Solid material container, solid material supply device, and solid material supply method

Abstract

The present invention addresses the problem of providing a solid material container capable of ascertaining the remaining amount in the container for a material that is solid in a standard state. A solid material container (11) is provided with: a bottomed cylindrical container main body (11A) having a body section (14), the center axis (C) of which extends in the vertical direction; a lid (11B) for closing the upper surface of the container main body (11A), which is an opening; and a plurality of thermocouples (15). The thermocouples (15) are inserted in the horizontal direction from the outside in the circumferential direction of the body section (14) toward the inside of the body section (14), the tips (15a) of the thermocouples (15) are positioned in the center of the body section (14), and the plurality of thermocouples (15) are arranged at two or more different heights at intervals in the vertical direction of the body section (14).

Description

Technical Field

[0001] The invention relates to a solid material container, a solid material supply device and a solid material supply method. Background Art

[0002] In recent years, in order to solve the problems caused by the miniaturization and high integration of semiconductor devices, new film-forming technologies using precursor materials that have not been used before are required. In the past, relatively easy-to-handle gas materials or liquid materials were widely used as precursor materials. On the other hand, some of the inorganic metal compounds and organic metal compounds of aluminum, hafnium, indium, molybdenum, tantalum, titanium, tungsten, yttrium, zirconium, etc. used in the most advanced devices are solid at standard temperature and standard pressure. Precursor materials that are solid at standard temperature and standard pressure (hereinafter referred to as "solid materials") cannot be directly transported to the chamber for the film-forming process. These solid materials usually have a higher melting point and a lower vapor pressure, so the solid materials need to be sublimated before being introduced into the film-forming chamber.

[0003] The solid material is contained in an airtight container (solid material container), and the solid material supply device sublimates the solid material in the solid material container and supplies it to the film forming process chamber. Therefore, the solid material supply device needs to know the usage amount and the timing of container replacement. Therefore, it is necessary to accurately know the remaining amount of solid material in the solid material container to a certain extent.

[0004] As a method for understanding the remaining amount of solid material in a solid material container, there are known methods of weight measurement and direct measurement of the temperature of the solid material. However, the weight measurement method cannot understand the remaining height of the solid material in the solid material container.

[0005] As a method for directly measuring the temperature of a solid material, Patent Document 1 discloses a technique for directly measuring the temperature of a solid material in a solid material container. Specifically, FIG. 11 of Patent Document 1 discloses a structure of a solid material container, wherein a thermocouple extending in a vertical direction is inserted through a top plate of the solid material container, and a plurality of sensors are provided on the thermocouple in the solid material container at desired intervals in the vertical direction.

[0006] Patent Document 1: Japanese Patent Publication No. 2012-052669

[0007] However, in the technology disclosed in Patent Document 1, since the thermocouple itself generates heat and the solid material near the thermocouple sublimates first, causing the material to disappear near the thermocouple, what is measured is the temperature of the gas phase rather than the temperature of the solid material, and there is a problem that proper margin monitoring cannot be performed. Summary of the invention

[0008] The present invention has been made in view of the above situation, and an object of the present invention is to provide a solid material container, a solid material supply device and a solid material supply method, which can grasp the remaining amount in the container of a material that is solid in a standard state.

[0009] In order to solve the above-mentioned problems, the present invention has the following means.

[0010] [1] A solid material container for filling a material that is solid at normal temperature and pressure (25°C, 1 atmosphere) and for supplying a gas that is volatilized or sublimated according to the vapor pressure of the material, the solid material container comprising:

[0011] The container body is a bottomed cylindrical container having a trunk, wherein the central axis of the trunk extends in a vertical direction;

[0012] a lid for closing an upper surface of the container body as an opening; and

[0013] Multiple thermocouples,

[0014] The thermocouple is inserted horizontally from the outer periphery of the trunk toward the center of the trunk, and the front end of the thermocouple is located in the center of the trunk.

[0015] The plurality of thermocouples are arranged at intervals in a vertical direction of the trunk at two or more different heights.

[0016] [2] The solid material container according to [1], wherein the plurality of thermocouples are arranged on the same line extending in the vertical direction of the trunk portion.

[0017] [3] The solid material container according to [1] or [2], further comprising a heater for heating the container body,

[0018] The heater can heat two or more regions divided in the vertical direction, respectively.

[0019] [4] The solid material container according to [3], wherein the heater is located around the container body.

