Forming material, forming method and novel compound
阅读说明：本技术 形成材料、形成方法以及新型化合物 (Forming material, forming method and novel compound ) 是由 町田英明 石川真人 须藤弘 于 2019-06-18 设计创作，主要内容包括：本发明涉及一种形成材料、形成方法以及新型化合物。提供一种新型化合物。一种新型化合物,由M[i-C<Sub>3</Sub>H<Sub>7</Sub>NC(R)N-i-C<Sub>3</Sub>H<Sub>7</Sub>]<Sub>2</Sub>(其中,M＝Co或Fe。R为n-C<Sub>3</Sub>H<Sub>7</Sub>或i-C<Sub>3</Sub>H<Sub>7</Sub>,但是不包括双(N,N’-二异丙基-2-甲基丙脒)铁)表示,所述化合物在25℃(1个大气压)下为液体。(The present invention relates to a forming material, a forming method, and a novel compound. Provided is a novel compound. A novel compound is prepared from M [ i-C ] 3 H 7 NC(R)N‑i‑C 3 H 7 ] 2 (wherein M ═ Co or Fe. R is n-C 3 H 7 Or i-C 3 H 7 But excluding bis (N, N' -diisopropyl-2-methylpropionamidine) iron), the compound is a liquid at 25 ℃ (1 atmosphere).)
1. A novel compound is prepared from M [ i-C ]3H7NC(R)N-i-C3H7]2A compound represented by (I), which is a liquid at 25 ℃ under 1 atmosphere, wherein M ═ Co or Fe, and R is n-C3H7Or i-C3H7But does not include iron bis (N, N' -diisopropyl-2-methylpropionamidine).
2. The novel compound of claim 1, wherein structural isomers are absent from the novel compound.
3. The novel compound of claim 1 or 2, wherein the novel compound is free of optical isomers.
4. The novel compound according to any one of claims 1to 3, wherein the vapor pressure of the compound at 100 ℃ is 0.35Torr or more.
5. A forming material for forming an M-based material, wherein M is one or two selected from the group consisting of Co and Fe,
the forming material has a composition consisting of M [ i-C3H7NC(R)N-i-C3H7]2A compound represented by formula (I), M ═ Co or Fe, R is n-C3H7Or i-C3H7But does not include iron bis (N, N' -diisopropyl-2-methylpropionamidine).
6. One method is a method for forming an M-based material, wherein M is one or two selected from the group consisting of Co and Fe,
will be composed of M [ i-C ]3H7NC(R)N-i-C3H7]2The compound is delivered into a chamber, the compound delivered into the chamber is decomposed, and M-system material is formed on a substrate, wherein M is Co or Fe, R is n-C3H7Or i-C3H7But does not include iron bis (N, N' -diisopropyl-2-methylpropionamidine).
Technical Field
The present invention relates to novel compounds.
Background
Co (metallic cobalt (e.g., film)) is required in the semiconductor field. The resistance of the Co is low. Therefore, it is widely expected to be used as a diffusion preventing film for copper wiring of a semiconductor circuit or a liner for copper wiring of a semiconductor circuit. Further, it has also been studied to use Co for the wiring of the semiconductor circuit itself.
The Co and Fe (metallic iron (e.g., film)) are magnetic materials. Therefore, there is a demand in the field of MEMS (micro electro mechanical systems). The Co, Fe are indispensable for materials such as next generation memories (e.g., MRAM).
FeSi2The absorption coefficient of the alloy film is very high (about 100 times that of single crystal Si). Therefore, if FeSi is used2When the alloy is applied to a solar cell, the alloy can be made into a thin film. Reported, FeSi2The theoretical photoelectric conversion efficiency of the alloy film is 16-23%. Thus, FeSi2The alloy attracts attention as a material for a thin film solar cell.
The Co and Fe-based film (e.g., Co film, cobalt oxide film, Fe film, iron oxide film, etc.) is formed by a chemical vapor deposition method (CVD method) or an atomic layer control deposition method (ALD method). In this case, as a raw material, for example, a β -diketone cobalt complex, a β -diketone iron complex, a cyclopentadienyl cobalt complex, and a cyclopentadienyl iron complex are proposed.
When a β -diketone complex (a compound having an O (oxygen atom)) is used as the raw material compound, O enters the inside of the formed film. Therefore, it is considered that no significant problem occurs when the film is a cobalt oxide film or an iron oxide film. However, when the target film is a film that does not originally contain oxygen (O), there is a concern that a problem may occur.
Cyclopentadienyl complexes (e.g. bis (cyclopentadienyl) cobalt; Cp)2Co) has no O (oxygen atom). Therefore, it is considered that, in the case of using the complex, O does not substantially enter the inside of the film. However, the decomposition temperature of the cyclopentadienyl cobalt complex is high. Therefore, there is a fear that C (carbon atom) enters the inside of the film. Using bis (cyclopentadienyl) iron (Cp)2Fe) as a raw material is also the same.
