Film deposition method, film deposition material, and new compound

Abstract

To provide a technique for forming a IV-group transition metal-containing film using a IV-group transition metal precursor rich in storage stability (heat stability), suitable for transportation because it is liquid at 25°C (1 atmosphere), and capable of stably supplying a raw material.SOLUTION: To provide a compound expressed by LM(NR1R2)3 (M is at least one selected from a group of Hf and Zr, L is halogen, and R1, R2 are alkyl groups).SELECTED DRAWING: Figure 5

Description

[Technical Field]

[0001] The present invention relates to, for example, Group IV transition metal compounds having specific ligands. [Background technology]

[0002] Group IV transition metal-containing films are used in semiconductor and electronic applications. Chemical vapor deposition (CVD) and atomic layer deposition (ALD) have been applied as deposition techniques to fabricate thin films for semiconductor devices. These methods enable the achievement of conformal films (metals, metal oxides, metal nitrides, metal silicides, and similar films) through the chemical reaction of metal-containing compounds (metal organic compounds: precursors).

[0003] Patent No. 4,562,169 discloses tetrakis(dialkylamido)hafnium compounds such as Hf(NMe2)4.

[0004] Patent No. 4,542,807 discloses tetrakis(alkoxy)hafnium compounds such as Hf(OtBu)4.

[0005] In Patent Publication No. 2004-137223, HfAl(OR 1 ) n (OR 2 ) 7-n has been disclosed.

[0006] In the published patent application 2004-137222, HfAL(OR 1 ) n (OCR 2 R 3 AOR 4 ) 7-n has been disclosed.

[0007] HfCl4 is disclosed in J. Appl. Phys. 94, 3641-3647 (2003).

[0008] J. Electrochem. Soc, 153 F39 (2006) discloses Cp2HfCl2. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Patent No. 4562169 [Patent Document 2] Patent No. 4542807 [Patent Document 3] JP 2004-137222 [Patent Document 4] JP 2004-137223 A [Non-patent literature]

[0010] [Non-Patent Document 1] J.Appl.Phys.94,3641-3647(2003) [Non-patent document 2] J.Electrochem.Soc,153 F39(2006) Summary of the Invention [Problem to be solved by the invention]

[0011] Previously proposed Hf (hafnium) precursors in this field have not necessarily possessed sufficient properties. This is at least in part due to the low thermal stability of the Hf precursor, which causes decomposition during transport to the Hf-containing film deposition process, making it difficult to stably supply the precursor. At least in part due to the low thermal stability of the Hf precursor, it is difficult to raise the deposition temperature of the Hf-containing film during the Hf-containing film deposition process, making it difficult to remove organic impurities from the Hf-containing film. At least in part due to the low vapor pressure (volatility) of the Hf precursor, it is difficult to transport the Hf precursor uniformly during the transport process. At least in part due to the low vapor pressure (volatility) of the Hf precursor, it is difficult to transport the Hf-containing film uniformly during the transport process. At least in part due to the low vapor pressure (volatility) of the Hf precursor, it results in a slow (small) deposition rate of the Hf-containing film during the Hf-containing film deposition process.

[0012] Hafnium halide compounds such as HfCl4 disclosed in Non-Patent Document 1 are solid at 25°C (1 atmosphere) and are difficult to transport uniformly in the process of transporting them to the deposition process of a Hf-containing film.

[0013] Tetrakis(dialkylamido)hafnium compounds such as Hf(NMe2)4 disclosed in Patent Document 1 have low thermal stability, and decomposition occurs during the transport process in the deposition process of Hf-containing films, making it difficult to transport them uniformly.

[0014] Tetrakis(alkoxy)hafnium compounds such as Hf(OtBu)4 disclosed in Patent Document 2 are prone to clustering due to trace amounts of moisture, making stable storage difficult.

[0015] Therefore, there remains a need in the art for Group IV transition metal precursors that have good shelf and thermal stability, high vapor pressure (volatility), uniform transport, and the ability to produce high quality, conformal Group IV transition metal-containing films by CVD and / or ALD processes.

