JP6605163B1 - Solid material container - Google Patents

Abstract

The present invention provides a means for quickly cooling a solid material container having an arbitrary shape without increasing the size of an apparatus for arranging the solid material container quickly by a simple technique and configuration. A solid material container (1) is a solid material container for vaporizing and supplying a solid material (2) accommodated therein, and a cooling gas introduction line for introducing a cooling gas into the solid material container (1). 10 and a cooling gas lead-out line 11 for leading the cooling gas out of the solid material container 1, and the cooling gas introduction line 10 is for injecting the cooling gas into the solid material container 1. Alternatively, two or more cooling gas ejection holes 21 are provided. [Figure 1] [Selection] Figure 1

Description

  The present invention relates to a solid material container for supplying semiconductor manufacturing material, for example, vapor of solid material for thin film manufacturing.

As the semiconductor industry advances, there is a need to use new semiconductor materials that will meet stringent thin film requirements. These materials are used in a wide range of applications to deposit and shape thin films in semiconductor products.
For example, the solid precursor material may include components for barrier layers, high dielectric constant / low dielectric constant insulating films, metal electrode films, interconnect layers, ferroelectric layers, silicon nitride layers or silicon oxide layers. . In addition, the solid precursor may include components that act as dopants for compound semiconductors and etching materials. Exemplary precursor materials include aluminum, barium, bismuth, chromium, cobalt, copper, gold, hafnium, indium, iridium, iron, lanthanum, lead, magnesium, molybdenum, nickel, niobium, platinum, ruthenium, silver, strontium , Tantalum, titanium, tungsten, yttrium and zirconium, and inorganic and organometallic compounds.

Some of this new material is in solid form at standard temperature and pressure and cannot be fed directly into the semiconductor deposition chamber for the manufacturing process.
Since these materials generally have a very high melting point and low vapor pressure, they must be heated, vaporized and sublimated inside the solid material container prior to supply to the deposition chamber.

In order to supply a sufficient amount of steam to be used in the semiconductor manufacturing process, it is required that there is sufficient heat input from the solid material container to the solid material during heating.
When the solid material is vaporized, the heat of vaporization is lost. Therefore, when the supply of the solid material vapor is started, the temperature of the surface of the solid material is lowered. Then, since the vapor pressure of the solid material is lowered at the portion where the temperature is lowered, the amount of vapor derived from the solid material container is lowered with the passage of the supply time. Such a variation in the amount of vapor derived is undesirable because it prevents uniform film formation in the semiconductor manufacturing process.
For this reason, the solid material container is generally designed to have a large weight. This is because by increasing the weight, the amount of heat that the solid material container itself has increases, and it becomes possible to quickly supply the amount of heat to the surface of the solid material whose temperature has decreased with vaporization.

By the way, the solid material container is disposed close to the semiconductor manufacturing apparatus in order to supply the solid material vapor to the semiconductor manufacturing apparatus. When the solid material inside the solid material container is consumed, the solid material container is replaced with another solid material container filled with the solid material.
In order to replace the solid material container, it is necessary to cool the solid material container to near room temperature from the viewpoint of safety. Moreover, it is necessary to cool as quickly as possible in consideration of the progress of the semiconductor process.

Methods for cooling the solid material container are disclosed in, for example, Patent Document 1 and Patent Document 2.
Patent Document 1 discloses an apparatus for heating a solid material by introducing a heat medium (for example, heat medium oil) into a space provided outside the container in which the solid material is stored. When the solid material container is cooled in this apparatus, a cooling medium (for example, cooling water) is introduced into the space into which the heat medium is introduced.
Patent Document 2 discloses an apparatus in which a solid material container is cooled by disposing a water-cooled casing so as to cover a bottom surface, a side surface, and an upper surface of the container in which the solid material is stored, and introducing cooling water into the water-cooled casing. To do.

