JP5407290B2 - Filling container and method for vaporizing and supplying low melting point compound using the filling container - Google Patents

Description

  The present invention relates to a filling container suitable for vaporizing and supplying a low melting point compound and a method for vaporizing and supplying a low melting point compound using the filling container.

  Conventionally, as a method for vaporizing a low-melting compound and supplying it to a target device or the like, various studies have been made, focusing on, for example, a container filled before supplying a low-melting compound.

In particular, in recent years, it has been desired to stably supply a liquid semiconductor film forming material to a semiconductor device. As an example, a filling container for supplying a liquid CVD raw material filled with a solid filling has been proposed (see, for example, Patent Document 1). However, this method specializes in raw materials that are liquid at room temperature, does not mention compounds that are solid at room temperature that melts when heated, and does not mention any viscosity of the target liquid. It was difficult to say that it was a highly versatile filling container. In addition, the carrier gas bubbles that become larger due to channeling of carrier gas saturated with the raw material or droplets from the rupture at the liquid level may adhere to the inner wall of the container or the lead-out pipe, or in the case of a liquid raw material with high viscosity. However, there has been no specific suggestion of a solution to various problems such as the raw material being less likely to be saturated in the carrier gas and the supply amount of the raw material being likely to fluctuate. Therefore, it has been desired to propose a filling container suitable for vaporizing and supplying a semiconductor film forming material having a particularly high viscosity, which is a low melting point compound, that is, a compound that is melted and liquidized when vaporized and supplied.
Japanese Patent Laid-Open No. 2005-166771

  The problem of the present invention is that the raw material is effectively saturated in the carrier gas, and the carrier gas saturated with the raw material adheres to the inner wall of the container or the lead-out pipe by splashing due to channeling or rupture at the liquid level. An object of the present invention is to provide a filled container that can solve various problems and can be used for a low-melting compound having relatively high viscosity.

An object of the present invention, there is provided a filled container provided with a carrier gas inlet and outlet, seen containing a solid packing, and a low-melting compound, low-melting compound, the liquefied low-melting compounds in vaporizing and supplying This is solved by a filling container having a viscosity of 1 centipoise or higher and a liquid surface of the low melting point compound that is lower than the uppermost part of the filling when it becomes a liquid .

  The problem of the present invention is also solved by a vaporization supply method for a low-melting-point compound, characterized in that the low-melting-point compound is supplied using the filled container.

  According to the present invention, there is provided a filled container suitable for vaporizing and supplying a low-melting-point compound, which solves various problems such as adhering to the inner wall of the container and the lead-out pipe due to splashing due to channeling of carrier gas saturated with the raw material and bursting at the liquid level Can be provided.

  The low melting point compound used in the present invention is in a liquid state at 20 ° C. because the temperature at the time of vaporization and supply is 20 to 200 ° C., and therefore needs to be in a liquid state at that temperature. A compound or a compound having a melting point at any temperature in the range of 20 to 150 ° C. is preferably used.

  In particular, when the low-melting-point compound is a semiconductor film-forming material, a metal-containing compound, which is a semiconductor film-forming material that is generally considered to have a high viscosity, and further at least one β-diketonate when a liquid is vaporized and supplied. It is suitable for use as a metal complex as a ligand.

  Examples of the metal of the metal-containing compound include Ca, Sr, Ba, Al, Ga, In, Cu, Zn, Ru, Y, Ln (lanthanoid), Pb, Mg, Sn, Co, Hf, Zr, and Ni. The constituted metal complex is preferably used because it is a metal for forming a semiconductor film.

  As the β-diketonato of the metal complex having β-diketonato as a ligand, those having acetylacetonato as the main skeleton are preferably used, and the acetylacetonato is, for example, an alkyl group or a cycloalkyl group. Hydrocarbon groups such as aralkyl groups and aryl groups; halogen atoms such as fluorine atoms; alkoxy groups such as methoxy groups, ethoxy groups, isopropoxy groups and t-butoxy groups; silyl ethers such as trimethylsilyloxy groups and triethylsilyloxy groups It may be substituted with a group or the like. Note that a plurality of positions may be substituted with these substituents, and the substituents may be further substituted with these substituents.