[0016] The problem to be solved by the present invention is to provide a technique for forming a Group IV transition metal-containing film, particularly a technique for forming a Group IV transition metal-containing film by CVD and / or ALD using a Group IV transition metal compound that has excellent storage stability (thermal stability), is liquid at 25°C (1 atmosphere), has high vapor pressure (volatility), and is suitable for uniform transport as a precursor for forming the Group IV transition metal-containing film. For example, the object of the present invention is to provide a technique that is convenient for forming a Hf(Zr)-containing film, particularly a technique for forming a Hf(Zr)-containing film by CVD and / or ALD using a Hf(Zr) compound that has excellent storage stability (thermal stability), is in a liquid state at 25°C (1 atmosphere), has high vapor pressure (volatility), and is suitable for uniform transport, as a precursor for forming the Hf(Zr)-containing film. [Means for solving the problem]

[0017] The present invention relates to a novel compound having the structural formula (or structure) LM(NR 1 R 2 )3 (wherein M is Hf (hafnium) or Zr (zirconium), L is a halogen group, and R 1 ,R 2 is an alkyl group, and R 1 and R 2 and may be different or the same.

[0018] The novel compound is, for example, a liquid at 25° C. (1 atmosphere).

[0019] In the novel compound, the alkyl group preferably has 1 to 4 carbon atoms.

[0020] In the novel compound, the alkyl group is more preferably any one selected from the group consisting of a methyl group (Me, -CH3) and an ethyl group (Et, -C2H5).

[0021] In the novel compound, more preferably, at least one of the alkyl groups is —C2H5.

[0022] In the novel compound, all of the alkyl groups are particularly preferably -C2H5.

[0023] In the novel compound, L is preferably Cl (chlorine).

[0024] More preferably, the novel compound is one in which L is Cl and the alkyl group is selected from the group consisting of -CH3 and -C2H5.

[0025] In the novel compound, it is particularly preferred that L is Cl and all of the alkyl groups are -C2H5.

[0026] In the novel compound, M is, for example, Hf.

[0027] In the novel compound, M is, for example, Zr.

[0028] The present invention provides a film-forming material suitable as a precursor for depositing a Group IV transition metal-containing film, the film-forming material being the novel compound, i.e., having the structural formula (or structure) LM(NR 1 R 2 )3 (wherein M is Hf or Zr, L is a halogen group, and R 1 ,R 2 is an alkyl group, and R 1 and R 2 and may be different or the same.

[0029] The film-forming material is preferably used in a technique for depositing the Group IV transition metal-containing film, such as a CVD or / and ALD technique.

[0030] The film-forming material (the novel compound) is liquid at, for example, 25° C. (1 atmosphere).

[0031] In the film-forming material (the novel compound), the alkyl group preferably has 1 to 4 carbon atoms.

[0032] More preferably, the alkyl group in the film-forming material (the novel compound) is any one selected from the group consisting of a methyl group (Me, -CH3) and an ethyl group (Et, -C2H5).

[0033] More preferably, in the film-forming material (the novel compound), at least one of the alkyl groups is —C 2 H 5 .

[0034] In the film-forming material (the novel compound), it is particularly preferable that all of the alkyl groups are -C2H5.

[0035] In the film-forming material (the novel compound), the L is preferably Cl (chlorine).

[0036] More preferably, in the film-forming material (the novel compound), L is Cl and the alkyl group is any one selected from the group consisting of -CH3 and -C2H5.

[0037] In the film-forming material (the novel compound), it is particularly preferable that L is Cl and all of the alkyl groups are -C2H5.

[0038] In the film-forming material (the novel compound), the M is, for example, Hf.

[0039] In the film-forming material (the novel compound), the M is, for example, Zr.