As a Co complex (having no O (oxygen atom)) or Fe complex (having no O (oxygen atom)), there has been proposed (N, N' -diisopropylpropionamidine) cobalt { Co [ i-C ]3H7NC(C2H5)N-i-C3H7]2The scheme of (1). (N, N' -diisopropylpropionamidine) iron { Fe [ i-C ] is proposed3H7NC(C2H5)N-i-C3H7]2The scheme of (1). When the proposed complex is used to form a film by a CVD method (or ALD method), a Co film or an Fe film having high purity is formed. The cobalt (N, N' -diisopropylpropionamidine) is a solid (melting point about 38 ℃ C.). The iron (N, N' -diisopropylpropionamidine) is a solid (melting point about 33 ℃ C.). If the compound which is solid at room temperature is heated to melt, the vapor is conveyed to the film forming reaction chamber. In this case, the pipe (pipe for steam delivery) also needs to be heated. When the pipe is not heated, the compound is solidified and accumulated in the pipe. The piping may be clogged. In the case of the above-mentioned melting point (33 ℃ C., 38 ℃ C.), almost no problem occurs in the film formation of the laboratory grade (small scale). However, the problem becomes large at the level of mass production in a factory. For example, solidification and clogging occur at a cooled portion of the pipe only because the portion is present. The production line is stopped. A lot of dies are wasted in consideration of a series of processes performed at a mass production level. The loss becomes large. In recent years, in a semiconductor mass production factory, a large amount of a raw material compound is fed into a reaction chamber. Direct liquid injection is used in such systems. The process feeds the feedstock directly into the vaporization chamber in liquid form. The compound (gas) vaporized in the vaporization chamber is fed into a film formation reaction chamber. In this case, it is naturally necessary that the solution is liquid at room temperature. In the case of the above solid (melting point (38 ℃ C., 33 ℃ C.)), it becomes liquid when heated. However, thermal energy is required. There is also concern about solidification plugging within the piping.
Further, a high purity product is essential for a semiconductor factory. Distillation is indispensable for obtaining a high purity product. When a compound that is solid at room temperature is distilled, the gas is solidified in a cooling section (condenser). Therefore, the distillation operation becomes difficult. By setting the cooling temperature to the melting point or higher, solidification can be prevented. However, temperature control is difficult. There is also a loss of thermal energy.
Disclosure of Invention
As described in the section "background art", a metal complex of a distillable liquid (liquid at 25 ℃ (1 atm)) is required (the metal M ═ Co, Fe). There has not been proposed a metal complex (M ═ Co, Fe) which is a distillable liquid (liquid at 25 ℃ (1 atm)) and in which isomers are not present, and from which a metal M (M ═ Co, Fe) can be obtained.
Accordingly, the present invention solves the above problems. For example, a technique is provided that can easily provide a high-quality M (M ═ Co, Fe) material (e.g., a film). For example, a Co complex is provided that is liquid (liquid at 25 ℃ (1 atmosphere)) and does not have isomers. For example, an Fe complex that is liquid (liquid at 25 ℃ (1 atmosphere)) and does not have isomers is provided.
In order to solve the above problems, intensive and thorough research has been conducted.
As a result, it was found that Co [ i-C ]3H7NC(n-C3H7)N-i-C3H7]2、Co[i-C3H7NC(i-C3H7)N-i-C3H7]2、Fe[i-C3H7NC(n-C3H7)N-i-C3H7]2(liquid at 25 deg.C (1 atm)). The compound is obtained in high purity by distillation operation. It is understood that when the compound is used, a high-quality film can be obtained by a CVD method (or an ALD method).
The present invention has been completed based on the above findings.
The invention provides a method for preparing a high-purity (1 atmosphere) catalyst at 25 deg.CUnder pressure) liquid from M [ i-C3H7NC(R)N-i-C3H7]2(wherein M ═ Co or Fe. R is n-C3H7Or i-C3H7) The compounds shown, but excluding iron bis (N, N' -diisopropyl-2-methylpropionamidine).
For example, a Co [ i-C ] liquid at 25 deg.C (1 atm) is proposed3H7NC(n-C3H7)N-i-C3H7]2。
For example, a Co [ i-C ] liquid at 25 deg.C (1 atm) is proposed3H7NC(i-C3H7)N-i-C3H7]2。
For example, an Fe [ i-C ] liquid at 25 deg.C (1 atm) is proposed3H7NC(n-C3H7)N-i-C3H7]2。
The compounds are novel compounds.
The compounds are free of structural isomers.
The functional group of the compound does not have an asymmetric carbon atom.
The compounds are free of optical isomers.
The vapor pressure (100 ℃) of the compound is 0.35Torr or more.
The present invention provides a forming material for forming an M (one or two selected from Co and Fe) material, wherein the forming material has a structure formed by M [ i-C ]3H7NC(R)N-i-C3H7]2(wherein M ═ Co or Fe. R is n-C3H7Or i-C3H7) The compounds shown, but excluding iron bis (N, N' -diisopropyl-2-methylpropionamidine).
