Method for measuring the remaining amount of solid material, method for supplying sublimation gas, and sublimation gas supply system

Abstract

To provide a measuring method capable of suppressing a residual quantity loss of a solid material in a solid material vessel when supplying sublimation gas of the solid material to a subsequent stage process.SOLUTION: There are provided: a first residual quantity calculation step for calculating a residual quantity of a solid material from such a consumption that sublimation gas is sent from a buffer tank to a subsequent stage process when replenishing sublimation gas into the buffer tank; a second residual quantity calculation step for calculating a residual quantity of the solid material from such a travel that the sublimation gas is sent from a solid material vessel into the buffer tank; and / or a changeover determination step for determining a changeover timing and an abnormality from the residual quantity of the solid material in the solid material vessel.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] This disclosure relates to a method for measuring the remaining amount of solid material in a solid material container, a sublimation gas supply method, and a sublimation gas supply system when supplying sublimation gas for a solid material to a subsequent process. [Background technology]

[0002] The semiconductor manufacturing process consists of multiple processes, and a thin-film deposition process is necessary to manufacture semiconductor integrated devices. In the thin-film deposition process, multiple layers of insulating and conductive materials are formed in layers to create semiconductor elements, thereby imparting functionality. The thin-film deposition process varies depending on the type and structure of the materials. For example, ALD (Atomic Layer Deposition) is a method of forming very thin films by stacking several atomic layers. The ALD (Atomic Layer Deposition) method is characterized by the repetition of a single, precisely controlled process in a specific sequence. In the first step, the wafer is covered with a precursor. In the second step, the precursor gas in the reaction chamber is purged with an inert gas (e.g., argon or nitrogen). In the third step, an oxidizing or reducing agent gas is introduced to react with the precursor, forming the desired material on the wafer surface. In the fourth step, the oxidizing or reducing agent gas in the reaction chamber is purged with an inert gas (e.g., argon or nitrogen). Because atomic layer deposition is performed through these steps, the consumption of each substance proceeds intermittently. Therefore, the precursor gas is consumed only in step 1 of the four steps. This allows for the replenishment of the precursor gas in the buffer container while other processes are underway after the precursor has been used. In addition to the ALD method, another gas-based film deposition process is CVD (Chemical Vapor Deposition). Furthermore, dry etching, a process used to form circuits, is another gas-based process besides film deposition.

[0003] Examples of precursors for film formation include inorganic compounds and organometallic compounds of 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. Because these materials have low vapor pressure, solid materials must be sublimated before being introduced into the reaction chamber. In conventional methods, raw material powder is heated in a vapor generation chamber to generate saturated vapor, and a carrier gas is brought into contact with the raw material vapor itself to supply the carrier gas containing the raw material powder to the film formation apparatus (see, for example, Patent Document 1).

[0004] Patent Document 2 discloses a method in which sublimation gas is sent from a solid material container to a buffer tank, temporarily stored there, and then supplied to a subsequent process. The configuration involves replenishing the gas consumed by supplying it to the subsequent process from the solid material container to the buffer tank.

[0005] ALD (Automated Laser Deposition) is one of the technologies necessary for manufacturing smaller and finer semiconductor devices. However, with the advancement of the semiconductor industry, the amount of low-vapor-pressure materials used for film deposition and other processes is increasing. Due to their low vapor pressure, these solid materials must be sublimated before being introduced into the deposition chamber. The temperature of the gas conduits (piping) must be kept higher than the sublimation point of the solid materials. Semiconductor manufacturing processes are complex, and adverse effects in one process affect all other processes. In other words, process interruptions directly lead to delays in the entire process. Therefore, a continuous supply of solid materials to semiconductor manufacturing equipment is one of the important components for ensuring throughput. Furthermore, customers are demanding cost reductions by using solid material to its limit. On the other hand, if the remaining amount of solid material falls below the supply limit and the supply of raw materials to the semiconductor manufacturing equipment is interrupted, it can cause significant damage to the wafers.

