KR20220136072A - Growth inhibitor for forming thin film for and deposition method for preparing film using the same - Google Patents

Abstract

The present invention relates to a compound for inhibiting thin film growth. In forming a thin film with a metal precursor and a reactive gas, formation of the thin film is inhibited by a coordination bond with at least one of an reactive gas supplied to a chamber and an reactive gas deposition body. An objective of the present invention is to provide the compound for inhibiting the thin film growth, capable of easily removing a process by-product, and a thin film formation method using the same.

Description

Compound for inhibiting thin film growth and thin film formation method using the same

The present invention relates to a compound for 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 the conventional CVD method and exhibits excellent step coverage. There are still problems for In addition, there is a disadvantage that process by-products in the produced thin film may remain, which may lead to deterioration of the film quality.

Accordingly, it is necessary to develop a compound for inhibiting thin film growth that can improve step coverage while reducing process by-products.

It is an object of the present invention to provide a compound for inhibiting thin film growth that can easily remove process by-products while having excellent step coverage and a method for forming a thin film using the same.

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 inhibiting thin film growth.

According to one embodiment, in forming a thin film with the metal precursor and the reactive gas, the compound for inhibiting the growth of the thin film inhibits the formation of the thin film by coordination with at least one of the reactive gas and the reactive gas deposited to the chamber. .

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

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

The bonding strength of the reactive gas and the compound for inhibiting thin film growth may be 25 kcal/mol or less.

At least one of oxygen and nitrogen of the reactive gas may provide an electron pair to the compound for inhibiting growth of the thin film to form a bond.

According to another embodiment, the compound for inhibiting the growth of the thin film may be represented by the following formula (1).

[Formula 1]

(In Formula 1, M is a metal including one of boron (B), aluminum (Al) and gallium (Ga), R _{1 ,} R ₂ , and R ₃ is each independently a C1 to C20 linear or branched alkyl group, and n is each independently an integer from 0 to 1).

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

The compound for inhibiting the growth of the thin film may be coordinated with at least one of the reactive gas and the reactive gas deposit.

The compound for inhibiting the growth of the 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 R _4, R ₅ , and R ₆ may each independently be a C1 to C15 linear or branched alkyl group.

The compound for inhibiting the growth of the thin film may be represented by the following formula (3).

[Formula 3]

(In Formula 3, M is a metal including one of boron (B), aluminum (Al) and gallium (Ga), R _{7 ,} R ₈ , and R ₉ is each independently a C1 to C20 linear or branched alkyl group).

The R _{7 ,} R ₈ , and R ₉ may each independently be a C1 to C15 linear or branched alkyl group.

Each of R ₄ to R ₆ may independently include one or more of CH ₃ , C ₂ H ₅ , C ₃ H ₇ , C ₄ H ₉ and C ₅ H ₁₁ .

Each of R ₇ to R ₉ may independently include one or more of CH ₃ , C ₂ H ₅ , C ₃ H ₇ , C ₄ H ₉ and C ₅ H ₁₁ .

M may be boron (B).

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

According to one embodiment, the method for forming the thin film includes: positioning a substrate in a chamber; supplying a compound for inhibiting thin film growth into the chamber; primary purging of the chamber; supplying a metal precursor into the chamber; , Secondary purging of the interior of the chamber, supplying a reactive gas into the chamber, and tertiary purging of the interior of the chamber may be included.

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 compound for inhibiting the growth of the thin film may be represented by the following formula (1).

[Formula 1]

(In Formula 1, M is a metal including one of boron (B), aluminum (Al) and gallium (Ga), R _{1 ,} R ₂ , and R ₃ is each independently a C1 to C20 linear or branched alkyl group, and n is each independently an integer from 0 to 1).

The compound for inhibiting the growth of the thin film may be a material that coordinates with at least one of the reactive gas and the reactive gas deposition material.

The method of forming the thin film may be to deposit a thin film including a metal oxide or a metal nitride on the substrate.

The thin film forming method may be to deposit the thin film by 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 compound for inhibiting thin film growth that can easily remove process by-products while having excellent step coverage, and a method for forming a thin film using the same.

1 is a TEM of the HfO ₂ thin film on the SiO ₂ substrate of Example 1 of the present invention.
Figure 2 is a TEM of the HfO ₂ thin film on the SiN substrate of Example 2 of the present invention.

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 ₃ (CH ₂ ) ₂ and (CH ₃ ) ₂ CH.

In addition, in the present specification, C ₄ H ₉ may be CH ₃ (CH ₂ ) _{3 ,} (CH ₃ ) ₂ CHCH _{2 ,} CH ₃ CH ₂ CHCH ₃ and (CH ₃ ) ₃ C.

In addition, in the present specification, C ₅ H ₁₁ is CH ₃ (CH ₂ ) _4, CHCH _{3 (} CH ₂ ) ₂ (CH ₃ ), CH ₂ CHCH ₃ CH ₂ CH ₃ , (CH ₂ ) ₂ CH(CH ₃ ) ₂ , CHCH ₃ CH(CH ₃ ) _{2 ,} C(CH ₃ ) ₂ CH ₂ CH ₃ and CH ₂ C(CH ₃ ) ₃ .

In addition, in the present specification, the 'reactive gas deposition body' may refer to a reactive gas included as a part of an oxide film or a nitride film by bonding with a metal on which the reactive gas is deposited.

In addition, in the present specification, 'bonding strength' is the standard enthalpy when the reactive gas and the compound for inhibiting thin film growth are separated after coordination bonding, and may refer to the dissociation enthalpy of the following chemical reaction type.

2Me _n H ₃ N BH ₃ (g) --> B ₂ H ₆ (g) + 2Me _n H _(3-n) N(g)

In addition, 'uniformity' in the present specification was calculated by the following equation based on TEM analysis of the thin film.

