KR101303782B1 - Liquid composition containing aminoether for deposition of metal-containing films - Google Patents

Abstract

The present invention relates to a) wherein at least one ligand is β-diketonate, β-ketoiminate, β-ketostearate, β-diiminate, alkyl, carbonyl, alkyl carbonyl, cyclopentadienyl, pyrrolyl At least one metal-ligand complex, selected from the group consisting of alkoxides, amidinates, imidazolyls, and mixtures thereof, wherein the metal is selected from elements of Groups 2-16 of the Periodic Table of the Elements; And b) R ¹ R ² NR ³ OR ⁴ NR ⁵ R ⁶ , R ¹ OR ⁴ NR ⁵ R ⁶ , O (CH ₂ CH ₂ ) ₂ NR ¹ , R ¹ R ² NR ³ N (CH ₂ CH ₂ ) ₂ O, R ¹ R ² NR ³ OR ⁴ N (CH ₂ CH ₂ ) ₂ O, O (CH ₂ CH ₂ ) ₂ NR ¹ OR ² N (CH ₂ CH ₂ ) ₂ O, and mixtures thereof, wherein R ^1-6 are independently C _{1 -10} linear alkyl, C _{1 -10} branched alkyl, C _{1 -10} cyclic alkyl, C ₆ -C ₁₀ aromatic, C _{1 -10} alkyl amines, C _{1 -10-alkyl-amino-alkyl,} a C _{1 -10} ether, C ₄ -C ₁₀ cyclic ether, C ₄ -C ₁₀ cyclic amino ether, and the formulation comprises at least one of the amino ether is selected from the group consisting of selected from the group consisting of and mixtures thereof; It is about.

Description

Liquid composition containing aminoether for depositing metal containing film {LIQUID COMPOSITION CONTAINING AMINOETHER FOR DEPOSITION OF METAL-CONTAINING FILMS}

Cross-References to Related Applications

This patent application claims priority to US Provisional Patent Application No. 61 / 240,359 filed September 8, 2009 and US Provisional Patent Application No. 61 / 240,436 filed September 8, 2009.

Field of technology

The present invention relates to solvent compositions useful for the liquid phase delivery of metal precursors in chemical vapor deposition (CVD) or atomic layer deposition (ALD).

Chemical vapor deposition is commonly used in the semiconductor industry to deposit thin films of various materials on selected substrates. In conventional chemical vapor deposition (CVD), the vapor of one or more volatile precursors is contacted with a solid substrate in a chemical vapor deposition reactor, which is preheated to a temperature higher than the thermal decomposition temperature of the at least one precursor. In order to deposit highly conformal films on complex surfaces such as deep trenches and other stepped structures, annular chemical vapor deposition is commonly used. For example, in an atomic layer deposition (ALD) method, a pulse of one precursor is separated from a pulse of a second precursor by a pulse of inert gas. In such cases, separate doses of volatile precursors prevent gas-phase reactions between highly reactive precursors and promote highly selective surface reactions. ALD is considered as one deposition method with the greatest potential to produce very thin conformal films of high K dielectric metal oxides.

While many vapor deposition techniques are described in the literature for the deposition of numerous materials, including silicon, silicon dioxide, aluminum oxide, titanium nitride, constant delivery of precursor vapors to the deposition reactor is known to include titanium, zirconium, strontium, barium, Still quite difficult for the deposition of films containing lanthanum and many other transition metals. This is mainly due to the lack of thermally stable liquid precursors having a relatively high vapor pressure for gas phase delivery. In many cases, the precursor is a solid and its sublimation temperature is very close to the decomposition temperature of the precursor.

Many precursor delivery systems are designed to address these problems. One method already widely used in the semiconductor industry for the delivery of metalorganic precursors is based on conventional bubbler technology, where the inert gas is bubbled through a pure liquid or molten precursor at elevated temperatures. . However, this method has several disadvantages. First, accurate temperature control of the bubbler is required during a single run and between different runs to maintain a constant delivery rate of the precursor. Many precursors have very low vapor pressures at moderate temperatures and must be heated to 100-200 ° C. to deliver sufficient precursor vapor to the deposition reactor by the bubbling method. However, long periods of time at these temperatures can cause pyrolysis of the precursors. Such precursors can also react with small amounts of moisture and oxygen introduced into the bubbler during multiple deposition cycles. Examples of precursors with limited thermal stability and / or high reactivity to moisture include metal alkylamides, metal alkoxides, metal cyclopentadienyl, metal ketoiminates, and the like. The product of pyrolysis can clog the delivery line and affect the delivery rate of the precursor. Solid precursors delivered from this molten phase may also clog these lines during multiple cooling / heating cycles.

An alternative delivery technique, direct liquid injection (DLI), is the ability to deliver higher flux precursor vapor to the chamber, stable operation for proper lifetime, gentle heat transfer to the precursor, and with existing commercial deposition chambers. There are several advantages for precursor delivery, including ease of integration. In this method, the liquid precursor or a solution of the precursor, and the solvent, are delivered to a heated vaporization system, whereby the liquid composition is transformed from liquid phase to gas phase. Advanced liquid refinement of the precursor to the vaporizer provides accurate and stable control of the precursor delivery rate. It is important that the precursor structure is maintained and does not decompose during the vaporization process. Indeed, the whole liquid precursor was delivered via DLI. The implementation of DLI, together with a suitable solvent, allows the delivery of a wide range of metalorganic precursors, including solids and highly viscous liquids, which may not be suitable for vapor delivery in a bubbling method.

Many solvents for DLI of metalorganic precursors in the prior art have been proposed, for example, for alkanes, glymes and polyamines for the delivery of metalorganic precursors.

The prior art generally describes solvents that can be used in combination with metalorganic precursors, but these do not exhibit particular advantages with regard to solubility and thermal requirements.

However, efforts are still underway to develop improved high viscosity compositions for DLI or solid metalorganic precursors with low vapor pressure.

Prior art in the general field of the present invention includes the following references:

The present invention provides a) β-diketonate, β-diketostearate, β-ketoiminate, β, wherein at least one ligand may be monodentate, bidentate and multidentate complexing to metal atoms -Diiminate, alkyl, carbonyl, cyclopentadienyl, pyrrolyl, imidazolyl, amidinate, alkoxide, and mixtures thereof, wherein the metal is a group 2 to 16 of the periodic table of elements At least one metal-ligand complex, selected from the elements; And b) R ¹ R ² NR ³ OR ⁴ NR ⁵ R ⁶ , R ¹ OR ⁴ NR ⁵ R ⁶ , O (CH ₂ CH ₂ ) ₂ NR ¹ , R ¹ R ² NR ³ N (CH ₂ CH ₂ ) ₂ O, R ¹ R ² NR ³ OR ⁴ N (CH ₂ CH ₂ ) ₂ O, O (CCH ₂ CH ₂ ) ₂ NR ¹ OR ² N (CH ₂ CH ₂ ) ₂ O, and mixtures thereof, wherein R ^1-6 are independently C _{1 -10} linear alkyl, C _{1 -10} branched alkyl, C _{1 -10} cyclic alkyl, C ₆ -C ₁₀ aromatic, C _{1 -10} alkyl amines, C _{1 -10-alkyl-amino-alkyl,} C _{1 -10} ether, C ₄ -C ₁₀ cyclic ether, C ₄ -C ₁₀ cyclic amino containing the amino ether is selected from the general formula consisting of from the group consisting of ether checked], a metal in the manufacture of a semiconductor device comprising a thin film A liquid formulation useful for the deposition of

1 shows bis (2,2 in 2,2′-oxybis (N, N-dimethylethanamine) stored at 25 ° C. (top graph line) and after heating at 160 ° C. for 1 hour (bottom graph line). This is a graph of the proton nuclear magnetic resonance (NMR) spectrum of a 0.75 M solution of -dimethyl-5- (dimethylaminoethyl-imino) -3-hexanonato-N, O, N ') strontium.
Figure 2 shows bis (2,2-dimethyl-5- (dimethylaminoethylimino) -3-hexanoneito-N, O, N 'in 2,2'-oxybis (N, N-dimethylethanamine). 0.7 M solution of strontium (dotted line, 0.42 wt% residue at 400 ° C.), and bis (2,2-dimethyl-5- (methylamino) in 2,2′-oxybis (N, N-dimethylethanamine) Graph of thermogravimetric analysis (TGA) of 0.5 M solution (dark line, 0.34 wt% residue at 400 ° C.) of propyl-imino) -3-hexanoneto-N, O, N ′) strontium.
FIG. 3 shows 1.1M bis (2,2-dimethyl-5- (dimethylaminoethyl-imino) -3-hexanoneto-N in 2,2'-oxybis (N, N-dimethylethanamine), respectively. , O, N ') bis (tert-butoxy) titanium (dotted line), and 1M bis (2,2-dimethyl-5- (dimethylaminoethyl-imino) -3-hexanoneto-N, O, Is a graph of thermal weight analysis (TGA) of N ') bis (iso-propoxy) titanium (dark line).
4 is a crystal structure of a 1/1 adduct complex between zirconium tert-butoxide and 2,2'-oxybis (N, N-dimethylethanamine), which is a 2,2'-oxybis ( N, N-dimethylethanamine) can be coordinated to the metal, thereby stabilizing the metal complex.
5 is a 1/1 addition complex between bis (tert-butyl-4,5-di-tert-amylimidazolyl) strontium and 2,2'-oxybis (N, N-dimethylethanamine) Crystal structure.
FIG. 6 shows bis (2,2-dimethyl-5- (dimethylaminoethyl-imino) in 2,2'-oxybis (N, N-dimethylethanamine) during pulsed vaporization in a DLI system. The pressure response of a 0.3 M solution of -3-hexanoneto-N, O, N ') strontium, showing the stability of the vaporization process after at least 54 hours of operation.
FIG. 7 shows a 0.05M solution of barium bis (2,5-di-tert-butyl-pyrrolyl) in 2,2'-oxybis (N, N-dimethylethanamine) during pulsed vaporization in a DLI system. The pressure response is shown and shows stability of the vaporization process after at least 54 hours of operation.
FIG. 8 shows 0.3M bis (2,2-dimethyl-5- (dimethylaminoethyl-imino) -3-hexanoneto dissolved in ozone and 2,2'-oxybis (N, N-dimethylethanamine). The temperature dependence of thermal ALD to deposit SrO using -N, O, N ') strontium.

The present invention is an improved novel solvent formulation for DLI of metalorganic precursors, which can use a single solvent system and can also use a solvent that combines the properties of at least two solvent molecules.

More specifically, the present invention relates to a metal β-dike, wherein a) the ligand can be monodentate, bidentate and multidentate complexed to a metal atom, and the metal is selected from Groups 2 to 15 elements of the Periodic Table of the Elements. Tonate, metal β-diketoesterate, metal β-ketoiminate, metal β-diiminate, metal alkyl, metal carbonyl, alkyl metal carbonyl, metal cyclopentadienyl, metal pyrrolyl, metal imida At least one metal complex selected from the group consisting of zolyl, metal amidate, and metal alkoxide; And b) an aminoether solvent having both tertiary amino and ether groups. 2. A liquid formulation useful for the deposition of thin films in the manufacture of semiconductor devices. Applicants have found that the precursor formulations containing the aminoether solvent have improved delivery of metalorganic precursors, preferably by DLI, as described in the examples, by a more stable vaporization process with small amounts of solid residues in the vaporizer apparatus. Was found.