[0040] The present invention provides a method for depositing a Group IV transition metal-containing film using the film-forming material [which film-forming material is the novel compound, i.e., having the structural formula (or structure) LM(NR 1 R 2 )3 (wherein M is Hf or Zr, L is a halogen group, and R 1 ,R 2 is an alkyl group, and R 1 and R 2and may be different from or the same as each other.) into a film formation chamber, and a Group IV transition metal-containing film is formed on a substrate placed in the film formation chamber.

[0041] The film formation method may be, for example, CVD or / and ALD technology.

[0042] The film-forming material (the novel compound) used in the film-forming method is liquid at, for example, 25° C. (1 atmosphere).

[0043] In the film-forming material (the novel compound) used in the film-forming method, the alkyl group preferably has 1 to 4 carbon atoms.

[0044] The film-forming material (the novel compound) used in the film-forming method is more preferably one in which the alkyl group is selected from the group consisting of -CH3 and -C2H5.

[0045] In the film-forming material (the novel compound) used in the film-forming method, more preferably, at least one of the alkyl groups is —C 2 H 5 .

[0046] In the film-forming material (the novel compound) used in the film-forming method, all of the alkyl groups are particularly preferably -C2H5.

[0047] In the film-forming material (the novel compound) used in the film-forming method, L is preferably Cl (chlorine).

[0048] More preferably, the film-forming material (the novel compound) used in the film-forming method is one in which L is Cl and the alkyl group is any one selected from the group consisting of -CH3 and -C2H5.

[0049] In the film-forming material (the novel compound) used in the film-forming method, it is particularly preferable that L is Cl and all of the alkyl groups are -C2H5.

[0050] In the film-forming material (the novel compound) used in the film-forming method, M is, for example, Hf.

[0051] In the film-forming material (the novel compound) used in the film-forming method, M is, for example, Zr.

[0052] Examples of Group IV transition metal-containing films include, but are not limited to, Group IV transition metal films, Group IV transition metal oxide films, Group IV transition metal nitride films, and Group IV transition metal oxynitride films. [Effects of the Invention]

[0053] The film-forming material proposed by the present invention is liquid at room temperature and atmospheric pressure (e.g., 25°C, 1 atmosphere), and can be transported more uniformly in the transport process in the deposition process of a Group IV transition metal-containing film. Furthermore, since the film-forming material is a compound with excellent thermal stability, it is less likely to decompose in the transport process of the Group IV transition metal-containing film, and can be transported more uniformly, resulting in a high-quality, conformal Group IV transition metal-containing film. [Brief explanation of the drawings]

[0054] [Figure 1] Magnetic resonance analysis (NMR) of ClHf(NEt2)3 [Figure 2] Thermogravimetric analysis (TG-DTA) of ClHf(NEt2)3 [Figure 3] NMR diagram of Hf(NEt2)4 [Figure 4] TG-DTA diagram of Hf(NEt2)4 [Figure 5] Comparison of TG-DTA of Synthesis Example 1 and Comparative Synthesis Example 1 [Figure 6] Schematic diagram of vapor pressure measuring device [Figure 7] Schematic diagram of the film formation device DETAILED DESCRIPTION OF THE INVENTION

[0055] The following detailed description provides preferred exemplary embodiments only and is not intended to limit the scope, applicability, or configuration of the present invention. Rather, it provides an enabling description for those skilled in the art for implementing preferred exemplary embodiments of the present invention. Various changes may be made in the function and arrangement of elements without departing from the spirit and scope of the present invention, as defined by the appended claims.

[0056] For example, the Group IV transition metal compound of the present invention is sometimes described as a complex, but because it is suitable for use in CVD and / or ALD, it is sometimes described as a precursor. Either notation can be considered to refer to the same thing.