Uniformity (%) = 1 - (M-m)/(M+m)

(Where M is the maximum thickness, m is the minimum thickness)

Compounds for inhibiting thin film growth

In one aspect of the present invention, the compound for inhibiting thin film growth inhibits thin film formation by coordination with at least one of the reactive gas and reactive gas vapor supplied to the chamber in forming a thin film with a metal precursor and a reactive gas. .

The compound for inhibiting thin film growth does not form a bond with the metal included in the metal precursor, but forms a coordination bond with at least one of the reactive gas and reactive gas deposits supplied to the chamber, thereby forming a metal oxide or metal While effectively suppressing the growth of the nitride (metal nitride), it is possible to reduce the process by-products because it is easy to remove after the formation of the metal oxide or metal nitride. 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.

In particular, since the compound for inhibiting thin film growth is not bound to a metal, it has the advantage of being applicable to various metal precursors without limitation.

The compound for inhibiting thin film growth can be used to deposit a thin film by atomic layer deposition (ALD), and without interfering with the adsorption of metal precursors, it effectively protects the substrate as a compound for inhibiting thin film growth and can be generated during the process. It has the advantage of effectively removing by-products.

Although the present invention is mainly described with ALD, it can be applied to all deposition methods such as CVD and PVD depending on the purpose and environment.

The metal precursor is not particularly limited if it is a metal precursor typically used in atomic layer deposition (ALD), but specifically may be a metal film precursor compound, a metal oxide film precursor compound, or a metal nitride film precursor compound, for example, the metal is 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 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-pentanoate], titanium bis[2,2-dimethyl-5-(2-methylethoxy)imino-3-heptanoate], zirconium tertiary butoxide, tetrakis(diethyl amido) 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(dimethyl amido) hafnium, silane, disilane, monochloro silane, dichloro silane, trichloro silane (SiCl ₃ H), hexachlorodi silane, diethyl silane, tetraethyl orthosilicate silane, diisopropylamino silane, bis(ter) Sherry-butylamino) silane, tetrakis(dimethylamino) silane, tetrakis(ethylmethylamino) silane, tetrakis(diethylamino) silane, tris(dimethylamino) silane, tris(ethylmethylamino) silane, tris( Diethylamino) silane, tris (dimethylhydrazino) silane, bis (diethylamino) silane, bis (diisopropylamino) silane, tris (isopropylamino) silane, (diisopropylamino) silane, tert- Butylimidomono(diethylamido)bis(iso-propylalkoxy)niobium, tert-butylimidomono(diethylamido)bis(tert-butylalkoxy)niobium, tert-butylimidomono(dimethylamido) Bis(iso-propylalkoxy)niobium, tert-butylimidomono(dimethylamido)bis(tert-butylalkoxy)niobium, tert-amylimidomono(diethylamido)bis(iso-propylaloxo)niobium , tert-ah Milimidomono(diethylamido)bis(tert-butylalkoxy)niobium, tert-amylimidomono(dimethylamido)bis(iso-propylalkoxy)niobium, tert-amylimidomono(dimethylamido)bis (tert-butyl alkoxy) niobium, tert-butylimidomono (tert-butylamido) bis (tert-butyl alkoxy) niobium, tert-butyl imidomono (di (trimethylsilyl) amido) bis (tert-butyl Alkoxo) Niobium, tert-butylimidomono(dimethylamido)bis(diethylhydroxylamino)niobium, tert-butylimidomono(diethylamido)bis(iso-propylalkoxy)tantalum, tert-butylimido Mono(diethylamido)bis(tert-butylalkoxy) tantalum, tert-butylimidomono(dimethylamido)bis(iso-propylalkoxy)tantalum, tert-butylimidomono(dimethylamido)bis(tert) -Butyl Alkoxo) 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-butylimidomono(di(trimethylsilyl)amido)bis(tert-butylalkoxy)tantalum and tert-butylimidomono(dimethylamido)bis(diethylhydro hydroxylamino) tantalum, but is not limited thereto.

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

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

Specifically, 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 ), and hydrazine (N ₂ H ₄ ) may be any one or more.

The bonding strength of the reactive gas and the compound for inhibiting thin film growth may be 25 kcal/mol or less, specifically 20 kcal/mol, more specifically 15 kcal/mol.

It is easy to remove the compound for inhibiting the growth of the thin film within the bonding strength range, thereby reducing the residual process by-products in the thin film.

At least one of oxygen and nitrogen of the reactive gas may provide an electron pair to the compound for inhibiting growth of the thin film to form a bond.

Specifically, when one of the reactive gas and reactive gas deposits and the compound for inhibiting thin film growth form a bond, the bond is formed while unilaterally providing an electron pair of oxygen and nitrogen of the reactive gas to the compound for inhibiting thin film growth. can be formed

The compound for inhibiting the growth of the thin film may be coordinated with one of the reactive gas and the reactive gas deposition material.

By forming a coordination bond between the compound for inhibiting the thin film growth and the reactive gas, it is possible to effectively suppress the growth of the thin film and implement a thin film having excellent step coverage, and it is easy to remove after the thin film is formed, thereby reducing process by-products and deterioration of the thin film. can prevent

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

[Formula 1]

(In Formula 1, M is a metal including one of boron (B), aluminum (Al) and gallium (Ga), R _{1 ,} R ₂ , and R ₃ is each independently a C1 to C20 linear or branched alkyl group, and n is each independently an integer from 0 to 1).

The thin film growth inhibitory compound is adsorbed first before adsorbing the metal precursor to the substrate, thereby effectively inhibiting the growth of metal oxide or metal nitride, while easily removing the metal oxide or metal nitride after formation. It has the effect of reducing process by-products.

The compound for inhibiting the growth of the thin film is, in order to effectively reduce process by-products, the R _{1 ,} R ₂ , and R ₃ may each independently be a C1 to C15 linear or branched alkyl group, specifically a C1 to C10 linear or branched alkyl group, more specifically, a C1 to C5 linear or branched alkyl group.