More specifically, DLI is a preferred delivery method for mass production processes whereby metalorganic precursors are used in semiconductor devices or other devices such as photovoltaic cells, MEMS and displays, where metal precursors, metal oxide films, It can be used to deposit a dielectric film or other film. Certain precursors based on selected deposition characteristics may have challenges for implementation into the DLI. Many precursors are viscous liquids, which require the addition of a solvent to improve the viscosity (<100 cP and more preferably <50 cP) necessary for delivery. For this reason, the addition of aminoether solvents provides high solubility and low viscosity, which allows good delivery. Other precursors may be solid at room temperature and may require dissolution in a solvent to be compatible with DLI.

In both cases, the solvent system performs several functions. First, the solvent system is one mechanism for heat transfer during the vaporization process. During the vaporization process, the solvent should not react with the precursor. Aminoethers containing both tertiary and ether groups do not cause any chemical reactions due to the lack of active hydrogens such as OH or NH groups as present in alcohols or primary and secondary amines, but aminoethers are polar ligands. (polar coordinating group). Lack of reactive groups is important to minimize reactivity with the precursors during the vaporization process. Other solvents, such as alcohols, may react with the precursors or exchange precursors and ligands, which may form precipitates in the injector system and / or downstream of the delivery line.

The second important point is that the weak coordinating effect of the solvent and precursor can provide an additional protective layer during the vaporization process. While commercial multiple injection system designs exist, the primary mechanism for vaporization is heat transfer to the precursors. During this process, heat may be transferred through the hot metal surface contact with the liquid system in the injector and / or through heat transfer with the hot carrier gas. In each of these cases, it is important that the metalorganic precursors are not performed at significantly elevated temperatures, which can cause pyrolysis. By having a solvent system that has some coordination function of both oxygen and nitrogen with high solubility, the vaporization process is believed to be gentler for the precursor example and allows for efficient vaporization into the gas phase. The coordination effect may not be strong or necessarily permanent under the conditions present, providing downstream impact on the deposition process. Thus, the solvent effect can provide additional stabilization in the gas phase during delivery.

Lower vapor pressure precursors, in particular when used in combination with multi-wafer process chambers, require higher vaporization temperatures to achieve proper precursor flux to the deposition chamber. Suitable solvents for DLI should provide good solubility for certain precursor examples to have a high precursor flux and also allow for efficient vaporization of certain precursors while minimizing residues in the vaporizer. High solubility of the precursor in the solvent is desirable to prevent rapid precipitation of the precursor during initial solvent evaporation and also to limit precursor dilution in the gas phase with solvent molecules. In many cases, however, it is quite difficult to find a solvent capable of dissolving more than 0.5 M metalorganic precursors. The solvent composition should also be stable at ambient conditions for long periods of time during storage and delivery. The solvent or solvent mixture must also not decompose during vaporization of the precursor and must not adversely adsorb or react on the growing film surface, which leads to unwanted impurities in the resulting film. In order to deliver the moisture-sensitive metalorganic precursor, the solvent must also be free of moisture. Matching the boiling point of the solvent with the vaporizer operating conditions is also important to prevent rapid vaporization of the solvent from the composition. Early vaporization of the solvent can result in substantial blockage of the injector system, minimizing the efficiency of the delivery process. However, it is important that the injector temperature is high enough so that higher precursor vapor pressures can be achieved, and the solvent system matches the needs of the precursor and deposition system.

To prevent precursor precipitation into the injector prior to vaporization, the solvent requires several unique properties. First, high solubility is important to minimize premature fall out or precipitation of precursors. Ideally, the solute concentration will be adjusted below the solubility limit in solvent to prevent premature injector blockage. This creates a predetermined solubility of the solute of> 0.5M in the solvent in order to have a predetermined working precursor concentration of 0.1M-0.5M. Even very low levels of precipitation can result in unacceptable failure rates for the injector system.

In order to have high precursor concentrations, it is usually required to operate the injection system at elevated temperatures (100 ° C.-250 ° C.). One reason for this is that high concentrations of precursor vaporizing into the gas phase may not exceed the vapor pressure of the precursor or condensation will occur in the line. For this reason, the injector temperature is selected based on the precursor physical properties and the desired precursor flux to the deposition chamber. The solvent system needs to be compatible with the injector temperature, which requires a solvent boiling point that matches the injector.

The vaporized precursor (s) and solvent are moved downstream to the deposition chamber. At this point in the process, the solvent ideally has minimal reaction with the substrate surface but does not inhibit precursor reaction with the surface. The aminoether solvent system will have minimal reactivity and will not inhibit the deposition process.

In some embodiments, the liquid formulation can be performed to deliver to a deposition process, such as chemical vapor deposition, cycle chemical vapor deposition, plasma-enhanced chemical vapor deposition, and atomic layer deposition. However, liquid formulations can be applied more widely in any deposition or gas phase process whereby the metalorganic precursors need to be delivered to the gas phase while maintaining the precursor structural preservation with minimal degradation.

It is desirable for a single solvent composition to lower the operating cost and also to prevent unwanted interactions between different solvents and precursors. With reference to solubility and boiling point matching, a mixture of solvents can handle solubility, but will present a problem that exhibits differences in both boiling point and heat of evaporation during vaporization.

Aminoether solvents have good solubility in selected aminoether solvents, good thermal stability in selected aminoether solvents, and certain physical properties, such as viscosity, density, and boiling point, for DLI systems in which their solutions are selected. Can be used with any suitable metal precursor.

The metal precursors described in the present invention include metals selected from Groups 2 to 16 of the Periodic Table of the Elements, specific examples of the metals are Mg, Ca, Sr, Ba, Y, La, Ce, Sm, Tb, Er, Yb , Lu, Ti, Zr, Hf, Fe, Co, Ni, Ru, Ir, Rh, Cu, Al, Sn, Pb, Sb, Bi, Te, Cr, Mo and W, β-dike to such metals Tonate, β-diketostearate, β-ketoiminate, β-diiminate, alkyl, carbonyl, cyclopentadienyl, pyrrolyl, imidazolyl, amidinate, alkoxide, and mixtures thereof At least one ligand selected from the group consisting of is bound, wherein the ligand may be monodentate, bidentate and multidentate which complexes to a metal atom.

Examples of metal-ligand complexes described in the present invention are described as the following classes:

(a) a metal β-diketonate having the formula:

[Wherein M is selected from Group 2 to Group 16 metals, specific examples of the metals are Mg, Ca, Sr, Ba, Y, La, Ce, Sm, Tb, Er, Yb, Lu, Ti, Zr, Hf Fe, Co, Ni, Ru, Ir, Rh, Cu, Al, Sn, Pb, Sb, Bi, Te; R ^{1 -3} are independently hydrogen, C _{1 -10} linear or branched alkyl, C _{1 -10} linear or branched alkoxy, C _{4 -10} cycloaliphatic, C _{6 -10} aryl, and C _{1 -10} linear or branched Selected from the group consisting of topographic fluorinated alkyl; x is 2, 3;

(b) metal β-ketoiminates having the formula:

[Wherein M is selected from Group 2 to Group 16 metals, specific examples of the metals are Mg, Ca, Sr, Ba, Y, La, Ce, Sm, Tb, Er, Yb, Lu, Ti, Zr, Hf Fe, Co, Ni, Ru, Ir, Rh, Cu, Al, Sn, Pb, Sb, Bi, Te; ^{1 -4} R is individually hydrogen, C _{1 -10} linear or branched alkyl, C _{1 -10} linear or branched alkoxy, C _{4 -10} cycloaliphatic, C _{6 -10} aryl, and C _{1 -10} linear or branched Selected from the group consisting of topographic fluorinated alkyl; x is 2, 3, 4;

(c) metal β-diiminates having the formula:

[Wherein M is selected from Group 2 to Group 16 metals, specific examples of the metals are Mg, Ca, Sr, Ba, Y, La, Ce, Sm, Tb, Er, Yb, Lu, Ti, Zr, Hf Fe, Co, Ni, Ru, Ir, Rh, Cu, Al, Sn, Pb, Sb, Bi, Te; ^{1 -5} R is individually hydrogen, C _{1 -10} linear or branched alkyl, C _{1 -10} linear or branched alkoxy, C _{4 -10} cycloaliphatic, C _{6 -10} aryl, and C _{1 -10} linear or branched Selected from the group consisting of topographic fluorinated alkyl; x is 2, 3, 4;

(d) metal β-ketoiminates having the formula:

[Wherein M is selected from Groups 2 to 16, and specific examples of metals are Mg, Ca, Sr, Ba, Y, La, Ce, Sm, Tb, Er, Yb, Lu, Fe, Co, Ni, Ru, Ir, Rh, Cu, Al, Pb, Sb, Bi, Te; ^{1 -6} R is hydrogen, C _{1 -10} linear or branched alkyl, C _{1 -10} linear or branched alkoxy, C _{4 -10} cycloaliphatic, C _{6 -10} aryl, and C _{1 -10} linear or branched fluorine Can be formed from the group consisting of alkylated alkyl; x is 2, 3;

(e) metal β-ketoiminates having the formula:

[Wherein M is a group 2 alkaline earth metal, and specific examples of the metal include Ca, Sr and Ba; R ¹ is a branched bulky alkyl group containing 4 to 10 carbon atoms; R ² is hydrogen, C _{1 -10} linear or branched alkyl, C _{1 -10} linear or branched alkoxy, C _{4 -10} aliphatic, and C _{6 -10} is selected from the group consisting of aryl; R ^{3 -5} is a linear or branched _minutes, from C _1-10 linear or branched alkyl, C _{1 -10} linear or branched alkyl, C _{4 -10} aliphatic, and C _{6 -10} aryl group consisting of a branched-fluoro Selected individually, preferably R ^{4 , 5} contains two carbon atoms to form a five membered coordination ring at the metal center; R ^{6 -7} are individually C _{1 -10} linear or branched alkyl, C _1-10 linear or branched fluoroalkyl is selected from alkyl, C _{4 -10} cycloaliphatic, C _{6 -10} aryl group consisting of these are May be linked to form a ring containing carbon, oxygen or nitrogen atoms;

(f) metal β-ketoiminates having the formula:

[Wherein M is a metal selected from Group 4 metals, including titanium, zirconium and hafnium; R ¹ is a branched bulky alkyl group containing 4 to 10 carbon atoms; R ² is hydrogen, C _{1 -10} linear or branched alkyl, C _{1 -10} linear or branched alkoxy, C _{4 -10} aliphatic, and C _{6 -10} is selected from the group consisting of aryl; R ^{3 -4} are individually C _{1 -10} linear or branched alkyl, C _{1 -10} are selected from linear or branched fluoro-alkyl, C _{4 -10} aliphatic, and C _{6 -10} aryl group consisting of a, preferably R ⁴ contains 2 to 3 carbon atoms, thus forming a 5- or 6-membered coordination ring in the metal center; R ^{5 -6} is a linear or branched, individually, C _{1 -10} linear or branched alkyl, C _{1 -10} linear or a branched fluoroalkyl consisting of alkyl, C _{4 -10} aliphatic, and C _6-10 aryl Selected from the group, these may be linked to form a ring containing carbon, oxygen or nitrogen atoms; R ⁷ is C _{1 -10} linear or branched alkyl, C _{1 -10} linear or branched fluoro-alkyl, C _{4 -10} aliphatic, and C _{6 -10} is selected from the group consisting of aryl; n is 1, 2, 3;

