KR20230102083A - Novel molybdenum precursor, deposition method of molybdenum-containing film and device comprising the same - Google Patents

Abstract

[화학식 2]

상기 화학식 1 및 화학식 2에서 R₁은 각각 독립적으로 C₁-C₆의 직쇄 또는 분기상 알킬기이며, R₂는 수소원자, 메틸기, 에틸기, n-프로필 또는 i-프로필기이며, 또한, 화학식 2에서 X는 할로겐 원자(F, Cl 또는 Br)이다.The present invention relates to a novel molybdenum-containing precursor comprising a molybdenum-containing compound represented by Formula 1 or Formula 2 below, a method for forming a molybdenum-containing thin film using the molybdenum-containing precursor, and the above It relates to a semiconductor device including a molybdenum-containing thin film.
[Formula 1]

[Formula 2]

In Formula 1 and Formula 2, R ₁ is each independently a C ₁ -C ₆ straight-chain or branched alkyl group, R ₂ is a hydrogen atom, methyl group, ethyl group, n-propyl or i-propyl group, and also Formula 2 where X is a halogen atom (F, Cl or Br).

Description

Novel molybdenum-containing precursor, method of forming a molybdenum-containing thin film using the same, and device including the molybdenum-containing thin film.

The present invention relates to a novel molybdenum-containing precursor, a method for forming a molybdenum-containing thin film using the same, and a device including the molybdenum-containing thin film. It relates to a molybdenum-containing precursor having improved structural stability and thermal stability in a thin film formation process using the same, a method for forming a molybdenum-containing thin film using the same, and a device including the molybdenum-containing thin film.

Molybdenum (Mo) is applied to electronic devices such as various semiconductors, displays, thin-film solar cells, electrodes, and gas sensors, and elements of semiconductor devices. To this end, a molybdenum-containing thin film is formed. For example, a molybdenum oxide thin film is introduced into a substrate to perform flame deposition, sputtering, ion plating, and coating-pyrolysis. -pyrolysis Thin films are formed by processes such as sol-gel, chemical vapor deposition (CVD), and atomic layer deposition (ALD).

As a precursor used to form such a metal-containing thin film, a metal halide, metal oxyhalide, or metal imidohalide such as MeCl ₄ O, MeO ₂ Cl ₂ , MeCl ₅ and the like is used (US Patent Application Publication No. US 2020-0131628 No., Korean Patent Publication No. 10-2019-0024823, Korean Patent Publication No. 10-2019-0024841). In addition, as the halide, oxyhalide, and imidohalide type metal precursors, compounds of group 5 metals such as niobium (Nb) and tantalum (Ta) and group 6 metals such as molybdenum (Mo) and tungsten (W) are known. has been

However, since the metal compound is in a solid state at room temperature, problems to be solved for the thin film formation process due to the nature of the precursor that must be supplied in a gaseous state to the substrate in the chamber, for example, when forming a thin film by vaporizing a solid phase, can form a high-quality thin film. There are problems such as no.

In addition, there are many examples of using a molybdenum precursor in the form of a ligand. For example, Korean Patent Registration Nos. 10-1485521 and 10-1485522 disclose a thermally stable and highly volatile aminothiolate ligand containing a ligand. Although a molybdenum precursor is disclosed, it can be used only in the process of forming a molybdenum sulfide thin film, and there is a problem in that elemental sulfur remains in the thin film forming process.

US Patent Publication No. US 2020-0131628 Republic of Korea Patent Publication No. 10-2019-0024823 Republic of Korea Patent Publication No. 10-2019-0024841 Republic of Korea Patent Registration No. 10-1485521 Republic of Korea Patent Registration No. 10-1485522

The present invention has been made in view of the prior art as described above, and an object of the present invention is to provide a molybdenum-containing precursor suitable for a thin film formation process using a novel molybdenum-containing compound.

In addition, it is an object of the present invention to provide a method capable of efficiently forming a thin film through structural stability and thermal stability of the molybdenum-containing precursor.

Another object thereof is to provide a device including a molybdenum-containing thin film manufactured using the molybdenum-containing precursor.

The molybdenum-containing precursor of the present invention for achieving the above object is characterized in that it includes a molybdenum-containing compound represented by Formula 1 or Formula 2 below.

[Formula 1]

[Formula 2]

In Formula 1 and Formula 2, R ₁ is each independently a C ₁ -C ₆ straight-chain or branched alkyl group, R ₂ is a hydrogen atom, methyl group, ethyl group, n-propyl or i-propyl group, and also Formula 2 where X is a halogen atom.

Specifically, the molybdenum-containing compound represented by Formula 1 is Mo(NtBu) ₂ (EMAMP) ₂ , Mo(NtBu) ₂ (EMAMP)(DMAMP) or Mo(NtBu) ₂ (EMA) ₂ , and The molybdenum-containing compound represented by 2 may be Mo(NtBu) ₂ (DMAMP)Cl or Mo(NtBu) ₂ (EMAMP)Cl (provided that EMAMP is ethylmethylaminomethylpropanol and DMAMP is dimethylaminopropanol). , EMA is ethylmethylamino, and DME is dimethoxyethane).

