CN117209545A - Preparation method of film containing IV group metal element and precursor composition thereof - Google Patents

Abstract

The invention discloses a compound containing Group IV metal elements. The chemical formula of the compound is: (Sn(CH ₃ ) ₃ )CpM (NR ¹ R ² ) ₃ (Formula I); in the chemical formula I , M is Ti, Zr or Hf, R ¹ and R ² are each independently a C1-C4 linear or branched alkyl group; the invention also provides a precursor composition for forming a film and a Group IV metal element-containing composition A method for preparing a membrane. The prerequisite composition contains a compound containing a Group IV metal element; the novel compound containing a Group IV metal element provided by the invention is liquid at normal temperature and has thermal stability, and is used to prepare a compound containing a Group IV metal element. A film of group metal elements can significantly increase the deposition rate.

Description

A method for preparing a film containing Group IV metal elements and its precursor composition

Technical field

The present invention relates to the technical field of oxide film preparation, and in particular to a preparation method of a film containing Group IV metal elements and its precursor composition.

Background technique

In the development process of the chip, the thickness of SiO ₂ as the oxide layer has dropped again and again, which makes the leakage phenomenon of the MOS tube very serious, so we can only choose an oxidation medium with a higher dielectric constant. Metal oxides have received widespread attention as the most promising high-K materials to replace _SiO2 gate dielectrics. Group 4 transition metals include zirconium, hafnium, and titanium. They are located in Group IV-B of the periodic table of elements. Their oxides have high permittivity, good thermal stability, and large band shifts to silicon. They are often used as One of the high-K materials replacing silicon-based gate insulators.

The process of obtaining oxide films using CVD or ALD technology is to first introduce a gas phase precursor, and then the precursor chemically reacts on the wafer surface. In order to be successfully used in production, the ideal precursor must be sufficiently reactive and stable enough to ensure safe operation, have an appropriate vapor pressure, and must be pure to ensure that the resulting film is not Can cause device problems (current leakage, threshold voltage drift, etc.).

Contents of the invention

The object of the present invention is to provide compounds containing Group IV metal elements, precursor compositions containing Group IV metal elements for forming films, and methods for preparing films containing Group IV metal elements.

To this end, the present invention adopts the following technical solutions:

In a first aspect, the present invention provides a compound containing a Group IV metal element. The chemical formula of the compound is expressed as:

(Sn(CH ₃ ) ₃ )CpM(NR ¹ R ² ) ₃ (Formula I);

In the chemical formula I, M is Ti, Zr or Hf,

R ¹ and R ² are each independently a C1-C4 linear or branched alkyl group.

Preferably, the compound containing Group IV metal elements is one or more of the following:

(Trimethylstannyl)cyclopentadienyltris(dimethylamino)M(IV)(M(TMSn-Cp)(NMe ₂ ) ₃ ), (trimethylstannyl)cyclopentadiene Tris(diethylamino)M(IV)(M(TMSn-Cp)(NEt ₂ ) ₃ ), (trimethylstannyl)cyclopentadienyltris(methylethylamino)M(IV )(M(TMSn-Cp)(NEtMe) ₃ ), (trimethylstannyl)cyclopentadienyltris(di-n-propylamino)M(IV)(M(TMSn-Cp)(NnPr ₂ ) ₃ ), (trimethylstannyl)cyclopentadienyl tris(diisopropylamino)M(IV)(M(TMSn-Cp)(N iPr ₂ ) ₃ ), (trimethylstannyl )Cyclopentadienyltris(di-n-butylamino)M(IV)(M(TMSn-Cp)(NnBu ₂ ) ₃ ), (trimethylstannyl)cyclopentadienyltris(diisobutyl ( _{trimethylstannyl} )cyclopentadienyl tris(di _- sec-butylamino)M(IV)(M( TMSn-Cp)(NsBu ₂ ) ₃ ), (trimethylstannyl)cyclopentadienyltris(di-tert-butylamino)M(IV)(M(TMSn-Cp)(NtBu ₂ ) ₃ ); The M is Ti, Zr or Hf.