[0006] Managing the remaining amount of solid materials in semiconductor manufacturing processes presents the following challenges: 1) Because solid material containers are made of metal, it is not possible to directly see inside the container. 2) Accurate weight measurement using a load cell (weighing scale) is difficult because the solid material container is connected to a gas conduit, and both the gas conduit and the container are heated. 3) The cumulative flow rate calculation method using a mass flow controller may result in large cumulative errors due to integration. Furthermore, it may not be feasible due to reasons such as equipment cost, temperature, and space requirements. Furthermore, simply detecting a drop in raw material gas pressure is insufficient to reliably identify abnormalities in the process line. Therefore, there is a need to solve these problems and develop a new method for measuring remaining quantities. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 3-141192 [Patent Document 2] International Publication No. 2021 / 067764 [Overview of the Initiative] [Problems that the invention aims to solve]

[0008] The purpose of this disclosure is to provide a measurement method, a sublimation gas supply method, and a sublimation gas supply system that can accurately measure the remaining amount of solid material in a solid material container when supplying sublimation gas for a solid material to a subsequent process. [Means for solving the problem]

[0009] The first sublimation gas supply system is A first solid material container (1A) containing solid material, A second solid material container (1B) containing solid material, The sublimation gas piping (5) is formed by the confluence of the first and second branch pipes (3A and 3B) that are led out from the first and second solid material containers (1A and 1B), respectively. A buffer tank (13) connected to the sublimation gas piping (5), An introduction pipe (14) for introducing sublimation gas from the buffer tank (13) to a subsequent process (for example, a chamber), A first pressure measuring means (4) is provided in the sublimation gas piping (5) (which may also be the first and second branch pipes (3A, 3B)), Between the first solid material container (1A) and the first pressure measuring means (4) (or between the first branch valve (2A) provided in the first branch pipe (3A), Between the second solid material container (1B) and the first pressure measuring means (4) (or between the second branch valve (2B) provided in the second branch pipe (3B), A second valve (10) is provided between the first pressure measuring means (4) and the buffer tank (13), A third valve (15) is provided in the aforementioned introduction piping (14), A second pressure measuring means (11) is provided between the second valve (10) and the third valve (15) (which may be directly provided in the buffer tank (13)), The first remaining amount calculation unit (121) calculates the remaining amount of solid material from the amount of sublimation gas consumed to send from the buffer tank (13) to the subsequent process, It may also be equipped with. The system may further include a second remaining amount calculation unit (122) that calculates the remaining amount of solid material from the amount of sublimation gas transferred from the first and second solid material containers to the buffer tank (13). The system may further include a first switching determination unit (131) that determines the switching time and any abnormalities based on the remaining amount of solid material in the first and second solid material containers.

[0010] The first remaining amount calculation unit (121) is, The pressure inside the buffer tank (13) before opening the third valve (15) while sublimation gas is stored in the buffer tank (13) (P open) and the pressure (P close ) in the buffer tank (13) when the third valve (15) is closed after sending the sublimation gas from the buffer tank (13) to the subsequent process, the first differential pressure ΔP1 with buffer ) and from the volume (V _1 ) of the buffer tank (13), the density (d) of the sublimation gas, and the first correction coefficient (C1), calculate the consumption (Consumption _1 ) of the sublimation gas sent from the buffer tank (13), and subtract the total amount of the calculated first consumption (Consumption r1 from the initial weight (W0) of the solid material contained in the solid material container that is currently supplying the sublimation gas to the buffer tank, and calculate the first remaining amount (W ) of the solid material contained in the solid material container. Regarding "the pressure (P open ) in the buffer tank (13) before opening the third valve (15)", "before opening the third valve (15)" means, for example, immediately before opening the third valve (15). Note that "immediately before" means before the sublimation gas supply system receives a signal from the subsequent process (for example, a film forming apparatus) and sends an open signal to the third valve (15) of the sublimation gas supply device.

[0011] The second remaining amount calculation unit (122) With the third valve (15) closed, the pressure (P close_1 ) in the buffer tank (13) and sending sublimation gas from any solid material container to the buffer tank (13), when the pressure in the buffer tank (13) reaches the set pressure (the first threshold value (Th1), the pressure (P ), the second differential pressure ΔP2 with ), and from the volume (V _full ) of the buffer tank (13), the density (d) of the sublimation gas, and the second correction coefficient (C2), calculate the consumption (Consumption buffer ) of the sublimation gas sent from the buffer tank (13), and from the initial weight (W0) of the solid material contained in the solid material container that is currently supplying the sublimation gas to the buffer tank, the calculated second consumption (Consumption fart ), calculate the consumption (Consumption _2 ) of the sublimation gas sent from the buffer tank (13), and subtract the total amount of the calculated second consumption (Consumption_2 Subtracting the entire amount of ) the second remaining amount of solid material (W) contained in the solid material container r2 You may also perform the calculation )