In this case, the molybdenum-containing precursor may include a solvent capable of dissolving the molybdenum-containing compound. In this case, the content of the solvent in the molybdenum-containing precursor is preferably 1 to 99% by weight. In addition, as the solvent, saturated hydrocarbons having 5 to 8 carbon atoms including pentane (n-Pentane), hexane (n-Hexane), heptane (n-Heptane), and octane (n-Octane), dimethoxyethane (DME ), diethylether, tetrahydrofuran (THF), ether, dialkoxyalkane, pyridine, acetonitrile, primary, secondary or tertiary amine Any one compound is mentioned.

In addition, the method of forming a molybdenum-containing thin film of the present invention is characterized by including depositing the molybdenum-containing precursor on a substrate.

In addition, the molybdenum-containing thin film may be a thin film made of molybdenum, molybdenum oxide, molybdenum nitride, molybdenum oxynitride or molybdenum sulfide.

In addition, the molybdenum-containing thin film may be formed by atomic layer deposition (ALD) or chemical vapor deposition (CVD).

In addition, the depositing may include positioning a substrate in a chamber, supplying the precursor for forming a molybdenum-containing thin film into the chamber and bringing it into contact with the substrate, supplying a vapor phase reactant including a reactive gas to the substrate. Contacting may be included.

In addition, the depositing step includes placing a substrate in a chamber, supplying the precursor for forming a molybdenum-containing thin film into the chamber to contact the substrate, and supplying a reactive gas to contact the substrate. It may be that Examples of the reactive gas include oxidizing gases such as water vapor (H ₂ O), oxygen (O ₂ ), ozone (O ₃ ) or hydrogen peroxide (H ₂ O ₂ ), hydrogen (H ₂ ), ammonia (NH ₃ ), and nitrogen monoxide ( NO), nitrous oxide (N ₂ O), nitrogen dioxide (NO ₂ ), hydrazine (N ₂ H ₄ ), and silane (SiH ₄ ), and at least one or more reducing gases such as may be applied.

In addition, the device of the present invention is characterized in that it comprises a molybdenum-containing thin film produced by the method for forming a molybdenum-containing thin film.

The molybdenum-containing precursor according to the present invention uses a novel molybdenum-containing compound containing an amino alcohol ligand, and the compound has excellent structural stability and thermal stability and high volatility, so that a high-quality thin film can be efficiently formed. show effect.

1 is a result of ¹ H-NMR analysis of Mo(NtBu) ₂ (Cl) ₂ DME.
2 is a result of ¹ H-NMR analysis of Mo(NtBu) ₂ (EMAMP) ₂ .
3 is a TGA analysis result of Mo(NtBu) ₂ (EMAMP) ₂ .
4 is a DSC analysis result of Mo(NtBu) ₂ (EMAMP) ₂ .
5 is a result of ¹ H-NMR analysis of Mo(NtBu) ₂ (EMAMP)Cl.
6 is a result of ¹ H-NMR analysis of Mo(NtBu) ₂ (EMA) ₂ .

Hereinafter, the present invention will be described in more detail. Terms or words used in this specification and claims should not be construed as being limited to ordinary or dictionary meanings, and the inventor may appropriately define the concept of terms in order to explain his or her invention in the best way. It should be interpreted as a meaning and concept consistent with the technical idea of the present invention based on the principle that there is.

The molybdenum-containing precursor according to the present invention uses a molybdenum-containing compound containing an amino alcohol ligand, and the molybdenum-containing compound is a compound represented by Formula 1 or Formula 2 below.

[Formula 1]

[Formula 2]

In Formula 1 and Formula 2, R ₁ is each independently a C ₁ -C ₆ straight-chain or branched alkyl group, R ₂ is a hydrogen atom, methyl group, ethyl group, n-propyl or i-propyl group, and also Formula 2 where X is a halogen atom (F, Cl or Br).

The molybdenum-containing compound has excellent structural stability and thus excellent thermal stability, and thus problems such as vaporization uniformity or carbon contamination, which are problematic in conventional molybdenum-containing precursors, may be reduced. In addition, it is suitable for application as a precursor for thin film forming process because of its excellent volatility.

The molybdenum-containing compound may be in a liquid state at room temperature, and in the case of a solid state depending on its chemical structure, it may be converted into a liquid state by dissolving in a solvent. The liquid precursor can greatly improve the efficiency of the thin film formation process because a conventional deposition method such as a liquid delivery system (LDS) can be applied. This is because the liquid precursor is advantageous in uniform supply of the precursor on the substrate, unlike the solid precursor.

