Lithium precursors for depositing lithium-containing layers, islands or clusters

Abstract

A method for forming a Li-containing film, island or cluster on a substrate includes the following steps: introducing a vapor of a silicon-free lithium precursor into a reactor, and depositing at least a part of the silicon-free lithium precursor onto the substrate using a chemical vapor deposition method to form the Li-containing film, island or cluster.

Description

[0001] Cross - reference to related applications

[0002] This application claims the benefit of U.S. Application No. 62912458, filed Oct. 8, 2019, and U.S. Application No. 62915263, filed Oct. 15, 2019, which are hereby incorporated by reference in their entirety for all purposes. Technical field

[0003] Disclosed are silicon - free lithium precursors for depositing lithium - containing films, islands, or clusters, their synthesis methods, and their use methods. In particular, the disclosed precursors exhibit good volatility and thermal stability. The disclosed precursors are liquids below 150 °C, preferably liquids at 50 °C, more preferably liquids at 25 °C, and the liquids are suitable for deposition techniques such as ALD applications and CVD applications. Background art

[0004] Li - containing films are well - known for their applications in forming surface coating layers or films for electrode materials in lithium - ion battery applications. Examples of Li - containing films include LiPON, lithium phosphate, lithium borate, lithium borophosphate, lithium niobate, lithium titanate, lithium zirconium oxide, etc. For the formation of some of these materials, especially the formation of lithium niobate, lithium titanate, lithium zirconate, etc., the absence or low presence of silicon is preferred. During the initial few cycles of a lithium - ion battery, it is observed that the decomposition of the electrolyte at the electrolyte / electrode interface forms a solid electrolyte interface (SEI) on the anode and / or cathode. Due to the consumption of lithium ions, it results in a capacity loss of the lithium - ion battery. Additionally, the formed SEI layer is non - uniform and unstable, making it possible for cracks and dendrites to appear and leading to thermal runaway. Furthermore, the formed SEI layer also generates a potential barrier, which makes the insertion in the electrode more difficult. Electrode surface coating by atomic layer deposition (ALD) and chemical vapor deposition (CVD) techniques has been used to form the desired SEI film, thus avoiding the formation of these unstable layers. Li - containing films are very promising candidates as protective electrode coatings due to their good conductivity and high electrochemical stability. Another important application of Li - containing films is the formation of solid electrolyte materials used in solid - state batteries. Solid - state batteries are solvent - free systems, having a longer lifespan, faster charging time, and higher energy density than conventional lithium - ion batteries. Solid - state batteries are considered the next technological stage in battery development. Lithium - containing film solid electrolytes, such as lithium phosphate, lithium borate, and lithium borophosphate, are deposited by ALD / CVD techniques. Even uniform and conformal Li - containing films can be obtained on complex architectures such as 3D batteries.

[0005] With the increasing demand for energy storage, higher capacity retention and improved safety performance are required. Li-containing films can effectively prevent or reduce the formation of the solid electrolyte interface (SEI), such as lithium phosphate, lithium phosphonitride oxide (LiPON), and different lithium metal oxides, such as lithium titanate, lithium zirconate, and lithium niobate. These materials are expected to improve the interface between the electrode and the electrolyte in current lithium-ion batteries or solid-state batteries. Li-containing films such as lithium niobate can also be used in high-frequency electronic devices, such as mobile applications. Lithium fluorite is also a material of interest for use in optics or as a potential gate dielectric due to its high bandgap and high dielectric constant.

[0006] Gordon et al.'s WO 00 / 67300 A1 discloses the synthesis of basic lithium amide precursors having the following general formula: MN(E 1 R 1 R 2 R 3 )(E 2 R 4 R 5 R 6 ), where M is an alkali metal: Li, Na, K; E 1 and E 2 = C, Si, Ge or Sn; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 are H, alkyl or fluoroalkyl. All compounds are liquids at 20 °C. The formation of alkali metal-containing films by CVD is disclosed.

[0007] Gordon et al.'s WO 02 / 27063 A2 discloses the use of LiN(SiMe 3 ) 2 , LiN(SiEtMe 2 ) 2 and Li(TMPD) as lithium precursors for the CVD and ALD of lithium phosphate. Diisopropyl phosphate is used as the phosphate precursor. TMPD represents 2,2,6,6-tetramethylpiperidine.

[0008] Pallem et al.'s WO 2011 / 002920 A2 discloses silicon-free lithium-containing precursors, namely, lithium alkyl amidinate and lithiumalkylcyclopentadienyl compounds having the following general formula: Li(R 1 R 2 R 3 R 4 R5 Cp).D, Li(NR-amd).D, and Li(NR-fmd).D, where D = a mono-, bi-, tri-, or polydentate neutral coordination ligand system; R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 is H or an alkyl group.

[0009] US 2012 / 0276305 by Hamalainen et al. discloses the synthesis of LiN(SiMe 3 ) 2 , LiOtBu, Li(thd), and Li(hfac) from commercial sources. They are used as lithium sources for forming lithium phosphate films by ALD. The disclosed phosphorus source is a phosphate ester reagent having the formula O=P(OR) 3 , where R is an alkyl group. In the examples, LiN(SiMe 3 ) 2 and LiOtBu are combined with trimethyl phosphate (TMPO) for the ALD of lithium phosphate. It is also disclosed that Li(thd) and Li(hfac) are used for Li 2 O, Li 2 CO 3 and other lithium-containing materials. All the lithium precursors disclosed by Hamalainen et al. are solids, have high melting points (typically above 150 °C), and have limited volatility and thermal stability.

[0010] More prior art for forming Li-containing films can include Chem.Mater.[Materials Chemistry], 6987-6993, 27(20), 2015 (ALD of Lithium Phosphorus Oxynitride); NanoLett.[Nano Letters], 1276-1281, 16(2), 2016 (Atomic / Molecular Layer Deposition of Lithium Terephthalate Films as High Rate Capability Li-Ion Battery Anodes); US 20170067161 (Method for producing lithium phosphorus oxynitride layer); Journal of Vacuum Science & Technology, A; Vacuum, Surfaces, and Films, 01B133 / 1-01B133 / 8, 35(1), 2017 (Enhanced process and composition control for atomic layer deposition with lithium trimethylsilanolate); RSC Advances[Royal Society of Chemistry Advances], 6315-6322, 2(15), 2012 (ALD of lithium nitride and carbonate using lithium silylamide); WO 2012076817 (Method for producing lithium-based layers by CVD); J.Mater.Chem.[Journal of Materials Chemistry], 8767 - 8771, 19(46), 2009 (ALD of Lithium-containing thin films [Atomic Layer Deposition of Lithium-containing thin films]); US 7,615,250 (Organoaluminum precursor compounds); US 8,871,304 ((Amide amino alkane) metal compound, method of manufacturing metal-containing thin film using said metal compound); Chem. Eur. J. [European Journal of Chemistry], 1091 - 1094, 5(3), 1999 (X-ray Crystal Structures and Some Solution Structures of Lithium Amides with Intramolecular Complexation of Lithium); US 6294495 (Tridentate ligand-containing metal catalyst complexes for olefin polymerization); Org. Lett. [Organic Letters], 5378 - 5381, 12(23), 2010 (Isomerization of Allyl Ethers Initiated by Lithium Diisopropylamide); Tetrahedron, 1657 - 1666, 58(9), 2002 (Use of lithium N,O-dimethylhydroxylamide as an efficient in situ protecting agent for aromatic aldehydes); J. Mater. Chem.[Journal of Materials Chemistry], 2877 - 2881, 20(14), 2010 (Lanthanum titanate and lithium lanthanum titanate films grown by atomic layer deposition).

[0011] Other concerned applications using lithium precursors include forming Li - containing clusters or islands.

[0012] Typically, silicon - containing lithium precursors such as LiN(SiMe 3 ) 2 can be used. Although such solid precursors are quite stable and have sufficient volatility, silicon will be partially retained in the resulting deposited film. When forming materials such as LiTiO 3 , LiNbO 3 or LiZrO x , the presence of silicon may be problematic, where silicon may lead to adverse electrochemical characteristics (related to the induced disorder of the material), and thus result in lower ionic conductivity. Therefore, a silicon - free lithium precursor for deposition applications needs to be found. SUMMARY OF THE INVENTION

[0013] Disclosed is a method for forming a Li - containing film, island or cluster on a substrate, the method comprising the steps of:

[0014] Introducing a lithium precursor having the following general formula:

[0015] [Li - NL 1 L 2 - D x y (I)

[0016] into a reactor in which the substrate is disposed, where

[0017] L 1 has the following general formula: C m H n , (C m H n ) - ER 1 R 2 ) or (C m H n ) - E′R 1 ), where

[0018] ·C m H n is a straight - chain, branched - chain or cyclic alkyl;

[0019] ​·m and n are independent integers, where 1 ≤ m ≤ 16 and 1 ≤ n ≤ 16;

[0020] ·E is B, N;

[0021] ·E′ is a divalent element;

[0022] ·R 1 and R 2 each independently selected from the group consisting of: linear, branched or cyclic alkyl, or linear, branched or cyclic alkyl substituted by other atoms or groups;

[0023] L 2 has the following general formula: (C p H q )-ER 3 R 4 or (C p H q )-E′R 3 , where

[0024] ·C p H q is linear, branched or cyclic alkyl;

[0025] ·p and q are independent integers, where 1 ≤ p ≤ 16 and 1 ≤ q ≤ 16;

[0026] ·E is B, N;

[0027] ·E′ is a divalent element;

[0028] ·R 3 and R 4 each independently selected from the group consisting of: linear, branched or cyclic alkyl, or linear, branched or cyclic alkyl substituted by other atoms or groups;

[0029] D is independently selected from monodentate, bidentate, tridentate or polydentate neutral coordination ligand systems;

[0030] x is an integer, where 0 ≤ x ≤ 4; and

[0031] y is the degree of association of the molecule, where 1 ≤ y ≤ 6; and

[0032] At least a portion of the lithium precursor is deposited onto the substrate using a chemical vapor deposition method to form the Li-containing film, island or cluster.

[0033] The disclosed method may include one or more of the following aspects:

[0034] ·L 1 is a C 1 -C 16 linear, branched or cyclic carbon chain, or is (C m Hn )-ER 1 R 2 or (C m H n )-E’R 1 in the form of, where

[0035] C m H n is an alkyl chain and can be a straight-chain, branched-chain or cyclic alkyl;

[0036] E represents B, N;

[0037] E′ represents a divalent element such as O, S;

[0038] m is an integer with a value of 1, or an integer ranging from 1 to 8;

[0039] n is an independent integer ranging from 2 to 16;

[0040] R 1 is independent and is selected from the group consisting of: hydrogen, straight-chain, branched-chain or cyclic C 1 -C 8 alkyl, or a straight-chain, branched-chain or cyclic alkyl substituted by other atoms or groups;

[0041] R 2 is independent and is selected from the group consisting of: hydrogen, straight-chain, branched-chain or cyclic C 1 -C 8 alkyl, or a straight-chain, branched-chain or cyclic alkyl substituted by other atoms or groups;

[0042] L 2 is (C p H q )-ER 3 R 4 or (C p H q )-E’R 3 in the form of, where

[0043] C p H q is an alkyl chain and can be a straight-chain, branched-chain or cyclic alkyl;

[0044] E represents B, N;

[0045] E′ represents a divalent element such as O, S;

[0046] p and q are independent integers ranging from 1 to 16, preferably p ranges from 1 to 8 and q ranges from 2 to 16, and most preferably p is different from m;

[0047] R 3 and R4 is independent and is selected from the group consisting of: hydrogen, a straight-chain, branched-chain or cyclic alkyl group, or a straight-chain, branched-chain or cyclic alkyl group substituted by other atoms or groups;

[0048] D is independently selected from monodentate, bidentate, tridentate or polydentate neutral coordination ligand systems, preferably monodentate or bidentate;

[0049] x is an integer between 0 and 4;

[0050] y represents the degree of association of the molecule and is between 1 and 6;

[0051] · The lithium precursor is silicon-free;

[0052] · The lithium precursor is selected from LiNMe(CH 2 CH 2 NMe 2 ), LiNMe(CH 2 CH 2 NMe 2 )(1,2-diethoxyethane), LiNMe(CH 2 CH 2 NMe 2 )(1,2-dimethoxyethane), LiNEt(CH 2 CH 2 NMe 2 ), LiNiPr(CH 2 CH 2 NMe 2 ), LiNtBu(CH 2 CH 2 NMe 2 ), LiNtBu(CH 2 CH 2 NEtMe), LiNtBu(CHMeCH 2 NMe 2 ), LiNtBu(CH 2 CHMeNMe 2 ), LiN(CH 2 CH 2 NMe 2 ), 2 LiN(CH 2 CH 2 NEt 2 ), 2 LiN(CH 2 CH 2 NiPr 2 ), 2 LiN(CH 2 CH 2 NEtMe)2 , LiN(CH 2 CH 2 CH 2 NMe 2 ) 2 , LiN(CHMeCH 2 NMe 2 ) 2 , LiN(CHMeCH 2 NMe 2 )(CH 2 CH 2 NMe 2 ), LiN(CH 2 CHMeNMe 2 ) 2 , LiN(CH 2 CHMeNMe 2 )(CH 2 CH 2 NMe 2 ), LiN(CHEtCH 2 NMe 2 )(CH 2 CH 2 NMe 2 ), LiN(CH 2 CHEtNMe 2 )(CH 2 CH 2 NMe 2 ), LiN(CMe 2 CH 2 NMe 2 )(CH 2 CH 2 NMe 2 ), LiN(CH 2 CMe 2 NMe 2 )(CH 2 CH 2 NMe 2 ), LiN(CH 2 CH 2 NMe 2 )(CH 2 CH 2 CH 2 NMe 2 ), LiNMe(CH 2 CH 2 OMe), LiNMe(CH 2 CH 2 OEt), LiNMe(CH 2 CH 2OiPr)LiNMe(CH 2 CH 2 OtBu)、LiNEt(CH 2 CH 2 OMe)、LiNEt(CH 2 CH 2 OEt)、LiNiPr(CH 2 CH 2 OMe)、LiNtBu(CH 2 CH 2 OMe)、LiN(CH 2 CH 2 OMe) 2 、LiN(CH 2 CH 2 OEt) 2 、LiN(CH 2 CH 2 OiPr) 2 、LiN(CH 2 CH 2 OtBu) 2 、LiN(CH 2 CH 2 NMe 2 )(CH 2 CH 2 OMe)、LiN(CH 2 CH 2 NMe 2 )(CH 2 CH 2 OEt)、LiN(CH 2 CH 2 NMe 2 )(CH 2 CH 2 OiPr)、LiN(CH 2 CH 2 NMe 2 )(CH 2 CH 2 OtBu)、LiNMe(CH 2 CH(OMe) 2 ) etc.;

[0053] · The lithium precursor is LiNtBu(CH 2 CH 2 NMe 2 )、LiNtBu(CH 2 CH 2 NEtMe)、LiNtBu(CHMeCH 2 NMe 2 )、LiNtBu(CH2 CHMeNMe 2 )、LiN(CH 2 CH 2 NEtMe) 2 、LiN(CH 2 CH 2 OEt) 2 、LiN(CH 2 CH 2 NMe 2 ) 2 、LiN(CH 2 CH 2 CH 2 NMe 2 ) 2 、LiN(CH 2 CH 2 NMeEt) 2 、LiN(CHMeCH 2 NMe 2 )(CH 2 CH 2 NMe 2 、LiN(CH 2 CHMeNMe 2 )(CH 2 CH 2 NMe 2 、LiN(CHEtCH 2 NMe 2 )(CH 2 CH 2 NMe 2 、LiN(CH 2 CHEtNMe 2 )(CH 2 CH 2 NMe 2 、LiN(CMe 2 CH 2 NMe 2 )(CH 2 CH 2 NMe 2 、LiN(CH 2 CMe 2 NMe 2 )(CH 2 CH 2 NMe 2 、LiN(CH 2 CH 2 NiPr 2 ) 2 、LiN(CH 2 CH 2 NMe2 )(CH 2 CH 2 CH 2 NMe 2 )、LiN(CH 2 CH 2 OEt) 2 、LiNMe(CH 2 CH 2 OEt)、LiNMe(CH 2 CH(OMe) 2 ) etc.;

[0054] · The lithium precursor is LiNMe(CH 2 CH 2 NMe 2 );

[0055] · The lithium precursor is LiNMe(CH 2 CH 2 NMe 2 )(1,2 - diethoxyethane);

[0056] · The lithium precursor is LiNMe(CH 2 CH 2 NMe 2 )(1,2 - dimethoxyethane);

[0057] · The lithium precursor is LiNEt(CH 2 CH 2 NMe 2 );

[0058] · The lithium precursor is LiNiPr(CH 2 CH 2 NMe 2 );

[0059] · The lithium precursor is LiNtBu(CH 2 CH 2 NMe 2 );

[0060] · The lithium precursor is LiNtBu(CH 2 CH 2 NEtMe);

[0061] · The lithium precursor is LiNtBu(CHMeCH 2 NMe 2 );

[0062] · The lithium precursor is LiNtBu(CH 2 CHMeNMe 2 );

[0063] · The lithium precursor is LiN(CH 2 CH 2 NMe 2 ) 2 ;

[0064] · The lithium precursor is LiN(CH 2 CH 2 NEt 2 ) 2 ;

[0065] · The lithium precursor is LiN(CH 2 CH 2 NiPr 2 ) 2 ;

[0066] · The lithium precursor is LiN(CH 2 CH 2 NEtMe) 2 ;

[0067] · The lithium precursor is LiN(CH 2 CH 2 CH 2 NMe 2 ) 2 ;

[0068] · The lithium precursor is LiN(CHMeCH 2 NMe 2 ) 2 ;