(g) metal β-ketoiminates having the formula:

[Wherein M is a metal selected from Group 11 metals, including copper, silver and gold; R ¹ is a branched bulky alkyl group containing 1 to 10 carbon atoms; R ² is hydrogen, C _{1 -10} linear or branched alkyl, C _{1 -10} linear or branched alkoxy, C _{4 -10} aliphatic, and C _{6 -10} is selected from the group consisting of aryl; R ^{3 -4} are individually C _{1 -10} linear or branched alkyl is selected from, the group as a C _1-10 linear or branched fluoroalkyl consisting of alkyl, C _{4 -10} aliphatic, and C _{6 -10} aryl, preferably R ⁴ contains from 2 to 3 carbon atoms to form a 5- or 6-membered coordination ring in the metal center; R ⁵ is independently C _{1 -10} ^-6 straight or branched alkyl, C _{1 -10} linear or a branched alkyl is selected from fluoro, C _{4 -10} aliphatic, and C _{6 -10} aryl group consisting of, these They may be linked to form a ring containing carbon, oxygen or nitrogen atoms; X is carbon or silicon;

(h) metal complexes having the formula:

[Wherein M is selected from Group 2 to Group 16 metals, specific examples of the metals are Mg, Ca, Sr, Ba, Y, La, Ce, Sm, Tb, Er, Yb, Lu, Ti, Zr, Hf Fe, Co, Ni, Ru, Ir, Rh, Cu, Al, Pb, Sb, Bi, Te; Each R is individually hydrogen, C _1-10 linear, branched, saturated or unsaturated alkyl, C _1-10 linear or branched alkoxy, C _4-10 alicyclic, C _6-10 aryl, C _1-10 linear or Branched fluorinated alkyl, cyclopentadienyl ("Cp"), alkyl substituted cyclopentadienyl, pyrrolyl, alkyl substituted pyrrolyl, imidazolyl, alkyl substituted imidazolyl, and derivatives thereof Selected from the group consisting of; x is 2, 3, 4; L is a neutral or monoanionic donor ligand containing oxygen or nitrogen atoms, for example NMe ₂ or OMe; n is 0, 1, 2, 3, 4; Representative metal complexes include Ru (EtCp), Ru (DMPD) (EtCp) (DMPD = 2,4-dimethyl-pentadienyl), EtCpTi (NMe ₂ ) ₃ , Cp ^* Ti (OMe) ₃ , EtCpHf (NMe ₂ ) ₃ , and EtCpZr (NMe ₂ ) ₃ , Sr ( ^t Bu ₃ Cp) ₂ , Ba ( ^t Bu ₃ Cp) ₂ , Sr ( ⁱ Pr ₃ Cp) ₂ , Ba ( ⁱ Pr ₃ Cp) ₂ where “Et "Is ethyl," Me "is methyl," ⁱ Pr "is iso-propyl and" ^t Bu "is tertiary butyl];

(i) alkyl metal carbonyls having the formula:

[Wherein M is selected from Group 2 to Group 16 metals, specific examples of the metals are Mg, Ca, Sr, Ba, Y, La, Ce, Sm, Tb, Er, Yb, Lu, Fe, Co, Ni , Ru, Ir, Rh, Cu, Al, Pb, Sb, Bi, Te; Each R is individually hydrogen, C _{1 -10} linear or branched alkyl, C _{1 -10} linear or branched alkoxy, C _{4 -10} cycloaliphatic, C _{6 -10} aryl, C _{1 -10} linear or branched fluorinated Selected from the group consisting of alkyl, cyclophendienyl and derivatives thereof; x is 2, 3, 4 and y is 1, 2, 3 or 4;

(j) metal carbonyls having the formula:

[Wherein M is selected from Group 8 to Group 10 metals, specific examples of the metal include Fe, Co, Ni, Ru, Ir, Rh; x is 1, 2, 3 and y is 4 to 12;

(k) metal alkoxides having the formula:

[Wherein M is selected from Group 2 to Group 16 metals, specific examples of the metals are Mg, Ca, Sr, Ba, Y, La, Ce, Sm, Tb, Er, Yb, Lu, Fe, Co, Ni , Ru, Ir, Rh, Cu, Al, Pb, Sb, Bi, Te; Each R is independently C _{1 -10} linear or branched alkyl, C _{1 -10} linear or branched alkenyl, C _{1 -10} linear or branched alkynyl, C ₄ -C ₁₀ cycloaliphatic, C _{6 -10} aryl , and C _{1 -10} linear or branched and selected from the group consisting of fluorinated alkyl; n is 2, 3, 4 or 5, including valences of M, representative metal complexes being Ti ( ⁱ PrO) ₄ , Hf (OBu ^t ) ₄ , Zr (OBu ^t ) ₄ , and Ta ₂ (OEt) ₁₀ Including;

(l) metal amides having the formula:

[Wherein M is selected from Group 2 to Group 16 metals, specific examples of the metals are Mg, Ca, Sr, Ba, Y, La, Ce, Sm, Tb, Er, Yb, Lu, Fe, Co, Ni , Ru, Ir, Rh, Cu, Al, Pb, Sb, Bi, Te; ^-2 R ¹ is independently C _{1 -10} linear or branched alkyl, C _{1 -10} linear or branched alkenyl, C _{1 -10} linear or branched alkynyl, C _{3 -10} linear or branched alkyl silyl, C _{4 -} C ₁₀ cycloaliphatic, C _{6 -10} aryl, and C _{1 -10} linear or branched and selected from the group consisting of fluorinated alkyl; n is an integer of 2, 3, 4 or 5, including atoms of M;

(m) metal alkoxy β-diketonates having the formula:

[Wherein M comprises a metal selected from the group consisting of Ti, Zr, and Hf; R ¹ is an alkyl group containing 1 to 10 carbon atoms; R ² is an alkyl group containing 1 to 10 carbon atoms; R ³ is selected from the group consisting of hydrogen or an alkyl group containing 1 to 3 carbon atoms; R ⁴ is an alkyl group containing 1 to 6 carbon atoms;

(n) metal amidates having the formula:

[Wherein M is selected from Group 2 to Group 16 metals, specific examples of the metals are Mg, Ca, Sr, Ba, Y, La, Ce, Sm, Tb, Er, Yb, Lu, Ti, Zr, Hf Fe, Co, Ni, Ru, Ir, Rh, Cu, Al, Sn, Pb, Sb, Bi, Te; ^{1 -3} R is individually hydrogen, C _{1 -10} linear or branched alkyl, C _{1 -10} linear or branched alkoxy, C _{4 -10} cycloaliphatic, C _{6 -10} aryl, and C _{1 -10} linear or branched Selected from the group consisting of topographic fluorinated alkyl; x is 2, 3, 4].

The solvent used in the present invention should be chemically compatible with the metalorganic precursor. The concentration of the solvent may vary in the range of 1% to 99% by weight, depending on the complex and aminoether used. Preferably, the boiling point of aminoether is higher than 120 ° C., more preferably the boiling point of aminoether is higher than 150 ° C. but less than 250 ° C., and the viscosity of the resulting solution is in the range of 1 to 50 cP, which is a liquid directly through a commercial vaporizer. It can be delivered by infusion.

Examples of aminoethers containing both tertiary amino and ether groups described herein are described in the following classes:

(a) the formula R ¹ R ² NR ³ OR ⁴ linear amino ether with NR ⁵ R ⁶ [wherein, R ¹ -R ⁶ are independently C _{1 -10} linear alkyl, C _{1 -10} branched alkyl, C _{1 -10} cyclic alkyl, C ₆ -C ₁₀ aromatic. Representative structures are as follows:

(b) linear aminoethers having the formula R ¹ OR ⁴ NR ⁵ R ⁶ wherein R ¹ and R ^4-6 are independently C _1-10 linear alkyl, C _1-10 branched alkyl, C _1-10 Cyclic alkyl and C ₆ -C ₁₀ aromatics. Representative structures are as follows:

(c) the formula O (CH ₂ CH ₂₎ a cyclic amino-ether having ₂ NR ¹ [wherein, R ¹ is C _{1 -10} linear alkyl, C _{1 -10} branched alkyl, C _{1 -10} cyclic alkyl, C ₆ -C ₁₀ aromatic. Representative structures are as follows:

(d) cyclic aminoethers having the formula R ¹ R ² NR ³ N (CH ₂ CH ₂ ) ₂ O, wherein R ^1-3 is individually C _1-10 linear alkyl, C _1-10 branched alkyl, C _1-10 cyclic alkyl, C ₆ -C ₁₀ aromatic. Representative structures are as follows:

(e) the formula ^{R 1 R 2 NR 3 OR 4} N (CH 2 CH 2) a cyclic amino-ether having ₂ O [wherein, R ^{1 -4} are individually C _{1 -10} linear alkyl, branched C _{1 -10} alkyl, C _{1 -10} cyclic alkyl, C ₆ -C ₁₀ aromatic Im. Representative structures are as follows:

(f) the formula _{O (CH 2 CH 2) 2} NR 1 OR 2 N (CH 2 CH 2) a cyclic amino-ether having ₂ O [wherein, R ^1-2 are individually C _{1 -10} linear alkyl, C _{1 -10} branched alkyl, C _{1 -10} alkyl ring. Representative structures are as follows:

Unless limited by any theory, aminoether solvents containing both amino and ether groups can provide advantages by only comparing solvents with ether or amine functional groups or other traditional solvent functional groups and physical mixtures of such solvents. It is considered to be. Unless optionally limited, these advantages include better solubility, better solution stability for long term storage, cleaner evaporation by flash evaporation, and a more stable overall DLI chemical vapor deposition process.

In one embodiment, the present invention provides a composition wherein a) one or more ligands are β-diketonate, β-ketoiminate, β-ketostearate, β-diiminate, alkyl, carbonyl, alkyl carbonyl, cyclopentadier Nil, pyrrolyl, alkoxide, amidinate, imidazolyl, and mixtures thereof, wherein the ligand can be monodentate, bidentate, and multidentate, which complexes to metal atoms, At least one metal-ligand complex selected from Groups 2-16 elements of the Periodic Table of the Elements; And b) R ¹ R ² NR ³ OR ⁴ NR ⁵ R ⁶ , R ¹ OR ⁴ NR ⁵ R ⁶ , O (CH ₂ CH ₂ ) ₂ NR ¹ , R ¹ R ² NR ³ N (CH ₂ CH ₂ ) ₂ O, R ¹ R ² NR ³ OR ⁴ N (CH ₂ CH ₂ ) ₂ O, O (CH ₂ CH ₂ ) ₂ NR ¹ OR ² N (CH ₂ CH ₂ ) ₂ O, and mixtures thereof R ^{1 -6} is independently C _{1 -10} linear alkyl, C _{1 -10} branched alkyl, C _{1 -10} cyclic alkyl, C ₆ -C ₁₀ aromatic, C _{1 -10} alkyl amines, C _{1 -10-alkyl} amino alkyl , C _{1 -10} ether, C ₄ -C ₁₀ cyclic ether, C ₄ -C ₁₀ Selected from the group consisting of cyclic amino ethers].

