JP2002527528A - Liquid compounds for forming materials containing alkaline earth metals - Google Patents

Abstract

(57) Abstract: A liquid precursor for forming an alkaline earth-containing material is provided. The liquid precursor comprises an alkaline earth metal β-diketonate bound to an amine. For example, a liquid compound was formed by reacting N, N ′, N ″ -trihexyldiethylenetriamine with barium 2,2,6,6-tetramethyl-3,5-heptanedionate. The coating containing the alkaline earth metal is deposited from the vapor of the precursor liquid and, optionally, from oxygen or another source of oxygen. This method may be used to deposit barium strontium titanate having a high dielectric constant. Liquid precursors may also be used for spray coating, spin coating, and sol-gel deposition of materials.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] This invention was made with United States Government support under United States National Science Foundation grant number NSF CHE 95-10245. The United States government may have certain rights in the invention.

[0002] Background of the Invention 1. FIELD OF THE INVENTION The present invention relates to chemical vapor deposition (CVD), spray coating, spin coating,
Or, it relates to a novel volatile liquid reagent which can be used in place of a less appropriate solid material in a film deposition process such as sol-gel deposition. These liquid reagents can be used to deposit materials containing alkaline earth metals, such as metal oxides or mixed metal oxides.

[0003] 2. 2. Description of the Related Art Chemical vapor deposition (CVD) is a widely used method for forming solid materials such as coatings or powders in the vapor phase from reactants. An easy-to-understand commentary on the CVD process has recently been published in “CVD of Nonmetals”, edited by WS Rees, Jr., VCH Publishers, Weinheim, Germany, 1996; Compound Semiconductors), Jones &
O'Brien (AC Jones and P. O'Brien), VCH, 1996;
Chemistry of Metal CVD ", Kodass & Hampden Smith (T. Kod
as and M. Hampden-Smith), VCH, 1994.

In a CVD process, the reactant vapor may be created by heating the liquid to a sufficiently high temperature, venting a stream of carrier gas through the liquid, and transporting the vapor to the CVD chamber. In low pressure CVD systems, the carrier gas may be omitted and the vapor may flow directly from the bubble generator to the low pressure CVD chamber.

[0005] In order for a CVD process to work successfully, it is necessary to create a vapor containing a controlled amount of a suitable reactive chemical. The solid can be used as a vapor source in a CVD process. However, when a solid is used in a bubble generator, the amount of vapor generated is often dependent on the particle size and shape, which varies over the duration of the sublimation process, so that the rate of vapor generation by sublimation of the solid can easily be increased. Not reproducible. Thus, the concentration of steam can change randomly,
Thereby, the growth rate and / or composition of the material formed by the CVD process can change. Similarly, different batches of solids can have different particle sizes and shapes, so the results of the CVD process can change as new batches of solid precursors are introduced into the system. These problems are particularly evident in the currently used CVD precursors for barium, strontium, and calcium, as described by Woksack, Freig & Hampdensmith (WA Wojtczak, P.
.F. Fleig, and MJ Hampden-Smith, “Advances in O
rganometallic Chemistry), Vol. 40, pp. 215-340.

[0006] Another problem with solids is that small amounts of contaminants on their surface can alter their sublimation rate. In contrast, liquid surfaces tend to be refreshed by the movement of the liquid, so that they tend to evaporate at a reproducible rate, even in the presence of small amounts of contaminants.

[0007] Some solid materials exhibit different vapor pressures depending on how a particular sample was prepared or how long it has been stored. For example, often Ba
(thd) - 2,2,6,6-tetramethyl-3,5-heptane dione barium be omitted as ₂ is used to deposit the barium strontium titanate (BST) film. Solid Ba (thd) ₂ exists in many oligomeric forms, ranging from trimers and tetramers of various lengths to polymers, depending on the method used for its synthesis.
Oligomeric interconversion rates are slow, often requiring weeks to months. Thus, the molecular composition of a Ba (thd) ₂ sample depends on how it was prepared and how long it has been stored. These oligomers have different vapor pressures. Thus, in the case of Ba (thd) ₂ , it is very difficult to predict the vapor pressure of any particular sample, and the deposition rate of BST from this solid source is not reproducible. In contrast, liquids typically exist as the only reproducible form at any given temperature and pressure.

[0008] Another problem with solids is that the sublimation rate is often slow, so that a sufficiently high vapor concentration cannot be produced. For example, Ba (thd) ₂ has a very low vapor pressure and the deposition rate is limited to low values. In contrast, liquids often have a higher vapor pressure than solids.

[0009] Another problem with solids is that moving between containers is less convenient than pumping a liquid.

[0010] Pyrolysis of solids is another problem that often affects the reproducibility of solid vapor sources. For example, solid beta-diketonates of barium, such as Ba (thd) ₂ , gradually decompose at their evaporation temperature, so that the amount of vapor generated decreases with time. Pyrolysis can also be a problem for liquid sources, but in the case of liquids, the effect can be negligible because the vapor generation is rapid or "rapid." This can be done by pumping the liquid at a controlled rate to a hot zone where the liquid evaporates rapidly. In such a "direct liquid injection" (DLI) system, each part of the liquid can be heated for a very short time to form a vapor of the heat-sensitive liquid without significant decomposition. Another advantage of the DLI system is that multi-component mixtures can be evaporated at a constant and reproducible ratio, even when the volatility of the components is different. Because of these advantages, DLI systems are becoming more widely used in CVD processes.

[0011] Solid feedstocks can be used in a DLI vapor source if a suitable liquid solvent is found to dissolve the solids. However, solvents can increase the irritability, toxicity, or corrosivity of the precursor solution, increase the incorporation of carbon or other impurities into the deposited coating,
It can cause other problems, such as increasing the volume of gaseous by-products that must be removed from the exhaust gas to prevent contamination. These problems with the solvent can be minimized if the solid is very soluble in the solvent because only a small amount of solvent is needed to prepare the liquid solution.

[0012] Due to all these problems, solid sources of steam are rarely used in commercial CVD systems. Either liquids or solids that are highly soluble in liquid solvents are more convenient and are more commonly used in CVD practice. Making this vapor from a liquid source would be much more reproducible and convenient than preparing it from a liquid source; however, barium, strontium, calcium, Or liquid compounds of magnesium have not been previously known.

The alkaline earth metal β-diketonate has a vapor pressure of amine (Gordon)
Et al., U.S. Patent No. 5,139,999, 1992), ether (Miller et al., U.S. Patent No. 4,501,602, 1985; Timmer et al., U.S. Patent No. 5,248,787, 19).
93; Potential for increased evaporation of them in the presence of Kirlin et al., US Pat. No. 5,280,012, 1994) or thioethers (Kirlin et al., US Pat. No. 5,225,561, 1993). is there. However, even when bound to these Lewis bases, the alkaline earth metal β-diketonates disclosed in these references are still solid at room temperature.