[0069] · The lithium precursor is LiN(CHMeCH 2 NMe 2 )(CH 2 CH 2 NMe 2 );

[0070] · The lithium precursor is LiN(CH 2 CHMeNMe 2 ) 2 ;

[0071] · The lithium precursor is LiN(CH 2 CHMeNMe 2 )(CH 2 CH 2 NMe 2 );

[0072] · The lithium precursor is LiN(CHEtCH 2 NMe 2 )(CH 2 CH 2 NMe 2 );

[0073] · The lithium precursor is LiN(CH 2 CHEtNMe 2 )(CH 2 CH 2 NMe 2 );

[0074] · The lithium precursor is LiN(CMe 2 CH 2 NMe 2 )(CH 2 CH 2 NMe 2 );

[0075] · The lithium precursor is LiN(CH 2 CMe 2 NMe 2 )(CH 2 CH 2 NMe 2 );

[0076] · The lithium precursor is LiN(CH 2 CH 2 NMe 2 )(CH 2 CH 2 CH 2 NMe 2 );

[0077] · The lithium precursor is LiNMe(CH 2 CH 2 OMe);

[0078] · The lithium precursor is LiNMe(CH 2 CH 2 OEt);

[0079] · The lithium precursor is LiNMe(CH 2 CH 2 OiPr);

[0080] · The lithium precursor is LiNMe(CH 2 CH 2 OtBu);

[0081] · The lithium precursor is LiNEt(CH 2 CH 2 OMe);

[0082] · The lithium precursor is LiNEt(CH 2 CH 2 OEt);

[0083] · The lithium precursor is LiNiPr(CH2 CH 2 OMe);

[0084] · The lithium precursor is LiNtBu(CH 2 CH 2 OMe);

[0085] · The lithium precursor is LiN(CH 2 CH 2 OMe) 2 ;

[0086] · The lithium precursor is LiN(CH 2 CH 2 OEt) 2 ;

[0087] · The lithium precursor is LiN(CH 2 CH 2 OiPr) 2 ;

[0088] · The lithium precursor is LiN(CH 2 CH 2 OtBu) 2 ;

[0089] · The lithium precursor is LiN(CH 2 CH 2 NMe 2 )(CH 2 CH 2 OMe);

[0090] · The lithium precursor is LiN(CH 2 CH 2 NMe 2 )(CH 2 CH 2 OEt);

[0091] · The lithium precursor is LiN(CH 2 CH 2 NMe 2 )(CH 2 CH 2 OiPr);

[0092] · The lithium precursor is LiN(CH 2 CH 2 NMe 2 )(CH 2 CH 2 OtBu);

[0093] · The lithium precursor is LiNMe(CH 2 CH(OMe) 2 ));

[0094] · The vapor deposition method is ALD, CVD, spraying, dip coating, slot coating, spin coating deposition, or a combination thereof;

[0095] · The vapor deposition method is ALD;

[0096] · The vapor deposition method is CVD;

[0097] · The temperature in the reaction chamber is within a temperature range below room temperature;

[0098] · The temperature range in the reaction chamber is from about 0 °C to about 600 °C;

[0099] · The temperature range in the reaction chamber is from about 15 °C to about 600 °C;

[0100] · The temperature range in the reaction chamber is from about 125 °C to about 250 °C;

[0101] · The temperature range of the reactor is from about 20 °C to about 1000 °C;

[0102] · For the plasma deposition process, the deposition temperature range is from about 20 °C to about 550 °C;

[0103] · For ALD and CVD, the deposition temperature range is from about 100 °C to about 500 °C;

[0104] · For ALD and CVD, the deposition temperature range is from about 250 °C to about 350 °C;

[0105] · For the thermal process, the deposition temperature range is from about 200 °C to about 800 °C;

[0106] · For the thermal process, the deposition temperature range is from about 400 °C to about 600 °C;

[0107] · For ALD, the deposition temperature is 100 °C;

[0108] · For ALD, the deposition temperature is 125 °C;

[0109] · For ALD, the deposition temperature is 135 °C;

[0110] · For ALD, the deposition temperature is 150 °C;

[0111] · For ALD, the deposition temperature is 175 °C;

[0112] · For ALD, the deposition temperature is 200 °C;

[0113] · For ALD, the deposition temperature is 250 °C;

[0114] · For ALD, the deposition temperature is 500 °C;

[0115] · For CVD, the deposition temperature is 200 °C;

[0116] · For CVD, the deposition temperature is 300 °C;

[0117] · For CVD, the deposition temperature is 400 °C;

[0118] · For CVD, the deposition temperature is 500 °C;

[0119] · The temperature of the substrate ranges from room temperature to about 600 °C;

[0120] · The lithium precursor is a silicon-free lithium precursor;

[0121] · The lithium precursor is a monomer, dimer, trimer, or a combination thereof;

[0122] · Further includes the step of delivering a co-reactant to the reactor;

[0123] · The co-reactant is selected from O 3 、O 2 、H 2 O, trimethyl phosphate, alkyl phosphate, alkyl phosphonimide, NO, N 2 O, H 2 O 2 、O radicals, or a combination thereof;

[0124] · The co-reactant is selected from N 2 、NH 3 、N 2 H 4 or alkyl hydrazine;

[0125] · The co-reactant is O 3 ;

[0126] · The lithium precursor is liquid at a temperature below 150 °C;

[0127] · The lithium precursor is liquid at 50 °C;

[0128] · The lithium precursor is liquid at 25 °C;

[0129] · The Li-containing film, island, or cluster is a film, island, or cluster of Li 2 O, LiOH, Li 2 S, Li 3 N, LiF, lithium carbonate, lithium aluminum fluoride, lithium aluminum oxide, lithium aluminum, lithium cobalt oxide, lithium titanate, lithium zirconate, lithium niobate, LiPON, lithium phosphate, lithium borate, lithium borophosphate, lithium niobate, lithium zirconium oxide, etc.

[0130] Also disclosed is a composition comprising a lithium precursor having the following general formula:

[0131] [Li-NL 1 L 2 -D x y (I)

[0132] wherein

[0133] L 1 has the following general formula: C m H n , (C m H n )-ER 1 R 2 ) or (C m H n )-E′R 1 ), wherein

[0134] ·C m H n is a straight-chain, branched-chain or cyclic alkyl group;

[0135] ·m and n are independent integers, 1 ≤ m ≤ 16, 1 ≤ n ≤ 16;

[0136] ·E is B, N;

[0137] ·E′ is a divalent element;

[0138] ·R 1 and R 2 each independently selected from the group consisting of: hydrogen, straight-chain, branched-chain or cyclic alkyl, or straight-chain, branched-chain or cyclic alkyl substituted by other atoms or groups;

[0139] L 2 has the following general formula: (C p H q )-ER 3 R 4 or (C p H q )-E′R 3 , wherein

[0140] ·C p H q is a straight-chain, branched-chain or cyclic alkyl group;

[0141] ·p and q are independent integers, 1 ≤ p ≤ 16, 1 ≤ q ≤ 16;

[0142] ·E is B, N;

[0143] ·E′ is a divalent element;

[0144] ·R 3 and R 4 ​Each independently selected from the group consisting of: straight-chain, branched-chain or cyclic alkyl, or straight-chain, branched-chain or cyclic alkyl substituted by other atoms or groups;

[0145] D is independently selected from monodentate, bidentate, tridentate or polydentate neutral coordination ligand systems;

[0146] x is an integer, 0 ≤ x ≤ 4; and

[0147] y is the degree of association of the molecule, 1 ≤ y ≤ 6.

[0148] The disclosed compositions include one or more of the following aspects:

[0149] ·L 1 is C 1 -C 16 a straight-chain, branched-chain or cyclic carbon chain, or of the form (C m H n )-ER 1 R 2 or (C m H n )-E’R 1 wherein

[0150] C m H n is an alkyl chain and can be straight-chain, branched-chain or cyclic alkyl;

[0151] E represents B, N;

[0152] E′ represents a divalent element such as O, S;

[0153] m is an integer with a value of 1, or an integer ranging from 1 to 8;

[0154] n is an independent integer ranging from 2 to 16;

[0155] R 1 is independent and selected from the group consisting of: hydrogen, straight-chain, branched-chain or cyclic C 1 -C 8 alkyl, or straight-chain, branched-chain or cyclic alkyl substituted by other atoms or groups;

[0156] R 2 is independent and selected from the group consisting of: hydrogen, straight-chain, branched-chain or cyclic C 1 -C 8 alkyl, or straight-chain, branched-chain or cyclic alkyl substituted by other atoms or groups;

[0157] ·L 2 is (C p H q )-ER 3 R4 or (C p H q )-E’R 3 in the form, where

[0158] C p H q is an alkyl chain and can be a straight-chain, branched-chain or cyclic alkyl;

[0159] E represents B, N;

[0160] E′ represents a divalent element, such as O, S;

[0161] p and q are independent integers ranging from 1 to 16, preferably p is included from 1 to 8 and q is included from 2 to 16, most preferably p is different from m;

[0162] R 3 and R 4 are independent and are selected from the group consisting of: hydrogen, straight-chain, branched-chain or cyclic alkyl, or straight-chain, branched-chain or cyclic alkyl substituted by other atoms or groups;

[0163] ·D is independently selected from monodentate, bidentate, tridentate or polydentate neutral coordination ligand systems, preferably monodentate or bidentate;

[0164] ·x is an integer included between 0 and 4;

[0165] ·y represents the degree of association of the molecule and is included between 1 and 6;

[0166] ·Provided that L 1 = Me, L 2 = {C p H q = CH 2 CH 2 , E = N, and R 3 and R 4 are both Me}, x = 0 is excluded;

[0167] ·Provided that L 1 = Et, L 2 = {C p H q = CH 2 CH 2 , E = N, and R 3 and R 4 are both Me}, x = 0 is excluded;

[0168] ·Provided that L 1 = iPr, L 2 = {C p H q = CH 2CH 2 , E = N, and R 3 and R 4 are both Me}, x = 0 is excluded;

[0169] · Provided that L 1 = tBu, L 2 ={C p H q = CH 2 CH 2 , E = N, and R 3 and R 4 are both Me}, x = 0 is excluded;

[0170] · Provided that L 1 = tBu, L 2 ={C p H q = CMeHCH 2 , E = N, and R 3 and R 4 are both Me}, x = 0 is excluded;

[0171] · Provided that L 1 = tBu, L 2 ={C p H q = CH 2 CHMe, E = N, and R 3 and R 4 are both Me}, x = 0 is excluded;

[0172] · Provided that L 1 ={C m H n = CH 2 CH 2 , E = N, R 1 and R 2 are both Me}, L 2 ={C p H q = CH 2 CH 2 , E = N, R 3 and R 4 are both Me}, x = 0 is excluded;

[0173] · Provided that L 1 ={C m H n = CH 2 CH 2 , E = N, R 1 and R 2 are both Et}, L 2 ={C pH q =CH 2 CH 2 , E = N, R 3 and R 4 are both Et}, x = 0 is excluded; and

[0174] · Provided that L 1 = Me, L 2 = {C p H q = CH 2 CH 2 , E’ = O, R 3 is Me}, x = 0 is excluded;

[0175] · The lithium precursor is selected from LiNMe(CH 2 CH 2 NMe 2 ), LiNMe(CH 2 CH 2 NMe 2 )(1,2 - diethoxyethane), LiNMe(CH 2 CH 2 NMe 2 )(1,2 - dimethoxyethane), LiNEt(CH 2 CH 2 NMe 2 ), LiNiPr(CH 2 CH 2 NMe 2 ), LiNtBu(CH 2 CH 2 NMe 2 ), LiNtBu(CH 2 CH 2 NEtMe), LiNtBu(CHMeCH 2 NMe 2 ), LiNtBu(CH 2 CHMeNMe 2 ), LiN(CH 2 CH 2 NMe 2 ) 2 , LiN(CH 2 CH 2 NEt 2 ), 2 , LiN(CH 2 CH 2 NiPr 2 ), 2 , LiN(CH 2 CH 2 NEtMe)2 , LiN(CH 2 CH 2 CH 2 NMe 2 ) 2 , LiN(CHMeCH 2 NMe 2 ) 2 , LiN(CHMeCH 2 NMe 2 )(CH 2 CH 2 NMe 2 ), LiN(CH 2 CHMeNMe 2 ) 2 , LiN(CH 2 CHMeNMe 2 )(CH 2 CH 2 NMe 2 ), LiN(CHEtCH 2 NMe 2 )(CH 2 CH 2 NMe 2 ), LiN(CH 2 CHEtNMe 2 )(CH 2 CH 2 NMe 2 ), LiN(CMe 2 CH 2 NMe 2 )(CH 2 CH 2 NMe 2 ), LiN(CH 2 CMe 2 NMe 2 )(CH 2 CH 2 NMe 2 ), LiN(CH 2 CH 2 NMe 2 )(CH 2 CH 2 CH 2 NMe 2 ), LiNMe(CH 2 CH 2 OMe), LiNMe(CH 2 CH 2 OEt), LiNMe(CH 2 CH 2OiPr)LiNMe(CH 2 CH 2 OtBu)、LiNEt(CH 2 CH 2 OMe)、LiNEt(CH 2 CH 2 OEt)、LiNiPr(CH 2 CH 2 OMe)、LiNtBu(CH 2 CH 2 OMe)、LiN(CH 2 CH 2 OMe) 2 、LiN(CH 2 CH 2 OEt) 2 、LiN(CH 2 CH 2 OiPr) 2 、LiN(CH 2 CH 2 OtBu) 2 、LiN(CH 2 CH 2 NMe 2 )(CH 2 CH 2 OMe)、LiN(CH 2 CH 2 NMe 2 )(CH 2 CH 2 OEt)、LiN(CH 2 CH 2 NMe 2 )(CH 2 CH 2 OiPr)、LiN(CH 2 CH 2 NMe 2 )(CH 2 CH 2 OtBu)、LiNMe(CH 2 CH(OMe) 2 ) etc.;

[0176] · The lithium precursor is selected from LiNtBu(CH 2 CH 2 NMe 2 )、LiNtBu(CH 2 CH 2 NEtMe)、LiNtBu(CHMeCH 2 NMe 2 )、LiNtBu(CH2 CHMeNMe 2 )、LiN(CH 2 CH 2 NEtMe) 2 、LiN(CH 2 CH 2 OEt) 2 、LiN(CH 2 CH 2 NMe 2 ) 2 、LiN(CH 2 CH 2 CH 2 NMe 2 ) 2 、LiN(CH 2 CH 2 NMeEt) 2 、LiN(CHMeCH 2 NMe 2 )(CH 2 CH 2 NMe 2 、LiN(CH 2 CHMeNMe 2 )(CH 2 CH 2 NMe 2 、LiN(CHEtCH 2 NMe 2 )(CH 2 CH 2 NMe 2 、LiN(CH 2 CHEtNMe 2 )(CH 2 CH 2 NMe 2 、LiN(CMe 2 CH 2 NMe 2 )(CH 2 CH 2 NMe 2 、LiN(CH 2 CMe 2 NMe 2 )(CH 2 CH 2 NMe 2 、LiN(CH 2 CH 2 NiPr 2 ) 2 、LiN(CH 2 CH 2 NMe2 )(CH 2 CH 2 CH 2 NMe 2 )、LiN(CH 2 CH 2 OEt) 2 、LiNMe(CH 2 CH 2 OEt)、LiNMe(CH 2 CH(OMe) 2 ) etc.;

[0177] · The lithium precursor is LiNMe(CH 2 CH 2 NMe 2 );

[0178] · The lithium precursor is LiNMe(CH 2 CH 2 NMe 2 )(1,2 - diethoxyethane);

[0179] · The lithium precursor is LiNMe(CH 2 CH 2 NMe 2 )(1,2 - dimethoxyethane);

[0180] · The lithium precursor is LiNEt(CH 2 CH 2 NMe 2 );

[0181] · The lithium precursor is LiNiPr(CH 2 CH 2 NMe 2 );

[0182] · The lithium precursor is LiNtBu(CH 2 CH 2 NMe 2 );

[0183] · The lithium precursor is LiNtBu(CH 2 CH 2 NEtMe);

[0184] · The lithium precursor is LiNtBu(CHMeCH 2 NMe 2 );

[0185] · The lithium precursor is LiNtBu(CH 2 CHMeNMe 2 );

[0186] · The lithium precursor is LiN(CH 2 CH 2 NMe 2 ) 2 ;

[0187] · The lithium precursor is LiN(CH 2 CH 2 NEt 2 ) 2 ;

[0188] · The lithium precursor is LiN(CH 2 CH 2 NiPr 2 ) 2 ;

[0189] · The lithium precursor is LiN(CH 2 CH 2 NEtMe) 2 ;

[0190] · The lithium precursor is LiN(CH 2 CH 2 CH 2 NMe 2 ) 2 ;

[0191] · The lithium precursor is LiN(CHMeCH 2 NMe 2 ) 2 ;

[0192] · The lithium precursor is LiN(CHMeCH 2 NMe 2 )(CH 2 CH 2 NMe 2 );

[0193] · The lithium precursor is LiN(CH 2 CHMeNMe 2 ) 2 ;

[0194] · The lithium precursor is LiN(CH 2 CHMeNMe 2 )(CH 2 CH 2 NMe 2 );

[0195] · The lithium precursor is LiN(CHEtCH 2 NMe 2 )(CH 2 CH 2 NMe 2 );

[0196] · The lithium precursor is LiN(CH 2 CHEtNMe 2 )(CH 2 CH 2 NMe 2 );

[0197] · The lithium precursor is LiN(CMe 2 CH 2 NMe 2 )(CH 2 CH 2 NMe 2 );

[0198] · The lithium precursor is LiN(CH 2 CMe 2 NMe 2 )(CH 2 CH 2 NMe 2 );

[0199] · The lithium precursor is LiN(CH 2 CH 2 NMe 2 )(CH 2 CH 2 CH 2 NMe 2 );

[0200] · The lithium precursor is LiNMe(CH 2 CH 2 OMe);

[0201] · The lithium precursor is LiNMe(CH 2 CH 2 OEt);

[0202] · The lithium precursor is LiNMe(CH 2 CH 2 OiPr);

[0203] · The lithium precursor is LiNMe(CH 2 CH 2 OtBu);

[0204] · The lithium precursor is LiNEt(CH 2 CH 2 OMe);

[0205] · The lithium precursor is LiNEt(CH 2 CH 2 OEt);

[0206] · The lithium precursor is LiNiPr(CH2 CH 2 OMe);

[0207] · The lithium precursor is LiNtBu(CH 2 CH 2 OMe);

[0208] · The lithium precursor is LiN(CH 2 CH 2 OMe) 2 ;

[0209] · The lithium precursor is LiN(CH 2 CH 2 OEt) 2 ;

[0210] · The lithium precursor is LiN(CH 2 CH 2 OiPr) 2 ;

[0211] · The lithium precursor is LiN(CH 2 CH 2 OtBu) 2 ;

[0212] · The lithium precursor is LiN(CH 2 CH 2 NMe 2 )(CH 2 CH 2 OMe);

[0213] · The lithium precursor is LiN(CH 2 CH 2 NMe 2 )(CH 2 CH 2 OEt);

[0214] · The lithium precursor is LiN(CH 2 CH 2 NMe 2 )(CH 2 CH 2 OiPr);

[0215] · The lithium precursor is LiN(CH 2 CH 2 NMe 2 )(CH 2 CH 2 OtBu);

[0216] · The lithium precursor is LiNMe(CH 2 CH(OMe) 2 )); And

[0217] · The lithium precursor has a purity in the range of from about 93 wt% or w / w to about 100% w / w, preferably in the range of from about 99% w / w to about 99.999% w / w, more preferably in the range of from about 99% w / w to about 100% w / w.

