KR20220143565A - Selective growth inhibitor for forming thin film for and deposition method for preparing film using the same - Google Patents

Abstract

According to the present invention, a compound for thin film growth suppression is the compound for selective thin film growth suppression which suppressing growth of a thin film by selectively forming combination with the thin film. The thin film comprises at least one between a metal nitride film and a metal oxide film.

Description

Compound for selective thin film growth inhibition and thin film formation method using the same

The present invention relates to a compound for selectively inhibiting thin film growth and a method for forming a thin film using the same.

In general, thin films such as dielectric films are deposited using deposition methods such as chemical vapor deposition (CVD), low pressure chemical vapor deposition (LPCVD), plasma-enhanced chemical vapor deposition (PECVD), and sputtering.

Methods based on chemical vapor deposition (CVD) may have adverse thermal effects on the device because thin films are deposited at relatively high temperatures. In addition, the CVD thin film has a non-uniform thickness, and the step coverage is not good.

On the other hand, atomic layer deposition (ALD) can be performed at a lower temperature than conventional chemical vapor deposition (CVD) and exhibits excellent step coverage. There is still a problem for implementing coverage, and there is a disadvantage that process by-products in the manufactured thin film remain, which may lead to deterioration of the film quality. In addition, in order to perform the selective deposition process, there is a problem in that a process is added, a process time is long, and the efficiency of the process is low, such as using a capping layer.

Accordingly, it is necessary to develop a compound for selective deposition of a thin film capable of improving step coverage and reducing process by-products while enabling selective deposition.

It is an object of the present invention to provide a compound for selective deposition and a method for forming a thin film using the same, which can improve step coverage and reduce process by-products while enabling selective deposition.

All of the above and other objects of the present invention can be achieved by the present invention described below.

One aspect of the present invention relates to a compound for selective thin film growth inhibition.

According to one embodiment, the selective thin film growth inhibitory compound is a compound for selective thin film growth inhibition that inhibits the growth of the thin film by selectively forming a bond with the thin film, and the thin film is a metal nitride film and a metal oxide film (Metal). oxide)).

The compound for selective thin film growth inhibition may be represented by the following formula (1).

[Formula 1]

(In Formula 1, in Formula 1, M is a metal including one of boron (B), aluminum (Al) and gallium (Ga), A, B and C are each independently O or N, o , p and q are each independently 0 or 1, and R _{1 ,} R ₂ and R ₃ are each independently a C1 to C20 linear or branched alkyl group).

The R _{1 ,} R ₂ and R ₃ may each independently be a C1 to C15 linear or branched alkyl group.

The R _{1 ,} R ₂ and R ₃ may each independently include one or more of CH ₃ , C ₂ H ₅ and C ₃ H ₇ .

The compound for selective thin film growth inhibition may be represented by the following formula (2).

[Formula 2]

(In Formula 2, M is a metal containing one of boron (B), aluminum (Al) and gallium (Ga), R _4, R ₅ , and R ₆ is each independently a C1 to C20 linear or branched alkyl group).

The R _4, R ₅ , and R ₆ may each independently be a C1 to C15 linear or branched alkyl group.

The R _{4 ,} R ₅ and R ₆ may each independently include one or more of CH ₃ , C ₂ H ₅ and C ₃ H ₇ .

M may be boron (B).

Another aspect of the present invention relates to a method for manufacturing a thin film formation method using a compound for selective thin film growth inhibition.

According to one embodiment, the manufacturing method comprises: locating a substrate on which at least one of a metal nitride film and a metal oxide film is formed in a chamber; supplying a compound for selective thin film growth inhibition into the chamber; Step, the step of supplying a metal precursor into the chamber, the step of purging the inside of the chamber second, the step of supplying a reactive gas into the chamber, and may include the steps of tertiary purging of the inside of the chamber.

The step of supplying the compound for selective thin film growth inhibition and primary purging may be repeated 5 to 50 times.

The steps of supplying the metal precursor, secondary purging, reactive gas supply, and tertiary purging may be repeated 10 to 1,000 times.

The compound for selective thin film growth inhibition may be represented by the following formula (1).

[Formula 1]

(In Formula 1, in Formula 1, M is a metal including one of boron (B), aluminum (Al) and gallium (Ga), A, B and C are each independently O or N, o , p and q are each independently 0 or 1, and R _{1 ,} R ₂ and R ₃ are each independently a C1 to C20 linear or branched alkyl group).