Special table 2010-533790 gazette JP 2014-114491 A

In the apparatus described in Patent Document 1, it is necessary to arrange a space for introducing a refrigerant and a heat medium outside the solid material container. The solid material itself has a large weight, but the weight is further increased by arranging a space for introducing the refrigerant and the heat medium, and it is difficult to replace and transport the container. Further, since the structure of the solid material container is complicated, the maintenance process becomes complicated, and the manufacture of the solid material container becomes difficult.
Furthermore, since it is necessary to alternately introduce the heat medium and the refrigerant into the same space, the refrigerant is contaminated by the heat medium remaining in the space mixed in the refrigerant, or the refrigerant is introduced into the heated space. As a result, the refrigerant is suddenly heated and a large amount of refrigerant vapor is generated.

  In the apparatus described in Patent Document 2, it is necessary to form a water channel through which cooling water flows in the water-cooled casing, and the apparatus becomes complicated. Further, it is necessary to dispose a water-cooled casing on the outside of the solid material container, and there is a problem that the apparatus becomes large.

  As described above, since the solid material container is heavy and has a large amount of heat, it takes time to cool it. In the apparatus for cooling the solid material container from the outside as described in Patent Document 1 or Patent Document 2, the apparatus for arranging the solid material container is enlarged. Further, when the solid material container is removed and replaced with another solid material container, a step of taking it out from the cooling device on the outside is necessary, and the replacement work becomes complicated. In addition, since the cooling device provided outside the solid material container needs to be arranged on the outer periphery of the solid material without gaps to increase heat conduction, it is manufactured according to the shape of the solid material container, A material container cannot be attached.

  In view of the above background, it is desired to develop a means for cooling a solid material container having an arbitrary shape without increasing the size of an apparatus for arranging the solid material container quickly by a simple technique and configuration.

The solid material container according to the present invention is:
A solid material container for vaporizing and supplying a solid material stored inside,
A cooling gas introduction line for introducing a cooling gas into the solid material container;
A cooling gas outlet line for extracting the cooling gas from the solid material container,
The cooling gas introduction line has one or more cooling gas ejection holes for ejecting the cooling gas into the solid material container.

The solid material container is connected to equipment (for example, a semiconductor manufacturing apparatus) that uses the solid material by piping. When supplying the solid material, the solid material container is heated by the heating means. The heating temperature is arbitrarily set according to the process using the solid material, the physical properties of the solid material, and the like, and is, for example, a temperature of 50 ° C. or higher and 300 ° C. or lower.
Due to the heat input from the heated solid material container, the temperature of the solid material inside the solid material container rises, and the solid material is vaporized or sublimated and led out to the outside of the solid material container.
Here, the heating means of the solid material container may be a thermostatic bath, an oil bath, a mantle heater, a tape heater, a jacket heater, or a block heater.

  When the derivation of the vapor of the solid material is stopped after the use of the solid material and the solid material container is to be replaced, the temperature of the solid material container needs to be lowered. The container temperature at the time of replacement is arbitrarily set depending on the viewpoint of safety and the material of the container, and is, for example, a temperature of 15 ° C. or more and 50 ° C. or less.

In the solid material container according to the present invention (1 shown in FIG. 1), the cooling gas is introduced from the cooling gas introduction line 10 and the solid material container 1 is cooled from the inside to quickly cool the container. Is possible. The cooling gas may be a gas having a temperature lower than the heating temperature of the solid material container 1, and may be a gas having a temperature of −50 ° C. or more and 50 ° C. or less, for example. The cooling gas may be inert to the solid material, and the gas species may be, for example, nitrogen, argon, helium, hydrogen, or dry air. The cooling gas may be cooled in advance. The cooling means is not particularly limited, and may be, for example, heat exchange with a refrigerant using a heat exchanger or cooling by a Peltier element. The refrigerant is not particularly limited, and may be liquid nitrogen, water, oil, or fluorinate.
In addition, the arrow in a figure is an arrow which shows the flow direction of gas.

  The introduction pressure of the cooling gas is not particularly limited, and can be, for example, 0.01 MPaA or more and 2 MPaA or less. The introduction pressure of the cooling gas can be determined according to the design of the solid material container 1 and the physical properties of the solid material filled in the container, and can be increased as the cooling gas introduction time elapses.