  The low-melting-point compound used in the present invention is preferably applied to a relatively high-viscosity compound in which droplets are likely to occur due to channeling of carrier gas saturated with raw materials or bursting on the liquid surface. The viscosity of the liquefied low melting point compound when it is actually vaporized and supplied is preferably used for a compound having a viscosity of 1 centipoise or more.

  The solid packing used in the present invention excludes materials that do not interact with the low melting point compound and are stable to heat (for example, those that are corroded by the low melting point compound and those that dissolve in the low melting point compound). ) Is not particularly limited, but, for example, metals such as stainless steel and titanium steel, and ceramics such as α-alumina and pyrex (registered trademark) glass are preferably used as the shape of the solid filling. Although not particularly limited, for example, a spherical shape, a cylindrical shape, a pellet shape, or the like is preferably used because of easy handling.

  The size of the solid filling is not particularly limited, but it is desirable that the solid filling is relatively densely provided in the filling container. Specifically, for example, the diameter is 0.1 mm to 20 mm in terms of a spherical shape. Those having the following are preferably used.

  The filling amount of the solid filling is appropriately adjusted according to the amount of raw material and the size and shape of the filling container. However, in order to prevent channeling and splashing and to increase the efficiency of thermal conductivity, The volume ratio of the filler is preferably 5 to 99%, more preferably 10 to 90%.

  In the filled container of the present invention, in order to prevent adverse effects (for example, adhering to the inside of the filled container or the carrier gas outlet) due to splashing of the low melting point compound saturated in the carrier gas on the liquid surface, When the compound becomes liquid, when the compound is vaporized and supplied, it is preferable that the liquid level be lower than the uppermost part of the packing, and the carrier gas inlet has a low melting point. More preferably, the compound is disposed below the liquid level when the liquid is in the liquid state, and the carrier gas outlet is disposed above the liquid surface when the low melting point compound is in the liquid state. .

  As described above, the distance between the filling and the liquid surface is preferably such that the liquid level is lower than the uppermost part of the filling, more preferably 5 mm or more, and particularly preferably 10 mm. By adjusting the distance between the filling and the liquid level so as to be lower, the effect of the present invention can be expressed more clearly.

  The position of the carrier gas introduction port is preferably disposed below the liquid surface when the low melting point compound is in a liquid state, more preferably 0.1 mm or more, particularly preferably 1 mm or more. By installing in, the effect of the present invention can be expressed more clearly.

  The position of the carrier gas introduction port needs to keep an appropriate distance from the bottom of the filling container in order to smoothly produce the bubbles of the carrier gas, and the distance is preferably 0.1 to 20 mm, more preferably 0. .5-10 mm.

  The diameter of the carrier gas inlet and outlet is not particularly limited as long as it is a size that does not hinder the supply due to clogging of the filler, etc., but preferably 0.1 to 20 mm, more preferably 0.5 to 10 mm. Those having an aperture in this range are more practical.

  In the case where the low melting point compound used in the present invention is a semiconductor film forming material, the filling container of the present invention is provided with a solid filling and a low melting point compound. The carrier gas can be circulated and supplied toward the substrate in the semiconductor manufacturing apparatus via the carrier gas outlet.

  The type of carrier gas, vaporization temperature, and vaporizer pressure can be appropriately selected according to the physical properties of the low melting point compound (for example, melting point, vapor pressure, viscosity, etc.). Examples of the carrier gas include , Nitrogen, helium, argon and the like. The vaporization temperature is preferably 20 to 200 ° C., more preferably 20 to 180 ° C., and the vaporizer pressure is preferably 1 Pa to 200 kPa, more preferably 1 Pa to 140 kPa. It is possible to perform a more stable supply by performing the above.

  Next, the present invention will be specifically described with reference to examples, but the scope of the present invention is not limited thereto.