Liquid precursors of many metals, including alkaline earth metals, have been successfully formed using mixtures of several β-diketonate ligands (Gordon et al., Symposium of the Society for Materials Science, 495, 63-67, 1998). However, because these liquid precursors are mixtures of many compounds, they are more difficult to purify and characterize than a single compound. For example, they cannot be purified by crystallization to form a single glassy solid upon cooling, rather than separating into pure single crystals. Some impurities can be removed by distillation, but high purity cannot be obtained by distillation over a narrow temperature range. Since mixtures of different components have different vapor pressures, the mixture is distilled over a wide range of temperatures. Another problem with using these liquid mixtures is that the more volatile components are distilled first, so that a constant vapor composition of such mixtures cannot be constantly transported from the bubble source. .

[0015] The main features of the SUMMARY OF THE INVENTION The present invention provides a pure liquid compound at room temperature, an alkaline earth metal,
In particular, it is to provide a chemical precursor that may be used for the deposition of materials containing barium, strontium, calcium, and magnesium.

It is a further feature of the present invention to provide a chemical precursor that readily evaporates without decomposition and leaves no non-volatile residue during the alkaline earth metal containing material deposition process.

A related feature of the present invention is a process for depositing an alkaline earth metal-containing material from a chemical compound that is liquid at room temperature.

Another related feature is to deposit some metal-containing materials by a chemical vapor deposition process that uniformly mixes all reactants before being transported to the heated surface of the substrate. is there.

Another feature of the present invention is a process for depositing an alkaline earth metal-containing material from a chemical precursor that evaporates easily without decomposition and leaves no non-volatile residue.

[0020] Another feature of the present invention is to provide a process for producing a high purity mixed metal oxide, including an alkaline earth metal oxide.

[0021] Another feature of the present invention is to provide a chemical vapor deposition process for forming metal oxides from stable and relatively non-hazardous reactants.

Another feature of the present invention is to provide a chemical vapor or solution deposition process for mixed metal oxides, wherein the precursor metal-containing compound is a stable and uniform liquid.

A further feature of the present invention is to provide a liquid mixture or solution suitable for spray coating, spin coating, or sol-gel deposition.

A further feature of the present invention is to provide a liquid precursor used to form titanium dioxide and other titanium-containing materials.

One particular feature of the present invention is to provide a method for depositing a barium strontium titanate coating having a high dielectric constant and high electrical resistance.

Another particular feature of the present invention is to provide a method for depositing barium titanate having ferroelectric properties.

The above features are substantially obtained by utilizing a composition comprising an alkaline earth metal β-diketonate having one or more specific amine ligands attached to the metal. In a preferred embodiment, the compound is liquid at 60 ° C., preferably at 20 ° C., and can be evaporated.

The alkaline earth β-diketonate has the following general formula:

Embedded image Wherein ¹ R and R ² may be an alkyl group, a fluoroalkyl group, or an alkyl group containing an oxygen or nitrogen containing species (eg, an amino, alcohol, or alkoxy species). R ³ may be hydrogen or an alkyl group, a fluoroalkyl group, or an alkyl group containing an oxygen or nitrogen containing species. In a preferred embodiment, the alkyl group contains less than 10 carbons, preferably less than 7 carbons. Preferred compositions of alkaline earth metal diketonates are 2,2,6,6-tetramethyl-3,5-heptanedione, abbreviation Hthd, 2,2,6,6-tetramethyl-3,5-octane Zeon, abbreviation H
tod, 3,3,7,7-tetramethyl-4,6-nonanedione, abbreviation Htnd, and 2,2,6-trimethylheptane-3,5-dione, including ligands derived from the abbreviation H3hd, In the H, indicates the presence of a hydrogen atom that is removed when the ligand binds to the alkaline earth metal.

Preferred amines have the general formula:

Embedded image Wherein n is not a negative integer and R ^a , R ^b , R ^c and R ^d are hydrogen, an alkyl group,
Or a substituted alkyl group, where n = 0 corresponds to a diamine, N = 1 corresponds to a triamine, and n = 2 corresponds to tetramine.

In another embodiment, preferred amines include N-substituted amines having the general formula:

Embedded image In the formula, n is not a negative integer, preferably in the range of 0 to 3, more preferably 0, 1
, 2 or 3, wherein n = 0 corresponds to diamine, N = 1 corresponds to triamine, and n = 2 corresponds to tetramine, and R ^a , R ^b , R ^c and R ^d are independent And is hydrogen, an alkyl group, a substituted alkyl group, or an aryl group. Substituted alkyl groups include those that have little effect on the volatility or melting point of the product alkaline earth metal β-diketonate compound, including fluoroalkyl groups, or alkyl groups containing oxygen-containing species, but It is not limited to. R ^a , R ^b , R ^c , R ^d and R ^e are selected to provide a volatile complex with the alkaline earth metal β-diketonate. One or more of the groups R ^a , R ^b , R ^c , R ^d and R ^e are desirably larger than a methyl group, and the total number of carbon atoms on the amine is desirably in the range of 4-20. N-alkyl substituted polyamines having alkyl chain lengths of about 4 to 8 carbon atoms promote the formation of liquid addition products. The viscosity of the liquid decreases as the number of carbon atoms in the alkyl chain increases. In a preferred embodiment, the amine ligand is N,
Triamines such as N ', N "-trihexyldiethylenetriamine.

The amine addition product of the alkaline earth metal β-diketonate is an alkaline earth metal β
Formed by reacting a diketonate with an amine. In the case of triamines, generally one equivalent of the alkaline earth metal β-diketonate is equivalent to one equivalent of the triamine.
Use equal volumes. Two equivalents of the diamine may be reacted with one equivalent of barium, strontium, calcium β-diketonate, but typically one equivalent of the diamine bound to magnesium β-diketonate.

In a most preferred embodiment, the amine addition product of the metal β-diketonate is liquid at room temperature. N-alkyl substituted polyamines having an alkyl chain length of about 4 to 8 carbon atoms have been found to promote the formation of liquid addition products. Liquid viscosity decreases as the number of carbon atoms in the alkyl chain increases.

In another embodiment of the present invention, the complexed alkaline earth metal β-diketonate is a solid that is very soluble in organic solvents. The metal β-diketonate compound is preferably at least 0.1 M, more preferably at least 0.5 M, and most preferably
It may be prepared at a concentration of 1.0 M or more.

In some cases, amine ligands having only two types of substituents are sufficient to obtain the properties described above. In other cases, three, four, or more different substituents on an amine ligand may be desirable.