  Although the introduction flow rate of the cooling gas can be arbitrarily determined, a flow rate at which the space portion in the solid material container 1 not filled with the solid material is replaced at least once per minute is preferable. On the other hand, if the flow rate is too small, the time required for cooling the container becomes long and the efficiency is lowered. On the other hand, if the flow rate is too large, the solid material is wound up inside the solid material container, which causes a problem in the subsequent piping and equipment. Considering the above, the flow rate of the cooling gas per minute is 30 times or more the volume of the portion of the internal space of the solid material container that is not filled with the solid material in the state before the use of the solid material container. The amount can be set to be double or less. Considering the phenomenon that the solid material is rolled up by the gas flow of the cooling gas, it is preferably 1 to 10 times, and more preferably 1 to 5 times.

The introduced cooling gas is used for cooling the solid material container 1. The cooling gas whose temperature has risen due to heat exchange between the solid material container 1 and the solid material 2 therein is led out from the cooling gas lead-out line 11 to the outside of the solid material container 1.
The derived cooling gas is accompanied by solid material vapor. In order to suppress the accompanying steam from condensing in the pipe, the cooling gas lead-out line 11 may be heated by a heating means (not shown). Examples of the heating means include, but are not limited to, a pipe block heater, a jacket heater, or a line heater.

The solid material container 1 is preliminarily provided with a carrier gas introduction line for introducing a carrier gas for entraining the solid material and a solid material outlet line for deriving the vapor of the solid material accompanying the carrier gas. It is common. In this case, the carrier gas introduction line or the solid material lead-out line can also serve as the cooling gas introduction line 10 or the cooling gas lead-out line 11.
For example, when the cooling gas lead-out line 11 also serves as the solid material lead-out line, the cooling gas lead-out line 11 may be branched and a gate valve may be provided as shown in FIG.

The position of the opening portion of the cooling gas introduction line 10 is inserted into the solid material 2 filled in the solid material container 1 inside the powdery or granular solid material (indicated by A in FIG. 1). May be arranged.
Moreover, the opening part may be arrange | positioned in the space (it shows by B in FIG. 1) inside the solid material container 1 where the solid material 2 is not arrange | positioned like arrangement | positioning in FIG.

The cooling gas introduction line 10 is provided with one or more cooling gas ejection holes 21 for ejecting the cooling gas into the solid material container.
2 to 6 are enlarged views of the distal end portion of the cooling gas lead-out line 10.
When the number of the cooling gas ejection holes 21 is one, as shown in FIG. 2, the cooling gas ejection holes 21a can be opened at the tip of the cylindrical cooling gas introduction line 10 (the portion corresponding to the bottom of the cylinder) As shown in FIG. 3, a cooling gas ejection hole 21 b may be opened on the side surface of the cylindrical cooling gas introduction line 10.
When two or more cooling gas ejection holes 21 are provided, a plurality of cooling gas ejection holes 21c may be provided on the side surface of the cooling gas introduction line 10 as shown in FIG. .

When the number of the cooling gas ejection holes 21 is one, the ejection area from which the cooling gas is ejected can be increased, so that the flow velocity of the cooling gas can be reduced and the scattering of the solid material due to the blowing of the cooling gas can be suppressed. .
When the number of cooling gas ejection holes 21 is 2 or more, it becomes possible to disperse the ejection direction of the cooling gas, so that it is possible to prevent the solid material from being unevenly distributed by blowing the gas from the specific direction to the solid material. It becomes possible.

  Thus, since the solid material container 1 can be cooled from the inside of the solid material container 1 by introducing the cooling gas into the solid material container 1, the container is cooled in a shorter time. be able to.

The cooling gas ejection hole 21 of the solid material container 1 according to the present invention is disposed above the surface of the solid material 2 accommodated inside the solid material container 1, and the cooling gas ejection hole 21 is configured so that the cooling gas is a solid material. You may form so that it may be ejected to the upper direction rather than the horizontal direction or the horizontal direction in the space in which the solid material 2 is not accommodated among the insides of the container 1.
The cooling gas introduction line 10 of the solid material container 1 according to the present invention is disposed so as to be vertically inserted into the solid material container 1 from the upper part of the solid material container 1, and two or more cooling gas ejection holes 21 are provided. However, it may be arranged in the vertical direction on the side surface of the cooling gas introduction line.