Preferably the formulation has a ligand of the metal-ligand complex, selected from the group consisting of monodentate, bidentate, multidentate and mixtures thereof.

In one embodiment, the formulation is liquid.

In other embodiments, the formulation is an amino ether [wherein, R ¹ -R ⁶ are independently C _{1 -10} linear alkyl, C _{1 -10} branched having the formula ^{R 1 R 2 NR 3 OR 4} NR 5 R 6 include alkyl, C _{1 -10} cyclic alkyl, C ₆ selected - from the group consisting of -C ₁₀ aromatic group.

In still other embodiments, the formulation of the formula R ¹ OR ⁴ NR amino ether having ⁵ R ⁶ [wherein, R ^{1 -6} is independently C _{1 -10} linear alkyl, C _{1 -10} branched alkyl, C _{1 -10} cyclic alkyl, selected from the group consisting of C ₆ -C ₁₀ aromatics.

Another embodiment is the formula O (CH ₂ CH ₂₎ a cyclic amino-ether having ₂ NR ¹ [wherein, R ¹ is C _{1 -10} linear alkyl, C _{1 -10} branched alkyl, C _{1 -10} cyclic alkyl, C ₆ -C ₁₀ aromatic.

Another embodiment is a cyclic amino ether having ₂ O the formula ^{R 1 R 2 NR 3 N (} CH 2 CH 2) [ wherein, R ^{1 -4} are individually C _{1 -10} linear alkyl, branched C _{1 -10} a formulation containing the alkyl, C _{1 -10} cyclic alkyl, C ₆ -C ₁₀ aromatic Im.

Another embodiment has the formula ^{R 1 R 2 NR 3 OR 4} N (CH 2 CH 2) a cyclic amino-ether having ₂ O [wherein, R ^{1 -4} are individually C _{1 -10} linear alkyl, C _{1 -10} minutes, a formulation comprising a branched alkyl, C _{1 -10} cyclic alkyl, C ₆ -C ₁₀ aromatic Im.

Alternatively, the formulation of the formula _{O (CH 2 CH 2) 2} NR 1 OR 2 N (CH 2 CH 2) a cyclic amino-ether having ₂ O [wherein, R ^{1 -2} are individually C _{1 -10} linear include alkyl, C _{1 -10} branched alkyl, C _{1 -10} amino cyclic ether containing a cyclic alkyl.

Preferably, the formulation comprises an aminoether selected from the group consisting of 2,2'-oxybis (N, N-dimethylethanamine), 4- [2- (dimethylamino) ethyl] morpholine, and mixtures thereof. It contains.

Preferably, the formulation contains aminoether 2,2'-oxybis (N, N-dimethylethanamine) with less than 20 ppm water.

Preferably, the formulation contains less than 100 ppm aminoether 2,2'-oxybis (N, N-dimethylethanamine) with additional compounds containing hydroxyl or amine functional groups.

In one embodiment, the present invention provides a) bis (2,2-dimethyl-5- (dimethylaminoethyl-imino) -3-hexanonaito-N, O, N ') strontium, bis (2,2- Dimethyl-5- (1-dimethylamino-2-propylimino) -3-hexanonato-N, O, N ') strontium, bis (2,2-dimethyl-5- (dimethylaminoethyl-imino) -3-hexanoato-N, O, N ') bis (tert-butoxy) titanium, tetrakis (2,2,6,6-tetramethyl-3,5-heptanedionato) cerium (IV) , Tris (2,2,6,6-tetramethyl-3,5-heptanedionato) lanthanum, Sr [( ^t Bu) ₃ Cp] ₂ , Ba [( ^t Bu) ₃ Cp] ₂ , LaCp ₃ , La (MeCp) ₃ , La (EtCp) ₃ , La ( ⁱ PrCp) ₃ , zirconium tert-butoxide, bis (tert-butyl-4,5-di-tert-amylimidazolyl) strontium, Bis (2-tert-butyl-4,5-di-tert-amlimidazolyl) barium, bis (2,5-di-tert-butyl-pyrrolyl) strontium, bis (2,5-di tert-butyl-pyrrolyl), _{barium, Ru (EtCp) 2, Ru} (EtCp) DMPD) and at least one metal selected from the group consisting of a mixture - Ligand complex; And b) at least one aminoether selected from the group consisting of 2,2'-oxybis (N, N-dimethylethanamine), 4- [2- (dimethylamino) ethyl] morpholine, and mixtures thereof. In a semiconductor device comprising a liquid formulation useful for the deposition of a metal-containing thin film, wherein "Me" is methyl, " ^t Bu" is tert-butyl, and " ⁱ Pr" is isopropyl "Et" is ethyl, "Cp" is cyclopentadienyl and "DMPD" is 2,4-dimethyl-pentadienyl.

Preferably, the formulation is packaged in a stainless steel container. More preferably, the interior of the container is electropolished. More preferably, the vessel has an inlet valve and an outlet valve. More preferably, the valve is a self acting valve. In one embodiment, the valve is a pneumatically actuated valve. In another embodiment, the valve is an electric solenoid operated valve. Preferably, the container has a diptube. In one embodiment, the tip tube is an outlet. In another embodiment, the diptube is an inlet.

Preferably the formulation comprises a chemical stabilizer. In one embodiment, the stabilizer is a free radical scavenger. In another embodiment. Stabilizers are polymerization inhibitors. In another embodiment, the stabilizer is an antioxidant.

Preferably the formulation has a viscosity of less than 50 cP.

In one embodiment, the formulation consists of 2,2'-oxybis (N, N-dimethylethanamine), and LaCp ₃ , La (MeCp) ₃ , La (EtCp) ₃ , or La ( ⁱ PrCp) ₃ Lanthanum complexes selected from the group. In another embodiment, the formulation comprises bis (2,2-dimethyl-5- (dimethylaminoethyl-imino) -3-hexanonaito-N, O, N ') strontium and 2,2'-oxybis ( N, N-dimethylethanamine). In another embodiment, the formulation is bis (2,2-dimethyl-5- (1-dimethylamino-2-propylimino) -3-hexanoneito-N, O, N ') strontium and 2,2 '-Oxybis (N, N-dimethylethanamine). Another embodiment includes Sr ( ^t Bu ₃ Cp) ₂ and 2,2′-oxybis (N, N-dimethylethanamine). Another embodiment includes Ba ( ^t Bu ₃ Cp) ₂ and 2,2′-oxybis (N, N-dimethylethanamine).

The invention also includes a chemical vapor deposition or atom comprising contacting a substrate under conditions for depositing a metal-containing film from a formulation of an aminoether with any of the above identified metal-ligand complexes and depositing such a metal-containing film. A method of depositing a metal-containing film by layer deposition.

In one embodiment, the invention relates to a substrate under conditions for depositing a metal-containing film from a formulation containing aminoethers of the class described above (a) to (f) and containing a metal-ligand complex. A method of depositing a metal-containing film by chemical vapor deposition or atomic layer deposition, including contacting and depositing such a metal-containing film.

In another embodiment, the present invention contacts the substrate under conditions for depositing a metal-containing film from a formulation containing aminoethers of the class described above and described in (a) to (f), and removing the metal-containing film. A method of depositing a metal-containing film by chemical vapor deposition or atomic layer deposition, including deposition.

Preferably, a process in which the formulation is delivered by direct liquid injection through a vaporizer is included.

In one aspect of the invention, the metal complex comprises a metal β-ketoiminate having the formula:

[Wherein, R ^{1 -6} are hydrogen, C _{1 -10} linear or branched alkyl, C _{1 -10} alkoxy, C ₄ -C ₁₀ cycloaliphatic, C ₆ -C ₁₀ aryl, and C _{1 -10} fluoride It may be selected from the group consisting of alkyl.

In general, these metal precursors are solids with melting points above 120 ° C. and low solubility in nonpolar solvents. Due to the very low vapor pressure, these precursors must be delivered at 180 to 200 ° C. by the bubbling method or DLI.

In order to allow more controlled delivery rates of these precursors, the DLI method is preferred. Applicants have found that the aminoether solvent has a good combination of physical properties for improved delivery of these precursors by DLI.

The solubility and thermal stability of 2,2-dimethyl-5- (dimethylaminoethyl-imino) -3-hexanonato-N, O, N ') strontium were compared in the various solvent formulations shown in Table 1. All solvents were dried to less than 20 ppm water in an activated 3mm molecular sieve. Solvent formulations with solubility of more than 0.5 M were further evaluated by ¹ H NMR of the samples at room temperature and by ¹ H NMR of the samples heated at 150-200 ° C. The screening list of solvents in Table 1 shows a comparison of a standard solvent system with an example of the aminoether solvent of the present invention, (2,2'-oxybis (N, N-dimethylethanamine).

Table 1. Solvents screened by solubility and thermal stability with bis (2,2-dimethyl-5- (dimethylaminoethyl-imino) -3-hexanonato-N, O, N ') strontium

The reactivity of the solvent with the precursor will lead to manufacturing problems, shelf life stability problems, and unacceptable performance due to clogging of the injector. Alcohol solvents such as 1-octanol have been observed to perform ligand exchange with the precursors. In some of the solvents, such as 2-nonanone and isoamyl acetate tests, the reaction with the precursors was only observed when the solution was heated to a higher temperature. Reactivity at elevated temperatures has been found to be very important for stability during the DLI process where the injector temperature is generally between 100 and 300 ° C.

Similar to the hydrocarbon solvent tested by the applicant, dibutyl ether was found to be stable, but with very low solubility. From the solvent screening test, both glycol type and aminoether solvents had good solubility and no reactivity with the solvent was observed. The aminoether solvents of the present invention showed the best combination of bp (180-200 ° C.), high solubility (> 0.75 M) and good thermal stability.

In particular, the direct liquid injection test is carried out with these solvent classes: bis (dimethylamino) ethylether (also called 2,2'-oxybis (N, N-dimethylethanamine), and di (propylene glycol) dimethylether ( DPGDME), followed by two solvents.

In Table 2, the main factor for the DLI performance is the 0.3 M solution of Sr ketoiminate complex in this solvent, bis (2,2-dimethyl-5- (1-dimethylamino-2-propyl-imino) -3- Comparisons were made between tests performed with hexanonato-N, O, N ') strontium solution. As briefly observed from Table 2, 2,2'-oxybis (N, N-dimethylethanamine) performed better in all cases. Continuous liquid pulsing of the precursors was performed during the testing of two solvent systems, using an off-line commercial vaporization system. Downstream pressure stability has been found in Applicants' laboratory to be used as an early indication of vaporization problems and to correlate with residue levels formed. During continuous operation of the DLI system, experiments with the DPGDME were found to have intermittent pressure spikes during operation. In addition, the DPGDME test was shown to produce a residue of 1 mg / hour in the injector. In relation to the desired delivery system uptime of continuous operation of more than one month, DPGDME solution does not provide acceptable residue levels for testing, and commercial vaporizer based estimates suggest that the injector may be used within 8 days of continuous operation. Will be blocked.