[0020] [5] A solid material supply device for supplying a gas generated by volatilization or sublimation of a solid material at normal temperature and pressure (25°C, 1 atm) according to vapor pressure, the solid material supply device comprising:

[0021] One or more solid material containers as described in any one of [1] to [4]; and

[0022] One or more connecting pipes communicated with the solid material container.

[0023] [6] A solid material supply method, for supplying a gas which is volatilized or sublimated according to the vapor pressure of a solid material at normal temperature and pressure (25°C, 1 atmosphere) using the solid material supply device described in [5], wherein:

[0024] In the solid material container to which the gas is supplied, a plurality of thermocouples arranged in a vertical direction are used to measure the temperature of the material in the solid material container and detect the remaining amount of the material in the solid material container.

[0025] [7] The solid material supply method according to [6], wherein a heating area of ​​the solid material container is changed according to a detected remaining amount of the material in the solid material container.

[0026] [8] The solid material supply method according to [6] or [7], wherein when the temperature difference between the temperature of the material closest to the bottom surface of the solid material container and the sublimation point of the material is greater than 20°C, it is determined that the remaining amount of the material is small.

[0027] The solid material container of the present invention can grasp the remaining amount in the container of a material that is solid under a standard state.

[0028] The solid material supply device and the solid material supply method of the present invention can grasp the remaining amount in the solid material container for the material that is solid under the standard state. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 It is a system diagram schematically showing a solid material supply device as one embodiment of the present invention.

[0030] Figure 2 It is a cross-sectional view schematically showing a solid material container as one embodiment of the present invention.

[0031] Figure 3 The drawings show a mantle heater provided in the solid material container according to the present embodiment, wherein (A) shows a top view, (B) shows a front view, and (C) shows a side view.

[0032] Figure 4 1 is a cross-sectional view schematically showing a solid material container used in an embodiment of the present invention.

[0033] Figure 5 It is a figure which shows the result of Example.

[0034] Figure 6 It is a figure which shows the result of a comparative example.

[0035] Figure 7 It is a figure which shows the result of a comparative example. DETAILED DESCRIPTION

[0036] Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

[0037] In addition, in the drawings used in the following description, in order to make it easier to see each structural element, the scale of the size is sometimes expressed differently according to the structural element, and the size ratio of each structural element is not necessarily the same as the actual one. In addition, the materials, sizes, etc. illustrated in the following description are examples, and the present invention is not necessarily limited to these, and can be appropriately changed and implemented within the scope of not changing its purpose.

[0038] <Solid material supply device>

[0039] First, as one embodiment of the present invention, Figure 1 The solid material supply device 50 shown will be described.

[0040] also, Figure 1 1 is a system diagram schematically showing the structure of a solid material supply device 50 as one embodiment of the present invention.

[0041] like Figure 1 As shown, the solid material supply device 50 of the present embodiment is a device that supplies a gas (gas, hereinafter sometimes referred to as "solid material vapor") formed by volatilization or sublimation of a material S that is solid at normal temperature and pressure (25°C, 1 atmosphere) according to vapor pressure into a reactor.

[0042] The solid material supply device 50 of the present embodiment is roughly configured to include the collection containers 1 and 2 , a jumper pipe 100 communicating with the collection containers 1 and 2 , respectively, and a first heater H100 for heating the jumper pipe 100 .

[0043] The jumper pipe 100 is a pipe connecting the collecting containers 1, 2 and the reaction furnace.

[0044] Although the solid material supply device 50 of the present embodiment is described as an example in which two collection containers 1 and 2 are provided, it is not limited to this. The number of collection containers can be one or more than three. In addition, from the perspective of controllability and the impact when an adverse situation occurs, it is preferred that the number of collection containers is less than three.

[0045] The collection container 1 comprises: three solid material containers 11, 12, 13 filled with solid material S; connecting pipes 11a, 12a, 13a connected to the solid material containers; and a collection pipe 10 connected to the solid material containers 11, 12, 13 via the connecting pipes.

[0046] The collection pipe 10 is provided with a heater H10 for heating the entire collection pipe 10 and ports E and F for purging.

[0047] Although the solid material supply device 50 of this embodiment is described by taking the scheme that the collection container 1 has three solid material containers as an example, it is not limited to this. The number of solid material containers can be one or more than three. From the perspective of controllability and the impact when an adverse situation occurs, the number of solid material containers is preferably nine or less.