The present invention provides a method for forming an M (one or two selected from Co and Fe) material, wherein M [ i-C ] is selected as a material3H7NC(R)N-i-C3H7]2(wherein M ═ Co or Fe. R is n-C3H7Or i-C3H7) The compound represented by (1) is transferred into a chamber, and the compound transferred into the chamber is decomposed to form an M-series material on a substrate. But does not include iron bis (N, N' -diisopropyl-2-methylpropionamidine).
Effects of the invention
The compound was liquid (liquid at 25 ℃ (1 atm)).
The compound is liquid, so that a high-purity product can be obtained through simple distillation operation.
The compounds are easily vaporized (high vapor pressure). The gas transport of the compound is stable. Therefore, a high-quality material (e.g., a film) can be obtained at low cost by the CVD method (or ALD method). The film forming efficiency is good. For example, a high-quality metal M (M ═ Co, Fe) film is efficiently formed. Alternatively, a high-quality M (Co, Fe) alloy film is efficiently formed.
The compound has no O (oxygen atom). Therefore, the formed film does not contain (substantially does not contain) O. Even if the formed film contains O, the O content is small.
Drawings
FIG. 1 is a schematic view of a CVD apparatus.
FIG. 2 is a schematic view of a CVD apparatus.
Fig. 3 is a vapor pressure graph.
Description of the symbols
1 raw material container, 2 substrate heater, 3 film forming chamber, 4 substrate, 5 flow controller, 6 nozzle, 7 carrier gas, 8 vaporizer, 9 raw material pressure feed gas, 10 additive gas for film forming, 11 raw material pressure feed gas pressure controller, 12 liquid flow controller
Detailed Description
The first invention of the present invention is a novel compound. The compound is M [ i-C3H7NC(R)N-i-C3H7]2(M ═ Co or Fe. R is n-C3H7Or i-C3H7). But does not include iron bis (N, N' -diisopropyl-2-methylpropionamidine). The compound is represented by the following [ formula 1]]And [ formula 2]]And [ formula 3]]And (4) showing. For example Co [ i-C3H7NC(n-C3H7)N-i-C3H7]2(bis (N, N' -diisopropylbutylamidine) cobalt). For example Co [ i-C3H7NC(i-C3H7)N-i-C3H7]2(bis (N, N' -diisopropyl-2-methylpropionamidine) cobalt). For example Fe [ i-C3H7NC(n-C3H7)N-i-C3H7]2(bis (N, N' -diisopropylbutanamidine) iron). The compound (complex) is liquid (liquid at 25 ℃ (1 atm)). Therefore, a high purity product of the compound is obtained simply by a distillation operation. The compounds are free of structural isomers. The functional group of the compound does not have an asymmetric carbon atom. The compounds are free of optical isomers. The importance of the absence of isomers is as follows. In the field of semiconductor in recent years, miniaturization and complication have been advanced. For example, the film may be formed on fine holes or grooves (the opening has a diameter of several tens of nanometers and a depth of 10 to 200 times, or more than 200 times, the diameter of the opening). In the case of such film formation, the ALD method is considered to be indispensable. In this case, the film-forming raw material molecule needs to be chemically adsorbed to the terminal group of the substrate (for example, -OH group, -NH group)2A base). In this chemisorption, it is preferable that the orientation or arrangement of the raw material molecules is ordered. When the raw material molecules are not bilaterally symmetric, or optically active (optical isomers), it is difficult to perform chemical adsorption by ordered arrangement. The film formed in this state has a low density and a high specific resistance. Therefore, the absence of isomers is preferred. In the case of no isomer, purification is simple. The compounds shown in the reference examples described later are isomeric. Therefore, it is not preferable as a film-forming material. Isolation (separation, purification) is extremely difficult (at present, impossible). The compounds of the invention have a high vapor pressure. For example, the vapor pressure (100 ℃) is 0.35Torr or more. The pressure is 0.4Torr or more. Is 0.47to 0.55 Torr. Co [ i-C3H7NC(n-C3H7)N-i-C3H7]2The vapor pressure (100 ℃) of (A) was 0.53 Torr. Co [ i-C3H7NC(i-C3H7)N-i-C3H7]2The vapor pressure (100 ℃) of (A) was 0.47 Torr. Fe [ i-C3H7NC(n-C3H7)N-i-C3H7]2The vapor pressure (100 ℃) of (A) was 0.55 Torr. The vapor pressure was determined using a gas saturation method. Film formation by CVD or ALD is easy.