Another aspect of the present invention relates to the use of vapors from an alkaline earth β-diketonate complexed with an amine, and optionally another oxygen-containing gas, to provide a material comprising an alkaline earth metal. It is to provide a method for chemical vapor deposition. This method may be used to form coatings including, but not limited to, barium, strontium, calcium, and magnesium. In a preferred embodiment, a homogeneous vapor mixture comprising an alkaline earth metal beta-diketonate complexed with an amine, oxygen, and optionally an inert carrier gas such as nitrogen is utilized. The vapor mixture is contacted with a substrate heated to a temperature sufficient to deposit a material comprising one or more alkaline earth metals. Typical deposition temperature is about 200-800
It is in the range of ° C. Typical deposition pressures range from normal atmospheric pressure to several millitorr.

In a preferred embodiment, a homogeneous liquid mixture of one or more other volatile metal-containing compounds and one or more metal β-diketonates complexed with an amine is utilized. The liquid mixture is evaporated to form a vapor mixture, optionally mixed with an oxygen-containing gas such as air and an inert carrier gas such as nitrogen. The vapor mixture is heated to a temperature sufficient to cause a reaction to form a material comprising two or more metal oxides. Alternatively, the reaction may be triggered by light or by the electrical energy of the plasma emission.

In another embodiment of the present invention, the multi-metal oxide is one or more complexed with one or more volatile metal-containing compounds and an amine in a deposition process described herein. Formed from a solution with a plurality of metal β-diketonates and a solvent. This method may be used to form a multi-metal oxide coating, including but not limited to barium ferrite, barium titanate, strontium bismuth tantalate, and barium strontium titanate.

Liquids of metal β-diketonates complexed with amines may also be used as undiluted or highly concentrated solutions in film deposition methods such as sol-gel formation, spray coating, or spin coating. Aryl-containing amines and / or high carbon number amines are well suited for such applications, and compounds having a higher carbon content of an alkyl or aryl group are less volatile than equivalent compounds having an alkyl-containing amine. May be obtained.

[0039] DETAILED DESCRIPTION OF THE INVENTION 1. Beta Diketone Ligand Table 1 lists the names of some beta diketone ligands that are suitable for the practice of the present invention. Table 1 also shows the number assigned by the chemical abstract to the compound. The general formula may be represented as ¹ RC (= O) CHR ³ C (= O) R ² , wherein ¹ R and R ² are alkyl groups,
It may be a fluoroalkyl group or an alkyl group containing an oxygen or nitrogen containing species (eg, an amino, alcohol, or alkoxy species). R ³ may be hydrogen or an alkyl group, a fluoroalkyl group, or an alkyl group containing an oxygen or nitrogen containing species. In a preferred embodiment, the alkyl group contains less than 10 carbons, preferably less than 7 carbons.

[0040]

Table 1 Some preferred β-diketone ligands

In this table, the number t is the number of twist angles corresponding to rotation around a CC single bond. The rotation angles of the methyl or tert-butyl groups with respect to the triple axis were not counted because these movements did not change the intermolecular interactions as much as other twists. As t increases, the number of configurations available to the ligand increases, thus increasing the ability of the compound to stop crystallization. Thus, the greater the t, the greater the ability of the ligand to maintain the compound in liquid form.

Some or all of the oxygen in the β-diketonate ligand may be replaced by sulfur or an isoelectric species such as NH or NR, wherein R is a hydrocarbon radical. For purposes of the present specification and claims, these isoelectrically substituted β-diketonate ligands should be considered as β-diketonate ligands.

Some or all of the hydrogens in the β-diketonate ligand may be replaced by fluorine. Fluorine substitution may be used to deposit fluoride instead of oxide. Fluorine substitution may also provide a higher vapor pressure of the precursor compound.

2. Synthesis of β-Diketonate Ligands The required β-diketone ligand may be prepared by known methods such as Claisen condensation of methyl ketone and ethyl ester in the presence of a strong base such as sodium hydride.

Embedded image For a detailed description of this technique, see Inorganic Synthesis, Vol. 23, 144.
Pp. 145 (1985).

A preferred method of synthesizing these β-diketone ligands is to first react the appropriate ketone with a strong base, such as sodium hydride, in the presence of an electron donor solvent, such as tetrahydrofuran (THF). Is to form a solution of sodium enolate:

Embedded image The enolate is then reacted with a suitable organic acid chloride, neutralized with a mineral acid, and filtered to remove the salt precipitate, forming the desired β-diketone:

Embedded image Then, distillation under low pressure gives the desired β-diketone in higher yield and better purity than conventional Claisen condensation. The excess starting ketone is recovered and recycled for further synthesis. This method is particularly effective when the R ² group is a tertiary alkyl group such as a tertiary butyl or tertiary amyl.

As a specific example of this method, the synthesis of β-diketone 2,2,6,6-tetramethyloctane-3,5-dione (Htod) is shown below. All experimental procedures were performed in nitrogen, either in glove boxes or Schlenk lines, unless otherwise specified. Sodium hydride (NaH) (14.23 g, 593 mmol) was added to dry tetrahydrofuran (THF
) Suspended in 400 ml and heated to 85 ° C. 4.4 m of pinacolone (70 ml, 560 mmol)
At l / min, hydrogen (H ₂ ) gas evolved vigorously after the first 10 ml. The addition was continued at a sufficiently low addition rate so that the reaction was not too violent and bubbles were not generated. After the addition was complete, the reaction was stirred at 85 ° C. until the bubbling ceased after about 10 minutes (ie, when no more bubbles were observed to pass through the oil bubbler that vented to the atmosphere). . The pale yellow suspension was then cooled to room temperature and filtered through celite to remove excess NaH. The clear pale yellow filtrate was cooled to 0 ° C. and the undiluted 2,2-dimethylbutyryl chloride (34.5 ml, 252 mmol) was added with stirring at 3.1 ml / min to give a very turbid pale yellow. A suspension was obtained. This was removed from the ice bath, stirred for 15 minutes and cooled again to 0 ° C. At this point, the mixture was 0.25 equivalent NaCl, 0.
It contained 25 equivalents of pinacolone, 0.25 equivalents of Na (β-diketonate), and 0.05 equivalents of Na (enolate). Next, 34 ml of concentrated aqueous HCl was added, resulting in a frangible white solid precipitate of NaCl in a clear, colorless solution. MgSO ₄ was added in an amount sufficient to absorb water and the mixture was stirred for 30 minutes before being filtered. The solid was washed with 100 ml of hexane and the washing was combined with the filtrate. Removal of the solvent and excess pinacolone using distillation gave a pale yellow liquid (46.02 g, 92%), which was analyzed by NMR analysis for the desired product, ie, 2,2,6,6-tetramethyloctane. -3,5-dione (Htod). The product was distilled at 147 mbar at 149 mbar.