[0048] The solid material S is not particularly limited as long as it is a material that is solid at normal temperature and pressure (25°C, 1 atm). The solid material S may be in a crystalline or powdery state, or may be supported on a support. In addition, the solid material S may be in a solid state during filling, may be in a solid state during transportation, or may be in a liquid state during filling or heating.

[0049] Examples of the solid material S include organic compounds, organometallic compounds, metal halides, metal oxyhalides, and mixtures thereof. More specifically, examples include inorganic metal compounds and organometallic compounds of germanium, gallium, aluminum, hafnium, indium, molybdenum, tantalum, titanium, tungsten, yttrium, zirconium, and the like.

[0050] As the solid material S, any one of the group consisting of these compounds may be used, or two or more of the group consisting of these compounds may be contained.

[0051] <Solid material container>

[0052] Next, the structure of a solid material container according to an embodiment of the present invention will be described by taking the solid material container 11 as an example. Figure 2 It is a schematic cross-sectional view for explaining the structure of the solid material container 11 according to the present embodiment.

[0053] like Figure 2 As shown, the solid material container 11 includes a bottomed cylindrical container body 11A, a lid 11B, and a plurality of thermocouples 15 , 15 . . . 15 for monitoring the internal temperature of the solid material container 11 .

[0054] The solid material container 11 is not particularly limited as long as it is a container that can be filled with the solid material S. Specifically, the solid material container 11 can be repeatedly used by supplying the solid material S filled inside in a gaseous state and then filling the solid material S inside again.

[0055] The container body 11A is not particularly limited, but is preferably a bottomed cylindrical container from the viewpoint of filling the inside with the solid material S. Specifically, the container body 11A has a trunk portion 14 with a central axis C extending in the vertical direction.

[0056] In the trunk portion 14, a plurality of thermocouples 15 are inserted horizontally from the outer periphery of the container body 11A toward the center. When the container body 11A is a bottomed cylinder, a plurality of thermocouples 15 are inserted horizontally from the radial direction toward the center. The front end 15a of the thermocouple 15 is a temperature measuring portion.

[0057] Here, the tip 15a of the thermocouple 15 is located at the center of the trunk portion 14 on the inner side of the trunk portion 14. Here, in the present application, the center of the trunk portion 14 refers to an area including the central axis C of the trunk portion 14 and within a required range from the central axis C. Since the temperature measuring portion as the tip 15a of the thermocouple 15 is located at the center of the trunk portion 14 (i.e., the container body 11A), it is not easily affected by the heat from the periphery of the container body 11A, and the temperature of the solid material S can be accurately measured.

[0058] Furthermore, when the radius of the inner diameter of the container body 11A is set to "r" mm, the length of the thermocouple 15 inserted into the inner side of the trunk portion 14 of the container body 11A may be, for example, "r±10" mm.

[0059] In addition, the plurality of thermocouples 15 inserted into the trunk portion 14 are arranged at two or more different heights at predetermined intervals in the vertical direction of the trunk portion 14 .

[0060] Here, the number of thermocouples 15 inserted into the body portion 14 is preferably two or more, and more preferably three or more in the height direction from the viewpoint of monitoring the remaining amount of the solid material S in the container body 11A (ie, the solid material container 11 ).

[0061] In addition, the interval when multiple thermocouples are arranged in the vertical direction is not particularly limited. In addition, the interval when multiple thermocouples are arranged in the vertical direction may be equal intervals or may not be equal intervals. In addition, by setting the intervals when multiple thermocouples are arranged in the vertical direction to equal intervals, it is possible to appropriately monitor the residual amount, so it is preferred (for example, residual amount 50%, residual amount 30%, etc.).

[0062] In addition, the height h of the thermocouple 15 inserted into the inner side of the body 14 of the container body 11A in the axial direction of the body 14 is preferably set at a position of 7 mm to 13 mm from the bottom surface and the upper surface (the lower surface of the lid) of the body 14. This makes it less susceptible to the influence of heat from the outer periphery (upper surface and bottom surface) of the container body 11A, and the temperature of the solid material S can be accurately measured.

[0063] In addition, the height h of the thermocouple 15 can be appropriately selected by considering the thermal conductivity of the material forming the body portion 14 and the covers 11B, 12B, and 13B.

