KR20210041809A - Precursor for silicon containing thin film, deposition method of film and semiconductor device of the same - Google Patents

Abstract

The present invention relates to a precursor for forming a silicon thin film, which includes reformed disilazane compound represented by chemical formula 1. In the chemical formula 1, R1 to R9 can be the same as or different from each other, and are a C_1 to C_6 straight-chain or branched alkyl group or alkylene group, a phenyl group which includes or does not include a substituent, a cycloalkyl group which includes or does not include the substituent, an amine group or an alkylsilyl group.

Description

A precursor for forming a silicon thin film, a method of forming a silicon thin film using the same, and a semiconductor device including the silicon thin film. {PRECURSOR FOR SILICON CONTAINING THIN FILM, DEPOSITION METHOD OF FILM AND SEMICONDUCTOR DEVICE OF THE SAME}

The present invention relates to a precursor for forming a silicon thin film, a method for forming a silicon thin film using the same, and a semiconductor device including the silicon thin film, and more particularly, to a silicon oxide film, a nitride film, and a precursor including a modified disilazane compound. The present invention relates to a precursor for forming a silicon thin film capable of forming a silicon thin film such as an oxynitride film, a method of forming a silicon thin film using the same, and a semiconductor device including the silicon thin film.

The disilazane compound is widely used as a precursor for forming a silicon thin film. Korean Patent Publication No. 10-1060911 discloses a technology for forming a silicon nitride thin film by introducing a monoalkylaminosilane precursor and a reactive gas, and in Korean Patent Publication No. 10-0323628, a bis(t-butylamino)silane is reacted. The silazane compound is applied to the formation of a silicon thin film by various reaction conditions and reaction gases, such as a technology for depositing a film of an oxygen-containing silicon compound selected from the group consisting of silicon dioxide and silicon oxynitride on a substrate by reacting with a gas. have.

In addition, Korean Patent Publication No. 10-1600327 uses a disilazane compound to prepare a precursor for an aminosilyl amino compound having three silyl groups, but such an aminosilyl amino compound has a structure that is easy to thermally decompose at high temperatures, so it is used. Therefore, when performing the deposition process of forming a thin film, only a low temperature deposition process of 300°C or less is effective, and it is understood that it can be effectively used under the condition of a substrate temperature of 100°C.

Therefore, a chemical structure with too little or too many silyl groups cannot be applied to high-temperature deposition process conditions, and a disilazane compound must be used. Development is needed.

Korean Patent Publication No. 10-1060911 Korean Patent Publication No. 10-0323628 Korean Registered Patent Publication No. 10-1600327

The present invention has been devised in view of the above-described conventional techniques, a precursor capable of performing a deposition process at a high temperature through a modified disilazane compound, a method of forming a silicon thin film using the same, and a semiconductor device including the silicon thin film Its purpose is to provide.

The precursor for forming a silicon thin film of the present invention for achieving the above object is characterized in that it comprises a modified disilazane compound represented by Chemical Formula 1.

[Formula 1]

In Formula 1, R ₁ to R ₉ may be the same as or different from each other, and a C ₁ -C ₆ straight or branched alkyl group or alkylene group, a phenyl group with or without a substituent, or a substituent with or without a substituent. It is a cycloalkyl group, an amine group, or an alkylsilyl group.

The precursor for forming a silicon thin film may additionally include a solvent, wherein the solvent is any _one of C 1 -C ₁₆ saturated or unsaturated hydrocarbons, ethers, glyme, esters, tetrahydrofuran, and tertiary amines, or It can be more than that. In addition, the solvent may be included in an amount of 1 to 99% by weight based on the total weight of the precursor composition for forming the silicon thin film.

The method for forming a silicon thin film according to the present invention includes depositing a silicon thin film on a substrate using the precursor for forming a silicon thin film.

The silicon thin film may be deposited by any one of atomic layer deposition, plasma enhanced chemical vapor deposition, or chemical vapor deposition.

In addition, the method of forming a silicon thin film may include the step of vaporizing the precursor for forming a silicon thin film and transferring it into the chamber.

