Novel sterically hindered chelating ligands and their corresponding organometallic complexes for the deposition of metal-containing films.

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 TO RELATED APPLICATIONS This application claims priority to U.S. Patent Application No. 63 / 407,325, filed September 16, 2022, the entire contents of which are incorporated herein by reference.

[0002] Organometallic complexes for the deposition of 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 of electrode materials in lithium-ion battery applications. Examples of lithium-containing thin films include lithium phosphate (LiPO), lithium oxynitride phosphate (LiPON), lithium borate, lithium borophosphate, lithium fluoride, lithium metal fluoride, lithium metal oxides such as lithium niobate, lithium titanate, and lithium zirconate. For the formation of some of these materials, particularly lithium niobate, lithium titanate, and lithium zirconate, it is preferable that silicon is absent.

[0004] During the first cycle of a lithium-ion battery, the formation of a solid electrolyte interface (SEI) on the anode and / or cathode is observed due to decomposition of the electrolyte at the electrolyte / electrode interface. The capacity loss of a lithium-ion battery occurs due to lithium consumption. Furthermore, the formed SEI layer is non-uniform and unstable, potentially generating cracks and dendrites, leading to thermal runaway. Additionally, the SEI layer also forms a barrier potential that makes intercalation into the electrode more difficult.

[0005] Coating the surface of electrodes using deposition techniques such as ALD or CVD is the method of choice for forming a targeted solid electrolyte interfacial thin film and thereby avoiding the formation of unstable layers. As a result, the decomposition of some components of the electrolyte 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 that offer the above advantages without the drawbacks of reduced ionic and electrical conductivity. Lithium-containing thin films are very promising candidates for 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-state electrolyte materials for use in solid-state batteries. Solid-state batteries are solvent-free systems that offer longer lifespans, shorter charging times, and higher energy densities than conventional lithium-ion batteries. Preventing the loss of elements, especially sulfur, in the solid electrolyte is crucial for long-term performance. Solid-state electrolyte materials are highly sensitive to air and moisture, requiring protective layers to improve performance and scalability. These are considered the next technological step in battery development. Following the same logic, solid-state microbatteries are being implemented in electronic circuits. Lithium-containing thin-film solid electrolytes, such as lithium phosphate, lithium borate, and lithium borophosphate, are deposited by ALD / CVD techniques. Uniform and conformal lithium-containing thin films can be obtained even in complex structures such as 3D batteries.

[0007] Deposition of metal (e.g., Li)-containing films / coatings requires a) sufficiently thermally stable and b) sufficiently volatilizable chemical precursors, i.e., c) the metal can be deposited by a deposition mechanism. The deposition mechanism can be thermal, chemical, surface-catalyzed, or other routes. Deposition of alloy or composite films often requires two or more chemical precursors that can be used together under compatible conditions. Co-reactants, such as oxidizers or reductants, are often also required, significantly improving the deposition process. Identifying metal-containing chemical precursors that meet these and other processing / application requirements is an ongoing challenge. Deposition of semiconductor and electrode materials can have significantly different process limitations and criteria, such as temperature and total thermal exposure limits ("thermal budgets").

[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 vapor deposition.

[0009] US Patent Application Publication No. 20090136677A1 describes a family of tridentate β-ketoiminate molecules suitable for use as vapor deposition precursors. [ka]

[0010] R4 is a C3-10 branched alkylene bridge having at least one chiral carbon atom. This ligand is limited to use with metals with a valence of 2 or more, and therefore cannot be used with alkali metals such as Na, K, or Li.

[0011] Several lithium precursors are known and have been evaluated for their deposition performance. 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 best-characterized lithium precursors are lithium tert-butoxide (LiO t Bu) and lithium hexamethyldisilazide [LiHMDS, also known as lithium bis(trimethylsilyl)amide]. LiO t The formation of high quality films ceases at 200°C for Bu and 250°C for LiHMDS.

