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

Abstract

A ligand L capable of forming a coordination complex with at least one metal atom, the ligand having the general formula: N (R1R2)-C (R3R4)-C (R5R6)-N (R7)-CH2-C (CR8R9R10) = O. The present disclosure describes the use of L with a metal M to form a ligand metal complex ML. The present disclosure describes the use of ML for vapor deposition processes.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. patent application No. 63 / 407,325, filed on September 16, 2022, the entire contents of which are incorporated herein by reference. Technical Field

[0003] Organometallic complexes for the deposition of metal-containing films, particularly for the manufacture of semiconductors and battery electrodes. Background Art

[0004] Lithium-containing films are well known for their use as surface coatings for electrode materials in lithium-ion battery applications. Examples of lithium-containing films include lithium phosphate (LiPO), lithium phosphorus oxynitride (LiPON), lithium borate, lithium borophosphate, lithium fluoride, lithium metal fluoride, lithium metal oxides such as lithium niobate, lithium titanate, lithium zirconium oxide, etc. The absence of silicon is preferred for the formation of some of these materials (especially lithium niobate, lithium titanate, lithium zirconium oxide).

[0005] During the first few cycles of lithium-ion batteries, a solid electrolyte interface (SEI) is observed to form on the anode and / or cathode by the decomposition of the electrolyte at the electrolyte / electrode interface. Due to the consumption of lithium, the capacity of the lithium-ion battery is lost. In addition, the SEI layer formed is non-uniform and unstable, cracks and dendrites may appear and lead to thermal runaway. In addition, these SEI layers also create a barrier that makes the embedding in the electrode more difficult.

[0006] Surface coating of electrodes by vapor deposition techniques such as ALD or CVD is the preferred method for forming the desired solid electrolyte interface thin film, thus avoiding the formation of unstable layers. Thus, the decomposition of some components of the liquid electrolyte is greatly reduced, and the dissolution of transition elements from cathode materials such as manganese is also avoided. Vapor deposition techniques are suitable for depositing very thin and conformal films to have the above advantages without the disadvantage of reduced ionic and electronic conductivity. Lithium-containing films are very promising candidates as protective electrode coatings due to their good conductivity and high electrochemical stability.

[0007] Another important application of lithium-containing films is to form solid electrolyte materials used in solid-state batteries. Solid-state batteries are solvent-free systems that have longer life, faster charging times and higher energy density than conventional lithium-ion batteries. Preventing the loss of solid electrolyte elements (especially sulfur) is critical to their long-term performance. Solid electrolyte materials are very sensitive to air and moisture and require protective layers to improve their performance and scalability. Solid-state batteries are considered to be the next technological stage in battery development. In 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 technology. Uniform and conformal lithium-containing films can even be obtained on complex architectures such as 3D batteries.

[0008] The vapor deposition of films / coatings containing metals (e.g., Li) requires sufficient: a) thermal stability and b) volatile chemical precursors, i.e., c) the ability to deposit metals via a deposition mechanism. The deposition mechanism can be thermal, chemical, surface catalytic, or other approaches. Deposition of alloys or combined films generally requires two or more chemical precursors that can be used together under compatible conditions. Co-reactants, such as oxidants or reductants, or significant improvements in the deposition process are generally required. Identifying chemical precursors containing metals that meet these and other process / application requirements is an ongoing challenge. Vapor deposition on semiconductor and electrode materials can have significantly different process limitations and standards, such as temperature and aggregate heat exposure limitations ("thermal budget").

[0009] N,N,O-tridentate ligands of metals such as lithium have been characterized in the field of catalysts. 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.

[0010] US20090136677A1 describes a class of tridentate beta-ketoiminate molecules suitable for use as vapor deposition precursors.

[0011]

[0012] R4 is a C3-10 branched alkylene bridge having at least one chiral carbon atom. This ligand is limited for use with metals having a valence of 2 or more and is therefore not suitable for use with alkali metals such as Na, K or Li.

[0013] Several lithium precursors are known and their deposition properties have been evaluated. 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-butylate (LiO t Bu) and lithium hexamethyldisilazide [LiHMDS, also known as lithium bis(trimethylsilyl)amide]. LiO t Bu stops forming good quality films at 200°C, and LiHMDS stops forming good quality films at 250°C.

[0014] Even at the highest possible temperatures, LiO t Bu also has a very low vapor pressure, and the preferred vapor pressure of ≥ 1 Torr is not possible. 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.

[0015] LiHMDS produces vapor deposited materials with both silicon and carbon contamination well above 1%. Jani, et al. "Lithium phosphate thin films grown by atomic layer deposition." Journal of The Electrochemical Society 159.3 (2012): A259.