[0218] There is also disclosed a precursor for forming a film, island or cluster, which precursor has the following general formula:

[0219] [Li-NL 1 L 2 -D x y (I)

[0220] where

[0221] L 1 has the following general formula: C m H n , (C m H n )-ER 1 R 2 ) or (C m H n )-E′R 1 ), where

[0222] · (C m H n ) is a straight-chain, branched-chain or cyclic alkyl;

[0223] · m and n are independent integers, 1 ≤ m ≤ 16, 1 ≤ n ≤ 16;

[0224] · E is B, N;

[0225] · E′ is a divalent element;

[0226] · R 1 and R 2 are each independently selected from the group consisting of hydrogen, straight-chain, branched-chain or cyclic alkyl, or straight-chain, branched-chain or cyclic alkyl substituted with other atoms or groups;

[0227] L 2 has the following general formula: (C p H q )-ER 3 R 4 or (C p H q )-E′R 3 , where

[0228] · C p H q is a straight-chain, branched-chain or cyclic alkyl; ​

[0229] · p and q are independent integers, where 1 ≤ p ≤ 16 and 1 ≤ q ≤ 16;

[0230] · E is B, N;

[0231] · E′ is a divalent element;

[0232] · R 3 and R 4 are each independently selected from the group consisting of: hydrogen, straight-chain, branched-chain or cyclic alkyl, or straight-chain, branched-chain or cyclic alkyl substituted by other atoms or groups;

[0233] D is independently selected from monodentate, bidentate, tridentate or polydentate neutral coordination ligand systems;

[0234] x is an integer, where 0 ≤ x ≤ 4; and

[0235] y is the degree of association of the molecule, where 1 ≤ y ≤ 6.

[0236] The disclosed precursors for forming films, islands or clusters include one or more of the following aspects:

[0237] · L 1 is C 1 -C 16 a straight-chain, branched-chain or cyclic carbon chain, or is in the form of (C m H n )-ER 1 R 2 or (C m H n )-E’R 1 where

[0238] C m H n is an alkyl chain and can be straight-chain, branched-chain or cyclic alkyl;

[0239] E represents B, N;

[0240] E′ represents a divalent element, such as O, S;

[0241] m is an integer with a value of 1, or an integer in the range from 1 to 8;

[0242] n is an independent integer in the range from 2 to 16;

[0243] R 1 is independent and is selected from the group consisting of: hydrogen, straight-chain, branched-chain or cyclic C 1 -C 8 alkyl, or straight-chain, branched-chain or cyclic alkyl substituted by other atoms or groups;

[0244] R 2is independent and is selected from the group consisting of: hydrogen, linear, branched or cyclic C 1 -C 8 alkyl, or linear, branched or cyclic alkyl substituted with other atoms or groups;

[0245] ·L 2 is of the form (C p H q )-ER 3 R 4 or (C p H q )-E’R 3 wherein

[0246] C p H q is an alkyl chain and can be linear, branched or cyclic alkyl;

[0247] E represents B, N;

[0248] E′ represents a divalent element such as O, S;

[0249] p and q are independent integers ranging from 1 to 16, preferably p is included from 1 to 8 and q is included from 2 to 16, most preferably p is different from m;

[0250] R 3 and R 4 are independent and are selected from the group consisting of: hydrogen, linear, branched or cyclic alkyl, or linear, branched or cyclic alkyl substituted with other atoms or groups;

[0251] ·D is independently selected from monodentate, bidentate, tridentate or polydentate neutral coordination ligand systems, preferably monodentate or bidentate;

[0252] ·x is an integer included between 0 and 4; and

[0253] ·y represents the degree of association of the molecule and is included between 1 and 6;

[0254] ·The precursor for forming a film, island or cluster is selected from LiNMe(CH 2 CH 2 NMe 2 )、LiNMe(CH 2 CH 2 NMe 2 )(1,2 - diethoxyethane), LiNMe(CH 2 CH 2 NMe 2 )(1,2 - dimethoxyethane), LiNEt(CH 2 CH 2 NMe 2)、LiNiPr(CH 2 CH 2 NMe 2 )、LiNtBu(CH 2 CH 2 NMe 2 )、LiNtBu(CH 2 CH 2 NEtMe)、LiNtBu(CHMeCH 2 NMe 2 )、LiNtBu(CH 2 CHMeNMe 2 )、LiN(CH 2 CH 2 NMe 2 ) 2 、LiN(CH 2 CH 2 NEt 2 ) 2 、LiN(CH 2 CH 2 NiPr 2 ) 2 、LiN(CH 2 CH 2 NEtMe) 2 、LiN(CH 2 CH 2 CH 2 NMe 2 ) 2 、LiN(CHMeCH 2 NMe 2 ) 2 、LiN(CHMeCH 2 NMe 2 )(CH 2 CH 2 NMe 2 )、LiN(CH 2 CHMeNMe 2 ) 2 、LiN(CH 2 CHMeNMe 2 )(CH 2 CH 2 NMe 2 )、LiN(CHEtCH 2 NMe 2 )(CH 2 CH 2 NMe 2 )、LiN(CH 2 CHEtNMe 2 )(CH2 CH 2 NMe 2 )、LiN(CMe 2 CH 2 NMe 2 )(CH 2 CH 2 NMe 2 )、LiN(CH 2 CMe 2 NMe 2 )(CH 2 CH 2 NMe 2 )、LiN(CH 2 CH 2 NMe 2 )(CH 2 CH 2 CH 2 NMe 2 )、LiNMe(CH 2 CH 2 OMe)、LiNMe(CH 2 CH 2 OEt)、LiNMe(CH 2 CH 2 OiPr)LiNMe(CH 2 CH 2 OtBu)、LiNEt(CH 2 CH 2 OMe)、LiNEt(CH 2 CH 2 OEt)、LiNiPr(CH 2 CH 2 OMe)、LiNtBu(CH 2 CH 2 OMe)、LiN(CH 2 CH 2 OMe) 2 、LiN(CH 2 CH 2 OEt) 2 、LiN(CH 2 CH 2 OiPr) 2 、LiN(CH 2 CH 2 OtBu) 2 、LiN(CH 2 CH 2 NMe 2 )(CH 2 CH 2 OMe)、LiN(CH2 CH 2 NMe 2 )(CH 2 CH 2 OEt), LiN(CH 2 CH 2 NMe 2 )(CH 2 CH 2 OiPr), LiN(CH 2 CH 2 NMe 2 )(CH 2 CH 2 OtBu), LiNMe(CH 2 CH(OMe) 2 ) etc.;

[0255] · Precursors for forming films, islands or clusters are LiNtBu(CH 2 CH 2 NMe 2 ), LiNtBu(CH 2 CH 2 NEtMe), LiNtBu(CHMeCH 2 NMe 2 ), LiNtBu(CH 2 CHMeNMe 2 ), LiN(CH 2 CH 2 NEtMe) 2 , LiN(CH 2 CH 2 OEt) 2 , LiN(CH 2 CH 2 NMe 2 ), 2 , LiN(CH 2 CH 2 CH 2 NMe 2 ), 2 , LiN(CH 2 CH 2 NMeEt) 2 , LiN(CHMeCH 2 NMe 2 )(CH 2 CH 2 NMe 2 ), LiN(CH 2 CHMeNMe 2 )(CH 2 CH 2 NMe2 )), LiN(CHEtCH 2 NMe 2 )(CH 2 CH 2 NMe 2 ), LiN(CH 2 CHEtNMe 2 )(CH 2 CH 2 NMe 2 ), LiN(CMe 2 CH 2 NMe 2 )(CH 2 CH 2 NMe 2 ), LiN(CH 2 CMe 2 NMe 2 )(CH 2 CH 2 NMe 2 ), LiN(CH 2 CH 2 NiPr 2 ) 2 , LiN(CH 2 CH 2 NMe 2 )(CH 2 CH 2 CH 2 NMe 2 ), LiN(CH 2 CH 2 OEt) 2 , LiNMe(CH 2 CH 2 OEt), LiNMe(CH 2 CH(OMe) 2 ) etc.;

[0256] · The film, island or cluster is LiNMe(CH 2 CH 2 NMe 2 );

[0257] · The film, island or cluster is LiNMe(CH 2 CH 2 NMe 2 )(1,2 - diethoxyethane);

[0258] · The film, island or cluster is LiNMe(CH 2 CH 2 NMe 2 )(1,2 - dimethoxyethane);

[0259] · The film, island or cluster is LiNEt(CH 2 CH 2 NMe 2 );

[0260] · The film, island or cluster is LiNiPr(CH 2 CH 2 NMe 2 );

[0261] · The film, island or cluster is LiNtBu(CH 2 CH 2 NMe 2 );

[0262] · The film, island or cluster is LiNtBu(CH 2 CH 2 NEtMe);

[0263] · The film, island or cluster is LiNtBu(CHMeCH 2 NMe 2 );

[0264] · The film, island or cluster is LiNtBu(CH 2 CHMeNMe 2 );

[0265] · The film, island or cluster is LiN(CH 2 CH 2 NMe 2 ) 2 ;

[0266] · The film, island or cluster is LiN(CH 2 CH 2 NEt 2 ) 2 ;

[0267] · The film, island or cluster is LiN(CH 2 CH 2 NiPr 2 ) 2 ;

[0268] · The film, island or cluster is LiN(CH 2 CH 2 NEtMe) 2 ;

[0269] · The film, island or cluster is LiN(CH 2 CH 2 CH 2 NMe 2 ) 2 ;

[0270] · The film, island or cluster is LiN(CHMeCH 2 NMe 2 ) 2 ;

[0271] · The film, island or cluster is LiN(CHMeCH 2 NMe 2 )(CH 2 CH 2 NMe 2 );

[0272] · The film, island or cluster is LiN(CH 2 CHMeNMe 2 ) 2 ;

[0273] · The film, island or cluster is LiN(CH 2 CHMeNMe 2 )(CH 2 CH 2 NMe 2 );

[0274] · The film, island or cluster is LiN(CHEtCH 2 NMe 2 )(CH 2 CH 2 NMe 2 );

[0275] · The film, island or cluster is LiN(CH 2 CHEtNMe 2 )(CH 2 CH 2 NMe 2 );

[0276] · The film, island or cluster is LiN(CMe 2 CH 2 NMe 2 )(CH 2 CH 2 NMe 2 );

[0277] · The film, island or cluster is LiN(CH 2 CMe 2 NMe 2 )(CH 2 CH 2 NMe 2 );

[0278] · The film, island or cluster is LiN(CH 2 CH 2 NMe 2)(CH 2 CH 2 CH 2 NMe 2 );

[0279] · The film, island or cluster is LiNMe(CH 2 CH 2 OMe);

[0280] · The film, island or cluster is LiNMe(CH 2 CH 2 OEt);

[0281] · The film, island or cluster is LiNMe(CH 2 CH 2 OiPr);

[0282] · The film, island or cluster is LiNMe(CH 2 CH 2 OtBu);

[0283] · The film, island or cluster is LiNEt(CH 2 CH 2 OMe);

[0284] · The film, island or cluster is LiNEt(CH 2 CH 2 OEt);

[0285] · The film, island or cluster is LiNiPr(CH 2 CH 2 OMe);

[0286] · The film, island or cluster is LiNtBu(CH 2 CH 2 OMe);

[0287] · The film, island or cluster is LiN(CH 2 CH 2 OMe) 2 ;

[0288] · The film, island or cluster is LiN(CH 2 CH 2 OEt) 2 ;

[0289] · The film, island or cluster is LiN(CH 2 CH 2 OiPr) 2 ;

[0290] · The film, island or cluster is LiN(CH 2 CH 2 OtBu) 2;

[0291] · The film, island or cluster is LiN(CH 2 CH 2 NMe 2 )(CH 2 CH 2 OMe);

[0292] · The film, island or cluster is LiN(CH 2 CH 2 NMe 2 )(CH 2 CH 2 OEt);

[0293] · The film, island or cluster is LiN(CH 2 CH 2 NMe 2 )(CH 2 CH 2 OiPr);

[0294] · The film, island or cluster is LiN(CH 2 CH 2 NMe 2 )(CH 2 CH 2 OtBu);

[0295] · The film, island or cluster is LiNMe(CH 2 CH(OMe) 2 ); and

[0296] · The precursor for forming the film, island or cluster has a purity ranging from about 93 wt% or w / w to about 100% w / w, preferably ranging from about 99% w / w to about 99.999% w / w, more preferably ranging from about 99% w / w to about 100% w / w.

[0297] Notation and nomenclature

[0298] The following detailed description and claims utilize many abbreviations, symbols and terms commonly known in the art, and include:

[0299] As used herein, the indefinite article "a or an" means one or more.

[0300] As used herein, "about" or "around / approximately" in the text or claims means ±10% of the stated value.

[0301] As used herein, "room temperature" in the text or claims means from about 20 °C to about 25 °C.

[0302] The term "ambient temperature" refers to the surrounding temperature of approximately 20°C to approximately 25°C.

[0303] As used in the disclosed embodiments, the term "independently" when used in the context of describing R groups should be understood to mean that the subject R group is selected independently not only relative to other R groups with the same or different subscripts or superscripts, but also relative to any other species of the same R group. For example, in the formula MR 1 x (NR 2 R 3 ) (4-x) where x is 2 or 3, two or three R 1 groups may (but need not) be the same as each other or the same as R 2 or R 3 . Further, it should be understood that unless otherwise specifically provided, the values of the R groups are independent of each other when used in different formulas.

[0304] As used in the disclosed embodiments, the term "hydrocarbyl group" refers to a functional group containing carbon and hydrogen; the term "alkyl group" refers to a saturated functional group containing only carbon and hydrogen atoms. The hydrocarbyl group can be saturated or unsaturated. Either term refers to a straight-chain, branched-chain or cyclic group. Examples of straight-chain alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, etc. Examples of branched-chain alkyl groups include, but are not limited to, tert-butyl. Examples of cyclic alkyl groups include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, etc.

[0305] As used in the disclosed embodiments, the abbreviation "Me" refers to methyl; the abbreviation "Et" refers to ethyl; the abbreviation "Pr" refers to propyl.

[0306] The term "island" or "cluster" as used herein refers to small agglomerations of a material laid or scattered on a surface, and the surface can range from as large as an entire wafer to as small as a trench or a line.

[0307] The term "substrate" refers to one or more materials on which a process is performed. The substrate can refer to a wafer having one or more materials on which a process is performed. The substrate can be any suitable wafer or carrier used in semiconductor, photovoltaic, flat panel, LCD-TFT device manufacturing, MEMS, lithium-ion battery manufacturing, electrochromic window manufacturing, organic or inorganic powders, electrodes, and / or deposited materials. The substrate can also have one or more different material layers already deposited thereon from previous manufacturing steps. For example, the carrier can include a silicon layer (e.g., crystalline, amorphous, porous, etc.), a silicon-containing layer (e.g., SiO 2, SiN, SiON, SiCOH, etc.), a metal-containing layer (e.g., copper, cobalt, ruthenium, tungsten, platinum, palladium, nickel, manganese, iron, aluminum, silver, gold, etc.), an organic layer such as amorphous carbon, fluorocarbon, fluorinated hydrocarbon, fluorine-containing material, or a combination thereof. In addition, the substrate can be flat or patterned, spherical, circular, or have no defined or regular shape. The substrate can include a layer of an oxide used as an electrode active material. Those of ordinary skill in the art will recognize that the terms "film" or "layer" as used herein refer to a certain thickness of a material laid or spread on a surface and the surface can be a trench or a line. Throughout the specification and claims, the wafer and any associated layers, islands, and / or clusters thereon are referred to as the substrate.