[0064] The cover 11B blocks the upper surface of the opening of the container body 11A. The cover 11B can be removed from the container body 11A. When the amount of solid material remaining in the solid material container 11 is small, the solid material can be added to the container body 11A from the opening of the upper surface by removing the cover 11B from the container body 11A.

[0065] like Figure 1 As shown, a connection pipe 11a is provided on the lid 11B of the solid material container 11. In addition, a remotely operable on-off valve V11a is provided on the connection pipe 11a, and the on-off valve V11a can be adjusted to any opening degree from fully open (opening degree 100%) to fully closed (opening degree 0%).

[0066] The connecting pipe 11 a is provided with a heater H11 a for heating the connecting pipe 11 a and ports A and B for purging.

[0067] The material of the solid material container 11 is not particularly limited, but a material with high thermal conductivity is preferred in order to improve the efficiency of heat transfer to the solid material S. Examples of such a material include stainless steel, aluminum, silicon carbide, aluminum nitride, aluminum oxide, and silicon nitride.

[0068] In addition to heat transfer efficiency, the solid material container 11 may also require corrosion resistance and strength of the material. When multiple properties are required for the solid material container 11, a structure of multiple materials stacked together may be used.

[0069] The material of the thermocouple 15 is not particularly limited as long as it has corrosion resistance and strength. Examples of such a material include SUS316L, SUS316, and SUS304.

[0070] The solid material container 11 may further include: a heater H11 for heating the solid material S filled in the solid material container 11 ; and a weight measuring device W11 for monitoring the weight of the solid material container 11 .

[0071] The heater H11 is not particularly limited as long as it can heat the solid material S in the solid material container 11, and can be appropriately selected from the following types: a type that heats from the outside of the solid material container 11 (for example, a mantle heater, a thermostatic bath, a high-frequency heating device, etc.), a type that heats from the inside of the solid material container 11 (for example, a rod heater, etc.). In addition, they can also be used at the same time. Among these types, a type that heats from the outside of the solid material container 11 is preferred because it is not affected by the solid material stored inside, and a mantle heater that is located around the solid material container 11 and covers the solid material container 11 for heating is more preferred.

[0072] Figure 3 These are diagrams showing a mantle heater H11 included in a solid material container 11 according to the present embodiment, wherein (A) is a plan view, (B) is a front view, and (C) is a side view.

[0073] like Figure 3 As shown in (B) and (C) of FIG. 1 , the mantle heater H11 is arranged to cover the periphery of the solid material container 11 , and has heaters H11A and H11B for heating the container body 11A and a heater H11C for heating the cover 11B.

[0074] The heaters H11A and H11B are divided in the vertical direction. Thus, the heaters H11A and H11B can independently heat two regions of the container body 11A divided in the vertical direction.

[0075] According to the solid material container 11 of the present embodiment, the heating state of the heaters H11A and H11B (i.e., the heating area of ​​the container body 11A) can be independently selected in conjunction with the remaining amount monitoring of the solid material S based on the thermocouple 15. For example, when the solid material container 11 is fully filled with the solid material S, the two areas of the container body 11A divided in the vertical direction are heated by the heaters H11A and H11B. Furthermore, when the solid material S is supplied and it is determined that the solid material S is less than half in the solid material container 11, the heater H11A can be stopped, and only the possible area of ​​the container body 11A divided in the vertical direction is heated by the heater H11B.

[0076] Since the two vertically divided regions of the solid material container 11 (container body 11A) can be heated independently by the vertically divided heaters H11A and H11B, empty burning of the upper portion of the solid material container 11 can be prevented when the remaining amount of solid material S is small.

[0077] In addition, if Figure 3As shown in (A) and (C), when the jacket heater H11 covers the periphery of the container body 11A, the heaters H11A and H11B are in the form of strips, and when the strip-shaped heaters H11A and H11B are wound around the container body 11A, it is preferred that the overlapping positions of the two ends of the heaters H11A and H11B are set to be on the same line as the line 14a extending in the vertical direction of the trunk 14 of the container body 11A. In addition, it is preferred that the insertion positions of the plurality of thermocouples 15 into the trunk 14 are arranged on the same line as the above-mentioned line 14a. By arranging the heaters H11A and H11B and the plurality of thermocouples 15 on the periphery of the container body 11A in this way, the plurality of thermocouples 15 and the heaters H11A and H11B can be arranged separately in a manner that does not interfere with each other.

