WO2014168312A1

WO2014168312A1 - Group iv transition metal-containing precursor compound, and method for depositing thin film using same

Info

Publication number: WO2014168312A1
Application number: PCT/KR2013/011370
Authority: WO
Inventors: 한원석
Original assignee: 주식회사 유피케미칼
Priority date: 2013-04-08
Filing date: 2013-12-09
Publication date: 2014-10-16
Also published as: KR20140121761A

Abstract

The present application relates to a group IV transition metal-containing precursor compound, to a method for preparing the precursor compound, to a precursor composition for deposition of a thin film comprising the precursor compound, and to a method for depositing the thin film using the precursor compound.

Description

Group 4 transition metal-containing precursor compound and thin film deposition method using the same

The present application relates to a Group 4 transition metal-containing precursor compound, a method for preparing the precursor compound, a precursor composition for thin film deposition including the precursor compound, and a method for depositing a thin film using the precursor compound.

HfO ₂ dielectric layer formed by depositing tetrakisethylmethylamidohafnium or tetrakisethylmethylamidozirconium [Zr (NEtMe) ₄ , TEMAZ] via atomic layer deposition (ALD) using ozone (O ₃ ), or ZrO ₂ dielectric layers have been used to fabricate semiconductor DRAMs (DRAM). For example, Korean Patent Laid-Open No. 10-2012-0038369 "Method for Manufacturing Semiconductor Device, Substrate Processing Device and Semiconductor Device" discloses forming a ZrO ₂ dielectric layer included in a semiconductor DRAM using TEMAZ. In addition, cyclopentadienyltris (dimethylamido) zirconium [CpZr (NMe ₂ ) ₃ ] having a pyrolysis temperature higher than TEMAZ may also be used to deposit a zirconium oxide film.

In order to increase the recording density of the semiconductor DRAM, it is preferable to form a high dielectric constant oxide film having a low aspect current in a structure having a higher aspect ratio. For this purpose, a zirconium oxide film or a hafnium oxide film can be formed using an atomic layer deposition method at a high temperature.

In order to shorten the time of the raw material supply cycle in the atomic layer deposition method, it is necessary to supply a large amount of zirconium or hafnium raw material in a short time, and for this purpose, it is preferable to use a liquid vaporization apparatus for instantaneously vaporizing the liquid raw material. In the liquid vaporization apparatus, the liquid is directly heated, and the liquid is directly vaporized by flash vaporization, so that the amount of raw material to be supplied can be precisely controlled. It is preferable that the zirconium raw material or hafnium raw material used for a liquid vaporization apparatus is a liquid at normal temperature. Raw materials that are solid at room temperature may also be heated to liquefy by melting above their melting point, or may be used in liquid vaporization devices in the form of solutions dissolved in a suitable solvent. When used in the form of a solution, the vapor pressure of the solvent should be less than the raw material to prevent the problem that the solvent evaporates in the liquid vaporization device to block the passage of the solution as a solid raw material.

Among the known zirconium or hafnium compounds, cyclopentadienyltris (dimethylamido) zirconium [CpZr (NMe ₂ ) ₃ ] compounds can be used for this purpose. Depending on the raw materials used in the atomic layer deposition method, the zirconium oxide film or the hafnium oxide film may differ in permittivity, leakage current, step coverage, etc., so that a new zirconium raw material compound or a new hafnium raw material can be selected so as to select the most suitable raw material for the desired purpose. The demand for compounds still exists in the semiconductor industry.

The present application is to provide a Group 4 transition metal-containing precursor compound represented by Formula 1 or Formula 2, a method for preparing the same, and a thin film deposition use thereof.

[Formula 1]

M ¹ (Cp ') _n (L) _4-n ;

In Chemical Formula 1,

M ¹ comprises Zr or Hf,

Cp 'comprises a cyclopentadienyl group which may be substituted by a C _1-4 alkyl group,

n is 1 or 2, and when n is 2, the two Cp's may be the same or different from each other,

L includes a C _1-3 alkyl group, a C _1-6 alkoxide group or -NHR ³ , wherein R ³ is a C _1-6 alkyl group, and when two or more L are two or more L, they may be the same or different from each other,

M ¹ is bonded to Cp ';

[Formula 2]

;

In Chemical Formula 2,

M ¹ comprises Zr or Hf,

Cp 'and Cp "each independently include a cyclopentadienyl group which may be substituted by a C _1-4 alkyl group,

L ¹ and L ² each independently include a C _1-3 alkyl group, a C _1-6 alkoxide group, or —NHR ³ , wherein R ³ is a C _1-6 alkyl group,

R ¹ and R ² each independently include hydrogen or a C _1-4 alkyl group,

M ¹ is bonded to Cp 'and Cp ".

However, the problem to be solved by the present application is not limited to the above-mentioned problem, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

A first aspect of the present application provides a Group 4 transition metal-containing precursor compound represented by Formula 1 or Formula 2 below:

[Formula 1]

M ¹ (Cp ') _n (L) _4-n ;

In Chemical Formula 1,

M ¹ comprises Zr or Hf,

M ¹ is bonded to Cp ';

[Formula 2]

;

In Chemical Formula 2,

M ¹ comprises Zr or Hf,

R ¹ and R ² each independently include hydrogen or a C _1-4 alkyl group,

M ¹ is bonded to Cp 'and Cp ".

A second aspect of the present application provides a method of preparing a Group 4 transition metal-containing precursor compound according to the first aspect, comprising:

M ¹ X ₄ and Cp'M ² are reacted in an organic solvent to form M ¹ (Cp ′) _n (X) _4-n ; And

Reacting the M ¹ (Cp ′) _n (X) _4-n and M ³ L in an organic solvent to form a Group 4 transition metal-containing precursor compound represented by Formula 1:

In M ¹ X ₄ and Cp'M ² , X includes a halo group, M ² and M ³ each independently include an alkali metal, and M ¹ , Cp ′, and L are each of the agent of the present application. Same as defined in 1 aspect.

A third aspect of the present application provides a method of preparing a Group 4 transition metal-containing precursor compound according to the first aspect, comprising:

Cp'M ¹ (NR'R ") ₃ and LH are reacted in an organic solvent to form a Group 4 transition metal-containing precursor compound represented by Formula 1:

In said Cp'M ¹ (NR'R ") ₃ , LH, R 'and R" are each independently of each other a C _1-4 alkyl group, M ¹ , Cp', and L are each in the first aspect of the present application Same as defined.

A fourth aspect of the present application provides a method of preparing a Group 4 transition metal-containing precursor compound according to the first aspect, comprising:

Cp'M ¹ (NR'R ") ₃ and Cp'H are reacted in an organic solvent to form Cp'M ¹ (NR'R") ₂ Cp '; And

Reacting the Cp'M ¹ (NR'R ") ₂ Cp 'and LH in an organic solvent to form a Group 4 transition metal-containing precursor compound represented by Formula 1:

In the Cp'M ¹ (NR'R ") ₃ , Cp'H, Cp'M ¹ (NR'R") and LH, R 'and R "are each independently a C _1-4 alkyl group, M ¹ And Cp 'are the same as defined above in each of the first aspects of the present application.

A fifth aspect of the present application provides a method of preparing a Group 4 transition metal-containing precursor compound according to the first aspect, comprising:

M ¹ (NR′R ″) ₄ and R ¹ R ² C (Cp'H) (Cp ″ H) are reacted in an organic solvent to form an intermediate compound represented by the following formula (3); And

Reacting the intermediate compound and LH in an organic solvent to form a Group 4 transition metal-containing precursor compound represented by Formula 2:

[Formula 2]

;

[Formula 3]

In M ¹ (NR ′ R ″) ₄ , R ¹ R ² C (Cp′H) (Cp ″ H), LH, Formula 2 and Formula 3, R ′ and R ″ are each independently C _{1- 4} alkyl group, M ¹ , Cp ', Cp ", R ¹ , R ² , L ¹ and L ² are the same as defined above in the first aspect of the present application.

A sixth aspect of the present application provides a precursor composition for depositing a Group 4 transition metal-containing thin film, comprising a Group 4 transition metal-containing precursor compound according to the first aspect of the present application.

A seventh aspect of the present application provides a method for depositing a Group 4 transition metal-containing thin film using the Group 4 transition metal-containing precursor compound according to the first aspect of the present application.