[0016] There is a particular need for ligands that can form lithium precursors with better volatility and vapor deposition temperatures below 200° C. Preferably, these lithium precursors can produce conformal, high-quality vapor deposited films with good step coverage and with low carbon and silicon content. Summary of the invention

[0017] The present invention may be understood with reference to the following embodiments presented in the form of numbered sentences:

[0018] 1. A ligand L, which is capable of forming a coordination complex with at least one metal atom, and which has the general formula:

[0019] 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

[0020] (Formula A)

[0021] or

[0022] 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

[0023]

[0024] And it is structurally represented by the following formula A:

[0025]

[0026] With SMILES formula:

[0027] [R2]N(C([R3])([R4])C([R5])([R6])N(CC(C([R8])([R9])[R10])=O)[R7])[R1],

[0028] And it is structurally represented by the following formula B:

[0029]

[0030] With SMILES formula:

[0031] [R2]N([R1])C([R4])(C([R6])(C([R11])([R12])N([R7])CC(C([R9])([R10])[R8]

[0032] )=O)[R5])[R3]

[0033] Where R 1 -R 12 Each independently selected from H, C 1 To C 4 Alkyl (when C 3 or C 4 when it is straight chain or branched); or C 1 -C 4 Alkylamino C 1-4 NR 2 , wherein R is independently selected from H, C 1 To C 4 Alkyl (when C 3 or C 4 when it is straight chain or branched).

[0034] 2. The ligand L as described in statement 1, further comprising a coordinated metal atom M to form a metal-containing chemical ML, structurally represented by:

[0035]

[0036] And has SMILES formula:

[0037] [R2][N@@]1([R1])C([R4])(C([R6])([N@]2([R7])C=C(O[M]12)C([R9])([R10

[0038] ])[R8])[R5])[R3],

[0039] or structurally represented by:

[0040]

[0041] And has SMILES formula:

[0042] [R2][N@]1([R1])[C@]([R4])([C@@]([R6])([C@@]([R11])([R12])[N@]2([R

[0043] 7])CC(C([R9])([R10])[R8])=[O][M]12)[R5])[R3],

[0044] wherein M is selected from Li, Na, or K.

[0045] 3. The metal-containing chemical according to claim 2, wherein M is Li.

[0046] 4. The ligand as described in statement 1 or the metal-containing chemical as described in statement 2, wherein R 8 , R 9 and R 10 Each is independently selected from methyl or ethyl.

[0047] 5. The ligand of statement 1 or the metal-containing chemical of statement 2, wherein M is Li and wherein R 8 , R 9 and R 10 Each is independently selected from methyl or ethyl.

[0048] 6. The metal-containing chemical according to claim 5, wherein R 8 , R 9 and R 10 Each is a methyl group.

[0049] 7. The ligand as described in statement 1 or the metal-containing chemical as described in statement 2, wherein R 1 -R 7 Each is independently selected from H, methyl, or ethyl.

[0050] 8. The metal-containing chemical according to claim 7, wherein R 1 -R 7 Each is independently selected from H or methyl.

[0051] 9. The metal-containing chemical according to claim 2, which is structurally represented by:

[0052]

[0053] And has SMILES formula:

[0054] CC(C)(C)C1=C[N@@]2(C)CC[N](C)(C)[M]2O1.

[0055] 10. The metal-containing chemical of clause 9, wherein M is Li.

[0056] 11. The metal-containing chemical of statement 2, wherein M is a multivalent metal and two or more ligands L are coordinated to M.

[0057] 12. The metal-containing chemical according to claim 11, wherein M is selected from calcium, magnesium, strontium, and barium.

[0058] 13. The metal-containing chemical of clause 2, wherein M is a polyvalent metal and two or more ligands coordinate to M, wherein M has one or more ligands L and one or more additional different ligands D to form a heteroleptic molecule M x LyDz, x≧2, y≧1, and z≧1.

[0059] 14. The metal-containing chemical of clause 13, wherein M is selected from niobium, tantalum, vanadium, zirconium, hafnium, titanium, tungsten, molybdenum, chromium, cobalt, nickel, copper, manganese, and zinc.

[0060] 15. The metal-containing chemical of clause 13, wherein M is niobium.

[0061] 16. A method for depositing a metal-containing film, comprising the steps of:

[0062] a) contacting a substrate with a gas phase of a metal-containing chemical as described in any one of clauses 1 to 15,

[0063] b) forming a deposition material on the substrate, the substrate comprising the metal from the metal-containing chemical.

[0064] 17. The method of clause 16, further comprising the step of exposing the substrate to a gas or vapor phase of one or more additional reactants.

[0065] 18. The method of clause 17, wherein M is Li and the deposited material is LiNbO x , and the one or more additional reactants include an oxygen source reactant and a niobium source reactant.

[0066] 19. The method of clause 17, wherein M is Li, the deposition material is LiPO, and the one or more additional reactants comprise an oxygen source reactant and a phosphorus source reactant.

[0067] 20. The method of clause 17, wherein M is Li, the deposition material is LiPNO, and the one or more additional reactants comprise an oxygen source reactant, a nitrogen source reactant, and a phosphorus source reactant.

[0068] 21. A method as described in statements 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.