In addition, the deposition may include a first step of providing a substrate to a reactor; A second step of introducing a silicon precursor including the modified disilazane compound represented by Chemical Formula 1 into the reactor; A third step of purging the reactor with purge gas; A fourth step of introducing a reactive gas into the reactor; And a fifth step of purging the reactor with a purge gas, and the second to fifth steps may be repeated until a deposition film having a desired thickness is formed.

At this time, the reactive gas is 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) , Nitrous oxide (N ₂ O), nitrogen dioxide (NO ₂ ), hydrazine (N ₂ H ₄ ), and may be any one or more of _{silane (SiH 4 ).}

In addition, the deposition may be performed at a temperature of 500° C. or less and a pressure in the range of 50 mTorr to 760 Torr.

The semiconductor device according to the present invention is characterized in that it includes a silicon thin film manufactured by the method of forming a silicon thin film.

According to the precursor and the method of forming a thin film using the same according to the present invention, a precursor capable of performing a deposition process at a high temperature through a modified disilazane compound, a method of forming a silicon thin film using the same, and a semiconductor device including the silicon thin film. Can provide.

Hereinafter, the present invention will be described in more detail. The terms or words used in the specification and claims should not be construed as being limited to their usual or dictionary meanings, and the inventor may appropriately define the concept of terms in order to describe his own 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 precursor for forming a silicon thin film according to the present invention is characterized in that it comprises a modified disilazane compound represented by Chemical Formula 1.

[Formula 1]

In Formula 1, R ₁ to R ₉ may be the same as or different from each other, and a C ₁ -C ₆ straight or branched alkyl group or alkylene group, a phenyl group with or without a substituent, or a substituent with or without a substituent. It is a cycloalkyl group, an amine group, or an alkylsilyl group.

The precursor for forming a silicon thin film is a precursor used in a deposition process for forming a silicon thin film, and the prepared silicon thin film may be any one of silicon, silicon oxide, silicon nitride, a combination thereof, or a laminated thin film thereof.

In general, the disilazane compound has a structure such as the following formula (2).

[Formula 2]

The disilazane compound of Formula 2 has a problem that it is difficult to use as a precursor when performing the deposition process under high temperature conditions because the amine group crosslinked to the two silicon atoms is decomposed at high temperature.

On the other hand, when the modified disilazane compound according to the present invention is applied as a precursor, since the thermal decomposition temperature is relatively high, stable deposition is possible even under relatively high temperature conditions. It can create an adsorption state.