The reactive gas may include at least one of an oxidizing agent and a nitriding agent.

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 It may be any one or more of nitrogen (N ₂ O), nitrogen dioxide (NO ₂ ), and hydrazine (N ₂ H ₄ ).

The reactive gas and the compound for inhibiting thin film growth may be electrically neutral.

The method of forming the thin film may include depositing a thin film including a metal nitride and a metal oxide on the substrate.

The thin film forming method may be to deposit the thin film by one or more processes of chemical vapor deposition (CVD), physical vapor deposition (PVD), and atomic layer deposition (ALD).

The compound for inhibiting thin film growth and the metal precursor may be transferred into the chamber by any one of a volatilization transfer method using vapor pressure, a direct liquid injection method, or a liquid transfer method.

The present invention has the effect of providing a selective film growth inhibitory compound capable of improving step coverage and reducing process by-products, and a method for forming a thin film using the same, while selective deposition is possible.

Hereinafter, the present invention will be described in more detail.

In describing the present invention, if it is determined that a detailed description of a related known technology may unnecessarily obscure the gist of the present invention, the detailed description thereof will be omitted.

When 'including', 'having', 'consisting', etc. mentioned in this specification are used, other parts may be added unless 'only' is used. When a component is expressed in the singular, the case in which the plural is included is included unless specifically stated otherwise.

In addition, in interpreting the components, it is interpreted as including an error range even if there is no separate explicit description.

In addition, in this specification, 'X to Y' representing a range means 'X or more and Y or less'.

In addition, in the present specification, C ₃ H ₇ is (CH ₂ ) ₂ CH ₃ or CH(CH ₃ ) ₂ .

Compounds for selective thin film growth inhibition

One aspect of the present invention is a compound for selectively inhibiting growth of a thin film is a compound for selectively inhibiting growth of a thin film by selectively forming a bond with a thin film, and the thin film is a metal nitride film and a metal oxide film ( metal oxide).

The compound for selective thin film growth inhibition has different energy required for bonding with the metal nitride layer and the metal oxide layer, and thus can be selectively coupled to the thin film, thereby selectively depositing the thin film.

Specifically, the energy required for bonding the compound for selective thin film growth inhibition and the metal oxide layer may be greater than the energy required for bonding the compound for selective thin film growth inhibition and the metal nitride layer.

The energy required for the bonding may mean energy for stabilization when a bonding reaction occurs between the central metal included in the selective thin film growth inhibitory compound and the thin film including the metal oxide layer and the metal nitride layer.

Accordingly, a desired thin film can be grown by selectively depositing a metal oxide film while effectively suppressing the growth of the metal nitride film, and step coverage characteristics of the metal nitride film can be improved.

The selective thin film growth inhibitory compound may exhibit an effect as a growth inhibitory agent by selectively forming a bond with a thin film including a metal nitride film and a metal oxide film.

The selective bonding may mean that the bonding force of one thin film is greater or smaller than that of another thin film.

In addition, the selective thin film growth inhibitory compound can be easily removed after the formation of the metal nitride film and the metal oxide film, thereby reducing process by-products. By effectively removing the by-products, it is possible to prevent the deterioration of the thin film, and it is possible to exhibit the effect of improving the step coverage and the thickness uniformity.

The selective thin film growth inhibitory compound can be used to deposit a thin film by atomic layer deposition (ALD), and although the present invention is mainly described with ALD, chemical vapor deposition (CVD) and physical vapor deposition according to the purpose and environment It can be applied to all deposition methods such as vapor deposition (PVD).

The thin film may be formed of a metal precursor, and the metal precursor is not particularly limited if it is a metal precursor typically used in atomic layer deposition (ALD), but specifically a metal film precursor compound, a metal oxide film precursor compound, or a metal nitride film precursor It may be a compound, for example, the metal is silicon, tungsten, cobalt, chromium, aluminum, hafnium, vanadium, niobium, germanium, lanthanide, actinide, gallium, tantalum, zirconium, ruthenium, copper, titanium, nickel , iridium and molybdenum.

