A preparation method of a film containing a group IV metal element and its precursor composition

Abstract

The present invention discloses a compound containing a metal element of Group IV, wherein 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 , R 2 Each is independently a C1-C4 straight-chain or branched alkyl group; the present invention also provides a precursor composition for forming a film and a method for preparing a film containing a Group IV metal element, wherein the precursor composition comprises a compound of a Group IV metal element; the novel compound containing a Group IV metal element provided by the present invention is liquid at room temperature and has thermal stability, and the use of the compound to prepare a film containing a Group IV metal element can significantly improve the deposition rate.

Description

Technical Field

[0001] The invention relates to the technical field of oxide film preparation, and in particular to a preparation method of a film containing a Group IV metal element and a precursor composition thereof. Background Art

[0002] In the development of chips, SiO as an oxide layer 2 The thickness of the MOS tube has been reduced again and again, which makes the leakage of the MOS tube very serious, so only an oxide medium with a higher dielectric constant can be selected. Metal oxide is the most promising alternative to SiO 2 High-K materials for gate dielectrics have received extensive attention. Group 4 transition metals include zirconium, hafnium, and titanium, which are located in Group IV-B of the periodic table. Their oxides have high dielectric constants, good thermal stability, and large band shifts to silicon, and are often used as one of the high-K materials to replace silicon-based gate insulators.

[0003] The process of obtaining oxide thin films using CVD or ALD technology is to first introduce a gaseous precursor, which then undergoes a chemical reaction on the wafer surface. To be successfully used in production, the ideal precursor must have sufficient reactivity, sufficient stability to ensure safe operation, and a suitable vapor pressure. At the same time, the precursor must be pure to ensure that the resulting film will not cause device problems (current leakage, threshold voltage drift, etc.). Summary of the invention

[0004] The object of the present invention is to provide a compound containing a metal element of Group IV, a precursor composition for forming a film containing a metal element of Group IV, and a method for preparing a film containing a metal element of Group IV.

[0005] To this end, the present invention adopts the following technical solutions:

[0006] In a first aspect, the present invention provides a compound containing a metal element of Group IV, wherein the chemical formula of the compound is:

[0007] (Sn(CH 3 ) 3 )CpM(NR 1 R 2 ) 3 (Formula I);

[0008] In the chemical formula I, M is Ti, Zr or Hf,

[0009] R 1 , R 2 Each is independently a C1-C4 straight or branched chain alkyl group.

[0010] Preferably, the compound containing a metal element of Group IV is one or more of the following:

[0011] (Trimethylstannyl)cyclopentadienyl tris(dimethylamino)M(IV)(M(TMSn-Cp)(NMe 2 ) 3 )、(trimethylstannyl)cyclopentadienyltris(diethylamino)M(IV)(M(TMSn-Cp)(NEt 2 ) 3 )、(trimethylstannyl)cyclopentadienyltris(methylethylamino)M(IV)(M(TMSn-Cp)(NEtMe) 3 )、(trimethylstannyl)cyclopentadienyltri(di-n-propylamino)M(IV)(M(TMSn-Cp)(NnPr 2 ) 3 )、(trimethylstannyl)cyclopentadienyltris(diisopropylamino)M(IV)(M(TMSn-Cp)(NiPr 2 ) 3 )、(trimethylstannyl)cyclopentadienyltri(di-n-butylamino)M(IV)(M(TMSn-Cp)(NnBu 2 ) 3 )、(trimethylstannyl)cyclopentadienyltris(diisobutylamino)M(IV)(M(TMSn-Cp)(NiBu 2 ) 3 )、(trimethylstannyl)cyclopentadienyltri(di-sec-butylamino)M(IV)(M(TMSn-Cp)(NsBu 2 ) 3 )、(trimethylstannyl)cyclopentadienyltri(di-tert-butylamino)M(IV)(M(TMSn-Cp)(NtBu 2 ) 3 ); wherein M is Ti, Zr or Hf.

[0012] Furthermore, the compound containing the metal element of Group IV is liquid at room temperature.

