KR101973700B1 - Manganese aminoamide amide precursors, preparation method thereof and process for the formation of thin film using the same - Google Patents

Abstract

The present invention relates to a novel manganese precursor having improved thermal stability and volatility, and a method for easily producing a high-quality manganese-containing thin film at an excellent growth rate at a low temperature by using the manganese precursor and a thin film produced thereby can do.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a manganese aminoamide amide precursor, a method for producing the same, and a method for forming a thin film using the same. BACKGROUND ART [0002]

More particularly, the present invention relates to a manganese aminoamide amide precursor having improved thermal stability and volatility and capable of easily producing a high quality manganese-containing thin film at a low temperature, a method for producing the same, And a thin film produced therefrom.

Silicon is advantageous in terms of physical properties, lifetime, and performance stability, but vacuum deposition and annealing are required to form a thin film. Costly display equipment is costly. In this regard, efforts are recently being made to use a metal oxide material as a semiconductor channel layer, which metal oxide has the potential of being a transparent element.

Manganese oxides present in various forms such as MnO, Mn ₃ O ₄ , Mn ₂ O ₃ and MnO ₂ are used for the production of electrode materials, electrochemical capacitors and soft magnetic materials . The manganese oxide is used as a substrate to synthesize a metal oxide perovskite compound having various electrical and magnetic properties such as colossal magnetoresistance and metal-insulator transitions. In particular, MnO ₂ exhibits electrochromic properties and is used as a catalyst for oxidation of hydrocarbons, oxidation and reduction of nitrogen oxides, and decomposition of ozone.

The manganese or manganese nitride (MnN _x ) thin film can be used as an electrode material of a semiconductor or a diffusion barrier film. Particularly, the manganese thin film can be used as an organic semiconductor electrode and a ferromagnetic electrode. The manganese nitride thin film can be used as a diffusion barrier film of copper and an adhesive layer of copper in the back-end-of- which is expected to be used as an adhesion layer.

Methods for preparing manganese-containing thin films include solution chemical processes such as anodic oxidation, electrodeposition, electrolytic deposition, spray-pyrolysis, and electorn beam evaporation, And is mainly manufactured by chemical vapor deposition (CVD), sputtering, molecular beam epitaxy, pulsed laser deposition, and the like. Currently, atomic layer deposition , ALD).

The precursors used for preparing manganese-containing thin films such as manganese, manganese nitride and manganese oxide include Mn (thd) ₃ , (thd = 2,2,6,6, -tetramethyl-3,5-heptanedionate) rate (manganese oxalate), manganese bis-cyclopentadienyl _{(MnCp 2, Mn (Me 4} Cp) 2, Mn (EtCp) 2), Mn (btsa) 2 (btsa = bis (trimethylsilyl) amide), bis (amide amino Homoleptic manganese precursors such as alkane and manganese are known. These precursors can lead to undesirable reactions on the gas, contamination by carbon or halogen, low thermal stability, low vapor pressure, deposition only at high temperatures, poor purity of the deposited film and poor surface roughness .

Manganese is an element in column 7 of the periodic table and the deposition of the manganese-containing thin film was still difficult due to the low thermal stability of the manganese source. As a result, there are few thermally stable, volatile manganese precursors available for CVD or ALD processes.

Therefore, when the manganese-containing thin film is produced by the CVD or ALD process, the degree of deposition, the control of the deposition, the crystallinity and the purity of the thin film to be formed are different depending on the characteristics of the manganese precursor used. It is necessary to develop a manganese precursor having excellent properties in terms of volatility and the like.

WO 2011/037090 WO 2012/060428

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems,

It is an object of the present invention to provide a novel manganese precursor which is improved in thermal stability and volatility and which is capable of easily producing a high quality manganese-containing thin film at a low temperature.

The present invention also provides a novel process for preparing the manganese precursor.

The present invention also provides a manganese-containing thin film deposition composition comprising the manganese precursor.

The present invention also provides a method for producing a manganese-containing thin film using the manganese precursor and a manganese-containing thin film prepared from the method.

In order to achieve the above object, the present invention provides a manganese aminoamide amide precursor represented by the following formula (1) as a novel manganese precursor.

[Chemical Formula 1]

In Formula ^1, R 1 to R ⁵ are each independently a C1 to a linear or branched alkyl group of C10, R ⁶ and R ⁷ are independently selected from C1 to C10 linear or branched alkyl group or tri (C1-C10) of each Alkylsilyl group; n is an integer of 1 or 2

The present invention also provides a method for preparing a manganese aminoamide amide precursor of Formula 1 by reacting a manganese compound of Formula 4 with a metal aminoamide of Formula 5 and a metal amide of Formula 6.