That is, the molybdenum-containing precursor is prepared by a volatilization transfer method in which volatilized gas of an organic solvent is transferred into a chamber, a direct liquid injection method in which a liquid precursor composition is directly injected, or a precursor composition is dissolved in an organic solvent. It is effective in performing the deposition process because all methods such as liquid transfer method can be applied. In addition, in the form of the complex compound, since ligand molecules can be dissociated and removed by heat supplied during the thin film formation process, carbon contamination does not occur.

Therefore, compared to the prior art of performing a thin film formation process with a general molybdenum-containing precursor such as molybdenum halide, the precursor can be more uniformly supplied on the thin film, leading to the formation of a high quality thin film. In addition, the molybdenum-containing compound can improve stability as a precursor in a deposition process through the application of a coordination ligand.

In addition, the molybdenum-containing precursor may include a solvent capable of dissolving the precursor, which means a dissolved state rather than a chemical bond to the molybdenum-containing compound.

The solvent includes saturated hydrocarbons having 5 to 8 carbon atoms including pentane, n-Hexane, heptane, and n-Octane, dimethoxyethane (DME), Diethylether, tetrahydrofuran (THF), ether, dialkoxyalkane, pyridine, acetonitrile, any one of primary, secondary or tertiary amines of compounds.

At this time, the content of the solvent relative to the molybdenum-containing precursor may be 1 to 99% by weight, preferably 10 to 99% by weight, more preferably 20 to 99% by weight.

In this way, when the molybdenum-containing compound is dissolved using a solvent, the concentration of molybdenum atoms can be lowered, so that suitable precursors can be provided in response to various deposition process conditions.

The method of forming a molybdenum-containing thin film of the present invention is performed by depositing the molybdenum-containing precursor on a substrate, wherein the molybdenum-containing thin film is atomic layer deposition (ALD) or chemical vapor deposition (CVD) can be formed by

In one embodiment, the deposition process may be performed by supplying the molybdenum-containing precursor to the substrate by a liquid transfer method. A liquid precursor composition is converted into a vapor phase through a vaporizer using a liquid delivery system (LDS). After changing, the deposition process may be carried out by transferring onto a substrate for forming a molybdenum-containing thin film.

The thus formed molybdenum-containing thin film can be applied to elements constituting semiconductor devices, such as low electrical resistance gap fills, liner layers for 3D-NAND, DRAM word line features, or interconnect materials in CMOS logic applications. By directly depositing a thin film containing molybdenum on the dielectric surface, there is no need to separately provide an intermediate layer, which has a low effective electrical resistivity, for example, for interconnections in CMOS structures and for word lines/bit lines in memory devices. Since it represents, it is possible to manufacture a high-quality semiconductor device. In addition to semiconductor devices, devices for electronic devices such as displays, thin-film solar cells, electrodes, gas sensors, and TFT channel materials may be manufactured.

Depositing the molybdenum-containing thin film may include placing a substrate in a chamber, supplying the molybdenum precursor into the chamber to contact the substrate, and supplying a vapor phase reactant including a reactive gas to the substrate. Contacting may be included.

That is, a molybdenum-containing precursor is brought into contact with a substrate to form a molybdenum-containing thin film, and then a reactive gas is brought into contact thereto to form a molybdenum thin film.

In this case, the substrate may use III-V semiconductor materials including silicon (Si), germanium (Ge), germanium tin (GeSn), silicon germanium (SiGe), silicon germanium tin (SiGeSn), and silicon carbide (SiC). there is. In addition, as the substrate, silicon oxide (SiO ₂ , SiO _x ), silicon nitride (Si ₃ N ₄ ), silicon oxynitride (SiON), silicon oxycarbide (SiOC), silicon oxycarbide nitride (SiOCN), silicon carbon Silicon-containing dielectric materials such as nitride (SiCN) can be used, aluminum oxide (Al ₂ O ₃ ), hafnium oxide (HfO ₂ ), tantalum oxide (Ta ₂ O ₅ ), zirconium oxide (ZrO ₂ ), titanium oxide Dielectric materials including metal oxides such as (TiO ₂ ), hafnium silicate (HfSiO _x ), and lanthanum oxide (La ₂ O ₃ ) may also be used.

In addition, when the deposition process is performed by the ALD process, the substrate may be heated to 200 to 500 °C, preferably 250 to 400 °C. In addition, in the deposition process, the pressure in the chamber may be adjusted to achieve direct deposition of the thin film. In the case of the ALD process, the deposition process may be performed under a chamber pressure of 0.1 to 300 Torr.

In addition, when a molybdenum thin film is formed by direct deposition on a dielectric surface, a process of purging the reaction chamber is performed together in the ALD process. For example, unreacted molybdenum-containing precursors and possible reaction by-products are removed from the substrate surface by purging with an inert gas.

In addition, after purging the reaction chamber, a vapor phase reactant including a reactive gas may be supplied to contact the substrate.