[0308] The term "wafer" or "patterned wafer" refers to a wafer having a stack of films (such as silicon-containing films) on a substrate and a patterned hard mask layer formed on the stack of films (such as silicon-containing films) for pattern etching. The term "wafer" or "patterned wafer" can also refer to a trench wafer having a certain aspect ratio.

[0309] The term "carrier" refers to a material composed of a composite of materials (such as an electrode active material, a binder, an electrolyte, and carbon).

[0310] It should be noted herein that the terms "film" and "layer" can be used interchangeably. It should be understood that a film can correspond to a layer or be related to a layer, and a layer can refer to a film. In addition, those of ordinary skill in the art will recognize that the terms "film" or "layer" as used herein refer to a certain thickness of a material laid or spread on a surface and the surface can range from as large as the entire wafer to as small as a trench or a line. Note that in this text, the terms "island" and "cluster" can be used interchangeably. It should be understood that an island can correspond to a cluster or be related to a cluster, and a cluster can refer to an island.

[0311] Note that in this text, the terms "deposition temperature", "process temperature", "substrate temperature", and "reactor temperature" can be used interchangeably. It should be understood that the substrate temperature or the reactor temperature or the process temperature can correspond to the deposition temperature or be related to the deposition temperature, and the deposition temperature can refer to the substrate temperature or the reactor temperature or the process temperature.

[0312] Note that in this text, the terms "precursor", "deposition compound", and "deposition gas" can be used interchangeably. It should be understood that a precursor can correspond to a deposition compound, or be related to a deposition compound, and a deposition compound can refer to a precursor.

[0313] Standard abbreviations for elements from the periodic table are used herein. It should be understood that elements may be referred to by these abbreviations (e.g., Li refers to lithium, 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.).

[0314] A unique CAS Registry Number (i.e., “CAS”) assigned by the Chemical Abstract Service is provided to identify the specific molecule(s) disclosed.

[0315] Note that lithium-containing films or islands made of materials such as lithium phosphate, lithium borate, and lithium borophosphate are listed throughout the specification and claims without reference to their proper stoichiometry. The lithium-containing films or islands may also include dopants such as B, C, N, and / or Ge.

[0316] Ranges may be expressed herein as from about one specific value and / or to about another specific value. When such a range is expressed, it should be understood that another embodiment is from a specific value and / or to another specific value, along with all combinations within the stated range. Any and all ranges recited in the disclosed embodiments include their endpoints (i.e., x = 1 to 4 or x in the range from 1 to 4 includes x = 1, x = 4, and any value therebetween), whether or not the term “including endpoints” is used.

[0317] References herein to “one embodiment” or “an embodiment” mean that a particular feature, structure, or characteristic described with respect to the embodiment can be included in at least one embodiment of the invention. The phrase “in one embodiment” appearing in different places in the specification is not necessarily all referring to the same embodiment, and separate or alternative embodiments are not necessarily mutually exclusive of other embodiments. The above also applies to the term “implement”. BRIEF DESCRIPTION OF THE DRAWINGS

[0318] For a further understanding of the nature and objects of the present invention, reference should be had to the following detailed description taken in conjunction with the accompanying drawings, in which like elements are given the same or similar reference numerals, and in which:[[]]

[0319] Figure 1 is a graph of the thermogravimetric analysis (TGA) (760 Torr) of LiN(CH 2 CH 2 NMe 2 ) 2 ;

[0320] Figure 2 is a graph of the TGA (15 Torr) of LiN(CH 2 CH 2 NMe 2 ) 2 ;

[0321] Figure 3 is the TGA (15 Torr) curve of LiN(CHMeCH 2 NMe 2 )(CH 2 CH 2 NMe 2 );

[0322] Figure 4 is the TGA (15 Torr) curve of LiN(CH 2 CH 2 NEt 2 ); 2 ;

[0323] Figure 5 is the TGA (15 Torr) curve of LiNMe(CH 2 CH 2 NMe 2 ); 2 ;

[0324] Figure 6 is the TGA (15 Torr) curve of LiNtBu(CH2CH2NMe2);

[0325] Figure 7 is the TGA (15 Torr) curve of the mixture of LiNtBu(CHMeCH 2 NMe 2 ) and LiNtBu(CH2CHMeNMe2) (6.5:1);

[0326] Figure 8 is the 1H NMR spectrum of the mixture of LiNtBu(CHMeCH 2 NMe 2 ) and LiNtBu(CH 2 CHMeNMe 2 ) in C 6 D 6 ; 1 ;

[0327] Figure 9 is the per-cycle growth (GPC) result at temperatures from 125 °C to 250 °C;

[0328] Figure 10 is the XPS result of the deposited Li 3 PO 4 film at temperatures from 125 °C to 250 °C;

[0329] Figure 11 is the Li deposited at temperatures from 125 °C to 250 °C in the case of using O 3 ​3 PO 4 Refractive index (RI) results of the film;

[0330] Figure 12 are the GPC results at 150 °C in the case of using O 3 ;

[0331] Figure 13 are the GPC results at 150 °C in the case of using O 3 ; the deposited Li 3 PO 4 film RI results;

[0332] Figure 14 are the GPC results at 135 °C in the case of using O 3 ;

[0333] Figure 15 are the GPC results at 135 °C in the case of using O 3 ; the deposited Li 3 PO 4 film RI results;

[0334] Figure 16 are the XPS results on the TiN substrate at 135 °C; and

[0335] Figure 17 are the XPS results at 135 °C in the case of not using O 3 ; Detailed implementation mode

[0336] Disclosed are compositions for forming lithium-containing films, islands or clusters containing silicon-free lithium precursors, methods for synthesizing silicon-free lithium precursors, and methods for using silicon-free lithium precursors to deposit lithium-containing films, islands or clusters. The disclosed silicon-free lithium precursors are liquid below 150 °C, preferably liquid at about 50 °C, and most preferably liquid at about 25 °C or room temperature. The disclosed silicon-free lithium precursors are suitable for ALD and CVD applications.

[0337] The disclosed silicon-free lithium precursor has the following general formula:

[0338] [Li-NL 1 L 2 -D x y (I)

[0339] where

[0340] L 1 has the following general formula: C m H n 、(C m H n )-ER​1 R 2 ) or (C m H n )-E′R 1 ), wherein

[0341] ·C m H n is a straight-chain, branched-chain or cyclic alkyl group;

[0342] ·m and n are independent integers, 1 ≤ m ≤ 16, 1 ≤ n ≤ 16;

[0343] ·E is B, N;

[0344] ·E′ is a divalent element;

[0345] ·R 1 and R 2 each independently selected from the group consisting of: straight-chain, branched-chain or cyclic alkyl groups, or straight-chain, branched-chain or cyclic alkyl groups substituted by other atoms or groups;

[0346] L 2 has the following general formula: (C p H q )-ER 3 R 4 or (C p H q )-E′R 3 , wherein

[0347] ·C p H q is a straight-chain, branched-chain or cyclic alkyl group;

[0348] ·p and q are independent integers, 1 ≤ p ≤ 16, 1 ≤ q ≤ 16;

[0349] ·E is B, N;

[0350] ·E′ is a divalent element;

[0351] ·R 3 and R 4 each independently selected from the group consisting of: straight-chain, branched-chain or cyclic alkyl groups, or straight-chain, branched-chain or cyclic alkyl groups substituted by other atoms or groups;

[0352] D is independently selected from monodentate, bidentate, tridentate or polydentate neutral coordination ligand systems;

[0353] x is an integer, 0 ≤ x ≤ 4; and

[0354] y is the degree of association of the molecule, 1 ≤ y ≤ 6.

[0355] Preferably, in general formula (I), D is monodentate or bidentate; E is N, B; E' is O, S; respectively, m is 1 ≤ m ≤ 8 and n is 2 ≤ n ≤ 16; p is 1 ≤ m ≤ 8 and q is 2 ≤ n ≤ 16.

[0356] More preferably, the disclosed silicon-free lithium precursor has the general formula (I), wherein:

[0357] L 1 is C 1 -C 16 a straight-chain, branched-chain or cyclic carbon chain, or is of the form (C m H n )-ER 1 R 2 or (C m H n )-E’R 1 where

[0358] ·C m H n is an alkyl chain and can be a straight-chain, branched-chain or cyclic alkyl;

[0359] ·E represents B, N;

[0360] ·E' represents a divalent element, such as O, S;

[0361] ·m is an integer with a value of 1, or an integer ranging from 1 to 8;

[0362] ·n is an independent integer ranging from 2 to 16;

[0363] ·R 1 is independent and is selected from the group consisting of: hydrogen, straight-chain, branched-chain or cyclic C 1 -C 8 alkyl, or a straight-chain, branched-chain or cyclic alkyl substituted by other atoms or groups;

[0364] ·R 2 is independent and is selected from the group consisting of: hydrogen, straight-chain, branched-chain or cyclic C 1 -C 8 alkyl, or a straight-chain, branched-chain or cyclic alkyl substituted by other atoms or groups;

[0365] L 2 is of the form (C p H q )-ER 3 R 4 or (C p H q )-E’R 3 where

[0366] ·Cp H q is an alkyl chain and can be a straight-chain, branched-chain or cyclic alkyl;

[0367] · E represents B, N;

[0368] · E′ represents a divalent element such as O, S;

[0369] · p and q are independent integers ranging from 1 to 16, preferably p is included from 1 to 8 and q is included from 2 to 16, most preferably p is different from m;

[0370] · R 3 and R 4 are independent and are selected from the group consisting of: hydrogen, straight-chain, branched-chain or cyclic alkyl, or straight-chain, branched-chain or cyclic alkyl substituted by other atoms or groups;

[0371] D is independently selected from monodentate, bidentate, tridentate or polydentate neutral coordination ligand systems, preferably monodentate or bidentate;

[0372] x is an integer included between 0 and 4; and

[0373] y represents the degree of association of the molecule and is included between 1 and 6,

[0374] provided that x = 0, p = 2, q = 4, E = N and L 2 、R 3 or R 4 are all methyls are excluded;

[0375] provided that x = 0, p = 2 or 3, q = 4 or 6, E = N, L 2 = tert-butyl, R 3 and R 4 are methyls are excluded;

[0376] provided that x = 0, m = p = 2, n = q = 4, E = N, R 1 、R 2 、R 3 、R 4 are all methyls are excluded;

[0377] provided that x = 0, m = p = 2, n = q = 4, E′ = O, R 1 and R 3 are all methyls are excluded;

[0378] provided that x = 0, m = 2, n = 4, E′ = O and R 1 is methyl is excluded;

[0379] provided that L 1 = Me, L 2 = {Cp H q =CH 2 CH 2 , E = N, and R 3 and R 4 are both Me}, x = 0 is excluded;

[0380] Provided that L 1 = Et, L 2 = {C p H q = CH 2 CH 2 , E = N, and R 3 and R 4 are both Me}, x = 0 is excluded;

[0381] Provided that L 1 = iPr, L 2 = {C p H q = CH 2 CH 2 , E = N, and R 3 and R 4 are both Me}, x = 0 is excluded;

[0382] Provided that L 1 = tBu, L 2 = {C p H q = CH 2 CH 2 , E = N, and R 3 and R 4 are both Me}, x = 0 is excluded;

[0383] Provided that L 1 = tBu, L 2 = {C p H q = CMeHCH 2 , E = N, and R 3 and R 4 are both Me}, x = 0 is excluded;

[0384] Provided that L 1 = tBu, L 2 = {C p H q = CH 2 CHMe, E = N, and R 3 and R 4 are both Me}, x = 0 is excluded;

[0385] Provided that L 1 = {C mH n =CH 2 CH 2 , E = N, R 1 and R 2 are both Me}, L 2 ={C p H q =CH 2 CH 2 , E = N, R 3 and R 4 are both Me}, x = 0 is excluded;

[0386] Provided that L 1 ={C m H n =CH 2 CH 2 , E = N, R 1 and R 2 are both Et}, L 2 ={C p H q =CH 2 CH 2 , E = N, R 3 and R 4 are both Et}, x = 0 is excluded; and

[0387] Provided that L 1 = Me, L 2 ={C p H q =CH 2 CH 2 , E’ = O, R 3 is Me}, x = 0 is excluded.

[0388] Exemplary examples of the silicon-free lithium precursors shown in general formula (I) include LiN t Bu(CH 2 CH 2 NMe 2 ), LiN t Bu(CH 2 CH 2 NEtMe), LiN t Bu(CHMeCH 2 NMe 2 ), LiN t Bu(CH 2 CHMeNMe 2 ), LiN(CH 2 CH 2 NEtMe) 2 , LiN(CH 2 CH2 OEt) 2 , LiN(CH 2 CH 2 NMe 2 ) 2 , LiN(CH 2 CH 2 CH 2 NMe 2 ) 2 , LiN(CH 2 CH 2 NMeEt) 2 , LiN(CHMeCH 2 NMe 2 )(CH 2 CH 2 NMe 2 ), LiN(CH 2 CHMeNMe 2 )(CH 2 CH 2 NMe 2 ), LiN(CHEtCH 2 NMe 2 )(CH 2 CH 2 NMe 2 ), LiN(CH 2 CHEtNMe 2 )(CH 2 CH 2 NMe 2 ), LiN(CMe 2 CH 2 NMe 2 )(CH 2 CH 2 NMe 2 ), LiN(CH 2 CMe 2 NMe 2 )(CH 2 CH 2 NMe 2 ), LiN(CH 2 CH 2 N i Pr 2 ) 2 , LiN(CH 2 CH 2 NMe 2 )(CH 2 CH 2 CH 2 NMe 2 ), LiN(CH 2 CH2 OEt) 2 , LiNMe(CH 2 CH 2 OEt), LiNMe(CH 2 CH(OMe) 2 ) etc.

[0389] The disclosed silicon-free lithium precursors include LiN(CH 2 CH 2 NMe 2 ) 2 , LiN(CHMeCH 2 NMe 2 )(CH 2 CH 2 NMe 2 ), LiN(CH 2 CHMeNMe 2 )(CH 2 CH 2 NMe 2 ), LiN(CHEtCH 2 NMe 2 )(CH 2 CH 2 NMe 2 ), LiN(CH 2 CHEtNMe 2 )(CH 2 CH 2 NMe 2 ), LiN(CMe 2 CH 2 NMe 2 )(CH 2 CH 2 NMe 2 ), LiN(CH 2 CMe 2 NMe 2 )(CH 2 CH 2 NMe 2 ), LiNtBu(CH 2 CH 2 NMe 2 ), LiNtBu(CH 2 CH 2 NEtMe), LiNtBu(CHMeCH 2 NMe 2 ), LiNtBu(CH 2 CHMeNMe 2 ), LiN(CH 2 CH2 NEtMe) 2 and LiN(CH 2 CH 2 OEt) 2 and LiNMe(CH 2 CH(OMe) 2 )。

[0390] The disclosed silicon-free lithium precursors are LiNtBu(CH 2 CH 2 NMe 2 )。The disclosed silicon-free lithium precursors are LiNtBu(CH 2 CH 2 NEtMe)。The disclosed silicon-free lithium precursors are LiNtBu(CHMeCH 2 NMe 2 )。The disclosed silicon-free lithium precursors are LiNtBu(CH 2 CHMeNMe 2 )。The disclosed silicon-free lithium precursors are LiN(CH 2 CH 2 NEtMe) 2 。The disclosed silicon-free lithium precursors are LiN(CH 2 CH 2 OEt) 2 。The disclosed silicon-free lithium precursors are LiN(CH 2 CH 2 NMe 2 ) 2 。The disclosed silicon-free lithium precursors are LiN(CH 2 CH 2 CH 2 NMe 2 ) 2 。The disclosed silicon-free lithium precursors are LiN(CH 2 CH 2 NMeEt) 2 。The disclosed silicon-free lithium precursors are LiN(CHMeCH 2 NMe 2 )(CH 2 CH 2 NMe 2 )。The disclosed silicon-free lithium precursors are LiN(CH 2 CHMeNMe 2 )(CH 2 CH 2 NMe 2 )。The disclosed silicon-free lithium precursors are LiN(CHEtCH 2 NMe 2 )(CH2 CH 2 NMe 2 )。The disclosed silicon-free lithium precursors are LiN(CH 2 CHEtNMe 2 )(CH 2 CH 2 NMe 2 )。The disclosed silicon-free lithium precursors are LiN(CMe 2 CH 2 NMe 2 )(CH 2 CH 2 NMe 2 )。The disclosed silicon-free lithium precursors are LiN(CH 2 CMe 2 NMe 2 )(CH 2 CH 2 NMe 2 )。The disclosed silicon-free lithium precursors are LiN(CH 2 CH 2 NiPr 2 ) 2 。The disclosed silicon-free lithium precursors are LiN(CH 2 CH 2 NMe 2 )(CH 2 CH 2 CH 2 NMe 2 )。The disclosed silicon-free lithium precursors are LiN(CH 2 CH 2 OEt) 2 。The disclosed silicon-free lithium precursors are LiNMe(CH 2 CH 2 OEt)。The disclosed silicon-free lithium precursors are LiNMe(CH 2 CH(OMe) 2 )

[0391] The disclosed silicon-free lithium precursors can be formulated in the following forms: monomers, dimers or trimers with different degrees of association, or combinations.

[0392] In addition, the disclosed silicon-free lithium precursors can be specified by the following sub-formulas.

