JP4247823B2 - High purity Al film forming material manufacturing method, high purity Al film forming material manufacturing apparatus, high purity Al film forming material, and Al film - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention provides a method and apparatus for producing a high-purity Al-based film forming material, a high-purity Al-based film forming material obtained using these methods and apparatuses, and further using this high-purity Al-based film forming material. The high-purity Al-based film formed in this way.
[0002]
[Problems to be solved by the invention]
Since trialkylamine alane [H ₃ Al: L _k ] (L is alkylamine) decomposes at a low temperature of 100 to 200 ° C. in the gas phase, it can be used for chemical vapor deposition (CVD). An aluminum film can be obtained. That is, since it decomposes at a low temperature, it is suitable for producing a vapor phase of an aluminum-based film with little carbon contamination.
[0003]
By the way, it has been found that problems still remain in Al-based films prepared using the above trialkylamine allane, such as III-V group compound semiconductors (AlGaN).
[0004]
That is, it can be seen that O (oxygen) causes the performance degradation in the compound semiconductors as described above, and the trialkylamine alane, which is a raw material constituting AlGaN, also has the least amount of oxygen (O). It has been requested to do.
[0005]
Therefore, the problem to be solved by the present invention is H ₃ Al: L _{k with} a small amount of oxygen (O), wherein k is 1 or 2, and L is an organic amine. An Al compound represented by the formula:
[0006]
[Means for Solving the Problems]
Formula H ₃ Al: in _{L k} [Formula, k is 1 or 2, L is an organic amine. Basically, there is no constituent element O in the Al compound represented by Therefore, when an Al-based film is prepared by decomposing the general formula H ₃ Al: L _k , O based on H ₃ Al: L _k should not be present in the film.
However, although it is a very small amount, it is a fact that O is present in the Al-based film.
Therefore, it is presumed that this O is either that O has been introduced due to the working environment during the film forming operation or that oxygen is contained in the raw material (H ₃ Al: L _k ). It came to.
[0007]
Therefore, first, a film forming work environment was carefully prepared. However, even in this way, O was observed in the Al-based film.
Therefore, the remaining cause has to be considered that oxygen is contained in the raw material (H ₃ Al: L _k ).
[0008]
And while examining the manufacturing process of H ₃ Al: L _k in detail, H ₃ Al: L _k is MAlH ₄ (M is an alkali metal such as Li), for example, LiAlH ₄ and L (organic amine) However, since this synthesis reaction vessel is made of glass, it has another hermeticity, and because of this, although there is little oxygen in the air, I came to think that it might be confused.
[0009]
Therefore, instead of the glass device H ₃ Al with a metal device: processing of producing a L _k, which is led to obtain than expected results. That is, when the amount of O in an Al-based film obtained by decomposing H ₃ Al: L _k obtained by reacting LiAlH ₄ with L using a metal device was examined, a conventional glass device Compared to the amount of O in the Al-based film obtained by decomposing H ₃ Al: L _k obtained by reacting LiAlH ₄ with L using LiO, the amount of O was one or more orders of magnitude less. . That is, the amount of dissolved oxygen in H ₃ Al: L _k was extremely small and highly pure.
[0010]
The present invention has been achieved based on the above findings.
That is, the problem is the general formula H ₃ Al: in _{L k} [Formula, k is 1 or 2, L is an organic amine. A production apparatus for producing an Al compound represented by the general formula H ₃ Al: L _k by reacting a raw material of the Al compound represented by
The production apparatus comprises a reaction device in a synthesis reaction step and a distillation device in a distillation step after the synthesis reaction step,
The apparatus for producing a high-purity Al-based film forming material, characterized in that the portion in contact with the Al compound represented by the general formula H ₃ Al: L _k in the reaction apparatus and / or distillation apparatus is made of metal. Solved by.
[0011]
Moreover, the general formula H ₃ Al: in _{L k} [Formula, k is 1 or 2, L is an organic amine. A production apparatus for producing an Al compound represented by the general formula H ₃ Al: L _k by reacting a raw material of the Al compound represented by
The production apparatus comprises a reaction device in a synthesis reaction step, a solid material removal device in a solid material removal step after the synthesis reaction step, and a distillation device in a distillation step after the synthesis reaction step,
A high-purity Al-based film characterized in that a portion in contact with the Al compound represented by the general formula H ₃ Al: L _k in the reaction apparatus, solid substance removal apparatus, and / or distillation apparatus is made of metal. Solved by the forming material manufacturing equipment.