The metal film precursor, the metal oxide film precursor, or the metal nitride film precursor may be a metal halide, a metal alkoxide, an alkyl metal compound, a metal amino compound, a metal carbonyl compound, and a substituted or unsubstituted cyclopentadienyl metal compound, but is not limited thereto. it is not

For example, the metal film precursor, the metal oxide film precursor, and the metal nitride film precursor are trisilylamine (TSA), disiloxane (DSO), disilylmethylamine (DSMA), disilylethylamine (DSEA), disilylisopropyl Amine (DSIPA), disilyltertbutylamine (DSTBA), diethylaminosilane, diisopropylaminosilane (DIPAS), ditertbutylaminosilane, silylpiperidine, silylpyrrolidine, bis(diethylamino) silane (BDEAS), bis(dimethylamino)silane (BDMAS), bis(tert-butylamino)silane (BTBAS), bis(trimethylsilylamino)silane (BITS), bispiperidinosilane, bispyrrolidinosilane, Silyl triflate, ditriplatosilane, tetrachloro titanium, tetrakis(isopropoxide) titanium, titanium halide, cyclopentadienyl titanium, titanium bis(isopropoxide)bis(2,2,6,6- Tetramethyl-3,5-heptanedionate), titanium bis(4-(2-methylethoxy)imino-2-pentanonate), titanium bis[4-(ethoxy)imino-2-pentano ate], titanium bis[2,2-dimethyl-5-(2-methylethoxy)imino-3-heptanoate], zirconium tertiary butoxide, tetrakis (diethylamido) zirconium, tetrakis ( Ethylmethylamido) zirconium, tetrakis (dimethylamido) zirconium, tetrakis (1-methoxy-2-methyl-2-propoxy) zirconium, zirconium tetrachloride, tetrakis (1-methoxy-2-methyl) -2-propoxy) hafnium, hafnium tetrachloride, hafnium tertiary butoxide, tetrakis (diethylamido) hafnium, tetrakis (ethylmethylamido) hafnium, tetrakis (dimethylamido) hafnium, tert-butyl Imidomono(diethylamido)bis(iso-propylalkoxy) niobium, tert-butylimidomono(diethylamido)bis(tert-butylalkoxy)niobium, tert-butylimidomono(dimethylamido)bis (iso-propyl alkoxy) niobium, tert-butylimidomono (dimethylamido) bis (tert-butyl alkoxy) niobium, tert-amylimido mono (diethylamido) bis (iso-propyl alkoxy) niobium, tert-Amylimidomono(diethylamido)bis(tert) -Butyl Alkoxo) Niobium, tert-Amylimidomono(dimethylamido)bis(iso-propylalkoxy)niobium, tert-Amylimidomono(dimethylamido)bis(tert-butylalkoxy)niobium,tert-butyl imidomono(tert-butylamido)bis(tert-butylalkoxy)niobium, tert-butylimidomono(di(trimethylsilyl)amido)bis(tert-butylaloxo)niobium, tert-butylimidomono(dimethyl amido)bis(diethylhydroxylamino)niobium, tert-butylimidomono(diethylamido)bis(iso-propylalkoxy)tantalum, tert-butylimidomono(diethylamido)bis(tert-butyl Alkoxo) tantalum, tert-butylimidomono(dimethylamido)bis(iso-propylalkoxy)tantalum, tert-butylimidomono(dimethylamido)bis(tert-butylalkoxy)tantalum, tert-amylimidomono (diethylamido)bis(iso-propylalkoxy) tantalum, tert-amylimidomono(diethylamido)bis(tert-butylalkoxy)tantalum, tert-amylimidomono(dimethylamido)bis(iso -Propylalkoxy) tantalum, tert-amylimidomono(dimethylamido)bis(tert-butylalkoxy)tantalum, tert-butylimidomono(tert-butylamido)bis(tert-butylalkoxy)tantalum, tert -butylimidomo(di(trimethylsilyl)amido)bis(tert-butylalkoxy)tantalum and tert-butylimidomono(dimethylamido)bis(diethylhydroxylamino)tantalum, but are limited thereto it doesn't happen

The compound for selective thin film growth inhibition may be represented by the following formula (1).

[Formula 1]

(In Formula 1, in Formula 1, M is a metal including one of boron (B), aluminum (Al) and gallium (Ga), A, B and C are each independently O or N, o , p and q are each independently 0 or 1, and R _{1 ,} R ₂ and R ₃ are each independently a C1 to C20 linear or branched alkyl group).

The selective thin film growth inhibitory compound may exhibit an effect of selectively depositing a metal oxide film while effectively inhibiting the growth of a metal nitride film. In addition, it is possible to implement a remarkably improved step coverage by showing a strong bonding force with the metal nitride film.