[0393] In one embodiment, the disclosed silicon-free lithium precursors can be lithium aminoamides, where in formula (I), L 1 = C m Hn ; L 2 =(C p H q )-NR 1 R 2 , the lithium amide has the following general formula:

[0394] [Li-N(C m H n )((C p H q )-NR 1 R 2 )-D x y (II)

[0395] wherein

[0396] ·C m H n and C p H q are each independently a straight-chain, branched-chain or cyclic alkyl group;

[0397] ·m, n, p, q are each independent integers, 1 ≤ m ≤ 16, 1 ≤ n ≤ 16, 1 ≤ p ≤ 16, 1 ≤ q ≤ 16, preferably n = 2m + 1 and / or q = 2p, more preferably 1 ≤ m ≤ 8, 1 ≤ p ≤ 8, 2 ≤ n ≤ 16, 2 ≤ q ≤ 16;

[0398] ·R 1 and R 2 are independently selected from hydrogen, straight-chain, branched-chain or cyclic alkyl groups, or straight-chain, branched-chain or cyclic alkyl groups substituted by other atoms or groups;

[0399] ·D is independently selected from monodentate, bidentate, tridentate or polydentate neutral coordination ligand systems, preferably monodentate or bidentate;

[0400] ·x is an integer, 0 ≤ x ≤ 4; and

[0401] ·y is the degree of association of the molecule, 1 ≤ y ≤ 6.

[0402] Exemplary examples of the silicon-free lithium precursors shown in general formula (II) include: LiNMe(CH 2 CH 2 NMe 2 ), LiNMe(CH 2 CH 2 NMe 2 )(1,2-diethoxyethane); LiNMe(CH 2 CH 2 NMe 2 )(1,2-dimethoxyethane); LiNEt(CH​2 CH 2 NMe 2 ),LiNiPr(CH 2 CH 2 NMe 2 ),LiNtBu(CH 2 CH 2 NMe 2 ),LiNtBu(CH 2 CH 2 NEtMe),LiNtBu(CHMeCH 2 NMe 2 ),LiNtBu(CH 2 CHMeNMe 2 ) etc. These molecules can be in monomeric form, but can form with different degrees of association, such as dimers or trimers.

[0403] Alternatively, the disclosed silicon-free lithium precursors can be lithium diaminoamide, where in formula (I), L 1 =(C m H n )-NR 1 R 2 ; L 2 =(C p H q )-NR 3 R 4 , and the lithium diaminoamide has the following general formula:

[0404] [Li-N((C m H n )-NR 1 R 2 )((C p H q )-NR 3 R 4 )-D x y (III)

[0405] where

[0406] ·C m H n and C p H q are each independently straight-chain, branched-chain or cyclic alkyl;

[0407] ​·m, n, p, and q are each independent integers, where 1 ≤ m ≤ 16, 1 ≤ n ≤ 16, 1 ≤ p ≤ 16, and 1 ≤ q ≤ 16. Preferably, n = 2m and / or q = 2p, and more preferably, 1 ≤ m ≤ 4, 1 ≤ p ≤ 4, 2 ≤ n ≤ 8, and 2 ≤ q ≤ 8;

[0408] ·R 1 、R 2 、R 3 and R 4 are each independently selected from hydrogen, linear, branched, or cyclic alkyl, and linear, branched, or cyclic alkyl substituted with other atoms or groups;

[0409] ·D is independently a monodentate, bidentate, tridentate, or polydentate neutral coordination ligand system. Preferably, D is monodentate or bidentate;

[0410] ·x is an integer, where 0 ≤ x ≤ 4; and

[0411] ·y is the degree of association of the molecule, where 1 ≤ y ≤ 6.

[0412] Exemplary examples of the silicon-free lithium precursor shown in general formula (III) include LiN(CH 2 CH 2 NMe 2 ) 2 、LiN(CH 2 CH 2 NEt 2 ) 2 、LiN(CH 2 CH 2 NiPr 2 ) 2 、LiN(CH 2 CH 2 NEtMe) 2 、LiN(CH 2 CH 2 CH 2 NMe 2 ) 2 、LiN(CHMeCH 2 NMe 2 ) 2 、LiN(CHMeCH 2 NMe 2 )(CH 2 CH 2 NMe 2 )、LiN(CH 2 CHMeNMe 2 ) 2 、LiN(CH 2 CHMeNMe 2 )(CH 2CH 2 NMe 2 )、LiN(CHEtCH 2 NMe 2 )(CH 2 CH 2 NMe 2 )、LiN(CH 2 CHEtNMe 2 )(CH 2 CH 2 NMe 2 )、LiN(CMe 2 CH 2 NMe 2 )(CH 2 CH 2 NMe 2 )、LiN(CH 2 CMe 2 NMe 2 )(CH 2 CH 2 NMe 2 )、LiN(CH 2 CH 2 NMe 2 )(CH 2 CH 2 CH 2 NMe 2 ) etc.

[0413] Alternatively, the disclosed silicon-free lithium precursors can be lithium alkoxyamides, where in formula (I), L 1 =C m H n ;L 2 =(C p H q )-OR 1 , and the lithium alkoxyamide has the following general formula:

[0414] [Li-N(C m H n )((C p H q )-OR 1 )-D x y (IV)

[0415] where

[0416] ·C m H n and C p H q ​Each is independently a straight-chain, branched-chain or cyclic alkyl group;

[0417] · m, n, p, q are each independently an integer, 1 ≤ m ≤ 16, 1 ≤ n ≤ 16, 1 ≤ p ≤ 16, 1 ≤ q ≤ 16, preferably n = 2m + 1 and / or q = 2p, more preferably 1 ≤ m ≤ 8, 1 ≤ p ≤ 8, 2 ≤ n ≤ 16, 2 ≤ q ≤ 16;

[0418] · R 1 is independently selected from hydrogen, a straight-chain, branched-chain or cyclic alkyl group, or a straight-chain, branched-chain or cyclic alkyl group substituted with other atoms or groups;

[0419] · D is independently selected from monodentate, bidentate, tridentate or polydentate neutral coordination ligand systems, preferably monodentate or bidentate;

[0420] · x is an integer, 0 ≤ x ≤ 4; and

[0421] · y is the degree of association of the molecule, 1 ≤ y ≤ 6.

[0422] Exemplary examples of the disclosed silicon-free lithium precursors shown in general formula (IV) include LiNMe(CH 2 CH 2 OMe), LiNMe(CH 2 CH 2 OEt), LiNMe(CH 2 CH 2 OiPr)LiNMe(CH 2 CH 2 OtBu), LiNEt(CH 2 CH 2 OMe), LiNEt(CH 2 CH 2 OEt), LiNiPr(CH 2 CH 2 OMe), LiNtBu(CH 2 CH 2 OMe), LiNMe(CH 2 CH(OMe) 2 ) etc.

[0423] Alternatively, the disclosed silicon-free lithium precursor can be a lithium dialkoxyamide, where in formula (I), L 1 =(C m H n )-OR 1 ; L 2 =(C p H q )-OR2 , the lithium dialkoxy amide has the following general formula:

[0424] [Li-N((C m H n )-OR 1 )((C p H q )-OR 2 )-D x y (V)

[0425] wherein

[0426] ·C m H n and C p H q are each independently a straight-chain, branched-chain or cyclic alkyl group;

[0427] ·m, n, p, q are each independent integers, 1 ≤ m ≤ 16, 1 ≤ n ≤ 16, 1 ≤ p ≤ 16, 1 ≤ q ≤ 16, preferably n = 2m and / or q = 2p, more preferably 1 ≤ m ≤ 4, 1 ≤ p ≤ 4, 2 ≤ n ≤ 8, 2 ≤ q ≤ 8;

[0428] ·R 1 and R 2 are each independently selected from hydrogen, straight-chain, branched-chain or cyclic alkyl groups, or straight-chain, branched-chain or cyclic alkyl groups substituted by other atoms or groups;

[0429] ·D is independently selected from monodentate, bidentate, tridentate or polydentate neutral coordination ligand systems, preferably monodentate or bidentate;

[0430] ·x is an integer, 0 ≤ x ≤ 4; and

[0431] ·y is the degree of association of the molecule, 1 ≤ y ≤ 6.

[0432] Exemplary examples of the silicon-free lithium precursors shown in general formula (V) include LiN(CH 2 CH 2 OMe) 2 , LiN(CH 2 CH 2 OEt) 2 , LiN(CH 2 CH 2 OiPr) 2 , LiN(CH 2 CH 2 OtBu) 2 etc.

[0433] ​Alternatively, the disclosed silicon-free lithium precursors can be lithium aminoalkoxyamide complexes, where in formula (I), L 1 =(C m H n )-NR 1 R 2 ; L 2 =(C p H q )-OR 3 , and the lithium aminoalkoxyamide has the following general formula:

[0434] [Li-N((C m H n )-NR 1 R 2 )((C p H q )-OR 3 )-D x y (VI)

[0435] where

[0436] ·C m H n and C p H q are each independently a straight-chain, branched-chain or cyclic alkyl group;

[0437] ·m, n, p, q are each independent integers, 1 ≤ m ≤ 16, 1 ≤ n ≤ 16, 1 ≤ p ≤ 16, 1 ≤ q ≤ 16, preferably n = 2m and / or q = 2p, more preferably 1 ≤ m ≤ 4, 1 ≤ p ≤ 4, 2 ≤ n ≤ 8, 2 ≤ q ≤ 8;

[0438] ·R 1 , R 2 and R 3 are independently selected from hydrogen, straight-chain, branched-chain or cyclic alkyl groups, or straight-chain, branched-chain or cyclic alkyl groups substituted with other atoms or groups;

[0439] ·D is independently selected from monodentate, bidentate, tridentate or polydentate neutral coordination ligand systems, preferably monodentate or bidentate;

[0440] ·x is an integer, 0 ≤ x ≤ 4; and

[0441] ·y is the degree of association of the molecule, 1 ≤ y ≤ 6.

[0442] Exemplary examples of the disclosed silicon-free lithium precursors shown in general formula (VI) include LiN(CH 2 CH 2 NMe 2 ​)(CH 2 CH 2 OMe), LiN(CH 2 CH 2 NMe 2 )(CH 2 CH 2 OEt), LiN(CH 2 CH 2 NMe 2 )(CH 2 CH 2 OiPr), LiN(CH 2 CH 2 NMe 2 )(CH 2 CH 2 OtBu), etc.

[0443] The disclosed silicon - free lithium precursors exhibit good volatility and thermal stability. Moreover, the disclosed silicon - free lithium precursors can be liquids or low - melting - point solids. The low melting point of the disclosed silicon - free lithium precursors can be < 150 °C, preferably less than 80 °C, and more preferably about 25 °C. The disclosed silicon - free lithium precursors are convenient for use in ALD and CVD applications.

[0444] The disclosed silicon - free lithium precursors have chelating functional groups to lower their melting points and improve their volatility. More specifically, for the electronic and steric properties of the disclosed silicon - free lithium precursors, for example, nitrogen or oxygen chelating functional groups are introduced as neutral donors. The coordination layer of the disclosed silicon - free lithium precursors is thus more saturated and less likely to undergo oligomerization. Therefore, when used in an ALD process or a CVD process, the vapor of the disclosed silicon - free lithium precursors can be more effectively delivered to the deposition reactor, thereby reducing the deposition time and producing a deposited film or island with high uniformity and conformality.

[0445] The disclosed silicon - free lithium precursors can be substantially non - pyrophoric. Pyrophoric substances spontaneously combust in air at 55 °C or lower, which poses a significant safety problem for industrial implementation. Additionally, due to the improved volatility of the disclosed silicon - free lithium precursors, the delivery of the disclosed silicon - free lithium precursors can be carried out in the temperature range between 100 °C and 150 °C without the disclosed silicon - free lithium precursors condensing and depositing Li - containing layers. The properties of the disclosed silicon - free lithium precursors, such as improved volatility, enable their delivery together with one or more metal - organic precursors to the deposition reactor through different delivery systems or the same delivery system. The formation of Li - containing films, islands, or clusters can be carried out on temperature - sensitive substrates such as lithium - ion battery electrodes.

[0446] To our knowledge, the disclosed silicon-free lithium precursors described by general formulas (I) to (VI) are disclosed herein for the first time in the deposition processes (such as CVD processes and ALD processes) for forming lithium-containing layers. The disclosed silicon-free lithium precursors can be used alone or in a mixture with enantiomers or diastereomers, different lithium precursors, one or more lithium precursors and one or more metal precursors (in solution or not in solution) in chemical deposition methods such as ALD or CVD to form Li-containing films or islands such as Li 2 O, LiOH, Li 2 S, Li 3 N, LiF, lithium carbonate, lithium aluminum fluoride, lithium aluminum oxide, lithium aluminum, lithium cobalt oxide, lithium titanate, lithium zirconate, lithium niobate, LiPON, lithium phosphate, lithium borate, lithium borophosphate, lithium niobate, lithium zirconium oxide, etc.

[0447] Preferably, the disclosed silicon-free lithium precursors have suitable properties for vapor deposition methods, such as a vapor pressure range from about 0.1 torr at 23 °C to about 1,000 torr at 23 °C, a melting point below 20 °C (preferably in liquid form at room temperature) and more preferably below -20 °C to prevent freeze / thaw problems, and exhibit 0 volume % or v / v to 1 % v / v decomposition / week at the temperature required to obtain an available vapor pressure (1 - 100 torr).

[0448] Although the disclosed silicon-free lithium precursors are ideally liquids and vaporized in bubbler or direct liquid injection systems, it is also possible to use sublimators (such as the sublimator disclosed in PCT publication WO 2009 / 087609 by Xu et al.) to vaporize solid precursors for ALD / CVD precursors. Alternatively, the solid precursors can be mixed or dissolved in a solvent to achieve an available melting point or viscosity for use through a direct liquid injection system. Although the disclosed silicon-free lithium precursors are ideally liquids, solid precursors for liquid phase deposition techniques such as spraying, slot coating, and spin coating deposition can be mixed or dissolved in a solvent to achieve an available melting point or viscosity to allow the precursor solution to flow into the reactor.

[0449] To ensure process reliability, the disclosed silicon-free lithium precursors can be purified by continuous or fractional batch distillation or sublimation to a purity ranging from about 93 wt% or w / w to about 100 wt%, preferably ranging from about 99% w / w to about 99.999% w / w, more preferably ranging from about 99% w / w to about 100% w / w before use. Those of ordinary skill in the art will recognize that the purity can be determined by 1Determined by 1H NMR or gas or liquid chromatography in conjunction with mass spectrometry. The composition forming the Li-containing film, island or cluster may contain any of the following impurities: ammonium salts; alkylamines, dialkylamines, alkylimines, THF, ethers, pentane, cyclohexane, heptane, toluene, metal halide compounds. Preferably, the total amount of these impurities is less than 0.1% w / w. The purified composition can be produced by recrystallization, sublimation, distillation and / or passing a gas or liquid through a suitable adsorbent (such as molecular sieve).

[0450] The disclosed composition forming the Li-containing film, island or cluster contains less than 5% v / v, preferably less than 1% v / v, more preferably less than 0.1% v / v, and even more preferably less than 0.01% v / v of any of its analogues or other reaction products. This embodiment can provide better process reproducibility. This embodiment can be produced by distillation of the composition forming the Li-containing film, island or cluster.

[0451] The concentration ranges of trace metals and metalloids in the purified composition forming the Li-containing film, island or cluster can each independently be from about 0 ppbw to about 100 ppbw, and more preferably from about 0 ppbw to about 10 ppbw. These metal or metalloid impurities include but are not limited to aluminum (Al), arsenic (As), barium (Ba), beryllium (Be), bismuth (Bi), cadmium (Cd), calcium (Ca), chromium (Cr), cobalt (Co), copper (Cu), gallium (Ga), germanium (Ge), hafnium (Hf), zirconium (Zr), indium (In), iron (Fe), lead (Pb), magnesium (Mg), manganese (Mn), tungsten (W), nickel (Ni), potassium (K), sodium (Na), strontium (Sr), thorium (Th), tin (Sn), titanium (Ti), uranium (U), vanadium (V) and zinc (Zn). The concentration range of X (where X = Cl, Br) in the purified composition forming the Li-containing film, island or cluster can be between about 0 ppmw and about 100 ppmw and more preferably between about 0 ppmw and about 10 ppmw.

[0452] Care should be taken to prevent the disclosed composition forming the Li-containing film, island or cluster from being exposed to water, because the disclosed silicon-free lithium precursor is very sensitive to moisture and may decompose when it encounters water.

[0453] Also disclosed is a method of using the disclosed composition forming the Li-containing film, island or cluster for vapor deposition (such as ALD or CVD techniques). The disclosed method provides the use of the composition forming the Li-containing film, island or cluster for depositing a Li-containing film or island. The disclosed method can be used for the manufacture of electrode materials in the lithium-ion battery industry.

[0454] The disclosed compositions for forming Li-containing films, islands or clusters can be used to deposit Li-containing films or islands using any deposition method known to those skilled in the art. Examples of suitable deposition methods include chemical vapor deposition (CVD) or atomic layer deposition (ALD) with or without plasma treatment, or liquid-based deposition. Exemplary CVD methods include thermal CVD, pulsed CVD (PCVD), low pressure CVD (LPCVD), sub-atmospheric CVD (SACVD) or atmospheric pressure CVD (APCVD), hot wire CVD or thermal filament CVD (also known as cat-CVD, where the hot wire serves as the energy source for the deposition method), hot wall CVD, cold wall CVD, aerosol-assisted CVD, direct liquid injection CVD, combustion CVD, hybrid physical CVD, metalorganic CVD, rapid thermal CVD, photo-initiated CVD, laser CVD, radical combination CVD, plasma enhanced CVD (PECVD) including but not limited to flowable PECVD, and combinations thereof. Exemplary ALD methods include thermal ALD, plasma enhanced ALD (PEALD), spatially separated ALD, time-separated ALD, selective or non-selective ALD, hot wire ALD (HWALD), radical combination ALD, and combinations thereof. Supercritical fluid deposition can also be used. The deposition method is preferably ALD, PE-ALD, or spatial ALD in order to provide suitable step coverage and film thickness control. Liquid-based deposition is exemplified by spin-on deposition (SOD), spray deposition, dip coating, and slot coating.