[Chemical Formula 4]

[Chemical Formula 5

[Chemical Formula 6]

In Formula 4 to 6, R ¹ to R ⁵ are each independently a C1 to C10 linear or branched alkyl group, R ⁶ and R ⁷ are each independently a C1 to C10 linear or branched alkyl group or tri (C1- of C10) alkyl silyl group, X ¹ and X ² is a halogen, M ¹ and M ² are each independently an alkali metal.

The present invention also provides a composition for thin film deposition comprising the manganese aminoamide amide precursor of Formula 1 above.

Also, the present invention provides a method for growing a manganese-containing thin film using the manganese aminoamide amide precursor of the above formula (1) and a manganese-containing thin film prepared therefrom.

The manganese precursor of the present invention is in the form of a heteroleptic dimer composed of two kinds of ligands of aminoamide and amide. It has lower toxicity than conventional homoleptic manganese precursor, and has properties of excellent thermal stability and volatility. A high-quality manganese-containing thin film, particularly a manganese thin film, a manganese nitride thin film or a manganese oxide thin film can be easily produced by using the same.

The manganese precursor of the present invention is an oxygen-free precursor, and can produce a manganese metal and a manganese nitride thin film which can be used as an electrode material of a semiconductor or a diffusion barrier film. In addition, the manganese precursor of the present invention can easily react with water (H ₂ O), oxygen (O ₂ ) or the like to form manganese oxides usable as raw materials for electrodes, magnetic materials, catalysts and the like of lithium ion batteries.

That is, the manganese aminoamide amide precursor according to the present invention is a precursor for manganese, manganese nitride, and manganese oxide thin films, a precursor for producing nano-sized manganese, manganese nitride and manganese oxide particles, and a precursor for producing LiAlMnO ₄ , LiCoMnO ₄ Lithium-manganese oxide for secondary battery), La _x Ca _y MnO ₃ (Self-cooling engine development), Mn / Ga alloy (magnetic-optical memory), and the like.

1 is TGA data of [Mn (etmpda) (diethylamino)] ₂ of Example 1. Fig.

Hereinafter, the present invention will be described in more detail. Unless otherwise defined, technical terms and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In the following description, And a description of the known function and configuration will be omitted.

The present invention relates to a heteroleptic manganese precursor to which two kinds of ligands having different reactivity are bonded, and more particularly to a manganese aminoamide amide precursor represented by the following formula (1).

[Chemical Formula 1]

In Formula ^1, R 1 to R ⁵ are each independently a C1 to a linear or branched alkyl group of C10, R ⁶ and R ⁷ are independently selected from C1 to C10 linear or branched alkyl group or tri (C1-C10) of each Alkylsilyl group; n is an integer of 1 or 2;

The manganese aminoamide amide precursor of the present invention is a novel compound having manganese as a central atom and having two ligands different from each other, that is, an aminoamide and an amide ligand, can have more improved volatility characteristics, . In addition, it has a merit of being in a solid state at room temperature and being easy to handle and having excellent storage stability. In addition, when a thin film is manufactured using the same, the growth rate of the thin film is excellent and a thin film can be manufactured at a relatively low temperature.

In one embodiment of the present invention, the manganese aminoamide amide precursor may be represented by the following general formula (2) or (3).

(2)

(3)

In Formula 2 and 3, R ¹ to R ⁵ are each independently a C1 to C10 linear or branched alkyl group, R ⁶ and R ⁷ are each independently a C1 to C10 linear or branched alkyl group or tri (C1- of C10) alkylsilyl group.

In one embodiment of the present invention, preferably, R ¹ to R ⁷ each independently may be a linear or branched alkyl group having ¹ to ⁷ carbon atoms, more preferably, R ¹ to R ⁷ are each independently C1 to C4 Of a linear or branched alkyl group.

In one embodiment of the present invention, R ¹ to R ⁷ are each independently selected from the group consisting of methyl, ethyl, propyl, iso-propyl, butyl, isobutyl iso-butyl or tert-butyl, more preferably R ¹ to R ⁴ are each independently methyl, R ⁵ to R ⁷ are each independently ethyl, propyl, isopropyl, butyl, Isobutyl or tert-butyl.

The present invention also provides a method for preparing the manganese aminoamide amide precursor of the above formula (1).

The manganese aminoamide amide precursor of Formula 1 may be prepared by reacting a manganese compound represented by Formula 4 with a metal aminoamide represented by Formula 5 and a metal amide represented by Formula 6.

[Chemical Formula 4]

[Chemical Formula 5

[Chemical Formula 6]

In Formula 4 to 6, R ¹ to R ⁵ are each independently a C1 to C10 linear or branched alkyl group, R ⁶ and R ⁷ are each independently a C1 to C10 linear or branched alkyl group or tri (C1- of C10) alkyl silyl group, X ¹ and X ² is a halogen, M ¹ and M ² are each independently an alkali metal.