The compound for inhibiting thin film growth is first adsorbed before adsorbing the metal precursor to the substrate, and can be easily removed after formation of the metal nitride or metal oxide film, thereby reducing process by-products.

In order for the selective thin film growth inhibitory compound to selectively bind strongly to the metal nitride film, R _{1 ,} R ₂ and R ₃ are each independently a C1 to C15 linear or branched alkyl group, specifically C1 to C10 linear or minute It may be a topographical alkyl group, more specifically, a C1 to C5 linear or branched alkyl group.

The R _{1 ,} R ₂ and R ₃ may each independently include one or more of CH ₃ , C ₂ H ₅ and C ₃ H ₇ .

In an embodiment, the compound for selectively inhibiting growth of a thin film may be represented by the following formula (2).

[Formula 2]

(In Formula 2, M is a metal containing one of boron (B), aluminum (Al) and gallium (Ga), R _4, R ₅ , and R ₆ is each independently a C1 to C20 linear or branched alkyl group).

The selective thin film growth inhibitory compound selectively binds strongly to the metal nitride film, the R _4, R ₅ , and R ₆ may each independently be a C1 to C15 linear or branched alkyl group, specifically, a C1 to C10 linear or branched alkyl group.

The R _{4 ,} R ₅ and R ₆ may each independently include one or more of CH ₃ , C ₂ H ₅ and C ₃ H ₇ .

The compound for selective thin film growth inhibition represented by Formula 2 is B(CH ₃ ) ₃ , B(CH ₃ ) ₂ (C ₂ H ₅ ), B(CH ₃ ) ₂ (C ₃ H ₇ ), B(CH ₃ ) )(C ₂ H ₅ ) ₂ , B(CH ₃ )(C ₃ H ₇ ) ₂ , B(CH ₃ )(C ₂ H ₅ )(C ₃ H ₇ ), B(C ₂ H ₅ ) ₃ , B(C ₂ H ₅ ) ₂ (C ₃ H ₇ ), B(C ₂ H ₅ )( C ₃ H ₇ ) ₂ , B(C ₃ H ₇ ) _{3 ,} Al(CH ₃ ) ₃ , Al(CH ₃ ) ₂ (C ₂ H ₅ ), Al(CH ₃ ) ₂ (C ₃ H ₇ ), Al (CH ₃ )(C ₂ H ₅ ) ₂ , Al(CH ₃ )(C ₃ H ₇ ) ₂ , Al(CH ₃ )(C ₂ H ₅ )(C ₃ H ₇ ), Al(C ₂ H ₅ ) ₃ , Al(C ₂ H ₅ ) ₂ (C ₃ H ₇ ), Al(C ₂ H ₅ )( C ₃ H ₇ ) ₂ , Al(C ₃ H ₇ ) _{3 ,} Ga(CH ₃ ) ₃ , Ga(CH ₃ ) ₂ (C ₂ H ₅ ), Ga(CH ₃ ) ₂ (C ₃ H ₇ ), Ga (CH ₃ )(C ₂ H ₅ ) ₂ , Ga(CH ₃ )(C ₃ H ₇ ) ₂ , Ga(CH ₃ )(C ₂ H ₅ )(C ₃ H ₇ ), Ga(C ₂ H ₅ ) ₃ , Ga(C ₂ H ₅ ) ₂ (C ₃ H ₇ ), Ga(C ₂ H ₅ )( It may include one or more of C ₃ H ₇ ) ₂ and Ga(C ₃ H ₇ ) ₃ , but is not limited thereto.

M may be boron (B).

Specifically, the compound is B(CH ₃ ) ₃ , B(CH ₃ ) ₂ (C ₂ H ₅ ), B(CH ₃ ) ₂ (C ₃ H ₇ ), B(CH ₃ )(C ₂ H ₅ ) ₂ , B(CH ₃ )(C ₃ H ₇ ) ₂ , B(CH ₃ )(C ₂ H ₅ )(C ₃ H ₇ ), B(C ₂ H ₅ ) ₃ , B(C ₂ H ₅ ) ₂ (C ₃ H ₇ ), B(C ₂ H ₅ )( It may include one or more of C ₃ H ₇ ) ₂ and B(C ₃ H ₇ ) ₃ , but is not limited thereto.

Thin film formation method

Another aspect of the present invention is a method for forming a thin film.