[0078] The same applies to the solid material containers 12 and 13 .

[0079] Next, a method of arranging the solid material S in the container body 11A will be described.

[0080] The thermocouple 15 is placed in the thermocouple insertion hole 15A provided in the container body 11A. At this time, it is preferable to insert the thermocouple 15 so that the tip end portion thereof reaches the center portion of the container body 11A.

[0081] Next, the solid material S is stored in the container body 11A. At this time, a space may exist between the solid material S and the inner wall of the container body 11A.

[0082] Alternatively, the solid material S may be heated to be liquid, and the obtained liquid may be injected into the container body 11A in which the thermocouple 15 is inserted, and then solidified.

[0083] After the solid material S is stored in the container body 11A, the upper opening of the container body 11A is sealed with the lid 11B. Next, a heater H11 is arranged around the container body 11A.

[0084] <Solid Material Supply Method>

[0085] Next, a solid material supply method using the solid material supply device 50 of the present embodiment will be described.

[0086] (Normal operation)

[0087] First, the jumper pipe 100 of the solid material supply device 50 is connected to the reaction furnace as a use point.

[0088] Next, in order to vaporize the solid material S, the heaters H11 , H12 , and H13 of the collective container 1 for supplying solid material vapor are started to operate, and the solid material containers 11 , 12 , and 13 are started to be heated.

[0089] Next, after the temperature and pressure in the solid material containers 11, 12, and 13 of the selected collection container 1 reach the set values ​​and a prescribed stabilization time has passed, the on-off valves installed in each pipeline are opened by remote operation, so that the solid material vapor can be supplied to the use point.

[0090] Next, after the supply of the solid material S is completed, the solid material vapor remaining in the pipes of all the collection containers 1 is discharged and purged. Finally, the on-off valves provided in each pipe are closed by remote operation to end the supply of the solid material.

[0091] The solid material supply method of the present embodiment monitors the remaining amount of the solid material S in each of the solid material containers 11 , 12 , and 13 when controlling the above-mentioned normal operation.

[0092] (Monitoring the remaining amount of solid materials in containers)

[0093] In the solid material supply method of the present embodiment, for each of the solid material containers 11, 12, 13, the temperature of the solid material S in the container is measured using a plurality of thermocouples 15 arranged in the vertical direction, and the remaining amount of the solid material S in the container is detected. Thus, excessive temperature rise of the solid material in the solid material container can be suppressed, and the solid material supply container can be replaced at an appropriate time.

[0094] Next, the case of the solid material container 11 will be described as an example.

[0095] Specifically, the temperature of each of the plurality of thermocouples 15 spaced apart in the vertical direction of the body 14 of the solid material container 11 is measured. Furthermore, the temperature difference between the temperature at each height of the solid material container 11 and the sublimation point of the solid material S is calculated. It is determined that the solid material S remains at the height where the thermocouple 15 with a temperature difference of less than 20°C is located. On the other hand, it is determined that the solid material S does not remain at the height where the thermocouple 15 with a temperature difference of more than 20°C is located. In this way, the remaining amount of the solid material S in the solid material container 11 can be monitored.

[0096] Furthermore, the solid material container 12 and the solid material container 13 are also monitored in the same manner.

[0097] In addition, in the solid material supply method of the present embodiment, when the gas of the solid material S is supplied from the solid material container 11, the mantle heater H11 is started to operate. Here, the remaining amount of the solid material S in the solid material container 11 is monitored, and when the height of the solid material S in the container decreases and is below the area covered by the heater 11A, the heating of the heater H11A can be stopped. In this way, by changing the heating area of ​​the solid material container 11 according to the detected remaining amount of the solid material S in the container, it is possible to prevent the solid material container 11 from burning empty and reduce energy consumption.

[0098] Furthermore, in the solid material supply method of the present embodiment, when the temperature difference between the temperature measured by the thermocouple 15 disposed at the position closest to the bottom surface of the solid material container 11 and the sublimation point of the material is 20° C. or more, it is determined that the remaining amount of the solid material S in the container is small. Thus, the solid material supply container with a low remaining amount of the solid material S in the container can be replaced at an appropriate timing, so that the gas of the solid material S can be stably supplied.