In one embodiment of the present invention, the reaction can be carried out in an organic solvent. Although the organic solvent usable is not limited, it is preferable to use an organic solvent having a high solubility with respect to the reactants, Preferably, hexane, diethylether, toluene, tetrahydrofuran (THF) and the like can be used, and more preferably tetrahydrofuran can be used.

The metal aminoamide of Formula 5 may be prepared by a known method. For example, the metal aminoamide of Formula 5 may be prepared by reacting diaminoethane of Formula 7 with an alkyl metal compound of Formula 8 below.

(7)

[Chemical Formula 8]

In the above formulas (7) and (8), R ¹ to R ⁵ and R 'are each independently a C ¹ to C 10 linear or branched alkyl group, and M ¹ is an alkylid metal.

The metal amide of formula (6) may be prepared by using a known method or may be a commercially available reagent.

The method for preparing the manganese aminoamide amide precursor of the present invention can be represented by the following reaction formula (1).

[Reaction Scheme 1]

In the above scheme ^1, R 1 to R ⁵ are each independently a C1 to a linear or branched alkyl group of C10, R ⁶ and R ⁷ are independently selected from C1 to C10 linear or branched alkyl group or tri (C1-C10) of each X ¹ and X ² are halogen, M ¹ and M ² are each independently an alkali metal, and n is an integer of 1 or 2.

According to Reaction Scheme 1, the manganese compound of Chemical Formula 4 and the metal aminoamide of Chemical Formula 5 are allowed to react at room temperature (rt) for 5 to 10 hours in a solvent such as hexane, diethyl ether, toluene or tetrahydrofuran Followed by addition of the metal amide of formula (VI) and the reaction may be carried out for 5 to 15 hours. Thus, the manganese aminoamide amide precursor of Formula 1 can be obtained.

Reactants in this reaction can be used in stoichiometric equivalents.

Since the manganese aminoamide amide precursor of the present invention is thermally stable, has good volatility and high reactivity, it can easily form a thin film at a low temperature and has a good growth rate.

The present invention also provides a composition for thin film deposition comprising the manganese aminoamide amide precursor of Formula 1 above.

When the manganese aminoamide amide precursor of the present invention can be used to produce a manganese-containing thin film, it has a high vapor pressure and reactivity and does not cause side reactions such as spontaneous decomposition or reaction with other materials even during continuous heating, A manganese-containing thin film can be produced.

The composition of the thin film deposition composition of the present invention includes the manganese aminoamide amide precursor, and the content of the manganese aminoamide amide precursor in the thin film deposition composition of the present invention may vary depending on the deposition conditions of the thin film, It can be included within a recognizable range.

Also, the present invention provides a method for growing a manganese-containing thin film using the manganese aminoamide amide precursor of the above formula (1) and a manganese-containing thin film prepared therefrom.

The manganese aminoamide amide precursor of the present invention can be produced by a known deposition method such as chemical vapor deposition (CVD), plasma enhanced chemical vapor deposition (PECVD), atomic layer deposition (ALD) Containing thin film can be produced by a known method such as a chemical vapor deposition (CVD) method or an atomic layer deposition (ALD) method, and more preferably, an atomic layer deposition (ALD) method.

The manganese-containing thin film is a manganese thin film, a manganese nitride thin film, or a manganese oxide thin film.

For example, in the case of using chemical vapor deposition (CVD), a manganese-containing thin film can be formed on various substrates by supplying reactants and organic materials including the manganese aminoamide amide precursor of the present invention to the reactor. Since the novel manganese aminoamide amide precursor of the present invention is thermally stable and has good volatility, a thin film can be produced under various conditions and a thin film of good quality can be produced even at a low temperature.

Further, in the case of using atomic layer deposition (ALD), for example, a manganese-containing thin film can be produced by the ALD process using the manganese aminoamide amide precursor of the present invention. In the ALD process, the reactants containing the manganese aminoamide amide precursor of the present invention are supplied to the deposition chamber in the form of pulses, and the pulses are chemically reacted with the wafer surface to achieve precise monolayer growth. Since the manganese aminoamide amide precursor of the present invention is thermally stable and has good volatility, a high quality manganese-containing thin film can be easily produced by the ALD process.

The manganese aminoamide amide precursors of the present invention are in a heteroleptic form and are more suitable for ALD processes.

The preparation of the thin film according to an embodiment of the present invention is preferably performed because it can produce a smooth and uniform thin film when the thin film is performed at a temperature ranging from 100 to 400 ° C.