[0012] LiO t Bu has a very low vapor pressure even at the highest possible temperatures, making it impossible to achieve the desired 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 deposited materials with both silicon and carbon contamination significantly greater than 1%. Haemaelaeinen, Jani, et al. "Lithium phosphate thin films grown by atomic layer deposition." Journal of the Electrochemical Society 159.3 (2012): A259. Summary of the Invention [Problem to be solved by the invention]

[0014] There is a particular need for ligands capable of forming lithium precursors that are more volatile and have deposition temperatures below 200° C. These lithium precursors should preferably be 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 with reference to the following embodiments, presented in numbered sentence format: 1. 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 )=O (Formula A), or N(R1R2)-C(R3R4)-C(R5R6)--C(R 11 R 12 )-N(R7)-CH2-C(CR8R9R 10 )=O (formula B) and For formula A, the SMILES formula is: [R2]N(C([R3])([R4])C([R5])([R6])N(CC(C([R8])([R9])[R10])=O)[R7])[R1] have [ka] It is structurally represented by For formula B, the SMILES formula is: [R2]N([R1])C([R4])(C([R6])(C([R11])([R12])N([R7])CC(C([R9])([R10])[R8])=O)[R5])[R3] have [ka] It is structurally represented by In the formula, R1~R 12 are each independently selected from H, C1-C4 alkyl (linear or branched if C3 or C4), or C1-C4 alkylamino C1-C4NR2, and R are each independently selected from H, C1-C4 alkyl (linear or branched if C3 or C4). 2. [ka] and is represented structurally by the SMILES formula: [R2][N@@]1([R1])C([R4])(C([R6])([N@]2([R7])C=C(O[M]12)C([R9])([R10])[R8])[R5])[R3] or [ka] and is represented structurally by the SMILES formula: [R2][N@]1([R1])[C@]([R4])([C@@]([R6])([C@@]([R11])([R12])[N@]2([R7])CC(C([R9])([R10])[R8])=[O][M]12)[R5])[R3] The ligand L according to sentence 1, further comprising a coordinated metal atom M, wherein M is selected from Li, Na or K, to form a metal-containing chemical compound ML having the formula: 3. The metal-containing chemical according to paragraph 2, wherein M is Li. 4. R8, R9 and R 10 are each independently selected from methyl or ethyl. 5. M is Li, and R, R and R 10 are each independently selected from methyl or ethyl. 6. R8, R9 and R 10 and each is methyl. 7. The ligand according to sentence 1 or the metal-containing chemical according to sentence 2, wherein R1 to R7 are each independently selected from H, methyl, or ethyl. 8. The metal-containing chemical according to sentence 7, wherein R1-R7 are each independently selected from H or methyl. 9. [ka] Structurally represented as, and in SMILES form: CC(C)(C)C1=C[N@@]2(C)CC[N](C)(C)[M]2O1 10. The metal-containing chemical substance of claim 2, wherein 10. The metal-containing chemical according to paragraph 9, wherein M is Li. 11. The metal-containing chemical according to paragraph 2, wherein M is a polyvalent metal and two or more ligands L are coordinated to M. 12. The metal-containing chemical according to paragraph 11, wherein M is selected from calcium, magnesium, strontium, and barium. 13. M is a polyvalent metal, and two or more ligands are coordinated to M, and M has one or more ligands L and one or more additional different ligands D to form a heteroleptic molecule M. x 3. The metal-containing chemical of paragraph 2, which forms LyDz, and where x≧2, y≧1, and z≧1. 14. The metal-containing chemical according to paragraph 13, wherein M is selected from niobium, tantalum, vanadium, zirconium, hafnium, titanium, tungsten, molybdenum, chromium, cobalt, nickel, copper, manganese, and zinc. 15. The metal-containing chemical according to paragraph 13, wherein M is niobium. 16. A method for depositing a metal-containing film, comprising: a) contacting a substrate with the vapor phase of a metal-containing chemical according to any one of sentences 1 to 15; b) forming a deposited material on the substrate that includes a metal from the metal-containing chemical; A method comprising: 17. The method of paragraph 16, further comprising exposing the substrate to a gas or vapor phase of one or more additional reactants. 