Specific examples of the modified disilazane compound according to Formula 1 include N,N-bis(dimethylaminodimethylsilyl)methanamine, N,N-bis(dimethylaminodimethylsilyl)ethanamine, N,N-bis(dimethyl Aminodimethylsilyl)propanamine, N,N-bis(dimethylaminodimethylsilyl)isopropanamine, N,N-bis(dimethylaminodimethylsilyl)butanamine, N,N-bis(dimethylaminodimethylsilyl)isobutanamine , N,N-bis(dimethylaminodimethylsilyl)pentanamine, N,N-bis(diethylaminodimethylsilyl)methanamine, N,N-bis(diethylaminodimethylsilyl)ethanamine, N,N-bis (Diethylaminodimethylsilyl)propanamine, N,N-bis(diethylaminodimethylsilyl)isopropanamine, N,N-bis(diethylaminodimethylsilyl)butanamine, N,N-bis(diethylamino Dimethylsilyl)isobutanamine, N,N-bis(diethylaminodimethylsilyl)pentanamine, N,N-bis(dipropylaminodimethylsilyl)methanamine, N,N-bis(dipropylaminodimethylsilyl)ethane Amine, N,N-bis(dipropylaminodimethylsilyl)propanamine, N,N-bis(dipropylaminodimethylsilyl)isopropanamine, N,N-bis(dipropylaminodimethylsilyl)butanamine, N, N-bis(dipropylaminodimethylsilyl)isobutanamine, N,N-bis(dipropylaminodimethylsilyl)pentanamine, N,N-bis(diisopropylaminodimethylsilyl)methanamine, N,N-bis (Diisopropylaminodimethylsilyl)ethanamine, N,N-bis(diisopropylaminodimethylsilyl)propanamine, N,N-bis(diisopropylaminodimethylsilyl)isopropanamine, N,N-bis( Diisopropylaminodimethylsilyl)butanamine, N,N-bis(diisopropylaminodimethylsilyl)isobutanamine, N,N-bis(diisopropylaminodimethylsilyl)pentanamine, N,N-bis(methyl Ethylaminodimethylsilyl)methanamine, N,N-bis(methylethylaminodimethylsilyl)ethanamine, N,N-bis(methylethylaminodimethylsilyl)propanamine, N,N-bis(methylethylaminodimethylsilyl) Isopropanamine, N,N-bis(methylethylaminodimethylsilyl)butanamine, N,N-bis(methylethylaminodimethylsilyl)isobutanamine, N,N-bis(methylethylaminodimethylsilyl)pentanamine, N,N-bis(dimethylaminodiethylsilyl)methanamine, N,N- ratio S(dimethylaminodiethylsilyl)ethanamine, N,N-bis(dimethylaminodiethylsilyl)propanamine, N,N-bis(dimethylaminodiethylsilyl)isopropanamine, N,N-bis(dimethylamino Diethylsilyl)butanamine, N,N-bis(dimethylaminodiethylsilyl)isobutanamine, N,N-bis(dimethylaminodiethylsilyl)pentanamine, N,N-bis(diethylaminodiethylsilyl) ) Methanamine, N,N-bis(diethylaminodiethylsilyl)ethanamine, N,N-bis(diethylaminodiethylsilyl)propanamine, N,N-bis(diethylaminodiethylsilyl)iso Propanamine, N,N-bis(diethylaminodiethylsilyl)butanamine, N,N-bis(diethylaminodiethylsilyl)isobutanamine, N,N-bis(diethylaminodiethylsilyl)pentane Amine, N,N-bis(dipropylaminodiethylsilyl)methanamine, N,N-bis(dipropylaminodiethylsilyl)ethanamine, N,N-bis(dipropylaminodiethylsilyl)propanamine, N,N-bis(dipropylaminodiethylsilyl)isopropanamine, N,N-bis(dipropylaminodiethylsilyl)butanamine, N,N-bis(dipropylaminodiethylsilyl)isobutanamine, N,N-bis(dipropylaminodiethylsilyl)pentanamine, N,N-bis(diisopropylaminodiethylsilyl)methanamine, N,N-bis(diisopropylaminodiethylsilyl)ethanamine, N,N-bis(diisopropylaminodiethylsilyl)propanamine, N,N-bis(diisopropylaminodiethylsilyl)isopropanamine, N,N-bis(diisopropylaminodiethylsilyl)butane Amine, N,N-bis(diisopropylaminodiethylsilyl)isobutanamine, N,N-bis(diisopropylaminodiethylsilyl)pentanamine, N,N-bis(methylethylaminodiethylsilyl) Methanamine, N,N-bis(methylethylaminodiethylsilyl)ethanamine, N,N-bis(methylethylaminodiethylsilyl)propanamine, N,N-bis(methylethylaminodiethylsilyl)isopropane Amine, N,N-bis(methylethylaminodiethylsilyl)butanamine, N,N-bis(methylethylaminodiethylsilyl)isobutanamine, N,N-bis(methylethylaminodiethylsilyl)pentanamine , N,N-bis(dimethylaminodiisopropylsilyl)methanamine, N,N-bis(dimethylaminodiisopropylsilyl)ethanamine, N,N-bis(dimethylaminodiisopropylsilyl)propanamine, N ,N-B S(dimethylaminodiisopropylsilyl)isopropanamine, N,N-bis(dimethylaminodiisopropylsilyl)butanamine, N,N-bis(dimethylaminodiisopropylsilyl)isobutanamine, N,N- Bis(dimethylaminodiisopropylsilyl)pentanamine, N,N-bis(diethylaminodiisopropylsilyl)methanamine, N,N-bis(diethylaminodiisopropylsilyl)ethanamine, N,N- Bis(diethylaminodiisopropylsilyl)propanamine, N,N-bis(diethylaminodiisopropylsilyl)isopropanamine, N,N-bis(diethylaminodiisopropylsilyl)butanamine, N, N-bis(diethylaminodiisopropylsilyl)isobutanamine, N,N-bis(diethylaminodiisopropylsilyl)pentanamine, N,N-bis(dipropylaminodiisopropylsilyl)methanamine, N,N-bis(dipropylaminodiisopropylsilyl)ethanamine, N,N-bis(dipropylaminodiisopropylsilyl)propanamine, N,N-bis(dipropylaminodiisopropylsilyl)isopropane Amine, N,N-bis(dipropylaminodiisopropylsilyl)butanamine, N,N-bis(dipropylaminodiisopropylsilyl)isobutanamine, N,N-bis(dipropylaminodiisopropylsilyl) ) Pentanamine, N,N-bis(diisopropylaminodiisopropylsilyl)methanamine, N,N-bis(diisopropylaminodiisopropylsilyl)ethanamine, N,N-bis(diisopropylamino Diisopropylsilyl)propanamine, N,N-bis(diisopropylaminodiisopropylsilyl)isopropanamine, N,N-bis(diisopropylaminodiisopropylsilyl)butanamine, N,N-bis (Diisopropylaminodiisopropylsilyl)isobutanamine, N,N-bis(diisopropylaminodiisopropylsilyl)pentanamine, N,N-bis(methylethylaminodiisopropylsilyl)methanamine, N ,N-bis(methylethylaminodiisopropylsilyl)ethanamine, N,N-bis(methylethylaminodiisopropylsilyl)propanamine, N,N-bis(methylethylaminodiisopropylsilyl)isopropanamine , N,N-bis(methylethylaminodiisopropylsilyl)butanamine, N,N-bis(methylethylaminodiisopropylsilyl)isobutanamine, N,N-bis(methylethylaminodiisopropylsilyl) Pentanamine, etc., but are not limited thereto, and having a functional group corresponding to Formula 1 It may contain a compound.