Further, the compound containing Group IV metal elements is liquid at normal temperature.

In a second aspect, the present invention provides a precursor composition for forming a film, comprising the compound containing a Group IV metal element described in the first aspect of the present invention.

Further, the precursor composition for forming a film is used to form an oxide film containing Group IV metal elements.

Preferably, the precursor composition for forming a film forms an oxide film containing Group IV metal elements through vapor deposition.

In a third aspect, the present invention provides a method for preparing a film containing Group IV metal elements, which includes the following steps:

A film containing a Group IV metal element is formed on a substrate by reacting the precursor composition for forming a film described in the second aspect of the present invention with a reactive gas.

Further, the preparation method of the film containing Group IV metal elements includes the following steps: reacting a precursor composition for forming the film with a reactive gas, and forming a Group IV metal element-containing film on the substrate through vapor deposition. Oxide film.

Preferably, the reaction gas is selected from the following: O ₂ , O ₃ , H ₂ O, H ₂ O ₂ , NO, N ₂ O, NO ₂ , oxygen radicals thereof, and mixtures thereof.

Preferably, the vapor deposition is selected from chemical vapor deposition, low pressure vapor deposition, plasma enhanced chemical vapor deposition, cyclic chemical vapor deposition, plasma enhanced cyclic chemical vapor deposition, atomic layer deposition and plasma enhanced atomic layer deposition. At least one of the layer deposition methods.

Beneficial effects of the present invention:

The invention provides a new type of compound containing Group IV metal elements. The new type of compound containing Group IV metal elements is liquid at normal temperature and has thermal stability; the method of the invention is used to prepare a compound containing Group IV metal elements. film, which can significantly increase the deposition rate.

Detailed ways

In order to enable those of ordinary skill in the art to easily implement the present invention, the specific implementation manner of the technical solution is further described below through specific examples. These embodiments are for the detailed description of the technical solution of the present invention. The present invention can be implemented in various forms and do not constitute any limitation on the present invention. Anyone can make limited modifications within the scope of the claims of the present invention. Within the scope of the claims of the present invention.

Throughout the description of the present invention, when a certain part is described as "including" a certain constituent element, it does not mean that other constituent elements are excluded, but that other constituent elements may also be included unless there is explicit statement to the contrary.

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

Throughout this specification, the term "alkyl" may include 1 to 12 carbon atoms, 1 to 10 carbon atoms, 1 to 8 carbon atoms, 1 to 5 carbon atoms, or 1 to 4 carbon atoms. straight or branched chain alkyl groups or all possible isomers thereof. For example, the alkyl group can be methyl (Me), ethyl (Et), n-propyl (nPr), isopropyl (iPr), n-butyl (nBu), tert-butyl (tBu), isobutyl (iBu), sec-butyl (sBu), etc., but may not be limited to these.

Throughout the description of the present invention, the term "Group IV metal element" refers to a chemical element belonging to Group IV of the periodic table of elements, which may include Ti, Zr or Hf.

Throughout the specification of this application, the term "Cp" is expressed by -C5H4 and refers to the abbreviation of "cyclopentadienyl".

Below, implementation examples of the present application are described in detail, but the present application may not be limited thereto.

In a first aspect, the present invention provides a compound represented by chemical formula I containing a Group IV metal element.

(Sn(CH ₃ ) ₃ )CpM(NR ¹ R ² ) ₃ (Formula I);

In the chemical formula I, M is Ti, Zr or Hf,

R ¹ and R ² are each independently a C1-C4 linear or branched alkyl group.

In an implementation example of the present application, R1 can be n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl, but is not limited thereto.

In an implementation example of the present application, R2 can be n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl, but is not limited thereto.

In an implementation example of the present application, as an example of the compound containing a Group IV metal element represented by the above chemical formula I, the following Ti, Zr or Hf compound can be used, but is not limited thereto.