When the Group 4 transition metal-containing precursor compound according to the present invention is used as a raw material, an oxide of Group 4 transition metal is included in a uniform thickness on a surface having a high aspect ratio using an organometallic chemical vapor deposition method or an atomic layer deposition method at a high temperature. A thin film can be formed, and the recording density of the semiconductor DRAM can be improved by using the thin film for manufacturing a semiconductor DRAM.

When using the Group 4 transition metal-containing precursor compound as a raw material and forming a thin film containing an oxide of Group 4 transition metal by organometallic chemical vapor deposition or atomic layer deposition, For example, even at a high temperature of about 320 ℃ to about 360 ℃ can exhibit an excellent step coverage effect.

Group 4 transition metal-containing precursor compound according to one embodiment of the present application, for example, (EtCp) ₂ Zr (Me) ₂ , ( ⁱ PrCp) ₂ Zr (Me) ₂ , CpZr (O ^sec Bu) ₃ , CpZr (O ³ Pen) ₃ , CpZr (NH ^t Bu) ₃ , Cp (EtCp) Zr (OMe) ₂ , Cp ( ⁱ PrCp) Zr (OMe) ₂ , (MeCp) (EtCp) Zr (OMe) ₂ , (EtCp ) ₂ Zr (OMe) ₂ , and Cp (EtCp) Zr (OEt) ₂ , and (MeCp) ₂ Zr (OEt) ₂ are liquid at room temperature, Cp (MeCp) Zr (OMe) ₂ , (MeCp) ₂ Zr (OMe) ₂ , Cp (MeCp) Zr (OEt) ₂ ,

, And

May be usefully used as a precursor composition for thin film deposition in that it is in a liquid state at a volatilization temperature, and particularly useful in a liquid raw material supply device used with an atomic layer deposition apparatus or a chemical vapor deposition apparatus.

1 is a graph showing the results of thermogravimetric analysis of a Group 4 transition metal-containing precursor compound prepared according to one embodiment of the present application.

Figure 2 is a graph showing the results of thermogravimetric analysis of Group 4 transition metal-containing precursor compound prepared according to an embodiment of the present application.

3 is a graph showing film growth per atomic layer deposition cycle of a zirconium oxide thin film formed according to an embodiment of the present application.

4A to 4F are transmission electron micrographs showing a cross section of a zirconium oxide thin film formed on a narrow, deep grooved substrate according to one embodiment of the present application.

5A to 5F are transmission electron micrographs showing a cross section of a zirconium oxide thin film formed on a narrow, deep grooved substrate according to one embodiment of the present application.

6 is a graph showing film growth per atomic layer deposition cycle of a zirconium oxide thin film formed according to an embodiment of the present application.

DETAILED DESCRIPTION Hereinafter, exemplary embodiments of the present disclosure will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present disclosure. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. In the drawings, parts irrelevant to the description are omitted for simplicity of explanation, and like reference numerals designate like parts throughout the specification.

Throughout this specification, when a portion is "connected" to another portion, this includes not only "directly connected" but also "electrically connected" with another element in between. do.

Throughout this specification, when a member is located "on" another member, this includes not only when one member is in contact with another member but also when another member exists between the two members.

Throughout this specification, when a part is said to "include" a certain component, it means that it can further include other components, without excluding the other components unless specifically stated otherwise.

As used throughout this specification, the terms "about", "substantially" and the like are used at, or in the sense of, numerical values when a manufacturing and material tolerance inherent in the stated meanings is indicated, Accurate or absolute figures are used to assist in the prevention of unfair use by unscrupulous infringers.

As used throughout this specification, the term "step to" or "step of" does not mean "step for."

Throughout this specification, the term "combination (s) thereof" included in the representation of a makushi form refers to one or more mixtures or combinations selected from the group consisting of the components described in the representation of makushi form, It means to include one or more selected from the group consisting of the above components.

Throughout this specification, the description of "A and / or B" means "A or B, or A and B."

Throughout this specification, the term "alkyl group" includes a linear or branched C _1-10 alkyl group, C _1-6 alkyl group, C _1-4 alkyl group, C _1-3 alkyl group, or C _3-6 alkyl group, respectively. It may be, for example, may include, but is not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, or all possible isomers thereof.

Throughout this specification, the term "alkoxide group" is a form in which the alkyl group and the oxygen atom as defined above are bonded, and may include a C _1-10 alkoxide group, a C _1-6 alkoxide group or a C _3-6 alkoxide group, eg For example, methoxide, ethoxide, propoxide, butoxide, pentoxide, hexoxide, hexoxide, octoside, nonoxide, desoxide, or all possible isomers thereof may be included, but is not limited thereto. You may not.

Throughout this specification, the term "halo group" means that a halogen element belonging to Group 17 of the periodic table is included in the compound in the form of a functional group, and the halogen element is, for example, F, Cl, Br, or I It may be, but may not be limited thereto.

Throughout this specification, the term "alkali metal" refers to a metal belonging to Group 1 of the periodic table, and may be Li, Na, Ca, Rb, or Cs, but may not be limited thereto.

Throughout this specification, the term “Group 4 transition metal” refers to a transition metal belonging to Group 4 of the periodic table, which may for example be Ti, Zr, or Hf, and in particular herein may mean Zr or Hf. However, this may not be limited. It is generally known that among Group 4 transition metals, especially Zr and Hf are almost indistinguishable from each other and the properties of Zr and Hf compounds are very similar. It is common sense for organometallic chemists that a compound in which Zr is substituted with Hf in a Zr compound can be synthesized in the same manner as the Zr compound, and that the properties of the synthesized Hf compound are very similar to that of the Zr compound.

Throughout this specification, the term "cyclopentadienyl (group)" may be abbreviated as Cp and refers to a 5-membered ring aromatic cyclic substituent of -C ₅ H ₅ .

Hereinafter, embodiments of the present disclosure have been described in detail, but the present disclosure may not be limited thereto.

[Formula 1]

M ¹ (Cp ') _n (L) _4-n ;

In Chemical Formula 1,

M ¹ comprises Zr or Hf,

n is 1 or 2, and when n is 2, the two Cp's may be the same or different from each other

L comprises a C _1-3 alkyl group, a C _1-6 alkoxide group or —NHR ³ , wherein said R ³ is a C _1-6 alkyl group and when two or more L are two or more L they may be the same or different from each other;

M ¹ is bonded to Cp ';

[Formula 2]

;

In Chemical Formula 2,

M ¹ comprises Zr or Hf; Cp 'and Cp "each independently include a cyclopentadienyl group which may be substituted by a C _1-4 alkyl group; L ¹ and L ² each independently represent a C _1-3 alkyl group, C _{1- 6} alkoxide group, or —NHR ³ , wherein R ³ is a C _1-6 alkyl group, R ¹ and R ² each independently comprise hydrogen or a C _1-4 alkyl group; and M ¹ is Bound to Cp 'and Cp ".

As a non-limiting example, the C _1-3 alkyl group may be a methyl group, an ethyl group, an n-propyl group, or an iso-propyl group, but may not be limited thereto.

As a non-limiting example, the C _1-6 alkoxide group is a methoxy, ethoxy, n-propoxide group, iso-propoxide group, n-butoxide group, iso-butoxide group, sec-butoxide group , but may include tert-butoxide group, 1-pentoxide group, 2-pentoxide group, or 3-pentoxide group, but may not be limited thereto. Throughout this specification, the n-propoxide group may be abbreviated as O ⁿ Pr as CH ₃ (CH ₂ ) ₂ O— and the iso-propoxide group is referred to as O ⁱ Pr as (CH ₃ ) ₂ CHO-. May be abbreviated and the n-butoxide group may be abbreviated to O ⁿ Bu as CH ₃ (CH ₂ ) ₃ O— and the iso-butoxide group is referred to as O ⁱ Bu as (CH ₃ ) ₂ CHCH ₂ O— May be abbreviated and the sec-butoxide group may be abbreviated to O ^sec Bu as CH ₃ CH ₂ CH (CH ₃ ) O— and the tert-butoxide group is referred to as O ^t Bu as (CH ₃ ) ₃ CO— It may be abbreviated, but may not be limited thereto. In addition, the 1-pentoxide group is abbreviated O ¹ Pen as CH ₃ (CH ₂ ) ₄ O— and the 2-pentoxide group is CH ₃ [CH ₃ (CH ₂ ) ₂ ] CHO— It is abbreviated as O ² Pen and the 3-pentoxide group may be abbreviated as O ³ Pen as (CH ₃ CH ₂ ) ₂ CHO-, but may not be limited thereto.