In comparison, bis (2,2-dimethyl-5- (1-dimethylamino-2-propyl-imino) -3-hexanoneto- in 2,2'-oxybis (N, N-dimethylethanamine) Testing of N, O, N ') strontium with a 0.3 M solution shows good pressure stability, at least 5 times lower residue levels, and run times greater than 1 month, based on continuous liquid operation.

Table 2: of 0.3 M bis (2,2-dimethyl-5- (1-dimethylamino-2-propyl-imino) -3-hexanoneito-N, O, N ') strontium in two different solvent systems Comparison of DLI Performance

Bis (2,2-dimethyl-5- (dimethylaminoethyl-imino) -3-hexanoneito-N, O, N ') strontium in 2,2'-oxybis (N, N-dimethylethanamine) The solution of was stable at 160 ° C. for at least 1 hour, as shown in FIG. 1. In addition, no thermal effect was observed when the solution was tested up to 220 ° C. by differential scanning calorimetry (“DSC”).

Also, a solution of strontium precursor in 2,2'-oxybis (N, N-dimethylethanamine) evaporates below 300 ° C. when heated under nitrogen flow in a TGA apparatus, yielding a very low solid residue (<1%). It was found to have (FIG. 2).

This is also consistent with the titanium precursor example in FIG. 3.

In one embodiment of the invention, the aminoether solvent contains less than 100 ppm water, preferably less than 20 ppm water, and more preferably 5 ppm water. Water may be removed with an aminoether solvent by any suitable means, for example fractional distillation, adsorption, chemical reaction. In one embodiment, water is removed by contacting the aminoether solvent with the molecular sieve in dynamic and static modes.

Unless limited to any theory, aminoethers can stabilize metal complexes in both liquid and gas phases and improve the delivery of precursors to deposition reactors by the formation of relatively weakly stable adducts with metal complexes.

FIG. 4 shows the crystal structure of a 1/1 addition complex between zirconium tert-butoxide and 2,2'-oxybis (N, N-dimethylethanamine), wherein the aminoether is 2,2'-oxy It is bound to the metal by both oxygen and nitrogen atoms from bis (N, N-dimethylethanamine), thereby making the zirconium complex as stable as possible by saturating the coordination environment, ie increasing the coordination number from 4 to 6 .

5 is a 1/1 addition complex between bis (tert-butyl-4,5-di-tert-amylimidazolyl) strontium and 2,2'-oxybis (N, N-dimethylethanamine) The crystal structure of is shown in which the aminoether is bonded to the metal center in a chelating manner using an ether oxygen atom and two tertiary amino groups.

Unless limited to any theory, it is also believed that aminoether solvents can improve delivery of metalorganic precursors by providing a low viscosity formulation with a shear thinning effect. The viscosity of this formulation decreases with higher shear rates, which may be important for delivery over narrow lines.

The liquid formulations of the present invention can be used with any delivery means currently used in any liquid injection CVD or ALD process. In one aspect of the invention, the liquid formulation comprising aminoether is delivered by direct liquid injection via a vaporizer. FIG. 6 shows bis (2,2-dimethyl-5- (dimethylaminoethyl-imino) -3-hexanoneto-N in 2,2′-oxybis (N, N-dimethylethanamine) in a DLI system. This shows a very stable pressure response during pulsed vaporization of a 0.3 M solution of, O, N ') strontium, indicating the stability of the vaporization process for 150 operating hours.

Several other formulations containing the same strontium precursor but no aminoether type solvent showed poor pressure response and intermittent pressure spiking or clogging. For example, Sr formulations with mixed solvent systems such as tetrahydrofuran (“THF”) and dodecane showed high static solubility due to the addition of THF. However, during the vaporization process, THF was vaporized early in the process and significant precipitation accumulated within 6 hours.

In addition, a single ether type solvent system with the same strontium precursor, for example dipropylene glycol dimethylether, gave the same unacceptable results. In this test, failure was observed due to lower solubility as well as reactivity with the precursor during vaporization.

In contrast, the pressure stability profile observed in FIG. 6 for the 2,2′-oxybis (N, N-dimethylethanamine) solvent system was over 150 hours. After the initial test, the injector system was inspected and no evidence of reprecipitation was observed. To demonstrate that the precursor did not form a gaseous complex with the system, the precursor was condensed downstream from the vaporizer. A comparison of the TGA results indicated that the precursor did not change from the starting material and no evidence of complexation was found.

In another aspect of the invention, a liquid formulation comprising an aminoether comprises contacting the substrate with vapor obtained by vaporization of the liquid formulation under suitable conditions for depositing a metal-containing film, by CVD or ALD. It is used to deposit metal-containing films. Suitable conditions for depositing a metal-containing film may include decomposing the metalorganic precursor chemically, thermally, photochemically, or by plasma activation. Deposition can be performed in the presence of other gas components. In one embodiment of the invention, film deposition is performed in the presence of at least one non-reactive carrier gas. Examples of non-reactive inert carrier gases include nitrogen, argon, helium and the like. In another embodiment, film deposition is performed in the presence of at least one reactive gas. Examples of reactive gases may include, but are not limited to, oxygen, water vapor, ozone, and the like. In another embodiment, the liquid formulations of the present invention are used to deposit high K metal oxide films by ALD.

FIG. 8 shows 0.3M bis (2,2-dimethyl-5- (dimethylaminoethyl-imino) -3-hexanone dissolved in ozone and 2,2'-oxybis (N, N-dimethylethanamine) The temperature dependence of the thermal ALD of SrO deposition using Ito-N, O, N ') strontium is shown. The ALD process window for this precursor / solvent formulation was below 320 ° C. For ALD type processes, the self-limiting reaction characteristics of the precursor and the substrate surface primarily define the deposition rate at a given temperature. Factors that may affect deposition rates may include, but are not limited to, the steric bulk of the precursor, the rate of reaction of the precursor with the substrate surface, and the rate of adsorption / desorption of the precursor on the substrate surface. During the deposition process, the change in deposition rate can be used as an indicator for modification to the precursor or substrate surface. If the precursors coordinate or react with the solvent system, it will be expected that the deposition rate characteristics will change. In Figure 7, the temperature dependence and deposition rate properties of the Sr precursor were found to be the same between the described DLI method and the bubbling method, where the strontium precursor was delivered as a pure precursor with a bubbling configuration. This comparison provides evidence that the solvent system is suitable for the deposition process.

The liquid composition of the present invention can be stored, transported to the application area and is pressurized stainless steel vessel, equipped with suitable valves and fittings, preferably by any of several means, for delivering liquid to the DLI system. It can be delivered to the DLI system using.

Comparative Example 1

Solubility of Bis (2,2-dimethyl-5- (dimethylaminoethyl-imino) -3-hexanoneito-N, O, N ') strontium in dibutyl ether, a high boiling point (bp: boiling poing) monoether

In a 2 ml volume corrected vial, 0.127 g of bis (2,2-dimethyl-5- (dimethylaminoethyl-imino) -3-hexanoneto-N, O, N ') strontium (0.25 mmol) and di Butyl ether was added to form 1 ml of the mixture. The mixture was kept at room temperature overnight, but a significant amount of insoluble solids was still present in the mixture, indicating that the solubility of this strontium in dibutyl ether is much lower than 0.25M.

Comparative Example 2

Solubility of Bis (2,2-dimethyl-5- (dimethylaminoethyl-imino) -3-hexanoneto-N, O, N ') strontium in N-methyl dicyclohexylamine (high bp monoamine)

In a 2 ml volume corrected vial, 0.127 g bis (2,2-dimethyl-5- (dimethylaminoethyl-imino) -3-hexanoneto-N, O, N ') strontium (0.25 mmol) and N -Methyl dicyclohexylamine was added to form 1 ml of the mixture. The mixture was kept at room temperature overnight, but insoluble solids were still present. Excess solvent was added to increase the volume of the mixture to 2 ml, but the material was still not completely dissolved, which was 2,2-dimethyl-5- (dimethylaminoethyl in N-methyl dicyclohexylamine (high bp monoamine) -Imino) -3-hexanoneto-N, O, N ') strontium solubility is less than 0.12M.

Example 3

Bis (2,2-dimethyl-5- (dimethylaminoethyl-imino) -3-hexanoneto-N in 2,2'-oxybis (N, N-dimethylethanamine) (high bp aminoether), O, N ') solubility

A sample of 2,2'-oxybis (N, N-dimethylethanamine) containing 389 ppm of water was dried overnight over an activated 3A molecular sieve to give a solvent containing less than 25 ppm of water. . 0.381 g bis (2,2-dimethyl-5- (dimethylaminoethyl-imino) -3-hexanoneto-N, O, N ') strontium (0.75 mmol) in 0.580 g 2,2'-oxy Mixing with bis (N, N-dimethylethanamine) gave 1 ml of a clear, almost colorless solution. Thus, bis (2,2-dimethyl-5- (dimethylaminoethyl-imino) -3-hexanoneito-N, O, N 'in 2,2'-oxybis (N, N-dimethylethanamine) The solubility of strontium is at least 0.75M.

Example 4

Bis (2,2-dimethyl-5- (dimethylaminoethyl-imino) -3-hexanoneito-N, O, N ') strontium in 2,2'-oxybis (N, N-dimethylethanamine) Thermal stability of the solution

Bis (2,2-dimethyl-5- (dimethylaminoethyl-imino) -3-hexa in 2,2'-oxybis (N, N-dimethylethanamine), prepared as described in Example 2 A 0.75 M solution of nonato-N, O, N ') strontium was transferred to a screw-cap NMR tube under nitrogen atmosphere. Samples were heated in an NMR tube at 160 ° C. for 1 hour. No precipitate or noticeable discoloration was observed during heating. No change was observed in the 1 H NMR spectrum of the solution before and after the heating, suggesting that the solution is thermally stable up to at least 160 ° C. (see FIGS. 1 and 2).

Example 5

Bis (2,2-dimethyl-5- (1-dimethylamino-2-propyl-imino) -3-hexanoneito-N, O in 2,2'-oxybis (N, N-dimethylethanamine) Solubility of strontium

A sample of 2,2'-oxybis (N, N-dimethylethanamine) containing 389 ppm water was dried overnight on an activated 3A molecular sieve to give a solvent containing less than 25 ppm water. 0.510 g of bis (2,2-dimethyl-5- (1-dimethylamino-2-propyl-imino) -3-hexanoneto-N, O, N ') strontium (0.95 mmol) Mix with 2'-oxybis (N, N-dimethylethanamine) to give 1 ml clear, light yellow solution. Accordingly, bis (2,2-dimethyl-5- (1-dimethylamino-2-propyl-imino) -3-hexanoneto- in 2,2'-oxybis (N, N-dimethylethanamine) The solubility of N, O, N ') strontium is at least 49.8 wt%, ˜0.95 M.