[0069] 22. A method as described in statements 18, 19 or 20, wherein the oxygen source reactant is ozone.

[0070] 23. The method of clause 18, wherein the niobium source reactant is a Group 5 transition metal-containing chemical having one of the following formulas:

[0071]

[0072] Where 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; C1-C5 linear, branched, or cyclic alkylsilyl; C1-C5 linear, branched, or cyclic alkylamino; or C1-C5 linear, branched, or cyclic fluoroalkyl.

[0073] 24. The method of claim 18, wherein the niobium source reactant comprises tert-butylimidobis(diethylamido)mono(tert-butylalkoxy)niobium(V), tert-butylimidomono(diethylamido)bis(tert-butylalkoxy)niobium(V), and combinations thereof.

[0074] 25. The method of clause 18, wherein the niobium source reactant is selected from tert-butylimido tris(diethylamido) niobium(V), tert-butylimido tris(dimethylamido) niobium(V), tert-butylimido tris(ethylmethylamido) niobium(V), or Nb(RCp)(NR2) 2 Members of the known class of (=NR) such as tert-butylimidobis(diethylamido)cyclopentadienyl niobium(V), tert-butylimidobis(dimethylamido)cyclopentadienyl niobium(V), tert-butylimidobis(dimethylamido)methylcyclopentadienyl niobium(V), and combinations thereof.

[0075] 26. The method of claim 19 or 20, wherein the phosphorus source reactant is selected from the group consisting of trimethyl phosphate (TMPO), diethyl phosphoramidate (DEPA), triethyl phosphate (TEPO), TMP, and combinations thereof.

[0076] 27. The method of claim 19 or 20, wherein the phosphorus source reactant comprises TMPO.

[0077] 28. The method of any one of clauses 16-27, wherein step a) and / or step b) is performed at a temperature above the melting point of the metal-containing chemical and at or below 200°C.

[0078] 29. The method of any one of clauses 16-27, wherein step a) and / or step b) is performed at a temperature above the melting point of the metal-containing chemical and at or below 175°C.

[0079] 30. The method of any one of clauses 16-27, wherein step a) and / or step b) is performed at a temperature above the melting point of the metal-containing chemical and at or below 150°C.

[0080] 31. A method as described in any of statements 16-30, wherein a) the substrate has a surface structure having an aspect ratio of 6.25 or less, and b) the deposited material on the substrate comprising the metal from the metal-containing chemical has a step coverage of 50% or more, such as 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or >99% for the surface structure.

[0081] 32. The method of any of clauses 16-31, wherein the method comprises atomic layer deposition (ALD), wherein steps a) and b) are repeated in an ALD cycle.

[0082] 33. The method of claim 32, wherein the growth rate of the deposited material per ALD cycle is 0.2 angstroms or greater, such as 0.3 or greater, 0.4 or greater, 0.5 or greater, 0.6 or greater, 0.7 or greater, 0.8 or greater, 0.9 or greater, 1.0 or greater, 1.1 or greater, or 1.2 or greater. BRIEF DESCRIPTION OF THE DRAWINGS

[0083] For a further understanding of the nature and purpose of the present invention, reference should be made to the following detailed description in conjunction with the accompanying drawings, in which like elements are given the same or similar reference numerals, and in which:

[0084] Figure 1 The TGA results of Example 1 are shown;

[0085] Figure 2 The TGA results of Example 6 are shown;

[0086] Figure 3 The effect of temperature on the deposition rate of Example 7 is shown;

[0087] Figure 4 shows the effect of temperature on the refractive index of the deposited material of Example 7; and

[0088] Figure 5 The effect of temperature on the atomic composition of the deposited material of Example 7 is shown. DETAILED DESCRIPTION

[0089] The inventors synthesized and tested a new tridentate N,N,O ligand for metals that form low melting solids, with good vaporization properties due to thermal stability and high volatility; making these ligand metals suitable for vapor deposition. The ligand structure in one species embodiment is represented by the following formula and structural representation:

[0090] Formula A:

[0091] 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

[0092]

[0093] SMILES style:

[0094] [R2]N(C([R3])([R4])C([R5])([R6])N(CC(C([R8])([R9])[R10])=O)[R7])[R1]

[0095] Formula B:

[0096] 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

[0097]

[0098] SMILES style:

[0099] [R2]N([R1])C([R4])(C([R6])(C([R11])([R12])N([R7])CC(C([R9])([R10])[R8]

[0100] )=O)[R5])[R3]

[0101] R 1 -R 12 Each independently selected from H, C 1 To C 4 Alkyl (when C 3 or C 4 when it is straight chain or branched); or C 1 -C 4 Alkylamino C 1-4 NR 2 , wherein R is independently selected from H, C 1 To C 4 Alkyl (when C 3 or C 4 when it is straight chain or branched).

[0102] The novel ligand species is capable of forming a tridentate chelating ligand ("L") with a metal ion. In a preferred embodiment, the metal ("M") is a monovalent metal ion, such as an alkali metal (e.g., Na + and Li + ), which forms the chelated chemical ML.