As a non-limiting example, R ³ in -NHR ³ may include a C _1-6 alkyl group or a C _3-6 alkyl group, for example, methylamino group, ethylamino group, n-propylamino group, iso-propylamino group, An n-butylamino group, iso-butylamino group, sec-butylamino group, tert-butylamino group, 1-pentylamino group, 2-pentylamino group, or may include 3-pentylamino group, but may not be limited thereto. Throughout this specification, the n-propylamino group may be abbreviated as NH ⁿ Pr as CH ₃ (CH ₂ ) ₂ NH—, and the iso-propylamino group may be abbreviated as NH ⁱ Pr as (CH ₃ ) ₂ CHNH- Wherein the n-butylamino group may be abbreviated NH ⁿ Bu as CH ₃ (CH ₂ ) ₃ NH— and the iso-butylamino group may be abbreviated NH ⁱ Bu as (CH ₃ ) ₂ CHCH ₂ NH— Wherein the ^sec -butylamino group may be abbreviated as NH ^sec Bu as CH ₃ CH ₂ CH (CH ₃ ) NH- and the tert-butylamino group may be abbreviated as NH ^t Bu as (CH ₃ ) ₃ CNH- It may be, but may not be limited thereto. In addition, the 1-pentylamino group is abbreviated NH ¹ Pen as CH ₃ (CH ₂ ) ₄ NH-, and the 2-pentylamino group is abbreviated NH ² Pen as CH ₃ [CH ₃ (CH ₂ ) ₂ ] CHNH-. The 3-pentylamino group may be abbreviated as NH ³ Pen as (CH ₃ CH ₂ ) ₂ CHNH-, but may not be limited thereto.

According to an embodiment of the present disclosure, L, L ¹ and L ² are each independently a methyl group, an ethyl group, a propyl group, an iso-propyl group, a methoxide group, an ethoxide group, an n-propoxide group, and iso It may include, but is not limited to, a propoxide group, an iso-butoxide group, a sec-butoxide group, a 3-pentoxide group, or a tert-butylamino group.

In Formula 1, when L is two or more, they may be the same or different from each other, but may not be limited thereto.

According to an embodiment of the present disclosure, wherein Cp 'and Cp "each independently comprise a cyclopentadienyl group which may be substituted by a C _1-4 alkyl group, wherein Cp' or Cp" is 1 to 5 substituents It may include, wherein 1 to 5 hydrogen atoms of the Cp 'or Cp "may be independently substituted by the C _1-4 alkyl group. For example, Cp (ie, C ₅ H ₅ ), a substituent C ₅ H ₄ (CH ₃ ) comprising one methyl group, C ₅ H ₄ (C ₂ H ₅ ) comprising one ethyl group, C ₅ H ₄ (CH ₂ containing one n-propyl group as a substituent) CH ₂ CH ₃ ), or may include C ₅ H ₄ (CH (CH ₃ ) ₂ ) including one iso-propyl group as a substituent, but may not be limited thereto.

For example, C ₅ H ₄ (C ₂ H ₅ ), which is a kind of Cp ′, may be abbreviated as EtCp, and C ₅ H ₄ (CH ₂ CH ₂ CH ₃ ) may be abbreviated as ⁿ PrCp, The C ₅ H ₄ (CH (CH ₃ ) ₂ ) may be abbreviated as ⁱ PrCp, but may not be limited thereto. As a non-limiting example, Cp ′ and Cp ″ may be each independently Cp, MeCp, EtCp, ⁿ PrCp, ⁱ PrCp, ⁱ BuCp, ^sec BuCp, or ^t BuCp, but may not be limited thereto.

When n is 2 in Formula 1, the two Cp's may be the same or different from each other. In addition, in Formula 2, Cp ′ and Cp ″ may be the same as or different from each other.

According to the exemplary embodiment of the present application, R ¹ and R ² may be the same or different from each other, and may include ones selected from the group consisting of methyl group, ethyl group, n-propyl group, and iso-propyl group, respectively. This may not be limited.

According to an embodiment of the present disclosure, the Group 4 transition metal-containing precursor compound may include (EtCp) ₂ Zr (Me) ₂ , ( ⁱ PrCp) ₂ Zr (Me) ₂ , CpZr (O ^sec Bu) ₃ , CpZr ( O ³ Pen) ₃ , CpZr (NH ^t Bu) ₃ , Cp (MeCp) Zr (OMe) ₂ , (MeCp) ₂ Zr (OMe) ₂ , Cp (EtCp) Zr (OMe) ₂ , Cp ( ⁱ PrCp) Zr (OMe) ₂ , (MeCp) (EtCp) Zr (OMe) ₂ , (EtCp) ₂ Zr (OMe) ₂ , Cp (MeCp) Zr (OEt) ₂ , Cp (EtCp) Zr (OEt) ₂ , (MeCp) ₂ Zr (OEt) ₂ ,

,

, (EtCp) ₂ Hf (Me) ₂ , ( ⁱ PrCp) ₂ Hf (Me) ₂ , ( ⁱ PrCp) ₂ Hf (Me) ₂ , CpHf (O ^sec Bu) ₃ , CpHf (O ³ Pen) ₃ , CpHf (NH ^t Bu) ₃ , Cp (MeCp) Hf (OMe) ₂ , (MeCp) ₂ Hf (OMe) ₂ , Cp (EtCp) Hf (OMe) ₂ , Cp ( ⁱ PrCp) Hf (OMe) ₂ , (MeCp ) (EtCp) Hf (OMe) ₂ , (EtCp) ₂ Hf (OMe) ₂ , Cp (MeCp) Hf (OEt) ₂ , Cp (EtCp) Hf (OEt) ₂ , (MeCp) ₂ Hf (OEt) ₂ ,

, And

It may be to include one selected from the group consisting of, but may not be limited thereto. (EtCp) ₂ Zr (Me) ₂ , ( ⁱ PrCp) ₂ Zr (Me) ₂ , CpZr (O ^sec Bu) ₃ , CpZr (O ³ Pen) ₃ , CpZr (NH ^t Bu) ₃ , Cp (EtCp) Zr (OMe) ₂ , Cp ( ⁱ PrCp) Zr (OMe) ₂ , (MeCp) (EtCp) Zr (OMe) ₂ , (EtCp) ₂ Zr (OMe) ₂ , Cp (EtCp) Zr (OEt ) ₂ , and (MeCp) ₂ Zr (OEt) ₂ is a liquid at room temperature, Cp (MeCp) Zr (OMe) ₂ , (MeCp) ₂ Zr (OMe) ₂ , Cp (MeCp) Zr (OEt) ₂ ,

, And

May be usefully used as a precursor for thin film deposition in the presence of a liquid at a volatilization temperature, but may not be limited thereto.

According to one embodiment of the present application, the Group 4 transition metal-containing precursor compound may include, but is not limited to, a liquid at room temperature or a liquid at a volatilization temperature. Accordingly, (EtCp) ₂ Zr (Me) ₂ , ( ⁱ PrCp) ₂ Zr (Me) ₂ , CpZr (O ^sec Bu) ₃ , CpZr (O ³ Pen) ₃ , CpZr (NH ^t Bu) which are liquid at room temperature ) ₃ , ( ⁿ PrCp) ₂ Zr (Me) ₂ , Cp (MeCp) Zr (OMe) ₂ , (MeCp) ₂ Zr (OMe) ₂ , Cp (EtCp) Zr (OMe) ₂ , Cp ( ⁱ PrCp) Zr (OMe) ₂ , (MeCp) (EtCp) Zr (OMe) ₂ , (EtCp) ₂ Zr (OMe) ₂ , Cp (MeCp) Zr (OEt) ₂ , Cp (EtCp) Zr (OEt) ₂ , (MeCp) ₂ Zr (OEt) ₂ and liquid at volatilization temperature

,

And other Group 4 transition metal-containing precursor compounds according to the first aspect of the present application, which are liquid at room temperature or liquid at volatilization temperature, can be usefully used when forming thin films using chemical vapor deposition or atomic layer deposition. However, this may not be limited.