Example 1 (filled container with solid filling and low melting point compound [1])
A filled container (FIG. 1) having the following conditions was prepared.
Solid packing; stainless steel sphere (3mmφ)
Low melting point compound: bis (acetylacetonato) (1,5-hexadiene) ruthenium (II) (hereinafter referred to as Ru-HDAC) 26 g
Melting point: 9 ° C
Filling container internal volume: 100ml
(The material of the filling container is SUS)
Solid packing volume; 80ml
80% volume ratio of filling material
Distance between solid filling and liquid level; 2cm
Distance between carrier gas inlet and liquid level; 6.5cm
Distance between carrier gas inlet and bottom; 0.3cm
Carrier gas inlet diameter; 4.35 mm
Diameter of carrier gas outlet; 4.35mm

Example 2 (filled container with solid packing and low melting point compound [2])
A filled container (FIG. 2) having the following conditions was prepared.
Solid packing; stainless steel sphere (5mmφ)
Low melting point compound; Ru-HDAC 100 g
Melting point: 9 ° C
Filling container internal volume: 500ml
(The material of the filling container is SUS)
Solid packing volume; 400ml
80% volume ratio of filling material
Distance between solid filling and liquid level; 2cm
Distance between carrier gas inlet and liquid level; 6.5cm
Distance between carrier gas inlet and bottom; 0.3cm
Carrier gas inlet diameter; 4.35 mm
Diameter of carrier gas outlet; 4.35mm

  The shape of each filling container and the filling state inside are shown in FIGS. The filling container [2] is a container having a filling port in its lid.

Example 1 (Supply of low melting point compound using filled container [1])
In the filling container [1], the vaporization temperature was 110 ° C., the vaporization pressure was 0.4 kPa, and helium was circulated at 15 sccm as a carrier gas, and the supplied Ru-HDAC was collected by a cooled trap and collected. The amount of Ru-HDAC was measured over time. The results are shown in Table 1.

Example 2 (Supply of low melting point compound using filled container [2])
In the filled container [2], the vaporization temperature is 110 ° C., the vaporization pressure is 10 kPa, and helium is circulated at 250 sccm as a carrier gas, and the supplied Ru-HDAC is collected with a cooled trap, and the collected Ru− The amount of HDAC was measured over time. The results are shown in Table 1.

Comparative Example 1 (Supply of low melting point compound using filled container [3])
In the filling container [3] (no solid packing is present), a trap in which the supplied Ru-HDAC is cooled while the vaporization temperature is 110 ° C., the vaporization pressure is 10 kPa, and helium is circulated at 250 sccm as a carrier gas. And the amount of the collected Ru-HDAC was measured over time. The results are shown in Table 1.

Examples 3 to 16 (supply of low melting point compound using filled container [1])
In Example 1, the change in the amount collected was measured over time in the same manner as in Example 1 except that the low melting point compound, the vaporization temperature, the flow rate of helium as the carrier gas, and the vaporization pressure were changed.

Comparative Example 2 (Supply of low melting point compound using filled container [3])
In Comparative Example 1, the change in the amount collected was measured over time in the same manner as in Comparative Example 1, except that the low melting point compound, the vaporization temperature, the flow rate of helium as the carrier gas, and the vaporization pressure were changed.

  In addition, the stable usage rate in Table 1 indicates the usage rate until the supply rate is lowered.