[0455] The deposition method should be selected so as not to damage the substrate due to the high energy impact of the deposition method on the substrate. The deposition should be uniform and / or conformal and at least produce a defect-free or pinhole-free layer, which is required in different relevant industrial applications. Such applications may be as an electronic barrier between other materials or layers such that there is no leakage of electricity across the barrier, or in some applications, there is no physical contact between the layers that are desired to be separated. It is particularly important to provide a defect-free layer in lithium ion battery technology, where an electrolyte that allows lithium ions to pass separates the lithium-containing layers, but where there should be no physical or electrical contact between the layers to avoid an irreversible decrease in battery efficiency. The layer should provide a minimum ionic resistance, such that the importance of controlling layer quality is therefore crucial.

[0456] The deposition process can be carried out in a reactor for treating flat or quasi-flat surfaces, such as in single-substrate, batch, roll-to-roll or spatial ALD reactors known in the art. There is also increasing consideration of combining powder reactors with ALD or CVD technologies for uniform coating on the electrode active materials of batteries. A vertical reaction chamber can be used to form a fluidized zone where the coating reaction occurs. It has been observed that the powder particles in the fluidized bed tend to adhere to each other, forming larger particle agglomerates, lumps. To prevent the formation of lumps, a vibrating gas stream is used, so a carefully selected vibrating gas stream is fed into the reaction chamber. According to the principle of Helmholtz resonance, the incoming gas stream is forced into the cavity, so that the vibration enters the outgoing gas stream. The outgoing vibrating gas stream is guided into the reaction chamber to prevent the formation of lumps.

[0457] The disclosed method for forming a Li-containing layer on a substrate includes: placing the substrate in a reactor, delivering the vapor of the disclosed composition for forming a Li-containing film, island or cluster into the reactor, and contacting the vapor with the substrate (and typically guiding the vapor to the substrate) to form a Li-containing layer on the surface of the substrate.

[0458] The disclosed method can include using a vapor deposition process to form a bimetallic-containing layer on a substrate, and more specifically, depositing a LiNbO 3 layer, a LiZrO x layer. The disclosed method can be used in the manufacture of lithium-ion batteries.

[0459] Generate the vapor of the composition for forming a Li-containing film, island or cluster, and then introduce it into the reaction chamber containing the substrate. The temperature and pressure in the reaction chamber and the temperature of the substrate are maintained under conditions suitable for depositing at least a part of the silicon-free Li-containing precursor onto the substrate in the gas phase. In other words, after introducing the vaporized composition into the reaction chamber, the conditions in the reaction chamber are adjusted so that at least a part of the precursor is deposited onto the substrate to form a Li-containing layer. Those of ordinary skill in the art will recognize that "depositing at least a part of the precursor" means that some or all of the precursor reacts with or adheres to the substrate.

[0460] A reaction chamber or reactor can be any enclosure or chamber of an apparatus in which a deposition process is carried out, such as, but not limited to, a parallel plate type reactor, a cold wall type reactor, a hot wall type reactor, a single wafer reactor, a multi-wafer reactor, or other such types of deposition systems. All of these exemplary reaction chambers are capable of serving as ALD or CVD reaction chambers. For all ALD and sub-atmospheric CVD, the reaction chamber can be maintained at a pressure ranging from about 0.5 millitorr to about 20 torr. The pressure range for sub-atmospheric CVD and atmospheric CVD can be up to 760 torr (atmospheric pressure). Additionally, the temperature inside the reaction chamber can range from a temperature below room temperature (such as about 0 °C) to about 600 °C. Preferably, the temperature inside the reaction chamber can range from about 15 °C to about 600 °C. More preferably, the temperature inside the reaction chamber can range from about 20 °C to about 600 °C. Those of ordinary skill in the art should recognize that the temperature can be optimized only through experimentation to achieve the desired results.

[0461] The temperature of the reactor can be controlled by controlling the temperature of the substrate holder or by controlling the temperature of the reactor wall. Apparatuses for cooling or heating the substrate are known in the art. The reactor wall is heated to a sufficient temperature to obtain the desired film, island, or cluster at a sufficient growth rate and with the desired physical state and composition. Non-limiting exemplary temperature ranges to which the reactor wall can be heated include from about 20 °C to about 600 °C. Alternatively, non-limiting exemplary temperature ranges to which the reactor wall can be heated include from about 20 °C to about 1000 °C. Alternatively, non-limiting exemplary temperatures to which the reactor wall can be heated include about 500 °C or higher. When a plasma deposition process is utilized, the deposition temperature range can be from about 20 °C to about 550 °C, preferably from about 125 °C to about 250 °C. Alternatively, when a thermal process is carried out, the deposition temperature range can be from about 300 °C to about 800 °C, preferably from about 400 °C to about 600 °C.

[0462] Alternatively, the substrate can be heated to a sufficient temperature to obtain the desired Li-containing film at a sufficient growth rate and with the desired physical state and composition. Non-limiting exemplary temperature ranges to which the substrate can be heated include from room temperature to about 600 °C. Preferably, the temperature of the substrate is maintained less than or equal to 500 °C.

[0463] The reactor is equipped with one or more substrates on which a film or island is deposited. A substrate is generally defined as the material on which a method is performed. The substrate can be any suitable substrate used in the semiconductor or lithium battery industries. Examples of suitable substrates include wafers or carriers such as silicon, silicon dioxide, and glass substrates. The carrier can have one or more layers of different materials deposited thereon from previous manufacturing steps. For example, the carrier can include a silicon layer (crystalline, amorphous, porous, etc.), a silicon oxide layer, a silicon nitride layer, a silicon oxynitride layer, a carbon-doped silicon oxide (SiCOH) layer, or a combination thereof. The disclosed silicon-free Li-containing precursor used in the lithium battery industry can be deposited on powders made of graphite, doped graphite especially silicon-doped graphite, silicon, and silicon alloys, or powders made of metal oxides (especially lithium nickel oxide, lithium nickel manganese oxide, lithium nickel cobalt oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, lithium iron phosphate, and the corresponding materials with dopants), or a combination thereof. Additionally, the wafer can include a copper layer or a noble metal layer (such as platinum, palladium, rhodium, or gold). The layer can include an oxide used as a dielectric material in MEMS, MIM, DRAM, RF front-end module, or FeRam technologies. The underlying material can include, for example, nickel oxide, manganese oxide, cobalt oxide, graphite carbon, or amorphous carbon. A plastic layer such as poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) [PEDOT:PSS] can also be used. The layer can be flat, spherical, circular, or patterned, or can have an irregular structure (see above). For example, the layer can be an underlying material made of hydrocarbon hydride (such as CH x , where x is greater than zero). Preferred underlying materials are graphite carbon or amorphous carbon, lithium nickel manganese oxide, lithium nickel manganese cobalt oxide, and lithium nickel cobalt aluminum oxide.

[0464] The disclosed process can deposit a Li-containing layer directly on the carrier or directly on one or more layers on top of the carrier. The substrate can be patterned or can include a complex three-dimensional structure. For example, any ALD / CVD technology can be used to deposit a conformal Li-containing film (such as lithium) having an aspect ratio ranging from about 20:1 to about 100:1. Additionally, those of ordinary skill in the art will recognize that the terms "film" or "layer" as used herein refer to a certain thickness of a material placed or spread on a surface and that the surface can be a trench or a line. Throughout the specification and claims, the wafer and any related layers thereon are referred to as the substrate. However, in many cases, the preferred substrate used can be selected from hydrocarbon hydride, silicon-based carbon, lithium metal oxide, or Si-type substrates.

[0465] The disclosed compositions for forming Li-containing films can be supplied in pure form or as blends with suitable solvents such as toluene, ethylbenzene, xylene, mesitylene, decane, dodecane, octane, hexane, pentane, tertiary amines, acetone, tetrahydrofuran, ethanol, ethyl methyl ketone, 1,4-dioxane, or others. The disclosed compositions can be present in the solvent at varying concentrations. For example, the resulting concentration can range from about 0.05 M to about 2 M.

[0466] The pure or blended compositions for forming Li-containing films, islands, or clusters are delivered in vapor form into a reactor by conventional means such as piping systems and / or flow meters. The vapor-form composition can be generated by vaporizing the pure or blended composition via conventional vaporization steps such as direct vaporization, distillation, by bubbling, or by using a sublimator (such as the sublimator disclosed in PCT Publication WO2009 / 087609 to Xu et al.). The pure or blended composition can be fed in liquid form into a vaporizer where it is vaporized and then introduced into the reactor. Alternatively, the pure or blended composition can be vaporized by delivering a carrier gas into a container containing the composition or by bubbling the carrier gas into the composition. The carrier gas can include, but is not limited to, Ar, He, or N 2 and mixtures thereof. Bubbling with the carrier gas can also remove any dissolved oxygen present in the pure or blended composition. Then the carrier gas and the composition are introduced into the reactor as a vapor.

[0467] If desired, the container can be heated to a temperature that allows the composition for forming the Li-containing film to be in its liquid phase and have a sufficient vapor pressure. The container can be maintained at a temperature in the range of, for example, 0 °C - 150 °C. Those skilled in the art will recognize that the temperature of the container can be adjusted in a known manner to control the amount of the composition for forming the Li-containing film that is evaporated.

[0468] In addition to the disclosed silicon-free lithium precursors, reactants or co-reactants can be introduced into the reactor. The co-reactant can be an oxygen-containing gas for depositing the Li-containing film. Oxygen-containing gases include, but are not limited to, oxidants such as O 3 、O 2 、H 2 O, trimethyl phosphate, alkyl phosphates, alkyl phosphonimides, NO, N 2 O, H 2 O 2 、O radicals and combinations thereof, preferably O 3 or O 2 . Typically, an O 3 / O 2 mixture is used for high-temperature (e.g., about 500 °C or higher) oxide deposition. Additionally, the co-reactant can be N 2 、NH 3, N 2 H 4 or an alkyl hydrazine.

[0469] The disclosed vapor deposition processes (e.g., ALD, CVD) typically include a step of removing excess co-reactant from the deposition surface by providing a purge step, which is effected by purging the reactor with an inert gas, or passing the substrate through a section under high vacuum and / or a carrier gas curtain.

[0470] The co-reactants listed above can be treated by plasma in order to decompose the co-reactants into their radical forms. When treated with plasma, N 2 can also be used as a reducing agent. For example, plasma can be generated at a power ranging from about 50 W to about 500 W, preferably from about 100 W to about 200 W. The plasma can be generated or present within the reactor itself. Alternatively, the plasma can generally be located at a position remote from the reactor, such as in a remotely located plasma system. Those skilled in the art will recognize methods and equipment suitable for such plasma treatment.

[0471] When the desired Li-containing film further contains another element, such as and not limited to P, Ga, Ge, As, B, Ta, Hf, Nb, Mg, Al, Sr, Y, Ba, Ca, As, Sb, Bi, Sn, Pb, Co, Ni, Fe, Mn, lanthanide elements, or a combination thereof, the co-reactant can include another precursor selected from but not limited to trimethyl phosphate, alkyl phosphate, alkyl phosphonimide.

[0472] The disclosed compositions for forming Li-containing films, islands or clusters and one or more co-reactants can be introduced into the reaction chamber simultaneously (e.g., CVD), sequentially (e.g., ALD) or in other combinations. For example, the composition for forming Li-containing films, islands or clusters can be introduced in one pulse and two additional reactants can be introduced together in separate pulses (e.g., modified ALD). Alternatively, the reaction chamber may already contain the co-reactant before introducing the disclosed composition for forming Li-containing films, islands or clusters. The co-reactant can be passed through a plasma system positioned or remote from the reaction chamber and decomposed into radicals. Alternatively, the composition for forming Li-containing films, islands or clusters can be introduced continuously into the reaction chamber while other reactants are introduced by pulses (e.g., pulsed CVD). In each instance, a purge or evacuation step can be performed after the pulse to remove the excess components introduced. Each pulse of the disclosed composition for forming Li-containing films, islands or clusters can last for a period ranging from about 0.01 seconds to about 200 seconds, alternatively from about 1 second to about 180 seconds, alternatively from about 10 seconds to about 160 seconds. The co-reactant can also be pulsed into the reactor. In such embodiments, each pulse of each co-reactant can last for a period ranging from about 0.01 seconds to about 120 seconds, alternatively from about 1 second to about 30 seconds, alternatively from about 2 seconds to about 20 seconds. In each instance, the purge pulse can last for a period ranging from about 0.01 seconds to about 50 seconds, alternatively from about 0.3 seconds to about 30 seconds, alternatively from about 1 second to about 20 seconds, alternatively from about 2 seconds to about 10 seconds. In another alternative, the composition for forming Li-containing films, islands or clusters and one or more co-reactants can be ejected simultaneously from a showerhead (without mixing the composition and the reactants), and below the showerhead, a pedestal holding several substrates is rotated (e.g., spatial ALD).

[0473] In a non-limiting exemplary ALD-type process, the vapor phase of the composition for forming Li-containing films, islands or clusters is introduced into a reaction chamber, in which at least a portion of a silicon-free Li-containing precursor reacts with a suitable substrate (such as Si, SiO 2 、Al 2 O 3 etc.) to form an adsorbed Li-containing layer or island. Then the excess composition can be removed from the reaction chamber by purging and / or evacuating the reaction chamber. H 2 or NH 3 is introduced into the reaction chamber, in which it reacts with the adsorbed Li-containing layer in a self-limiting manner. Any excess H or NH 3 is removed from the reaction chamber by purging and / or evacuating the reaction chamber. If the desired film is a Li 3 N film, this two-step process can provide the desired film thickness or can be repeated until a film with the required thickness is obtained.

[0474] Alternatively, if the desired Li-containing film, island or cluster contains a second element (i.e., LiM, where M is P, Ga, Ge, As, B, Ta, Hf, Nb, Mg, Al, Sr, Y, Ba, Ca, As, Sb, Bi, Sn, Pb, Co, a lanthanide element or a combination thereof), after the above two-step process, the vapor of the second precursor can be introduced into the reaction chamber. The second precursor will be selected based on the nature of the deposited LiM film, island or cluster. After being introduced into the reaction chamber, the second precursor is brought into contact with the substrate. Any excess second precursor is removed from the reaction chamber by purging and / or evacuating the reaction chamber. Again, H 2 or NH 3 can be introduced into the reaction chamber to react with the second precursor. The excess H 2 or NH 3 is removed from the reaction chamber by purging and / or evacuating the reaction chamber. If the desired film, island or cluster thickness has been reached, the process can be terminated. However, if a thicker film, island or cluster is desired, the entire four-step process can be repeated. By alternately providing the silicon-free Li-containing precursor, the second precursor, and H 2 or NH 3 , a film with the desired composition and thickness can be deposited.

[0475] The disclosed silicon-free lithium precursor can contain any of the following impurities: undesired co-generic species; solvents; chlorinated metal compounds; or other reaction products. In an alternative, the total amount of these impurities is less than 0.1% w / w.

[0476] Solvents such as hexane, pentane, dimethyl ether, or anisole can be used in the synthesis of the precursor. The concentration range of the solvent in the disclosed Si-containing precursor can be from about 0% w / w to about 5% w / w, preferably from about 0% w / w to about 0.1% w / w. If both the solvent and the precursor have similar boiling points, it may be difficult to separate the solvent from the precursor. Cooling the mixture can produce a solid precursor in the liquid solvent that can be separated by filtration. Vacuum distillation can also be used, provided that the precursor product is not heated above about its decomposition point.

[0477] In an alternative, the disclosed silicon-free lithium precursor contains less than 5% v / v, preferably less than 1% v / v, more preferably less than 0.1% v / v, and even more preferably less than 0.01% v / v of any of its undesired co-generic species, reactants or other reaction products. This alternative can provide better process reproducibility. This alternative can be achieved by distillation of the disclosed silicon-free lithium precursor.

[0478] In another alternative, the disclosed silicon-free lithium precursor may contain one or more of the same kind of Li-containing precursors, reactants, or other reaction products between 5% v / v and 50% v / v, especially when the mixture provides improved process parameters or when it is too difficult or expensive to separate the target compound. For example, a mixture of two Li-containing precursors may produce a stable liquid mixture suitable for vapor deposition.

[0479] This application also discloses a method or process for forming a Li-containing layer on a substrate using an ALD or CVD process in a reaction chamber. The disclosed silicon-free lithium precursor can be used to deposit a Li-containing film or island using ALD or CVD methods known to those skilled in the art.

[0480] The disclosed vapor deposition process (such as ALD, CVD) can be carried out on a substrate having a temperature of about room temperature or higher, preferably about 100 °C or higher, more preferably about 200 °C or higher, using the disclosed silicon-free lithium precursor. The disclosed ALD process can be carried out on a substrate having a temperature ranging from about room temperature to about 750 °C, more preferably from 50 °C to about 500 °C, even more preferably from 100 °C to about 250 °C, using the disclosed Li-containing precursor.

[0481] The exposure time of the substrate in the disclosed vapor deposition process (such as ALD, CVD) using the disclosed precursor can range from 1 millisecond to 5 minutes, preferably from 1 second to 60 seconds. The exposure time of the co-reactant in the disclosed ALD process using the disclosed precursor can range from 1 millisecond to 1 minute, preferably from 100 milliseconds to 30 seconds.

[0482] The pressure in the reaction chamber is maintained under conditions suitable for the reaction of the precursor with the surface. For example, the pressure in the chamber can be maintained between about 0.1 millitorr and about 1000 torr, preferably between about 0.1 torr and about 400 torr, more preferably between about 1 torr and about 100 torr, even more preferably between about 1 torr and about 10 torr.