(Trimethylstannyl)cyclopentadienyl tris(dimethylamino)Ti(IV)(Ti(TMSn-Cp)(NMe ₂ ) ₃ );

(Trimethylstannyl)cyclopentadienyl tris(diethylamino)Ti(IV)(Ti(TMSn-Cp)(NEt ₂ ) ₃ );

(Trimethylstannyl)cyclopentadienyltris(methylethylamino)Ti(IV)(Ti(TMSn-Cp)(NEtMe) ₃ );

(Trimethylstannyl)cyclopentadienyl tris(di-n-propylamino)Ti(IV)(Ti(TMSn-Cp)(NnPr ₂ ) ₃ );

(Trimethylstannyl)cyclopentadienyltris(diisopropylamino)Ti(IV)(Ti(TMSn-Cp)(NiPr ₂ ) ₃ );

(Trimethylstannyl)cyclopentadienyltris(di-n-butylamino)Ti(IV)(Ti(TMSn-Cp)(NnBu ₂ ) ₃ );

(Trimethylstannyl)cyclopentadienyltris(diisobutylamino)Ti(IV)(Ti(TMSn-Cp)(NiBu ₂ ) ₃ );

(Trimethylstannyl)cyclopentadienyl tris(di-sec-butylamino)Ti(IV)(Ti(TMSn-Cp)(NsBu ₂ ) ₃ );

(Trimethylstannyl)cyclopentadienyl tris(di-tert-butylamino)Ti(IV)(Ti(TMSn-Cp)(NtBu ₂ ) ₃ );

(Trimethylstannyl)cyclopentadienyl tris(dimethylamino)Zr(IV)(Zr(TMSn-Cp)(NMe ₂ ) ₃ );

(Trimethylstannyl)cyclopentadienyltris(diethylamino)Zr(IV)(Zr(TMSn-Cp)(NEt ₂ ) ₃ );

(Trimethylstannyl)cyclopentadienyltris(methylethylamino)Zr(IV)(Zr(TMSn-Cp)(NEtMe) ₃ );

(Trimethylstannyl)cyclopentadienyltris(di-n-propylamino)Zr(IV)(Zr(TMSn-Cp)(NnPr ₂ ) ₃ );

(Trimethylstannyl)cyclopentadienyltris(diisopropylamino)Zr(IV)(Zr(TMSn-Cp)(NiPr ₂ ) ₃ );

(Trimethylstannyl)cyclopentadienyltris(di-n-butylamino)Zr(IV)(Zr(TMSn-Cp)(NnBu ₂ ) ₃ );

(Trimethylstannyl)cyclopentadienyltris(diisobutylamino)Zr(IV)(Zr(TMSn-Cp)(NiBu ₂ ) ₃ );

(Trimethylstannyl)cyclopentadienyl tris(di-sec-butylamino)Zr(IV)(Zr(TMSn-Cp)(NsBu ₂ ) ₃ );

(Trimethylstannyl)cyclopentadienyl tris(di-tert-butylamino)Zr(IV)(Zr(TMSn-Cp)(NtBu ₂ ) ₃ );

(Trimethylstannyl)cyclopentadienyltris(dimethylamino)Hf(IV)(Hf(TMSn-Cp)(NMe ₂ ) ₃ );

(Trimethylstannyl)cyclopentadienyltris(diethylamino)Hf(IV)(Hf(TMSn-Cp)(NEt ₂ ) ₃ );

(Trimethylstannyl)cyclopentadienyltris(methylethylamino)Hf(IV)(Hf(TMSn-Cp)(NEtMe) ₃ );

(Trimethylstannyl)cyclopentadienyltris(di-n-propylamino)Hf(IV)(Hf(TMSn-Cp)(NnPr ₂ ) ₃ );

(Trimethylstannyl)cyclopentadienyltris(diisopropylamino)Hf(IV)(Hf(TMSn-Cp)(NiPr ₂ ) ₃ );