When the cooling gas is ejected in the direction of the solid material 2, the solid material in the solid material container 1 is swollen by the ejection of the cooling gas, and the devices such as valves and pressure gauges connected to the solid material container are closed. , or to leak, there likely to create a large amount of powdery material or to block the piping flows into the downstream pipe.
The cooling gas ejection hole 21 of the solid material container 1 according to the present invention is opened in a space (a space indicated by B in FIG. 1) in which the solid material 2 is not stored, and the cooling gas ejection direction is horizontal or horizontal. It arrange | positions so that it may become an upper direction than a direction.

For example, in FIG. 3, the cooling gas injection hole 21 b is disposed above the solid material 2 on the side surface of the cooling gas introduction line 10 inserted in the direction perpendicular to the solid material container 1. The gas derived from 21 b is ejected in the horizontal direction with respect to the solid material container 1.
For example, in FIG. 4, a plurality of cooling gas ejection holes 21c are arranged in the vertical direction on the side surface of the cooling gas introduction line 10 inserted in the vertical direction with respect to the solid material container 1, and are led out from the cooling gas ejection holes 21c. The gas to be ejected in the horizontal direction with respect to the solid material container 1. The cooling gas ejection holes 21c may be arranged in a vertical row in the vertical direction, but may be arranged in a plurality of rows as shown in FIG.
With this structure, it is possible to suppress the phenomenon that the flow of the cooling gas blows directly onto the solid material 2 and the solid material rises.

  The cooling gas introduction line 10 of the solid material container 1 according to the present invention is inserted into the solid material container 1 from the upper part of the solid material container 1 in the vertical direction, and then L-shaped at the end of the solid material container 1 side. The cooling gas ejection holes 21 are open in the horizontal direction with respect to the solid material container 1 by being curved in a shape.

For example, in FIG. 5, the cooling gas introduction line 10 inserted in the direction perpendicular to the solid material is curved at L at the end on the solid material container 1 side, and the cooling gas ejection hole 21 d faces the horizontal direction. Since it is opened, the cooling gas ejection holes are ejected in the horizontal direction.
As another example, in FIG. 6, the cooling gas introduction line 10 inserted in the direction perpendicular to the solid material is curved at L at the end on the solid material container 1 side, and the cooling gas ejection hole 21 d is inclined. It opens at an angle, and the cooling gas is ejected upward from the horizontal direction.
As another example, in FIG. 7, the cooling gas introduction line 10 inserted in the direction perpendicular to the solid material is curved in a U shape at the end on the solid material container 1 side, and the cooling gas ejection hole 21e is Open upward.
By curving the cooling gas introduction line 10 in the solid material container 1 in this way, the jet direction of the cooling gas is adjusted and the cooling gas is not directly blown onto the solid material, thereby suppressing the rising of the solid material. It becomes possible to do.

In the solid material container 1 according to the present invention, a cold trap 30 for cooling the cooling gas and a cooling gas led out from the cold trap 30 are reintroduced into the solid material container 1 after the cooling gas outlet line 11. A cooling gas return line 31 may further be provided.
The cooling gas is led out from the cooling gas lead-out line 11 after cooling the solid material container 1. Here, the derived cooling gas is accompanied by vaporized solid material vapor. The solid material vapor may condense and deposit due to a decrease in temperature, which may cause clogging of piping and generation of particles. Therefore, a cold trap 30 is provided and cooled after being led out from the solid material container. As a result, the solid material contained in the cooling gas is condensed and remains in the cold trap. By reducing the solid material content contained in the cooling gas in this way, it is possible to suppress a phenomenon in which the solid material is deposited in the downstream pipe of the solid material container 1 and is thereby blocked.
The cooled gas with the solid material reduced may be introduced again into the solid material container as a cooling gas. By adopting such a configuration, the cooling gas can be reused, and the cold heat of the cold trap can be used for cooling the solid material container, so that energy efficient cooling can be performed. .