[0057] The CVD is not limited to CVD in the narrow sense, but also includes CVD in the broad sense and similar CVD. Similarly, the ALD is not limited to ALD in the narrow sense, but also includes ALD in the broad sense and similar ALD. Examples include pulsed CVD, laser CVD, cyclic CVD (CCVD), metalorganic CVD (MOCVD), plasma-enhanced CVD (PECVD), high-density PECVD, photon-assisted CVD, plasma-photon-assisted CVD (PPECVD), thermal chemical vapor deposition, low-temperature chemical vapor deposition, chemically assisted vapor deposition, hot-filament chemical vapor deposition, CVD of liquid polymer precursors, deposition from supercritical fluids, low-energy CVD (LECVD), and plasma-enhanced ALD (PEALD). Other examples include CVD and ALD that employ radiation (X-rays, electron beams, electromagnetic waves, or light).

[0058] The Group IV transition metal-containing film includes, for example, a metal film (a film consisting of only a Group IV transition metal), an alloy film (an alloy film containing a Group IV transition metal), an oxide film (an oxide film or silicon oxide film containing a Group IV transition metal), a nitride film (a nitride film or silicon nitride film containing a Group IV transition metal), an oxynitride film (an oxynitride film containing a Group IV transition metal), a carbide film (a carbide film containing a Group IV transition metal), a silicide film (a silicide film containing a Group IV transition metal), and other films of various compositions, and includes any type of film as long as it contains Hf (and / or Zr) as one of its components.

[0059] The first invention is a novel compound represented by the following general formula (I).

[0060] General formula (I) LM(NR 1 R 2 )3 (wherein M is Hf or Zr, L is a halogen, and R 1 ,R 2 is an alkyl group, and R 1 and R 2 may be different or the same.)

[0061] The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms. Examples include a methyl group (-CH3), an ethyl group (-C2H5), a propyl group (-C3H7), and a butyl group (-C4H9). More preferably, it is any group selected from the group consisting of -CH3 and -C2H5. It is particularly preferred that at least one alkyl group is -C2H5. It is even more preferred that all alkyl groups are -C2H5.

[0062] Examples of the L (halogen) include Cl (chlorine), Br (bromine), I (iodine), and F (fluorine), and Cl is preferred.

[0063] From the viewpoint of being a liquid at room temperature (for example, 25°C (1 atmosphere)) and having a high vapor pressure (volatility), it is particularly preferable that L is Cl and all alkyl groups are -CH. Although only Hf is disclosed as M in the examples below, those skilled in the art will easily understand that Hf can be replaced with Zr.

[0064] The typical halogen compound HfCl4 is a solid at 25°C (1 atmosphere) and has a low vapor pressure (volatility), so it is easy to understand that the structure in which the substituents bonded to the Group IV transition metal M consist of one halogen group and three amino groups is important. A typical amide compound, Hf[N(CH3)2]4, is a solid at 25°C (1 atmosphere) and has a low vapor pressure (volatility), so it is easy to understand that the "structure in which the amino group is -N(C2H5)2" is important. Although Hf[N(C2H5)2]4 is a liquid at 25°C (1 atmosphere), its vapor pressure (volatility) is low, so it can be understood that the structure in which the substituents bonded to the Group IV transition metal M consist of one halogen group and three amino groups is important. It will be understood that the amino group is preferably -N(C2H5)2.

[0065] When a Group IV transition metal-containing film is deposited, decomposition can easily result in the incorporation of impurities, particularly carbon (C). To deposit a high-purity Group IV transition metal-containing film, it is important not only to deposit the film at a higher temperature without decomposing the Group IV transition metal precursor, but also to minimize the number of organic components contained in the Group IV transition metal precursor, i.e., the number of substituents bonded to the Group IV transition metal M (the number of alkyl groups in the case of alkyl groups). It is important that the substituents bonded to the Group IV transition metal M have a structure consisting of one halogen and three amino groups, with Cl being the preferred halogen.

[0066] The second invention is a film-forming material for a Group IV transition metal film used to form a Group IV transition metal-containing film. The material is at least a compound represented by the general formula (I) (the compound described above), where "at least" means that the compound represented by the general formula (I) may be used alone or in combination with other materials (compounds). In other words, it is not excluded that the material may be in the form of a composition.