[0099] As described above, according to the solid material container 11 of the present embodiment, the plurality of thermocouples 15 inserted into the trunk 14 of the container body 11A can be arranged at two or more different heights at required intervals in the vertical direction of the trunk 14. Thus, the temperature can be measured at a plurality of positions in the vertical direction of the container body 11A, and the position where the solid material S remains and the position where the solid material S does not remain can be grasped based on the temperature difference, so that the remaining amount of the solid material S in the solid material container 11 can be monitored.

[0100] In addition, according to the solid material container 11 of the present embodiment, the plurality of thermocouples 15 are inserted in the horizontal direction from the trunk portion 14 which is the side surface of the container body 11A. Therefore, even if a gap is formed around the thermocouple 15 due to the sublimation of the solid material S by the heating of the thermocouple 15, the gap is filled by the dead weight of the solid material S. Therefore, as long as the solid material S is present at the same height as the thermocouple 15, the temperature of the solid material S can be accurately measured. As a result, the remaining amount of the solid material S in the solid material container 11 can be monitored.

[0101] According to the solid material supply device 50 and the solid material supply method of the present embodiment, the solid material supply device 50 is provided with the solid material containers 11, 12, 13 and the connecting pipes 11a, 12a, 13a respectively connected to the solid material containers 11, 12, 13. Thus, the remaining amount of the solid material S in each of the solid material containers 11, 12, 13 can be monitored, so that the solid material supply container with a low remaining amount of the solid material S in the container can be replaced at an appropriate time.

[0102] In addition, according to the solid material supply device 50 and the solid material supply method of the present embodiment, materials that are solid at standard temperature and standard pressure and are represented by inorganic metal compounds and organic metal compounds such as germanium, gallium, aluminum, hafnium, indium, molybdenum, tantalum, titanium, tungsten, yttrium, and zirconium can be supplied to the reaction furnace in a gaseous state and stably for a long time.

[0103] In addition, the technical scope of the present invention is not limited to the above-mentioned embodiment, and various changes can be added without departing from the gist of the present invention.

[0104] Example

[0105] Hereinafter, the present invention will be described in further detail using Examples and Comparative Examples, but the present invention is not limited to these Examples.

[0106] <Example>

[0107] use Figure 1 The solid material supply device shown monitors the remaining amount of solid material in the solid material container when gas supply of the solid material is performed.

[0108] In addition, solid material containers use Figure 4 The structure shown.

[0109] (Solid material container)

[0110] · Diameter of container body: 139.8mm

[0111] ·Thermocouple tip position in the radial direction of the container body: (from the peripheral wall) 69.9 mm

[0112] Number of thermocouples: Seven thermocouples are set at intervals of 50 mm in the vertical direction ( Figure 4 Symbols 1 to 7)

[0113] Solid material: molybdenum oxychloride (sublimation point: 130° C.), filled to a height between the third and fourth thermocouples from the top.

[0114] Heating temperature: 150℃

[0115] Gas supply time: Gas supply was started when the temperature in the solid material container reached 130° C., and this time was defined as the gas supply start time 0 seconds.

[0116] Figure 5 is a diagram showing the results of the embodiment. Figure 5 In FIG. 1 , the X-axis represents the time from the start of gas supply, and the Y-axis represents the temperature of the thermocouple at each height of the solid material container. In addition, Figure 5 The values ​​of each series in Figure 4 The symbols for the thermocouples in are the same.

[0117] like Figure 5 As shown, for the first to third thermocouples from the top in the container, their temperatures immediately exceeded 150°C from 0 seconds after the gas supply started, which was 20°C higher than the sublimation point of the solid material. Therefore, it was determined that there was no solid material in the container and the gas phase was being measured.

[0118] In addition, the temperature of the fourth thermocouple from the top in the container was lower than 130°C from 0 seconds to 3000 seconds after the start of gas supply, which was not more than 20°C higher than the sublimation point of the solid material, so it was determined that the solid material in the container was being measured.

[0119] Afterwards, as the material gas supply progressed, when more than 40,000 to 50,000 seconds had passed since the start of the gas supply, the temperature of the fourth thermocouple rose and exceeded 20°C compared to the sublimation point of the solid material. Therefore, it was determined that there was no solid material at the height of the fourth thermocouple in the container and that the gas phase was being measured.

[0120] In addition, the fifth to sixth thermocouples from the top in the container have a temperature lower than 130° C. from 0 seconds after the gas supply start time, which is 20° C. less than the sublimation point of the solid material, and therefore are determined to be measuring the solid material in the container.