[0013] In a second aspect, the present invention provides a precursor composition for forming a film, comprising the compound containing a Group IV metal element as described in the first aspect of the present invention.

[0014] Furthermore, the precursor composition for forming a film is used to form an oxide film containing a Group IV metal element.

[0015] Preferably, the precursor composition for forming a film is used to form an oxide film containing a Group IV metal element by vapor deposition.

[0016] In a third aspect, the present invention provides a method for preparing a film containing a Group IV metal element, comprising the following steps:

[0017] A film containing a Group IV metal element is formed on a substrate by reacting the precursor composition for forming a film as described in the second aspect of the present invention with a reaction gas.

[0018] Furthermore, the method for preparing the film containing Group IV metal elements comprises the following steps: a precursor composition for forming a film reacts with a reaction gas to form an oxide film containing Group IV metal elements on the substrate by vapor deposition.

[0019] Preferably, the reaction gas is selected from the following: 2 , O 3 , H 2 O, H 2 O 2 、NO、N 2 O、NO 2 , oxygen free radicals thereof, and mixtures thereof.

[0020] Preferably, the vapor deposition is at least one method 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.

[0021] Beneficial effects of the present invention:

[0022] The present invention provides a novel compound containing a metal element of Group IV, which is liquid at room temperature and has thermal stability. The deposition rate can be significantly increased by preparing a film containing a metal element of Group IV using the method of the present invention. DETAILED DESCRIPTION

[0023] In order to enable ordinary technicians in the field to easily implement the present invention, the specific implementation methods of the technical solution of this description are further described below through specific examples. These embodiments are for the purpose of describing the technical solution in detail. The present invention can be implemented in various forms and does not constitute any limitation to the present invention. Any limited number of modifications made by anyone within the scope of protection of the claims of the present invention are still within the scope of protection of the claims of the present invention.

[0024] Throughout the specification of the present invention, when a part is described as “comprising” a certain constituent element, unless there is an explicit description to the contrary, it does not mean that other constituent elements are excluded but that other constituent elements may be included.

[0025] Throughout the specification of the present invention, the description of "A and / or B" means "A or B, or A and B".

[0026] Throughout the specification of the present invention, the term "alkyl" may include a linear or branched alkyl group having 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, or all possible isomers thereof. For example, the alkyl group may 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 thereto.

[0027] Throughout the specification of the present invention, the term "Group IV metal element" refers to a chemical element belonging to Group IV in the periodic table, and may include Ti, Zr or Hf.

[0028] Throughout the present specification, the term "Cp" is expressed by -C5H4, which is the abbreviation of "cyclopentadienyl".

[0029] The following is a detailed description of an implementation example of the present application, but the present application is not limited thereto.

[0030] In a first aspect of the present invention, a compound containing a metal element of Group IV represented by Chemical Formula I is provided.

[0031] (Sn(CH 3 ) 3 )CpM(NR 1 R 2 ) 3 (Formula I);

[0032] In the chemical formula I, M is Ti, Zr or Hf,

[0033] R 1 , R 2 Each is independently a C1-C4 straight or branched chain alkyl group.

[0034] 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.

[0035] 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.

[0036] In an implementation example of the present application, the compound containing the metal element of Group IV represented by the above chemical formula I may be the following Ti, Zr or Hf compounds, but is not limited thereto.

[0037] (Trimethylstannyl)cyclopentadienyltris(dimethylamino)Ti(IV)(Ti(TMSn-Cp)(NMe 2) 3 );

[0038] (Trimethylstannyl)cyclopentadienyltris(diethylamino)Ti(IV)(Ti(TMSn-Cp)(NEt 2 ) 3 );

[0039] (Trimethylstannyl)cyclopentadienyltris(methylethylamino)Ti(IV)(Ti(TMSn-Cp)(NEtMe) 3 );

[0040] (Trimethylstannyl)cyclopentadienyltris(di-n-propylamino)Ti(IV)(Ti(TMSn-Cp)(NnPr 2 ) 3 );

[0041] (Trimethylstannyl)cyclopentadienyltris(diisopropylamino)Ti(IV)(Ti(TMSn-Cp)(NiPr 2 ) 3 );