Example 6

Bis (2,2-dimethyl-5- (1-dimethylamino-2-propyl-imino) -3-hexanoneito-N, O in 2,2'-oxybis (N, N-dimethylethanamine) TGA in 35% by weight solution of strontium

Samples of bis (2,2-dimethyl-5- (1-dimethylamino-2-propyl-imino) -3-hexanoneto-N, O, N ') strontium and its 2,2'-oxybis ( A 35 wt% solution in N, N-dimethylethanamine) was characterized by TGA (up to 300 ° C. at 5 ° C./min, isothermal at 300 ° C. for 0.5 h). Very little residue was observed for the pure compound (0.61 wt%) and for its 35 wt% solution (0.71 wt%). The solvent was completely removed from the precursor, indicating that this solution is a good candidate for DLI.

Example 7

Bis (2,2-dimethyl-5- (dimethylaminoethyl-imino) -3-hexanoneito-N, O, N ') strontium in 2,2'-oxybis (N, N-dimethylethanamine) Characterization of

Bis (2,2-dimethyl-5- (dimethylaminoethyl-imino) -3-hexanoneito-N, O, N ') strontium in 2,2'-oxybis (N, N-dimethylethanamine) A sample of 40 wt% solution (˜0.7 M) of was characterized by TGA (400 ° C. at 10 ° C./min) with very little residue (0.42 wt%). The solvent was completely removed from the precursor, indicating that this solution is a good candidate for DLI.

Example 8

Solubility of Bis (2,2-dimethyl-5- (dimethylaminoethyl-imino) -3-hexanonato-N, O, N ') strontium in 4- [2- (dimethylamino) ethyl] morpholine

A sample of 4- [2- (dimethylamino) ethyl] morpholine containing 2990 ppm water was dried over an activated 3A molecular sieve to give a solvent containing less than 100 ppm water. 0.502 g of bis (2,2-dimethyl-5- (dimethylaminoethyl-imino) -3-hexanoneto-N, O, N ') strontium (0.99 mmol) was added to 0.608 g of 4- [2- ( Mix with dimethylamino) ethyl] morpholine to give ~ 1 ml of a mixture containing a small amount of insoluble material. Excess solvent was added in small portions (0.05 g) until all material was dissolved. The total weight of the clear colorless solution was 1.35 g, ˜1.25 ml, which was bis (2,2-dimethyl-5- (dimethylaminoethyl-imino)-in 4- [2- (dimethylamino) ethyl] morpholine. 3-hexanonato-N, O, N ') strontium to indicate that the solubility is 37.2% by weight or -0.8M.

Example 9

Bis (2,2-dimethyl-5- (1-dimethylamino-2-propyl-imino) -3-hexanoneto-N, O, N 'in 4- [2- (dimethylamino) ethyl] morpholine Solubility of Strontium

A 4- [2- (dimethylamino) ethyl] morpholine sample containing 2990 ppm water was dried over an activated 3A molecular sieve to give a solvent containing less than 100 ppm water. 0.595 g bis (2,2-dimethyl-5- (1-dimethylamino-2-propyl-imino) -3-hexanoneto-N, O, N ') strontium (1.1 mmol) Mix with-[2- (dimethylamino) ethyl] morpholine to afford -1 ml of a clear pale yellow solution. Thus, 2,2-dimethyl-5- (1-dimethylamino-2-propyl-imino) -3-hexanoneto-N, O, N 'in 4- [2- (dimethylamino) ethyl] morpholine The solubility of strontium is at least 54.5 wt% or ˜1.1 M.

Example 10

Bis (2,2-dimethyl-5- (dimethylaminoethyl-imino) -3-hexanonato-N, O, N ') bis in 2,2'-oxybis (N, N-dimethylethanamine) Solubility of (tert-butoxy) titanium

1.02 g of bis (2,2-dimethyl-5- (dimethylaminoethyl-imino) -3-hexanoneto-N, O, N ') bis (tert-butoxy) titanium Mixing with 2'-oxybis (N, N-dimethylethanamine) gave 2.22 ml of a greenish brown solution. Thus, 2,2-dimethyl-5- (dimethylaminoethyl-imino) -3-hexanoneto-N, O, N ') strontium in 2,2'-oxybis (N, N-dimethylethanamine) The solubility of is 1M or more.

Example 11

Bis (2,2-dimethyl-5- (dimethylaminoethyl-imino) -3-hexanonato-N, O, N ') bis in 2,2'-oxybis (N, N-dimethylethanamine) Solubility of (iso-propoxy) titanium

0.95 g of bis (2,2-dimethyl-5- (dimethylaminoethyl-imino) -3-hexanoneto-N, O, N ') bis (iso-propoxy) titanium Mixing with '-oxybis (N, N-dimethylethanamine) gave 2.12 ml of a greenish brown solution. Thus, 2,2-dimethyl-5- (dimethylaminoethyl-imino) -3-hexanoneto-N, O, N ') strontium in 2,2'-oxybis (N, N-dimethylethanamine) The solubility of is 1.1M or more.

Example 12

Solubility of Tetrakis (2,2,6,6-tetramethyl-3,5-heptanedionato) cerium (IV) in 2,2'-oxybis (N, N-dimethylethanamine)

0.50 g (0.72 mmol) of tetrakis (2,2,6,6-tetramethyl-3,5-heptanedionate) cerium (IV) in 16.2 g (101 mmol) of 2,2'-oxybis (N, N-dimethylethanamine) to prepare a 3% by weight solution.

Example 13

Solubility of Tris (2,2,6,6-tetramethyl-3,5-heptanedionato) lanthanum in 2,2'-oxybis (N, N-dimethylethanamine)

0.50 g (0.72 mmol) of tris (2,2,6,6-tetramethyl-3,5-heptanedionate) lanthane in 4.0 g (25 mmol) of 2,2'-oxybis (N, N-dimethylethane Amine) to prepare an 11% by weight solution.

Example 14

Solubility of Sr ( ^t Bu ₃ Cp) ₂ in 2,2'-oxybis (N, N-dimethylethanamine)

0.50 g (0.90 mmol) of Sr ( ^t Bu ₃ Cp) ₂ is dissolved in 5.0 g (31.25 mmol) of 2,2'-oxybis (N, N-dimethylethanamine) to give Sr [( ^t Bu) ₃ Cp ₂ , a 9% by weight solution was prepared.

Example 15

Solubility of Ba ( ^t Bu ₃ Cp) ₂ in 2,2′-oxybis (N, N-dimethylethanamine)

0.50g (0.83mmol) of Ba ^(t Bu ₃ Cp) ₂ to 5.0g (31.25mmol) 2,2'- oxybis (N, N- dimethyl-ethanamine) mixed with Ba ^(t Bu ₃ Cp) ₂ A 9 wt% solution of was prepared.

Example 16

Solubility of La (MeCp) ₃ in 2,2'-oxybis (N, N-dimethylethanamine)

0.20g (0.83mmol) La (MeCp) ₃ was dissolved in 2,2'-oxybis (N, N- dimethyl-ethanamine) of 3.3g (20.6mmol) La (MeCp) ₃ to 6% by weight solution of the Prepared.

Example 17

Bis (2,2-dimethyl-5- (dimethylaminoethyl-imino) -3-hexanoneito-N, O, N ') strontium in 2,2'-oxybis (N, N-dimethylethanamine) Viscosity of 0.6M solution

Viscosity was measured using an AR-G2 rheometer (TA Instruments, New Castle, DE). The temperature was adjusted to the desired temperature using a Peltier heating element. A parallel plate shape of 60 mm diameter was used. After loading the sample, 600 sec was allowed for thermal equilibrium before shear rate sweep measurements. Viscosity was measured at a shear rate ranging from 1 to 200 s ⁻¹ . Data points at low shear rates (<6s ⁻¹ ) were considered unreliable and were not reported here. Viscosity results are shown in Table 3. All reported viscosities have 36 centipoise (1 cP = 0.01 P = 1 mPas) units. Bis (2,2-dimethyl-5- (dimethylaminoethyl-imino) -3-hexanoneito-N, O, N ') strontium in 2,2'-oxybis (N, N-dimethylethanamine) The 0.6M solution of was found to be shear thinning with a viscosity of less than 10 centipoise.

TABLE 3

Example 18

Preparation of adducts of Sr ( ^t Bu ₃ Cp) ₂ with 2,2′-oxybis (N, N-dimethylethanamine)

0.19 g (1.18 mmol) of 2,2'-oxybis (N, N-dimethylethanamine) was added to a foggy solution of 0.65 g (1.18 mmol) Sr ( ^t Bu ₃ Cp) ₂ in hexane at room temperature. Added. After the reaction mixture was stirred for several hours, all volatiles (including solvent) were removed under vacuum and 0.74 g of off-white waxy solid was separated.

¹ H NMR (500 MHz, C ₆ D ₆ ): δ = 5.96 (s, 4H), 3.46 (t, 4H), 2.46 (t, 4H), 2.15 (s, 12H), 1.44 (s, 36H), 1.39 (s, 18 H).

Example 19

Preparation of adducts of Ba ( ^t Bu ₃ Cp) ₂ with 2,2′-oxybis (N, N-dimethylethanamine)

0.03 g (0.20 mmol) of 2,2'-oxybis (N, N-dimethylethanamine) was added to an aerosol solution of 0.12 g (0.20 mmol) Ba ( ^t Bu ₃ Cp) ₂ in hexane at room temperature. After the reaction mixture was stirred for several hours, all volatiles (including solvent) were removed under vacuum and 0.15 g of off-white waxy solid was separated.

¹ H NMR (500 MHz, C ₆ D ₆ ): δ = 5.96 (s, 4H), 3.46 (t, 4H), 2.46 (t, 4H), 2.15 (s, 12H), 1.44 (s, 36H), 1.39 (s, 18 H).

Example 20

Preparation of adducts of zirconium tert-butoxide with 2,2'-oxybis (N, N-dimethylethanamine)

To a solution of 0.56 g (1.46 mmol) Zr ( ^t BuO) ₄ in hexane at room temperature was added 0.23 g (1.46 mmol) 2,2'-oxybis (N, N-dimethylethanamine). After stirring the reaction mixture for several hours, the volatiles (including the solvent) were removed and crystals began to form. Before all the volatiles were removed, the mixture was heated to a homogeneous solution and allowed to recrystallize at -40 ° C. Crystals were characterized as the desired Zr ( ^t BuO) _4. (NMe ₂ CH ₂ CH ₂ ) ₂ O) adduct by x-ray analysis.