The modified disilazane compound according to Formula 1 may be prepared through the following reaction schemes 1 to 3.

[Scheme 1]

[Scheme 2]

[Scheme 3]

That is, the modified disilazane compound of Formula 1 through a process of reacting a dialkyldichlorosilane with an amine compound with a primary amine to prepare a silylamine compound, and then reacting a secondary amine thereto and reacting with silylamine chloride again. Will be manufactured.

It was shown that the modified disilazane compound has improved thermal stability compared to the conventional disilazane compound by bonding the _{functional group R 5 to the amine group crosslinked by two silicon atoms.} In particular, _{it has been shown that such thermal stability is improved when hydrocarbons instead of hydrogen are bonded to R 5} .If the number of carbons exceeds 6, the volume of the molecule becomes too large and the vapor pressure is poor, making it difficult to handle as a precursor for deposition. There was a problem in that it became a state or the synthesis yield was lowered.

When preparing a silicon thin film by applying the above precursor, a thin film is formed through atomic layer deposition or plasma enhanced chemical vapor deposition as well as conventional chemical vapor deposition. can do.

In addition, depending on the deposition method, the precursor may be dissolved in a solvent to form a liquid, and then introduced into a chamber to perform a deposition process. In this case, the solvent may be a C ₁ -C ₁₆ saturated or unsaturated hydrocarbon, ether, glyme, ester, tetrahydrofuran, tertiary amine, or a mixture thereof. Examples of the C ₁ -C ₁₆ saturated or unsaturated hydrocarbon include toluene and heptane, and the tertiary amine includes dimethylethylamine.

In addition, when the solvent is included, it is preferably included in an amount of 1 to 99% by weight based on the total weight of the precursor for forming the silicon thin film.

The method for forming a silicon thin film of the present invention is characterized in that it includes the step of depositing a silicon thin film on a substrate using the precursor for forming a silicon thin film.

In this case, the precursor for forming the silicon thin film may additionally include a solvent, and the solvent may be included in an amount of 1 to 99% by weight based on the total weight of the precursor for forming the silicon thin film.