Examples of the reactive gas include forming gas (H ₂ + N ₂ ), ammonia (NH ₃ ), hydrazine (N ₂ H ₄ ), alkylhydrazine, hydrogen (H ₂ ), hydrogen atom (H ), hydrogen plasma, hydrogen radical, hydrogen Any one or more of the exciton species, alcohols, aldehydes, carboxylic acids, boron or amines may be used. In addition, reactive gases in the form of precursors may be used, such as silane (SiH ₄ ), disilane (Si ₂ H ₆ ), trisilane (Si ₃ H ₈ ), germane (GeH ₄ ), digermain (Ge ₂ H ₆ ), borane (BH ₃ ), diborane (B ₂ H ₆ ), any one or more may be used.

In addition, conditions such as time and flow rate for contacting the substrate with the reactive gas may be conditions according to a typical thin film forming process. Therefore, molybdenum oxide, molybdenum nitride, molybdenum oxynitride, and molybdenum sulfide thin films can be formed by introducing such a reactive gas.

When an oxygen source is provided as the reactive gas, a metal oxide thin film may be formed. The oxygen source may be introduced into the reactor in the form of one or more oxygen sources, or may be incidentally present in other precursors used in the deposition process. Suitable oxygen source gases include, for example, water (H ₂ O) (eg, deionized water, purified water, and/or distilled water), oxygen (O ₂ ), oxygen plasma, ozone (O ₃ ), N ₂ O, NO ₂ , carbon monoxide (CO), carbon dioxide (CO ₂ ), and combinations thereof.

For example, when deposited by an ALD or cyclic CVD process, the precursor pulse may have a pulse duration greater than 0.01 second, the oxygen source may have a pulse duration less than 0.01 second, and the water pulse duration may have a pulse width of less than 0.01 seconds.

Further, the purge width between the pulses may be as small as 0 seconds, or may be continuously pulsed without a purge in the middle. The oxygen source may be provided at a molecular weight lower than a 1:1 ratio to the precursor, whereby at least some carbon may remain in the as-deposited dielectric film.

In addition, an oxynitride film may be formed by further including nitrogen in the metal oxide thin film. The thin film is deposited using the method described above and may be formed in the presence of a nitrogen containing source. Nitrogen-containing sources may be introduced into the reactor in the form of one or more nitrogen sources and may be concomitantly present among other precursors used in the deposition process. Suitable nitrogen containing source gases may include, for example, ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen/hydrogen, ammonia plasma, nitrogen plasma, nitrogen/hydrogen plasma, and mixtures thereof.

For example, the nitrogen-containing source may include an ammonia plasma or hydrogen/nitrogen plasma source gas introduced into the reactor at a flow rate ranging from about 1 to about 2000 sccm or from about 1 to about 1000 sccm. The nitrogen containing source may be introduced for a time ranging from about 0.1 to about 100 seconds. In embodiments where the thin film is deposited by an ALD or cyclic CVD process, the precursor pulse may have a pulse width greater than 0.01 seconds, the nitrogenous oxygen source may have a pulse width less than 0.01 seconds, and the water pulse width may have a pulse width of less than 0.01 seconds.

In another embodiment, the purge width between pulses can be as low as 0 seconds or can be pulsed continuously without intervening purges.

In addition, one or more purge gases may be included in the deposition process. The purge gas used to purge unconsumed reactants and/or reaction by-products is an inert gas that does not react with the precursors. Such a purge gas may include argon (Ar), nitrogen (N ₂ ), helium (He), neon, hydrogen (H ₂ ), or a mixture thereof, but is not limited thereto. For example, a purge gas such as Ar is supplied to the reactor at a flow rate ranging from 10 to about 2000 sccm for about 0.1 to 1000 seconds, thereby purging unreacted materials and by-products that may remain in the reactor.

Additionally, each step of supplying precursors, sources of oxygen, nitrogen, sulfur, and/or other precursors, source gases, and/or reagents may vary the time of supplying those materials to alter the stoichiometric composition of the thin film being formed. It can be done by doing

Energy is applied to at least one of the molybdenum-containing precursor for forming a thin film, an oxygen-containing source, a nitrogen-containing source, a sulfur-containing source, or a combination thereof to cause a reaction and form a thin film on a substrate, including heat, plasma, pulsed plasma, helicon plasma, high-density plasma, inductively coupled plasma, X-ray, e-beam, photon, remote plasma methods, and combinations thereof, but are not limited thereto. For example, a secondary RF frequency source can be used to modify plasma characteristics at the substrate surface. In embodiments where the deposition involves plasma, the plasma-generating process may include a direct plasma generation process in which plasma is generated directly in the reactor, or alternatively a remote plasma generation process in which plasma is generated external to the reactor and provided to the reactor. .