Example 21

Synthesis of bis (2-tert-butyl-4,5-di-tert-amylimidazolyl) (2,2'-oxybis (N, N-dimethylethylamine) strontium

Under nitrogen blanket, 2.68 g (0.005 mol) of strontium bis (hexamethyldisyrylamide) bis (tetrahydrofuran) dissolved in 20 ml of anhydrous hexane was dissolved in 2.68 g of 40 ml of anhydrous hexane over 5 minutes at room temperature. 0.01 mol) of 2-3 tert-butyl-4,5-di-tert-amylimidazole and 0.80 g (0.005 mol) of 2,2'-oxybis (N, N-dimethylethylamine) Dropped in Within 30 minutes a white precipitate was observed to form, but it slowly dissolved to form a slightly cloudy solution which was then stirred overnight. After stirring overnight, a second precipitate was observed. Thereafter, 60 ml of additional hexane was added and the mixture was refluxed to dissolve the precipitate. This solution was then filtered, the filtrate was slowly cooled to -5 ° C over 2 hours, and then the crystalline product was filtered off. Yield 3.25 g (43% of theory).

Example 22

Bis (2,2-dimethyl-5- (dimethylamino-ethylimino) -3-hexanoneto-N, O, N ') strontium in 2,2'-oxybis (N, N-dimethylethanamine) Direct liquid injection performance

Bis (2,2-dimethyl-5- (dimethylamino-ethylimino) -3-hexanoneto-N, O, N ') strontium in 2,2'-oxybis (N, N-dimethylethanamine) The 0.3M solution of was pulsed with a heated injection liquid vaporization system for 150 hours of continuous performance. Pulsing into the injection system was controlled by a liquid flow controller with a 10 second liquid flow (0.3 gpm) followed by a 30 second flow stop. Continuous pulsing was performed for 150 hours. Strontium precursor was condensed downstream from the injector and analyzed for purity. The TGA results for the precursor examples were compared well with the initial precursor residue levels and volatility, demonstrating no evidence for precursor degradation. 6 shows an example for pressure reaction during liquid working time, which demonstrates the stability of the vaporization process. Preliminary testing of solvent / precursor systems with incompatibility demonstrated poor pressure response and intermittent pressure spiking or clogging.

Example 23

Bis (2,2-dimethyl-5- (1-dimethylamino-2-propyl-imino) -3-hexanoneito-N, O in 2,2'-oxybis (N, N-dimethylethanamine) N ') Direct liquid injection performance of strontium

Bis (2,2-dimethyl-5- (1-dimethylamino-2-propyl-imino) -3-hexanoneito-N, O in 2,2'-oxybis (N, N-dimethylethanamine) 0.3 M solution of strontium was pulsed with a heated liquid injection vaporization system for a continuous run of 150 hours. Pulsing into the injection system was controlled by a liquid flow controller with a 10 second liquid flow (0.3 gpm) followed by a 30 second flow stop. Continuous pulsing was performed for 150 hours. Strontium precursor was condensed downstream from the injector and analyzed for purity. The TGA results for the precursor examples were compared well with the initial precursor residue levels and volatility, demonstrating no evidence for precursor degradation. Preliminary testing of solvent / precursor systems with incompatibility demonstrated poor pressure response and intermittent pressure spiking or clogging.

Example 24

Direct liquid injection performance of bis (2,5-di-tert-butyl-pyrrolyl) barium in 2,2'-oxybis (N, N-dimethylethanamine)

Inject a 0.05 M solution of bis (2,5-di-tert-butyl-pyrrolyl) barium in 2,2'-oxybis (N, N-dimethylethanamine) heated for 50 hours of continuous run Pulsed with vaporization system. Pulsing into the injection system was controlled by a liquid flow controller with a 10 second liquid flow (0.3 gpm) followed by a 30 second flow stop. Continuous pulsing was performed for 50 hours. The barium precursor was condensed downstream from the injector and analyzed for purity. The TGA results for the precursor examples were compared well with the initial precursor residue levels and volatility, demonstrating no evidence for precursor degradation. Preliminary testing of solvent / precursor systems with incompatibility demonstrated poor pressure response and intermittent pressure spiking or clogging.

Example 25

Bis (2,2-dimethyl-5- (1-dimethylamino-2-propyl-imino) -3-hexanoneito-N dissolved in 2,2'-oxybis (N, N-dimethylethanamine) ALD Deposition of SrO Using, O, N ') Strontium

This example is bis (2,2-dimethyl-5- (1-dimethylamino-2) which is an Sr ketoiminate precursor dissolved in ozone and 2,2'-oxybis (N, N-dimethylethanamine). A general ALD deposition using -propyl-imino) -3-hexanonato-N, O, N ') strontium is described. The deposition temperature ranged from 250 to 450 ° C. and DLI (direct liquid injection) with vaporizer was used to deliver the Sr precursor. The deposition chamber pressure range was about 1.5 torr depending on the gas flow rate. The dip tube side of the metal vessel containing the Sr precursor solution in 2,2'-oxybis (N, N-dimethylethanamine) was connected to a DLI vaporizer, and the solution was injected into the vaporizer and converted to steam. One cycle of ALD for SrO consisted of four steps:

1. Injecting a 0.3 M solution of Sr precursor into a vaporizer, introducing Sr precursor vapor into a deposition chamber and chemically adsorbing the Sr precursor onto a heated substrate;

2. Ar purging: purging any non-adsorbed Sr precursor with Ar;

3. Ozone pulsing: introducing ozone into the deposition chamber to react with the Sr precursor adsorbed on the heated substrate; And

4. Ar purging: purging any unreacted ozone and byproducts with Ar.

In this example, an SrO film was deposited, which shows the deposition temperature dependence of the SrO film. Injection time was 5 seconds, Ar purging time after Sr pulse was 10 seconds, ozone pulse time was 5 seconds, and Ar purging time after ozone pulse was 10 seconds. This was repeated 100 cycles.

This result is shown in FIG. 8, where the ALD process window averaged approximately 320 ° C. or less.

Claims (40)

a) one or more ligands are β-diketonate, β-ketoiminate, β-ketostearate, β-diiminate, alkyl, carbonyl, alkyl carbonyl, cyclopentadienyl, pyrrolyl, alkoxide, alkoxy At least one metal-ligand complex, selected from the group consisting of midinate, imidazolyl, and mixtures thereof, wherein the metal is selected from Groups 2-16 elements of the Periodic Table of the Elements; And
b) R ¹ R ² NR ³ OR ⁴ NR ⁵ R ⁶ , R ¹ OR ⁴ NR ⁵ R ⁶ , O (CH ₂ CH ₂ ) ₂ NR ¹ , R ¹ R ² NR ³ N (CH ₂ CH ₂ ) ₂ O , R ¹ R ² NR ³ OR ⁴ N (CH ₂ CH ₂ ) ₂ O, O (CH ₂ CH ₂ ) ₂ NR ¹ OR ² N (CH ₂ CH ₂ ) ₂ O, and mixtures thereof, wherein R ^{1 -6} is independently C _{1 -10} linear alkyl, C _{1 -10} branched alkyl, C _{1 -10} cyclic alkyl, C ₆ -C ₁₀ aromatic, C _{1 -10} alkyl amines, C _{1 -10-alkyl-amino-alkyl,} C _1-10 ether, C ₄ -C ₁₀ cyclic ether, C ₄ -C ₁₀ cyclic amino ether, and a formulation comprising one or more amino ether is selected from the group consisting of selected from the group consisting of a mixture thereof. The formulation of claim 1, wherein the ligand of the metal-ligand complex is selected from the group consisting of monodentate, bidentate, multidentate, and mixtures thereof. The formulation of claim 1, wherein the formulation is in liquid phase. The compound of claim 1, wherein the formulation is of formula R ¹ R ² NR ³ OR ⁴ NR ⁵ R ⁶ wherein R ¹ -R ⁶ are independently C _1-10 linear alkyl, C _1-10 branched alkyl, C ₁ Selected from the group consisting of _-10 cyclic alkyl and C ₆ -C ₁₀ aromatics. The compound of claim 1, wherein the formulation is of formula R ¹ OR ⁴ NR ⁵ R ⁶ wherein R ¹ and R ^4-6 are independently C _1-10 linear alkyl, C _1-10 branched alkyl, C _1-10 Selected from the group consisting of cyclic alkyl and C ₆ -C ₁₀ aromatics. The formulation of claim 1, wherein the formulation is of formula O (CH ₂ CH ₂ ) ₂ NR ¹ , wherein R ¹ is C _1-10 linear alkyl, C _1-10 branched alkyl, C _1-10 cyclic alkyl, and C ₆ -C ₁₀ aromatic; selected from the group consisting of cyclic aminoethers. The compound of claim 1 wherein the formulation is of formula R ¹ R ² NR ³ N (CH ₂ CH ₂ ) ₂ O wherein R ^1-3 is independently C _1-10 linear alkyl, C _1-10 branched alkyl, And cyclic aminoethers selected from the group consisting of C _1-10 cyclic alkyl and C ₆ -C ₁₀ aromatic. The compound of claim 1, wherein the formulation is of formula R ¹ R ² NR ³ OR ⁴ N (CH ₂ CH ₂ ) ₂ O, wherein R ^1-4 is independently C _1-10 linear alkyl, C _1-10 branched Alkyl, C _1-10 cyclic alkyl, and C ₆ -C ₁₀ aromatic; and a cyclic aminoether. The formulation of claim 1, wherein the formulation is of formula O (CH ₂ CH ₂ ) ₂ NR ¹ OR ² N (CH ₂ CH ₂ ) ₂ O wherein R ^1-2 is independently C _1-10 linear alkyl, C _{1 -10} branched alkyl and C _1-10 cyclic alkyl]. The formulation of claim 1 wherein the aminoether is selected from the group consisting of the following compounds, and mixtures thereof:

The formulation of claim 4 wherein the metal-ligand complex is selected from the group consisting of the following compounds, and mixtures thereof:
(a) a metal β-diketonate having the formula:

[Wherein M is selected from Group 2 to Group 16 metals, R ^1-3 is independently hydrogen, C _1-10 linear or branched alkyl, C _1-10 linear or branched alkoxy, C _4-10 alicyclic Group, C _6-10 aryl, and C _1-10 fluorinated alkyl; x is 2, 3 or 4;
(b) metal β-ketoiminates having the formula:

[Wherein M is selected from Group 2 to Group 16 metals, R ^1-4 is individually hydrogen, C _1-10 linear or branched alkyl, C _1-10 linear or branched alkoxy, C _4-10 alicyclic Group, C _6-10 aryl, and C _1-10 linear or branched fluorinated alkyl; x is 2, 3 or 4;
(c) metal β-diiminates having the formula:

[Wherein M is selected from Group 2 to Group 16 metals, R ^1-5 is individually hydrogen, C _1-10 linear or branched alkyl, C _1-10 linear or branched alkoxy, C _4-10 alicyclic Group, C _6-10 aryl, and C _1-10 linear or branched fluorinated alkyl; x is 2, 3, or 4;
(d) metal β-ketoiminates having the formula:

[Wherein M is selected from Group 2 to Group 16 metals; R ^1-3 and R ^5-6 are individually hydrogen, C _1-10 linear or branched alkyl, C _1-10 linear or branched alkoxy, C _4-10 alicyclic, C _6-10 aryl, and C _{1 -10} linear or branched fluorinated alkyl; R ⁴ is C _1-10 linear or branched alkyl, C _1-10 linear or branched alkoxy, C _4-10 alicyclic, C _6-10 aryl, and C _1-10 linear or branched fluorinated alkyl Selected from the group consisting of; x is 2 or 3;
(e) metal β-ketoiminates having the formula:

[Wherein M is an alkaline earth metal selected from Group 2; R ¹ is a branched alkyl group containing 4 to 10 carbon atoms; R ² is hydrogen, C _1-10 linear or branched alkyl, C _1-10 linear or branched alkoxy, C _4-10 alicyclic, C _6-10 aryl, and C _1-10 linear or branched fluorinated Selected from the group consisting of alkyl; R ^3-5 is individually C _1-10 linear or branched alkyl, C _1-10 linear or branched alkoxy, C _4-10 alicyclic, C _6-10 aryl, and C _1-10 linear or branched fluorine Selected from the group consisting of alkylated alkyl, R ^6-7 is individually C _1-10 linear or branched alkyl, C _1-10 linear or branched alkoxy, C _4-10 alicyclic, C _6-10 aryl, And C _1-10 linear or branched fluorinated alkyl, and a ring containing an oxygen or nitrogen atom.
(f) metal β-ketoiminates having the formula:

[Wherein M is a metal ion selected from Group 4 metals; R ¹ is a branched alkyl group containing 4 to 10 carbon atoms; R ² is individually hydrogen, C _1-10 linear or branched alkyl, C _1-10 linear or branched alkoxy, C _4-10 alicyclic, C _6-10 aryl, and C _1-10 linear or branched fluorine It may be selected from the group consisting of alkylated alkyl; R ^3-4 is individually C _1-10 linear or branched alkyl, C _1-10 linear or branched alkoxy, C _4-10 alicyclic, C _6-10 aryl, and C _1-10 linear or branched fluorine Selected from the group consisting of alkylated alkyl; R ^5-6 is individually C _1-10 linear or branched alkyl, C _1-10 linear or branched alkoxy, C _4-10 alicyclic, C _6-10 aryl, and C _1-10 linear or branched fluorine Alkylated and a ring containing an oxygen or nitrogen atom; R ⁷ is C _1-10 linear or branched alkyl, C _1-10 linear or branched alkoxy, C _4-10 alicyclic, C _6-10 aryl, and C _1-10 linear or branched fluorinated alkyl Selected from the group consisting of; n is 1, 2 or 3;
(g) metal β-ketoiminates having the formula:

[Wherein M is a metal ion selected from Group 11; R ¹ is a branched alkyl group containing 1 to 10 carbon atoms; R ² is hydrogen, C _1-10 linear or branched alkyl, C _1-10 linear or branched alkoxy, C _4-10 alicyclic, C _6-10 aryl, and C _1-10 linear or branched fluorinated Selected from the group consisting of alkyl; R ^3-4 is individually C _1-10 linear or branched alkyl, C _1-10 linear or branched alkoxy, C _4-10 alicyclic, C _6-10 aryl, and C _1-10 linear or branched fluorine Selected from the group consisting of alkylated alkyl; R ^5-6 is individually C _1-10 linear or branched alkyl, C _1-10 linear or branched alkoxy, C _4-10 alicyclic, C _6-10 aryl, and C _1-10 linear or branched fluorine Alkylated and a ring containing an oxygen or nitrogen atom; X is carbon or silicon;
(h) metal complexes having the formula:

[Wherein M is selected from Group 2 to Group 16 metals, R is hydrogen, C _1-10 linear, branched, saturated or unsaturated alkyl, C _1-10 linear or branched alkoxy, C _4-10 alicyclic , C _6-10 aryl, and C _1-10 linear or branched fluorinated alkyl, cyclopentadienyl, alkyl substituted cyclopentadienyl, pyrrolyl, alkyl substituted pyrrolyl, imidazolyl and alkyl substituted Selected from the group consisting of imidazolyl; x is 2, 3 or 4; L is NMe ₂ or OMe, where Me is methyl; n is 0, 1, 2, 3 or 4;
(i) alkyl metal carbonyls having the formula:

[Wherein M is selected from Group 2 to Group 16 metals; R is hydrogen, C _1-10 linear or branched alkyl, C _1-10 linear or branched alkoxy, C _4-10 alicyclic, C _6-10 aryl, and C _1-10 linear or branched fluorinated alkyl And cyclophendienyl; x is 2, 3 or 4; y is 1, 2, 3 or 4;
(j) metal carbonyls having the formula:

[Wherein M is selected from Group 8 to Group 10 metals; x is 1, 2 or 3; y is 4 to 12;
(k) metal alkoxides having the formula:

[Wherein M is selected from Group 2 to Group 16 metals; R is selected from the group consisting of C _1-10 alkyl, C _1-10 alkenyl, C _1-10 alkynyl, C ₅ -C ₁₀ alicyclic, C _6-12 aryl, and fluorinated C _1-10 alkyl Become; n is 2, 3, 4, or 5;
(l) metal amides having the formula:

[Wherein M is selected from Group 2 to Group 16 metals; R ^1-2 is independently C _1-10 linear or branched alkyl, C _1-10 linear or branched alkenyl, C _1-10 linear or branched alkynyl, C _3-10 linear or branched alkylsilyl, C ₅ -C ₁₀ alicyclic, C _6-12 aryl, and linear or branched fluorinated C _1-10 alkyl; n is 2, 3, 4 or 5;
(m) metal alkoxy β-diketonates having the formula:

[Wherein M comprises a metal selected from the group consisting of Ti, Zr, and Hf; R ¹ is an alkyl group containing 1 to 10 carbon atoms; R ² is an alkyl group containing 1 to 10 carbon atoms; R ³ is selected from the group consisting of hydrogen and alkyl groups containing 1 to 3 carbon atoms; R ⁴ is an alkyl group containing 1 to 6 carbon atoms;
(n) metal amidates having the formula:

[Wherein M is selected from Group 2 to Group 16 metals, R ^1-3 are individually hydrogen, C _1-10 linear or branched alkyl, C _1-10 linear or branched alkoxy, C _4-10 alicyclic Group, C _6-10 aryl, and C _1-10 linear or branched fluorinated alkyl; x is 2, 3 or 4. The method of claim 1, wherein the aminoether is selected from the group consisting of 2,2'-oxybis (N, N-dimethylethanamine), 4- [2- (dimethylamino) ethyl] morpholine, and mixtures thereof. Formulation. The formulation of claim 12 wherein the aminoether is 2,2'-oxybis (N, N-dimethylethanamine) with less than 20 ppm water. 13. The formulation of claim 12 wherein the aminoether is 2,2'-oxybis (N, N-dimethylethanamine) with additional compounds containing less than 100 ppm hydroxyl or amine functionality. a) bis (2,2-dimethyl-5- (dimethylaminoethyl-imino) -3-hexanonato-N, O, N ') strontium, bis (2,2-dimethyl-5- (1-dimethyl Amino-2-propylimino) -3-hexanonato-N, O, N ') strontium, bis (2,2-dimethyl-5- (dimethylaminoethyl-imino) -3-hexanonato-N , O, N ') bis (tert-butoxy) titanium, tetrakis (2,2,6,6-tetramethyl-3,5-heptanedionato) cerium (IV), tris (2,2,6 , 6-tetramethyl-3,5-heptanedionato) lanthanum, Sr ( ^t Bu ₃ Cp) ₂ , Ba ( ^t Bu ₃ Cp) ₂ , Sr ( ⁱ Pr ₃ Cp) ₂ , Ba ( ⁱ Pr ₃ Cp) ₂ , LaCp ₃ , La (MeCp) ₃ , La (EtCp) ₃ , La ( ⁱ PrCp) ₃ , zirconium tert-butoxide, bis (2-tert-butyl-4,5-di-tert-amyl Imidazolyl) strontium, bis (2-tert-butyl-4,5-di-tert-amyl imidazolyl) barium, bis (2,5-di-tert-butyl-pyrrolyl) strontium, bis (2,5-di-tert-butyl-pyrrolyl), barium, Ru (EtCp) _2, Ru (EtCp) (DMPD) and their metal is one mixture selected from the group consisting of over-Li De complexes; And
b) at least one aminoether selected from the group consisting of 2,2'-oxybis (N, N-dimethylethanamine), 4- [2- (dimethylamino) ethyl] morpholine, and mixtures thereof ,
Liquid formulations useful for depositing metal-containing thin films in the manufacture of semiconductor devices. The formulation of claim 1 which is present in a stainless steel container. The formulation of claim 16 wherein the interior of the vessel is electropolish. The formulation of claim 16 wherein the vessel has an inlet valve and an outlet valve. The formulation of claim 18 wherein the valve is an automatic actuated valve. 20. The formulation of claim 19 wherein the valve is a pneumatic actuated valve. 20. The formulation of claim 19 wherein the valve is an electric solenoid actuated valve. The formulation of claim 16, wherein the vessel has a diptube. The formulation of claim 22 wherein the diptube is an outlet. The formulation of claim 22 wherein the diptube is an inlet. The formulation of claim 1 comprising a chemical stabilizer. The formulation of claim 25, wherein the stabilizer is a free radical scavenger. The formulation of claim 25 wherein the stabilizer is a polymerization inhibitor. The formulation of claim 25, wherein the stabilizer is an antioxidant. The formulation of claim 1 having a viscosity of less than 50 cP. The compound of claim 1, which is from 2,2′-oxybis (N, N-dimethylethanamine), and LaCp ₃ , La (MeCp) ₃ , La (EtCp) ₃ , or La ( ⁱ PrCp) ₃ . A formulation comprising a lanthanum complex selected. 2. Bis (2,2-dimethyl-5- (dimethylaminoethyl-imino) -3-hexanonaito-N, O, N ') strontium and 2,2'-oxybis (N, N-dimethylethanamine). 2. Bis (2,2-dimethyl-5- (1-dimethylamino-2-propylimino) -3-hexanoneito-N, O, N ') strontium and 2,2'-oxy Formulations comprising bis (N, N-dimethylethanamine). The formulation of claim 1 comprising Sr ( ^t Bu ₃ Cp) ₂ and 2,2′-oxybis (N, N-dimethylethanamine). The formulation of claim 1 comprising Ba ( ^t Bu ₃ Cp) ₂ and 2,2′-oxybis (N, N-dimethylethanamine). The formulation of claim 1 comprising Sr ( ⁱ Pr ₃ Cp) ₂ and 2,2′-oxybis (N, N-dimethylethanamine). The formulation of claim 1 comprising Ba ( ⁱ Pr ₃ Cp) ₂ and 2,2′-oxybis (N, N-dimethylethanamine). A method of depositing a metal-containing film by chemical vapor deposition or atomic layer deposition, comprising contacting a substrate under conditions for depositing a metal-containing film from the formulation of claim 1 and depositing such a metal-containing film. A method of depositing a metal-containing film by chemical vapor deposition or atomic layer deposition, comprising contacting a substrate under conditions for depositing a metal-containing film from the formulation of claim 10 and depositing such a metal-containing film. A method of depositing a metal-containing film by chemical vapor deposition or atomic layer deposition, comprising contacting a substrate under conditions for depositing a metal-containing film from the formulation of claim 11 and depositing such a metal-containing film. 38. The method of claim 37, wherein the formulation is delivered by direct liquid injection through a vaporizer.

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