18.M is Li and the deposited material is LiNbO x and the one or more additional reactants comprise an oxygen source reactant and a niobium source reactant. 19. The method of sentence 17, wherein M is Li, the deposited material is LiPO, and the one or more additional reactants include an oxygen source reactant and a phosphorus source reactant. 20. The method of sentence 17, wherein M is Li, the deposited material is LiPNO, and the one or more additional reactants include an oxygen source reactant, a nitrogen source reactant, and a phosphorus source reactant. 21. The method of paragraphs 18, 19 or 20, wherein the oxygen source reactant is selected from ozone, hydrogen peroxide, oxygen, water, methanol, ethanol, isopropanol, nitric oxide, nitrogen dioxide, nitrous oxide, carbon monoxide, carbon dioxide and combinations thereof. 22. The method of paragraphs 18, 19, or 20, wherein the oxygen source reactant is ozone. 23. The niobium source reactant has the formula: [ka] (wherein M is Nb, and each R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently selected from H, a C1-C5 linear, branched or cyclic alkyl group, a C1-C5 linear, branched or cyclic alkylsilyl group, a C1-C5 linear, branched or cyclic alkylamino group, or a C1-C5 linear, branched or cyclic fluoroalkyl group. 19. The method of claim 18, wherein the Group 5 transition metal-containing chemical has one of the following: 24. The method of paragraph 18, wherein the niobium source reactant comprises tert-butylimidobis(diethylamido)mono(tert-butylalkoxo)niobium(V), tert-butylimidomono(diethylamido)bis(tert-butylalkoxo)niobium(V), and combinations thereof. 25. The method of paragraph 18, wherein the niobium source reactant is selected from the known group of tert-butylimidotris(diethylamido)niobium(V), tert-butylimidotris(dimethylamido)niobium(V), tert-butylimidotris(ethylmethylamido)niobium(V) or Nb(RCp)(NR2)2 (=NR), such as tert-butylimidobis(diethylamido)cyclopentadienylniobium(V), tert-butylimidobis(dimethylamido)cyclopentadienylniobium(V), tert-butylimidobis(dimethylamido)methylcyclopentadienylniobium(V), and combinations thereof. 26. The method of paragraph 19 or 20, wherein the phosphorus source reactant is selected from trimethyl phosphate (TMPO), diethyl phosphoramidate (DEPA), triethyl phosphate (TEPO), TMP, and combinations thereof. 27. The method of paragraph 19 or 20, wherein the phosphorus source reactant comprises TMPO. 28. The method according to any one of sentences 16 to 27, wherein step a) and / or step b) are carried out at a temperature higher than the melting point of the metal-containing chemical and not higher than 200°C. 29. The method according to any one of sentences 16 to 27, wherein step a) and / or step b) are carried out at a temperature higher than the melting point of the metal-containing chemical and not higher than 175°C. 30. The method according to any one of sentences 16 to 27, wherein step a) and / or step b) are carried out at a temperature higher than the melting point of the metal-containing chemical and not higher than 150°C. 31. A method according to any one of sentences 16 to 30, wherein a) the substrate has a surface structure with an aspect ratio of 6.25 or less, and b) the metal-containing material from the metal-containing chemical deposited on the substrate has a step coverage of the surface structure of 50% or more, for example 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or >99%. 32. The method of any one of sentences 16 to 31, wherein steps a) and b) comprise atomic layer deposition (ALD) repeated in an ALD cycle. 33. The method of claim 32, wherein the growth rate per ALD cycle of the deposited material is 0.2 Angstroms or more, e.g., 0.3 or more, 0.4 or more, 0.5 or more, 0.6 or more, 0.7 or more, 0.8 or more, 0.9 or more, 1.0 or more, 1.1 or more, or 1.2 or more.