Other β-diketones are obtained by substituting other ketones for pinacolone
And / or produced in a similar manner by substituting other acid chlorides for 2,2-dimethylbutyryl chloride. For β-diketones where R ³ = methyl, the required ethyl ketone is not commercially available. These ethyl ketones were synthesized by ethylating the appropriate commercially available acid chloride with diethylaluminum chloride as the ethyl source according to the following reaction:

Embedded image

As a specific example of this method, tert-amylethyl ketone (4,4-dimethyl-3-hexanone) was formed as follows: 21.3 ml of 2,2-dimethylbutyryl chloride were dried and dried. The solution was cooled to 30 ° C., mixed with 40 ml of degassed dichloromethane, CH ₂ Cl ₂ . Diethylaluminum chloride dissolved in _{CH 2 Cl 2 40 ml, (} CH 3 CH 2) 2 AlCl 19.18 g
Was added at a rate of about 1 drop / sec while maintaining the temperature of the reaction mixture at -35 to -30 ° C. The first few drops produced some smoke, after which the smoke disappeared. After complete addition,
The liquid solution was warmed at 25 ° C. for 1 hour and stirred at 25 ° C. for another hour. The solution was transferred slowly to the mixture which is stirred vigorously sulfate H ₂ SO ₄ 25 ml, 25 ml of water and ice 250 g by the cannula. A white precipitate formed with some foam, after which the precipitate gradually dissolved. The organic phase was removed, the aqueous phase was washed with dichloromethane, and the organic phase and the combined washings were dried over magnesium sulfate MgSO ₄ . Filter the mixture,
Removal of the solvent from the filtrate under reduced pressure gave 11.33 g (57%) of a very pale yellow liquid. NMR confirmed that the product was 4,4-dimethyl-3-hexanone.

No commercial raw material is found for tert-amyl methyl ketone, which is necessary to make some of the preferred β-diketones. Tert-amyl methyl ketone is prepared by converting 2,2-dimethylbutyryl chloride to methylaluminum sesquichloride Me ₃ A using a method similar to that just described for 4,4-dimethyl-3-hexanone.
It can be synthesized by methylation with l ₂ Cl ₃ .

[0050] 3. Synthesis of Alkaline Earth β-Diketonates Compounds can be formed between these β-diketonate ligands and most metals. The two ligands can bind to metal ions in oxidation state +2, including beryllium, magnesium, calcium, strontium, and barium. Many different reactions can be used to attach a beta-diketonate ligand to a metal. Particular examples of methods of preparation are described in Inorganic Syntheses, Volume 2, pages 17-20 (1946) for beryllium; and calcium,
For strontium and barium, see Vol. 31, pp. 1-7 (1997). In particular, an alkaline earth metal may be reacted with a β-diketone ligand to form a metal β-diketonate compound:

Embedded image

As a specific example of this method, the preparation of 2,2,6,6-tetramethyl-3,5-octanedione barium, Ba (tod) ₂ is described below. When 1.29 g of barium metal and 3.728 g of 2,2,6,6-tetramethyl-3,5-octanedione (tod) were added to the flask, hydrogen bubbles began to be generated immediately. The reaction appeared to be slower with the addition of 25 ml of benzene. After bubbling ammonia gas through the mixture for 2 minutes, the generation of bubbles became severe. After 30 minutes, bubble formation slowed and ammonia was bubbled again for 5 minutes. The process was continued for 4 hours until almost no metal remained. The pressure was reduced for a few minutes to remove the dissolved ammonia. The mixture was then filtered through celite to give a clear, colorless solution. The benzene solvent is removed by evaporation under reduced pressure to yield a glassy solid
3.9 g (78%) were obtained.

[0052] 4. Amine A variety of amines may be used in the practice of the present invention. Polyamines having 2, 3 or 4 nitrogens are preferred, but triamines (3 nitrogens) are most preferred. Some specific preferred amines are listed in Table 2, as well as the numbers assigned by Chemical Abstract Services to those amines already reported.

[0053]

Table 2 Some preferred amines of the general formula, R ^a R ^b NCH ₂ CH ₂ (NR ^a CH ₂ CH ₂ ) _n NR ^a R ^b The numerical value t in Table 2 is the angle variable (the torsion angle corresponding to the rotation around the CC single bond).
Is the number of Angles that caused the methyl or tert-butyl groups to rotate about three times their axis were not counted, as these movements did not change the intermolecular interactions as much as other twist angles. As t increases, the number of configurations available to the amine increases, thus increasing the ability of the amine addition product to inhibit crystallization. Such higher t increases the ability of the amine to maintain the addition product compound in liquid form and reduce viscosity and melting point.

Some or all of the hydrogen atoms in the amine ligand may be replaced with fluorine.
Fluoride may be deposited instead of oxide using fluorine substitution. Fluorine substitution may also provide a higher vapor pressure of the precursor compound.

[0055] 5. Amine Synthesis The amines required in the practice of the present invention can be synthesized by a number of methods. For embodiments using a polyamine where all nitrogens are saturated with the same alkyl group, it is convenient to use reductive alkylation using an aldehyde as the alkyl source and sodium cyanoborohydride as the reducing agent. For example, when fully alkylating a triamine, the general reaction is shown as follows:

Embedded image

In one embodiment using this type of amine, the R group in this formula is a methyl group. Thus, the pendant group on the nitrogen is an ethyl group, and the amine is N, N,
N ', N ", N" -pentaethyldiethylenetriamine, abbreviated as pedeta. This material, according to published methods with respect to similar reactions, prepared by reacting diethylene triamine _{H 2 NCH 2 CH 2 NHCH 2} CH 2 NH 2 with acetaldehyde CH ₃ CHO, sodium cyanoborohydride NaBH ₃ CN in acetonitrile solution (RF Borch and AI Hassid), Journal of Organic Chemistry
37, 1673-1674, 1972).

In another preferred embodiment, it is desirable to attach two different groups to each terminal nitrogen. Thus, more randomness and disorder are incorporated into the molecule, further inhibiting crystallization and maintaining the disordered liquid state of the material. A particularly desirable form of this embodiment combines a small group such as a hydrogen or methyl group on each terminal nitrogen with a second larger group such as a butyl, amyl (pentyl), or hexyl group. The presence of smaller groups also allows for a tight bond with the metal center with a minimum of steric bulk of the ligand. The synthesis of this type of polyamine can be carried out as follows. A commercially available unsubstituted polyamine is first acylated with an anhydride under conditions that allow only one acyl group to be attached to each nitrogen. Next, the obtained polyamide is reduced with lithium aluminum hydride.

