this ALD process to non-uniform surfaces, a test Si wafer with trenches was used as the substrate. At an aspect ratio of 6.25, the step coverage was 87%. The maximum aspect ratio tested was 18. Even at this severe aspect ratio, the ALD layer was continuous. The step coverage at this dimension was 65%, suggesting that the ALD deposition process attenuates at very distant surfaces. Nevertheless, the minimum thickness achieved at the bottom of the trench was 14.9 nm, which is sufficient for many applications. For many applications, such as battery electrode materials, step coverage of less than 100% is acceptable. Further optimization of the parameters is expected to improve these results compared to these preliminary experiments.

[0046] Example 8 - Deposition of LiNbOx on a substrate As an example of diverse material deposition, we selected binary deposition of LiNbO3. Li-OC(tBu)=CHNMe(CH2)2NMe2 from Example 1 was used as the Li source precursor. For niobium, we selected tert-butylimidobis(diethylamide)mono(tert-butylalcoxo)niobium(V), a source precursor described in U.S. Patent No. 10106887B2. One reason for selecting tert-butylimidobis(diethylamide)mono(tert-butylalcoxo)niobium(V) was that it extended the ALD temperature window for NbOx deposition to at least 150°C. To balance the ALD windows of the Li and Nb source precursors with the GPC, we selected a temperature of 175°C. Similarly, for the preliminary evaluation, a blank silicon wafer was used as the substrate. The tested process conditions were as follows:

[0047] [Table 1]

[0048] The ALD cycle parameters are as follows:

[0049] [Table 2]

[0050] The Nb-ozone subcycle forms a layer of NbOx. The lithium precursor reacts with this NbOx to form LiNbOx material. The total deposition growth rate of LiNbOx is 0.68 angstroms. Pulse dose experiments confirmed that the formation of LiNbOx is a self-terminating ALD reaction. The stoichiometric ratio of the deposited material was approximately LiNbO2. This is consistent with the RI of the deposited material being 1.9, compared to 2.2 for LiNbO3. The deposition was further tested on a trenched silicon wafer. Step coverage was >99% even with an aspect ratio of 15. The deposited layer was continuous, and no gaps or visible defects were observed in slices scanned with an SEM. Further optimization of parameters (such as ozone addition) is expected to bring the atomic composition of the deposited material very close to that of LiNbO3, ultimately resembling the results obtained with LiPOx.

[0051] Example 9 - Exemplary M x LyDz synthesis: [ka] Synthesis: t BuN=NbCl3 was added to 2 equivalents of NaOEt and 1 equivalent of Li{OC(tBu)=CHN(Me)(CH2CH2NMe2)} in THF, and the mixture was stirred for 16 hours. The mixture was filtered and purified by distillation (110°C / 0.1 torr). 1H NMR(C6D6,400MHz):4.561ppm(4H,tm),4.002ppm(1H,s),2.610ppm(1H,t,3J=11.6Hz),2.334ppm(1H,d,2J=14.7Hz),2.382ppm(3H,s),2.108p pm(3H,s),1.975ppm(3H,s),1.323ppm(1H,d,3J=14.7Hz),1.239ppm(1H,t,3J=11.6Hz),1.163ppm(6H,m),1.108ppm(9H,s),1.006ppm(9H,s).

[0052] Example 9: Li-OC( t Composition of Bu)=CHN[(CH2)2OMe]2 [ka] A ligand synthesized by reacting O=C(tBu)CH2Cl and HN[(CH2)3NMe2]2 in a 1:1 ratio at 50-60°C in THF / ACN containing TEA, K2CO3, or NaHCO3. 1 H NMR(CDCl3,400MHz):2.144ppm(12H,s),2.193ppm(4H,t,3J=7.2Hz),1.541ppm( 1H,p,3J=7.2Hz),2.475ppm(4H,t,3J=7.2Hz),3.465ppm(2H,s),1.075ppm(9H,s)

[0053] This complex was prepared by reacting O=C(tBu)CH2N[(CH2)3NMe2]2 with BuLi, LiNH2, or LiH in hexane, pentane, or MTBE. Purification of the crude material by sublimation yielded a yellow solid (45%). ¹H NMR (C6D6, 400MHz): 4.155 ppm (¹H, br s), 2.495 ppm (⁴H, br s), 2.188 ppm (¹²H, br s), 2.1-2.3 ppm (⁴H, br m), 2.320 ppm (⁴H, br d, 3J=11.1Hz), 1.400 ppm (⁹H, br s) 13C NMR(C6D6,101MHz):173.6,98.8,70.6,58.4,57.9,36.4,29.3.