The M may include one of boron (B), aluminum (Al), and gallium (Ga).

M is a group 13 metal having three valence electrons, and can easily form a coordination bond like a transition metal, and can form a coordination bond by receiving an electron pair of oxygen and nitrogen of the reactive gas. Accordingly, process by-products can be effectively removed and step coverage can be improved.

M may include an alkyl group or an alkoxy group as a ligand.

In an embodiment, the compound for inhibiting growth of the 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 compound for inhibiting the growth of the thin film is, in order to effectively reduce process by-products, 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, more specifically a C1 to C5 linear or branched alkyl group.

For example, R ₄ to R ₆ may each independently include one or more of CH ₃ , C ₂ H ₅ , C ₃ H ₇ , C ₄ H ₉ and C ₅ H ₁₁ .

The compound for inhibiting thin film growth represented by Formula 2 is B(CH ₃ ) ₃ , B(C ₂ H ₅ ) ₃ , B(C ₃ H ₇ ) ₃ , B(C ₄ H ₉ ) ₃ , B(C ₅ ) H ₁₁ ) _{3 ,} B(CH ₃ ) ₂ (C ₂ H ₅ ), B(CH ₃ ) ₂ (C ₃ H ₇ ), B(CH ₃ ) ₂ (C ₄ H ₉ ), B(CH ₃ ) ₂ (C ₅ H ₁₁ ) _, B(CH ₃ )(C ₂ H ₅ ) ₂ , B(CH ₃ )(C ₂ H ₅ )(C ₃ H ₇ ), B(CH ₃ )(C ₂ H ₅ )( C ₄ H ₉ ), B(CH ₃ )(C ₂ H ₅ )(C ₅ H ₁₁ ) _, B(CH ₃ )(C ₃ H ₇ ) _{2 ,} B(CH ₃ )(C ₃ H ₇ )(C ₄ H ₉ ) _, B(CH ₃ )(C ₃ H ₇ )(C ₅ H ₁₁ ) _, B(CH ₃ )(C ₄ H ₉ ) _{2 ,} B(CH ₃ )(C ₄ H ₉ )(C ₅ ) H ₁₁ ) _, B(CH ₃ )(C ₅ H ₁₁ ) _2, B(C ₂ H ₅ ) ₂ (C ₃ H ₇ ), B(C ₂ H ₅ ) ₂ (C ₄ H ₉ ), B(C ₂ H ₅ ) ₂ (C ₅ H ₁₁ ), B(C ₂ H ₅ )(C ₃ H ₇ ) _2, B(C ₂ H ₅ )(C ₃ H ₇ )(C ₄ H ₉ ), B(C ₂ H ₅ )(C ₃ H ₇ )(C ₅ H ₁₁ ) _, B(C ₃ H ₇ ) ₂ (C ₄ H ₉ ), B(C ₃ H ₇ ) ₂ (C ₅ H ₁₁ ) _, B(C ₃ H ₇ )(C ₄ H ₉ ) ₂ , B(C ₃ H ₇ )(C ₅ H ₁₁ ) _2, B(C ₄ H ₉ ) ₂ (C ₅ H ₁₁ ), B(C ₄ H ₉ )(C ₅ H ₁₁ ) _{2 ,} Al(CH ₃ ) ₃ , Al(C ₂ H ₅ ) ₃ , Al(C ₃ H ₇ ) ₃ , Al(C ₄ H ₉ ) ₃ , Al (C ₅ H ₁₁ ) _3, Al(CH ₃ ) ₂ (C ₂ H ₅ ), Al(CH ₃ ) ₂ (C ₃ H ₇ ), Al(CH ₃ ) ₂ (C ₄ H ₉ ), Al(CH ₃ ) ₂ (C ₅ H ₁₁ ) _, Al(CH ₃ )(C ₂ H ₅ ) ₂ , Al(CH ₃ )(C ₂ H ₅ )(C ₃ H ₇ ), Al(CH ₃ )(C ₂ H ₅ )(C ₄ H ₉ ), Al(CH ₃ )(C ₂ H ₅ )(C ₅ H ₁₁ ) _, Al(CH ₃ )(C ₃ H ₇ ) _{2 ,} Al(CH ₃ )(C ₃ H ₇ ) )(C ₄ H ₉ ) _, Al(CH ₃ )(C ₃ H ₇ )(C ₅ H ₁₁ ) _, Al(CH ₃ )(C ₄ H ₉ ) _{2 ,} Al(CH ₃ )(C ₄ H ₉ ) (C ₅ H ₁₁ ) _, Al(CH ₃ )(C ₅ H ₁₁ ) _{2 ,} Al(C ₂ H ₅ ) ₂ (C ₃ H ₇ ), Al(C ₂ H ₅ ) ₂ (C ₄ H ₉ ), Al(C ₂ H ₅ ) ₂ (C ₅ H ₁₁ ), Al(C ₂ H ₅ )(C ₃ H ₇ ) _2, Al(C ₂ H ₅ )(C ₃ H ₇ )(C ₄ H ₉ ), Al(C ₂ H ₅ )(C ₃ H ₇ )(C ₅ H ₁₁ ) _, Al(C ₃ H ₇ ) ₂ (C ₄ H ₉ ), Al(C ₃ H ₇ ) ₂ (C ₅ H ₁₁ ) _, Al(C ₃ H ₇ )(C ₄ H ₉ ) ₂ , Al(C ₃ H ₇ )(C ₅ H ₁₁ ) _{2 ,} Al(C ₄ H ₉ ) ₂ (C ₅ H ₁₁ ), Al(C ₄ H ₉ )(C ₅ H ₁₁ ) _{2 ,} Ga(CH ₃ ) ₃ , Ga(C ₂ H ₅ ) ₃ , Ga(C ₃ H ₇ ) ₃ , Ga(C ₄ H ₉ ) ₃ , Ga (C ₅ H ₁₁ ) _3, Ga(CH ₃ ) ₂ (C ₂ H ₅ ), Ga(CH ₃ ) ₂ (C ₃ H ₇ ), Ga(CH ₃ ) ₂ (C ₄ H ₉ ), Ga(CH ₃ ) ₂ (C ₅ H ₁₁ ) _, Ga(CH ₃ )(C ₂ H ₅ ) ₂ , Ga(CH ₃ )(C ₂ H ₅ )(C ₃ H ₇ ), Ga(CH ₃ )(C ₂ H ) ₅ )(C ₄ H ₉ ), Ga(CH ₃ )(C ₂ H ₅ )(C ₅ H ₁₁ ) _, Ga(CH ₃ )(C ₃ H ₇ ) _{2 ,} Ga(CH ₃ )(C ₃ H ₇ ) )(C ₄ H ₉ ) _, Ga(CH ₃ )(C ₃ H ₇ )(C ₅ H ₁₁ ) _, Ga(CH ₃ )(C ₄ H ₉ ) _{2 ,} Ga(CH ₃ )(C ₄ H ₉ ) (C ₅ H ₁₁ ) _, Ga(CH ₃ )(C ₅ H ₁₁ ) _{2 ,} Ga(C ₂ H ₅ ) ₂ (C ₃ H ₇ ), Ga(C ₂ H ₅ ) ₂ (C ₄ H ₉ ), Ga(C ₂ H ₅ ) ₂ (C ₅ H ₁₁ ), Ga(C ₂ H ₅ )(C ₃ H ₇ ) _2, Ga(C ₂ H ₅ )(C ₃ H ₇ )(C ₄ H ₉ ), Ga(C ₂ H ₅ )(C ₃ H ₇ )(C ₅ H ₁₁ ) _, Ga(C ₃ H ₇ ) ₂ (C ₄ H ₉ ), Ga(C ₃ H ₇ ) ₂ (C ₅ H ₁₁ ) _, Ga(C ₃ H ₇ )(C ₄ H ₉ ) ₂ , Ga(C ₃ H ₇ )(C ₅ H ₁₁ ) _{2 ,} Ga(C ₄ H ₉ ) ₂ (C ₅ H ₁₁ ) and Ga(C ₄ H ₉ )(C ₅ H ₁₁ ) ₂ It may include one or more of, but is not limited thereto.