In addition, when supplying the precursor for forming the molybdenum-containing thin film, silicon (Si), titanium (Ti), An additional metal precursor including at least one metal (M′) selected from germanium (Ge), strontium (Sr), barium (Ba), hafnium (Hf), and a lanthanide atom may be further selectively supplied. The additional metal precursor may be an alkylamide-based compound or an alkoxy-based compound containing the metal.

The supply of the additional metal precursor may be carried out in the same way as the supply method of the molybdenum-containing precursor, and the additional metal precursor may be supplied onto a substrate for thin film formation together with the molybdenum-containing precursor, or molybdenum-containing precursor. It may be supplied sequentially after completion of the supply of the denum-containing precursor.

The molybdenum-containing precursor and the additional metal precursor as described above may maintain a temperature of 150 to 600 ° C., preferably 150 to 450 ° C. temperature can be maintained.

In addition, before supplying the reactive gas after the supplying of the molybdenum-containing precursor for thin film formation, the molybdenum-containing precursor and the additional metal precursor are assisted in moving onto the substrate, or the reactor has an appropriate pressure for deposition, In addition, in order to discharge impurities present in the chamber to the outside, a process of purging an inert gas such as argon (Ar), nitrogen (N ₂ ), or helium (He) in the reactor may be performed. At this time, it is preferable that the inert gas is purged so that the pressure in the reactor is 1 to 5 Torr.

After completion of the supply of the precursors, a reactive gas may be supplied into the reactor, and one treatment process selected from the group consisting of heat treatment, plasma treatment, and light irradiation may be performed in the presence of the reactive gas.

The reactive gases include water vapor (H ₂ O), oxygen (O ₂ ), ozone (O ₃ ), hydrogen peroxide (H ₂ O ₂ ), hydrogen (H ₂ ), ammonia (NH ₃ ), nitrogen monoxide (NO), suboxides Any one of nitrogen (N ₂ O), nitrogen dioxide (NO ₂ ), hydrazine (N ₂ H ₄ ), and silane (SiH ₄ ) or a mixture thereof may be used. When carried out in the presence of an oxidizing gas such as water vapor, oxygen, or ozone, a silicon oxide thin film may be formed, and when carried out in the presence of a reducing gas such as hydrogen, ammonia, hydrazine, or silane, a thin film of metal alone or metal nitride may be formed. can

In addition, the heat treatment, plasma treatment, or light irradiation treatment process is to provide thermal energy for deposition of the metal precursor, and may be performed according to a conventional method. Preferably, in order to produce a metal thin film having a desired physical state and composition at a sufficient growth rate, the treatment process is preferably performed so that the temperature of the substrate in the reactor is 100 to 1,000 ° C, preferably 300 to 500 ° C. do.

In addition, in the treatment process, as described above, to help the movement of the reactive gas onto the substrate, to have an appropriate pressure for deposition in the reactor, and to release impurities or by-products present in the reactor to the outside, A process of purging an inert gas such as argon (Ar), nitrogen (N ₂ ), or helium (He) may be performed.

As described above, the input of the molybdenum-containing precursor, the input of the reactive gas, the input of the additional metal precursor, and the input of the inert gas are treated as one cycle. A molybdenum-containing thin film may be formed by repeating the process for one cycle or more.

The molybdenum-containing thin film manufactured by the method for forming a molybdenum-containing thin film as described above becomes a component constituting elements of semiconductors and electronic devices, and through this, various types of elements can be manufactured. Examples of semiconductor devices including the molybdenum-containing thin film include memory devices such as 3D-NAND and DRAM, gate electrodes for semiconductors, capacitor electrodes of DRAM, channel materials of TFTs, and the like.

Hereinafter, the effects of the present invention will be described through examples.

A molybdenum-containing precursor was synthesized through the following reaction pathway.

Synthesis Example 1. (Bistibutylimido-dichloro-dimethoxyethane) Molybdenum Mo (NtBu) ₂ Cl ₂ Synthesis of (DME)

10.0 g (48.6 mmol) of sodium molybdate and 300 ml of dimethoxyethane were added to the flask. After the mixture was stirred at -78°C, Mo(NtBu) ₂ (Cl ) ₂ (DME) intermediate was prepared. The solution was stirred at -78°C for 30 minutes, then warmed to room temperature and further reacted at reflux for 12 hours. By filtering the mixture and evaporating the solvent and volatiles under vacuum. A dark green solid Mo(NtBu) ₂ (Cl) ₂ (DME) reaction intermediate was obtained. ¹ H-NMR (Bruker AV400MHz HD (solvent: using benzene-d6) for the obtained solid compound was measured, and the results are shown in FIG. 1.

^1H NMR (C ₆ D ₆ , 25° C.): 1.42 (S, 18H), 3.23 (s, 4H), 3.49 (s, 6H)

In addition, the compounds of Synthesis Examples 2-1 to 2-3 below may be prepared using Mo(NtBu) ₂ Cl ₂ (DME) prepared in Synthesis Example 1.