[0483] The disclosed silicon-free lithium precursor and co-reactant can be introduced into the reactor sequentially (ALD) or simultaneously (CVD). The reactor can be purged with an inert gas between the introduction of the precursor and the introduction of the co-reactant. Alternatively, the substrate can be moved from one area for precursor exposure to another area for co-reactant exposure (spatial ALD).

[0484] Depending on the specific process parameters, the deposition may be carried out for different lengths of time. Typically, the deposition can be continued for the desired or necessary length of time to produce a film with the necessary thickness. Depending on the specific deposition process, the typical film thickness can vary from atomic monolayers to several hundred micrometers, preferably between 0.5 and 100 nm, more preferably between 1 and 50 nm. The deposition process can also be carried out many times as necessary to obtain the desired film.

[0485] In a non-limiting exemplary ALD-type process, the vapor phase of the disclosed silicon-free lithium precursor is introduced into a reactor, where the Li-containing precursor is physically adsorbed or chemically adsorbed on a substrate. Then, the excess composition can be removed from the reactor by purging and / or evacuating the reactor. The desired gas (e.g., O 3 ) is introduced into the reactor, where it reacts with the physically adsorbed or chemically adsorbed precursor in a self-limiting manner. Any excess reducing gas is removed from the reactor by purging and / or evacuating the reactor. If the desired film is a Li-containing film, this two-step process can provide the desired film thickness or can be repeated until a film with the necessary thickness is obtained.

[0486] The Li-containing films or islands formed by vapor deposition processes using the disclosed silicon-free Li-containing precursors include Li 2 O, LiOH, Li 2 S, Li 3 N, LiF, lithium carbonate, lithium aluminum fluoride, lithium aluminum oxide, lithium aluminum, lithium cobalt oxide, lithium titanate, lithium zirconate, lithium niobate, LiPON, lithium phosphate, lithium borate, lithium borophosphate, etc.

[0487] The disclosed silicon-free lithium precursors have the following advantages. The disclosed silicon-free lithium precursors do not contain silicon. Although silicon-containing lithium precursors, such as the most common precursor LiHMDS (e.g., Li(SIMe 3 ) 2 ) are very stable and have sufficient volatility, silicon will be partially retained in the deposited film. When forming materials such as LiTiO 3 , LiNbO 3 or LiZrO x , the presence of silicon can be problematic, where silicon may cause adverse electrochemical characteristics (related to the induced disorder of the material), and thus result in lower ionic conductivity.

[0488] The disclosed silicon-free lithium precursors are high-melting-point and low-volatility lithium sources. Lithium compounds exist as various aggregates in solution and in the solid state. These molecules typically have a polymeric structure, typically a trimeric or tetrameric structure, resulting in high molecular weight, high melting point, and low volatility. For example, n-BuLi is a tetramer in diethyl ether and a hexamer in cyclohexane. Li(SiMe3 ) 2 It has been reported that it is a trimer in the solid state, and LiOtBu is allegedly transformed into a hexamer. The use of liquid precursors or low-melting solid precursors is well known in the industry, especially in the semiconductor industry. Additionally, these precursors are convenient, enabling accurate measurement and / or control of the flow rate. When the volatility of the precursor is not very strong and thus heating is required, the way to deliver the precursor is to heat only a part of the precursor in the tank so that it is delivered quickly, while the remaining part of the precursor remains under ambient conditions in this tank called the "mother tank". Thus, it is important to feed the heated tank in a practical manner. Liquids or low-melting solids can be transferred and filled (transfilled) by simply opening a valve. The melting point should thus be significantly lower than that of Li(OtBu) or Li(SiMe 3 ) 2 low, for example below 150 °C, preferably below 80 °C, more preferably below 25 °C. Furthermore, considering its morphological changes, the delivery of a stable feed rate of high-melting solids is a challenge: typically, small particles with a higher surface-to-bulk ratio are consumed faster than larger particles. Conversely, the particles may coalesce, making the feed rate potentially unstable. The disclosed silicon-free lithium precursors with low melting points can overcome these problems.

[0489] The disclosed silicon-free lithium precursors are lithium precursors that are very sensitive to moisture and self-ignite. One of the well-known lithium sources is organolithium compounds such as alkyllithium and aminolithium. They are generally highly reactive, moisture-sensitive, and sometimes self-igniting substances. Special safety requirements are necessary. They are usually commercially available in solution. However, as a lithium precursor source, the disclosed silicon-free lithium precursors may require lower special safety requirements than organolithium compounds.

[0490] The known ALD / CVD processes for forming lithium-containing films are typically carried out at temperatures between 250 °C and 350 °C. This temperature range is acceptable if the deposition occurs on components such as powders of active materials. This temperature range may not be suitable for deposition on temperature-sensitive materials such as lithium-ion battery electrodes. The disclosed silicon-free lithium precursors are liquids below 150 °C, preferably liquids at 50 °C, more preferably liquids at 25 °C, which is suitable for deposition on temperature-sensitive materials such as lithium-ion battery electrodes.

[0491] Whether using CVD, ALD, or other film coating / deposition techniques, the industry is looking for cost-effective deposition techniques. To minimize the process time, co-injection of the lithium precursor and the metal precursor into the reactor is preferred. This will require the use of chemically compatible lithium precursors and metal precursors if they are introduced together. The disclosed silicon-free lithium precursors will meet these requirements.

[0492] Other concerned applications using lithium precursors include forming Li-containing clusters or islands. In some cases, just a small amount of Li-containing material in the form of islands or clusters (e.g., discontinuous deposits) is sufficient to improve the electrochemical behavior of the material. In photovoltaic or semiconductor applications, it is also known that trace amounts of lithium on the surface are beneficial for the crystal growth of the material to be deposited, such as copper indium gallium selenide (CIGS), copper zinc tin sulfide (CZTS) absorber layers, two-dimensional materials such as molybdenum or tungsten chalcogenides, resulting in larger-sized microcrystals and thus significantly improving their physical properties, especially their electronic properties such as carrier mobility. These trace amounts of lithium can form islands or clusters, for example, using vapor deposition techniques.

[0493] Examples

[0494] The following non-limiting examples are provided to further illustrate embodiments of the present invention. However, these examples are not intended to cover all cases and are also not intended to limit the scope of the invention described herein.

[0495] In the following Examples 9-13, deposition experiments were carried out under the following conditions.

[0496] Reactor temperature: from 0 °C to 600 °C;

[0497] Reactor pressure: 1 torr;

[0498] Lithium precursor cartridge temperature: 110 °C;

[0499] Lithium precursor cartridge pressure: 20 torr;

[0500] N of lithium precursor 2 Bubbling flow rate: 40 sccm;

[0501] Trimethyl phosphate (TMPO) cartridge temperature: 80 °C;

[0502] TMPO cartridge pressure: 20 torr;

[0503] N of TMPO 2 Bubbling flow rate: 40 sccm;

[0504] Substrate: Si or TiN;

[0505] Deposition method: ALD;

[0506] Number of cycles: 200; and

[0507] Pulse conditions in the cycle: lithium precursor: 60 seconds or 160 seconds; purge: 20 seconds; TMPO: 10 seconds; purge: 30 seconds; O 3 : 5 seconds; purge: 5 seconds.

[0508] The composition of the deposited films was studied by X-ray photoelectron spectroscopy (XPS) and refractive index (RI).

[0509] Example 1: LiN(CHCH 2 NMe 2 ) 2 Synthesis

[0510] In a 100 mL flask, N(CH 2 CH 2 NMe 2 ) 3 (5.11 g, 22.0 mmol) was dissolved in pentane (200 mL). A solution of tBuLi in pentane (1.9 M, 11.6 mL, 22 mmol) was added dropwise to the flask at -78 °C. After stirring at room temperature for 1 hour, all volatiles were removed under reduced pressure to obtain LiN(CH 2 CH 2 NMe 2 ) 2 The solid was then dissolved in a small amount of pentane (about 10 mL). The resulting solution was cooled at -30 °C to obtain LiN(CH 2 CH 2 NMe 2 ) 2 A yellow crystalline solid (2.90 g, 17.6 mmol, 79% yield) was obtained. The yellow crystalline solid can be further purified by sublimation at 100°C under dynamic vacuum. 1 H NMR (C 6 D 6 , 400 MHz) was measured at 1.80-2.20 ppm (m, 12H), 2.20-2.30 ppm (m, 2H), 3.05-3.20 ppm (m, 2H), 3.40-3.50 ppm (m, 2H). Figure 1 It shows that LiN(CH 2 CH 2 NMe 2 ) 2 Graph of Thermogravimetric Analysis (TGA) (760 Torr) showing weight loss versus temperature under conditions representative of delivery conditions (10°C / min). Figure 2 It shows that LiN(CH 2 CH 2 NMe 2 ) 2 A graph of the TGA (15 Torr) of , showing the relationship between weight loss and temperature under conditions representative of delivery conditions (10°C / min).

[0511] Example 2: Synthesis of LiN(CHMeCH 2 NMe 2 (CH 2 CH 2 NMe 2 )

[0512] In a 100 mL Schlenk tube, HN(CHMeCH 2 NMe 2 (CH 2 CH 2 NMe 2 )(1.34 g, 7.70 mmol) was dissolved in pentane (20 mL). At 0 °C, a solution of nBuLi in hexane (1.6 M, 4.8 mL, 7.7 mmol) was added dropwise. After stirring the reaction mixture at room temperature for 1 h, all volatiles were removed under reduced pressure to obtain the crude compound of LiN(CHMeCH 2 NMe 2 (CH 2 CH 2 NMe 2 )(1.37 g, quantitative yield). The compound was purified by recrystallization from a pentane solution at -30 °C. Figure 3 Figure shows the thermogravimetric analysis (top: 760 Torr; bottom: 15 Torr) curves of LiN(CHMeCH 2 NMe 2 (CH 2 CH 2 NMe 2 ) showing the relationship between weight loss and temperature under conditions (10 °C / min) representative of delivery conditions.

[0513] Example 3: Synthesis of LiN(CH 2 CH 2 NEt 2 ) 2 In a 100 mL Schlenk tube, HN(CH

[0514] CH 2 CH 2 NEt 2 )(3.92 g, 18.2 mmol) was dissolved in pentane (30 mL). At 0 °C, a solution of nBuLi in hexane (1.6 M, 11.4 mL, 18.2 mmol) was added dropwise. After stirring the reaction mixture at room temperature for 1 h, all volatiles were removed under reduced pressure to obtain LiN(CH 2 (CH 2 CH 2 NEt 2 )( 2The crude compound (4.01 g, quantitative yield). The crude compound was purified by recrystallization from a pentane solution at -30 °C. 1 1H NMR (C6D6, 400 MHz) measured at 0.95 ppm (t, 12H), 2.3 - 3.2 ppm (m, 12H), 3.38 ppm (t, 4H). Figure 4 shows LiN(CH 2 CH 2 NEt 2 ) 2 TGA (15 Torr) curve of

[0515] Example 4: Synthesis of LiNMe(CH 2 CH 2 NMe 2 )

[0516] In a 500 mL flask, N,N,N'-trimethylethylenediamine (11.7 g, 114 mmol) was dissolved in pentane (250 mL). At 0 °C, a solution of nBuLi in pentane (1.6 M, hexane, 71 mL, 114 mmol) was added to the flask. After stirring at room temperature for 1 hour, all volatiles were removed under reduced pressure to obtain a white solid of LiNMe(CH 2 CH 2 NMe 2 ) (12.3 g, 113 mmol, 99% yield). The white solid was crystallized from a pentane solution at -30 °C. 1 1H NMR (C 6 D 6 , 400 MHz) measured at 1.99 ppm (brs, 6H), 2.44 ppm (t, 2H), 3.10 (brs, 3H), 3.20 (brs, 2H). Figure 5 shows LiNMe(CH 2 CH 2 NMe 2 ) 2 TGA (15 Torr) curve of

[0517] Example 5: Synthesis of LiNtBu(CH 2 CH 2 NMe 2 )

[0518] In a 100 mL Schlenk tube, HNtBu(CH 2 CH 2 NMe2 (4.58 g, 31.7 mmol) was dissolved in pentane (50 mL). At 0 °C, a solution of nBuLi in hexane (1.6 M, 19.8 mL, 31.7 mmol) was added dropwise. After stirring the reaction mixture at room temperature for 1 hour, all volatiles were removed under reduced pressure to obtain the crude compound of LiNtBu(CH 2 CH 2 NMe 2 )(4.07 g, quantitative yield). The crude compound was purified by recrystallization from a pentane solution at -30 °C. 1 1H NMR (C6D6, 400 MHz) measured at 1.33 ppm (s, 9H), 1.95 ppm (s, 6H), 2.3 - 2.5 ppm (brs, 2H), 3.2 ppm (t, 2H). Figure 6 The TGA (15 Torr) curve of LiNtBu(CH 2 CH 2 NMe 2 ) is shown, demonstrating the relationship between weight loss and temperature under the conditions (10 °C / min) representative of the delivery conditions.

[0519] Example 6: Synthesis of a mixture (6.5:1) of HNtBu(CHMeCH 2 NMe 2 ) and HNtBu(CH 2 CHMeNMe 2 )

[0520] In a 2 L flask, tBuNH 2 (600 mL, 5.70 mol) was dissolved in deionized water (400 mL). While cooling with an ice bath, a solution of 2-chlorodimethylaminopropane hydrochloride (300 g, 1.90 mol) in deionized water (400 mL) was slowly added to the flask. The reaction solution was stirred overnight at room temperature. A solution of NaOH (153 g, 3.82 mol) in deionized water (300 mL) was added slowly. The aqueous phase was divided into 4 portions. Each portion was extracted with pentane (100 mL × 5). After drying over MgSO 4 , the organic phase was evaporated under reduced pressure to obtain a crude liquid. The crude liquid was distilled under static vacuum to remove dissolved solids. The liquid was fractionated (65 °C, 10 kPa) to obtain a colorless liquid (175 g, 58% yield) of HNtBu(CHMeCH 2 NMe 2 ) and HNtBu(CH 2 CHMeNMe 2 )(6.5:1). HNtBu(CHMeCH 2 NMe 2 )'s1 1H NMR (C6D6, 400 MHz) shows signals at 0.78 ppm (d, 3H), 1.09 ppm (s, 9H), 1.39 ppm (brs, 1H), 2.08 ppm (s, 6H), 2.39 ppm (m, 1H), 2.50 ppm (m, 1H), 2.71 ppm (m, 1H). HNtBu(CH 2 CHMeNMe 2 )'s 1 1H NMR (C 6 D 6 , 400 MHz) shows signals at 1.07 ppm (d, 3H), 1.11 ppm (s, 9H), 1.60 ppm (brs, 1H), 1.88 ppm (m, 1H), 2.03 ppm (s, 6H), 2.12 ppm (m, 1H), 2.78 ppm (m, 1H).

[0521] Example 7: Synthesis of a mixture (6.5:1) of LiNtBu(CHMeCH 2 NMe 2 ) and LiNtBu(CH 2 CHMeNMe 2 )

[0522] In a 500 mL flask, a mixture (ratio 6.5:1, 70.9 g, 448 mmol) of HNtBu(CHMeCH 2 NMe 2 ) and LiNtBu(CH 2 CHMeNMe 2 ) was dissolved in pentane (100 mL). At 0 °C, a solution of nBuLi in hexane (1.6 M, 280 mL, 448 mmol) was added dropwise. After stirring the reaction mixture at room temperature for 1 hour, the solvent was removed under reduced pressure to obtain a yellow crude liquid (quantitative yield). The liquid was distilled at 100 °C under dynamic vacuum to obtain a slightly yellow liquid (66.8 g, 407 mmol, 91% yield) of a mixture of LiNtBu(CHMeCH 2 NMe 2 ) and LiNtBu(CH 2 CHMeNMe 2 ). Figure 7 Shows a mixture of LiNtBu(CHMeCH 2 NMe 2 ) and LiNtBu(CH 2 CHMeNMe 2The graph of TGA (15 Torr) with a ratio of (6.5:1) shows the relationship between weight loss and temperature under the condition (10 °C / min) representing the delivery conditions. Figure 8 is LiNtBu(CHMeCH 2 NMe 2 ) and LiNtBu(CH 2 CHMeNMe 2 ) in C 6 D 6 of the mixture of 1 1H NMR spectrum.

[0523] Example 8: Deposition of Lithium Phosphate

[0524] Using the following cycle pattern, in sequential mode, using LiN(CH 2 CH 2 NMe 2 ) 2 and trimethyl phosphate (TMPO), deposit a Li-containing film on a silicon substrate by ALD: Pulse LiN(CH 2 CH 2 NMe 2 ) 2 . Let N 2 flow for 30 seconds to purge excess LiN(CH 2 CH 2 NMe 2 ) 2 . Pulse TMPO for 10 seconds at a flow rate of 5 sccm. The number of cycles is 200. The temperature and pressure conditions are set at 250 °C and 2 Torr. Deposited a film of about , indicating that the growth rate per cycle is The formed film has a refractive index of about 1.50. The film composition measured by XPS is determined to be generally Li 3.1 PO 4.7 , corresponding to the target range of the material composition.