[0012]
In particular, this is solved by a high purity Al-based film forming material manufacturing apparatus characterized in that a metal packing is provided at a joint portion between the apparatuses in the above apparatus.
[0013]
Moreover, the general formula H ₃ Al: in _{L k} [Formula, k is 1 or 2, L is an organic amine. A production method of producing an Al compound represented by the general formula H ₃ Al: L _k by reacting a raw material of the Al compound represented by
This is solved by a method for producing a high-purity Al-based film forming material, characterized in that the contact portion of the general formula H ₃ Al: L _k is performed using an apparatus made of a metal.
For example, the reaction apparatus in the synthesis reaction step of the Al compound of the general formula H ₃ Al: _Lk , the apparatus in the solid removal process after the synthesis reaction process, or the apparatus in the distillation process after the synthesis reaction process is made of metal. Become. Furthermore, metal packing is used for the joint portion of these devices.
[0014]
And when the above technologies were adopted, H ₃ Al: L _k having a much lower oxygen content was obtained than when manufactured using a glass device. In other words, such H ₃ Al: L is the Al-based film prepared by using the _k serves as O amount is extremely small, and the resulting like compound semiconductor Group III-V systems, high-performance It was a thing.
[0015]
In the present invention, the general formula H ₃ Al: L _k [wherein k is 1 or 2 and L is an organic amine. It is preferable that L (organic amine) and the solvent used in the synthesis of the Al compound represented by the above formula are those subjected to dehydration and deoxygenation treatment.
[0016]
Moreover, the general formula H ₃ Al: _H 3 in the process of manufacturing the Al compound represented by _{L k} Al: _{L k} synthetic steps, the general formula H ₃ Al to the reactor of the synthesis reaction step: represented by _{L k} an exhaust step of the vacuum MAlH 4 which is a raw material of Al compound _(M is an alkali metal such Li) and MAlH ₄ supplying step of supplying an inert atmosphere, the inside of the reaction system of the synthesis reaction step that synthesis reaction step A solvent supplying step for supplying a solvent into the reaction device of L, and L for supplying an L (organic amine) that is a raw material of the Al compound represented by the general formula H ₃ Al: L _k into the reaction device in the synthesis reaction step It is preferable to have a supply process. The order of these steps is not particularly limited.
[0017]
In the present invention, the organic amine (L) is not particularly limited, but is preferably a trialkylamine, a saturated cyclic amine, or an unsaturated cyclic amine, particularly trimethylamine, dimethylethylamine, N-methylpyrrolidine, or Most preferred is N-methyl-3-pyrroline.
[0018]
The present invention also relates to a high-purity Al film forming material produced by the above-described method for producing a high-purity Al film forming material. In particular, the present invention relates to a high-purity Al-based film forming material that is used in a CVD method (chemical vapor deposition method) and is manufactured by the above-described method for manufacturing a high-purity Al-based film forming material. Or it is used for ALE method (atomic layer growth method), Comprising: It is related with the high purity Al type film forming material manufactured by the manufacturing method of the said high purity Al type film forming material.
[0019]
The present invention also relates to an Al-based film characterized in that the high-purity Al-based film forming material is decomposed and an Al-based film is provided on a substrate.
[0020]
DETAILED DESCRIPTION OF THE INVENTION
The apparatus for producing a high-purity Al-based film forming material according to the present invention reacts with MAlH ₄ (M is an alkali metal such as Li) and L (organic amine) to produce a general formula H ₃ Al: L _k [in the general formula , K is 1 or 2, and L is an organic amine. The production apparatus comprises a reaction apparatus in a synthesis reaction step and a distillation apparatus in a distillation step after the synthesis reaction step, and the reaction apparatus or The portion of the distillation apparatus that comes into contact with the Al compound represented by the general formula H ₃ Al: L _k is made of metal. In the reaction, a solid material may be formed, which may need to be removed. In such a case, a solid removal step is required after the synthesis reaction step. The solid matter removing device necessary for this solid matter removal is also made of metal. In general formula H 3 _Al: parts Al compound represented by L _k is in contact, i.e. not the inner surface side only, it is of course entirely may be made of metal. Actually, not only the inner surface side but also the members constituting the apparatus are made of metal. However, even if the portion where the Al compound represented by the general formula H ₃ Al: L _k does not contact, for example, the attached portion is made of a material other than metal, it does not hinder the features of the present invention. Absent. Furthermore, the packing provided in the joint part between apparatuses is a metal packing.