According to one embodiment, the manufacturing method comprises: locating a substrate on which at least one of a metal nitride film and a metal oxide film is formed in a chamber; supplying a compound for selective thin film growth inhibition into the chamber; Step, the step of supplying a metal precursor into the chamber, the step of purging the inside of the chamber second, the step of supplying a reactive gas into the chamber, and may include the steps of tertiary purging of the inside of the chamber.

The thin film forming method may be to deposit the thin film by one or more processes of chemical vapor deposition (CVD), physical vapor deposition (PVD), and atomic layer deposition (ALD).

In the present invention, the purging may be 100 to 8,000 sccm, specifically 200 to 6,000 sccm, more specifically 300 to 3,000 sccm, and even more specifically 300 to 1,000 sccm, within which the thin film growth rate per cycle is preferred. range, it is possible to control the physical properties of the thin film including the metal nitride film and the metal oxide film, there is an effect that the process by-products are reduced.

The thin film forming method may be carried out at a deposition pressure in the range of 0.1 to 10 Torr, specifically, at a deposition pressure in the range of 0.5 to 5 Torr, more specifically at a deposition pressure in the range of 0.5 to 2.5 Torr, There is an effect of obtaining a thin film of uniform thickness within the range.

In the present invention, the deposition temperature and the deposition pressure may be measured as the temperature and pressure formed in the deposition chamber, or may be measured as the temperature and pressure applied to the substrate in the deposition chamber.

The thin film forming method preferably includes the steps of: raising the temperature in the chamber to the deposition temperature before introducing the growth inhibitor for the selective thin film formation into the chamber; and/or purging by injecting an inert gas into the chamber before injecting the compound for selective thin film growth inhibition into the chamber.

In addition, the present invention is a thin film manufacturing apparatus capable of implementing the above thin film forming method, a deposition chamber, a first vaporizer for evaporating a compound for selective thin film growth inhibition, and a first transport for transporting a vaporized compound for selective thin film growth inhibition into the deposition chamber It may include a thin film manufacturing apparatus including a means, a second vaporizer for vaporizing the metal precursor, and a second transfer means for transferring the vaporized metal precursor into the deposition chamber. Here, the vaporizer and transfer means are not particularly limited if they are vaporizers and transfer means commonly used in the art to which the present invention belongs.

Hereinafter, each step will be described in detail.

First, the compound for selectively inhibiting growth of a thin film according to the present invention is supplied onto a substrate for forming a thin film. In this case, as the substrate for forming the thin film, it can be used without particular limitation as long as it is used for semiconductor manufacturing, which needs to be coated by a thin film due to a technical action. Specifically, a silicon substrate (Si), a silica substrate (SiO ₂ ), a silicon nitride substrate (SiN), a silicon oxynitride substrate (SiON), a titanium nitride substrate (TiN), a tantalum nitride substrate (TaN), a tungsten substrate (W) or a noble metal substrate, for example, a platinum substrate (Pt), a palladium substrate (Pd), a rhodium substrate (Rh) or a gold substrate (Au) may be used, and the substrate is a metal nitride film and a metal oxide film thereon One or more of them may be further formed.

The feeding time of the compound for selective thin film growth inhibition may be 1 to 10 seconds, specifically 1 to 5 seconds, more specifically 2 to 4 seconds per cycle, effectively inhibiting the growth of the thin film in the above range It can be done and has the advantage of being economically high.

In the present invention, one or more of a liquid mass flow controller (LMFC) method and a vapor flow controller (VFC) method may be applied to the supply of the compound for selective thin film growth inhibition.

In an embodiment, when the compound for selective thin film growth inhibition is supplied in the LMFC method, the feeding time of the compound for selective thin film growth inhibition is based on a volume of 15 to 20 L and a flow rate of 0.5 to 5 mg/s of the chamber, More specifically, it may be based on a volume of 18L and a flow rate of 1 to 2 mg/s of the chamber.

In another embodiment, when the compound for selective thin film growth inhibition is supplied in the VFC method, the carrier gas 80 sccm to 350 sccm, specifically 150 sccm to 250 sccm, may supply the vaporized compound for selective thin film growth inhibition. Here, the carrier gas may be argon.

After injecting the selective thin film growth inhibitory compound or selective thin film growth inhibiting composition into a vaporizer, it is changed into a vapor phase and transferred to a deposition chamber to be adsorbed on the substrate, and the non-adsorbed selective thin film growth inhibitory compound is purged (purging) ) do.