M ¹ X ₄ and Cp'M ² are reacted in an organic solvent to form M ¹ (Cp ′) _n (X) _4-n ; And reacting the M ¹ (Cp ′) _n (X) _4-n and M ³ L in an organic solvent to form a Group 4 transition metal-containing precursor compound represented by Formula 1:

[Formula 1]

M ¹ (Cp ') _n (L) _4-n ;

M ¹ , Cp ′, n, and L in Formula 1 are the same as defined in the first aspect of the present application, respectively; In M ¹ X ₄ And Cp'M ² , X includes a halo group, and M ² and M ³ each independently include an alkali metal.

[Formula 1]

M ¹ (Cp ') _n (L) _4-n ;

In the above Cp'M ¹ (NR'R ") ₃ , LH, and Formula 1, R 'and R" may be the same or different from each other, and each independently include a C _1-4 alkyl group; M ¹ , Cp ′, and L are the same as defined above in the first aspect of the present application, respectively.

[Formula 1]

M ¹ (Cp ') _n (L) _4-n ;

In the above Cp'M ¹ (NR'R ") ₃ , Cp'H, Cp'M ¹ (NR'R"), LH and Formula 1, R 'and R "may be the same or different from each other, and each independently And C _1-4 alkyl group, M ¹ , Cp ′, n, and L are the same as defined above in the first aspect of the present application.

[Formula 2]

;

[Formula 3]

In M ¹ (NR ′ R ″) ₄ , R ¹ R ² C (Cp′H) (Cp ″ H), LH, Formula 2, and Formula 3, R ′ and R ″ may be the same as or different from each other. Each independently comprises a C _1-4 alkyl group; M ¹ , Cp ′, Cp ″, R ¹ , R ² , L ¹ and L ² are the same as defined above in each of the first aspects herein.

According to one embodiment of the present application, the organic solvent may be one selected from the group consisting of toluene, benzene, hexane, pentane, tetrahydrofuran, dichloromethane, chloroform, ether, and combinations thereof, but It may not be limited.

A sixth aspect of the present application provides a precursor composition for depositing a Group 4 transition metal-containing thin film including a Group 4 transition metal-containing precursor compound according to the first aspect of the present application.

The second to seventh aspects of the present application are each a method for producing a Group 4 transition metal-containing precursor compound according to the first aspect of the present application, a precursor composition for thin film deposition including the precursor compound, and the precursor compound As a method of depositing a thin film, detailed descriptions of parts overlapping with the first aspect of the present application have been omitted, but the descriptions of the first aspect of the present disclosure are not described in each of the second to seventh aspects of the present application. The same may be applied even if omitted.

According to the exemplary embodiment of the present disclosure, depositing the thin film may be performed by organometallic chemical vapor deposition (MOCVD) or atomic layer deposition (ALD), but may not be limited thereto.

According to the exemplary embodiment of the present application, the thin film may include, but may not be limited to, a Group 4 transition metal-containing oxide, nitride, or oxynitride.

For example, the thin film in each of the sixth and seventh aspects of the present application includes a ZAZ multilayer film in which zirconium oxide (ZrO ₂ ) / aluminum oxide (Al ₂ O ₃ ) / zirconium oxide (ZrO ₂ ) is sequentially formed. It may be, but may not be limited thereto.

Hereinafter, preferred embodiments of the present application are described. However, the following examples are only illustrated to aid the understanding of the present application, but the content of the present invention is not limited to the following examples.

The relationship between the compounds synthesized in Examples 1 to 16 and Formula 1 and Formula 2 expressed as general formulas are summarized in Table 1 below.

Table 1

EXAMPLE

Example 1 Synthesis of (EtCp) ₂ Zr (Me) ₂

In a flame dried 250 mL Schlenk flask, 17.8 g (189 mmol, 2.2 eq) of ethylcyclopentadiene (EtCpH) was dissolved in 100 mL of diethyl ether and kept at -30 ° C. To the flask maintained at -30 ° C, 118 mL (189 mmol, 2.2 equiv) of n-BuLi solution (1.6 M in hexane) was slowly added dropwise to prepare a mixed solution, and the mixed solution was stirred at room temperature for 3 hours. 20 g (86 mmol, 1 equivalent) of zirconium chloride [Zirconium (IV) chloride, ZrCl ₄ ] dissolved in 50 mL of diethyl ether was slowly added dropwise to the stirred solution at 0 ° C., and then further stirred at room temperature for 3 hours. Stirred. Then 118 mL (189 mmol, 2.2 equiv) of MeLi solution (1.6 M in diethyl ether) was slowly added dropwise at 20 ° C., followed by stirring at room temperature for further 12 h. When the reaction was completed, the solvent and volatile side reactions in the solution was removed under reduced pressure and extracted with 200 mL of normal hexane. The normal hexane extract was filtered through a Celite pad and a glass frit to remove the solvent under reduced pressure, and then distilled under reduced pressure to obtain a pale yellow liquid compound.

Yield: 19.03 g (72.1%);

Elemental analysis: calcd (C ₁₆ H ₂₄ Zr) C, 62.48; H, 7.86. Found C, 62.23; H, 7.89;

Boiling point (b.p): 121 ° C., 0.35 torr;

¹ H-NMR (400 MHz, C ₆ D _6, 25 ° C.): δ 5.695, 5.516 (m, 8H, C ₅ H ₄ -CH ₂ CH ₃ ), 2.384 (q, 4H, C ₅ H ₄ -C H ₂ CH ₃ ), 1.081 (t, 6H, C ₅ H ₄ -CH ₂ C H ₃ ), -0.150 (s, 6H, Zr-C H ₃ ).

Example 2: Synthesis of ( ⁱ PrCp) ₂ Zr (Me) ₂

In a flame-dried 250 mL Schlenk flask, 20.4 g (189 mmol, 2.2 equiv) of isopropylcyclopentadiene ( ⁱ PrCpH) was dissolved in 100 mL of diethyl ether and kept at -30 ° C. To the flask maintained at -30 ° C, 118 mL (189 mmol, 2.2 equiv) of n-BuLi solution (1.6 M in hexane) was slowly added dropwise, and the mixture was stirred at room temperature for 3 hours. 20 g (86 mmol, 1 equivalent) of zirconium chloride [Zirconium (IV) chloride, ZrCl ₄ ] dissolved in 50 mL of diethyl ether was slowly added dropwise to the stirred solution at 0 ° C., and then further stirred at room temperature for 3 hours. Stirring was performed. Then 118 mL (189 mmol, 2.2 equiv) of MeLi solution (1.6 M in diethyl ether) was slowly added dropwise at 20 ° C., followed by stirring at room temperature for additional 12 hours. When the reaction was completed, the solvent and volatile side reactions in the solution was removed under reduced pressure, and then extracted with 200 mL of normal hexane. The normal hexane extract was filtered through a Celite pad and a glass frit, and the filtrate obtained was freed of solvent under reduced pressure, and then distilled under reduced pressure to obtain a pale yellow liquid compound.

Yield: 20.54 g (71.3%);

Elemental analysis: calcd (C ₁₈ H ₂₈ Zr) C, 64.41; H, 8.41. Found C, 63.34; H, 8. 37;

Boiling point (b.p): 116 ° C., 0.35 torr;

¹ H-NMR (400 MHz, C ₆ D _6, 25 ° C.): δ 5.742, 5.573 (m, 8H, C ₅ H ₄ -CH (CH ₃ ) ₂ ), 2.743 (m, 2H, C ₅ H _4- C H (CH ₃ ) ₂ ), 1.121 (d, 12H, C ₅ H ₄ -CH (CH ₃ ) ₂ ), 0.119 (s, 6H, Zr-C H ₃ ).

Example 3: Preparation of CpZr (O ^sec Bu) ₃

In a flame dried 1000 mL Schlenk flask, 100.0 g (0.347 mol) of CpZr (NMe ₂ ) ₃ was dissolved in 300 mL of hexane and kept at 0 ° C. Thus, 77.1 g (1.040 mol) of 2-butanol was slowly added to the flask maintained at 0 ° C., and then the reaction solution was slowly heated to room temperature. Thereafter, the reaction was completed by stirring for 15 hours while the reaction solution was maintained at room temperature.

After the reaction was completed, the solvent was removed under reduced pressure, and then distilled under reduced pressure to obtain a pale yellow liquid compound represented by the following Chemical Formula 4.