Embedded image

According to this method, the terminal nitrogen has one hydrogen (secondary amine), and the skeleton nitrogen or plural nitrogens have an alkyl group and do not directly bind hydrogen (tertiary amine). A polyamine is obtained. This N, N ', N'' - triethyl diethylenetriamine _{(tedeta), (CH 3 CH} 2 NHCH 2 CH 2) 2 NCH 2 CH 3, N, N', N '' - tri diethylenetriamine (tpdeta), ( _{CH 3 (CH 2) 2 NHCH} 2 CH 2) 2 N (CH 2) 2 CH 3, N, N ', N''- tributyl diethylenetriamine _{(tbdeta), (CH 3 (} CH 2) 3 NHCH 2 CH 2) ₂ N (CH ₂ ) ₃ CH ₃ ,
N, N ', N'' - triamyl diethylenetriamine _{(tadeta), (CH 3 (} CH 2) 4 NHCH 2 CH 2) 2 N
(CH ₂ ) ₄ CH ₃ , and N, N ′, N ″ -trihexyldiethylenetriamine (thdeta), (C
_{H 3 (CH 2) 5 NHCH} 2 CH 2) is suitable for generating _{2 N (CH 2) 5 CH} 3.

The preparation of triethyldiethylenetriamine (tedeta) by this method is as follows: diethylenetriamine H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ NH _{2 A} solution of 10 ml of diethyl ether in 40 ml (Et ₂ O) is treated with acetic anhydride (Et ₂ O). CH ₃ CO) ₂ O was added at a rate of 2 drops / sec to 70 ml of a 0 ° C. Et ₂ O solution of 46 ml. After the addition was complete, the solution was stirred at 25 ° C. for 30 minutes and then refluxed for 2 hours. The solution was cooled and the solvent and acetic acid by-product were evaporated, yielding a very viscous light brown liquid. This material was dissolved in 100 ml of tetrahydrofuran (THF) and slowly added dropwise to a solution of 23 g of LiAlH _{4 in} 100 ml of THF. The heat of the reaction was maintained at reflux. Bubbles were generated at each drop (perhaps due to reaction with traces of residual acetic acid). After the addition was complete, the mixture was maintained at reflux for an additional hour until bubbling ceased. After cooling to 0 ° C., the mixture was quenched with 23 ml of water, 23 ml of 15% aqueous sodium hydroxide (NaOH), 200 ml of hexane and finally 69 ml of water. The mixture was filtered, the solid was washed with 150 ml of hexane, and the combined organic liquid was dried over magnesium sulfate. After several hours, the magnesium sulfate hydrate was filtered off and the solvent was removed in vacuo to give a colorless liquid. Distillation at 25 mbar pressure yielded 11.3 g of the main fraction at 109-111 ° C (65%, based on diethylenetriamine). NMR confirmed that the product was N, N ′, N ″ -triethyldiethylenetriamine (tedeta). When acetic anhydride is replaced with propionic anhydride, butyric anhydride, valeric anhydride, or hexanoic anhydride in this method, N,
N ', N "-tripropyldiethylenetriamine (tpdeta), N, N', N" -tributyldiethylenetriamine (tbdeta), N, N ', N "-triamyldiethylenetriamine (t
adeta), or N, N ', N "-trihexyldiethylenetriamine (thdeta).

The dialkylethylenediamine was prepared by the following reaction:

Embedded image

Synthesis of N, N ′, N ″ -dihexyldiethylenetriamine (thdeta), (CH ₃ (CH ₂ ) ₅ NHCH ₂ ) ₂ : In a 500 ml flask, ethylenediamine (7.79 ml, 120 mmol) was added to tetrahydrofuran 150 Dissolved in ml. To this solution, add hexanoic anhydride (59.44 ml
, 260 mmol) was added dropwise over 40 minutes with vigorous stirring and the solution became very turbid. The reaction was then refluxed at 78 ° C. for 4 hours. The excess anhydride was quenched by the addition of 0.2 ml of distilled water and volatiles including hexanoic acid, a by-product, were removed in vacuo. The resulting solid amide was washed twice with 25 ml of hexane on a Buchner funnel (under air) and compressed and dried. In another 500 ml flask, lithium aluminum hydride (11.5 g, 300 mmol) was suspended in 150 ml of diethyl ether and cooled to 0 ° C. The previously synthesized solid powder amide was gradually added while generating H ₂ gas. The amide addition rate must be slow enough to control foam formation. The mixture was refluxed at 37 ° C. overnight. The resulting mixture was then cooled to 0 ° C. and quenched as follows: 1) Water (11.6 g, 640 mmol) was added dropwise with vigorous stirring. 2) If the mixture becomes increasingly cloudy, a 15% w / w aqueous solution of sodium hydroxide (11.
6 g) was added dropwise with vigorous stirring. Hexane was added in sufficient quantity so that the mixture was not too hard to stir. 3) When water (34.8 g, 1.93 mol) was added again, the mixture became easier to stir. The solution was filtered and the filtrate was stirred with magnesium sulfate overnight. The mixture was filtered and volatiles were removed in vacuo to give clear, colorless dihexylethylenediamine (dheda). Then dheda
Was distilled at 84-90 ° C. under a vacuum of 90 mTorr (15.5 g, 58% yield). NMR: C ₆ D ₆ in in ¹ H (2.62,4 protons, singlet), (2.52,4 protons, triplet), (1.42,
(4 protons, quartet), (1.26, 12 protons, multiplet), (0.88, 6 protons,
Triplet).

In this method, when hexanoic anhydride is replaced with butyric anhydride or valeric anhydride, N, N′-dibutylethylenediamine (dbeda), (CH ₃ (CH ₂ ) ₃ NHCH ₂ ) ₂ , or N, N ′, respectively. - diamyl ethylenediamine (daeda), it is _{(CH 3 (CH 2) 4} NHCH 2) 2 is obtained.

Related preferred amines have one methyl group attached to each terminal nitrogen in addition to the —CH ₂ R group. Polyamines of this type can be formed from the abovementioned polyamines by reductive methylation using formaldehyde and a reducing agent such as formic acid (Clark-Eschweiler method):

Embedded image Detailed descriptions for performing this type of reaction are provided by Icke, RN Icke, BB Wisegarver and GA Alles, Organic Synthesis (Organic S.
3, volume 723-725 (1955). This method comprises N, N′-diethyl-N, N′-dimethylethylenediamine (dedmeda), N, N ′, N ″ -triethyl-N, N′-dimethyldiethylenetriamine (tedmdeta), N, N′-dimethyl -N,
N ', N''-tripropyldiethylenetriamine (dmtpdeta), N, N', N ''-tributyl
-N, N'-dimethyldiethylenetriamine (tbdmdeta), N, N ', N''-triamyl-N,N'
-Dimethyldiethylenetriamine (tadmdeta) and N, N ', N''-trihexyl-N
Suitable for the synthesis of amines such as, N'-dimethyldiethylenetriamine (thdmdeta).