[0012] The first switching determination unit (131) is, When sublimation gas is supplied from any solid material container to the buffer tank (13), if the pressure in the buffer tank (13) does not exceed the first threshold (Th1) within a predetermined period, it is determined whether the pressure value in the solid material container has decreased from the pressure value when the second valve (10) was opened (for example, by more than a predetermined value, within a predetermined range, or by 10% to 20% or more), or whether the pressure value in the solid material container exceeds the second threshold (Th2). If the pressure value in the solid material container has not decreased from the pressure value when the second valve (10) was opened or the pressure value in the solid material container exceeds the second threshold (Th2), it is determined that there is an abnormality in the sublimation gas piping (5) downstream of the first pressure measuring means (4). If the pressure value in the solid material container has decreased from the pressure value when the second valve (10) was opened or the pressure value in the solid material container has not exceeded the second threshold (Th2), the latest first remaining amount (W r1 ), latest second remaining capacity (W r2 ), determine whether the average or weighted average of both is less than the third threshold (Th3), and then determine the latest first remaining amount (W r1 ), latest second remaining capacity (W r2 ), if the average or weighted average of both is not less than the third threshold (Th3), it is determined that there is an abnormality in the sublimation gas piping (5) upstream of the first pressure measuring means (4) or in any of the branch pipes, and the latest first remaining amount (W r1 ), latest second remaining capacity (W r2 ), if the average or weighted average of both of these is less than the third threshold (Th3), it may be decided to switch to a different solid material container from the aforementioned solid material container. The "pressure value when the second valve (10) is opened" is, for example, the pressure measured by the first pressure measuring means (4).

[0013] The second sublimation gas supply system is A first solid material container (1A) containing solid material, A second solid material container (1B) containing solid material, The sublimation gas piping (5) is formed by the confluence of the first and second branch pipes (3A and 3B) that are led out from the first and second solid material containers (1A and 1B), respectively. A buffer tank (13) connected to the sublimation gas piping (5), An introduction pipe (14) for introducing sublimation gas from the buffer tank (13) to a subsequent process (for example, a chamber), The first and second solid material containers (1A and 1B) are each provided with third and fourth pressure measuring means (4A and 4B), The first branch valve (2A) is provided in the first branch pipe (3A), The second branch valve (2B) is provided in the second branch pipe (3B), A second valve (10) is provided in the sublimation gas piping (5), A third valve (15) is provided in the aforementioned introduction piping (14), A second pressure measuring means (11) is provided between the second valve (10) and the third valve (15) (which may be directly provided in the buffer tank (13)), The first remaining amount calculation unit (121) calculates the remaining amount of solid material from the amount of sublimation gas consumed to send from the buffer tank (13) to the subsequent process, It may also be equipped with. The system may further include a second remaining amount calculation unit (122) that calculates the remaining amount of solid material from the amount of sublimation gas transferred from the first and second solid material containers to the buffer tank (13). The system may further include a second switching determination unit (132) that determines the switching time and any abnormalities based on the remaining amount of solid material in the first and second solid material containers. The second switching determination unit (132) is, When supplying sublimation gas from any solid material container to the buffer tank (13), if the pressure in the buffer tank (13) does not exceed a first threshold (Th1) within a predetermined period, it is determined whether the pressure value in the solid material container has decreased from the pressure value when the second valve (10) was opened (for example, by a predetermined value or more, within a predetermined range or by 10% to 20% or more), or whether the pressure value in the solid material container exceeds a second threshold (Th2). If the pressure value in the solid material container has not decreased from the pressure value when the second valve (10) was opened or the pressure value in the solid material container exceeds the second threshold (Th2), it is determined that there is an abnormality in the branch pipe or sublimation gas piping (5) downstream of the solid material container. If the pressure value in the solid material container has decreased from the pressure value when the second valve (10) was opened or the pressure value in the solid material container does not exceed the second threshold (Th2), it may be determined to switch to a different solid material container.