In another embodiment, the compound for inhibiting thin film growth may be represented by the following formula (3).

[Formula 3]

(In Formula 3, M is a metal including one of boron (B), aluminum (Al) and gallium (Ga), R _{7 ,} R ₈ , and R ₉ is each independently a C1 to C20 linear or branched alkyl group).

In order to effectively reduce the process by-products, the compound for inhibiting thin film growth is R _{7 ,} R ₈ , and R ₉ may each independently represent a C1 to C15 linear or branched alkyl group, specifically a C1 to C10 linear or branched alkyl group, more specifically, a C1 to C5 linear or branched alkyl group.

For example, R ₇ to R ₉ may each independently include one or more of CH ₃ , C ₂ H ₅ , C ₃ H ₇ , C ₄ H ₉ and C ₅ H ₁₁ .

The compound for inhibiting thin film growth represented by Formula 3 is B(OCH ₃ ) ₃ , B(OC ₂ H ₅ ) ₃ , B(OC ₃ H ₇ ) ₃ , B(OC ₄ H ₉ ) ₃ , B(OC ₅ ) H ₁₁ ) _{3 ,} B(OCH ₃ ) ₂ (OC ₂ H ₅ ), B(OCH ₃ ) ₂ (OC ₃ H ₇ ), B(OCH ₃ ) ₂ (OC ₄ H ₉ ), B(OCH ₃ ) ₂ (OC ₅ H ₁₁ ) _, B(OCH ₃ )(OC ₂ H ₅ ) ₂ , B(OCH ₃ )(OC ₂ H ₅ )(OC ₃ H ₇ ), B(OCH ₃ )(OC ₂ H ₅ )( OC ₄ H ₉ ), B(OCH ₃ )(OC ₂ H ₅ )(OC ₅ H ₁₁ ) _, B(OCH ₃ )(OC ₃ H ₇ ) _2, B(OCH ₃ )(OC ₃ H ₇ )(OC ₄ H ₉ ) _, B(OCH ₃ )(OC ₃ H ₇ )(OC ₅ H ₁₁ ) _, B(OCH ₃ )(OC ₄ H ₉ ) _2, B(OCH ₃ )(OC ₄ H ₉ )(OC ₅ H ₁₁ ) _, B(OCH ₃ )(OC ₅ H ₁₁ ) _2, B(OC ₂ H ₅ ) ₂ (OC ₃ H ₇ ), B(OC ₂ H ₅ ) ₂ (OC ₄ H ₉ ), B(OC ₂ H ₅ ) ₂ (OC ₅ H ₁₁ ), B(OC ₂ H ₅ )(OC ₃ H ₇ ) _2, B(OC ₂ H ₅ )(OC ₃ H ₇ )(OC ₄ H ₉ ), B(OC ₂ H ₅ )(OC ₃ H ₇ )(OC ₅ H ₁₁ ) _, B(OC ₃ H ₇ ) ₂ (OC ₄ H ₉ ), B(OC ₃ H ₇ ) ₂ (OC ₅ H ₁₁ ) _, B(OC ₃ H ₇ )(OC ₄ H ₉ ) ₂ , B(OC ₃ H ₇ )(OC ₅ H ₁₁ ) _2, B(OC ₄ H ₉ ) ₂ (OC ₅ H ₁₁ ), B(OC ₄ H ₉ )(OC ₅ H ₁₁ ) _{2 ,} Al(OCH ₃ ) ₃ , Al(OC ₂ H ₅ ) ₃ , Al(OC ₃ H ₇ ) ₃ , Al(OC ₄ H ₉ ) ₃ , Al (OC ₅ H ₁₁ ) _3, Al(OCH ₃ ) ₂ (OC ₂ H ₅ ), Al(OCH ₃ ) ₂ (OC ₃ H ₇ ), Al(OCH ₃ ) ₂ (OC ₄ H ₉ ), Al(OCH ₃ ) ₂ (OC ₅ H ₁₁ ) _, Al(OCH ₃ )(OC ₂ H ₅ ) ₂ , Al(OCH ₃ )(OC ₂ H ₅ )(OC ₃ H ₇ ), Al(OCH ₃ )(OC ₂ H ₅ )(OC ₄ H ₉ ), Al(OCH ₃ )(OC ₂ H ₅ )(OC ₅ H ₁₁ ) _, Al(OCH ₃ )(OC ₃ H ₇ ) _{2 ,} Al(OCH ₃ )(OC ₃ H ₇ ) )(OC ₄ H ₉ ) _, Al(OCH ₃ )(OC ₃ H ₇ )(OC ₅ H ₁₁ ) _, Al(OCH ₃ )(OC ₄ H ₉ ) _{2 ,} Al(OCH ₃ )(OC ₄ H ₉ ) (OC ₅ H ₁₁ ) _, Al(OCH ₃ )(OC ₅ H ₁₁ ) _{2 ,} Al(OC ₂ H ₅ ) ₂ (OC ₃ H ₇ ), Al(OC ₂ H ₅ ) ₂ (OC ₄ H ₉ ), Al(OC ₂ H ₅ ) ₂ (OC ₅ H ₁₁ ), Al(OC ₂ H ₅ )(OC ₃ H ₇ ) _{2 ,} Al(OC ₂ H ₅ )(OC ₃ H ₇ )(OC ₄ H ₉ ), Al(OC ₂ H ₅ )(OC ₃ H ₇ )(OC ₅ H ₁₁ ) _, Al(OC ₃ H ₇ ) ₂ (OC ₄ H ₉ ), Al(OC ₃ H ₇ ) ₂ (OC ₅ H ₁₁ ) _, Al(OC ₃ H ₇ )(OC ₄ H ₉ ) ₂ , Al(OC ₃ H ₇ )(OC ₅ H ₁₁ ) _{2 ,} Al(OC ₄ H ₉ ) ₂ (OC ₅ H ₁₁ ), Al(OC ₄ H ₉ )(OC ₅ H ₁₁ ) _{2 ,} Ga(OCH ₃ ) ₃ , Ga(OC ₂ H ₅ ) ₃ , Ga(OC ₃ H ₇ ) ₃ , Ga(OC ₄ H ₉ ) ₃ , Ga (OC ₅ H ₁₁ ) _3, Ga(OCH ₃ ) ₂ (OC ₂ H ₅ ), Ga(OCH ₃ ) ₂ (OC ₃ H ₇ ), Ga(OCH ₃ ) ₂ (OC ₄ H ₉ ), Ga(OCH ₃ ) ₂ (OC ₅ H ₁₁ ) _, Ga(OCH ₃ )(OC ₂ H ₅ ) ₂ , Ga(OCH ₃ )(OC ₂ H ₅ )(OC ₃ H ₇ ), Ga(OCH ₃ )(OC ₂ H ₅ )(OC ₄ H ₉ ), Ga(OCH ₃ )(OC ₂ H ₅ )(OC ₅ H ₁₁ ) _, Ga(OCH ₃ )(OC ₃ H ₇ ) _{2 ,} Ga(OCH ₃ )(OC ₃ H ₇ ) )(OC ₄ H ₉ ) _, Ga(OCH ₃ )(OC ₃ H ₇ )(OC ₅ H ₁₁ ) _, Ga(OCH ₃ )(OC ₄ H ₉ ) _{2 ,} Ga(OCH ₃ )(OC ₄ H ₉ ) (OC ₅ H ₁₁ ) _, Ga(OCH ₃ )(OC ₅ H ₁₁ ) _{2 ,} Ga(OC ₂ H ₅ ) ₂ (OC ₃ H ₇ ), Ga(OC ₂ H ₅ ) ₂ (OC ₄ H ₉ ), Ga(OC ₂ H ₅ ) ₂ (OC ₅ H ₁₁ ), Ga(OC ₂ H ₅ )(OC ₃ H ₇ ) _2, Ga(OC ₂ H ₅ )(OC ₃ H ₇ )(OC ₄ H ₉ ), Ga(OC ₂ H ₅ )(OC ₃ H ₇ )(OC ₅ H ₁₁ ) _, Ga(OC ₃ H ₇ ) ₂ (OC ₄ H ₉ ), Ga(OC ₃ H ₇ ) ₂ (OC ₅ H ₁₁ ) _, Ga(OC ₃ H ₇ )(OC ₄ H ₉ ) ₂ , Ga(OC ₃ H ₇ )(OC ₅ H ₁₁ ) _{2 ,} Ga(OC ₄ H ₉ ) ₂ (OC ₅ H ₁₁ ) and Ga(OC ₄ H ₉ )(OC ₅ H ₁₁ ) ₂ may include, but is not limited to.

In addition, in Formula 1, substituents bonded to the central metal M may be substituted by a combination of an alkoxy group and an alkyl group.

M may be boron (B).