Synthesis Example 2-1. (bistybutylimido-bisethylmethylaminomethylpropanol)molybdenum Mo(NtBu) ₂ (EMAMP) ₂ synthesis of

에서 헥산 200㎖ 중 에틸메틸아미노프로판올 12.75 g (97.2mmol)에 천천히 적가하여 반응시켜 Li-EMAMP를 제조하였다. 용액을 -78℃에서 30분 동안 교반한 후 실온으로 가온하고, 실온에서 4시간 동안 추가로 교반을 하였다. 톨루엔 300㎖를 -78℃에서 반응 중간체 Mo(NtBu)₂(Cl)₂(DME)를 함유하는 플라스크에 투입하였다. 새로 제조된 Li-EMAMP 용액의 전체 양을 반응 중간체 Mo(NtBu)₂(Cl)₂(DME)를 함유하는 플라스크에 천천히 적가하여 반응하였다. 용액을 -78℃에서 30분 동안 교반한 후 실온으로 가온하고, 반응 용액을 실온에서 밤새 교반을 하였다. 혼합물을 여과하고 용매 및 휘발물질을 진공 하에 증발시켰다. 생성된 연주황색 액체를 165℃ 및 34mTorr에서 증류하였다. 수율은 10g(74 %) 이었다. 수득한 액상의 화합물을 ¹H-NMR(Bruker사 AV400MHz HD (용매: benzene-d6 사용)로 측정하였으며 결과는 도 2와 같다.38.9 ml (97.2 mmol) of n-BuLi hexane solution (2.5 M) was added to -78

Li-EMAMP was prepared by slowly adding dropwise to 12.75 g (97.2 mmol) of ethylmethylaminopropanol in 200 ml of hexane. The solution was stirred at −78° C. for 30 min, then warmed to room temperature and further stirred at room temperature for 4 h. 300 mL of toluene was charged to the flask containing the reaction intermediate Mo(NtBu) ₂ (Cl) ₂ (DME) at -78 °C. The entire amount of the freshly prepared Li-EMAMP solution was slowly added dropwise to the flask containing the reaction intermediate Mo(NtBu) ₂ (Cl) ₂ (DME) to react. The solution was stirred at -78 °C for 30 minutes and then warmed to room temperature, and the reaction solution was stirred at room temperature overnight. The mixture was filtered and the solvent and volatiles were evaporated under vacuum. The resulting pale yellow liquid was distilled at 165° C. and 34 mTorr. The yield was 10 g (74%). The obtained liquid compound was measured by ¹ H-NMR (Bruker AV400MHz HD (solvent: using benzene-d6), and the results are shown in FIG. 2.

¹ H NMR (C ₆ D ₆ , 25° C.): 0.94 (t, 6H), 1.40 (s, 12H), 1.47 (s, 18H), 2.39 (s, 6H), 2.51 (s, 4H), 2.82 ( q, 4H)

In addition, while raising the temperature at 10 ° C. / min in an atmosphere in which nitrogen flows at 200 ml / min with respect to the obtained light yellow liquid, the weight loss percentage according to the temperature change is measured by TGA (TA instrument SDT Q600), The results are shown in Figure 3. Looking at the results of Figure 3, it can be seen that 3.6% residual mass remains during the TGA analysis measured at 10 °C / min. These results suggest that the resulting compound exhibits volatility and thermal stability suitable for the deposition process.

In addition, while raising the temperature at 10 ° C. / min in an atmosphere in which nitrogen flows at 50 ml / min with respect to the obtained pale yellow liquid, the heat flow according to the temperature change was measured by DSC (TA Instrument DSC 25). As a result, the thermal decomposition temperature was shown at 289 ° C during the DSC analysis measured at 10 ° C / min as in FIG. 4, suggesting that the thermal stability was excellent.

Synthesis Example 2-2. (bistybutylimido-ethylmethylaminomethylpropanol-chloro)molybdenum Mo(NtBu) ₂ Synthesis of (EMAMP)Cl

Li-EMAMP was prepared by slowly adding 19.5 ml (48.6 mmol) of n-BuLi hexane solution (2.5 M) dropwise to 6.38 g (48.6 mmol) of ethylmethylaminopropanol in 200 ml of hexane at -78 ° C. The solution was stirred at −78° C. for 30 min, then warmed to room temperature and further stirred at room temperature for 4 h. 300 mL of toluene was charged to the flask containing the reaction intermediate Mo(NtBu) ₂ (Cl) ₂ (DME) at -78 °C. The entire amount of the freshly prepared Li-EMAMP solution was slowly added dropwise to the flask containing the reaction intermediate Mo(NtBu) ₂ (Cl) ₂ (DME) to react. The solution was stirred at -78 °C for 30 minutes and then warmed to room temperature, and the reaction solution was stirred at room temperature overnight. The mixture was filtered and the solvent and volatiles were evaporated under vacuum. The resulting pale yellow liquid was distilled at 151 °C and 177 mTorr. The yield was 16.7 g (85%). The obtained liquid compound was measured by ¹ H-NMR (Bruker AV400MHz HD (solvent: using benzene-d6), and the results are shown in FIG. 5 .