[ formula 1]
[ formula 2]
[ formula 3]
The second invention of the present invention is a forming material. This is a material for forming an M (M ═ one or two selected from the group consisting of Co and Fe) system material. The M-based material is, for example, a Co-based film. Such as a Co metal film. For example a Co alloy film. For example, a film of CoX (X is a non-metal element such as N, B (particularly an element other than O)) or a semiconductor element). For example, Fe film. For example, an Fe metal film. For example, a FeCo alloy film. For example, an Fe alloy film. For example, a FeX (X is a non-metal element (e.g., N, B, etc. (particularly, an element other than O)) or a semiconductor element) film. For example, a FeCoX (X is a non-metal element (e.g., N, B, etc. (particularly, an element other than O)) or a semiconductor element) film. The material is not limited to a film. It may also be a thicker material than the concept of a film. The material has the compound (complex: selected from Co [ i-C ]3H7NC(n-C3H7)N-i-C3H7]2、Co[i-C3H7NC(i-C3H7)N-i-C3H7]2、Fe[i-C3H7NC(n-C3H7)N-i-C3H7]2One or two or more of the groups). Examples of the materialsSuch as the compound dissolved in a solvent. When the compound is used, a high-quality film can be efficiently obtained by a CVD method (or an ALD method).
The third invention of the present invention is a method. The method is a forming method. The method comprises the following steps: the compound (complex: selected from Co [ i-C ]3H7NC(n-C3H7)N-i-C3H7]2、Co[i-C3H7NC(i-C3H7)N-i-C3H7]2、Fe[i-C3H7NC(n-C3H7)N-i-C3H7]2One or two or more of group) into a chamber, the compound (complex) to be transported is decomposed to set the M-based material on a substrate. The method includes, for example, a step of transferring the compound (complex) into a chamber. The method includes a step of disposing the M-based material on a substrate by decomposition of the compound (complex) transferred into the chamber. The method employs, for example, a CVD method. For example, ALD method is used. The chamber is, for example, a film forming chamber (also referred to as a decomposition chamber or a reaction chamber).
The M-based material (e.g., film) obtained as described above has a very small amount of O, C (impurity component). I.e., high purity.
In the film formation process, it is difficult to cause troubles. For example, the film formation was performed by vaporization and decomposition of the compound (raw material (x) (g)), after 0.7x (g) of the raw material was consumed, the film formation operation was stopped, the inside of the pipe connecting the raw material container and the film formation chamber was observed, and no clogging of the inside of the pipe (clogging due to solidification of the raw material) was observed.
Specific examples are given below. However, the present invention is not limited to the following examples. Various modifications and applications are also included in the present invention as long as the advantages of the present invention are not seriously impaired.
[ example 1]
[ cobalt bis (N, N' -diisopropylbutylamidine) ]
The reaction is carried out under an inert gas atmosphere. 0.285mAn ol of N, N' -diisopropylcarbodiimide was slowly added dropwise to 280ml of a diethyl ether solution containing 0.284mol of N-propyllithium. Thereafter, stirring was performed at room temperature for 4 hours. The reaction mixture was slowly added dropwise to 0.142mol of cobalt chloride (CoCl)2) Suspended in 100ml of tetrahydrofuran. Thereafter, stirring was carried out for 24 hours. After the solvent was distilled off, 500ml of n-hexane was added. Insoluble matter was filtered. After the solvent was distilled off, the mixture was distilled under reduced pressure (0.1 torr). Bis (N, N' -diisopropylbutylamidine) cobalt was obtained in 89% yield.
The obtained 300g of cobalt bis (N, N' -diisopropylbutylamidine) was purified by distillation under reduced pressure. The vaporized cobalt bis (N, N' -diisopropylbutanamidine) (vapor) was liquefied during passage through an air-cooled tube and captured in a container. In this case, the air-cooled tube was left to cool at room temperature without being particularly cooled or heated. The recovery rate was 98%.
The purified product (bis (N, N' -diisopropylbutylamidine) cobalt) was crystallized by cooling. The crystallized cobalt bis (N, N' -diisopropylbutanamidine) was slowly warmed. Melting at 15-16 deg.C. The cobalt bis (N, N' -diisopropylbutanamidine) was liquid (at 25 ℃ (1 atm)). In the vacuum distillation using an oil rotary vacuum pump, the boiling point was 102 ℃.
The refined product has high purity. The analytical values (in wt. ppm) based on the metal impurity analysis (ICP-MS) are as follows. Na < 0.1, Mg < 0.1, Fe < 0.4, Zn < 0.3, Ti < 0.1, Cu < 0.1, Cd < 0.1, Mn < 0.1, Ni < 1.1, Pb < 0.1
The film forming operation was performed using the film forming apparatus of fig. 1. FIG. 1 is a schematic view of a film forming apparatus. In fig. 1, 1 denotes a raw material container. And 2, a substrate heater (holding and heating the substrate). And 3, a film forming chamber (decomposition reactor). And 4, a substrate. And 5 is a flow controller. And 6 is a spray head. 7 is a carrier gas (Ar or N)2Etc. inert gas). 10 is an additive gas (for example, Ar, N) introduced into the
Packaging the refined product (bis (N, N' -diisopropylbutylamidine) cobalt)Into the raw material container 1. The raw material container 1 is heated to 90 ℃ by a heater (not shown) attached to the raw material container 1. Nitrogen gas (carrier gas) was supplied at a rate of 20 ml/min to carry out bubbling. Thereby, the cobalt bis (N, N' -diisopropylbutamidine) is introduced into the
The film formed as described above is excellent in-plane uniformity. The membranes were investigated using XPS (X-ray photoelectronic Spectroscopy). The amount of C in the film is 4 at% or less. The amount of O in the film is 1 at% or less. The N content in the film is 0.4 at% or less. The specific resistance of the film was 19. mu. omega. cm.