[0064] 6. Synthesis and Utilization of Alkaline Earth Metal β-Diketonate Complexed with Amine The novel metal β-diketonate complexed with an amine of the present invention is a suitable amine converted to an alkaline earth metal β-diketonate (M (β-dk) It may be formed by simply reacting with ₂ ). (M (β-dk) ₂ ) + amine → (M (β-dk) ₂ ) amine The liquid amine and the product act as a solvent for the reaction. If the amine addition product is a solid, a small amount of solvent needs to be added to facilitate the reaction. Alternatively, the reaction to form the alkaline earth metal β-diketonate may be performed in the presence of an amine.

Larger alkaline earth metal, barium and strontium β-diketonates may use amines with up to 4 nitrogen atoms coordinated to the metal, while smaller calcium usually binds only a few nitrogen There are three and magnesium usually has only two nitrogens attached.

The novel metal β-diketonates complexed with the amines of the present invention are generally liquid at room temperature. These liquid vapors may be formed in a thin film deposition apparatus or by spraying into a carrier gas preheated to about 250 ° C. Spraying may be performed pneumatically or ultrasonically. Alkaline earth metal β complexed with amine
Diketonates are generally used in organic solvents including hydrocarbons such as dodecane, tetradecane, xylene and mesitylene, as well as alcohols, ethers, esters,
Completely miscible with ketones and chlorinated hydrocarbons. These solutions generally have lower viscosities than pure liquids, and in some cases it may be preferable to spray and evaporate the solution over pure liquids. Metal beta-diketonates complexed with their amines, which are solid at room temperature, are generally very soluble in organic solvents. Such solutions can also be deposited by thin film deposition equipment or spraying. Thin film deposition equipment is manufactured by Artisan Industries (Waltham, Mass.). Commercial equipment for direct liquid evaporation (DLI) is available from MKS Instruments (Andover, Mass.), Advanced Technology Materials Inc. (Danbury, Connecticut), Novellus Systems Inc. (San Jose, Calif.) And COVA Technologies (Chiverton) ,
California). Ultrasonic atomizers are manufactured by Sonotec Corporation (Milton, NY) and Setac Technologies (Omaha, NE).

The method of the present invention can be performed by standard equipment well known in the chemical vapor deposition (CVD) art. CVD equipment contacts a vapor of a reactant with a heated substrate onto which material is deposited. CVD processes can operate at a variety of pressures, including certain normal atmospheric pressures, and lower pressures. Commercially available atmospheric pressure CVD furnaces are manufactured in the United States by Watkins Johnson (Scotts Valley, Calif.), BTU International (North Billerica, Mass.) And Sierra Term (Watsonville, Calif.). Commercially available atmospheric pressure CVD equipment for coating glass on float production lines are available in the United States from Pilkington-Liby-Owens Ford (Toledo, Ohio), PPG Industries (Pittsburgh, PA), and AFG Industries (Kings Port, Tennessee). Low-pressure CVD equipment includes Applied Materials (Santa Clara, CA), Spire Corporation (Bedford, Mass.), Materials Research Corporation (
Gilbert, Arizona), Novellus Systems, Inc. (San Jose, CA), Encore Corporation (Somerset, NJ),
And NZ Applied Technologies (Woburn, Mass.).

The liquids and solutions described herein may also be used as metal-containing precursors for other types of deposition processes such as spray coating, spin coating, or sol-gel formation of mixed metal oxides. The high solubility and miscibility of these precursors is an advantage in forming the required solution.

Example 1 A liquid compound was composed of Ba (thd) ₂ and N, N ′, N ″ -trihexyldiethylenetriamine (thd
After reacting equimolar amounts of eta) in hexane until all solids were dissolved, the solution was prepared by warming under reduced pressure to remove hexane. A viscous pale yellow liquid remained. The compound is a monomer as determined by the freezing point depression method. The viscosity of this liquid compound is increased by the additional N, N ', N''for easier handling and evaporation.
It can be reduced by dissolving it in a high boiling solvent such as a hydrocarbon such as trihexyldiethylenetriamine (thdeta) or mesitylene. When such a solution was sprayed ultrasonically and passed through a tube furnace at 250 ° C., it completely evaporated to mist drops, demonstrating its usefulness as a vapor source.

Examples 2 to 9 Using the same method, liquid compounds of barium β-diketonate and amine shown in Table 3 were formed and volatilized.

[0071]

Table 3 Liquid amine complex of barium β-diketonate

As shown in Table 3, all liquid compounds of barium β-diketonate and amine have an angle variable of 7 or more. All liquids with the lowest viscosity have an angle variable of 15
Or more. Liquids with an angle variable less than 10 are very viscous. Molecular weights were determined by freezing point depression in p-xylene solution for four of the compounds and gave values similar to those expected for the monomer ("molecular complexity" was approximately 1).

Examples 10-17 Other combinations of barium β-diketonate and amine were found to be solid at room temperature and had low melting points, typically below 100 ° C, more preferably below 60 ° C. there were. They are very soluble in organic solvents and their concentrated solutions can be used in liquid injection systems. Typical preferred concentrations are above 1 molar, but lower concentrations, such as 0.5 molar, result in lower viscosity solutions. Table 4 describes some of these very soluble solid compounds of barium β-diketonate with amines.

[0074]

Table 4 Examples of solid barium β-diketonate amine compounds with low melting point and high solubility As shown in Table 4, all of these examples of low melting, highly soluble solids have additional angular variables of 3-10.

Example 18 Synthesis of Sr (tod) ₂ : Strontium metal (1.82 g, 21 mmol) and 2,2,6,6-tetramethyloctane-3,5-dione (Htod) (8.23 g, 42 mmol) ) Were mixed in the flask; air bubbles began to evolve from the metal surface. Add tetrahydrofuran (thf) 7
5 ml was added and NH ₃ gas was bubbled through the solution via syringe for 1 minute. The reaction became very vigorous and was stirred for 2 hours, with periodic bubbling of NH ₃ through the solution to maintain activation of the metal. The NH ₃ was removed in vacuo and the solution was filtered to remove any small amount of suspended powder. Removal of the volatiles in vacuo gave a waxy white solid. This solid was pumped at 60 ° C. for 3 hours to completely remove thf from Sr (tod) ₂ (6.5 g, 65% yield). ¹ H NMR (in CDCl ₃ ): (5.57 ppm, 1 proton, wide singlet)
, (1.42 ppm, 2 protons, quartet), (1.05 ppm, 9 protons, singlet), (
1.01 ppm, 6 protons, singlet), (0.72 ppm, 3 protons, triplet).

Synthesis of Sr (tod) ₂ thdeta: In a 10 ml flask, Sr (tod) ₂ (1.16 g, 2.4 mmol)
And N, N ′, N ″ -trihexyldiethylenetriamine (0.849 g, 2.4 mmol) were mixed with 5 ml of benzene. The solution was stirred for several minutes until the solid dissolved. Obtained Sr (to
d) The ₂ · thdeta solution was stirred at 50 ° C. for 3 hours in vacuo to remove benzene. The resulting liquid had a viscosity at 40 ° C. of 489 centipose. Spray the liquid ultrasonically, 250 ℃
After passing through a tube furnace, the water vaporized completely into mist-like water droplets, proving its usefulness as a vapor source.