[0067] The third invention is a method for forming a Group IV transition metal-containing film using the above-mentioned film-forming material as a precursor. CVD or ALD techniques are preferably used for film formation in the present invention.

[0068] In the field of metal-containing film deposition, substrate temperature is an important process variable. Typical substrate temperatures are about 150°C to about 550°C. Higher substrate temperatures can promote faster film growth rates. Therefore, it is desirable to find Group IV transition metal precursors that can deposit Group IV transition metal-containing films at higher temperatures without decomposition. Compounds represented by the general formula (I) satisfy this need.

[0069] In the field of metal-containing film deposition, substrate temperature is an important process variable. Typical substrate temperatures are about 150°C to about 550°C. Higher substrate temperatures can promote faster film growth rates. Therefore, it is desirable to find Group IV transition metal precursors that can deposit Group IV transition metal-containing films at higher temperatures without decomposition. Compounds represented by the general formula (I) above meet this need.

[0070] In the field of metal-containing film deposition, it is recognized that precursors that are liquid under the process conditions for metal-containing film deposition are preferable to precursors that are solid under the process conditions for metal-containing film deposition. Liquid precursors can transport precursors more uniformly during the transport process in the metal-containing film deposition process than solid precursors. In one embodiment, a carrier gas is bubbled through the metal-containing film precursor under suitable process conditions. Bubbling a gas through a liquid is an effective means of providing a longer gas-liquid contact time and a larger gas-liquid contact area, with the goal of achieving a gas flow saturated with vaporized liquid precursor. Achieving a saturated carrier gas maximizes the precursor transport rate and is advantageous for operating the metal-containing film deposition process. The compounds represented by the general formula (I) satisfy the above requirements. [Example]

[0071] The present invention will be described in more detail below, but the following description is merely a preferred exemplary embodiment and is not intended to limit the present invention. Various modifications are also included as long as they do not depart from the spirit and scope of the present invention as defined in the claims.

[0072] [Example 1] [Synthesis Example 1: ClHf(NEt2)3] The synthesis was carried out under a nitrogen atmosphere. A vessel containing 170 g of HfCl4 and 300 ml of toluene was cooled to 0 to 10°C, and a mixed solution of 117 g of diethylamine and 200 ml of toluene was slowly added dropwise. The mixture was stirred in the vessel. Next, 683.6 g of nBuLi / nHexane (15 wt%) was slowly added dropwise. During this time, the vessel was cooled to 0 to 10°C, and the mixture was stirred. Then, cooling was stopped, and the temperature inside the vessel gradually returned to room temperature. After stirring at room temperature, the vessel was heated to 85°C, and heating and stirring were continued for 3 hours. Then, heating was stopped, and the temperature inside the vessel gradually returned to room temperature. The resulting reaction mixture was filtered, and the solvent of the reaction mixture solution was removed by distillation under reduced pressure. The resulting crude product was purified by distillation to obtain a pale yellow liquid.

[0073] 1 The H-NMR spectrum (see Figure 1) indicates that the resulting pale yellow liquid is ClHf(NEt2)3.

[0074] From the TG-DTA graph (see Figure 2), the volatilization rate was 97.38%, and the temperature at which the weight loss rate reached 50% (T 50 ) is found to be 186.3°C. The novel compound is a material with high vaporizability and high vapor pressure, and can be said to be a suitable precursor for forming a Hf-containing film.

[0075] [Comparative synthesis example 1: Hf(NEt2)4] The synthesis was carried out under a nitrogen atmosphere. A vessel containing 29.2 g of diethylamine and 50 ml of hexane was cooled to 0-10°C, and 170.9 g of nBuLi / nHexane (15 wt%) was slowly added dropwise. Next, 32 g of HfCl4 was slowly added. During this time, the vessel was cooled to 0-10°C, and the mixture was stirred. Then, cooling was stopped, and the temperature inside the vessel gradually returned to room temperature. After stirring at room temperature, the vessel was heated to 85°C, and heating and stirring were continued for 5 hours. Then, heating was stopped, and the temperature inside the vessel gradually returned to room temperature. The resulting reaction mixture was filtered, and the solvent of the reaction mixture was removed by distillation under reduced pressure. The resulting crude product was purified by distillation to obtain a pale yellow liquid.