[0103] Formula A1:

[0104]

[0105] SMILES style:

[0106] [R2][N@@]1([R1])C([R4])(C([R6])([N@]2([R7])C=C(O[M]12)C([R9])([R10

[0107] ])[R8])[R5])[R3]

[0108] Formula B1:

[0109]

[0110] SMILES style:

[0111] [R2][N@]1([R1])[C@]([R4])([C@@]([R6])([C@@]([R11])([R12])[N@]2([R

[0112] 7])CC(C([R9])([R10])[R8])=[O][M]12)[R5])[R3],

[0113] However, the tridentate ligand L is able to chelate higher valent metals (M +x L x ) or combined with other metal ligands (D) to produce heteroleptic ligand metal (M +x L y D z For example, M can be chelated by two ligands L to form Ca +2 L 2 (See Example X below) or chelate with different ligands to form D-Ca +2 -LCa +2 .

[0114] The chemical (ML) formed from the monovalent metal and the ligand L generally has a melting point below 150°C and is therefore a low melting solid. Preferred materials have a melting point below 70°C. Liquid chemicals or low melting solids that form liquids upon heating are preferred as chemical precursors for the vapor deposition process. Sublimated solids are also used, but the handling and management of sublimated precursors is more complicated and is generally associated with higher losses of the chemical due to thermal degradation.

[0115] Also highly relevant to use in vapor deposition processes is the vapor pressure achievable with a chemical precursor. This parameter is related to the rate and quality of deposited M-containing material. Vapor pressure generally trends inversely with thermal stability. It is important to avoid using chemical precursors that cannot achieve sufficient vapor pressure without using temperatures that also result in significant thermal degradation of the chemical precursor. These compensating parameters are typically evaluated using thermogravimetric analysis ("TGA"). See, for example, ASTM E2008-17(2021), Standard Test Method for Volatility by Thermogravimetric Analysis. TGA Evaluation of Vapor Deposition Precursors evaluates the temperature profile of the volatilization curve to define the 50% point ("T 50 ”) and the complete gasification temperature (“T 完全 This is typically done both at atmospheric pressure and in vacuum (e.g., 15 Torr) to represent these two common vapor deposition process conditions. TGA also enables a simple assessment of thermal stability through the weight of residual material that does not evaporate further with increasing temperature. Finally, the resulting vapor pressure can be plotted against a temperature / weight curve to provide a rough estimate of volatility, T 50 And thermal stability are the three parameters for performance evaluation.

[0116] For the vapor deposition process, it is preferred to have a T as low as possible 50, and the lowest possible temperature at which the chemical precursor vapor pressure reaches 1 Torr (“T 1托 ”). In particular, a vapor pressure of 1 Torr should be at a temperature at which thermal degradation is minimized. (For sublimating solids, the balance of parameters is more challenging.)

[0117] Chemicals (ML) formed from a monovalent metal and a ligand L typically have a T at or below 150°C and above the melting point. 1托 These same chemicals generally exhibit good evaporation, where a) T 50 At or below 250°C and above the melting point temperature; and b) TGA residue is less than 1% by weight.

[0118] Due to the above properties, the metal M complexed with the ligand L is particularly suitable for coating cathode electrode materials, which include catalyst carbon support structures, such as single-walled fullerenes (Ceo and C72), multi-walled fullerenes, single-walled or multi-walled nanotubes, nanohorns, and / or carbon support structures having a density of about 0.2 g / cm3 to about 1.9 g / cm3, such as specialty carbons such as VULCAN or Imerys' SUPER C65.

[0119] Due to these aforementioned properties, the chemistry formed from the monovalent metal and the ligand L (ML) is well suited for vapor deposition processes that require low temperatures due to substrate temperature and / or co-reactant exposure limitations. LiTHD and LiO t Bu has 1 Torr pressure at over 150°C, producing longer pulses and / or higher dep T, which is disadvantageous for many electrode materials in terms of absolute temperature exposure and also the thermal budget of these materials. Cathode materials, for example, can experience lattice changes, oxygen loss, composition changes, etc. at temperatures of 200 degrees or more. For deposited materials that are negatively affected by silicon contamination, ligand L provides a silicon-free precursor chemistry capable of depositing Si-contaminated M-containing films. This is an advantage over LiTMSO and LiHMDS, both of which produce silicon-contaminated deposits, which is particularly problematic at the lowest ALD temperatures available for these chemistries.