[Formula 4]

;

Yield: 95.04 g (73%);

Boiling point (bp): 107 ° C. (0.3 torr);

¹ H-NMR (C ₆ D ₆ ): δ 6.306 (s, 5H, C ₅ H ₅ ), 3.956 (m, 3H, OC H (CH ₃ ) (CH ₂ CH ₃ )), 1.424 (m, 6H, OCH (CH ₃ ) (C H ₂ CH ₃ ) ), 1.159 (d, 9H, OCH (C H ₃ ) (CH ₂ CH ₃ )), 0.985 (t, 9H, OCH (CH ₃ ) (CH ₂ C H ₃ )).

On the other hand, with respect to Example 3, Figure 1 is a graph showing the thermal weight analysis results of CpZr (O ^sec Bu) ₃ , a Group 4 transition metal-containing precursor compound according to Example 3. As shown in FIG. 1, CpZr (O ^sec Bu) _{3, which} is a Group 4 transition metal-containing precursor compound of the present application, can be confirmed that a rapid weight loss occurs at 150 ° C. to 280 ° C. in a thermogravimetric analysis (TGA) graph. Half-life T _1/2 was 202 degreeC.

Example 4: Preparation of CpZr (O ³ Pen) ₃

In a flame dried 1000 mL Schlenk flask, 100.0 g (0.347 mol) of CpZr (NMe ₂ ) ₃ was dissolved in 300 mL of hexane and kept at 0 ° C. To this flask maintained at 0 ° C., 91.7 g (1.040 mol) of 3-pentanol was slowly added, and the reaction solution was slowly heated to room temperature. Thereafter, the reaction was completed by stirring for 15 hours while the reaction solution was maintained at room temperature.

After the reaction was completed, the solvent was removed under reduced pressure, and then distilled under reduced pressure to obtain a yellow liquid compound represented by the following Chemical Formula 5:

[Formula 5]

;

Yield: 107.14 g (74%);

Boiling point (bp): 120 ° C. (0.3 torr);

¹ H-NMR (C ₆ D ₆ ): δ 6.326 (s, 5H, C ₅ H ₅ ), 3.713 (m, 3H, OC H (CH ₂ CH ₃ ) ₂ ), 1.445 (m, 12H, OCH (C H ₂ CH ₃ ) ₂ ), 0.985 (t, 18H, OCH (CH ₂ C H ₃ ) ₂ ).

On the other hand, with respect to Example 4, Figure 2 is a graph showing the thermal weight analysis results of CpZr (O ³ Pen) _{3 which} is a Group 4 transition metal-containing precursor compound according to the fourth embodiment. As shown in FIG. 2, CpZr (O ³ Pen) _{3, which} is a Group 4 transition metal-containing precursor compound of the present application, was found to have a rapid weight loss at 150 ° C. to 250 ° C. in a thermogravimetric analysis (TGA) graph. Half-life T _1/2 was 229 degreeC.

Example 5: Preparation of CpZr (NH ^t Bu) ₃

In a flame dried 1000 mL Schlenk flask, 30.0 g (0.114 mol) of CpZrCl ₃ were dissolved in 300 mL of hexane and kept at 0 ° C. In this flask maintained at 0 ° C., 132 mL (0.343 mol) of n-BuLi solution (2.6 M in hexane) and 25.1 g (0.343 mol) of tert-butylamine were dissolved in 200 mL of hexane. In-situ prepared LiNH ^t Bu was slowly added, and the reaction solution was slowly heated to room temperature. The reaction was then completed by stirring the reaction solution at room temperature for 15 hours.

After the reaction was completed, the resultant was filtered through a pad of celite and glass frit to remove the solvent by placing the filtrate under reduced pressure, and then distilled under reduced pressure to give a yellow liquid compound represented by the following formula (6). :

[Formula 6]

;

Yield: 14.47 g (34%);

Boiling point (bp): 122 ° C. (0.3 torr);

¹ H-NMR (C ₆ D ₆ ): δ 6.160 (s, 5H, C ₅ H ₅ ), 4.364 (br, 3H, N H C (CH ₃ ) ₃ ), 1.226 (s, 27H, NHC (C H ₃ ) ₃ ).

Example 6: Preparation of Cp (MeCp) Zr (OMe) ₂

In a flame dried 1000 mL Schlenk flask, 100.0 g (0.347 mol, 1 equiv) of CpZr (NMe ₂ ) ₃ was dissolved in 300 mL of toluene and kept at 0 ° C. Thus, 27.8 g (0.347 mol, 1 equivalent) of methylcyclopentadiene (MeCpH) was slowly added dropwise to the flask maintained at 0 ° C, and the mixture was stirred at room temperature for 5 hours. To the solution was added 22.2 g (0.693 mol, 2 equiv) of methanol slowly at 0 ° C. and then stirred for an additional 5 hours at room temperature to complete the reaction.

After the reaction was completed as such, the solvent and the volatile side reactions were removed under reduced pressure, and then distilled under reduced pressure to obtain a yellow solid compound.

Yield: 74.34 g (72.1%);

Elemental analysis: calcd (C ₁₃ H ₁₈ O ₂ Zr) C, 52.48; H, 6. 10; O, 10.76. Found C, 51.59; H, 6. 13; 0, 10.49;

Boiling point (b.p): 106 ° C., 0.30 torr;

¹ H-NMR (400 MHz, C ₆ D _6, 25 ° C.): δ 6.003, 5.843, 5.740 (m, 9H, C ₅ H _5, C ₅ H ₄ -CH ₃ ), 3.835 (s, 6H, OC H ₃ ), 2.051 (s, 3H, C ₅ H ₄ -C H ₃ ).

Example 7: Preparation of (MeCp) ₂ Zr (OMe) ₂

In a flame dried 1000 mL Schlenk flask, 100.0 g (0.309 mol) of Zr (NEtMe) ₄ was dissolved in 300 mL of toluene and kept at 0 ° C. 49.5 g (0.618 mol, 2 equivalents) of methylcyclopentadiene were slowly added dropwise to the flask maintained at 0 ° C., and the mixed solution was refluxed for 5 hours. The reaction was completed by slowly adding 19.8 g (0.618 mol, 2 equiv) of methanol to the solution at 0 ° C. and refluxing for an additional 3 hours.

Yield: 71.43 g (74.2%);

Elemental analysis: calcd (C ₁₄ H ₂₀ O ₂ Zr) C, 53.98; H, 6. 47; O, 10.27. Found C, 54.23; H, 6.39; 0, 10.34;

Boiling point (b.p): 111 ° C., 0.30 torr;

¹ H-NMR (400 MHz, C ₆ D _6, 25 ° C.): δ 5.838, 5.783 (m, 8H, C ₅ H ₄ -CH ₃ ), 3.869 (s, 6H, OC H ₃ ), 2.050 (s, 6H, C ₅ H ₄ -C H ₃ ).

Example 8: Preparation of Cp (EtCp) Zr (OMe) ₂

In a flame dried 1000 mL Schlenk flask, 100.0 g (0.347 mol) of CpZr (NMe ₂ ) ₃ was dissolved in 300 mL of toluene and kept at 0 ° C. Thus, 32.6 g (0.347 mol, 1 equivalent) of ethylcyclopentadiene (EtCpH) was slowly added dropwise to the flask maintained at 0 ° C, and the mixture was stirred at room temperature for 5 hours. To the solution was added 22.2 g (0.693 mol, 2 equiv) of methanol slowly at 0 ° C. and then stirred for an additional 5 hours at room temperature to complete the reaction.

After the reaction was completed as such, the solvent and the volatile side reactions were removed under reduced pressure, and then distilled under reduced pressure to obtain a yellow liquid compound.

Yield: 79.57 g (73.7%);

Elemental analysis: calcd (C ₁₄ H ₂₀ O ₂ Zr) C, 53.98; H, 6. 47; O, 10.27. Found C, 52.92; H, 6. 37; 0, 10.15;

Boiling point (b.p): 109 ° C., 0.30 torr;

¹ H-NMR (400 MHz, C ₆ D _6, 25 ° C.): δ 6.002, 5.862, 5.785 (m, 9H, C ₅ H _5, C ₅ H ₄ -CH ₂ CH ₃ ), 3.799 (s, 6H, OC H ₃ ), 2.469 (q, 2H, C ₅ H ₄ -C H ₂ CH ₃ ), 1.116 (t, 3H, C ₅ H ₄ -CH ₂ C H ₃ ).