[0042] (Trimethylstannyl)cyclopentadienyltris(di-n-butylamino)Ti(IV)(Ti(TMSn-Cp)(NnBu 2 ) 3 );

[0043] (Trimethylstannyl)cyclopentadienyltris(diisobutylamino)Ti(IV)(Ti(TMSn-Cp)(NiBu 2 ) 3 );

[0044] (Trimethylstannyl)cyclopentadienyltris(di-sec-butylamino)Ti(IV)(Ti(TMSn-Cp)(NsBu 2 ) 3 );

[0045] (Trimethylstannyl)cyclopentadienyltris(di-tert-butylamino)Ti(IV)(Ti(TMSn-Cp)(NtBu 2 ) 3 );

[0046] (Trimethylstannyl)cyclopentadienyl tris(dimethylamino)Zr(IV)(Zr(TMSn-Cp)(NMe 2 ) 3 );

[0047] (Trimethylstannyl)cyclopentadienyltris(diethylamino)Zr(IV)(Zr(TMSn-Cp)(NEt 2 ) 3 );

[0048] (Trimethylstannyl)cyclopentadienyltris(methylethylamino)Zr(IV)(Zr(TMSn-Cp)(NEtMe) 3 );

[0049] (Trimethylstannyl)cyclopentadienyltris(di-n-propylamino)Zr(IV)(Zr(TMSn-Cp)(NnPr 2 ) 3 );

[0050] (Trimethylstannyl)cyclopentadienyltris(diisopropylamino)Zr(IV)(Zr(TMSn-Cp)(NiPr 2 ) 3 );

[0051] (Trimethylstannyl)cyclopentadienyltris(di-n-butylamino)Zr(IV)(Zr(TMSn-Cp)(NnBu 2 ) 3 );

[0052] (Trimethylstannyl)cyclopentadienyltris(diisobutylamino)Zr(IV)(Zr(TMSn-Cp)(NiBu 2 ) 3 );

[0053] (Trimethylstannyl)cyclopentadienyltris(di-sec-butylamino)Zr(IV)(Zr(TMSn-Cp)(NsBu 2 ) 3 );

[0054] (Trimethylstannyl)cyclopentadienyl tris(di-tert-butylamino)Zr(IV)(Zr(TMSn-Cp)(NtBu 2 ) 3 );

[0055] (Trimethylstannyl)cyclopentadienyltris(dimethylamino)Hf(IV)(Hf(TMSn-Cp)(NMe 2 ) 3 );

[0056] (Trimethylstannyl)cyclopentadienyltris(diethylamino)Hf(IV)(Hf(TMSn-Cp)(NEt 2 ) 3 );

[0057] (Trimethylstannyl)cyclopentadienyltris(methylethylamino)Hf(IV)(Hf(TMSn-Cp)(NEtMe) 3 );

[0058] (Trimethylstannyl)cyclopentadienyltris(di-n-propylamino)Hf(IV)(Hf(TMSn-Cp)(NnPr 2 ) 3 );

[0059] (Trimethylstannyl)cyclopentadienyltris(diisopropylamino)Hf(IV)(Hf(TMSn-Cp)(NiPr 2 ) 3 );

[0060] (Trimethylstannyl)cyclopentadienyltris(di-n-butylamino)Hf(IV)(Hf(TMSn-Cp)(NnBu 2 ) 3 );

[0061] (Trimethylstannyl)cyclopentadienyltris(diisobutylamino)Hf(IV)(Hf(TMSn-Cp)(NiBu 2 ) 3 );

[0062] (Trimethylstannyl)cyclopentadienyltris(di-sec-butylamino)Hf(IV)(Hf(TMSn-Cp)(NsBu 2 ) 3 );

[0063] (Trimethylstannyl)cyclopentadienyltris(di-tert-butylamino)Hf(IV)(Hf(TMSn-Cp)(NtBu 2 ) 3 );

[0064] In an implementation example of the present application, the compound containing the Group IV metal element is liquid and stable at room temperature.