[0016] For a fuller understanding of the nature and objects of the present invention, reference should be made to the following detailed description taken in conjunction with the accompanying drawings, in which like elements are designated with the same or similar reference numerals, and in which: [Brief explanation of the drawings]

[0017] [Figure 1] FIG. 1 shows the TGA results for Example 1. [Figure 2] FIG. 2 shows the TGA results for Example 6. [Figure 3] FIG. 3 shows the effect of temperature on the deposition rate for Example 7. [Figure 4] FIG. 4 shows the effect of temperature on the refractive index of the deposited material of Example 7. [Figure 5] FIG. 5 shows the effect of temperature on the atomic composition of the deposited material of Example 7. DETAILED DESCRIPTION OF THE INVENTION

[0018] The present inventors have synthesized and tested novel tridentate N,N,O ligands for metals that form low-melting solids and have excellent vaporizability and high volatility due to thermal stability, making these coordinated metals suitable for vapor deposition. The ligand structures in one group of embodiments are represented by the following formula and structural representation: 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 are each independently selected from H, C1-C4 alkyl (linear or branched if C3 or C4), or C1-C4 alkylamino C1-C4NR2, and R are each independently selected from H, C1-C4 alkyl (linear or branched if C3 or C4).

[0019] This new family of ligands is capable of forming tridentate chelating ligands ("L") with metal ions. In a preferred embodiment, the metal ("M") is an alkali metal (e.g., Na) forming a chelating chemical ML. + and Li +) and other monovalent metal ions. 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 does not bind the higher valent metal alone (M +x L x ) or in combination with other metal ligands (D) to form heteroleptic coordination metals (M +x L y D z ) can also be formed. For example, M can be Ca +2 and is chelated by two ligands L to form Ca +2 L2 (see Example X below) or chelated with a different ligand to form D-Ca +2 -L can be formed.

[0021] The chemical entity (ML) formed by the monovalent metal and the ligand L typically has a melting point below 150°C and is therefore a low-melting solid. Preferred species have melting points below 70°C. Liquid chemicals or low-melting solids that form liquids upon heating are preferred as chemical precursors for vapor deposition processes. While subliming solids are also used, handling and management of sublimable precursors is more complex and is often associated with higher chemical losses due to thermal decomposition.

[0022] Also highly relevant for use in vapor deposition processes is the vapor pressure achievable for the chemical precursor. This parameter correlates with the rate and quality of the deposited M-containing material. Vapor pressure generally exhibits 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 opposing parameters are commonly evaluated using thermogravimetric analysis ("TGA"). See, for example, ASTM E2008-17(2021), Standard Test Methods for Volatility Rate by Thermogravimetry. TGA evaluation of vapor deposition precursors involves determining the 50% point (T 50 ) and the complete evaporation temperature (T full The temperature profile of the volatilization curve is evaluated to define the volatility, T. This is often performed at both atmospheric pressure and vacuum (e.g., 15 torr) to represent two common vapor deposition process conditions. TGA also allows for a simple assessment of thermal stability by the weight of the residual material that does not further evaporate as the temperature increases. Finally, the resulting vapor pressure can be plotted against the temperature / weight curve to determine the volatility, T. 50 The effects of the three parameters of solubility, solubility, and thermal stability can be evaluated.

[0023] In the deposition process, T 50 The temperature at which the vapor pressure of the chemical precursor reaches 1 torr ("T") should be as low as possible. 1torr It is preferable to keep the vapor pressure as low as possible. In particular, a vapor pressure of 1 torr should be reached at a temperature that minimizes thermal decomposition (balancing this parameter is more difficult for sublimable solids).

[0024] The chemical compound formed by the monovalent metal and the ligand L (ML) is usually formed at a temperature T below 150°C and above the melting point. 1torr These same chemicals typically have a T below 250°C and above their melting point.50 and b) exhibits excellent evaporation with a TGA residue of less than 1 wt. %.

[0025] Due to the above properties, the metal M complexed with the ligand L is particularly suitable for use in coating cathode electrode materials comprising catalytic carbon supporting structures such as single-walled fullerenes (Ceo and C72), multi-walled fullerenes, single-walled or multi-walled nanotubes, nanohorns and / or carbon supporting structures having a density of about 0.2 g / cm to about 1.9 g / cm, such as specialty carbons such as VULCAN or Imerys' SUPER C65.

[0026] Due to these aforementioned properties, chemistries formed with monovalent metals and ligands L(ML) are well suited for use in vapor deposition processes requiring low temperatures due to temperature and / or substrate limitations on exposure to co-reactants. t Bu achieves pressures of 1 Torr above 150°C, resulting in longer pulses and / or higher dep T, which adversely affect many electrode materials in terms of absolute temperature exposure 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 temperatures above 200°C. For deposited materials adversely affected by silicon contamination, the L ligand provides a silicon-free chemical precursor that allows for the deposition of M-containing films without Si contamination. This is an advantage over LiTMSO and LiHMDS, both of which produce silicon-contaminated deposits, which are particularly problematic at the lowest ALD temperatures available for these chemistries.