The cold trap is cooled by a cooling medium such as liquid nitrogen or dry ice. When the cooling gas accompanied by the vapor of the solid material is introduced there, the solid material in the gaseous state condenses and remains in the cold trap as a liquid or solid state, and the cooling gas is cold with the temperature lowered. Derived from the trap.
The cooling gas derived from the cold trap is used as the cooling gas again as it is or after adding a new cooling gas.

It is a figure which shows the structural example of a solid material container. It is an enlarged view of the structural example of the cooling gas introduction line of a solid material container. It is an enlarged view of the structural example of the cooling gas introduction line of a solid material container. It is an enlarged view of the structural example of the cooling gas introduction line of a solid material container. It is an enlarged view of the structural example of the cooling gas introduction line of a solid material container. It is an enlarged view of the structural example of the cooling gas introduction line of a solid material container. It is a figure which shows the structural example of a solid material container. It is a figure which shows the structural example of a solid material container.

(Example)
The solid material container 1 shown in FIG. 1 to which the cooling gas introduction line 10 having the shape shown in FIG. 3 , FIG. 4 or FIG. 6 was attached was manufactured, and the cooling state after heating was confirmed.
The solid material container 1 was a solid material container (container weight 20 kg) made of stainless steel having an internal volume of 18 L and a wall thickness of 0.28 cm. Here, 10 kg of alumina was introduced as a solid material, and the outer wall surface temperature of the container was heated to 250 ° C. or 150 ° C. by a thermostatic bath. After the container outer wall surface temperature reached 250 ° C. or 150 ° C., it was held for 5 hours. Thereafter, heating by the thermostatic bath was stopped, and cooling gas was introduced from the cooling gas introduction line 10. The cooling gas was nitrogen gas having a temperature of 20 ° C. and a flow rate of 15 SLM. In the internal space of the solid material container, the volume of the portion that is not filled with the solid material in the state before the start of use is 8 L, so the flow rate of the cooling gas per minute is 1.9 times the volume.

(Example 1)
In the cooling gas introduction line 10 having the cooling gas ejection holes 21b having the shape shown in FIG. 3, the pipe diameter was ½ inch and the opening area was 0.71 cm ² . The opening part was arrange | positioned 5 mm above the front-end | tip of piping.

(Example 2)
In the cooling gas introduction line 10 having the cooling gas ejection holes 21 c having the shape shown in FIG. 4, the diameter of each cooling gas ejection hole 21 c was 1 mm, and the number of the cooling gas ejection holes 21 was 32. 32 cooling gas ejection holes 21 are arranged in a vertical direction at intervals of 5 mm, and each of the eight cooling gas ejection holes 21 is arranged in four rows on the side wall surface of the cooling gas introduction line. .

(Example 3)
In the cooling gas introduction line 10 having the cooling gas ejection holes 21 e having the shape shown in FIG. 6, the cooling gas introduction line 10 is inserted into the solid material container 1 and then 70% from the bottom of the entire height of the solid material container 1. It was curved into an L shape at the height position. The initial filling height of the solid material is 50% of the total height of the solid material container 1 from the bottom, so the L-shaped curved portion is at a position higher than the filling height of the solid material. . The tip of the curved pipe was cut at an oblique direction of 45 ° C., and the cut end was used as a cooling gas ejection hole 21e.

In Examples 1, 2, and 3, when the heating temperature of the solid material container is 250 ° C., the time required from the start of introduction of the cooling gas until the outer wall surface temperature of the solid material container 1 reaches 50 ° C. is measured. As a result, in all cases, the required time was 800 minutes.
In the case of the shape shown in FIG. 6 (Example 3), a graph showing the transition of the outer wall surface temperature of the container is shown in Table 1. When the cooling gas indicated by the dotted line in Table 1 is not introduced, it takes a long time (1800 minutes or more) to cool the outer wall surface temperature of the container to 50 ° C. or less. However, when the cooling gas indicated by the solid line is introduced, the cooling is performed. Time has been greatly reduced. From this, it can be said that the container cooling effect by introduction of the cooling gas was sufficiently obtained.
In addition, the container outer wall surface temperature measured the surface of the side surface center part of the cylindrical-shaped solid material container 1 with the thermocouple.