[0065] In a second aspect of the present invention, there is provided a precursor composition for forming a film containing a compound of a Group IV metal element.

[0066] The above contents recorded in the first aspect of the present application are all applied to the second aspect of the present application.

[0067] In an implementation example of the present application, the precursor composition for forming a film is used to form an oxide film containing a Group IV metal element.

[0068] In an implementation example of the present application, the precursor composition for forming a film is used to form an oxide film containing a Group IV metal element by vapor deposition.

[0069] In a third aspect, the present invention provides a method for preparing a film containing a Group IV metal element.

[0070] The above contents recorded in the second aspect of the present application are all applied to the third aspect of the present application.

[0071] In an implementation example of the present application, the preparation method comprises the following steps:

[0072] A film containing a Group IV metal element is formed on a substrate by reacting the precursor composition for forming a film as described in the second aspect of the present invention with a reaction gas.

[0073] In an implementation example of the present application, the method for preparing a film containing a Group IV metal element comprises the following steps: a precursor composition for forming a film reacts with a reaction gas to form an oxide film containing a Group IV metal element on the substrate by vapor deposition. For example, the reaction gas is selected from the following: 2 , O 3 , H 2 O, H 2 O 2 、NO、N 2 O、NO 2 , oxygen free radicals thereof, and mixtures thereof, but not limited thereto. For example, the vapor deposition is at least one 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, but not limited thereto.

[0074] Example 1 Compound 1 [Zr(TMSn-Cp)(NMe 2 ) 3 Preparation of

[0075] Tetrakis(dimethylamino)zirconium and n-hexane were mixed and dissolved, and TMSn-Cp was slowly added dropwise at a molar ratio of 1:1 at room temperature, and stirred for 3.5 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure to obtain compound 1.

[0076] Calculated value by elemental analysis-(C 14 H 31 N 3 SnZr); measured values ​​are: C82.64, H15.25, N 20.63.

[0077] Example 2 Compound 2[Zr(TMSn-Cp)(NEt 2 ) 3 Preparation of

[0078] Tetrakis(diethylamino)zirconium and n-hexane were mixed and dissolved, and TMSn-Cp was slowly added dropwise at a molar ratio of 1:1 at room temperature, and stirred for 3 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure to obtain compound 2.

[0079] Calculated value by elemental analysis-(C 20 H 43 N 3 SnZr); measured values ​​are: C121.62, H21.79, N 21.28.

[0080] Example 3 Compound 3[Hf(TMSn-Cp)(NMe 2 ) 3 Preparation of

[0081] After tetrakis(dimethylamino)hafnium and n-hexane were mixed and dissolved, TMSn-Cp was slowly added dropwise at a molar ratio of 1:1 at room temperature, and stirred for 4 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure to obtain compound 1.

[0082] Calculated value by elemental analysis-(C 14 H 31 N 3 SnHf); measured values ​​are: C83.14, H15.31, N 20.71.

[0083] Example 4 Using compound 1 and ozone (O 3 Preparation of zirconium oxide film by atomic layer deposition of ) gas

[0084] Compound 1[Zr(TMSn-Cp)(NMe 2 ) 3 ] was used as a precursor to perform an experiment to form a zirconium oxide film on a silicon substrate using atomic layer deposition (ALD). The specific steps are as follows:

[0085] 1) The substrate (silicon) is heated to 300°C to 330°C;

[0086] 2) heating the precursor compound to a temperature of 115° C.;

[0087] 3) introducing inert gas argon into the reaction container, and then introducing the precursor compound 1 gas into an ALD reactor for performing atomic layer deposition, and repeatedly performing 200 ALD raw material supply cycles: after supplying the precursor compound 1 gas to the ALD reactor for 5 seconds, supplying argon for 5 seconds, and then supplying ozone (O 3 ) and then, argon gas is supplied again for 5 seconds, and this is repeated. The internal pressure of the ALD reactor is maintained at 2.9 Torr, and the substrate temperature is maintained at 300°C. When the supply time of the Group IV metal precursor gas is increased during the ALD raw material supply cycle, the constant film growth is beneficial for uniformly forming a Group IV metal element film on the entire surface of a substrate having fine concave-convex (grooves) on the surface.