[0014] The third sublimation gas supply system is A solid material container (1A, 1B, 1C) containing at least two solid materials, The sublimation gas piping (5) is formed by the convergence of branch pipes (3A, 3B, 3C) leading out from each of the solid material containers, At least one buffer tank (13A, 13B) connected to the sublimation gas piping (5), At least one introduction pipe (14A, 14B) for introducing sublimation gas from each of the at least one buffer tanks (13A, 13B) to at least one subsequent process (chambers RA, RB), A first pressure measuring means (4 (4A, 4B, 4C)) is provided in the sublimation gas piping (5) (or may be provided in each of the branch pipes (3A, 3B, 3C)), A first valve (or each branch valve (2A, 2B, 2C) provided in each branch pipe) is provided between the solid material container (1A, 1B, 1C) and the first pressure measuring means (4), Between the first pressure measuring means (4) and the at least one buffer tank (13A, 13B) (or between at least one second valve (10A, 10B) provided in each branch pipe (15A, 15B) branching from the sublimation gas piping (5) to each buffer tank, At least one third valve (15A, 15B) is provided in the aforementioned introduction piping (14A, 14B), A second pressure measuring means (11A, 11B) is provided between the second valve (10A, 10B) and the third valve (15A, 15B) (it may also be provided directly in each buffer tank (13A, 13B)), The first remaining amount calculation unit (121) calculates the remaining amount of solid material from the amount of sublimation gas consumed to send sublimation gas from the buffer tanks (13A, 13B) to the subsequent processes (chambers RA, RB), It may also be equipped with. The system may further include a second remaining amount calculation unit (122) that calculates the remaining amount of solid material from the amount of sublimation gas transferred from the solid material container to the buffer tanks (13A, 13B). The system may further include a first switching determination unit (131) that determines the switching time and any abnormalities based on the remaining amount of solid material in the solid material container. Furthermore, if each of the solid material containers (1A, 1B, 1C) is provided with pressure measuring means (4A, 4B, 4C) and the branch pipes (3A, 3B, 3C) are provided with branch valves (2A, 2B, 2C), a second switching determination unit (132) may be provided to determine the switching time and any abnormalities based on the remaining amount of solid material in the solid material containers.

[0015] The first, second, and third sublimation gas supply systems may be incorporated into ALD equipment, CVD equipment, etching equipment, and the like.

[0016] The method of supplying sublimation gas is: A supply step of supplying sublimation gas from a buffer tank to a subsequent process, A supply stop step that stops the supply of sublimation gas from the buffer tank to the subsequent process, The system includes a sublimation gas replenishment step of replenishing sublimation gas in the buffer tank when the supply is stopped. The aforementioned sublimation gas replenishment step is, A first remaining amount calculation step calculates the remaining amount of solid material from the amount of sublimation gas consumed to send sublimation gas from the buffer tank to the subsequent process, A second remaining amount calculation step, which calculates the remaining amount of solid material from the amount of sublimation gas transferred from the solid material container to the buffer tank, and / or The system includes a switching determination step that determines the switching time and any abnormalities based on the remaining amount of solid material in the solid material container. The first remaining amount calculation step is: The pressure inside the buffer tank (13) (P) before opening the third valve (15) to send the sublimation gas to the subsequent process while the sublimation gas is stored in the buffer tank (13) close The first differential pressure ΔP1 between ) and the volume (V) of the buffer tank (13) buffer From the density of the sublimation gas (d) and the first correction coefficient (C1), the first consumption of sublimation gas sent from the buffer tank (13) is calculated. _1 ) is calculated, and the first consumption amount (Consumption) calculated is obtained from the initial weight (W0) of the solid material contained in the solid material container that is currently supplying sublimation gas to the buffer tank. _1 Subtracting the entire amount of ) the first remaining amount of solid material (W) contained in the solid material container r1 You may also perform the calculation ) "Pressure inside buffer tank (13) before opening third valve (15) (P close In this context, "before opening the third valve (15)" refers to, for example, the moment immediately before opening the third valve (15). "Immediately before" means before the sublimation gas supply system receives a signal from the downstream process (for example, the film deposition apparatus) and sends an open signal to the third valve (15) of the sublimation gas supply system. The second remaining amount calculation step is: With the third valve (15) for sending to the next process closed, the pressure (P) inside the buffer tank (13) close_1) and sublimation gas is sent from one of the solid material containers to the buffer tank (13), and the pressure in the buffer tank (13) reaches the set pressure (P _full The second differential pressure ΔP2 between ) and the volume (V) of the buffer tank (13) buffer ), from the density of the sublimation gas (d) and the second correction factor (C2), the buffer tank (13) fart Second consumption of sublimation gas sent _2 ) is calculated, and the second consumption amount (Consumption) is calculated from the initial weight (W0) of the solid material contained in the solid material container that is currently supplying sublimation gas to the buffer tank. _2 Subtracting the entire amount of ) the second remaining amount of solid material (W) contained in the solid material container r2 You may also perform the calculation ) The aforementioned switching decision step is: When supplying sublimation gas from any solid material container to a buffer tank (13) for sending to a subsequent process, if the pressure in the buffer tank (13) does not exceed a first threshold (Th1) within a predetermined period, it is determined whether the pressure value in the solid material container has decreased (for example, by a predetermined value or more, within a predetermined range or by 10% to 20% or more) from the pressure value when the second valve (10) located between the first pressure measuring means and the second pressure measuring means is opened, or whether the pressure value in the solid material container exceeds a second threshold (Th2). If the pressure value inside the solid material container has not decreased from the pressure value when the second valve (10) located between the first pressure measuring means and the second pressure measuring means is open, or if the pressure value inside the solid material container exceeds the second threshold (Th2), it is determined that there is an abnormality in the sublimation gas piping (5) downstream of the first pressure measuring means (4). If the pressure value inside the solid material container has decreased from the pressure value when the second valve (10) located between the first pressure measuring means and the second pressure measuring means is open, or if the pressure value inside the solid material container has not exceeded the second threshold (Th2), the latest first remaining amount (W r1 ), latest second remaining capacity (W r2 ), determine whether the average or weighted average of both is less than the third threshold (Th3), and then determine the latest first remaining amount (Wr1 ), latest second remaining capacity (W r2 ), if the average or weighted average of both is not less than the third threshold (Th3), it is determined that there is an abnormality in the sublimation gas piping (5) upstream of the first pressure measuring means (4) or in any of the branch pipes, and the latest first remaining amount (W r1 ), latest second remaining capacity (W r2 ), if the average or weighted average of both of these is less than the third threshold (Th3), it may be decided to switch to a different solid material container from the aforementioned solid material container. Another switching decision step is: When sublimation gas is supplied from any solid material container to the buffer tank (13), if the pressure in the buffer tank (13) does not exceed a first threshold (Th1) within a predetermined period, it is determined whether the pressure value in the solid material container has decreased (for example, by a predetermined value or more, within a predetermined range or by 10% to 20% or more) from the pressure value when the second valve (10) located between the first pressure measuring means and the second pressure measuring means is opened, or whether the pressure value in the solid material container exceeds a second threshold (Th2), and the pressure value in the solid material container is determined to be lower than the pressure value when the first pressure measuring means is opened. If the pressure value has not decreased from the pressure value when the second valve (10) located between the stage and the second pressure measuring means was opened, or if the pressure value in the solid material container exceeds the second threshold (Th2), it may be determined that there is an abnormality in the branch pipe or sublimation gas piping (5) downstream of the solid material container. If the pressure value in the solid material container has decreased from the pressure value when the second valve (10) located between the first pressure measuring means and the second pressure measuring means was opened, or if the pressure value in the solid material container does not exceed the second threshold (Th2), it may be determined to switch to a different solid material container.