The film forming operation was performed using the apparatus of fig. 1. The purified product (bis (N, N' -diisopropylbutylamidine) cobalt) was charged into the raw material container 1. The raw material container 1 was heated to 90 ℃ by a heater attached to the raw material container 1. Nitrogen gas (carrier gas) was supplied at a rate of 20 ml/min to carry out bubbling. Thereby, the cobalt bis (N, N' -diisopropylbutanamidine) was introduced into the
The film formed as described above was uniformly applied to the inner walls of the pores (aperture diameter of the opening portion 100nm, depth 1 μm). The step coverage is excellent. The films were investigated using XPS. The amount of C in the film is 2 at% or less. The amount of O in the film is 1 at% or less. The N content in the film is 0.2 at% or less. The specific resistance of the film at the flat portion was 20. mu. omega. cm.
The film forming operation was performed using the film forming apparatus of fig. 2. FIG. 2 is a schematic view of a film forming apparatus. In fig. 2, 1 denotes a raw material container. And 2 is a substrate heater. And 3, a film forming chamber (decomposition reactor). And 4, a substrate. And 6 is a spray head. And 8 is a vaporizer. Gas (e.g. He, Ar, N) for pressure feeding of 9 as raw material2And the like. The raw material is pressure-fed from the raw material container 1to the vaporizer 8).
The film forming operation was performed using the apparatus of fig. 2. The purified product (bis (N, N' -diisopropylbutylamidine) cobalt) was charged into the raw material container 1. Using N2The gas is used as the raw material
The film formed as described above is excellent in-plane uniformity. The films were investigated using XPS. The amount of C in the film is 3 at% or less. The amount of O in the film is 1 at% or less. The N content in the film is 0.4 at% or less. The specific resistance of the film was 19. mu. omega. cm.
[ example 2]
[ bis (N, N' -diisopropyl-2-methylpropionamidine) cobalt ]
The reaction is carried out under an inert gas atmosphere. 0.21mol of N, N' -diisopropylcarbodiimide was slowly added dropwise to 300ml of a pentane solution containing 0.21mol of lithium isopropyl. Thereafter, stirring was performed at room temperature for 4 hours. The reaction mixture was slowly added dropwise to 0.1mol of cobalt chloride (CoCl)2) Suspended in 200ml of tetrahydrofuran. Thereafter, stirring was carried out for 24 hours. After the solvent was distilled off, 500ml of n-hexane was added. Insoluble matter was filtered. After the solvent was distilled off, the mixture was distilled under reduced pressure (0.1 torr). Bis (N, N' -diisopropyl-2-methylpropionamidine) cobalt was obtained in a yield of 70%.
The obtained 300g of cobalt bis (N, N' -diisopropyl-2-methylpropionamidine) was purified by distillation under reduced pressure. The volatilized cobalt bis (N, N' -diisopropyl-2-methylpropionamidine) was liquefied during passage through an air-cooled tube and captured in a container. In this case, the air-cooled tube was left to cool at room temperature without being particularly cooled or heated. The recovery rate was 95%.
The purified product (bis (N, N' -diisopropyl-2-methylpropionamidine) cobalt) was crystallized by cooling. The crystallized cobalt bis (N, N' -diisopropyl-2-methylpropionamidine) was slowly warmed. Melting at 11-12 deg.C. The cobalt bis (N, N' -diisopropyl-2-methylpropionamidine) was liquid (at 25 ℃ and 1 atm). In the vacuum distillation using an oil rotary vacuum pump, the boiling point was 110 ℃.
The refined product has high purity. The analytical values (in wt. ppm) based on the metal impurity analysis (ICP-MS) are as follows. Na < 0.1, Mg < 0.1, Fe < 0.4, Zn < 0.3, Ti < 0.1, Cu < 0.1, Cd < 0.1, Mn < 0.1, Ni < 1.1, Pb < 0.1
The film forming operation was performed in the same manner as in example 1 using the film forming apparatus shown in fig. 1. The purified product (bis (N, N' -diisopropyl-2-methylpropionamidine) cobalt) was charged into the raw material container 1. The raw material container 1 was heated to 90 ℃ by a heater attached to the raw material container 1. Nitrogen gas (carrier gas) was supplied at a rate of 20 ml/min to carry out bubbling. Thereby, the cobalt bis (N, N' -diisopropyl-2-methylpropionamidine) is introduced into the
The film formed as described above is excellent in-plane uniformity. The films were investigated using XPS. The amount of C in the film is 4 at% or less. The amount of O in the film is 1 at% or less. The N content in the film is 0.4 at% or less. The specific resistance of the film was 20. mu. omega. cm.