Example 9: Preparation of Cp ( ⁱ PrCp) Zr (OMe) ₂

In a flame dried 1000 mL Schlenk flask, 100.0 g (0.347 mol) of CpZr (NMe ₂ ) ₃ was dissolved in 300 mL of toluene and kept at 0 ° C. Such added dropwise to the flask maintaining the 0 ℃, an isopropyl-cyclo-penta-diene ^{(isopropylcyclopentadiene, i PrCpH) 37.5 g} (0.347 mol, 1 eq) then slowly, the mixture was stirred at room temperature for 5 hours. To the solution was added 22.2 g (0.693 mol, 2 equiv) of methanol slowly at 0 ° C. and then stirred for an additional 5 hours at room temperature to complete the reaction.

Yield: 81.12 g (71.9%);

Elemental analysis: calcd (C ₁₅ H ₂₂ O ₂ Zr) C, 55.34; H, 6.81; O, 9.83. Found C, 54.87; H, 6.76; 0, 9.45;

Boiling point (b.p): 116 ° C., 0.30 torr;

¹ H-NMR (400 MHz, C ₆ D _6, 25 ° C.): δ 6.011, 5.851, 5.785 (m, 9H, C ₅ H _5, C ₅ H ₄ -CH (CH ₃ ) ₂ ), 3.814 (s, 6H, OC H ₃ ), 2.857 (sept. 1 H, C ₅ H ₄ -C H (CH ₃ ) ₂ ), 1.200 (d, 6H, C ₅ H ₄ -CH (C H ₃ ) ₂ ).

Example 10 Preparation of (MeCp) (EtCp) Zr (OMe) ₂

In a flame dried 1000 mL Schlenk flask, 100.0 g (0.331 mol) of (MeCp) Zr (NMe ₂ ) ₃ was dissolved in 300 mL of toluene and kept at 0 ° C. Thus, 31.1 g (0.331 mol, 1 equivalent) of ethyl cyclopentadiene was slowly added dropwise to the flask maintained at 0 ° C., and then the mixed solution was stirred at room temperature for 5 hours. To the solution was added 21.2 g (0.661 mol, 2 equiv) of methanol slowly at 0 ° C. and then stirred at room temperature for an additional 5 hours to complete the reaction.

Yield: 78.76 g (73.2%);

Elemental analysis: calcd (C ₁₅ H ₂₂ O ₂ Zr) C, 55.34; H, 6.81; O, 9.83. Found C, 56.04; H, 6.79; 0, 9.71;

Boiling point (b.p): 114 ° C., 0.30 torr;

¹ H-NMR (400 MHz, C ₆ D _6, 25 ° C.): δ 5.852, 5.787 (m, 8H, C ₅ H ₄ -CH ₃ , C ₅ H ₄ -CH ₂ CH ₃ ), 3.860 (s, 6H , OC H ₃ ), 2.495 (q, 2H, C ₅ H ₄ -C H ₂ CH ₃ ), 2.052 (s, 3H, C ₅ H ₄ -C H ₃ ), 1.143 (t, 3H, C ₅ H ₄ -CH ₂ C H ₃ ).

Example 11: Preparation of (EtCp) ₂ Zr (OMe) ₂

In a flame dried 1000 mL Schlenk flask, 100.0 g (0.309 mol) of Zr (NEtMe) ₄ was dissolved in 300 mL of toluene and kept at 0 ° C. Thus, 58.2 g (0.618 mol, 2 equivalents) of ethylcyclopentadiene was slowly added dropwise to the flask maintained at 0 ° C, and the mixture was refluxed for 5 hours. To the solution was completed by adding 19.8 g (0.618 mol, 2 equiv) of methanol slowly at 0 ° C. and refluxing for an additional 3 hours.

Yield: 76.28 g (72.7%);

Elemental analysis: calcd (C ₁₆ H ₂₄ O ₂ Zr) C, 56.59; H, 7. 12; O, 9.42. Found C, 55.98; H, 7.09; 0, 9.29;

Boiling point (b.p): 119 ° C., 0.30 torr;

¹ H-NMR (400 MHz, C ₆ D _6, 25 ° C.): δ 5.863 (m, 8H, C ₅ H ₄ -CH ₂ CH ₃ ), 3.853 (s, 6H, OC H ₃ ), 2.497 (q, 4H, C ₅ H ₄ -C H ₂ CH ₃ ), 1.149 (t, 6H, C ₅ H ₄ -CH ₂ C H ₃ ).

Example 12 Preparation of Cp (MeCp) Zr (OEt) ₂

In a flame dried 1000 mL Schlenk flask, 100.0 g (0.347 mol) of CpZr (NMe ₂ ) ₃ was dissolved in 300 mL of toluene and kept at 0 ° C. Thus, 27.8 g (0.347 mol, 1 equivalent) of methylcyclopentadiene was slowly added dropwise to the flask maintained at 0 ° C, and the mixed solution was stirred at room temperature for 5 hours. To the solution was completed 31.9 g (0.693 mol, 2 equiv) of ethanol slowly at 0 ° C., followed by stirring at room temperature for an additional 5 hours.

Yield: 82.48 g (73.1%);

Elemental analysis: calcd (C ₁₅ H ₂₂ O ₂ Zr) C, 55.34; H, 6.81; O, 9.83. Found C, 54.79; H, 6. 74; 0, 9.48;

Boiling point (b.p): 114 ° C., 0.30 torr;

¹ H-NMR (400 MHz, C ₆ D _6, 25 ° C.): δ 6.018, 5.856, 5.769 (m, 9H, C ₅ H ₅ , C ₅ H ₄ -CH ₃ ), 4.002 (q, 4H, OC H ₂ CH ₃ ), 2.084 (s, 3H, C ₅ H ₄ -C H ₃ ), 1.141 (t, 6H, OCH ₂ C H ₃ ).

Example 13: Preparation of Cp (EtCp) Zr (OEt) ₂

In a flame dried 1000 mL Schlenk flask, 100.0 g (0.347 mol) of CpZr (NMe ₂ ) ₃ was dissolved in 300 mL of toluene and kept at 0 ° C. Thus, 32.6 g (0.347 mol, 1 equivalent) of ethylcyclopentadiene (EtCpH) was slowly added dropwise to the flask maintained at 0 ° C, and the mixture was stirred at room temperature for 5 hours. To the solution was completed 31.9 g (0.693 mol, 2 equiv) of ethanol slowly at 0 ° C., followed by stirring at room temperature for an additional 5 hours.

Yield: 84.62 g (71.9%);

Elemental analysis: calcd (C ₁₆ H ₂₄ O ₂ Zr) C, 56.59; H, 7. 12; O, 9.42. Found C, 55.97; H, 7. 25; 0, 9.23;

Boiling point (b.p): 109 ° C., 0.30 torr;

¹ H-NMR (400 MHz, C ₆ D _6, 25 ° C.): δ 6.019, 5.874, 5.837 (m, 9H, C ₅ H _5, C ₅ H ₄ -CH ₂ CH ₃ ), 3.990 (q, 4H, OC H ₂ CH ₃ ), 2.533 (q, 2H, C ₅ H ₄ -C H ₂ CH ₃ ), 1.136 (m, 6H, OCH ₂ C H _3, C ₅ H ₄ -CH ₂ C H ₃ ).

Example 14 Preparation of (MeCp) ₂ Zr (OEt) ₂

In a flame dried 1000 mL Schlenk flask, 100.0 g (0.309 mol) of Zr (NEtMe) ₄ was dissolved in 300 mL of toluene and kept at 0 ° C. 49.5 g (0.618 mol, 2 equivalents) of methylcyclopentadiene were slowly added dropwise to the flask maintained at 0 ° C., and the mixed solution was refluxed for 5 hours. The reaction was completed by slowly adding 28.5 g (0.618 mol, 2 equiv) of ethanol to the solution at 0 ° C. and then stirring at room temperature for an additional 5 hours.