[0021]
The method for producing a high-purity Al-based film forming material according to the present invention comprises reacting MAlH ₄ (M is an alkali metal such as Li) and L (organic amine) to form a general formula H ₃ Al: L _k [in the general formula , K is 1 or 2, and L is an organic amine. Wherein the contact portion of the general formula H ₃ Al: L _k is made of a metal. For example, the reaction apparatus in the synthesis reaction step of the Al compound of the general formula H ₃ Al: _Lk , the apparatus in the solid removal process after the synthesis reaction process, or the apparatus in the distillation process after the synthesis reaction process is made of metal. Become. In particular, all the devices are made of metal. It should be noted that even if the portion where the Al compound represented by the general formula H ₃ Al: L _k does not come into contact, for example, an additional portion is made of a material other than metal, it does not hinder the features of the present invention. Absent. Furthermore, metal packing is used for the joint portion of these devices. Then, the general formula H ₃ Al: _H 3 in the process of manufacturing the Al compound represented by _{L k} Al: _{L k} synthetic steps, the general formula H ₃ Al to the reactor of the synthesis reaction step: represented by _{L k} an exhaust step of the vacuum MAlH 4 which is a raw material of Al compound _(M is an alkali metal such Li) and MAlH ₄ supplying step of supplying an inert atmosphere, the inside of the reaction system of the synthesis reaction step that synthesis reaction step A solvent supplying step for supplying a solvent into the reaction device of L, and L for supplying an L (organic amine) that is a raw material of the Al compound represented by the general formula H ₃ Al: L _k into the reaction device in the synthesis reaction step And have a supply process.
[0022]
In the present invention, the general formula H ₃ Al: L _k [wherein k is 1 or 2 and L is an organic amine. The L and the solvent used in the synthesis of the Al compound represented by the above are dehydrated and deoxygenated.
[0023]
In the present invention, the organic amine (L) is not particularly limited, but is a trialkylamine, a saturated cyclic amine, or an unsaturated cyclic amine. In particular, trimethylamine, dimethylethylamine, N-methylpyrrolidine, or N-methyl-3-pyrroline.
[0024]
The high-purity Al-based film forming material according to the present invention is manufactured by the above-described method for manufacturing a high-purity Al-based film forming material. In particular, it is used in a CVD method (chemical vapor deposition method) and is manufactured by the above-described method for manufacturing a high-purity Al-based film forming material. Further, it is used in the ALE method (atomic layer growth method) and is manufactured by the above-described method for manufacturing a high-purity Al-based film forming material.
[0025]
An Al-based film according to the present invention is an Al-based film provided on a substrate by decomposing the high-purity Al-based film forming material.
[0026]
This will be described in more detail below.
FIG. 1 is a schematic view of an apparatus for producing a high purity Al-based film forming material according to the present invention.
This manufacturing apparatus is roughly divided into general formulas H ₃ Al: L _k [k is 1 or 2. L is an organic amine. The reaction apparatus 1 in which the synthesis reaction of the Al compound is performed, the filtration apparatus 2 in which solids are removed after the synthesis reaction process, and the solvent concentration / distillation apparatus (purification apparatus) 3 in which distillation is performed after the filtration process are performed. In addition, 4 is an initial distillation waste pipe, 5 is a container for storage and transportation (main distillation collection container) filled with distilled and purified H ₃ Al: L _k , 6 is a connection to a vacuum pump, and 7 is a stop. It is a valve.
[0027]
Basically, the reaction apparatus 1, the filtration apparatus 2, the solvent concentration / distillation apparatus (purification apparatus) 3, and the storage / transport container (main distillation collection container) 5 are all made of metal such as stainless steel. Has been. Although not shown, a connecting portion between the reaction device 1 and the filtering device 2, a connecting portion between the filtering device 2 and the solvent concentration / distillation device (purification device) 3, and a solvent concentration / distillation device (purification). A copper packing is provided at a connecting portion between the (device) 3 and the container (main distillation collecting container) 5.
[0028]
That is, in the process from H ₃ Al: L _k synthesized in the synthesis reaction step from the reactor 1 to the container 5, a manufacturing apparatus in which all the portions in contact with H ₃ Al: L _k are made of metal was used. This is a major feature.
[0029]
Then, _H 3 Al with the device: in detail describing a method for producing a _{L k.}
[Production of N-methylpyrrolidine alane]
First, a commercially available lithium aluminum hydride (LiAlH ₄ ) was placed in the reactor (reaction vessel) 1 under an argon atmosphere. Then, the lid of the reaction vessel 1 was closed, and the inside of the reaction vessel 1 was evacuated to a vacuum with a vacuum pump.