[0054] Example 10 - Li-OC( t Composition of Bu)=CHN[(CH2)2OMe]2 [ka] O=C( t Bu)CH2N[(CH2)3NMe2]2:TEA, in THF / ACN containing K2CO3 or NaHCO3, O=C( t A ligand synthesized by reacting Bu)CH2Cl and HN[(CH2)3NMe2]2 in a 1:1 ratio at 50-60°C. 1 H NMR(CDCl3,400MHz):2.144ppm(12H,s),2.193ppm(4H,t,3J=7.2Hz),1.541ppm( 1H,p,3J=7.2Hz),2.475ppm(4H,t,3J=7.2Hz),3.465ppm(2H,s),1.075ppm(9H,s)

[0055] This complex is formed in hexane, pentane, or MTBE with O=C( t Bu)CH2N[(CH2)3NMe2]2 was prepared by reacting it with BuLi, LiNH2, or LiH. The crude product was purified by sublimation to produce a yellow solid (45%). 1 H NMR(C6D6,400MHz):4.155ppm(1H,br s),2.495ppm(4H,br s),2.188ppm(12H,br s),2.1-2.3ppm(4H,br m),2.320ppm(2H,br d,3J=11.1Hz),1.400ppm(9H,br s). 13 C NMR(C6D6,101MHz):173.6,98.8,70.6,58.4,57.9,36.4,29.3.

[0056] Industrial applicability The present invention has at least industrial applicability with respect to chemical precursors suitable for use in the deposition of materials for semiconductor manufacturing or battery electrodes.

[0057] While the present invention has been described in relation to its specific embodiments, it will be apparent to those skilled in the art, based on the foregoing description, that many alternative, modified, and altered forms are obvious. Therefore, the present invention is intended to encompass all such alternative, modified, and altered forms that fall within the spirit and broad scope of the appended claims. The present invention may appropriately include, consist of, or essentially consist of the disclosed elements, and may be carried out without any undisclosed elements. Furthermore, where there are terms indicating order, such as first and second, they should be understood in an illustrative sense, not in a restrictive sense. For example, it may be recognized by those skilled in the art that certain steps can be combined into a single step.

[0058] All references identified herein are incorporated into this application by reference, not only in their entirety but also in their entirety, as each specifically cited.

[0059] Legal definitions and principles of interpretation The singular forms "a," "an," and "that" can refer to multiple objects unless the context clearly indicates a different meaning.

[0060] In the claims, “contains” is an open transitional clause. This means that the elements of the claims identified thereafter are a non-exclusive list (i.e., other things can be additionally included, and they remain within the scope of “contains”). As used herein, “contains” may be replaced with the more restrictive transitional clauses “essentially become from” and “consist of” unless otherwise indicated herein.

[0061] In patent claims, “to provide” is defined as to provide, supply, make available, or prepare something. Unless otherwise expressly stated in the claims, this process may be performed by any actor.

[0062] "Optional" or "optionally" means that the event or situation described thereafter may or may not occur. The description includes both cases where the event or situation occurs and where it does not.

[0063] In this specification, a range may be expressed as approximately one specific value and / or approximately another specific value. Where such a range is expressed, another embodiment should be understood as all combinations within the said range from that one specific value and / or another specific value.

[0064] Any reference in this specification to “one embodiment” or “a particular embodiment” means that certain functions, structures, or features described in relation to an embodiment may be included in at least one embodiment of the present invention. The phrase “in one embodiment” appearing in various parts of this specification does not necessarily refer to the same embodiment, nor is another or alternative embodiment necessarily mutually exclusive with other embodiments. The same applies to the term “implementation.”

[0065] In this specification, "about," "around," or "approximately" in the text or claims means ±10% of the stated value.

[0066] technical definition In this specification, "room temperature" in the text or claims means approximately 20°C to approximately 25°C.

[0067] The term "ambient conditions" means that the ambient temperature (i.e., ambient temperature) is approximately 20°C to 25°C, and the ambient pressure (ambient pressure) is approximately 1 atm or 1 bar.

[0068] The term "substrate" refers to one or more materials on which a process is performed. A substrate may also have one or more layers of different materials that have already been deposited in a previous manufacturing process.

[0069] Those skilled in the art will recognize that the terms “film” or “layer” as used herein refer to the thickness of any material laid or spread on a surface, which may be a trench or a line.

[0070] This specification uses standard abbreviations for elements in the periodic table. It should be understood that elements may be referred to by these abbreviations (for example, Si refers to silicon, N to nitrogen, O to oxygen, C to carbon, H to hydrogen, F to fluorine, etc.).

[0071] A unique CAS registry number (i.e., "CAS") assigned by the Chemical Abstract Service is provided to make the disclosed molecule more easily identifiable.

[0072] The aspect ratio of a geometric shape is the ratio of its size in different dimensional directions. In most cases, the aspect ratio is expressed as two integers (x:y) separated by a colon. The values ​​x and y represent the ratio of width to height, rather than the actual width and height. For example, 8:5, 16:10, and 1.6:1 are all ways of representing the same aspect ratio. Even for objects with more than two dimensions, such as a hypercube, the aspect ratio can be defined as the ratio of the longest side to the shortest side.