[0121] According to the embodiment of the present invention, it is possible to confirm and monitor the remaining amount of the solid material in the solid material container.

[0122] <Comparative Example>

[0123] The solid material supply device and the solid material container of the embodiment are used, and a thermocouple is inserted vertically from the upper surface of the solid material container, and the thermocouple is arranged so that its front end is located near the bottom of the solid material container.

[0124] Figure 6 is a graph showing the results of the comparative example. Figure 6 In FIG. 1 , the X-axis represents the time from the start of gas supply, and the Y-axis represents the temperature of the thermocouple.

[0125] like Figure 6 As shown, the temperature of the thermocouple is constant from 0 seconds to 700 seconds from the start of gas supply, and it is determined that the temperature of the solid material is being measured.

[0126] When the time exceeds 700 seconds from the start of gas supply, since the temperature of the thermocouple rises, it is determined that no solid material exists around the thermocouple and that the gas phase is being measured.

[0127] Figure 7This is a graph showing the results of the comparative example. Specifically, it shows the state of the solid material when the temperature of the thermocouple rises after more than 700 seconds from the start of gas supply, the heating of the solid material container is stopped, and the lid of the solid material container is removed after the temperature drops to room temperature (25°C).

[0128] like Figure 7 As shown, when a thermocouple is inserted vertically from the upper surface of the solid material container, sublimation of the solid material occurs near the thermocouple, resulting in a gap around the thermocouple, making it impossible to monitor the remaining amount of the solid material in the container.

[0129] Description of Reference Numerals

[0130] 1.2 Collection container

[0131] 10 Collection pipeline

[0132] 11, 12, 13 Solid material supply container

[0133] 11a, 12a, 13a Connecting pipes

[0134] 11A Container body

[0135] 11B Cover

[0136] 14 Trunk

[0137] 14a Straight Line

[0138] 15 Thermocouple

[0139] 15a Front end (temperature measurement unit)

[0140] 100 Jumper Pipe

[0141] 50 Solid material supply device

[0142] C Center axis

[0143] H10 Heater

[0144] H11, H12, H13 mantle heaters

[0145] H11a, H12a, H13a Heaters

[0146] H100 Heater

[0147] S Solid material

[0148] V11a, V12a, V13a On / Off Valves

[0149] W11, W12, W13 Weight Measuring Instruments

Claims

1. A solid material container for filling a material that is solid at room temperature and pressure, i.e., 25° C. and 1 atmosphere, and for supplying a gas that is volatilized or sublimated according to the vapor pressure of the material, the solid material container comprising: The container body is a bottomed cylindrical container having a trunk, wherein the central axis of the trunk extends in a vertical direction; a lid for closing an upper surface of the container body as an opening; and Multiple thermocouples, The thermocouple is inserted horizontally from the outer periphery of the trunk toward the center of the trunk, and the front end of the thermocouple is located in the center of the trunk. The plurality of thermocouples are arranged at intervals in a vertical direction of the trunk at two or more different heights.

2. The solid material container according to claim 1, wherein: The plurality of thermocouples are arranged on the same line extending in the vertical direction of the trunk portion.

3. The solid material container according to claim 1, further comprising a heater for heating the container body, The heater can heat two or more regions divided in the vertical direction, respectively.

4. The solid material container according to claim 3, wherein: The heater is located around the container body.

5. A solid material supply device for supplying a gas which is volatilized or sublimated according to the vapor pressure of a material which is solid at normal temperature and pressure, i.e., 25° C. and 1 atmosphere, the solid material supply device comprising: One or more solid material containers according to any one of claims 1 to 4; and One or more connecting pipes communicated with the solid material container.

6. A solid material supply method, for supplying a gas which is volatilized or sublimated according to the vapor pressure of a material which is solid at normal temperature and pressure (i.e., 25°C and 1 atmosphere) using the solid material supply device according to claim 5, In the solid material container to which the gas is supplied, a plurality of thermocouples arranged in a vertical direction are used to measure the temperature of the material in the solid material container and detect the remaining amount of the material in the solid material container.

7. The solid material supply method according to claim 6, wherein: The heating area of ​​the solid material container is changed according to the detected remaining amount of the material in the solid material container.

8. The solid material supply method according to claim 6, wherein: When the temperature difference between the temperature of the material closest to the bottom surface of the solid material container and the sublimation point of the material is 20° C. or more, it is determined that the remaining amount of the material is small.

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