[0120] Metal M is chelated or otherwise coordinated with the ligand L described herein and can be used as an M source gas phase precursor for vapor deposition of M-containing materials on a substrate. Gas phase deposition such as chemical vapor deposition and atomic layer deposition are well known in the art. The deposited material can also contain other atoms from other co-reactants or gas phase precursors. Common co-reactants are oxygen source reactants and phosphorus source reactants and nitrogen source reactants, which can provide O, N, or P as dopants, or react with ML gas phase precursors to form materials such as oxides or nitrides of M, such as MOx, MNx, MONx, MPO, MPON, etc., depending on the vapor deposition process. The specific examples herein are LiNbOx and LiPOx, but many other materials can be used together with different combinations of precursors and co-reactants. Those skilled in the art can choose from a variety of known oxygen source reactants, phosphorus source reactants and nitrogen source reactants to design a vapor deposition process. The oxygen source reactant includes O 2 , O 3 , H 2 O, H 2 O 2 ,NO,NO 2 , carboxylic acids, alcohols, diols, free radicals thereof, and combinations thereof. The nitrogen source reactants include N 2 , H 2 NH 3 , hydrazine (such as N 2 H 4 、MeHNNH 2 , MeHNNHMe), organic amines (such as NMeH 2 ,NEtH 2 、NMe 2 H、NEt 2 H.NMe 3 , NEt 3 、(SiMe 3 ) 2 NH), pyrazoline, pyridine, diamines (such as ethylenediamine), free radical species thereof, and mixtures thereof. Phosphorus source reactants include trimethyl phosphate (TMPO), diethylpyrophosphoramide (DEPA), triethyl phosphate (TEPO), TMP, and combinations thereof.

[0121] Examples

[0122] Example 1 - Synthesis

[0123]

[0124] O=C(tBu)CH2NMe(CH2)2NMe2 Li-OC(tBu)=CHNMe(CH2)2NMe2

[0125] O=C(tBu)CH2NMe(CH2)2NMe2: Ligand synthesized by 1:1 reaction of O=C(tBu)CH2Cl and HNMe[(CH2)2NMe2 in THF / ACN with TEA, K2CO3, or NaHCO3 at 50°C-60°C. 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)

[0126] The complex was prepared by reaction of O=C(tBu)CH2NMe[(CH2)2NMe2 with BuLi, LiNH2, or LiH in hexane, pentane, or MTBE. The crude material was purified by distillation to give a white solid with a yield of 85%. Melting point = 68°C.

[0127] 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.

[0128] TGA was performed under the following measurement conditions: sample weight of 11.4 mg, closed cup under N2 at 1 atm (complete evaporation temperature at 305° C.); sample weight of 10.4 mg, open cup under N2 at 1 atm (complete evaporation temperature T 完全 = 254°C); 30.1 mg sample weight, open cup at 15 Torr under N2 (complete evaporation temperature T 完全 =178°C). The temperature ramp rate was set to 10.0°C / min. Under N2 at 1 atm, the 50% evaporation T of the open cup TGA method was used. 50 =225℃.

[0129] These results are presented graphically in Figure 1 As shown, at T 完全 The residues were negligible (less than 1% by weight).

[0130] Example 2-5 - Additional Synthesis

[0131] The same synthesis was carried out with the following variation of Example 1:

[0132] ● Example 2: Changing positions R1, R2 and R7 to ethyl

[0133] ● Example 3: Changing position R7 to n-butyl

[0134] ● Example 3: Changing position R7 to ethyl

[0135] ●Example 5: M is Na

[0136] The synthesis of ML was carried out in the same manner as in Example 1, wherein L had a different alkyl group as described above. For M = Na, Na was provided as NaNH2 for forming ML. Similar results were obtained in terms of yield and purity.

[0137] Example 6 - Exemplary M +2 L 2 Synthesis of (M=Ca)

[0138]

[0139] Synthesis: Na{OC(tBu)=CHN(Me)(CH 2 CH 2 NMe 2 )} was added to 0.5 equivalent of CaI in THF 2 and stirred for 16 hours. Filtered and sublimed (120°C / 0.1 Torr) 1H NMR (C6D6, 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).

[0140] TGA measurements were performed under the following measurement conditions: sample weight of 6.2 mg, open cup under N2 at 1 atm (complete evaporation temperature at 280°C), temperature ramp rate set to 10.0°C / min. 50% evaporation using open cup TGA method under N2 at 1 atm; T 50 =230℃, such as Figure 2 as shown in .

[0141] Example 7 - LiPOx deposition on substrate

[0142] Li-OC(tBu)=CHNMe(CH2)2NMe2 from Example 1 was used as the Li source for atomic layer deposition (ALD) of LiPOx films on blank silicon wafers as test substrates. Trimethyl phosphate (TMPO) is a prior art standard phosphate source used with prior art Li precursors. Therefore, we chose TMPO as a co-reactant.

[0143] Preliminary characterization:

[0144] • Li-OC(tBu)=CHNMe(CH2)2NMe2 thermally decomposes at 250° C. Therefore, a baseline design for experimental parameter evaluation was performed at 200° C. to avoid parasitic CVD.

[0145] • Under the conditions tested (ozone as co-reactant), pulse time dose ramping of both precursors showed self-limited growth at 0.9 angstroms / cycle. This confirms that 200 degree deposition is an ALD process.