Examples 19 to 22 Strontium β-diketonate in Table 5 was synthesized by a method similar to that described in Example 18.

[0078]

TABLE 5 Strontium β-diketonate liquid amine complex Viscosity is higher than that of C, which rotates alkyl groups that are less symmetric than methyl or tert-butyl groups
It decreases as the number of -C single bonds (described in the column of #var in Table 5) increases. For strontium compounds, the lowest viscosities were observed for compounds with an angular variable of 12 or more.

After several weeks at room temperature, one batch (out of four) of St (thd) ₂ -taeda partially crystallized. X-ray analysis of the crystal showed three unequal monomer molecules,
One of them is shown in FIG. The other two molecular units show similar seven-coordinate strontium centers, but differ in the twist angles of the three pentyl chains attached to the three nitrogens. Freezing point depression showed that the amine complexing material was also monomeric in the p-xylene solution. This structure is described in E. Berg and NM Herre
ra, Anal. Chem. Acta, Vol. 60, p. 117 (1972)); Drake, Haas Source, Malik & Otway (SR Drake, MB Hurtsthouse, KMA Malik and DJ)
As shown by Otway, J. Chem. Soc. Dalton Trams, 1993, p. 2883), in contrast to the absence of amine ligands, Sr (thd) ₂ in crystalline solids exhibits trimeric properties. is there.

All of the strontium compounds in Table 5 successfully and instantaneously evaporated.

Examples 23 to 26 The liquid calcium compounds described in Table 6 were prepared. The following method is typical.

Synthesis of Ca (thd) ₂ : Ca particles (0.54 g, 13.5 mmol), 2,2,6,6 in a 100 ml round bottom flask
-Tetramethylheptane-3,5-dione (Hthd) (5.0 g, 27.1 mmol) and ethanol (2.50 g, 54.3 mmol) were mixed in 30 ml of tetrahydrofuran (thf),
Refluxed overnight. A very small amount of the black suspended powder was removed by filtration. Volatiles were removed in vacuo to give a clear filtrate. Next, the white solid was dried under vacuum at 50 ° C. for 3 hours to obtain 4.43 g of Ca (thd) ₂ (yield 86%). ¹ H NMR (d ₅ - in pyridine) :( 5.92 ppm, 1 protons, singlet), (1.23 ppm, 18 protons, singlet)
.

Synthesis of Ca (thd) ₂ .dheda: In a 5-drum vial, add Ca (thd) ₂ (1.00 g, 2.4 mmo
l) was combined with N, N'-dihexylethylenediamine (dheda) (0.56 g, 2.4 mmol) and heated to 45 ° C. Transparent liquid Ca (thd) ₂ · dheda was formed quantitatively. ¹ H
NMR (d ₅ - in pyridine) :( 5.91 ppm, 2 protons, singlet), (2.77 ppm, 4 protons, multiplet), (2.64 ppm, 4 protons, quartet), (1.68 ppm, 2 protons, Multiplet), (1.51 ppm, 4 protons, quartet), (1.23 ppm, 36 protons,
(Singlet), (1.1-1.4 ppm, 6 protons, broad multiplet), (0.83 ppm, 6 protons, triplet).

[0084]

TABLE 6 Liquid amine complex of calcium β-diketonate

The calcium compounds in Table 6 all successfully evaporated instantaneously.

Examples 27 to 31 The liquid magnesium compounds described in Table 7 were prepared. Magnesium β-diketonate was formed by reacting magnesium ethoxide with the appropriate Hβ diketone:

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Synthesis of Mg (thd) ₂ : In a 100 ml round bottom flask, Mg (OEt) ₂ was added with dimethoxyethane (DME
) And a DME solution of 2,2,6,6-tetramethylheptane-3,5-dione (Hthd) was added via cannula. The solution was refluxed at 90 ° C. overnight. The resulting cloudy solution was solidified in vacuo and dissolved in 50 ml of tetrahydrofuran (thf). A small amount of solid was filtered off and volatiles were removed again to give 5.6 g (82% yield) of white Mg (thd) ₂ . ¹ H NMR (d ₅ - in pyridine) :( 5.75 ppm, 1 protons, singlet), (1.23
ppm, 18 protons, singlet).

Synthesis of Mg (thd) ₂ .dheda: In a 10 ml flask, Mg (thd) ₂ (3.80 g, 97.0 mmol)
And theda (2.22 g, 97.0 mmol) were mixed without addition of solvent. After gentle warming, a clear, slightly yellow liquid Mg (thd) ₂ .dheda was formed. This material at 72 ° C
Distilled at 7 mTorr (4.03 g, 67% yield). NMR: ¹ H (5.76, 2 protons, singlet), (2.58 ppm, 4 protons, broad singlet), (2.41 ppm, 4 protons, broad multiplet), (1.46 ppm, broad singlet) in C ₆ D ₆ Term, 2 protons), (1.40-1.10 ppm, 1
6 protons, broad multiplet hidden under singlet), (1.26 ppm, 18 protons, singlet), (0.90 ppm, 6 protons, triplet).

[0089]

[Table 7] Liquid amine complex of magnesium β-diketonate

In the case of the magnesium compound, a low viscosity was recognized in a compound having a small angle variable of 8. All of the magnesium compounds in Table 7 evaporated instantaneously, and the three compounds whose vapor pressures were described were successfully vacuum distilled under the given conditions.

Example 32 Ba (thd) ₂ · thdeda from Example 1 was sprayed from a sonotec ultrasonic nozzle projecting into a stream of nitrogen gas at 80 Torr pressure preheated to 250 ° C. The atomized water droplets evaporated to form a clear vapor mixture. The steam mixture was passed through a 450 ° C. tube furnace. A coating on barium carbonate BaCO _{3 was} deposited on the inner wall of the tube furnace, on a silicon substrate placed inside the heating zone of the furnace.

Example 33 Titanium bis (n-butoxide) bis (tod) was formed by reacting titanium n-butoxide with Htod. 5.78 g (0.017 mol) of titanium n-butoxide was placed in a glass reaction flask, and 15 ml of hexane was added. Htod 6.74 g (0.034
mol) was added and stirred for 10 minutes, and the hexane solvent was removed in vacuo. N is a by-product
The reaction mixture was heated to 80 ° C. in vacuo to remove butanol until no further bubbling occurred. 9.65 g (97%) of a clear, pale yellow liquid titanium bis (n-butoxide) bis (tod) product was recovered.