[0027] A metal M chelated or otherwise coordinated with a ligand L described herein can be used as an M-source vapor-phase precursor for vapor-phase deposition of an M-containing material on a substrate. Vapor-phase deposition techniques, such as chemical vapor deposition and atomic layer deposition, are well known in the art. The deposited material may also include other co-reactants or other atoms from the vapor-phase precursor. Common co-reactants are oxygen-source reactants, phosphorus-source reactants, and nitrogen-source reactants. Depending on the vapor-phase deposition process, these may provide O, N, or P as dopants or may react with the ML vapor-phase precursor to form oxides or nitrides of M, such as MOx, MNx, MONx, MPO, and MPON materials. 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-phase 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 (e.g., N2H4, MeHNNH2, MeHNNHMe), organic amines (e.g., NMeH2, NEtH2, NMe2H, NEt2H, NMe3, NEt3, (SiMe3)2NH), pyrazolines, pyridines, diamines (e.g., ethylenediamine), their radical species, and mixtures thereof. Phosphorus source reactants include trimethyl phosphate (TMPO), diethyl phosphoramidate (DEPA), triethyl phosphate (TEPO), TMP, and combinations thereof. [Example]

[0028] Example 1 - Synthesis [ka] O=C(tBu)CH2NMe(CH2)2NMe2: A ligand synthesized by reacting O=C(tBu)CH2Cl with HNMe[(CH2)2NMe2 in a 1:1 ratio using TEA, NMe2CO3, or NaHCO3 in THF / ACN at 50-60°C. 1H NMR (CDCl3, 400 MHz): 3.412 (2H, br s), 2.488 (2H, t, 3J = 7.7 Hz), 2.327 (2H, t, 3J = 7.7 Hz), 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)CHNMe[(CH)NMe with BuLi, LiNH, or LiH in hexane, pentane, or MTBE. The crude material was purified by distillation to give 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 atmosphere of N2 (total evaporation temperature 305 °C); sample weight 10.4 mg, open cup in 1 atmosphere of N2 (total evaporation temperature T full = 254 °C); sample weight 30.1 mg, open cup in 15 torr N2 (complete evaporation temperature T full The heating rate was set at 10.0°C / min. The 50% evaporation T was measured using an open-cup TGA method in N2 at 1 atmosphere. 50 =225℃.

[0031] These results are presented graphically in Figure 1. As shown, Tfull In this case, the residue is negligible (less than 1% by weight).

[0032] Examples 2-5 - Additional Synthesis The same synthesis was carried out with the following variations of Example 1. Example 2: Changing the positions of R1, R2, and R7 to ethyl Example 3: Changing the position of R7 to n-butyl Example 3: Changing the position of R7 to ethyl Example 5: M is Na

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

[0034] Example 6 - Exemplary M +2 Synthesis of L2, M=Ca [ka] Synthesis: Na{OC(tBu)=CHN(Me)(CHCHNMe)} was added to 0.5 equivalents of CaI in THF, stirred for 16 hours, filtered, and sublimed (120 °C / 0.1 Torr). 1H NMR (CD, 400 MHz): 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] The TGA measurement was performed under the following measurement conditions: sample weight 6.2 mg, open cup (complete evaporation temperature 280 °C) in N2 at 1 atmosphere, and the heating rate was set to 10.0 °C / min. 50% evaporation using the open cup TGA method in N2 at 1 atmosphere: T 50 = 230°C (see Figure 2).

[0036] Example 7 – LiPOx deposition on substrate Li-OC(tBu)=CHNMe(CH)NMe (Example 1) was used as the Li source for atomic layer deposition (ALD) of LiPO films on blank silicon wafers as test substrates. Trimethyl phosphate (TMPO) is a standard phosphate source in the art for use with conventional Li precursors. Therefore, TMPO was chosen as the co-reactant.

[0037] Preliminary characterization: Li-OC(tBu)=CHNMe(CH2)2NMe2 thermally decomposes at 250°C. Therefore, to avoid parasitic CVD, the basic design of the experimental parameter evaluation was performed at 200°C. Increasing the pulse time of both precursors showed self-limiting growth at 0.9 Å / cycle under the conditions tested (ozone as co-reactant), confirming that the deposition at 200°C was an ALD process. An oxygen source was required to form LiPOx. Without ozone, ALD did not occur.