The composition for selective thin film growth inhibition may be applied as a selective thin film growth inhibitory composition including a solvent depending on the structure of the compound for selective thin film growth inhibition. The solvent may be included in an amount of 0.1 wt% to 99 wt%, specifically 0.1 wt% to 50 wt%, more specifically 1 wt% to 20 wt% of the composition for selective thin film growth inhibition.

The selective thin film growth inhibitory compound or selective thin film growth inhibitory composition delivery method uses vapor pressure for selective thin film growth inhibitory compound (or selective thin film growth inhibitory composition) or a vaporized gas of an organic solvent to improve thin film properties. A liquid transfer method (LDS: Liquid) in which a composition for selective thin film growth inhibition is dissolved in an organic solvent, or a direct liquid injection method that directly injects a liquid composition for selective thin film growth inhibition Delivery System) can be applied.

The compound for selective thin film growth inhibition may be represented by the following formula (1).

[Formula 1]

(In Formula 1, in Formula 1, M is a metal including one of boron (B), aluminum (Al) and gallium (Ga), A, B and C are each independently O or N, o , p and q are each independently 0 or 1, and R _{1 ,} R ₂ and R ₃ are each independently a C1 to C20 linear or branched alkyl group).

The selective thin film growth inhibitory compound may exhibit an effect of selectively depositing a metal oxide film while effectively inhibiting the growth of a metal nitride film. In addition, it is possible to implement a remarkably improved step coverage by showing a strong bonding force with the metal nitride film.

The compound for inhibiting thin film growth is first adsorbed before adsorbing the metal precursor to the substrate, and can be easily removed after formation of the metal nitride or metal oxide film, thereby reducing process by-products.

Next, after injecting the prepared metal precursor or precursor composition into the vaporizer, the vapor phase is transferred to the deposition chamber to be adsorbed on the substrate, and the non-adsorbed metal precursor is purged.

The precursor composition may be applied as a precursor composition including a solvent depending on the structure of the metal precursor. The solvent may be included in an amount of 0.1 wt% to 99 wt%, specifically 0.1 wt% to 50 wt%, and more specifically 1 wt% to 20 wt% of the precursor composition.

The metal precursor or precursor composition delivery method is a volatilization transport method in which a volatilized gas of an organic solvent for improving properties of a metal precursor (or precursor composition) or thin film is transferred into a chamber using vapor pressure, and a liquid precursor composition is directly injected. A direct liquid injection method or a liquid delivery system (LDS) in which a precursor composition is dissolved in an organic solvent and transferred may be applied.

Next, a reactive gas is supplied. The reactive gas may include at least one of an oxidizing agent and a nitriding agent, and specifically, water vapor (H ₂ O), oxygen (O ₂ ), ozone (O ₃ ), hydrogen peroxide (H ₂ O ₂ ), hydrogen (H ₂ ), ammonia (NH ₃ ), nitric oxide (NO), nitrous oxide (N ₂ O), nitrogen dioxide (NO ₂ ), and hydrazine (N ₂ H ₄ ) may be any one or more of.

The reactive gas and the compound for inhibiting thin film growth may be electrically neutral. In this case, compared to applying a compound for inhibiting growth of a thin film that is not electrically neutral, it is easier to remove after formation of a metal nitride film and a metal oxide film, thereby reducing process by-products. By effectively removing the by-products, it is possible to prevent the deterioration of the thin film, and it is possible to exhibit the effect of improving the step coverage and the thickness uniformity.

The metal precursor adsorbed on the substrate may react with the oxidizing agent to form a metal oxide layer, and may react with the nitriding agent to form a metal nitride layer.

Next, the unreacted residual reactive gas is purged using an inert gas. Accordingly, it is possible to remove not only the excess reactive gas but also the generated process by-products.

In particular, by applying the compound for selective thin film growth inhibition of the present invention, the efficiency of removing the selective thin film growth inhibitory compound and process by-products is significantly improved in the step of supplying the reactive gas into the chamber and the third purging step, and impurities in the thin film The content may also be reduced.

As above, supplying a compound for selective thin film growth inhibition, primary purging, supplying a metal precursor, secondary purging, supplying reactive gas and tertiary purging are unit cycles, The above unit cycle may be repeated to form a thin film having a desired thickness.

In the unit cycle, the step of supplying the compound for selective thin film growth inhibition and the first purging may be repeated 5 to 50 times, specifically 10 to 50 times, and more specifically 20 to 50 times.