(Trimethylstannyl)cyclopentadienyltris(di-n-butylamino)Hf(IV)(Hf(TMSn-Cp)(NnBu ₂ ) ₃ );

(Trimethylstannyl)cyclopentadienyltris(diisobutylamino)Hf(IV)(Hf(TMSn-Cp)(NiBu ₂ ) ₃ );

(Trimethylstannyl)cyclopentadienyl tris(di-sec-butylamino)Hf(IV)(Hf(TMSn-Cp)(NsBu ₂ ) ₃ );

(Trimethylstannyl)cyclopentadienyl tris(di-tert-butylamino)Hf(IV)(Hf(TMSn-Cp)(NtBu ₂ ) ₃ );

In an implementation example of the present application, the compound containing a Group IV metal element is liquid and stable at normal temperature.

A second aspect of the present invention provides a precursor composition for forming a film containing a compound of a Group IV metal element.

The above contents described in the first aspect of this application are all applicable to the second aspect of this application.

In an implementation example of the present application, the precursor composition for forming a film is used to form an oxide film containing Group IV metal elements.

In an implementation example of the present application, the precursor composition for forming a film is used to form an oxide film containing Group IV metal elements through vapor deposition.

A third aspect of the present invention provides a method for preparing a film containing Group IV metal elements.

The above contents described in the second aspect of this application are all applicable to the third aspect of this application.

In an implementation example of the present application, the preparation method includes the following steps:

A film containing a Group IV metal element is formed on a substrate by reacting the precursor composition for forming a film described in the second aspect of the present invention with a reactive gas.

In an implementation example of the present application, the method for preparing a film containing Group IV metal elements includes the following steps: reacting a precursor composition for forming a film with a reactive gas, and forming it on the substrate through vapor deposition. Oxide film containing Group IV metal elements. For example, the reaction gas is selected from the following: O ₂ , O ₃ , H ₂ O, H ₂ O ₂ , NO, N ₂ O, NO ₂ , oxygen radicals thereof, and mixtures thereof, but is not limited thereto. For example, the vapor deposition is selected from the group consisting of chemical vapor deposition, low pressure vapor deposition, plasma enhanced chemical vapor deposition, cyclic chemical vapor deposition, plasma enhanced cyclic chemical vapor deposition, atomic layer deposition and plasma enhanced atomic layer deposition. At least one of the methods, but not limited to this.

Example 1 Preparation of Compound 1 [Zr(TMSn-Cp)(NMe ₂ ) ₃ ]

After mixing and dissolving tetrakis(dimethylamino)zirconium and n-hexane, slowly add TMSn-Cp dropwise at a molar ratio of 1:1 at room temperature, and stir for 3.5 hours. After the reaction was completed, the solvent was distilled off under reduced pressure to obtain compound 1.

The calculated value through elemental analysis - (C ₁₄ H ₃₁ N ₃ SnZr); the measured value is: C 82.64, H15.25, N 20.63.

Example 2 Preparation of Compound 2 [Zr(TMSn-Cp)(NEt ₂ ) ₃ ]

After mixing and dissolving tetrakis(diethylamino)zirconium and n-hexane, TMSn-Cp was slowly added dropwise at room temperature at a molar ratio of 1:1, and the reaction was stirred for 3 hours. After the reaction was completed, the solvent was distilled off under reduced pressure to obtain compound 2.

The calculated value through elemental analysis is - (C ₂₀ H ₄₃ N ₃ SnZr); the measured values are: C 121.62, H21.79, N 21.28.

Example 3 Preparation of Compound 3 [Hf(TMSn-Cp)(NMe ₂ ) ₃ ]

After mixing and dissolving tetrakis(dimethylamino)hafnium and n-hexane, slowly add TMSn-Cp dropwise at a molar ratio of 1:1 at room temperature, and stir for 4 hours. After the reaction was completed, the solvent was distilled off under reduced pressure to obtain compound 1.