[0076] 1 The H-NMR spectrum (see Figure 3) indicates that the resulting pale yellow liquid is Hf(NEt2)4.

[0077] From the TG-DTA graph (see Figure 4), the volatilization rate was 97.52%, T 50 It turns out that the temperature is 209.0℃. Hf(NEt2)4 has a lower vaporizability than ClHf(NEt2)3 and is therefore not a suitable precursor for forming Hf-containing films.

[0078] CpHf(NEt2)3 [a compound in which Cl in ClHf(NEt2)3 is replaced by Cp (cyclopentadienyl group)] was a liquid at 25°C (1 atm), but 50 The temperature was 198.3°C. CpHf(NEt2)3 has a lower vaporizability than ClHf(NEt2)3 and is therefore not a suitable precursor for forming Hf-containing films.

[0079] [Example 2] FIG. 6 is a schematic diagram of the vapor pressure measuring device, in which 1 is a vessel, 2 is a pressure gauge, 3 is a heater, and 4 is a vacuum pump. The vapor pressure of the compounds obtained in Example 1 was measured using the apparatus shown in Figure 6. Specifically, the vapor pressure of the novel compounds ClHf(NEt2)3, Hf(NEt2)4, and CpHf(NEt2)3 was measured. A comparison of the vapor pressures at the same temperature (90°C) is shown in Table 1. Table-1 JPEG2025133246000002.jpg32156

[0080] The ClHf(NEt2)3 (Synthesis Example 1) is a liquid at 25°C (1 atmosphere) and has a vapor pressure of 1.93 torr at 90°C. The Hf(NEt2)4 (Comparative Synthesis Example 1) is a liquid at 25°C (1 atmosphere) and has a vapor pressure of 0.62 torr at 90°C. The only difference between the two compounds is the presence or absence of one halogen (Cl) bonded to Hf. HfCl4, in which four substituents bonded to Hf are Cl, is a solid at 25°C (1 atm), and T 50 It is a material with poor (low) volatility, with a temperature of 258.6°C. It is unlikely that using a substituent of a compound with poor (low) volatility would result in an increase in volatility and vapor pressure. In other words, no one would have predicted that changing one of the substituents of Hf(NEt2)4 to Cl would significantly increase the vapor pressure from 0.62 torr (90°C) to 1.93 torr (90°C). This finding was first discovered by the present inventors. This indicates that ClHf(NEt2)3 may be a better choice than Hf(NEt2)4 and HfCl4 as a precursor in the deposition process of metal-containing films. ClHf(NEt2)3 contains fewer organic components than Hf(NEt2)4. Therefore, when ClHf(NEt2)3 is used as a film deposition material, it is expected that the amount of impurities in the deposited film will be lower than when Hf(NEt2)4 is used. From this perspective, ClHf(NEt2)3 would be a better choice as a film deposition material.

[0081] CpHf(NEt2)3 is liquid at 25°C (1 atm) and has a vapor pressure of 0.45 torr at 90°C, which is significantly lower than that of ClHf(NEt2)3. This makes ClHf(NEt2)3 a better choice than CpHf(NEt2)3 for use as a precursor in metal-containing film deposition processes. ClHf(NEt2)3 contains fewer organic components than CpHf(NEt2)3. Therefore, when ClHf(NEt2)3 is used as a film-forming material, it is expected that the amount of impurities in the deposited film will be lower than when CpHf(NEt2)3 is used. From this perspective, ClHf(NEt2)3 would be a better choice as a film-forming material.