In addition, in the unit cycle, the steps of supplying the metal precursor, secondary purging, reactive gas supply, and tertiary purging are repeated 10 to 1,000 times, specifically 50 to 500 times, and more specifically 100 to 300 times. can do.

There is an effect that the properties of the desired thin film are well expressed in the range of the process conditions and the number of times.

As another embodiment, a metal film formed by the method for forming the 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 random access memory (RAM).

In addition, the semiconductor device has the same configuration as a typical semiconductor device, except that the metal-containing thin film according to the present invention is included in a material film requiring high dielectric properties, such as DRAM in the device.

That is, in a capacitor in which a lower electrode, a dielectric thin film, and an upper electrode are sequentially stacked, the lower electrode and the upper electrode may include a metal material, and the shape of the lower electrode may be a flat plate, a cylinder, a pillar shape, or the like. may have various shapes, in this case, as the dielectric thin film, a thin film formed by the process of applying the compound for inhibiting thin film growth of the present invention may be applied.

The crystallinity, dielectric properties, and leakage current characteristics of the dielectric thin film may be improved by depositing the dielectric thin film on the cylindrical or pillar-shaped lower electrode by the method described above.

Hereinafter, the configuration and operation of the present invention will be described in more detail through preferred embodiments of the present invention. However, these are presented as preferred examples of the present invention and cannot be construed as limiting the present invention in any sense.

Content not described here will be omitted because it can be technically inferred sufficiently by those skilled in the art.

Example 1

The substrate on which SiO ₂ (Silicon Oxide) is deposited is prepared by performing RTA (Rapid Temperature Annealing) at 500° C. for 3 minutes. Triethyl boron (Triethyl boron) as a compound for inhibiting thin film growth and Diisopropylamino silane (DIPAS) as a metal precursor were prepared, respectively. The prepared thin film growth inhibitory compound was placed in a canister and heated to 30° C. to prepare. The compound for inhibiting the growth of the thin film vaporized in the vapor phase in the canister was added to the deposition chamber loaded with the substrate for 3 seconds without a separate carrier gas. At this time, the pressure in the chamber was controlled to 2 Torr, and then nitrogen gas was supplied at 300 sccm for 10 seconds to perform nitrogen purging. At this time, the pressure in the reaction chamber was controlled to 1.2 Torr. This process was repeated 30 times to sufficiently apply the compound for inhibiting thin film growth to the substrate, and then DIPAS was added. DIPAS was put in a separate canister and heated to 30° C., and then DIPAS vaporized in the canister without a separate carrier gas was put into the deposition chamber for 2 seconds. At this time, the pressure in the chamber was controlled to 1.6 Torr, and then nitrogen gas was supplied at 300 sccm for 10 seconds to perform nitrogen purging. At this time, the pressure in the reaction chamber was controlled to 1.2 Torr. Next, ozone as a reactive gas was introduced into the reaction chamber for 1 second, and then nitrogen purging was performed for 10 seconds. At this time, the substrate on which the thin film is to be formed is SiO ₂ , and the substrate was heated to 150°C. This process was repeated 100 times to form a SiO ₂ thin film.

Example 2

A SiO ₂ thin film was formed in the same manner as in Example 1 except that the deposited substrate was a silicon nitride (SiN) substrate.

Examples 1 and 2 were performed simultaneously in the same chamber.

Comparative Example 1

A SiO ₂ thin film was formed in the same manner as in Example 1 except that a compound for selective thin film growth inhibition was not used.

Comparative Example 2

A SiO ₂ thin film was formed in the same manner as in Example 2 except that a compound for selective thin film growth inhibition was not used.

In Comparative Example 1 and Comparative Example 2, processes were performed simultaneously in the same chamber.

Assessment Methods

(1) Deposition thickness: The deposition thickness of the SiO ₂ thin film deposited in Examples 1 to 2 and Comparative Examples 1 to 2 is shown in Table 1 below.

Example comparative example One 2 One 2 Deposition thickness (nm) 6.2 nm 4.8 nm 5.5 nm 3.9 nm

(2) GPC (growth per cycle): The GPC of the SiO ₂ thin film deposited in Examples 1 and 2 and Comparative Examples 1 and 2 is shown in Table 2 below.

Example comparative example One 2 One 2 GPC (Å/cycle) 0.62 0.48 0.55 0.39

As can be seen in Tables 1 and 2, it can be seen that Examples 1 and 2 to which the compound for selective thin film growth inhibition is applied suppresses thin film deposition compared to Comparative Examples 1 and 2. In addition, in Example 2 in which the deposited substrate is SiN, the thin film deposition is more effectively suppressed, and it can be confirmed that the selective thin film growth inhibitory compound selectively inhibits the thin film deposition.