Specifically, B(CH ₃ ) ₃ , B(C ₂ H ₅ ) ₃ , B(C ₃ H ₇ ) ₃ , B(C ₄ H ₉ ) ₃ , B(C ₅ H ₁₁ ) _{3 ,} B(CH ₃ ) ) ₂ (C ₂ H ₅ ), B(CH ₃ ) ₂ (C ₃ H ₇ ), B(CH ₃ ) ₂ (C ₄ H ₉ ), B(CH ₃ ) ₂ (C ₅ H ₁₁ ) _, B( CH ₃ )(C ₂ H ₅ ) ₂ , B(CH ₃ )(C ₂ H ₅ )(C ₃ H ₇ ), B(CH ₃ )(C ₂ H ₅ )(C ₄ H ₉ ), B(CH ₃ )(C ₂ H ₅ )(C ₅ H ₁₁ ) _, B(CH ₃ )(C ₃ H ₇ ) _{2 ,} B(CH ₃ )(C ₃ H ₇ )(C ₄ H ₉ ) _, B(CH ₃ ) )(C ₃ H ₇ )(C ₅ H ₁₁ ) _, B(CH ₃ )(C ₄ H ₉ ) _{2 ,} B(CH ₃ )(C ₄ H ₉ )(C ₅ H ₁₁ ) _, B(CH ₃ ) (C ₅ H ₁₁ ) _2, B(C ₂ H ₅ ) ₂ (C ₃ H ₇ ), B(C ₂ H ₅ ) ₂ (C ₄ H ₉ ), B(C ₂ H ₅ ) ₂ (C ₅ H ₁₁ ), B(C ₂ H ₅ )(C ₃ H ₇ ) _2, B(C ₂ H ₅ )(C ₃ H ₇ )(C ₄ H ₉ ), B(C ₂ H ₅ )(C ₃ H ₇ )(C ₅ H ₁₁ ) _, B(C ₃ H ₇ ) ₂ (C ₄ H ₉ ), B(C ₃ H ₇ ) ₂ (C ₅ H ₁₁ ) _, B(C ₃ H ₇ )(C ₄ H ₉ ) ₂ , B(C ₃ H ₇ )(C ₅ H ₁₁ ) _2, B(C ₄ H ₉ ) ₂ (C ₅ H ₁₁ ), B(C ₄ H ₉ )(C ₅ H ₁₁ ) _{2 ,} B(OCH ₃ ) ₃ , B(OC ₂ H ₅ ) ₃ , B(OC ₃ H ₇ ) ₃ , B(OC ₄ H ₉ ) ₃ , B (OC ₅ H ₁₁ ) _3, B(OCH ₃ ) ₂ (OC ₂ H ₅ ), B(OCH ₃ ) ₂ (OC ₃ H ₇ ), B(OCH ₃ ) ₂ (OC ₄ H ₉ ), B(OCH ₃ ) ₂ (OC ₅ H ₁₁ ) _, B(OCH ₃ )(OC ₂ H ₅ ) ₂ , B(OCH ₃ )(OC ₂ H ₅ )(OC ₃ H ₇ ), B(OCH ₃ )(OC ₂ H ) ₅ )(OC ₄ H ₉ ), B(OCH ₃ )(OC ₂ H ₅ )(OC ₅ H ₁₁ ) _, B(OCH ₃ )(OC ₃ H ₇ ) _2, B(OCH ₃ )(OC ₃ H ₇ ) )(OC ₄ H ₉ ) _, B(OCH ₃ )(OC ₃ H ₇ )(OC ₅ H ₁₁ ) _, B(OCH ₃ )(OC ₄ H ₉ ) _2, B(OCH ₃ )(OC ₄ H ₉ ) (OC ₅ H ₁₁ ) _, B(OCH ₃ )(OC ₅ H ₁₁ ) _{2 ,} B(OC ₂ H ₅ ) ₂ (OC ₃ H ₇ ), B(OC ₂ H ₅ ) ₂ (OC ₄ H ₉ ), B(OC ₂ H ₅ ) ₂ (OC ₅ H ₁₁ ), B(OC ₂ H ₅ )(OC ₃ H ₇ ) _2, B(OC ₂ H ₅ )(OC ₃ H ₇ )(OC ₄ H ₉ ), B(OC ₂ H ₅ )(OC ₃ H ₇ )(OC ₅ H ₁₁ ) _, B(OC ₃ H ₇ ) ₂ (OC ₄ H ₉ ), B(OC ₃ H ₇ ) ₂ (OC ₅ H ₁₁ ) _, B(OC ₃ H ₇ )(OC ₄ H ₉ ) ₂ , B(OC ₃ H ₇ )(OC ₅ H ₁₁ ) _{2 ,} B(OC ₄ H ₉ ) ₂ (OC ₅ H ₁₁ ) and B(OC ₄ H ₉ )(OC ₅ H ₁₁ ) ₂ may include, but is not limited to.

Thin film formation method

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

According to one embodiment, the thin film forming method includes the steps of positioning a substrate in a chamber, supplying a compound for inhibiting thin film growth into the chamber, purging the interior of the chamber first, and supplying a metal precursor into the chamber. Step, the step of purging the inside of the chamber secondary, the step of supplying a reactive gas into the chamber, and may include the steps of purging the interior of the chamber tertiary.

The thin film forming method may be to deposit the thin film by atomic layer deposition (ALD).

In the present invention, the purging may be 300 to 10,000 sccm, specifically 400 to 5,000 sccm, more specifically 400 to 3,000 sccm, and even more specifically 400 to 1,000 sccm, within which the thin film growth rate per cycle is preferred. It has the effect of reducing the range and reducing process by-products.

The atomic layer deposition (ALD) is very advantageous in the manufacture of integrated circuits (ICs) requiring a high aspect ratio, and in particular, excellent conformality and uniform coverage (conformality) due to a self-limiting thin film growth mechanism ( uniformity) and precise thickness control.

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

In addition, the present invention provides an ALD chamber, a first vaporizer for vaporizing a compound for inhibiting thin film growth, a first transporting means for transporting the vaporized compound for inhibiting thin film growth into the ALD chamber as a thin film manufacturing apparatus capable of implementing the thin film forming method; It may include a thin film manufacturing apparatus including a second vaporizer for vaporizing the metal precursor and a second transfer means for transferring the vaporized metal precursor into the ALD 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 inhibiting thin film growth 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), etc. may be used, and the substrate has a conductive layer or an insulating layer thereon This may be further formed.

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

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

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

After injecting the compound for inhibiting thin film growth or the composition for inhibiting thin film growth into a vaporizer, it is changed into a vapor phase and transferred to a deposition chamber to be adsorbed on the substrate, and the unadsorbed compound for inhibiting thin film growth is purged.