[0146] • An oxygen source is required to form LiPOx. ALD does not occur in the absence of ozone.

[0147] The design of experimental parameters from the preliminary tests at 200 °C was then used to evaluate the effect of temperature on ALD of LiPOx.

[0148] Experimental conditions:

[0149]

[0150] Pulse conditions:

[0151]

[0152] like Figure 3-5 As shown in , the temperatures tested were 125° C., 150° C., 175° C., and 200° C. LiPOx was deposited as a uniform continuous film over this temperature range.

[0153] according to Figure 3 , the main difference (as one would expect) is the deposition rate, where the maximum deposition rate is at 200°C. However, even at 125°C, each cycle of ALD forms a 0.36 angstrom thick deposit, which is a commercially viable deposition rate. This is in contrast to the prior art molecules discussed above where deposition stops at or above 200°C.

[0154] Figure 4 It shows that the refractive index of the deposited material remains stable over the entire temperature range and its value is close to that of Li 3 PO 4 (RI1.59).

[0155] Figure 5 The atomic percentages are shown, with silicon, N, and C all below the detection limit (which is less than 1%). Consistent with the RI measurements, the deposited material has Li 2.8 PO 3.8 The composition is very close to Li 3 PO 4 This combination of low temperature ALD, GPC rate, and composition is an important advance that will enable LiPOx deposition on a variety of temperature / thermal budget-constrained substrates, especially materials for Li-ion battery electrodes.

[0156] Good step coverage of non-uniform substrate surfaces is important for good electrode / cathode performance because 1) thicker points will inhibit Li-ion transport and 2) thinner points will lead to TM loss (e.g. Mn migration out of the cathode) and / or dendrite formation. To evaluate the applicability of this ALD process to non-uniform surfaces, a test Si wafer with grooves was used as a substrate. At an aspect ratio of 6.25, the step coverage was 87%. The maximum aspect ratio tested was 18. Even at this demanding aspect ratio, the ALD layer was continuous. The step coverage at this size was 65%, indicating that the ALD deposition process attenuates on extremely distant surfaces. Nevertheless, the minimum thickness achieved at the bottom of the groove was 14.9 nm, which is sufficient for many applications. In many applications such as battery electrode materials, a step coverage of less than 100% is acceptable. We expect that these results will be improved compared to these preliminary experiments through further parameter optimization.

[0157] Example 8 - LiNbOx deposition on substrate

[0158] As an example of diverse material deposition, we selected LiNbO 3 Binary deposition. Li-OC(tBu)=CHNMe(CH2)2NMe2 of Example 1 was used as the Li source precursor. For niobium, we selected the source precursor tert-butylimidobis(diethylamido)mono(tert-butylalkoxy)niobium(V) described in US10106887B2. One reason for selecting tert-butylimidobis(diethylamido)mono(tert-butylalkoxy)niobium(V) is that its ALD temperature window for NbOx deposition extends at least as low as 150°C. A temperature of 175°C was selected to balance the ALD windows and GPC of the Li and Nb source precursors. A blank silicon wafer was again used as a substrate for preliminary evaluation. The process conditions tested were:

[0159]

[0160] The ALD cycle parameters are:

[0161]

[0162] The Nb-ozone subcycle forms a layer of NbOx. The lithium precursor reacts with the NbOx to form the LiNbOx material. The total deposition growth rate of LiNbOx is 0.68 angstroms. Pulse dose experiments confirm that LiNbOx formation is a self-limiting ALD reaction. The stoichiometry of the deposited material is approximately LiNbO 2 With LiNbO 3 This is consistent with the RI of 1.9 for the deposited material, compared to an RI of 2.2 for the deposited material. The deposition was further tested on silicon wafers with grooves. Even at an aspect ratio of 15, the step coverage was >99%. The deposited layers were continuous and there were no gaps or visible defects in the slices scanned by the SEM. It is expected that with further parameter optimization (such as ozone dose), the atomic composition of the deposited material will be very close to that of LiNbO 3 , similar to the results finally obtained with LiPOx.

[0163] Example 9 - For exemplary M x Synthesis of LyDz

[0164]

[0165] t BuN=Nb(OEt) 2 {OC( t Bu)=CHN(Me)(CH 2 CH 2 NMe 2 )}

[0166] Synthesis: After 16 hours, t BuN=NbCl 3 Add to 2 equivalents of NaOEt and 1 equivalent of Li{OC( t Bu)=CHN(Me)(CH 2 CH 2 NMe 2 )} and stirred. Filter and purify by distillation (110°C / 0.1 Torr) 1 H NMR (C 6 D 6,400MHz):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),2.108ppm(3 H,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).

[0167] Example 9: Li-OC( t Bu)=CHN[(CH 2 ) 2 OMe] 2 Synthesis

[0168]

[0169] O=C(tBu)CH2N[(CH2)3NMe2]2 (left); Li-OC(tBu)=CHN[(CH2)3NMe2]2 (right)

[0170] O=C(tBu)CH2N[(CH2)3NMe2]2: Ligand synthesized by 1:1 reaction of O=C(tBu)CH2Cl and HN[(CH2)3NMe2]2 in THF / ACN with TEA, K2CO3, or NaHCO3 at 50°C-60°C.