Thereafter, dehydrated and deoxygenated toluene (solvent) was injected into the reaction vessel 1 with the valve open (the outside air was shut off at the time of injection). Next, the dehydrated and deoxygenated N-methylpyrrolidine was also injected into the reaction vessel 1 with the valve open (the outside air was shut off at the time of injection).
And it stirred for 1 day or more and made it react.
[0030]
Then, the solid substance was removed from the produced reaction product with the filtration apparatus 2.
Next, the solid substance removed from the filtration device 2 was concentrated and distilled with a solvent concentration / distillation device (purification device) 3 to obtain the target product (N-methylpyrrolidine alane).
[0031]
The above production was attempted several times. The yield at that time was 50 to 75%.
Then, an Al film was formed by the CVD method using N-methylpyrrolidine alane obtained as described above.
On the other hand, for comparison, N-methylpyrrolidine alane was obtained by a conventional method using a glass manufacturing apparatus as a reaction apparatus, a filtration apparatus, and a distillation apparatus, and an Al film was formed by CVD using this N-methylpyrrolidine alane. A film was formed.
[0032]
Then, after examining the number of O in these films, (number of oxygen atoms in the Al-based film obtained by the present invention) / (number of oxygen atoms in the Al-based film obtained by the conventional synthesis method) < 0.1.
That is, according to the present invention, a high-purity Al-based film forming material capable of forming a film with little oxygen mixing was obtained.
[0033]
[Production of trimethylamine alane]
The production of N-methylpyrrolidine alane was carried out in the same manner using trimethylamine instead of N-methylpyrrolidine.
Then, an Al film was formed by the CVD method using the trimethylamine allane obtained as described above.
On the other hand, for comparison, trimethylamine alane was obtained by a conventional method using a glass manufacturing apparatus as a reaction apparatus, a filtration apparatus, and a distillation apparatus, and an Al film was formed by CVD using this trimethylamine allan.
Then, after examining the number of O in these films, (number of oxygen atoms in the Al-based film obtained by the present invention) / (number of oxygen atoms in the Al-based film obtained by the conventional synthesis method) < 0.1.
That is, according to the present invention, a high-purity Al-based film forming material capable of forming a film with little oxygen mixing was obtained.
[0034]
[Production of dimethylethylamine alane]
In the production of N-methylpyrrolidine alane, dimethylethylamine was used instead of N-methylpyrrolidine.
And Al film | membrane was formed into a film by CVD method using the dimethylethylamine alane obtained as mentioned above.
On the other hand, for comparison, dimethylethylamine allan was obtained by a conventional method using a glass manufacturing apparatus as a reaction apparatus, a filtration apparatus, and a distillation apparatus, and an Al film was formed by CVD using this dimethylethylamine allane.
Then, after examining the number of O in these films, (number of oxygen atoms in the Al-based film obtained by the present invention) / (number of oxygen atoms in the Al-based film obtained by the conventional synthesis method) < 0.1.
That is, according to the present invention, a high-purity Al-based film forming material capable of forming a film with little oxygen mixing was obtained.
[0035]
[Production of N-methyl-3-pyrroline alane]
The production of N-methylpyrrolidine alane was carried out in the same manner using N-methyl-3-pyrroline instead of N-methylpyrrolidine.
Then, an Al film was formed by a CVD method using N-methyl-3-pyrrolinealane obtained as described above.
On the other hand, for comparison, N-methyl-3-pyrroline alane was obtained by a conventional method using a glass manufacturing apparatus as a reaction apparatus, a filtration apparatus, and a distillation apparatus, and this N-methyl-3-pyrroline alane was used. An Al film was formed by a CVD method.
Then, after examining the number of O in these films, (number of oxygen atoms in the Al-based film obtained by the present invention) / (number of oxygen atoms in the Al-based film obtained by the conventional synthesis method) < 0.1.
That is, according to the present invention, a high-purity Al-based film forming material capable of forming a film with little oxygen mixing was obtained.
[0036]
In the above, the example using toluene as the solvent has been described. However, any substance such as toluene, heptane and the like which are inert to the organic metal can be used.
[0037]
【The invention's effect】
It is possible to form an Al-based film with high purity, particularly low oxygen. And a high performance semiconductor element etc. are obtained.