Although the embodiments of the present invention have been described above, the present invention is not limited to the above embodiments, but may be manufactured in a variety of different forms, and those of ordinary skill in the art to which the present invention pertains will appreciate the technical spirit of the present invention. However, it will be understood that the invention may be embodied in other specific forms without changing essential features. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive.

Claims (18)

It is a compound for selective thin film growth inhibition that inhibits the growth of the thin film by selectively forming a bond with the thin film,
The thin film is a compound for selective thin film growth inhibition comprising at least one of a metal nitride film and a metal oxide film.
A compound for selective thin film growth inhibition represented by the following formula (1):
[Formula 1]

(In Formula 1, in Formula 1, M is a metal including one of boron (B), aluminum (Al) and gallium (Ga), A, B and C are each independently O or N, o , p and q are each independently 0 or 1, and R _{1 ,} R ₂ and R ₃ are each independently a C1 to C20 linear or branched alkyl group).
3. The method of claim 2,
Wherein R _1, R ₂ and R ₃ are each independently a C1 to C15 linear or branched alkyl group for selective thin film growth inhibition.
3. The method of claim 2,
The R _{1 ,} R ₂ and R ₃ are each independently CH ₃ , C ₂ H ₅ and C ₃ H ₇ A compound for selective thin film growth inhibition comprising at least one.
3. The method of claim 2,
A compound for selective thin film growth inhibition represented by the following formula (2).
[Formula 2]

(In Formula 2, M is a metal containing one of boron (B), aluminum (Al) and gallium (Ga), R _4, R ₅ , and R ₆ is each independently a C1 to C20 linear or branched alkyl group).
6. The method of claim 5,
The R _4, R ₅ , and R ₆ are each independently a C1 to C15 linear or branched alkyl group, a compound for selective thin film growth inhibition.
6. The method of claim 5,
The R _{4 ,} R ₅ and R ₆ are each independently CH ₃ , C ₂ H ₅ and C ₃ H ₇ A compound for selective thin film growth inhibition comprising at least one.
6. The method of claim 2 or 5,
wherein M is boron (B), a compound for selective thin film growth inhibition.
locating a substrate on which at least one of a metal nitride film and a metal oxide film is formed in a chamber;
supplying a compound for selective thin film growth inhibition into the chamber;
first purging the inside of the chamber;
supplying a metal precursor into the chamber;
Secondary purging of the inside of the chamber;
supplying a reactive gas into the chamber; and
tertiary purging of the inside of the chamber;
A thin film forming method comprising a.
10. The method of claim 9,
A thin film forming method repeating the step of supplying the compound for selective thin film growth inhibition and primary purging 5 to 50 times.
10. The method of claim 9,
A method of forming a thin film in which the steps of supplying the metal precursor, secondary purging, reactive gas supply, and tertiary purging are repeated 10 to 1,000 times.
10. The method of claim 9,
The selective thin film growth inhibitory compound is a thin film formation method represented by the following Chemical Formula 1:
[Formula 1]

(In Formula 1, in Formula 1, M is a metal including one of boron (B), aluminum (Al) and gallium (Ga), A, B and C are each independently O or N, o , p and q are each independently 0 or 1, and R _{1 ,} R ₂ and R ₃ are each independently a C1 to C20 linear or branched alkyl group).
10. The method of claim 9,
The reactive gas includes at least one of an oxidizing agent and a nitriding agent.
10. The method of claim 9,
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 ), and hydrazine (N ₂ H ₄ ) Any one or more of a thin film forming method.
10. The method of claim 9,
The reactive gas and the compound for inhibiting the growth of the thin film are electrically neutral thin film forming method.
10. The method of claim 9,
The method for forming the thin film is to deposit a thin film including a metal nitride and a metal oxide on the substrate.
10. The method of claim 9,
The thin film forming method is a thin film forming method of depositing a thin film by one or more processes of chemical vapor deposition (CVD), physical vapor deposition (PVD), and atomic layer deposition (ALD).
10. The method of claim 9,
The thin film growth inhibitory compound and the metal precursor are transferred into the chamber by any one of a volatilization transfer method using vapor pressure, a direct liquid injection method, or a liquid transfer method.