[0017] A method for measuring the remaining amount of solid material in a solid material container is: When replenishing sublimation gas to the buffer tank, A first remaining amount calculation step calculates the remaining amount of solid material from the amount of sublimation gas consumed to send sublimation gas from the buffer tank to the subsequent process, A second remaining amount calculation step, which calculates the remaining amount of solid material from the amount of sublimation gas transferred from the solid material container to the buffer tank, and / or The system includes a switching determination step that determines the switching time and any abnormalities based on the remaining amount of solid material in the solid material container.

[0018] Information processing equipment, At least one processor, The system includes a memory that stores commands for executing a remaining amount measurement method for measuring the remaining amount of solid material in the solid material container or a sublimation gas supply method. The processor may perform the remaining amount measurement method.

[0019] The remaining amount measurement or sublimation gas supply program is This is a program that implements either a method for measuring the remaining amount of solid material in the solid material container or a method for supplying sublimation gas, using at least one processor. A computer-readable recording medium that stores computer instructions is This is a computer-readable recording medium that stores commands for executing a remaining amount measurement method for measuring the remaining amount of solid material in the solid material container or the sublimation gas supply method.

[0020] The first and second remaining amount calculation units and the first and second switching determination units may be composed of an information processing device (e.g., a computer, server) having memory, a processor, and software programs, or dedicated circuits, firmware, etc. The information processing device may be on-premise, in the cloud, or a combination of both. Examples of pressure measuring means, such as the first and second pressure measuring means, include Pruddon tube pressure gauges and diaphragm pressure gauges.

[0021] The aforementioned sublimation gas supply system is Each heating section is for heating each fixed material container (1A, 1B, 1C), Each of the buffer tanks (13, 13A, 13B) has a heating section for heating them, Means for heating or maintaining the temperature of the sublimation gas piping (5), inlet piping (14, 14A, 14B), and each branch pipe (3A, 3B, 3C, 14A, 14B), Means for heating or keeping warm each branch valve (2A, 2B, 2C, 10A, 10B, 15A, 15B), and the second and third valves (10, 15), It may also be equipped with. This configuration prevents the condensation and solidification of sublimation gas.