[0073] Conformability and step coverage both refer to the degree of variation in film thickness on a surface, particularly in topologically distinct regions of the surface. This is especially relevant to surfaces with microstructures having various aspect ratios. In the above example, perfect (100%) conformability means that there are no cusps and the top surface, trench sidewalls, and, where applicable, trench bottom are all the same thickness. When a single percentage of conformability is given, it is the minimum conformability measurement corresponding to the maximum relative thickness deviation of the entire film at two selected locations on the surface. The two locations may correspond to the location with the highest aspect ratio or to locations with a specific aspect ratio, such as 6:1 or less. Film thickness is evaluated by several methods, such as scanning electron microscopy of a cut substrate. A film is generally considered "conformable" if it has at least 20%, preferably at least 50%, conformability.

[0074] Many additional modifications to the details, materials, processes, and component arrangements described herein to illustrate the nature of the present invention will be understood to be possible by those skilled in the art within the principles and scope of the invention as expressed in the appended claims. Accordingly, the present invention is not limited to the specific embodiments shown above.

Claims

【Request Item 1】 【Chemistry 1】 The general formula that is structurally represented by: N(R1 R2) - C(R3 R4) - C(R5 R6) - N(R7) - CH2 - C(CR8 R9 R10) = O (Equation A), or 【Chemistry 2】 The general formula that is structurally represented by: N(R 1 R 2 )-C(R 3 R 4 )-C(R 5 R 6 )-C(R 11 R 12 )-N(R 7 )-CH 2 -C(CR 8 R 9 R 10 )=O (Formula B) Ligand L represented by the formula, wherein R1 to R12 are each independently selected from H, C1 to C4 alkyl (linear or branched in the case of C3 or C4) or C1 to C4 alkylamino C1 to C4 NR2, and R is each independently selected from H, C1 to C4 alkyl (linear or branched in the case of C3 or C4), and ligand L, 【Transformation 3】 A coordinating metal atom M is required to form a metal-containing chemical substance whose structure is represented by the following: A metal-containing chemical substance containing M, where M is selected from Li or Na.

2. The metal-containing chemical substance according to claim 1, wherein M is Li.

3. R ８ , R ９ and R １０ The metal-containing chemical substance according to claim 1, wherein each is independently selected from methyl or ethyl.

4. M is Li, and R ８ , R ９ and R １０ The metal-containing chemical substance according to claim 1, wherein each is independently selected from methyl or ethyl.

5. R ８ , R ９ and R １０ are each methyl, the metal-containing chemical substance according to claim 4.

6. R １ ~R ７ The metal-containing chemical substance according to claim 1, wherein each is independently selected from H, methyl, or ethyl.

7. R １ ~R ７ The metal-containing chemical substance according to claim 6, wherein each is independently selected from H or methyl. 【Request Item 8】 【Chemistry 4】 A metal-containing chemical substance according to claim 1, which is structurally represented as follows.

9. The metal-containing chemical substance according to claim 8, wherein M is Li.

10. A method for depositing a metal-containing film, a) A step of bringing a substrate into contact with the gas phase of a metal-containing chemical substance as described in claim 1, b) A step of forming a deposited material containing the metal from the metal-containing chemical substance on the substrate. A method that includes this.

11. The method according to claim 10, further comprising the step of exposing the substrate to the gas or gas phase of one or more additional reactants.

12. M is Li, and the deposited material is LiNboO ｘ The method according to claim 11, wherein the additional reactants include an oxygen source reactant and a niobium source reactant.

13. The method according to claim 11, wherein M is Li, the deposited material is LiPO or LiPON, and the additional reactants include an oxygen source reactant and a phosphorus source reactant, and for LiPON, the additional reactants further include a nitrogen source reactant.

14. The method according to claim 12 or 13, wherein the oxygen source reactant is ozone.

15. The niobium-based reactant is given by the following formula: 【Transformation 5】 (wherein M is Nb, and each R １ , R ２ , R ３ , R ４ , R ５ and R ６ (Independently selected from H, C1-C5 linear, branched or cyclic alkyl groups, C1-C5 linear, branched or cyclic alkylsilyl groups, C1-C5 linear, branched or cyclic alkylamino groups, or C1-C5 linear, branched or cyclic fluoroalkyl groups) The method according to claim 12, comprising a group 5 transition metal-containing chemical substance having one of the above or Nb(RCp)(NR2)2(=NR)(Formula III), or selected from tert-butylimidotris(diethylamide)niobium(V), tert-butylimidotris(dimethylamide)niobium(V), and tert-butylimidotris(ethylmethylamide)niobium(V) and combinations of the above.

16. The method according to claim 13, wherein the phosphorus source reactant is trimethyl phosphate (TMPO), diethyl phosphoramidate (DEPA), triethyl phosphate (TEPO), TMP, or a combination thereof.

17. The method according to claim 10, wherein step a) and / or step b) are carried out at a temperature higher than the melting point of the metal-containing chemical substance and 200°C or less.

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