¹ H NMR (C ₆ D ₆ , 25° C.): 0.77 (t, 3H), 1.25 (s, 3H), 1.26 (s, 3H), 1.41 (s, 18H), 2.31 (d, 1H), 2.42 ( s, 3H), 2.70 (d, 1H), 3.10 (q, 4H)

Synthesis Example 2-3. (bistybutylimido-ethylmethylaminomethylpropanol-dimethylpropanol)molybdenum Mo(NtBu) ₂ Synthesis of (EMAMP)(DMAMP)

Li-DMAMP was prepared by slowly adding 19.5 ml (48.6 mmol) of n-BuLi hexane solution (2.5 M) dropwise to 5.69 g (48.6 mmol) of dimethylaminopropanol in 200 ml of hexane at -78 ° C. The solution was stirred at −78° C. for 30 min, then warmed to room temperature and further stirred at room temperature for 4 h. 300 mL of toluene was charged to the flask containing the reaction intermediate Mo(NtBu) ₂ (EMAMP)(Cl) at -78 °C. The entire amount of the freshly prepared Li-DMAMP solution was slowly added dropwise to the flask containing the reaction intermediate Mo(NtBu) ₂ (EMAMP)(Cl) to react. The solution was stirred at -78 °C for 30 minutes and then warmed to room temperature, and the reaction solution was stirred at room temperature overnight. The mixture was filtered and the solvent and volatiles were evaporated under vacuum. The resulting pale yellow liquid was distilled at 151°C and 41 mTorr. The yield was 13 g (73%).

Synthesis Example 3. (bistibutylimido-bisethylmethylamino)molybdenum Mo(NtBu) ₂ (EMA) ₂ synthesis of

10.0 g (48.6 mmol) of sodium molybdate and 300 ml of dimethoxyethane were added to the flask. After the mixture was stirred at -78°C, Mo(NtBu) ₂ (Cl ) ₂ (DME) intermediate was prepared. The solution was stirred at -78°C for 30 minutes, then warmed to room temperature and further reacted at reflux for 12 hours. By filtering the mixture and evaporating the solvent and volatiles under vacuum. A dark green solid Mo(NtBu) ₂ (Cl) ₂ (DME) reaction intermediate was obtained. 38.9 ml (97.2 mmol) of n-BuLi hexane solution (2.5 M) was slowly added dropwise to 11.49 g (194.4 mmol) of ethylmethylamine in 200 ml of hexane at -78° C. to prepare Li-EMA. The solution was stirred at −78° C. for 30 min, then warmed to room temperature and further stirred at room temperature for 4 h. 300 mL of toluene was charged to the flask containing the reaction intermediate Mo(NtBu) ₂ (Cl) ₂ (DME) at -78 °C. The entire amount of the freshly prepared Li-EMA solution was slowly added dropwise to the flask containing the reaction intermediate Mo(NtBu) ₂ (Cl) ₂ (DME) to react. The solution was stirred at -78 °C for 30 minutes and then warmed to room temperature, and the reaction solution was stirred at room temperature overnight. The mixture was filtered and the solvent and volatiles were evaporated under vacuum. The resulting pale yellow liquid was distilled at 150° C. and 32 mTorr. The yield was 12 g (70%). The obtained liquid compound was measured by ¹ H-NMR (Bruker AV400MHz HD (solvent: using benzene-d6), and the results are shown in FIG. 6 .

1H NMR (C ₆ D ₆ , 25° C.): 1.23 (t, 6H), 1.40 (s, 18H), 3.48 (s, 6H), 3.65 (q, 4H)

In addition, the compound of Synthesis Example 4 below can be prepared using Mo(NtBu) ₂ (EMA) ₂ prepared in Synthesis Example 1.

Synthesis Example 4. (bistibutylimido-bisethylmethylaminomethylpropanol)molybdenum Mo(NtBu) ₂ (EMAMP) ₂ synthesis of

10.0 g (28.2 mmol) of Mo(NtBu) ₂ (EMA) ₂ and 100 ml of dimethoxyethane were added to the flask. The mixture was prepared by slowly adding 7.77 g (59.2 mmol) of ethylmethylaminopropanol dropwise after stirring at -78°C. The solution was stirred at −78° C. for 30 min then warmed to room temperature and stirred overnight at room temperature. The mixture was filtered and the solvent and volatiles were evaporated under vacuum. The resulting pale yellow liquid was distilled at 165° C. and 46 mTorr. The yield was 11 g (78%).