Similarly, the graph which shows transition of the container outer wall surface temperature when the heating temperature of the solid material container is 150 ° C. in Example 3 is shown in Table 2.
When the cooling gas indicated by the dotted line in Table 2 is not introduced, cooling takes a long time (900 minutes or more) until the outer wall surface temperature reaches 50 ° C., but when the cooling gas indicated by the solid line is introduced. The cooling time was greatly shortened (about 480 minutes). From this, it can be said that the container cooling effect by introduction of the cooling gas was sufficiently obtained.

Then, when the upper direction than the blowing direction horizontal direction of the cooling gas to cooling gas inlet line 1 0 is bent in an L shape as shown in FIG. 6 (Example 3), the cooling gas inlet line 1 0 In the case of not curving ( Comparative Example 1), it was confirmed whether or not the solid material flew up inside the solid material container 1. In Comparative Example 1 and Example 3, the height of the cooling gas ejection hole 21 was the same, but in the case of Example 3, the ejection direction of the cooling gas was higher than the horizontal direction, In the case of Comparative Example 1, the vertical direction is the downward direction.
The kind and flow rate of the cooling gas at the time of cooling were the same as described above, and the presence / absence of the rising of the solid material was confirmed by the presence / absence of particles detected by the particle counter provided in the cooling gas lead-out line 11.
In Comparative Example 1, the number of detected particles having a diameter of 0.1 μm or more was 1000 per cf. On the other hand, in the case of Example 3, the detected amount of particles having a diameter of 0.1 μm or more was 10 or less per cf. From this, it is more likely that the solid material is blown up in the horizontal direction or in the upward direction than the horizontal direction with respect to the solid material container 1 rather than the case where the cooling gas is jetted in the direction directly hitting the surface of the solid material. It was confirmed that the accompanying particles can be suppressed from the subsequent stage.

1. 1. Solid material container Solid material 10. 10. Cooling gas introduction line Cooling gas lead-out line 21. Cooling gas outlet

Claims (8)

A solid material container for vaporizing and supplying a solid material stored inside,
A cooling gas introduction line for introducing a cooling gas into the solid material container;
A cooling gas outlet line for extracting the cooling gas from the solid material container,
The cooling gas inlet line, possess one or more cooling gas jetting holes for jetting the cooling gas into the solid material container,
The cooling gas ejection hole is disposed above the surface of the solid material stored in the solid material container,
The cooling gas ejection hole is formed such that the cooling gas is ejected in a horizontal direction or upward from the horizontal direction in a space in which the solid material is not stored in the solid material container. Solid material container. The cooling gas introduction line is disposed so as to be vertically inserted into the solid material container from above the solid material container.
The solid material container according to claim 1, wherein two or more of the cooling gas ejection holes are arranged in a vertical direction on a side surface of the cooling gas introduction line.   The cooling gas introduction line is inserted into the interior of the solid material container in the vertical direction from the top of the solid material container, and then curved in an L shape at the end on the solid material container side, thereby the cooling gas. 2. The solid material container according to claim 1, wherein the ejection holes are opened in a horizontal direction with respect to the solid material container. The flow rate per minute of the cooling gas when ejected from the cooling gas ejection hole is not filled with the solid material in the internal space of the solid material container before the start of use of the solid material container. The solid material container according to any one of claims 1 to 3 , further comprising a cooling gas flow rate adjusting mechanism that adjusts a flow rate of the cooling gas so that the volume of the portion is 1 to 30 times the volume of the portion. The solid material container according to any one of claims 1 to 4 , wherein a temperature of the cooling gas is -50 ° C or higher and 50 ° C or lower. The temperature of the cooling gas introduced into the solid material container, is cooled to a temperature of -50 ° C. or higher 50 ° C. or less, further comprising a gas cooling mechanism, according to any one of claims 1 to 5 Solid material container. The solid material container according to any one of claims 1 to 6 , wherein the cooling gas is at least one gas selected from the group consisting of nitrogen gas, helium gas, argon gas, and hydrogen gas. . Wherein downstream of the cooling gas outlet line, further are of the cold trap for cooling gas is cooled, the cooling gas return line to the cooling gas is introduced again into the solid material container derived from the cold trap, claim 1 The solid material container according to claim 7.

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