Specifically, the method of manufacturing a silicon thin film using the precursor for a silicon thin film of Chemical Formula 1 may be carried out according to a method of manufacturing a silicon thin film by conventional deposition except for using the compound of Chemical Formula 1 as a precursor. .

That is, the first step of providing the substrate to the reactor; A second step of introducing a silicon precursor including the modified disilazane compound represented by Chemical Formula 1 into the reactor; A third step of purging the reactor with purge gas; A fourth step of introducing a reactive gas into the reactor; And a fifth step of purging the reactor with a purge gas, and the second to fifth steps may be repeated until a deposition film having a desired thickness is formed. In addition, the deposition may be performed at a temperature of 500° C. or less and a pressure in the range of 50 mTorr to 760 Torr. In addition, various thin films such as an oxide film, a nitride film, and an oxynitride film may be formed according to the type of the reactive gas. In addition, as described above, the silicon precursor including the modified disilazane compound represented by Formula 1 may be the modified disilazane compound, or may be a composition in which the modified disilazane compound and a solvent are mixed. have.

First, a precursor for a silicon thin film including a modified disilazane compound represented by Formula 1 is supplied onto a substrate for forming a silicon thin film located in a reactor. At this time, the substrate for forming a silicon thin film may be used without particular limitation as long as it is used for semiconductor manufacturing, which needs to be coated with a silicon thin film due to a technical action. Specifically, silicon substrate (Si), silica substrate (SiO ₂ ), silicon nitride substrate (SiN), silicon oxynitride substrate (SiON), titanium nitride substrate (TiN), tantalum nitride substrate (TaN), tungsten substrate (W) or a noble metal substrate, for example, a platinum substrate (Pt), a palladium substrate (Pd), a rhodium substrate (Rh), a gold substrate (Au), or the like may be used.

In addition, a liquid transfer method in which the precursor for forming a silicon thin film is transferred through a volatilized gas, a liquid injection method or a liquid transfer method in which the precursor for forming a silicon thin film is dissolved in an organic solvent and transferred may be used. The method of transferring the precursor for forming a silicon thin film to a volatilized gas is to place a container containing the precursor for forming a silicon thin film in a thermostat, and then bubble it with an inert gas such as helium, neon, argon, krypton, xenon, or nitrogen to form a silicon thin film. After evaporating the precursor for formation, it is transferred onto a substrate for forming a metal thin film, or the precursor for forming a liquid silicon thin film is converted into a gas phase through a vaporizer using a liquid delivery system (LDS), and then a silicon thin film is formed. It can be carried out by transferring it onto the substrate for use.

In addition, a combined liquid delivery and flash vaporization process unit such as a turbo vaporizer manufactured by MSP Corporation (Shoreview, MN) will be used to enable the delivery of low volatile substances in a volumetric manner. And this leads to reproducible transport and thermal decomposition-free deposition of the precursor. In liquid delivery formulations, the precursors of the present invention can be delivered in pure liquid form, or can be used as a composition containing a solvent. Thus, the precursor composition may comprise a solvent component of suitable character as it may be desirable and advantageous for certain end-use applications for forming a film on a substrate in one embodiment.

In one embodiment, a silicon film deposited using the thin film formation method of the present invention is formed in the presence of oxygen using an oxygen source, a reagent, or a precursor containing oxygen. The oxygen source may be introduced into the reactor in the form of one or more oxygen sources and/or may be incidentally present in other precursors used in the deposition process. Suitable oxygen source gases are, for example, water (H ₂ O) (e.g. 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, the oxygen source may include an oxygen 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 oxygen source may be introduced for a time in the range of about 0.1 to about 100 seconds. In one particular embodiment, the oxygen source comprises water having a temperature of 10° C. or higher. In embodiments in which the film is deposited by an ALD or cyclic CVD process, the precursor pulse may have a pulse duration greater than 0.01 seconds, the oxygen source may have a pulse width less than 0.01 seconds, and the water pulse The width can have a pulse width of less than 0.01 seconds.

In another embodiment, the purge width between pulses may be as small as 0 seconds, or it is continuously pulsed without purge in the middle. The oxygen source or reagent is provided at a molecular weight lower than a 1:1 ratio relative to the silicon precursor, thereby leaving at least some of the carbon in the as-deposited dielectric film.