The abbreviations for the low melting point compounds are as follows.
Ru-HDAC; bis (acetylacetonato) (1,5-hexadiene) ruthenium Zn-MOPD; bis (2-methoxy-6-methyl-3,5-heptanedionato) zinc Al-MOPD; tris (2-methoxy-6) -Methyl-3,5-heptanedionato) aluminum Ga-MOPD; tris (2-methoxy-6-methyl-3,5-heptaneedionato) gallium In-MOPD; tris (2-methoxy-6-methyl-3,5-heptaneedionato ) Indium Y-MOPD; Tris (2-methoxy-6-methyl-3,5-heptanedionato) yttrium La-MOPD; Tris (2-methoxy-6-methyl-3,5-heptaneedionato) lanthanum Pb-MOPD; 2-methoxy-6-methyl-3,5-heptanedionato) lead Mg-E PD; bis (2-ethoxy-6-methyl-3,5-heptanedionato) magnesium Sn-MOPD; bis (2-methoxy-6-methyl-3,5-heptaneedionato) tin Hf-MOHD; tetrakis (2-methoxy- 3,5-heptanedionato) hafnium Co-MOPD; bis (2-methoxy-6-methyl-3,5-heptaneedionato) cobalt Cu-MOPD; bis (2-methoxy-6-methyl-3,5-heptaneedionato) copper Cu -EOPD; bis (2-ethoxy-6-methyl-3,5-heptanedionato) copper Cu-SOPD; bis (2,6-dimethyl-2-trimethylsilyloxy-3,5-heptaneedionato) copper

  When the filled container of the present invention is used, even when a raw material having a high viscosity is used, it adheres to the inner wall of the container or the lead-out pipe due to splashing due to channeling of the saturated carrier gas or rupture at the liquid level. No phenomenon was observed. Further, it was clear that the low melting point compound was stably vaporized and supplied, as compared with the comparative example. In addition, when the filling container which does not contain the solid packing of a comparative example was used, adhesion of the low melting-point compound was seen many on the container inner wall and carrier gas outlet.

  From the results, it is clear that the filling container of the present invention functions as a filling container suitable for vaporizing and supplying a low melting point compound, and is further adopted in a method for vaporizing and supplying a low melting point compound using the filling container. It was. This suggests that, for example, when a semiconductor film forming material is used as the low melting point compound, there is a high possibility that the vaporization and supply of the raw material to the semiconductor manufacturing apparatus can be performed stably and sufficiently.

  The present invention relates to a filling container suitable for vaporizing and supplying a low melting point compound and a method for vaporizing and supplying a low melting point compound using the filling container.

Filling container [1]; a filling container provided with a solid filling and a low melting point compound. Filling container [2]; a filling container including a solid packing and a low melting point compound (having a filling port in the lid). Filling container [3]; a filling container that does not contain a solid filling and is provided with only a low-melting-point compound. It is a top view of filling container [1]. It is a front view of filling container [1]. It is a side view of filling container [1] (right and left are the same). It is a rear view of filling container [1]. It is a bottom view of filling container [1]. It is a top view of filling container [2]. It is a front view of filling container [2]. It is a side view of filling container [2] (right and left are the same). It is a rear view of filling container [2]. It is a bottom view of filling container [2].

Explanation of symbols

1: Valve 2: Carrier gas introduction pipe 3: Solid filling 4: Low melting point compound 5: Filling port

Claims (8)

A filled container having a carrier gas inlet and outlet, solid packing, and a low-melting compound seen including,
The viscosity of the liquefied low melting point compound when vaporizing and supplying the low melting point compound is 1 centipoise or more,
A filled container in which when the low melting point compound becomes liquid, the liquid level is lower than the uppermost part of the filling.   The filled container according to claim 1, wherein the low melting point compound is a compound having a melting point in a liquid state at 20 ° C or in a range of 20 to 150 ° C. The carrier gas inlet is disposed below the liquid level when the low melting point compound is in a liquid state, and the carrier gas outlet is above the liquid level when the low melting point compound is in a liquid state. The filling container according to claim 1 or 2, which is arranged. The filled container according to any one of claims 1 to 3, wherein the low melting point compound is a metal-containing compound. The filled container according to claim 4, wherein the metal-containing compound is a metal complex having at least one β-diketonate as a ligand. 6. The filled container according to claim 5 , wherein the metal complex having at least one β-diketonate as a ligand is a semiconductor film forming material. A method for vaporizing and supplying a low-melting-point compound, wherein the low-melting-point compound is supplied using the filled container according to any one of claims 1 to 6 . The method for vaporizing and supplying a low melting point compound according to claim 7, wherein the low melting point compound is supplied to a semiconductor manufacturing apparatus.

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