The composition for inhibiting thin film growth may be applied as a composition for inhibiting thin film growth including a solvent depending on the structure of the compound for inhibiting thin film growth. 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 inhibiting growth of the thin film.

The method for delivering the compound for inhibiting the growth of the thin film or the composition for inhibiting the growth of the thin film is a volatilization method in which a compound for inhibiting the growth of a thin film using vapor pressure (or a composition for inhibiting the growth of a thin film) or a volatilized gas of an organic solvent for improving the properties of the thin film is transferred into a chamber. A transfer method, a direct liquid injection method for directly injecting a liquid thin film growth inhibitory composition, or a liquid transfer method (LDS: Liquid Delivery System) for dissolving a thin film growth inhibitory composition in an organic solvent and transferring it can be applied. can

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

[Formula 1]

(In Formula 1, M is a metal including one of boron (B), aluminum (Al) and gallium (Ga), R _{1 ,} R ₂ , and R ₃ is each independently a C1 to C20 linear or branched alkyl group, and n is each independently an integer from 0 to 1).

The compound for inhibiting the growth of the thin film may be a material that coordinates with at least one of the reactive gas and the reactive gas deposition material.

The thin film growth inhibitory compound is adsorbed first before adsorbing the metal precursor to the substrate, thereby effectively inhibiting the growth of metal oxide or metal nitride, while easily removing the metal oxide or metal nitride after formation. It has the effect of 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 metal precursor adsorbed on the substrate may react with the oxidizing agent to form a metal oxide, and may react with the nitriding agent to form a metal nitride.

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 inhibiting the growth of the thin film of the present invention, the efficiency of removing the compound and process by-products for inhibiting the growth of the thin film in the step of supplying the reactive gas into the chamber and the third purging step is significantly improved, and the impurity content of the thin film is also can be reduced.

As described above, the step of supplying the compound for inhibiting thin film growth, the first purging step, the step of supplying the metal precursor, the second purging step, the step of supplying the reactive gas and the third purging step are unit cycles, and the desired The above unit cycle may be repeated to form a thin film having a thickness.

The unit cycle may be, for example, 1 to 1000 times, specifically 50 to 500 times, and more specifically 80 to 300 times, in which the desired thin film properties are well expressed.

The prepared thin film preferably has a thickness of 20 nm or less, a resistivity value of 0.1 to 400 μΩ·cm, an impurity content of 10,000 ppm or less, a step coverage ratio of 90% or more, and a uniformity of the thin film of 80% or more. have.

The thickness of the thin film may be 1 to 20 nm, specifically 5 to 15 nm, more specifically 5 to 10 nm, and within the above range, the thin film has excellent properties.

The resistivity value of the thin film may be 0.1 to 400 μΩ·cm, specifically 50 to 400 μΩ·cm, and more specifically 340 to 370 μΩ·cm, and within the above range, the thin film properties are excellent.

The impurity content of the thin film may be 1 to 9,000 ppm, specifically 100 to 8,500 ppm, and more specifically 1,000 to 8,200 ppm, and within the above range, the thin film has excellent properties.

The step coverage of the thin film may be 80% to 96%, specifically 90% to 96%, more specifically 92% to 96%, and the uniformity of the thin film is 80% to 99%, specifically 85% % to 98%, more specifically 90% to 96%, and even more specifically 93% to 96%, and in the above range, even a thin film having a complex structure can be easily deposited on a substrate, so it can be applied to next-generation semiconductor devices There are possible advantages.

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 of, 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

Tributyl borate was prepared as a compound for inhibiting thin film growth, and TEMAHf was prepared as a metal precursor. The prepared thin film growth inhibitory compound was placed in a canister and heated to 40 °C. A vaporized source was supplied using argon flowing at 200 sccm using a VFC (Vapor Flow Controller) as a carrier gas. After the compound for inhibiting the growth of the thin film vaporized in the canister was put into the deposition chamber loaded with the substrate for 3 seconds, argon gas was supplied at 700 sccm for 30 seconds to perform argon purging. At this time, the pressure in the reaction chamber was controlled to 1.5 Torr. Next, put the prepared TEMAHf in a separate canister, heat it to 80 °C, flow argon at a flow rate of 700 sccm, put TEMAHf vaporized in the canister into the vapor phase for 3 seconds, and then supply argon gas at 500 sccm for 10 seconds to argon. Purging was performed. At this time, the pressure in the reaction chamber was controlled to 1.5 Torr. Next, ozone as a reactive gas was introduced into the reaction chamber for 5 seconds, and then argon 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 250 °C. This process was repeated 100 times to form an HfO ₂ thin film.

Example 2

Tributyl borate was prepared as a compound for inhibiting thin film growth, and TEMAHf was prepared as a metal precursor. The prepared thin film growth inhibitory compound was placed in a canister and heated to 40 °C. A vaporized source was supplied using argon flowing at 200 sccm using a VFC (Vapor Flow Controller) as a carrier gas. After the compound for inhibiting the growth of the thin film vaporized in the canister was put into the deposition chamber loaded with the substrate for 3 seconds, argon gas was supplied at 700 sccm for 30 seconds to perform argon purging. At this time, the pressure in the reaction chamber was controlled to 1.5 Torr. Next, put the prepared TEMAHf in a separate canister, heat it to 80 °C, flow argon at a flow rate of 700 sccm, put TEMAHf vaporized in the canister into the vapor phase for 3 seconds, and then supply argon gas at 500 sccm for 10 seconds to argon. Purging was performed. At this time, the pressure in the reaction chamber was controlled to 1.5 Torr. Next, ozone as a reactive gas was introduced into the reaction chamber for 5 seconds, and then argon purging was performed for 10 seconds. At this time, the substrate on which the thin film is to be formed was SiN, and the substrate was heated to 250 °C. This process was repeated 100 times to form an HfO ₂ thin film.