[0171] 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) The complex was prepared by reaction of O=C(tBu)CH2N[(CH2)3NMe2]2 with BuLi, LiNH2, or LiH in hexane, pentane, or MTBE. The crude material was purified by sublimation to give a yellow solid yield (45%). 1H 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)

[0172] 13 C NMR(C6D6,101MHz):173.6,98.8,70.6,58.4,57.9,36.4,29.3.

[0173] Example 10 - Li-OC ( t Bu)=CHN[(CH 2 ) 2 OMe] 2 Synthesis

[0174]

[0175] O=C( t Bu)CH 2 N[(CH 2 ) 3 NMe 2 ] 2 (left); Li-OC( t Bu)=CHN[(CH2) 3 NMe 2 ] 2 (right)

[0176] O=C( t Bu)CH 2 N[(CH 2 ) 3 NMe 2 ] 2 :Through O=C( t Bu)CH 2 Cl and

[0177] HN[(CH 2 ) 3 NMe 2 ] 2 At 50℃-60℃, THF / ACN and TEA, K 2 CO 3 , or NaHCO 3 The ligand was synthesized in a 1:1 reaction.

[0178] 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) The complex was detected by O=C( t Bu)CH 2N[(CH 2 ) 3 NMe 2 ] 2 With BuLi, LiNH 2 , or LiH in hexane, pentane, or MTBE. The crude material was purified by sublimation to give a yellow solid yield (45%).

[0179] 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).

[0180] 13 C NMR(C6D6,101MHz):173.6,98.8,70.6,58.4,57.9,36.4,29.3.

[0181] Industrial Applicability

[0182] The invention is at least industrially applicable to chemical precursors suitable for use in depositing semiconductor manufacturing materials or battery electrodes.

[0183] Although the present invention has been described in conjunction with specific embodiments of the present invention, it is obvious that, in view of the foregoing description, many alternatives, modifications and variations will be clear to those skilled in the art. Therefore, it is intended to include all such alternatives, modifications and variations that fall within the spirit and broad scope of the appended claims. The present invention can suitably include disclosed elements, be composed of disclosed elements or be substantially composed of disclosed elements, and can be implemented in the absence of undisclosed elements. In addition, if there is language related to sequence, such as first and second, it should be understood in an exemplary sense rather than in a restrictive sense. For example, it will be appreciated by those skilled in the art that some steps can be combined into a single step.

[0184] All references identified herein are each hereby incorporated by reference into this application in their entirety, and for the specific information for which each reference is cited, the specific information is provided.

[0185] Legal Definitions and Principles of Interpretation

[0186] The singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise.

[0187] "Comprising" in the claims is an open transition term, which means that the subsequently identified claim elements are a non-exclusive list (i.e., anything else may be additionally included and remain within the scope of "comprising"). Unless otherwise indicated herein, "comprising" as used herein may be replaced by the more restrictive transition terms "consisting essentially of" and "consisting of".

[0188] "Providing" in the claims is defined to mean supplying, furnishing, making available, or preparing something. The step may instead be performed by any actor in the absence of explicit language in the claims.

[0189] Optional or optionally means that the subsequently described event or circumstance may or may not occur. The description includes instances where the event or circumstance occurs and instances where it does not occur.

[0190] Ranges may be expressed herein as from about one particular value and / or to about another particular value. When such a range is expressed, it is to be understood that another embodiment is from the one particular value and / or to the other particular value, along with all combinations within said range.

[0191] References herein to "one embodiment" or "an embodiment" mean that a particular feature, structure, or characteristic described with respect to that embodiment may be included in at least one embodiment of the present invention. The phrase "in one embodiment" appearing in different places in the specification does not necessarily all refer to the same embodiment, nor are separate or alternative embodiments necessarily mutually exclusive of other embodiments. The same applies to the term "implementation."

[0192] As used herein, "about" or "around or approximately" in the text or claims means ±10% of the stated value.

[0193] Technical Definition

[0194] As used herein, "room temperature" in the text or claims means from about 20°C to about 25°C.

[0195] The term "ambient conditions" refers to an ambient temperature of about 20°C to about 25°C (ie, surrounding temperature) and an ambient pressure of about 1 atm or 1 bar (surrounding temperature).

[0196] 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 from previous fabrication steps.

[0197] One of ordinary skill in the art will recognize that the term "film" or "layer" as used herein refers to a thickness of a material laid or spread over a surface and that the surface may be grooves or lines.

[0198] Standard abbreviations for elements from the periodic table of the elements are used herein. It should be 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.).

[0199] Unique CAS Registry Numbers (ie, "CAS") assigned by Chemical Abstracts Services are provided to help better identify the disclosed molecules.