In another embodiment, nitrogen may be further included in the silicon oxide film. The film is deposited using the method described above and can be formed in the presence of a nitrogen containing source. The nitrogen containing source may be introduced into the reactor in the form of one or more nitrogen sources and may be incidentally present in 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. In certain embodiments, the nitrogen containing source comprises 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 can be introduced for a time in the range of about 0.1 to about 100 seconds. In embodiments in which the film is deposited by an ALD or cyclic CVD process, the precursor pulse can have a pulse width of greater than 0.01 seconds, the nitrogen-containing oxygen source can have a pulse width of less than 0.01 seconds, and the water pulse width is It can have a pulse width of less than 0.01 seconds.

In another embodiment, the purge width between pulses may be as low as 0 seconds, or may be continuously pulsed without purge in the middle.

In addition, the deposition method may include one or more purge gases. The purge gas used to purge unconsumed reactants and/or reaction by-products is an inert gas that does not react with the precursor. The 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 in the range of 10 to about 2000 sccm for about 0.1 to 1000 seconds, thereby purging unreacted substances and by-products that may remain in the reactor.

In addition, each step of supplying a precursor, an oxygen source, a nitrogen-containing source, and/or other precursor, source gas, and/or reagent takes the time to supply the materials to alter the stoichiometric composition of the dielectric film being formed. It can be done by changing.

Energy is applied to one or more of a precursor for forming a silicon thin film, an oxygen-containing source, or a combination thereof to induce a reaction and form a dielectric film or coating on the substrate, heat, plasma, pulsed plasma, helicon plasma , High-density plasma, inductively coupled plasma, X-ray, e-beam, photon, remote plasma method, and combinations thereof, but are not limited thereto. For example, a secondary RF frequency source can be used to modify the plasma characteristics at the substrate surface. In embodiments where the deposition includes 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 outside the reactor and provided to the reactor. .

In addition, when the precursor for forming the silicon thin film is supplied, silicon (Si), titanium (Ti), germanium (Ge), and strontium are used as additional metal precursors to further improve the electrical properties, that is, capacitance of the finally formed silicon thin film. (Sr), niobium (Nb), barium (Ba), hafnium (Hf), tantalum (Ta), and a metal precursor containing at least one metal (M") selected from a lanthanide atom may be optionally further supplied. The metal precursor may be an alkylamide-based compound or an alkoxy-based compound containing the metal.

The supply of the metal precursor may be performed in the same manner as the method of supplying the precursor for forming a silicon thin film, and the metal precursor may be supplied together with the precursor for forming a silicon thin film onto the substrate for forming a thin film, or the supply of the metal precursor is completed. It may be supplied sequentially afterwards.

The precursor for forming a silicon thin film as described above and optionally a metal precursor is preferably maintained at a temperature of 150 to 600° C. until it is supplied into the reaction chamber in order to contact the substrate for forming the metal film, and more preferably 150 to 450 It is good to keep the temperature in ℃.

In addition, prior to the supply of the reactive gas after the supplying of the precursor for forming a silicon thin film, the precursor for forming the silicon thin film and optionally the metal precursor are assisted to move onto the substrate, or the inside of the reactor is made to have an appropriate pressure for deposition, and A process of purging an inert gas such as _{argon (Ar), nitrogen (N 2} ), or helium (He) in the reactor may be performed in order to discharge the impurities present in the chamber to the outside. 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 the supply of the precursors for forming a silicon thin film as described above is completed, a reactive gas is supplied into the reactor, and in the presence of the reactive gas, one type of treatment process selected from the group consisting of heat treatment, plasma treatment, and light irradiation may be performed.

The reactive gas is 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), nitrous oxide. 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 performed in the presence of an oxidizing gas such as water vapor, oxygen, ozone, a silicon oxide thin film may be formed, and when performed in the presence of a reducing gas such as hydrogen, ammonia, hydrazine, or silane, a thin film of silicon alone or silicon nitride may be formed. I can.