Comparative Example 1

In Example 1, the HfO ₂ thin film was formed on the SiO ₂ substrate in the same manner as in Example 1, except that the compound for inhibiting the growth of the thin film was not used and the step of purging the compound for inhibiting the growth of the non-adsorbed thin film was omitted. did.

Comparative Example 2

An HfO ₂ thin film was formed on the SiN substrate in the same manner as in Example 1, except that the compound for inhibiting thin film growth was not used in Example 2 and the step of purging the compound for inhibiting growth of the non-adsorbed thin film was omitted. .

Assessment Methods

(1) Deposition rate: The deposition rates of the HfO ₂ thin films deposited in Examples 1 to 2 and Comparative Example 1 are shown in Table 1 below.

Example comparative example One 2 One 2 Deposition rate (Å/cycle) 0.67 0.63 0.85 0.78

(2) Thickness and uniformity: The thickness and uniformity of the HfO ₂ thin films deposited in Examples 1 to 2 and Comparative Example 1 were confirmed using TEM, and the TEM photograph of Example 1 is shown in FIG. 1, Example 2 The TEM picture is shown in FIG. 2 . The thickness of the 8-point thin film of Example 1 is shown in Table 2 below, and the thickness of the 8-point thin film of Example 2 is shown in Table 3 below. Average thin film thickness and uniformity results are shown in Tables 4 and 5, respectively. The uniformity was calculated by the following equation based on TEM analysis of the thin film.

Uniformity (%) = 1 - (M-m)/(M+m)

(Where M is the maximum thickness, m is the minimum thickness)

Point One 2 3 4 5 6 7 8 thin film thickness 6.74 6.36 7.04 6.18 6.98 7.04 6.92 6.18

Point One 2 3 4 5 6 7 8 thin film thickness 6.61 6.24 6.49 5.81 6.65 6.24 6.31 5.99

Example comparative example One 2 One 2 average thickness 6.68 6.29 8.45 7.8

Example One 2 Uniformity (%) 93 93

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 (22)

In forming a thin film with a metal precursor and a reactive gas,
A compound for inhibiting thin film growth by coordinating with at least one of the reactive gas supplied to the chamber and at least one of the reactive gas deposits.
According to claim 1,
The reactive gas and the compound for inhibiting the growth of the thin film are electrically neutral compounds for inhibiting the growth of the thin film.
According to claim 1,
The reactive gas is a compound for inhibiting thin film growth comprising at least one of an oxidizing agent and a nitriding agent.
According to claim 1,
The bonding strength of the reactive gas and the compound for inhibiting thin film growth is 25 kcal/mol or less of a compound for inhibiting thin film growth.
4. The method of claim 3,
A compound for inhibiting thin film growth, wherein at least one of nitrogen and oxygen of the reactive gas provides an electron pair to the compound for inhibiting thin film growth to form a bond.
A compound for inhibiting thin film growth represented by the following formula (1).
[Formula 1]

(In Formula 1, M is a metal including one of boron (B), aluminum (Al) and gallium (Ga), R _{1 ,} R ₂ , and R ₃ is each independently a C1 to C20 linear or branched alkyl group, and n is each independently an integer from 0 to 1).
7. The method of claim 6,
The R _{1 ,} R ₂ , and R ₃ are each independently a C1 to C15 linear or branched alkyl group for inhibiting thin film growth.
7. The method of claim 6,
The compound for inhibiting the growth of the thin film is a compound for inhibiting the growth of the thin film, which is a material that coordinates with at least one of the reactive gas and the reactive gas deposit.
7. The method of claim 6,
A compound for inhibiting thin film growth 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).
10. The method of claim 9,
The R _4, R ₅ , and R ₆ are each independently a C1 to C15 linear or branched alkyl group for inhibiting thin film growth.
7. The method of claim 6,
A compound for inhibiting thin film growth represented by the following formula (3).
[Formula 3]

(In Formula 3, M is a metal including one of boron (B), aluminum (Al) and gallium (Ga), R _{7 ,} R ₈ , and R ₉ is each independently a C1 to C20 linear or branched alkyl group).
12. The method of claim 11,
The R _{7 ,} R ₈ , and R ₉ are each independently a C1 to C15 linear or branched alkyl group for inhibiting thin film growth.
10. The method of claim 9,
The R ₄ to R ₆ are each independently CH ₃ , C ₂ H ₅ , C ₃ H ₇ , C ₄ H ₉ and C ₅ H ₁₁ A compound for inhibiting thin film growth comprising at least one.
12. The method of claim 11,
The R ₇ to R ₉ are each independently CH ₃ , C ₂ H ₅ , C ₃ H ₇ , C ₄ H ₉ and C ₅ H ₁₁ A compound for inhibiting thin film growth comprising at least one.
12. The method of claim 9 or 11,
wherein M is boron (B), a compound for inhibiting thin film growth.
positioning the substrate in the chamber;
supplying a compound for inhibiting thin film growth 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.
17. The method of claim 16,
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.
17. The method of claim 16,
The compound for inhibiting the growth of the thin film is a thin film forming method represented by the following Chemical Formula 1:
A method of forming a thin film represented by the following Chemical Formula 1:
[Formula 1]

(In Formula 1, M is a metal including one of boron (B), aluminum (Al) and gallium (Ga), R _{1 ,} R ₂ , and R ₃ is each independently a C1 to C20 linear or branched alkyl group, and n is each independently an integer from 0 to 1).
17. The method of claim 16,
The thin film growth inhibitory compound is a material that coordinates with at least one of the reactive gas and the reactive gas vapor deposition method.
17. The method of claim 16,
The method of forming the thin film is to deposit a thin film including a metal nitride or a metal oxide on the substrate.
17. The method of claim 16,
The thin film forming method is a thin film forming method of depositing a thin film by atomic layer deposition (ALD).
17. The method of claim 16,
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.

Images