The present invention provides a thin film produced by the above method, wherein the thin film can be formed on various substrates. At this time, the substrate may be a metal substrate, an inorganic substrate, or an organic-inorganic hybrid substrate, but is not limited thereto. A non-limiting example of the metal substrate may be a foil, a sheet, a film or the like and may be formed of copper (Cu), aluminum (Al), iron (Fe), silver (Ag) (Pd), nickel (Ni), chromium (Cr), molybdenum (Mo), tungsten (W), stainless steel or alloys thereof, For example, it may be a graphite sheet, a carbon fabric, a glass fabric, a glass paper, a ceramic paper, a glass sheet, - Non-limiting example of the inorganic hybrid substrate may be a polymer film containing inorganic particles, FRP (Fiber Reinforced Plastic) produced by impregnating a glass fiber or carbon fiber with a resin, and the like.

The present invention may be better understood by the following examples, which are for the purpose of illustrating the invention and are not intended to limit the scope of protection defined by the appended claims.

Example  1. [Mn ( active ) ( diethylamino )] ₂ Manufacturing

Dissolve the shoe Lenk _{MnCl 2 (0.50 g, 4.0 mmol} , 1 eq) to the flask in tetrahydrofuran Lithium (2- (diethylamino) -2- methylpropyl) for -2-ehtylamide (0.60 g, 4.0 mmol, 1 eq) After stirring at room temperature for 6 hours, lithium diethylamide (0.31 g, 4.0 mmol, 1 eq) was added and stirred at room temperature for 12 hours. The reaction mixture was filtered, and the solvent was distilled off under reduced pressure. The solvent was extracted with hexane to obtain a brown solid compound (0.6 g, 60%).

FT-IR (cm ^-1 ): 2955 (s), 2926 (s), 2874 (s), 2828 (s), 2664 (m), 2565 (w), 1381 (w), 1362 (s), 1345 (s), 1331 (w), 1304 (w), 1276 (m), 1232 (s), 1106 (w), 1080 (w), 1035 (m), 1009 (s), 990 (s), 973 (m), 837 (m), 791 (m), 776 (m), 598 (w), 538 (s), 477 (w).

Anal. Calcd for C ₂₄ H ₅₈ Mn ₂ N ₆ .2H ₂ O: C, 49.99; H, 10.84; N, 14.57. Found: C, 49.57; H, 10.84; N; 14.81.

Experimental Example  1. Analysis of manganese precursor materials

Thermogravimetric analysis (TGA) was used to determine the thermal stability, volatility and decomposition temperature of [Mn (etmpda) (diethylamino)] ₂ in Example 1 above. In the TGA method, argon gas was introduced at a pressure of 1.5 bar / min while heating the product to 900 ° C at a rate of 10 ° C / minute.

It was observed that the [Mn (etmpda) (diethylamino)] ₂ of Example 1 had a mass loss from room temperature and a mass loss of more than 50% occurred at 400 ° C (FIG.

Claims (9)

delete A manganese aminoamide amide precursor represented by the following formula (3).
(3)

In Formula 3, R ¹ to R ⁵ are each independently a C1 to a linear or branched alkyl group of C10, R ⁶ and R ⁷ are independently selected from C1 to C10 linear or branched alkyl group or tri (C1-C10) of each Alkylsilyl group. 3. The method of claim 2,
Wherein R ¹ to R ⁷ are each independently a C1 to C7 linear or branched alkyl group. 3. The method of claim 2,
R ¹ to R ⁷ are each independently selected from the group consisting of methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl or tert- tert-butyl) manganese aminoamide amide precursor. Reacting a manganese compound represented by the following formula (4) with a metal aminoamide represented by the formula (5) and a metal amide represented by the formula (6) to prepare a manganese aminoamide amide precursor represented by the following formula (1).
[Chemical Formula 1]

[Chemical Formula 4]

[Chemical Formula 5

[Chemical Formula 6]

In formula (I) and 4 to 6, R ¹ to R ⁵ are each independently a C1 to a linear or branched alkyl group of C10, R ⁶ and R ⁷ are each independently a linear or branched alkyl group or tri C1 to C10 ( C 1 -C 10) alkylsilyl group, X ¹ and X ² are halogen, M ¹ and M ² are each independently an alkali metal, and n is an integer of 2. A composition for manganese-containing thin film deposition comprising a manganese aminoamide amide precursor according to any one of claims 2 to 4. A method for growing a manganese-containing thin film using a manganese aminoamide amide precursor according to any one of claims 2 to 4. 8. The method of claim 7,
Wherein the thin film growth process is performed by chemical vapor deposition (CVD) or atomic layer deposition (ALD). A manganese-containing thin film prepared using the manganese aminoamide amide precursor according to any one of claims 2 to 4.

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