Yield: 75.44 g (71.9%);

Elemental analysis: calcd (C ₁₆ H ₂₄ O ₂ Zr) C, 56.59; H, 7. 12; O, 9.42. Found C, 56.93; H, 7.04; 0, 9.35;

Boiling point (b.p): 118 ° C., 0.30 torr;

¹ H-NMR (400 MHz, C ₆ D _6, 25 ° C.): δ 5.860, 5.796 (m, 8H, C ₅ H ₄ -CH ₃ ), 4.038 (q, 4H, OC H ₂ CH ₃ ), 2.070 ( s, 6H, C ₅ H ₄ -C H ₃ ), 1.157 (t, 6H, OCH ₂ C H ₃ ).

Example 15 Preparation of (Cp ₂ CMe ₂ ) Zr (OMe) ₂

In a flame dried 1000 mL Schlenk flask, 100.0 g (0.309 mol, 1 equiv) of Zr (NEtMe) ₄ was dissolved in 300 mL of toluene and kept at 0 ° C. To this flask maintained at 0 ° C., 53.2 g (0.309 mol, 1 equivalent) of dimethylmethylenedicyclopentadiene (HCp) ₂ CMe ₂ ] was slowly added dropwise, and the mixture was refluxed for 5 hours. I was. To the solution was completed by adding 19.8 g (0.618 mol, 2 equiv) of methanol slowly at 0 ° C. and then stirring at room temperature for an additional 5 hours.

After completion of the reaction, the mixture was placed under reduced pressure to remove the solvent and volatile side reactions, and then distilled under reduced pressure to obtain a yellow solid compound represented by the following Chemical Formula 7:

[Formula 7]

;

Yield: 65.68 g (65.7%);

Elemental analysis: calcd (C ₁₅ H ₂₀ O ₂ Zr) C, 55.68; H, 6. 23; 0, 9.89. Found C, 55.47; H, 6. 17; 0, 9.92;

Boiling point (b.p): 115 ° C., 0.30 torr;

¹ H-NMR (400 MHz, C ₆ D _6, 25 ° C.): δ 6.183, 5.504 (m, 8H, (C ₅ H ₄ ) ₂ C (CH ₃ ) ₂ ), 3.805 (s, 6H, OC H ₃ ), 1.531 (s, 6H, (C ₅ H ₄ ) ₂ C (C H ₃ ) ₂ ).

Example 16: Preparation of (Cp ₂ CMe ₂ ) Zr (OEt) ₂

In a flame dried 1000 mL Schlenk flask, 100.0 g (0.309 mol, 1 equiv) of Zr (NEtMe) ₄ was dissolved in 300 mL of toluene and kept at 0 ° C. Thus, 53.2 g (0.309 mol, 1 equivalent) of dimethylmethylenedicyclopentadiene was slowly added dropwise to the flask maintained at 0 ° C, and the mixture was refluxed for 5 hours. The reaction was completed by slowly adding 28.5 g (0.618 mol, 2 equiv) of ethanol to the solution at 0 ° C. and then stirring at room temperature for an additional 5 hours.

After the reaction was completed, the reaction mixture was placed under reduced pressure to remove the solvent and volatile side reactions, and then distilled under reduced pressure to obtain a yellow solid compound represented by the following Chemical Formula 8:

[Formula 8]

;

Yield: 68.12 g (62.7%);

Elemental analysis: calcd (C ₁₇ H ₂₄ O ₂ Zr) C, 58.07; H, 6.88; O, 9.10. Found C, 57.88; H, 6.96; 0, 9.17;

Boiling point (b.p): 121 ° C., 0.30 torr;

¹ H-NMR (400 MHz, C ₆ D _6, 25 ° C.): δ 6.192, 5.567 (m, 8H, (C ₅ H ₄ ) ₂ C (CH ₃ ) ₂ ), 3.958 (q, 4H, OC H ₂ CH ₃ ), 1.560 (s, 6H, (C ₅ H ₄ ) ₂ C (C H ₃ ) ₂ ), 1.140 (t, 6H, OCH ₂ C H ₃ ).

Example 17 Formation of Zirconium Oxides by Atomic Layer Deposition of ( ⁱ PrCp) ₂ Zr (Me) ₂

An experiment was performed in which a zirconium oxide film was formed using atomic layer deposition (ALD) using ( ⁱ PrCp) ₂ Zr (Me) ₂ obtained in Example 2 as a precursor. In this case, the substrate was a silicon wafer on which titanium nitride (TiN) was deposited. The substrate was heated to 300 ° C to 350 ° C. In addition, the precursor compound contained in a stainless steel vessel was heated to a temperature of 120 ℃, the precursor compound was fed to the ALD reactor for performing atomic layer deposition by passing argon (Ar) gas at a flow rate of 50 sccm through the vessel. . The internal pressure of the ALD reactor was maintained at 3 torr. The precursor compound gas was supplied to the ALD reactor for 15 seconds, and then argon gas was supplied for 5 seconds, then ozone (O ₃ ) gas was supplied for 14 seconds, and then ALD was again supplied with argon gas for 5 seconds. One cycle was completed and this was repeated 200 times. The thickness per cycle of the zirconium oxide thin film formed by the above process is shown in FIG. 3. 3 is a graph showing film growth per atomic layer deposition cycle of a zirconium oxide thin film formed according to the present embodiment. As shown in FIG. 3, it was confirmed that a zirconium oxide film was formed with a constant film thickness within the temperature range applied to the substrate.

Example 18 Formation of Zirconium Oxide Film Using Cp (EtCp) Zr (OMe) ₂ and Atomic Layer Deposition

Experiments were performed using Cp (EtCp) Zr (OMe) ₂ prepared according to Example 8 as a precursor and forming a zirconium oxide film using atomic layer deposition (ALD). At this time, a wafer having a hole pattern having an aspect ratio of 40: 1 (50 nm in diameter and 2 μm in depth) was used as the substrate. The substrate was heated to 300 ° C and 350 ° C. In addition, the precursor compound contained in a stainless steel vessel was heated to a temperature of 110 ℃, and the precursor compound was fed to the ALD reactor for performing atomic layer deposition by passing argon (Ar) gas at a flow rate of 50 sccm through the vessel. . The internal pressure of the ALD reactor was maintained at 3 torr. The precursor compound gas was supplied to the ALD reactor for 15 seconds, and then argon gas was supplied for 5 seconds, then ozone (O ₃ ) gas was supplied for 14 seconds, and then ALD was supplied again by supplying argon gas for 5 seconds. One cycle was completed and this was repeated 200 times. The cross section of the zirconium oxide thin film formed according to the above process was measured using a transmission electron microscope (TEM), and the results are shown in FIGS. 4A to 4F. 4A to 4C are observations of the upper end, the middle end, and the lower end of the hole pattern, respectively, and the TEM analysis results of the zirconium oxide film formed by heating the temperature of the substrate to 300 ° C., and FIGS. 4D to 4F are hole patterns, respectively. The upper end, the stop part and the lower end of the film were observed, and the TEM analysis result of the zirconium oxide film formed by heating the temperature of the base material to 350 ° C. 4A to 4F, it was confirmed that a film was formed evenly on both the surface of the substrate and the inside of the hole.

Example 19: Zirconium Oxide Formation Using (Cp ₂ CMe ₂ ) Zr (OMe) ₂ and Atomic Layer Deposition

Experiments were performed using (Cp ₂ CMe ₂ ) Zr (OMe) ₂ prepared according to Example 15 as a precursor and forming a zirconium oxide film using atomic layer deposition (ALD). At this time, a wafer piece having a hole pattern with an aspect ratio of 40: 1 (50 nm in diameter and 2 μm in depth) was used as the substrate. The substrate was heated to 300 ° C and 350 ° C. In addition, the precursor compound contained in a stainless steel vessel was heated to a temperature of 120 ℃, and the precursor compound was fed to the ALD reactor for performing atomic layer deposition by passing argon (Ar) gas at a flow rate of 50 sccm through the vessel. . The internal pressure of the ALD reactor was maintained at 3 torr. The precursor compound gas was supplied to the ALD reactor for 15 seconds, and then argon gas was supplied for 5 seconds, then ozone (O ₃ ) gas was supplied for 14 seconds, and then ALD was supplied again by supplying argon gas for 5 seconds. One cycle was completed and this was repeated 200 times. The cross section of the zirconium oxide thin film formed according to the above process was measured using a transmission electron microscope (TEM), and the results are shown in FIGS. 5A to 5F. 5A to 5C are observations of the upper end, the middle end, and the lower end of the hole pattern, respectively, and are results of TEM analysis of a zirconium oxide film formed by heating the temperature of the substrate to 300 ° C. The upper end, the stop part and the lower end of the film were observed, and the TEM analysis result of the zirconium oxide film formed by heating the temperature of the base material to 350 ° C. 5A to 5F, it was confirmed that a film was formed evenly on both the surface of the substrate and the inside of the hole.