[0022] [effect] By calculating the consumption of solid material without using mass flow meters, mass flow controllers, or load cells, the remaining amount in the solid material container can be determined. The solid material in the container can be used up to its supply limit. As a result, the loss of raw material solid material can be reduced. If the supply pressure drops, it can be determined whether this is due to solid material consumption or a piping malfunction. In the case of normal consumption or an abnormality, a continuous supply of sublimation gas can be achieved by switching the solid material container. [Brief explanation of the drawing]

[0023] [Figure 1] An outline of the sublimation gas supply system according to Embodiment 1 is shown. [Figure 2A] A flowchart for measuring the remaining amount according to Embodiment 1 is shown. [Figure 2B] A flowchart for measuring remaining quantity is shown. [Figure 3] An outline of an ALD apparatus equipped with a sublimation gas supply system according to Embodiment 1 is shown. [Figure 4] An outline of the sublimation gas supply system according to Embodiment 2 is shown. [Figure 5] A flowchart for measuring the remaining amount according to Embodiment 2 is shown. [Figure 6] An outline of the sublimation gas supply system according to Embodiment 3 is shown. [Figure 7] An outline of the sublimation gas supply system according to Embodiment 4 is shown. [Figure 8]A flowchart for measuring the remaining amount according to Embodiment 4 is shown. [Figure 9] An outline of an ALD apparatus equipped with a sublimation gas supply system according to Embodiment 4 is shown. [Figure 10] An outline of the sublimation gas supply system according to Embodiment 5 is shown. [Figure 11] An outline of the sublimation gas supply system (integrated into a CVD apparatus) according to Embodiment 6 is shown. [Figure 12] A flowchart of the operation according to Embodiment 6 is shown. [Modes for carrying out the invention]

[0024] Some embodiments of the present invention are described below. The embodiments described below illustrate just one example of the present invention. The present invention is not limited in any way to the embodiments described below and includes various modifications that are implemented without changing the gist of the present invention. Not all of the configurations described below are necessarily essential to the present invention. In this specification, "upstream" and "downstream" are based on the flow of sublimation gas in the sublimation gas supply system.

[0025] (Embodiment 1) Figure 1 shows a schematic of the first sublimation gas supply system. The first sublimation gas supply system 1 comprises a first solid material container 1A that contains a predetermined amount of solid material, a second solid material container 1B that contains a predetermined amount of solid material (the same solid material as described above), a sublimation gas piping 5 formed by the confluence of first and second branch pipes 3A and 3B that lead out from the first and second solid material containers 1A and 1B respectively, a buffer tank 13 connected to the sublimation gas piping 5, and an introduction pipe 14 for introducing sublimation gas from the buffer tank 13 to a subsequent process (e.g., a chamber). Each solid material container 1A and 1B is provided with a heating unit (electric jacket), each heating unit (e.g., electric jacket) for heating the buffer tank 13, and means (e.g., hot air heater, electric jacket) for heating or maintaining the temperature of the sublimation gas piping 5, the introduction pipe 14, and each branch pipe 3A and 3B.

[0026] The first sublimation gas supply system 1 includes a first pressure measuring means 4 provided in the sublimation gas piping 5, a first branch valve 2A provided in the first branch pipe 3A, a second branch valve 2B provided in the second branch pipe 3B, a second valve 10 provided between the first pressure measuring means 4 and the buffer tank 13, a third valve 15 provided in the introduction pipe 14, and a second pressure measuring means 11 provided between the second valve 10 and the buffer tank 13.

[0027] The first sublimation gas supply system 1 includes a first remaining amount calculation unit 121 that calculates the remaining amount of solid material from the amount of sublimation gas consumed to send from the buffer tank 13 to the subsequent process, and a first switching determination unit 131 that determines the switching time and any abnormalities from the remaining amounts of solid material in the first and second solid material containers. In another embodiment, the system further includes a second remaining amount calculation unit 122 that calculates the remaining amount of solid material from the amount of sublimation gas transferred from the first and second solid material containers to the buffer tank 13.

[0028] The first remaining amount calculation unit 121 calculates the pressure P in the buffer tank 13 before opening the third valve 15 while sublimation gas is stored in the buffer tank 13 (for example, before opening the third valve 15 means immediately before opening the third valve 15. Note that immediately before means before the sublimation gas supply system receives a signal from the downstream process and sends an open signal to the third valve 15 of the sublimation gas supply device). open Then, when the third valve 15 is closed after sending the sublimation gas from the buffer tank 13 to the subsequent process, the pressure P inside the buffer tank 13 is... close The first differential pressure ΔP1 and the volume V of the buffer tank 13. buffer From the density d of the sublimation gas and the first correction coefficient C1, the amount of sublimation gas consumed (Consumption) sent from the buffer tank 13 is calculated. _1 The first consumption (Consumption) is calculated from the initial weight (W0) of the solid material contained in the solid material container that is currently supplying sublimation gas to the buffer tank. _1 Subtracting the total amount of ) from the first remaining amount of solid material (W) contained in the solid material container. r1 ) is calculated.