If the cobalt bis (N, N '-diisopropyl-2-methylpropionamidine) of example 2 and the cobalt bis (N, N' -diisopropyl-butylamidine) of the example 1 are compared, the following is made. The boiling point of the compound of example 2 (110 ℃/in the reduced pressure distillation by oil rotary vacuum pump) was higher than that of the compound of example 1 (102 ℃/in the reduced pressure distillation by oil rotary vacuum pump). The vapor pressure of the compound of example 2 is lower than that of the compound of said example 1at the same temperature. This means that the compound of example 1 is preferred in film formation. The yield (70%) of the compound of example 2 was lower than the yield (89%) of the compound of example 1. The reagent "lithium isopropyl" used for synthesizing the compound of example 2 is expensive. Thus, the compound of example 1 is inexpensive. The compound of example 1 is also preferable from the viewpoint of cost.
[ example 3]
[ bis (N, N' -diisopropylbutylamidine) iron ]
The reaction is carried out under an inert gas atmosphere. 0.22mol of N, N' -diisopropylcarbodiimide was slowly added dropwise to 210ml of a diethyl ether solution containing 0.21mol of N-propyllithium. Thereafter, stirring was performed at room temperature for 4 hours. The reaction mixture was slowly added dropwise to 0.1mol of ferric chloride (FeCl)2) Suspended in 80ml of tetrahydrofuran. Thereafter, stirring was carried out for 24 hours. After the solvent was distilled off, 400ml of n-hexane was added. Insoluble matter was filtered. After the solvent was distilled off, the mixture was distilled under reduced pressure (0.1 torr). Bis (N, N' -diisopropylbutanamidine) iron was obtained in 91% yield.
The obtained 300g of iron bis (N, N' -diisopropylbutanamidine) was purified by distillation under reduced pressure. The vaporized iron bis (N, N' -diisopropylbutylamidine) vapor was liquefied during passage through an air-cooled tube and captured in a container. In this case, the air-cooled tube was left to cool at room temperature without being particularly cooled or heated. The recovery rate was 97%.
The purified product (iron bis (N, N' -diisopropylbutylamidine)) was crystallized by cooling. The crystallized iron bis (N, N' -diisopropylbutanamidine) was slowly warmed. Melting at 12 deg.C. The iron bis (N, N' -diisopropylbutanamidine) is liquid (at 25 ℃ and 1 atm). In the vacuum distillation using an oil rotary vacuum pump, the boiling point was 99 ℃.
The refined product has high purity. The analytical values (in wt. ppm) based on the metal impurity analysis (ICP-MS) are as follows. Na < 0.1, Mg < 0.1, Zn < 0.3, Ti < 0.1, Cu < 0.1, Co < 0.4, Cd < 0.1, Mn < 0.1, Ni < 1.1, Pb < 0.1
The film forming operation was performed using the apparatus of fig. 1. The purified product (iron bis (N, N' -diisopropylbutylamidine)) was charged into the raw material container 1. The raw material container 1 was heated to 90 ℃ by a heater attached to the raw material container 1. Nitrogen gas (carrier gas) was supplied at a rate of 20 ml/min to carry out bubbling. Thereby, the iron bis (N, N' -diisopropylbutamidine) is introduced into the
The film formed as described above is excellent in-plane uniformity. The films were investigated using XPS. The amount of C in the film is 2 at% or less. The amount of O in the film is 1 at% or less. The N content in the film is 0.4 at% or less.
The film forming operation was performed using the apparatus of fig. 1. The purified product (iron bis (N, N' -diisopropylbutylamidine)) was charged into the raw material container 1. The raw material container 1 was heated to 90 ℃ by a heater attached to the raw material container 1. Nitrogen gas (carrier gas) was supplied at a rate of 20 ml/min to carry out bubbling. Thereby, the iron bis (N, N' -diisopropylbutanamidine) was introduced into the
The film formed as described above was uniformly applied to the inner walls of the pores (aperture diameter of the opening portion 50nm, depth 1 μm). The step coverage is excellent. The films were investigated using XPS. The amount of C in the film is 2 at% or less. The amount of O in the film is 1 at% or less. The N content in the film is 0.2 at% or less.
The film forming operation was performed using the film forming apparatus of fig. 2. The refined product (bis (N, N' -diisopropylbutamidine) iron)Is charged into the raw material container 1. Using N2The gas is used as the raw material
The film formed as described above is excellent in-plane uniformity. The films were investigated using XPS. The amount of C in the film is 4 at% or less. The amount of O in the film is 1 at% or less. The N content in the film is 0.3 at% or less.
Reference example 1 (Japanese Kokai publication 2006-511716(WO2004/046417A1)) ]
Japanese patent publication No. 2006-511716 discloses compounds represented by the following formula.
Wherein R is1、R2、R3、R4、R5、R6Is hydrogen, alkyl, aryl, alkenyl, alkynyl, trialkylsilyl or fluoroalkyl or other non-metallic atom or group. M is a metal element selected from the group consisting of Co, Fe, Ni, Mn, Ru, Zn, Ti, V, Cr, Eu, Mg, and Ca.
The following compounds are listed as specific examples in Japanese patent application laid-open No. 2006-511716(WO2004/046417A 1).