[0038] The experimental parameter design from the preliminary test at 200 °C was then used to evaluate the effect of temperature on the ALD of LiPOx.

[0039] Experimental conditions: Reactor temperature: X°C Reactor pressure: 1 torr Carrier N2: 80sccm Canister T: 110℃ Canister P: 30 torr N2 in Li bubbling FR: 30sccm TMPO canister T: 80℃ TMPO canister P: 15 torr N2 in P bubbling FR: 30sccm 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 temperatures tested were 125, 150, 175, and 200°C. LiPOx was deposited as a uniform, continuous film over this temperature range.

[0042] According to Figure 3, the main difference is the deposition rate (as expected), which reaches a maximum at 200 °C. However, even at 125 °C, each ALD cycle produced a 0.36 Å thick deposit, a commercially viable deposition rate. This is in contrast to the prior art molecules mentioned above, where deposition stops above 200 °C.

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

[0044] Figure 5 shows the atomic percentages, with silicon, N, and C all below the detection limit (less than 1%). In agreement with the RI measurements, the composition of the deposited material is Li 2.8 PO 3.8 This combination of low-temperature ALD, GPC speed, and composition is a significant advancement that will enable LiPOx deposition on a variety of substrates with limited temperature / thermal budgets, especially those used in Li-ion battery electrodes.

[0045] Good step coverage on uneven substrate surfaces is important for good electrode / cathode performance because: 1) thick spots inhibit Li-ion transport, and 2) thin spots cause TM loss (e.g., Mn migration from the cathode) and / or dendrite formation. To evaluate the applicability of this ALD process to uneven surfaces, trenched test Si wafers were used as substrates. At an aspect ratio of 6.25, step coverage was 87%. The maximum aspect ratio tested was 18. Even at this severe aspect ratio, the ALD layer was continuous. Step coverage at this dimension was 65%, suggesting that the ALD deposition process decays at very distant surfaces. Nevertheless, the minimum thickness achieved at the trench bottom 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. With further optimization of the parameters, these results are expected to improve compared to these preliminary experiments.

[0046] Example 8 – Deposition of LiNbOx on a substrate As an example of diverse material deposition, binary deposition of LiNbO was selected. Li-OC(tBu)=CHNMe(CH)NMe from Example 1 was used as the Li source precursor. For niobium, tert-butylimidobis(diethylamido)mono(tert-butylalkoxo)niobium(V), a source precursor described in U.S. Pat. No. 10,106,887 B2, was selected. One of the reasons for selecting tert-butylimidobis(diethylamido)mono(tert-butylalkoxo)niobium(V) was that it extended the ALD temperature window for NbO deposition to at least as low as 150°C. A temperature of 175°C was selected to balance the ALD windows of the Li and Nb source precursors with GPC. Blank silicon wafers were also used as substrates for the preliminary evaluation. The process conditions tested 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 the LiNbOx material. The total deposition growth rate of LiNbOx is 0.68 Å. Pulse-dose experiments confirmed that the formation of LiNbOx was a self-limiting ALD reaction. The stoichiometry of the deposited material was approximately LiNbO2. This is consistent with the RI of the deposited material being 1.9 compared to RI of 2.2 for LiNbO3. The deposition was further tested on trenched silicon wafers. Step coverage was >99%, even at an aspect ratio of 15. The deposited layer was continuous, with no gaps or visible defects visible in SEM-scanned slices. With further optimization of parameters (e.g., ozone dosage), the atomic composition of the deposited material is expected to be very close to that of LiNbO3, ultimately similar to that obtained with LiPOx.

[0051] Example 9 - Exemplary M x Synthesis of LyDz: [ka] Synthesis: t BuN=NbCl was added to 2 equivalents of NaOEt and 1 equivalent of Li{OC(tBu)=CHN(Me)(CHCHNMe)} in THF and stirred for 16 hours, 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 Synthesis of (Bu)=CHN[(CH2)2OMe]2 [ka] O=C(tBu)CH2N[(CH2)3NMe2]2: A ligand synthesized by reacting O=C(tBu)CH2Cl with HN[(CH2)3NMe2]2 in a 1:1 ratio in THF / ACN containing TEA, K2CO3, or NaHCO3 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)