[0029] The second remaining amount calculation unit 122 calculates the pressure P inside the buffer tank 13 when the third valve 15 is closed. close_1 Then, sublimation gas is sent from one of the replenishing solid material containers to the buffer tank 13, and the pressure in the buffer tank 13 reaches the set pressure (the pressure P when the first threshold (Th1) is reached). _full The second differential pressure ΔP2 and the volume V of the buffer tank 13. buffer From the density d of the sublimation gas and the second correction coefficient C2, buffer tank 13 fart The first sublimation gas that was sent two Consumption _2 The calculation is performed, and the number is calculated from the initial weight (W0) of the solid material contained in the solid material container that is currently supplying sublimation gas to the buffer tank. two Consumption _2 Subtracting the total amount of ) the second remaining amount of solid material contained in the solid material container (W r2 ) is calculated.

[0030] The first switching determination unit 131, when supplying sublimation gas from any solid material container to the buffer tank 13, determines whether the pressure value in the solid material container has decreased from the pressure value when the second valve 10 was opened by, for example, a predetermined value or within a predetermined range or by 10% to 20% or more, or whether the pressure value in the solid material container exceeds the second threshold Th2, if the pressure value in the buffer tank 13 has not exceeded the first threshold Th1 within a preset period. If the pressure value in the solid material container has not decreased from the pressure value when the second valve 10 was opened or the pressure value in the solid material container exceeds the second threshold Th2, it is determined that there is an abnormality in the sublimation gas piping 5 downstream of the first pressure measuring means 4. The first switching determination unit 31 determines the latest first remaining amount W if the pressure value in the solid material container has decreased from the pressure value when the second valve 10 was opened or the pressure value in the solid material container has not exceeded the second threshold Th2. r1 Latest second remaining W r2 Then, determine whether the average or weighted average of both is less than the third threshold Th3. Latest first remaining amount W r1 Latest second remaining W r2 If the average or weighted average of both of these is not less than the third threshold Th3, it is determined that there is an abnormality in the sublimation gas piping 5 upstream of the first pressure measuring means 4 or in any of the branch pipes, and the latest first remaining amount W r1 Latest second remaining W r2 If the average or weighted average of both of these values ​​is less than the third threshold Th3, it is determined that a switch to a different solid material container will be made.

[0031] Figure 2A shows the operation flow of the first sublimation gas supply system. Here, we focus on the point at which the sublimation gas in the buffer tank 13 is consumed and calculate the remaining amount.

[0032] (S0) Sublimation gas is pre-supplied from the first solid material container 1A to the buffer tank 13, maintaining a predetermined gas pressure (>first threshold (Th1)). The first branch valve 2A is open, and the second valve 10 is closed. The second solid material container 1B is a spare for switching, and the second branch valve 2B is closed. The third valve 15 is closed.

[0033] (S1) The pressure (P) inside the buffer tank 13 before opening the third valve 15 (for example, before opening the third valve 15 means immediately before opening the third valve 15. Note that immediately before means before the sublimation gas supply system receives a signal from the downstream process and sends an open signal to the third valve 15 of the sublimation gas supply device). open ) is measured (measured by the second pressure measuring means 11 when the valve is open). Sublimation gas is sent from the buffer tank 15 to the subsequent process. Pressure (P open ) may be stored in memory. (S2) The third valve 15 is opened. Sublimation gas is supplied to the subsequent process. The time for which the third valve 15 is open is set according to the requirements of the subsequent process. As sublimation gas is supplied, the pressure in the buffer tank 15 decreases (measured by the second pressure measuring means 11).

[0034] S3 includes S3-1 through S3-5, and S4 includes S4-1 through S4-3. (S3-1) Close the third valve 15. Stop the supply of sublimation gas. The time when the third valve 15 is closed is called downtime. As sublimation gas is supplied, the pressure in the buffer tank 15 decreases (measured by the second pressure measuring means 11). (S3-1) Pressure inside buffer tank 13 when third valve 15 is closed (P close ) is measured (measured by the second pressure measuring means 11). Pressure (P close ) may be stored in memory. (S3-2) Calculate the first differential pressure ΔP1 (ΔP1 = P open -P close ). This is calculated by the first remaining amount calculation unit 21. (S3-4) Volume V of buffer tank 13buffer From the first differential pressure ΔP1, the density d of the sublimation gas, and the first correction coefficient C1, the first consumption of sublimation gas sent from the buffer tank 13 is calculated. _1 The calculation is performed by the first remaining amount calculation unit 21. Consumption _1 [kg]=V buffer [m 3 ]×ΔP1[Pa] / 0.1013[MPa]×d[kg / m 3 ]×C1(1) The first correction coefficient C1 is optional. The first correction coefficient C1 is a coefficient determined from the demonstration data after the device is installed, and may be selected from a range such as 0.8 to 1.2. (S3-5) From the initial weight W0 of the solid material contained in the first solid material container 1A, the first consumption amount calculated in S6 (Consumption _1 Subtract the amount of solid material remaining in the first solid material container 1A from the amount consumed by the buffer tank. r1 This can be calculated by the first remaining amount calculation unit 21. First remaining amount W r1 [kg]=Initial weight W0-Consumption _1 [kg] (2)