Bis (N, N' -diisopropylacetamidinato) cobalt ([ Co (iPr-AMD)))2]): in the above formula, M ═ Co, R1＝R4＝CH3，R2＝R3＝R5＝R6i-Pr: solid (melting point 72 ℃ C.). Sublimating at 40 deg.C (50 mTorr).
Bis (N, N' -di-tert-butylacetamidinate) cobalt ([ Co (iBu-AMD)2]): in the above formula, M ═ Co, R1＝R4＝CH3，R2＝R3＝R5＝R6i-Bu: solid (melting point 90 ℃ C.). Sublimating at 45 deg.C (50 mTorr).
Bis (N, N' -di-sec-butylacetamidinate) cobalt ([ Co (sec-Bu-AMD)2]): in the above formula, M ═ Co, R1＝R4＝CH3，R2＝R3＝R5＝R6sec-Bu: the boiling point was 55 deg.C (60 mTorr). Note that, in japanese unexamined patent publication No. 2006-511716, it is not explicitly described whether the compound is a liquid or a solid. Namely, the following are described in Japanese patent laid-open No. 2006-511716: the reaction mixture was stirred overnight, followed by removal of volatiles at room temperature and in vacuo. The solid was dissolved in dry hexane, filtered, and hexane was removed from the filtrate in vacuo at room temperature, resulting in a crude yield of 82% of cobalt bis (N, N' -di-tert-butylacetamidinate). This liquid was purified by distillation (at 60mTorr, 55 ℃). ". However, hexane insolubles (here, lithium chloride) were removed from the reaction mixture by filtration, after which hexane was concentrated off. This material was crude. It is not a pure product. Even if the target substance is a solid, the target substance sufficiently has a characteristic of a liquid at that time (i.e., an impurity state (form of a mixture)). Without purification, it is impossible to determine whether the target product is a liquid or a solid. The vapor pressure of this compound was lower than that of the compound (bis (N-t-butyl-N' -ethyl-propionamidine) cobalt) of reference example 2 (Japanese unexamined patent publication No. 2011-63848) at the same temperature. At the same reduced pressure, the boiling point of cobalt bis (N, N '-di-sec-butylacetamidinate) was 15 ℃ higher than that of cobalt bis (N-tert-butyl-N' -ethyl-propionamidine).
The separation of cobalt bis (N, N' -di-sec-butylacetamidinate) is not possible in the prior art. The isolation could not be performed. Sec-butyl has an asymmetric carbon. There are S and R entities. As shown below, the compound exists in seven isomers. Crystallization hardly occurs in the case of a mixture of seven isomers.
S: s configuration
R: r configuration
Bis (N, N' -di-tert-butylacetamidinate) iron ([ Fe (tBu-AMD)2]): in the above formula, M ═ Fe, R1＝R4＝CH3，R2＝R3＝R5＝R6i-Bu: solid (melting point 107 ℃ C.). Sublimating at 55 deg.C (60 mTorr).
Bis (N, N' -diisopropylacetamidinato) iron ([ Fe (iPr-AMD)2]2): solid (melting point 110 ℃ C.). Sublimating at 70 deg.C (50 mTorr).
(N, N' -diisopropylacetamidinato) copper dimer ([ Cu (iPr-AMD)]2): and (3) a solid. Sublimating at 70 deg.C (50 mTorr).
Lanthanum tris (N, N' -diisopropylacetamidinate) ([ La (iPr-AMD)3]): and (3) a solid. Sublimating at 80 deg.C (40 mTorr).
Lanthanum tris (N, N' -diisopropyl-2-tert-butylacetamidinate) ([ La (iPr-iBuAMD)3]): solid (melting point 140 ℃ C.). Sublimating at 120 deg.C (50 mTorr).
Bis (N, N' -diisopropylacetamidinato) nickel ([ Ni (iPr-AMD)2]): solid (melting point 55 ℃ C.). Sublimating at 35 deg.C (70 mTorr).
Manganese bis (N, N' -diisopropylacetamidinate) ([ Mn (iPr-AMD)2]2): and (3) a solid. Sublimating at 65 deg.C (50 mTorr).
Manganese bis (N, N' -di-tert-butylacetamidinate) ([ Mn (iBu-AMD)2]): solid (melting point 100 ℃ C.). Sublimating at 55 deg.C (60 mTorr).
Tris (N, N' -diisopropylacetamidinato) titanium ([ Ti (iPr-AMD)3]): and (3) a solid. Sublimating at 70 deg.C (50 mTorr).
Vanadium tris (N, N' -diisopropylacetamidinate) ([ V (iPr-AMD)3]): and (3) a solid. Sublimating at 70 deg.C (45 mTorr).
(N, N' -diisopropylacetamidinato) silver ([ Ag (iPr-AMD) ] x (1: 1 mixture of x ═ 2 and x ═ 3) a solid (melting point 95 ℃) which sublimes at 80 ℃ (40 mTorr).