[0053] This complex was prepared by reacting O=C(tBu)CHN[(CH)NMe] with BuLi, LiNH, or LiH in hexane, pentane, or MTBE. The crude material was purified by sublimation to yield a yellow solid (45%). 1H NMR (CD, 400 MHz): 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 (2H, br d, 3J = 11.1 Hz), 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 Synthesis of (Bu)=CHN[(CH2)2OMe]2 [ka] O=C( t Bu)CH2N[(CH2)3NMe2]2: O=C( in THF / ACN containing TEA, K2CO3 or NaHCO3 t A ligand synthesized by reacting Bu)CH2Cl with 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 can be synthesized by the reaction of O=C( t It was prepared by reacting Bu)CHN[(CH)NMe] with BuLi, LiNH, or LiH. The crude material was purified by sublimation to yield 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 industrial applicability at least with respect to chemical precursors suitable for use in semiconductor manufacturing or in depositing materials for battery electrodes.

[0057] While the present invention has been described in connection with specific embodiments thereof, it will be apparent to those skilled in the art that many alternatives, modifications, and variations will be apparent in light of the foregoing description. Accordingly, the present invention is intended to embrace all such alternatives, modifications, and variations that fall within the spirit and broad scope of the appended claims. The present invention may suitably comprise, consist of, or consist essentially of disclosed elements, or may be practiced without elements not disclosed. Furthermore, where there are terms indicating a sequence, such as first and second, they should be understood in an illustrative sense and not in a limiting sense. For example, one skilled in the art may recognize that certain steps can be combined into a single step.

[0058] All references identified herein are incorporated by reference in their entirety into this application, as well as the specific information for which each is cited.

[0059] Legal definitions and principles of interpretation The singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise.

[0060] The term "comprising" in the claims is an open transitional phrase. It means that the claim elements identified thereafter are a non-exclusive list (i.e., other things can be included and still fall within the scope of the "comprising"). As used herein, "comprising" can be replaced with the more narrow transitional phrases "consisting essentially of" and "consisting of," unless otherwise indicated herein.

[0061] "Providing" in the claims is defined to mean providing, supplying, making available, or preparing something. Unless there is express language to the contrary in the claims, this step may be performed by any actor.

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

[0063] Ranges may be expressed herein as from about one particular value and / or to about another particular value, and when such a range is expressed, it is to be understood that another embodiment is all combinations within said range from the one particular value and / or to the other particular value.

[0064] References herein to "one embodiment" or "an embodiment" mean that a particular feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment of the invention. The appearances of the phrase "in one embodiment" in various places in this specification do not necessarily all refer to the same embodiment, nor are other or alternative embodiments necessarily mutually exclusive of other embodiments. The same applies to the term "implementation."

[0065] As used herein, the terms "about," "around," or "approximately" in the text or claims mean ±10% of the stated value.

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

[0067] The term "ambient conditions" means an environmental temperature (ie, ambient temperature) of about 20° C. to about 25° C. and an environmental pressure (ambient pressure) of about 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 already deposited on it in a previous manufacturing step.

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

[0070] Standard abbreviations for elements of the periodic table are used herein. It is understood that elements may be referred to by these abbreviations (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.).

[0071] Unique CAS Registry Numbers assigned by the Chemical Abstract Service (i.e., "CAS") are provided to facilitate easier identification of the disclosed molecules.

[0072] The aspect ratio of a geometric shape is the ratio of its sizes in different dimensional directions. Aspect ratios are most often expressed as two integers (x:y) separated by a colon. The values ​​x and y do not represent the actual width and height, but rather the ratio between width and height. For example, 8:5, 16:10, and 1.6:1 are all ways of expressing the same aspect ratio. For objects with more than two dimensions, such as a hypercuboid, the aspect ratio can also be defined as the ratio between the longest and shortest sides.

[0073] Conformality 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 particularly relevant for surfaces with microstructures with varying aspect ratios. Perfect (100%) conformality in the above example means zero cusp, meaning the top surface, trench sidewalls, and, if applicable, the bottom of the trench are all the same thickness. When a single conformality percentage is given, it is a measure of the minimum conformality corresponding to the maximum deviation in the relative thickness of the entire film at two selected points on the surface. The two points may correspond to points with the highest aspect ratio or points with a specific aspect ratio, such as 6:1 or less. Film thickness is assessed by several methods, such as scanning electron microscopy of sectioned substrates. A film is generally "conformal" if it has a conformality of at least 20%, preferably at least 50%.