An equimolar amount of Ba (thd) ₂ .thdeta of Example 1 and titanium bis (n-butoxide) bis (tod) were mixed. The liquid mixture was pumped into the ultrasonic atomizer at a flow rate of 0.10 cc / min, through which 400 standard cc / min of nitrogen gas was bubbled at 80 torr.
The resulting mist was mixed with dry air flowing at 200 standard cc / min, and the combined mixture was heated at 80 Torr and a tube reactor (internal diameter 25 mm
). A clear coating was formed on the inner wall of the tube along with the glass and the silicon substrate of the tube furnace. The coating was determined by RBS to be barium titanate, BaTiO ₃ with some carbon contaminants. Carbon was removed by annealing at 600 ° C. for 10 minutes in a stream of oxygen gas.

Example 34 A CVD similar to Example 33, wherein the precursor of barium from Example 1, strontium from Example 18, and titanium from Example 33 were mixed in a molar ratio of 7: 3: 10. The experiment was performed at a substrate temperature of 500 ° C. The resulting barium strontium titanate coating contained any carbon contaminants, which were removed by annealing at 600 ° C. for 10 minutes in a stream of oxygen gas.

Examples 35-39 Several additional examples of liquid barium compounds were prepared. These examples showed even lower viscosities than the other barium compounds listed in Tables 3 and 4. 2,2,
Barium compounds based on 6-trimethylheptane-3,5-dione (H3hd) ligand have a particularly low viscosity, and these liquids can be easily handled.

[0096]

Table 8 Further examples of liquid barium compounds

The liquid precursor of the present invention, in combination with bismuth and tantalum precursors,
A method of depositing a strontium bismuth tantalate coating having ferroelectric properties may be provided. Similarly, barium ferrites having magnetic properties may be formed by combining iron-containing precursors with the precursors of the present invention.

The liquids and solutions disclosed in these examples all appeared to be non-combustible according to methods published by the United States Department of Transportation. One test requires that about 5 ml of the liquid or solution be placed on a non-flammable porous solid so that no spontaneous combustion occurs. Another test involves dropping 0.5 ml of the liquid or solution onto Whatman 3 filter paper and observing that no burning or charring of the paper occurs.

[0099] Precursors generally react slowly with moisture in the surrounding air and must be stored in a dry atmosphere such as nitrogen.

It will be apparent to those skilled in the art that many equivalents to the specific embodiments herein which are specifically described herein may be ascertained using recognition or routine-only experimentation.
Such equivalents are to be interpreted as falling within the scope of the appended claims.

[Brief description of the drawings]

FIG. 1 shows a compound of strontium bis (2,2,6,6-tetramethylheptane-3,5-dionate) and N, N ′, N ″ -triamyldiethylenetriamine (Sr (thd) ₂ · t
x-ray crystal structure of the compound (can be abbreviated as adeta).

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C23C 16/40 C23C 16/40 // C07F 3/00 C07F 3/00 EF 3/02 3/02 Z 3/04 3/04 7/28 7/28 F 9/00 9/00 Z 9/94 9/94 (81) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR , GB, GR, IE, IT, LU, MC, NL, PT, SE), CA, JP, KR, US (72) Inventor Teff Daniel Mesa East Superstition Springs Boulevard 7125 Arizona, USA Unit 4 / 28- Building 3 Apartment 2007 F-term (reference) 4H006 AA01 AA03 AB91 4H048 AA01 AA03 AB91 VA60 VB10 4H049 VN05 VP01 VQ24 VU24 4H050 AA01 AA03 AB91 4K030 AA11 BA01 BA18 BA42 FA10

Claims (21)

[Claims] 1. Alkaline earth metal β-diketonate (and its isoelectric derivatives)
A composition of matter for use in the formation of alkaline earth-containing materials, comprising a compound comprising: and a compound which is liquid at 60 ° C. and is capable of evaporating. 2. An alkaline earth metal β-diketonate (and its isoelectric derivative)
A composition of matter used in the formation of alkaline earth-containing materials, comprising a compound comprising: and a compound which is liquid at 20 ° C. and is capable of evaporating. 3. The β-diketonate has the following formula: ¹ RC (= O) CHR ³ C (= O) R ² , wherein ¹ R and R ² are independently selected, an alkyl group, a fluoroalkyl And R ³ can be hydrogen, an alkyl group, a fluoroalkyl group, or an alkyl group substituted with another element, wherein the group is an alkyl group substituted with another element, or an aryl group substituted with another element. Composition of the substance. 4. The composition according to claim 3, wherein the ¹ R and R ² groups contain 4 or 5 carbons. 5. The composition of claim ^{3, wherein the} R ³ group contains less than 2 carbons. 6. The composition according to claim 4, wherein the β-diketonate ligand is selected from the ligands listed in Table 1 of the specification. 7. An amine having the formula: R ^a N (R ^b ) CH ₂ CH ₂ {N (R ^c ) CH ₂ CH ₂ } _n N (R ^d ) R ^e , wherein R ^a , R ^b , R ^c , R ^d , and R ^e are independently selected and are hydrogen or an alkyl group, a fluoroalkyl group, an alkyl group containing an oxygen or nitrogen-containing species, or an aryl group, wherein n is a negative integer 3. A composition of matter according to claim 1 or claim 2, which is not. 8. The composition of matter according to claim 7, wherein the value of n is 0, 1, or 2. 9. The composition of matter according to claim 7, wherein the value of n is 1. 10. The composition of claim 7, wherein at least one of the R ^a , R ^b , R ^c , R ^d , and R ^e groups contains more than one carbon atom. 11. The composition of matter of claim 7, wherein the amine is selected from Table 2 of the specification. 12. The composition of matter of claim 1, wherein the amine complex of barium β-diketonate is selected from Table 4 of the specification. 13. The composition of matter of claim 2, wherein the compound is selected from Tables 3, 5, 6, 7 or 8 of the specification. 14. The composition of matter of claim 1, wherein the compound has a solubility in a liquid solvent of greater than 1 mole. 15. The composition of matter according to claim 1, wherein the compound has a solubility in the liquid solvent of greater than 0.5 mole. 16. A method of forming a material comprising an alkaline earth metal, comprising: providing a liquid comprising a compound comprising an alkaline earth metal β-diketonate (and its isoelectric derivative) and an amine; And, in a deposition process, contacting the liquid or its vapor with a heated surface to deposit a material containing an alkaline earth metal. 17. The method of claim 16, wherein the deposited material comprises one or more metal oxides. 18. The method of claim 16, wherein the metal or metals are selected from the group consisting of barium, strontium, and titanium. 19. The method of claim 16, wherein the metal or metals are selected from the group consisting of strontium, bismuth, niobium, and tantalum. 20. The method of claim 16, wherein a sol-gel process is used to deposit the material comprising one or more metals or metal oxides. 21. The method according to claim 16, wherein a spray coating or spin coating process is used to deposit the material comprising one or more metals or metal oxides.