[0200] The aspect ratio of a geometric shape is the ratio of its dimensions in different dimensions. The aspect ratio is 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 the width and the height. As examples, 8:5, 16:10, 1.6:1 are all ways to express the same aspect ratio. In objects with more than two dimensions, such as a hyperrectangle, the aspect ratio can still be defined as the ratio of the longest side to the shortest side.

[0201] Both conformality and step coverage refer to the degree of variation in the thickness of the film on a surface, especially on topologically different areas of the surface. This is particularly relevant to surfaces with microstructures having various aspect ratios. Complete (100%) conformality for the above example means that there is zero cusping, and the top surface, the sidewalls of the grooves, and, when applicable, the bottom of the grooves have all the same thickness. If a single conformality percentage is given, it is the minimum conformality measurement corresponding to the maximum deviation of the relative thickness of the overall film at two selected points on the surface. These two points can correspond to the highest aspect ratio point, or, for example, a point with a specific aspect ratio such as 6:1 or less. The thickness of the film is evaluated by a variety of methods, such as scanning electron microscopy of a sliced ​​substrate. If the film is at least 20% conformal, preferably at least 50% conformal, the film is generally "conformal".

[0202] It is to be understood that those skilled in the art may make many additional changes to details, materials, steps and arrangements of parts within the principles and scope of the invention as set forth in the appended claims, which are described herein to explain the nature of the invention. Therefore, the invention is not intended to be limited to the specific embodiments given in the above examples.

Claims

1. A ligand L, which is capable of forming a coordination complex with at least one metal atom, and which has the general formula: N(R1R2)-C(R3R4)-C(R5R6)-N(R7)-CH2-C(CR8R9R 10 )=O (Formula A), It is structurally represented by: or N(R1R2)-C(R3R4)-C(R5R6)--C(R 11 R 12 )-N(R7)-CH2-C(CR8R9R 10 )=O (Formula B), which is structurally represented by: Where R1-R 12 Each is independently selected from H, C1 to C4 alkyl (when C3 or C4 is straight chain or branched); or C1-C4 alkylamino C 1-4 NR2, wherein each R is independently selected from H, C1 to C4 alkyl (when C3 or C4 is linear or branched).

2. The ligand of claim 1, further comprising a coordinated metal atom M to form a metal-containing chemical, structurally represented by: or wherein M is selected from Li, Na, or K.

3. The metal-containing chemical according to claim 2, wherein: M is Li.

4. The ligand according to claim 1 or the metal-containing chemical according to claim 2, wherein R8, R9 and R 10 Each is independently selected from methyl or ethyl.

5. The ligand according to claim 1 or the metal-containing chemical according to claim 2, wherein M is Li, and wherein R8, R9 and R 10 Each is independently selected from methyl or ethyl.

6. The metal-containing chemical according to claim 5, wherein: R8, R9 and R 10 Each is a methyl group.

7. The ligand according to claim 1 or the metal-containing chemical according to claim 2, wherein: R1-R7 are each independently selected from H, methyl, or ethyl.

8. The metal-containing chemical according to claim 7, wherein: R1-R7 are each independently selected from H or methyl.

9. The metal-containing chemical according to claim 2, which is structurally represented by:

10. The metal-containing chemical according to claim 9, wherein: M is Li.

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

12. The metal-containing chemical according to claim 2, wherein: M is a polyvalent metal and two or more ligands are bonded to M, wherein M has one or more ligands L and one or more additional different ligands D to form a heteroleptic molecule M x LyDz, x≧2, y≧1, and z≧1.

13. A method for depositing a metal-containing film, comprising the steps of: a) contacting a substrate with a gas phase of a metal-containing chemical according to any one of claims 1 to 12, b) forming a deposition material on the substrate, the substrate comprising the metal from the metal-containing chemical.

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

15. The method of claim 14, wherein: M is Li, and the deposited material is LiNbO x , and the additional reactants include an oxygen source reactant and a niobium source reactant.

16. The method of claim 14, wherein: M is Li, the deposition 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. The method according to claim 15 or 16, wherein: The oxygen source reactant is ozone.

18. The method of claim 15, wherein: The niobium source reactant comprises a Group 5 transition metal-containing chemical having one of the following formulas: Where 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; C1-C5 linear, branched, or cyclic alkylsilyl; C1-C5 linear, branched, or cyclic alkylamino; or C1-C5 linear, branched, or cyclic fluoroalkyl; or Nb(RCp)(NR2)2(=NR) (Formula III); or selected from tert-butylimide tris(diethylamido) niobium(V), tert-butylimide tris(dimethylamido) niobium(V) and tert-butylimide tris(ethylmethylamido) niobium(V); and combinations of the foregoing.

19. The method of claim 16, wherein: The phosphorus source reactant is trimethyl phosphate (TMPO), diethyl pyrophosphoramide (DEPA), triethyl phosphate (TEPO), TMP and a combination thereof.

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 at or below 200°C.

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