[0074] It will be understood that many additional variations in the details, materials, steps and arrangements of parts described herein to explain the nature of the invention may be made by those skilled in the art within the principles and scope of the invention as expressed in the appended claims. Accordingly, the invention is not limited to the specific embodiments in the examples set forth above.

Claims

1. a ligand L capable of forming a coordination complex with at least one metal atom, 【Chemical 1】 The general formula structurally represented by: N (R １ R ２ )-C(R ３ R ４ )-C(R ５ R ６ )-N(R ７ )-CH ２ -C (CR ８ R ９ R １０ )=O (Formula A), or 【Chemistry 2】 The general formula 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) wherein R １ ~R １２ are each independently H, C １ ~C ４ Alkyl (C ３ Or C ４ (straight chain or branched chain in the case of C) or C １ ~C ４ Alkylamino C １ ~C ４ NR ２ R is independently selected from H, C1-C4 alkyl (C ３ or C ４ The ligand L is selected from the group consisting of: 【Request 2】 【Chemical 3】 10. The ligand of claim 1, further comprising a coordinating metal atom M to form a metal-containing chemical structurally represented by:

3. 3. The metal-containing chemical of claim 2, wherein M is Li.

4. R ８ , R ９ and R １０ is each independently selected from methyl or ethyl.

5. M is Li and R ８ , R ９ and R １０ is each independently selected from methyl or ethyl.

6. R ８ , R ９ and R １０ and n is 1 or 2. The metal-containing chemical of claim 5, wherein each is methyl.

7. R １ ~R ７ are each independently selected from H, methyl, or ethyl.

8. R １ ~R ７ is independently selected from H or methyl.

9. 【Chemical 4】 3. The metal-containing chemical of claim 2, structurally represented as:

10. 10. The metal-containing chemical of claim 9, wherein M is Li.

11. 3. The metal-containing chemical of claim 2, wherein M is a polyvalent metal and two or more ligands L are coordinated to M.

12. M is a polyvalent metal, and two or more ligands are coordinated to M, and M has one or more ligands L and one or more additional different ligands D to form a heteroleptic molecule M. ｘ 3. The metal-containing chemical of claim 2, which forms LyDz, where x≧2, y≧1, and z≧1.

13. 1. A method of depositing a metal-containing film, comprising: a) contacting a substrate with the vapor phase of a metal-containing chemical according to any one of claims 2 to 12; b) forming a deposited material on the substrate that includes the metal from the metal-containing chemical; A method comprising:

14. 14. The method of claim 13, further comprising exposing the substrate to a gas or vapor phase of one or more additional reactants.

15. M is Li and the deposited material is LiNbO ｘ and the additional reactants comprise an oxygen source reactant and a niobium source reactant.

16. 15. The method of claim 14, 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.

17. 17. The method of claim 15 or 16, wherein the oxygen source reactant is ozone.

18. The niobium source reactant has the following formula: 【Chemistry 5】 (wherein M is Nb, and each R １ , R ２ , R ３ , R ４ , R ５ and R ６ are independently selected from H, a C1-C5 linear, branched, or cyclic alkyl group, a C1-C5 linear, branched, or cyclic alkylsilyl group, a C1-C5 linear, branched, or cyclic alkylamino group, or a C1-C5 linear, branched, or cyclic fluoroalkyl group. or Nb(RCp)(NR)(=NR) (Formula III), or Nb(RCp)(NR)(=NR) (Formula III), or selected from tert-butylimidotris(diethylamido)niobium(V), tert-butylimidotris(dimethylamido)niobium(V), and tert-butylimidotris(ethylmethylamido)niobium(V), and combinations of the foregoing.

19. 17. The method of claim 16, wherein the phosphorus source reactant is trimethyl phosphate (TMPO), diethyl phosphoramidate (DEPA), triethyl phosphate (TEPO), TMP, and combinations thereof.

20. 20. The method of any one of claims 13 to 19, wherein step a) and / or step b) is carried out at a temperature above the melting point of the metal-containing chemical and up to 200°C.

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