Magnesium bis (N, N' -di-tert-butylacetamidinate) ([ Mg (iBu-AMD)2])：
Lithium N, N' -di-sec-butylacetamidinate:
n, N' -Di-sec-butylacetamidinicopper (I) dimer ([ Cu (sec-Bu-AMD)]2): solid (melting point 77 ℃ C.). Sublimating at 55 deg.C (50 mTorr).
Tris (N, N' -di-tert-butylacetamidinate) bismuth dimer ([ Bi (iBu-AMD)3]2): solid (melting point 95 ℃ C.). Sublimating at 70 deg.C (80 mTorr).
Strontium bis (N, N' -di-tert-butylacetamidinate) ([ St (iBu-AMD)2]n): and (3) a solid. Sublimating at 130 deg.C (90 mTorr).
Tris (N, N' -diisopropylacetamidinato) ruthenium ([ Ru (iPr-AMD)3])：
Reference example 2 (Japanese patent laid-open publication 2011-
Japanese patent application laid-open publication No. 2011-63848 discloses the following compounds.
Bis (N-tert-butyl-N' -ethyl-propionamidine) cobalt (II) (Co (tBu-Et-Et-AMD)2)：
The compound was liquid (25 ℃ (1 atm)).
However, the compound represented by the above formula is a mixture of isomers (see below). At present, separation (isolation) and purification cannot be carried out. Even if only one isomer can be isolated, the cobalt amidine complex undergoes ligand exchange. Thus, the original mixture is returned. The mixture is such that the molar melting point is lowered and appears to be liquid.
This compound is liquid but has high viscosity. Therefore, it is difficult to perform the film forming operation by the method described in the above embodiment.
The vapor pressure of the compound of example 1 (bis (N, N '-diisopropylbutylamidine) cobalt) was 0.53Torr (100 ℃ C.), whereas the vapor pressure of bis (N-tert-butyl-N' -ethyl-propionamidine) cobalt was 0.31Torr (100 ℃ C.). I.e. the vapour pressure of the compound is low. This is a major disadvantage in film formation.
Reference example 1 (Japanese patent application laid-open No. 2006-511716) is described below.
"comparative example 2. example 18 (the compound in this example is bis (N, N' -diisopropylacetamidinato) cobalt) was repeated using only the cobalt precursor and no hydrogen. No thin film was observed to be deposited on the substrate surface. "
When bis (N-t-butyl-N' -ethyl-propionamidine) cobalt is used, metallic cobalt is hardly deposited when hydrogen alone is used, as in the case of comparative example 2 of Japanese patent application laid-open No. 2006-511716. However, when hydrogen and ammonia are used in combination, metallic cobalt accumulates. In the case of ammonia alone, cobalt nitride is mixed. When bis (N, N' -diisopropylbutylamidine) cobalt is used, highly pure metal cobalt is deposited due to the combination of hydrogen and ammonia. Even when only ammonia is used, metallic cobalt having high purity is deposited. This means that when bis (N-tert-butyl-N' -ethyl-propionamidine) cobalt is used, the degree of freedom of the film formation operation is small. That is, bis (N, N' -diisopropylbutylamidine) cobalt is preferably used.
Bis (N, N' -di-tert-butyl-acetamidinato) nickel (II) (Ni (tBu-AMD)2): solid (melting point 87 ℃ C.).
[ reference example 3(WO2013/051670A1) ]
WO2013/051670a1 discloses compounds represented by the following formula.
Bis (N, N' -diisopropylpropionamidine) cobalt (Co [ i-C)3H7NC(C2H5)N-i-C3H7]2): in the above formula, M ═ Co, R1＝R4＝C2H5，R2＝R3＝R5＝R6i-Pr: solid (melting point 38 ℃ C.).
Reference example 4 (Japanese patent laid-open publication No. 2016-172894)
Japanese laid-open patent publication 2016-172894 discloses a compound represented by the following formula.
[R1-N-C(R2)＝N-R3]2Fe
[[R1-N-C(R2)＝N-R3]2Fe]2
(R2Is an alkyl group having 2 to 6 carbon atoms, R1、R3Is an alkyl
(N, N' -diisopropylpropionamidine) iron (Fe [ iso-C)3H7NC(C2H5)N-iso-C3H7]2): solid (melting point about 33 ℃ C.)
Comparative example 1
The film forming operation was performed using the apparatus of fig. 1. The compound of reference example 2 (Co (tBu-Et-Et-AMD)2) Is charged into the raw material container 1. The raw material container 1 was heated to 90 ℃ by a heater attached to the raw material container 1. Nitrogen gas (carrier gas) was supplied at a rate of 20 ml/min to carry out bubbling. Thus, the Co (tBu-Et-Et-AMD) was added for 5 seconds2Is introduced into the
The specific resistance of the film at the flat portion formed as described above was 60 μ Ω cm.
Comparative example 2
The compound of reference example 1 ([ Co (sec-Bu-AMD) was used2]) And was performed based on the comparative example 1.
The specific resistance of the film at the flat portion thus formed was 75 μ Ω cm.
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