[Example] Thin film formation process

A thin film formation process was performed by a bubble deposition method using the synthesized precursor. A deposition process was performed using an atomic layer deposition apparatus to deposit a molybdenum nitride thin film using bis-butylimido-bisethylmethylaminomethylpropanol)molybdenum. Molybdenum nitride thin film was deposited by sequentially injecting a molybdenum precursor and ammonia into a reactor in an atmosphere of 400 to 500 ° C. using an atomic layer deposition equipment (12" ATOMIC PREMIUM manufactured by CN1 Co., Ltd.).

At this time, in order to confirm the electrical characteristics of the deposited thin film according to the temperature, the process temperature was spilt in the reaction temperature range of 400 to 500 ° C., and the sheet resistance value of the molybdenum nitride thin film according to the process temperature was measured.

Reaction temperature range (℃) Sheet resistance [Ω/□] 400 6700 450 2800 500 521

In order to supply a stable precursor for molybdenum nitride in the process, the precursor storage container (Canister) was heated to 130 ° C or higher, the precursor was supplied to the reaction furnace using argon (Ar) gas as a carrier gas, and ammonia was used as a reactant. Molybdenum nitride was deposited using

In addition, the atomic layer deposition conditions are as shown in Table 2 below, and the molybdenum nitride deposition process cycle was repeated using this process as one cycle to deposit a thin film.

Flow rate of argon gas to purge the inside of the reaction chamber 1000 sccm Precursor supply time 6s Precursor purge time 30s ammonia supply time 3s ammonia purge time 15s

Through deposition experiments, it was confirmed that a molybdenum nitride thin film could be deposited by the ALD method using the precursor according to the present invention, and it was confirmed that the quality of the manufactured thin film was also good. Therefore, it was found that using the molybdenum-containing precursor of the present invention can effectively form a high-quality molybdenum-containing thin film.

Although the present invention has been described with preferred embodiments as described above, it is not limited to the above embodiments, and various modifications can be made by those skilled in the art within the scope of not departing from the spirit of the present invention. and change is possible. Such modifications and variations are intended to fall within the scope of this invention and the appended claims.

Claims (11)

A molybdenum-containing precursor comprising a molybdenum-containing compound represented by Formula 1 or Formula 2 below.

[Formula 1]

[Formula 2]

In Formula 1 and Formula 2, R ₁ is each independently a C ₁ -C ₆ straight-chain or branched alkyl group, R ₂ is a hydrogen atom, methyl group, ethyl group, n-propyl or i-propyl group, and also Formula 2 where X is a halogen atom.
The method of claim 1,
The molybdenum-containing compound represented by Formula 1 is Mo(NtBu) ₂ (EMAMP) ₂ , Mo(NtBu) ₂ (EMAMP)(DMAMP) or Mo(NtBu) ₂ (EMA) ₂ ,
The molybdenum-containing compound represented by Formula 2 is Mo (NtBu) ₂ (DMAMP) Cl or Mo (NtBu) ₂ (EMAMP) Cl.
The method of claim 1,
The molybdenum-containing precursor comprises a solvent capable of dissolving the molybdenum-containing compound.
The method of claim 3,
The solvent is a saturated hydrocarbon having 5 to 8 carbon atoms including pentane (n-Pentane), hexane (n-Hexane), heptane (n-Heptane), and octane (n-Octane), dimethoxyethane (DME), Diethylether, tetrahydrofuran (THF), ether, dialkoxyalkane, pyridine, acetonitrile, primary, secondary or tertiary amine A molybdenum-containing precursor, characterized in that it is a compound.
The method of claim 3,
Molybdenum-containing precursor, characterized in that the content of the solvent in the molybdenum-containing precursor is 1 to 99% by weight.
A method of forming a molybdenum-containing thin film comprising depositing the molybdenum-containing precursor according to claim 1 or 3 on a substrate.
The method of claim 6,
The method of forming a molybdenum-containing thin film, characterized in that the molybdenum-containing thin film is a thin film made of molybdenum, molybdenum oxide, molybdenum nitride, molybdenum oxynitride or molybdenum sulfide.
The method of claim 6,
The method of forming a molybdenum-containing thin film, characterized in that the molybdenum-containing thin film is formed by atomic layer deposition (ALD) or chemical vapor deposition (CVD).
The method of claim 6,
In the deposition step,
positioning a substrate within the chamber;
supplying the precursor for forming the molybdenum-containing thin film into the chamber and bringing it into contact with the substrate;
supplying a gaseous reactant containing a reactive gas to contact the substrate;
Method for forming a molybdenum-containing thin film comprising a.
The method of claim 6,
In the deposition step,
positioning a substrate within the chamber;
supplying the precursor for forming the molybdenum-containing thin film into the chamber and bringing it into contact with the substrate;
supplying a reactive gas to contact the substrate;
Method for forming a molybdenum-containing thin film comprising a.
An element comprising a molybdenum-containing thin film manufactured by the molybdenum-containing thin film forming method of claim 6.

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