In addition, the heat treatment, plasma treatment, or light irradiation treatment process is for providing thermal energy for deposition of a 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, it is preferable to perform the above treatment so that the temperature of the substrate in the reactor is 100 to 1,000°C, preferably 300 to 500°C. .

In addition, during the treatment process, as described above, in order to assist the movement of the reactive gas onto the substrate or 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 introduction of the precursor for forming a silicon thin film, the introduction of the reactive gas, and the introduction of the inert gas are performed in one cycle. A metal-containing thin film can be formed by repeating one or more cycles.

In the method of manufacturing such a silicon-containing thin film, by using a precursor for forming a silicon thin film having excellent thermal stability, the deposition process can be carried out at a higher temperature than the conventional one during the deposition process, and particle contamination or impurities such as carbon due to thermal decomposition of the precursor. High purity silicon, silicon oxide or silicon nitride thin films can be formed without contamination. Accordingly, the silicon-containing thin film formed according to the manufacturing method of the present invention is useful as a high-k material film in a semiconductor device, particularly a DRAM, CMOS, etc. in a semiconductor memory device.

In yet another embodiment, a silicon thin film formed by the method of forming the silicon thin film and a semiconductor device including the thin film are provided. Specifically, the semiconductor device may be a semiconductor device including a metal insulator metal (MIM) for a random access memory (RAM).

In addition, the semiconductor device is the same as the configuration of a conventional semiconductor device, except that the silicon-containing thin film according to the present invention is included in a material film requiring high dielectric properties such as DRAM in the device. Detailed description of is omitted.

Although the present invention has been described with reference to a preferred embodiment as described above, it is not limited to the above embodiment, and various modifications and variations by those of ordinary skill in the art within the scope not departing from the spirit of the present invention. It is possible to change. Such modifications and variations should be viewed as falling within the scope of the present invention and the appended claims.

Claims (11)

A precursor for forming a silicon thin film comprising a modified disilazane compound represented by Chemical Formula 1.

[Formula 1]

In Formula 1,
R ₁ and R ₉ may be the same as or different from each other, and a C ₁ -C ₆ straight or branched alkyl group or alkylene group, a phenyl group with or without a substituent, a cycloalkyl group with or without a substituent, an amine group, or It is an alkylsilyl group.
The method according to claim 1,
A precursor for forming a silicon thin film, characterized in that it further comprises a solvent.
The method according to claim 2,
The solvent is _{a precursor for forming a silicon thin film, characterized in that one or more of C 1} -C ₁₆ saturated or unsaturated hydrocarbons, ethers, glyme, esters, tetrahydrofuran, and tertiary amines.
The method according to claim 2,
The solvent is a precursor for forming a silicon thin film, characterized in that contained in 1 to 99% by weight based on the total weight of the precursor composition for forming the silicon thin film.
A method of forming a silicon thin film comprising the step of depositing a silicon thin film on a substrate using the precursor for forming a silicon thin film according to claim 1 or 2.
The method of claim 5,
The silicon thin film is deposited by any one of atomic layer deposition, plasma enhanced chemical vapor deposition, or chemical vapor deposition. .
The method of claim 5,
And vaporizing the precursor for forming a silicon thin film and transferring it into the chamber.
The method of claim 5,
The deposition,
A first step of providing a substrate to the reactor;
A second step of introducing a silicon precursor including the modified disilazane compound represented by Chemical Formula 1 into the reactor;
A third step of purging the reactor with purge gas;
A fourth step of introducing a reactive gas into the reactor; And
And a fifth step of purging the reactor with a purge gas;
A method of forming a silicon thin film, characterized in that the second to fifth steps are repeated until a deposition film having a desired thickness is formed.
The method of claim 8,
The reactive gas is 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), nitrous oxide. Nitrogen (N ₂ O), nitrogen dioxide (NO ₂ ), hydrazine (N ₂ H ₄ ), and silane (SiH ₄ ) any one or more of the silicon thin film forming method.
The method of claim 8,
The deposition is performed at a temperature of 500° C. or less and a pressure in the range of 50 mTorr to 760 Torr.
A semiconductor device comprising a silicon thin film manufactured by the method of forming a silicon thin film of claim 5.