[Brief description of the drawings]
FIG. 1 is a schematic diagram of a manufacturing apparatus according to the present invention.
DESCRIPTION OF SYMBOLS 1 Reaction apparatus 2 Filtration apparatus 3 Solvent concentration / distillation container 4 First distillate pipe 5 Main distillate collection container

Claims (15)

Formula H ₃ Al: in _{L k} [Formula, k is 1 or 2, L is an organic amine. A production method of producing an Al compound represented by the general formula H ₃ Al: L _k by reacting a raw material of an Al compound represented by
A method for producing a high-purity Al-based film forming material, which is performed using an apparatus in which the portion of the general formula H ₃ Al: _Lk that contacts is made of metal. Formula H 3 _Al: process for producing a high-purity Al-based film-forming material of claim 1, the reaction apparatus is characterized in that it consists of any metallic in the synthesis reaction step Al compound of L _k. Formula H 3 _Al: process for producing a high-purity Al-based film-forming material according to claim 1, L _k apparatus in solids removal step after the synthesis reaction step of Al compound of is characterized in that it consists of any metallic. Formula H 3 _Al: process for producing a high-purity Al-based film-forming material according to claim 1, apparatus in the distillation step after the synthesis reaction step of Al compound of L _k is equal to or consisting of those of the metal. The method for producing a high-purity Al-based film forming material according to any one of claims 1 to 4, wherein a metal packing is used for a joint portion between the apparatuses. Formula H ₃ Al: in _{L k} [Formula, k is 1 or 2, L is an organic amine. The method for producing a high-purity Al-based film forming material according to any one of claims 1 to 5, wherein L used in the synthesis of the Al compound represented by formula (1) is dehydrated and deoxygenated. . Formula H ₃ Al: in _{L k} [Formula, k is 1 or 2, L is an organic amine. The method for producing a high-purity Al-based film forming material according to any one of claims 1 to 5, wherein the solvent used in the synthesis of the Al compound represented by formula (1) is one that has been dehydrated and deoxygenated. . Formula H ₃ Al: in _{L k} [Formula, k is 1 or 2, L is an organic amine. A production method of producing an Al compound represented by the general formula H ₃ Al: L _k by reacting a raw material of an Al compound represented by
Synthesis the general formula H ₃ into the reactor of Step Al: MAlH ₄ (M is an alkali metal) and MAlH ₄ supplying step of supplying an inert atmosphere which is a raw material of Al compound represented by _{L k,}
An exhaust process for evacuating the reactor,
A solvent supply step of supplying a solvent into the reaction apparatus;
An L supply step for supplying L (organic amine) which is a raw material of the Al compound represented by the general formula H ₃ Al: L _k into the reactor. A method for producing any high-purity Al-based film forming material. Formula H ₃ Al: in _{L k} [Formula, k is 1 or 2, L is an organic amine. A production apparatus for producing an Al compound represented by the general formula H ₃ Al: L _k by reacting a raw material of an Al compound represented by
The production apparatus comprises a reaction device in a synthesis reaction step and a distillation device in a distillation step after the synthesis reaction step,
The apparatus for producing a high-purity Al-based film forming material, characterized in that the portion in contact with the Al compound represented by the general formula H ₃ Al: L _k in the reaction apparatus and / or distillation apparatus is made of metal. . Formula H ₃ Al: in _{L k} [Formula, k is 1 or 2, L is an organic amine. A production apparatus for producing an Al compound represented by the general formula H ₃ Al: L _k by reacting a raw material of the Al compound represented by
The production apparatus comprises a reaction device in a synthesis reaction step, a solid material removal device in a solid material removal step after the synthesis reaction step, and a distillation device in a distillation step after the synthesis reaction step,
A high-purity Al-based film characterized in that a portion in contact with the Al compound represented by the general formula H ₃ Al: L _k in the reaction apparatus, solid substance removal apparatus, and / or distillation apparatus is made of metal. Manufacturing equipment for forming materials. 11. The apparatus for producing a high-purity Al-based film forming material according to claim 9 or 10, wherein a metal packing is provided at a joint portion between the apparatuses. A high-purity Al film forming material produced by the method for producing a high-purity Al film forming material according to claim 1. The high-purity Al-based film forming material according to claim 12, which is used in a CVD method. The high-purity Al-based film forming material according to claim 12, which is used in an ALE method. 15. An Al-based film, wherein the high-purity Al-based film forming material according to claim 12 is decomposed and an Al-based film is provided on a substrate.

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