[0525] Example 9: Perform ALD of Li 2 CH 2 NMe 2 ) 2 from 125 °C to 250 °C for Li 3 PO 4 film

[0526] Using a fluidized bed reactor, using LiN(CH 2 CH 2 NMe 2 ) 2, Trimethyl phosphate (TMPO) and ozone (O 3 ), at a temperature ranging from 125 °C to 250 °C, Li was deposited on a Si wafer by ALD after 200 ALD cycles 3 PO 4 film. The pulse of LiN(CH 2 CH 2 NMe 2 ) 2 was 60 seconds. Figure 9 is the growth per cycle (GPC) at a temperature from 125 °C to 250 °C. The reactor temperature varied from 125 °C to 250 °C. Figure 10 is the XPS result of the deposited Li 3 PO 4 film. Based on XPS analysis, the film deposited under these conditions has relatively constant atomic percentages over a wide range of temperatures. For example, at 125 °C, Li: 34.6%, P: 13.9%, O: 48.6%, C: 2.3%, N: 0.6%. Additionally, see Figure 11 , the refractive index is 1.56, close to the refractive index of bulk Li 3 PO 4 (1.59). In this way, under these conditions, the deposited material is thus lithium phosphate Li 3 PO 4 . The growth of Li 3 PO 4 film at low deposition temperatures (e.g., <200 °C) is quite unexpected and has never been reported to our knowledge. Above 200 °C, the GPC reaches above This thickness is inconsistent with self-saturation and the ALD process. However, as long as the resulting Li 3 PO 4 layer provides an effective interface between the electrolyte and the electrode material (which is alleged to catalyze the decomposition of the electrolyte at extreme voltages), then the process can be meaningful.

[0527] Example 10: Li 2 CH 2 NMe 2 ) 2 was used to perform ALD of Li 3 PO 4 film at 150 °C

[0528] Using a fluidized bed reactor, using LiN(CH 2 CH 2 NMe 2 ) 2 , TMPO and O 3, at a temperature of 150 °C, Li was deposited on a Si wafer by ALD after 200 ALD cycles 3 PO 4 film. The reactor temperature was 150 °C. The pulses of LiN(CH 2 CH 2 NMe 2 ) 2 were 60 seconds and 160 seconds. After 60 seconds (about 1.4 cc) of LiN(CH 2 CH 2 NMe 2 ) 2 60 seconds, the GPC( Figure 12 ) reached The refractive index was 1.56( Figure 13 ). This Li 3 PO 4 deposition process is thus very attractive for many battery applications, especially for protective coatings of lithium-ion batteries and solid-state batteries.

[0529] Example 11: Li 2 CH 2 NMe 2 ) 2 was used to perform ALD of Li 3 PO 4 film on a Si wafer at 135 °C

[0530] Using a fluidized bed reactor, using LiN(CH 2 CH 2 NMe 2 ) 2 , TMPO and O 3 , at a temperature of 135 °C, Li 3 PO 4 film was deposited on a Si wafer by ALD after 200 ALD cycles. The reactor temperature was 135 °C. The pulses of LiN(CH 2 CH 2 NMe 2 ) 2 were 60 seconds and 160 seconds. Figure 14 are the GPC results at 135 °C. Figure 15 are the RI results of the Li 3 PO 4 film deposited at 135 °C. At low temperatures (e.g., T < 150 °C), self-saturation of GPC was observed. To our knowledge, there is no report on Li 3 PO 4 ALD at T < 150 °C.

[0531] In addition, using a patterned Si wafer, under the same conditions, the film obtained on the patterned Si wafer (aspect ratio = 6.25 to 18) has a good conformality of almost 70%.

[0532] Example 12: LiN(CH 2 CH 2 NMe 2 ) 2 was used for ALD of the Li 3 PO 4 film on a TiN substrate at 135 °C.

[0533] Using a fluidized bed reactor, LiN(CH 2 CH 2 NMe 2 ) 2 , TMPO and O 3 were used, and at a temperature of 135 °C, a Li 3 PO 4 film was deposited on a TiN wafer by ALD after 200 ALD cycles. The reactor temperature was 135 °C. Growth of the Li 3 PO 4 film was also observed on the TiN substrate ( Figure 16 ).

[0534] Example 13: ALD of the Li 3 PO 3 film was carried out at 135 °C without using O 4 .

[0535] Using a fluidized bed reactor, LiN(CH 2 CH 2 NMe 2 ) 2 and TMPO were used, and at a temperature of 135 °C, a Li 3 PO 3 film was deposited on a Si wafer by ALD after 200 ALD cycles without using O 4 . The reactor temperature was 135 °C. According to XPS analysis, an extremely thin film containing lithium, phosphorus, and oxygen was observed. See Figure 17 . However, the GPC was extremely low (0.05%).

[0536] Predictive Example 1: Expected formation of a Li-containing film using LiN(CH 2 CH 2 NMe 2 ) 2 .

[0537] A silicon substrate or an amorphous carbon substrate is introduced into an ALD or CVD reactor. Then, the substrate is heated to a set point ranging from 100 °C to 500 °C for each experiment under a nitrogen atmosphere. After the temperature reaches the set point, LiN(CH 2 CH 2 NMe 2 ) 2 precursor, reactant, and carrier gas flow into the reactor to deposit a film on the substrate. During this step, water vapor or oxygen is used as the reactant, nitrogen is used as the carrier gas, and the pressure is maintained at 2 Torr. As a result, with water vapor as the reactant, lithium oxide films will be deposited by ALD at 100 °C, 120 °C, 150 °C, 175 °C, 200 °C, and 250 °C. Lithium oxide films will also be obtained by CVD at 200 °C, 300 °C, and 400 °C, while a lithium oxide film is deposited by CVD at 500 °C. On the other hand, with oxygen as the reactant, lithium oxide films will be deposited by ALD at 100 °C, 120 °C, 150 °C, 175 °C, 200 °C, and 250 °C.

[0538] Predictive Example 2: Expected formation of a Li-containing film using LiN(CH 2 CH 2 NMe 2 ) 2 A silicon substrate or an amorphous carbon substrate is introduced into an ALD or CVD reactor. Then, the substrate is heated to a set point ranging from 100 °C to 500 °C for each experiment under a nitrogen atmosphere. After the temperature reaches the set point, LiN(CH

[0539] and NbCp(=NtBu)(NMe 2 CH 2 NMe 2 ) 2 precursor mixture, reactant, and carrier gas flow into the reactor to deposit a film on the substrate. During this step, water vapor or oxygen is used as the reactant, nitrogen is used as the carrier gas, and the pressure is maintained at 2 Torr. As a result, with water vapor as the reactant, lithium niobate films will be deposited by ALD at 100 °C, 120 °C, 150 °C, 175 °C, 200 °C, and 250 °C. Lithium niobate films will also be obtained by CVD at 200 °C, 300 °C, and 400 °C, while a lithium niobate film is deposited by CVD at 500 °C. On the other hand, with oxygen as the reactant, lithium niobate films will be deposited by ALD at 100 °C, 120 °C, 150 °C, 175 °C, 200 °C, and 250 °C. 2 ) 2 Predictive Example 3: Using LiN(CH

[0540] CH 2 CH 2 NMe2 ) 2 Expected formation of Li-containing islands

[0541] A silicon substrate or an amorphous carbon substrate is introduced into an ALD or CVD reactor. Then, the substrate is heated to a set point from 100 °C to 500 °C for each experiment under a nitrogen atmosphere. After the temperature reaches the set point, LiN(CH 2 CH 2 NMe 2 ) 2 precursor, reactant, and carrier gas flow into the reactor to deposit islands on the substrate. During this step, water vapor or oxygen is used as the reactant, nitrogen is used as the carrier gas, and the pressure is maintained at 2 Torr. As a result, with water vapor as the reactant, Li-containing islands will be formed by ALD at 100 °C, 120 °C, 150 °C, 175 °C, 200 °C, and 250 °C using a very limited number of cycles, typically less than 10 times. When the CVD process duration is limited to seconds to minutes, Li-containing islands will also be obtained by CVD at 200 °C, 300 °C, and 400 °C.

[0542] It should be understood that many additional changes in details, materials, steps, and arrangements of parts described and elucidated herein to explain the nature of the present invention can be made by those skilled in the art within the principles and scope of the present invention as expressed in the appended claims. Therefore, the present invention is not intended to be limited to the specific embodiments given in the examples and / or drawings above.

[0543] Although embodiments of the present invention have been shown and described, those skilled in the art can modify them without departing from the spirit or teachings of the present invention. The embodiments described herein are merely exemplary and not restrictive. Many variations and modifications of the compositions and methods are possible and within the scope of the present invention. Therefore, the scope of protection is not limited to the embodiments described herein, but is only defined by the subsequent claims, the scope of which should include all equivalents of the subject matter of the claims.

Claims

1. A method for forming a Li-containing film, island or cluster on a substrate, the method comprising the steps of: introducing a silicon-free lithium precursor having the following general formula [Li-NL 1 L 2 -D x y (I)​ into a reactor in which the substrate is disposed, where L 1 has the following general formula: C m H n 、(C m H n )-ER 1 R 2 or (C m H n )-E′R 1 , where ●C m H n is a straight-chain, branched-chain or cyclic alkyl group; ● m and n are independent integers, 1 ≤ m ≤ 16, 1 ≤ n ≤ 16; ● E is B, N; ● E′ is a divalent element; ●R 1 and R 2 each independently selected from the group consisting of: hydrogen, linear, branched or cyclic alkyl, or linear, branched or cyclic alkyl substituted by other atoms or groups; L 2 has the following general formula: (C p H q )-ER 3 R 4 or (C p H q )-E′R 3 , where ●C p H q is a straight-chain, branched-chain or cyclic alkyl group; ● p and q are independent integers, 1 ≤ p ≤ 16, 1 ≤ q ≤ 16; ● E is B, N; ● E′ is a divalent element; ●R 3 and R 4 each independently selected from the group consisting of: hydrogen, straight-chain, branched-chain or cyclic alkyl, or straight-chain, branched-chain or cyclic alkyl substituted by other atoms or groups; D is independently selected from monodentate, bidentate, tridentate or polydentate neutral coordination ligand systems; x is an integer, 0 ≤ x ≤ 4; and y is the degree of association of the molecule, 1 ≤ y ≤ 6; and depositing at least a portion of the silicon-free lithium precursor onto the substrate using a method of chemical vapor deposition, spraying, dip coating, slot coating, spin coating deposition or a combination thereof to form the Li-containing film, island or cluster.

2. The method according to claim 1, wherein L 1 is C 1 -C 16 a straight-chain, branched-chain or cyclic carbon chain, or is (C m H n )-ER 1 R 2 or (C m H n )-E′R 1 in the form, where ●C m H n is a straight-chain, branched-chain or cyclic alkyl group; ● E represents B, N; ● E′ represents a divalent element; ● m is an integer having a value of 1, or an integer in the range from 1 to 8; ● n is an independent integer in the range from 2 to 16; ●R 1 is independent and is selected from the group consisting of: hydrogen, a straight-chain, branched-chain or cyclic C 1 -C 8 alkyl group, or a straight-chain, branched-chain or cyclic alkyl group substituted by other atoms or groups; ●R 2 is independent and is selected from the group consisting of: hydrogen, straight-chain, branched-chain or cyclic C 1 -C 8 alkyl, or straight-chain, branched-chain or cyclic alkyl substituted by other atoms or groups; L 2 is (C p H q )-ER 3 R 4 or (C p H q )-E′R 3 of the form, where ●C p H q is a straight-chain, branched-chain or cyclic alkyl group; ● E represents B, N; ● E′ represents a divalent element; ● p and q are independent integers in the range from 1 to 16; ●R 3 and R 4 are independent and are selected from the group consisting of: hydrogen, straight-chain, branched-chain or cyclic alkyl, or straight-chain, branched-chain or cyclic alkyl substituted by other atoms or groups; ● D is independently selected from monodentate, bidentate, tridentate or polydentate neutral coordination ligand systems; ● x is an integer included between 0 and 4; and ● y represents the degree of association of the molecule and is included between 1 and 6.

3. The method according to claim 2, wherein E' in formula (C m H n )-E′R 1 represents O or S.

4. The method according to claim 2, wherein E' in formula (C p H q )-E′R 3 represents O or S.

5. The method according to claim 2, wherein p is included from 1 to 8 and q is included from 2 to 16.

6. The method according to claim 2, wherein p is different from m.

7. The method according to claim 2, wherein D is independently selected from monodentate or bidentate neutral coordination ligand systems.

8. The method according to claim 1, wherein The silicon-free lithium precursor is selected from LiNMe(CH 2 CH 2 NMe 2 )、LiNMe(CH 2 CH 2 NMe 2 )(1,2 - diethoxyethane)、LiNMe(CH 2 CH 2 NMe 2 )(1,2 - dimethoxyethane)、LiNEt(CH 2 CH 2 NMe 2 )、LiNiPr(CH 2 CH 2 NMe 2 )、LiNtBu(CH 2 CH 2 NMe 2 )、LiNtBu(CH 2 CH 2 NEtMe)、LiNtBu(CHMeCH 2 NMe 2 )、LiNtBu(CH 2 CHMeNMe 2 )、LiN(CH 2 CH 2 NMe 2 ) 2 、LiN(CH 2 CH 2 NEt 2 ) 2 、LiN(CH 2 CH 2 NiPr 2 ) 2 、LiN(CH 2 CH 2 NEtMe) 2 、LiN(CH 2 CH 2 CH 2 NMe 2 ) 2 、LiN(CHMeCH 2 NMe 2 ) 2 、LiN(CHMeCH 2 NMe 2 )(CH 2 CH 2 NMe 2 )、LiN(CH 2 CHMeNMe 2 ) 2 、LiN(CH 2 CHMeNMe 2 )(CH 2 CH 2 NMe 2 )、LiN(CHEtCH 2 NMe 2 )(CH 2 CH 2 NMe 2 )、LiN(CH 2 CHEtNMe 2 )(CH 2 CH 2 NMe 2 )、LiN(CMe 2 CH 2 NMe 2 )(CH 2 CH 2 NMe 2 )、LiN(CH 2 CMe 2 NMe 2 )(CH 2 CH 2 NMe 2 )、LiN(CH 2 CH 2 NMe 2 )(CH 2 CH 2 CH 2 NMe 2 )、LiNMe(CH 2 CH 2 OMe)、LiNMe(CH 2 CH 2 OEt)、LiNMe(CH 2 CH 2 OiPr)LiNMe(CH 2 CH 2 OtBu)、LiNEt(CH 2 CH 2 OMe)、LiNEt(CH 2 CH 2 OEt)、LiNiPr(CH 2 CH 2 OMe)、LiNtBu(CH 2 CH 2 OMe)、LiN(CH 2 CH 2 OMe) 2 、LiN(CH 2 CH 2 OEt) 2 、LiN(CH 2 CH 2 OiPr) 2 、LiN(CH 2 CH 2 OtBu) 2 、LiN(CH 2 CH 2 NMe 2 )(CH 2 CH 2 OMe)、LiN(CH 2 CH 2 NMe 2 )(CH 2 CH 2 OEt)、LiN(CH 2 CH 2 NMe 2 )(CH 2 CH 2 OiPr)、LiN(CH 2 CH 2 NMe 2 )(CH 2 CH 2 OtBu) or LiNMe(CH 2 CH(OMe) 2 )。 9. The method according to claim 1, wherein The silicon-free lithium precursor is selected from LiNtBu(CH 2 CH 2 NMe 2 )、LiNtBu(CH 2 CH 2 NEtMe)、LiNtBu(CHMeCH 2 NMe 2 )、LiNtBu(CH 2 CHMeNMe 2 )、LiN(CH 2 CH 2 NEtMe) 2 、LiN(CH 2 CH 2 OEt) 2 、LiN(CH 2 CH 2 NMe 2 ) 2 、LiN(CH 2 CH 2 CH 2 NMe 2 ) 2 、LiN(CH 2 CH 2 NMeEt) 2 、LiN(CHMeCH 2 NMe 2 )(CH 2 CH 2 NMe 2 )、LiN(CH 2 CHMeNMe 2 )(CH 2 CH 2 NMe 2 )、LiN(CHEtCH 2 NMe 2 )(CH 2 CH 2 NMe 2 )、LiN(CH 2 CHEtNMe 2 )(CH 2 CH 2 NMe 2 )、LiN(CMe 2 CH 2 NMe 2 )(CH 2 CH 2 NMe 2 )、LiN(CH 2 CMe 2 NMe 2 )(CH 2 CH 2 NMe 2 )、LiN(CH 2 CH 2 NiPr 2 ) 2 、LiN(CH 2 CH 2 NMe 2 )(CH 2 CH 2 CH 2 NMe 2 )、LiN(CH 2 CH 2 OEt) 2 、LiNMe(CH 2 CH 2 OEt) or LiNMe(CH 2 CH(OMe) 2 )。 10. The method according to claim 1, wherein The silicon-free lithium precursor is LiN(CH 2 CH 2 NMe 2 ) 2 .

11. The method according to claim 1, wherein the silicon-free lithium precursor is a monomer, dimer, trimer or a combination thereof.

12. The method according to claim 1, wherein the silicon-free lithium precursor is a liquid at a temperature below 150 °C.

13. The method according to claim 1, wherein the chemical vapor deposition method is ALD.

14. The method according to claim 1, wherein the chemical vapor deposition method is CVD.

15. The method according to any one of claims 1 to 14, further comprising the step of delivering a co-reactant to the reactor, the co-reactant being selected from O 3 、O 2 、H 2 O, trimethyl phosphate, alkyl phosphate, alkyl phosphonimide, NO, N 2 O, H 2 O 2 , O radicals or combinations thereof.

16. The method according to claim 15, wherein The co-reactant is O 3 .

17. The method according to any one of claims 1 to 14, wherein The Li-containing film, island or cluster is Li 2 O, LiOH, Li 2 S, Li 3 N, LiF, lithium carbonate, lithium aluminum fluoride, lithium aluminum oxide, lithium aluminum, lithium cobalt oxide, lithium titanate, lithium zirconate, lithium niobate, LiPON, lithium phosphate, lithium borate, lithium borophosphate, lithium niobate, lithium zirconium oxide film, island or cluster.

18. The method according to any one of claims 1 to 14, wherein the temperature inside the reactor ranges from 0 °C to 600 °C.

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