The calculated value through elemental analysis is - (C ₁₄ H ₃₁ N ₃ SnHf); the measured values are: C83.14, H15.31, N 20.71.

Example 4 Preparation of zirconium oxide film using atomic layer deposition method of compound 1 and ozone (O ₃ ) gas

Compound 1 [Zr(TMSn-Cp)(NMe ₂ ) ₃ ] prepared in Example 1 was used as a precursor, and an experiment for forming a zirconium oxide film on a silicon substrate was performed using atomic layer deposition (ALD). Specific steps are as follows:

1) The substrate (silicon) is heated to 300°C to 330°C;

2) Heating the precursor compound to a temperature of 115°C;

3) Pour inert gas argon into the reaction vessel, then pass the precursor compound 1 gas into the ALD reactor used to perform the atomic layer deposition method, and repeat the ALD raw material supply cycle 200 times: before supplying the ALD After the precursor compound 1 gas is supplied to the reactor for 5 seconds, argon gas is supplied for 5 seconds, then ozone (O ₃ ) is supplied for 5 seconds, and argon gas is supplied again for 5 seconds, and the process is repeated. The internal pressure of the ALD reactor was maintained at 2.9 Torr, and the substrate temperature was maintained at 300°C. The constant film growth when the Group IV metal precursor gas supply time is increased in the ALD raw material supply cycle is beneficial to uniformly forming a Group IV metal element-containing film over the entire surface of a substrate with fine unevenness (groove) on the surface. Condition.

After detection, a film with a uniform thickness of about 7 nm was formed on the entire surface of the substrate.

Example 5 Preparation of zirconium oxide film using atomic layer deposition method of compound 2 and ozone (O ₃ ) gas

Compound 2 [Zr(TMSn-Cp)(NEt ₂ ) ₃ ] prepared in Example 2 was used as a precursor, and an experiment was performed to form a zirconium oxide film on a silicon substrate using atomic layer deposition (ALD). Specific steps are as follows:

1) Use the ALD reactor as in Example 4. The substrate is heated to 300°C to 330°C.

2) Heating the precursor compound 2 to a temperature of 110°C;

3) Pass the inert gas argon into the reaction vessel, and pass the argon (Ar) gas at a flow rate of 60 sccm through the vessel, thereby supplying the precursor compound 2 to the ALD reactor for performing the atomic layer deposition method. The internal pressure of the ALD reactor was maintained at 3 Torr. An ALD raw material supply cycle in which the gas of the precursor compound 2 is supplied to the ALD reactor for 5 seconds, argon gas is supplied for 5 seconds, and ozone (O3 is supplied for 5 seconds) is repeatedly executed 200 times. ), supply argon gas again for 5 seconds. Ensure constant oxide film growth in each ALD raw material supply cycle within the substrate temperature range.

Example 6 Preparation of hafnium oxide film using atomic layer deposition method of compound 3 and ozone (O ₃ ) gas

Compound 3 [Hf(TMSn-Cp)(NMe ₂ ) ₃ ] prepared in Example 3 was used as a precursor, and an experiment was performed to form a hafnium oxide film on a silicon substrate using atomic layer deposition (ALD). Specific steps are as follows:

1) Use the ALD reactor as in Example 4. The substrate is heated to 300°C to 330°C.

2) Heating the precursor compound 3 to a temperature of 110°C;

3) The inert gas argon is introduced into the reaction vessel, and the argon (Ar) gas with a flow rate of 60 sccm is passed through the vessel, thereby supplying the precursor compound 3 to the ALD reactor for performing the atomic layer deposition method. The internal pressure of the ALD reactor was maintained at 3 Torr. An ALD raw material supply cycle in which the gas of the precursor compound 3 is supplied to the ALD reactor for 5 seconds, argon gas is supplied for 5 seconds, and ozone (O3 is supplied for 5 seconds) is repeatedly executed 200 times. ), supply argon gas again for 5 seconds. Ensure constant oxide film growth in each ALD raw material supply cycle within the substrate temperature range.