[0082] [Example 3] Figure 7 is a schematic diagram of a film formation apparatus, in which 1 is a vessel, 2 is a vaporizer, 3 is a heater, 4 is a substrate, 5 is a decomposition reactor, 6 is a heater, and 7 is a vacuum pump. An Hf-based film was formed on a substrate 5 using the apparatus shown in Fig. 7. That is, an Hf-based thin film was formed using the novel compound ClHf(NEt2)3 (Synthesis Example 1) as a precursor. The precursor in a container 1 was supplied to a vaporizer using a pressurized gas (e.g., nitrogen gas), and the vaporized precursor was introduced into a decomposition reactor 5, whereupon an Hf-based film was formed on a heated substrate 4. The Hf-based film obtained by the above method was confirmed to have excellent inner surface uniformity and high purity by X-ray photoelectron spectroscopy (XPS).

[0083] [Example 4] Example 3 is an example in which the film is formed by chemical vapor deposition, while Example 4 is an example in which the film is formed by atomic controlled deposition. This film had excellent uniformity on the inner surface, and the formation of a highly pure film was confirmed by XPS.

[0084] It will be understood that many further variations in the details of materials, steps, components, etc., described and shown herein to explain the nature of the invention, may be made by those skilled in the art within the principles and scope of the invention as expressed in the appended claims.

[0085] As such, it is not intended that the present invention be limited to the foregoing examples and / or embodiments.

Claims

1. 1. A method of depositing a Group IV transition metal-containing film, comprising: LM (NR １ R ２ ) ３ (M is Hf or Zr. L is a halogen. R １ , R ２ is an alkyl group.) is supplied into a film-forming chamber to form the film on a substrate. Film formation method.

2. L is Cl, The R １ , R ２ Ga-C ２ H ５ is 10. The method of claim 1.

3. The M is Hf. The method of claim 1 or claim 2.

4. The M is Zr The method of claim 1 or claim 2.

5. The compound is a liquid at 25°C (1 atmosphere).

10. The method of claim 1.

6. The L is Cl.

10. The method of claim 1.

7. The alkyl group has 1 to 4 carbon atoms.

10. The method of claim 1.

8. The alkyl group is —CH ３ , -C ２ H ５ It is one selected from the group 10. The method of claim 1.

9. At least one alkyl group is —C ２ H ５ is 10. The method of claim 1.

10. A material used in depositing a Group IV transition metal-containing film, comprising: The material is LM (NR １ R ２ ) ３ (M is at least one selected from the group consisting of Hf and Zr. L is a halogen. R １ , R ２ is an alkyl group. Film deposition materials.

11. The compound is a liquid at 25°C (1 atmosphere). The film-forming material of claim 10.

12. The L is Cl. The film-forming material of claim 10.

13. The alkyl group has 1 to 4 carbon atoms. The film-forming material of claim 10.

14. The alkyl group is —CH ３ , -C ２ H ５ It is one selected from the group The film-forming material of claim 10.

15. The alkyl group is —CH ３ , -C ２ H ５ and L is Cl. The film-forming material of claim 10.

16. At least one alkyl group is —C ２ H ５ is The film-forming material according to claim 14 or 15.

17. M is Hf The film-forming material of claim 10.

18. M is Zr The film-forming material of claim 10.

19. LM (NR １ R ２ ) ３ (M is at least one selected from the group consisting of Hf and Zr. L is a halogen. R １ , R ２ is an alkyl group. New compound.

20. The compound is a liquid at 25°C (1 atmosphere).

20. The novel compound of claim 19.

21. The L is Cl.

20. The novel compound of claim 19.

22. The alkyl group has 1 to 4 carbon atoms.

20. The novel compound of claim 19.

23. The alkyl group is —CH ３ , -C ２ H ５ It is one selected from the group 20. The novel compound of claim 19.

24. The alkyl group is —CH ３ , -C ２ H ５ and L is Cl.

20. The novel compound of claim 19.

25. At least one alkyl group is —C ２ H ５ is 25. The novel compound of claim 23 or claim 24.

26. M is Hf 20. The novel compound of claim 19.

27. M is Zr 20. The novel compound of claim 19.

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