The precursor compound gas was supplied to the ALD reactor for 9 seconds, and then argon gas was supplied for 5 seconds, and then ozone (O ₃ ) gas was supplied for 14 seconds, and then ALD was supplied with argon gas for 5 seconds. The cycle was repeated to form a zirconium oxide film on a flat wafer heated to 300 ° C, 320 ° C, and 350 ° C. The film growth per ALD cycle with temperature is shown in FIG. 6. In the temperature range of 300 ℃ to 350 ℃ it can be seen that almost no change in film growth per ALD cycle.

The foregoing description is for the purpose of illustration, and Those skilled in the art will understand that the present invention can be easily modified in other specific forms without changing the technical spirit or essential features of the present application. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form.

The scope of the present application is indicated by the following claims rather than the above description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents are included in the scope of the present application. Should be interpreted as

Claims

A Group 4 transition metal-containing precursor compound, represented by Formula 1 or Formula 2 below:

[Formula 1]

M 1 (Cp ') n (L) 4-n ;

In Chemical Formula 1,

M 1 comprises Zr or Hf,

Cp 'comprises a cyclopentadienyl group which may be substituted by a C 1-4 alkyl group,

n is 1 or 2, and when n is 2, the two Cp's may be the same or different from each other

L comprises a C 1-3 alkyl group, a C 1-6 alkoxide group or —NHR 3 , wherein said R 3 is a C 1-6 alkyl group and when two or more L are two or more L they may be the same or different from each other;

M 1 is bonded to Cp ';

[Formula 2]

;

In Chemical Formula 2,

M 1 comprises Zr or Hf,

Cp 'and Cp "each independently include a cyclopentadienyl group which may be substituted by a C 1-4 alkyl group,

L 1 and L 2 each independently include a C 1-3 alkyl group, a C 1-6 alkoxide group, or —NHR 3 , wherein R 3 is a C 1-6 alkyl group,

R 1 and R 2 each independently include hydrogen or a C 1-4 alkyl group,

M 1 is bonded to Cp 'and Cp ".
The method of claim 1,

L, L 1 and L 2 are each independently a methyl group, ethyl group, propyl group, iso-propyl group, methoxide group, ethoxide group, n-propoxide group, iso-propoxide group, iso- A group 4 transition metal-containing precursor compound comprising a butoxide group, sec-butoxide group, 3-pentoxide group, or tert-butylamino group.
The method of claim 1,

Wherein Cp 'and Cp ", each independently, Group 4 transition metal-containing precursor compound containing Cp, MeCp, EtCp, n PrCp, i PrCp, i BuCp, sec BuCp, or t BuCp.
The method of claim 1,

The Group 4 transition metal-containing precursor compound is one comprising a liquid at room temperature or a liquid at a volatile temperature, Group 4 transition metal-containing precursor compound.
The method of claim 1,

The Group 4 transition metal-containing precursor compound includes (EtCp) 2 Zr (Me) 2 , ( i PrCp) 2 Zr (Me) 2 , CpZr (O sec Bu) 3 , CpZr (O 3 Pen) 3 , CpZr ( NH t Bu) 3 , Cp (MeCp) Zr (OMe) 2 , (MeCp) 2 Zr (OMe) 2 , Cp (EtCp) Zr (OMe) 2 , Cp ( i PrCp) Zr (OMe) 2 , (MeCp) (EtCp) Zr (OMe) 2 , (EtCp) 2 Zr (OMe) 2 , Cp (MeCp) Zr (OEt) 2 , Cp (EtCp) Zr (OEt) 2 , (MeCp) 2 Zr (OEt) 2 ,
,
, (EtCp) 2 Hf (Me) 2 , ( i PrCp) 2 Hf (Me) 2 , ( i PrCp) 2 Hf (Me) 2 , CpHf (O sec Bu) 3 , CpHf (O 3 Pen) 3 , CpHf (NH t Bu) 3 , Cp (MeCp) Hf (OMe) 2 , (MeCp) 2 Hf (OMe) 2 , Cp (EtCp) Hf (OMe) 2 , Cp ( i PrCp) Hf (OMe) 2 , (MeCp ) (EtCp) Hf (OMe) 2 , (EtCp) 2 Hf (OMe) 2 , Cp (MeCp) Hf (OEt) 2 , Cp (EtCp) Hf (OEt) 2 , (MeCp) 2 Hf (OEt) 2 ,
, And
Group 4 transition metal-containing precursor compound, including those selected from the group consisting of.
A process for preparing a Group 4 transition metal-containing precursor compound according to any one of claims 1 to 5 comprising:

M 1 X 4 and Cp'M 2 are reacted in an organic solvent to form M 1 (Cp ′) n (X) 4-n ; And

Reacting the M 1 (Cp ′) n (X) 4-n and M 3 L in an organic solvent to form a Group 4 transition metal-containing precursor compound represented by Formula 1 below:

[Formula 1]

M 1 (Cp ') n (L) 4-n ;

In Chemical Formula 1

M 1 , Cp ', n, and L are the same as defined in claim 1, respectively,

In M 1 X 4 And Cp'M 2 , X includes a halo group, and M 2 and M 3 each independently include an alkali metal.
A process for preparing a Group 4 transition metal-containing precursor compound according to any one of claims 1 to 5 comprising:

Cp'M 1 (NR'R ") 3 and LH are reacted in an organic solvent to form a Group 4 transition metal-containing precursor compound represented by Formula 1 below:

[Formula 1]

M 1 (Cp ') n (L) 4-n ;

In the Cp'M 1 (NR'R ") 3 , LH and Formula 1, R 'and R" may be the same or different from each other, and each independently include a C 1-4 alkyl group,

M 1 , Cp ', n, and L are the same as defined in claim 1, respectively.
A process for preparing a Group 4 transition metal-containing precursor compound according to any one of claims 1 to 5 comprising:

Cp'M 1 (NR'R ") 3 and Cp'H are reacted in an organic solvent to form Cp'M 1 (NR'R") 2 Cp '; And

The Cp'M 1 (NR'R ") 2 Cp 'and LH are reacted in an organic solvent to form a Group 4 transition metal-containing precursor compound represented by Formula 1 below:

[Formula 1]

M 1 (Cp ') n (L) 4-n ;

In the Cp'M 1 (NR'R ") 3 , Cp'H, Cp'M 1 (NR'R") , LH and Formula 1,

R 'and R "may be the same or different from each other, and each independently include a C 1-4 alkyl group,

M 1 , Cp ', n, and L are the same as defined in claim 1, respectively.
A process for preparing a Group 4 transition metal-containing precursor compound according to any one of claims 1 to 5 comprising:

M 1 (NR'R ") 4 and R 1 R 2 C (Cp'H) (Cp" H) Reacting in an organic solvent to form an intermediate compound represented by the following formula (3);

Reacting the intermediate compound and LH in an organic solvent to form a Group 4 transition metal-containing precursor compound represented by Formula 2:

[Formula 2]

;

[Formula 3]

In Chemical Formula 2 or Chemical Formula 3,

In M 1 (NR ′ R ″) 4 , R 1 R 2 C (Cp′H) (Cp ″ H), LH, Formula 2, and Formula 3, R ′ and R ″ may be the same as or different from each other. Each independently include a C 1-4 alkyl group,

M 1 , Cp ', Cp ", R 1 , R 2 , L 1 and L 2 are the same as defined in claim 1, respectively.
A precursor composition for depositing a Group 4 transition metal-containing thin film, comprising the Group 4 transition metal-containing precursor compound according to any one of claims 1 to 5.
A method of depositing a Group 4 transition metal-containing thin film, using the Group 4 transition metal-containing precursor compound according to any one of claims 1 to 5.
The method of claim 11,

Depositing the thin film comprises organometallic chemical vapor deposition (MOCVD) or atomic layer deposition (ALD).
The method of claim 11,

Wherein said thin film comprises a Group 4 transition metal-containing oxide, nitride or oxynitride.