Compared with the atomic layer deposition method using the previously known CpZr[N(CH ₃ ) ₂ ] ₃ compound gas, the atomic layer deposition method using the new Zr or Hf compound of the present invention has a faster growth rate and a faster deposition rate of the oxide film .

The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, etc. may be made without departing from the spirit and principles of the present invention. All simplifications should be equivalent substitutions, and are all included in the protection scope of the present invention.

Claims (10)

1. A compound containing a Group IV metal element, characterized in that the chemical formula of the compound is expressed as: (Sn(CH ₃ ) ₃ )CpM(NR ¹ R ² ) ₃ (Formula I); in the chemical formula I, M is Ti, Zr or Hf, R ¹ and R ² are each independently C1-C4 straight chain or branched alkyl. 2. The compound containing Group IV metal elements according to claim 2, characterized in that the compound is one or more of the following: (trimethylstannyl) cyclopentadienyl tris( Dimethylamino)M(IV)(M(TMSn-Cp)(NMe ₂ ) ₃ ), (trimethylstannyl)cyclopentadienyl tris(diethylamino)M(IV)(M( TMSn-Cp)(NEt ₂ ) ₃ ), (trimethylstannyl)cyclopentadienyl tris(methylethylamino)M(IV)(M(TMSn-Cp)(NEtMe) ₃ ), ( Trimethylstannyl)cyclopentadienyltris(di-n-propylamino)M(IV)(M(TMSn-Cp)(NnPr ₂ ) ₃ ), (trimethylstannyl)cyclopentadiene Tris(diisopropylamino)M(IV)(M(TMSn-Cp)(NiPr ₂ ) ₃ ), (trimethylstannyl)cyclopentadienyl tris(di-n-butylamino)M( IV)(M(TMSn-Cp)(NnBu ₂ ) ₃ ), (trimethylstannyl)cyclopentadienyl tris(diisobutylamino)M(IV)(M(TMSn-Cp)(NiBu ₂ ) ₃ ), (trimethylstannyl)cyclopentadienyltris(di-sec-butylamino)M(IV)(M(TMSn-Cp)(NsBu ₂ ) ₃ ), (trimethylstannyl base) cyclopentadienyl tris(di-tert-butylamino)M(IV)(M(TMSn-Cp)(NtBu ₂ ) ₃ ); the M is Ti, Zr or Hf. 3. The compound containing Group IV metal elements according to claim 1, characterized in that the compound is liquid at normal temperature. 4. A precursor composition for forming a film, characterized in that it contains the compound containing a Group IV metal element according to any one of claims 1 to 3. 5. The precursor composition for forming a film according to claim 4, characterized in that the precursor composition is used to form an oxide film containing Group IV metal elements. 6. The precursor composition for forming a film according to claim 5, characterized in that the precursor composition is used to form an oxide film containing Group IV metal elements by vapor deposition. 7. A method for preparing a film containing Group IV metal elements, characterized by comprising the following steps: by making the precursor composition for forming a film according to any one of claims 4-6 and The reactive gas reacts to form a film containing Group IV metal elements on the substrate. 8. The method for preparing a film containing a Group IV metal element according to claim 7, characterized in that an oxide film containing a Group IV metal element is formed on the substrate by vapor deposition. 9. The preparation method of a film containing Group IV metal elements according to claim 7, characterized in that the reaction gas is selected from the following: _O2 , _O3 , _H2O , _{H2O2 ,} NO, N ₂ O, NO ₂ , their oxygen radicals, and mixtures thereof. 10. The preparation method of a film containing Group IV metal elements according to claim 8, characterized in that the vapor deposition is selected from the group consisting of chemical vapor deposition, low pressure vapor deposition, plasma enhanced chemical vapor deposition, and cyclic chemical vapor deposition. At least one of deposition, plasma-enhanced cyclic chemical vapor deposition, atomic layer deposition, and plasma-enhanced atomic layer deposition.