[0088] It was found that a film having a uniform thickness of about 7 nm was formed on the entire surface of the substrate.

[0089] Example 5 Using compound 2 and ozone (O 3 Preparation of zirconium oxide film by atomic layer deposition of ) gas

[0090] Compound 2[Zr(TMSn-Cp)(NEt 2 ) 3 ] was used as a precursor to perform an experiment to form a zirconium oxide film on a silicon substrate using atomic layer deposition (ALD). The specific steps are as follows:

[0091] 1) Use the ALD reactor as in Example 4. The substrate is heated to 300°C to 330°C.

[0092] 2) heating the precursor compound 2 to a temperature of 110° C.;

[0093] 3) Inert gas argon is introduced into the reaction container, and argon (Ar) gas with a flow rate of 60 sccm is passed through the container, thereby supplying the precursor compound 2 to an ALD reactor for performing an atomic layer deposition method. The internal pressure of the ALD reactor is maintained at 3 Torr. The ALD raw material supply cycle is repeatedly performed 200 times, in which the ALD raw material supply cycle supplies the precursor compound 2 gas to the ALD reactor for 5 seconds, then supplies argon for 5 seconds, then supplies ozone (O3) for 5 seconds, and then supplies argon for 5 seconds again. Ensure that the oxide film growth is constant in each ALD raw material supply cycle within the substrate temperature range.

[0094] Example 6 Using compound 3 and ozone (O 3 Preparation of Hafnium Oxide Film by Atomic Layer Deposition of ) Gas

[0095] Compound 3[Hf(TMSn-Cp)(NMe 2 ) 3 ] was used as a precursor to perform an experiment to form a hafnium oxide film on a silicon substrate using atomic layer deposition (ALD). The specific steps are as follows:

[0096] 1) Use the ALD reactor as in Example 4. The substrate is heated to 300°C to 330°C.

[0097] 2) heating the precursor compound 3 to a temperature of 110° C.;

[0098] 3) Inert gas argon is introduced into the reaction container, and argon (Ar) gas with a flow rate of 60 sccm is passed through the container, thereby supplying the precursor compound 3 to an ALD reactor for performing an atomic layer deposition method. The internal pressure of the ALD reactor is maintained at 3 Torr. The ALD raw material supply cycle is repeatedly performed 200 times, in which the ALD raw material supply cycle supplies the precursor compound 3 gas to the ALD reactor for 5 seconds, then supplies argon for 5 seconds, then supplies ozone (O3) for 5 seconds, and then supplies argon for 5 seconds again. Ensure that the oxide film growth is constant in each ALD raw material supply cycle within the substrate temperature range.

[0099] The atomic layer deposition method using the novel Zr or Hf compound of the present invention is different from the conventional method using CpZr[N(CH 3 ) 2 ] 3 Compared with the atomic layer deposition method using compound gases, the oxide film growth rate is faster and the deposition rate is faster.

[0100] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. A compound containing a metal element of Group IV, It is characterized in that 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 , R 2 Each is independently a C1-C4 straight or branched chain alkyl group.

2. A precursor composition for forming a film, It is characterized in that The method comprises the compound containing a Group IV metal element according to claim 1.

3. A method for preparing a film containing a Group IV metal element, It is characterized in that The method comprises the following steps: forming a film containing a Group IV metal element on a substrate by reacting the precursor composition for forming a film according to claim 2 with a reaction gas.

4. The method for preparing a film containing a Group IV metal element according to claim 3, It is characterized in that An oxide film containing a Group IV metal element is formed on the substrate by vapor deposition.

5. The method for preparing a film containing a Group IV metal element according to claim 3, It is characterized in that The reaction gas is selected from: 2 , O 3 , H 2 O, H 2 O 2 、NO、N 2 O、NO 2 and mixtures thereof.

6. The method for preparing a film containing a Group IV metal element according to claim 4, It is characterized in that The vapor deposition is at least one method selected from chemical vapor deposition and atomic layer deposition.