[0035] (S4-1) After closing the third valve 15, the second valve 10 is opened. This allows the sublimation gas from the first solid material container 1A to be sent to the buffer tank 13. (S4-2) Within a predetermined period (downtime), it is determined whether the pressure in the buffer tank 13 is above the first threshold Th1 (pressure measured by the second pressure measuring means 11 > first threshold Th1). (S4-3) When the pressure in the buffer tank 13 exceeds the first threshold Th1, the second valve 10 is closed. This stores sublimation gas at a predetermined pressure in the buffer tank 13. Sublimation gas can be supplied at any time as required by the subsequent process. The first threshold Th1 is set, for example, to a pressure value that allows sublimation gas to be supplied to the subsequent process. Steps S1 through S4-2 are repeated. However, the next remaining amount W r1 When calculating in S3-5, the initial weight W0 is replaced by the first remaining weight W calculated immediately before. r1 Use this. First remaining amount W r1 [kg] = Previous remaining amount W r1 -Consumption _1 [kg] The remaining amount is calculated by repeating the process as described above, and is equivalent to the following formula. First remaining amount W r1 [kg] = Initial weight W0 - ΣConsumption _1 [kg] (3)

[0036] The following steps describe a method for determining the switching time and any abnormalities based on the remaining amount of solid material in the solid material container. In this method, if pressure replenishment (sublimation gas replenishment) to the buffer tank is not possible or can not be done in time while the supply of sublimation gas to the downstream process is stopped, it is determined that the solid material container has reached its replenishment limit (empty). If pressure replenishment is not possible in time, this may indicate a decrease in the amount of sublimation gas from the solid material container (supply limit level) or an abnormality such as blockage in the piping line, such as a valve. In this method, the solid material container and piping are heated during supply, so there is a risk of condensation (solidification) of sublimation gas in the piping line, such as valves, and this method can prevent false detections caused by this. (S5-1) In S4-2, if the pressure in the buffer tank 13 does not exceed the first threshold Th1 within a predetermined period (downtime) (i.e., the pressure measured by the second pressure measuring means 11 < first threshold Th1), it is determined whether the pressure value in the first solid material container 1A (pressure measured by the first pressure measuring means 4) has decreased from the pressure value when the second valve 10 was open (S4-1) (for example, by a predetermined value or more, within a predetermined range or by 10% or more and 20% or more pressure) (i.e., the pressure measured by the first pressure measuring means 4 when the second valve 10 is closed is compared with the pressure measured by the first pressure measuring means 4 when the second valve 10 is open to determine whether it has decreased), or whether the pressure value in the first solid material container 1A (pressure measured by the first pressure measuring means 4) exceeds the second threshold Th2. The determination is made with the second valve 10 open. The second threshold Th2 is, for example, a value that is greater than or equal to a predetermined value, within a predetermined range, or 10% to 20% lower than the initial internal pressure of the solid material container (initial pressure value measured by the first pressure measuring means 4) when replenishing sublimation gas into the buffer tank. (S5-2) In S5-1, if the pressure is decreasing or exceeds the second threshold Th2, it is determined that there is an abnormality in the sublimation gas piping 5 downstream of the first pressure measuring means 4. For example, it is determined that there is an abnormality such as blockage of the second valve 10. (S6-1) In S5-1, if the amount has not decreased or has not exceeded the second threshold Th2, the latest first remaining amount W determined in S3 and S4 r1 The determination is made as to whether or not it is smaller than the third threshold Th3. Examples of the third threshold Th3 include 8% to 12% of the initial weight W0, 8% to 11%, 8% to 10%, 8% to 9%, 8%, and 7%. (S6-2) The most recent (calculated immediately before) first remaining amount W r1 If the pressure is not less than the third threshold Th3, it is determined that there is an abnormality in the sublimation gas piping 5 or the first branch pipe 3A upstream of the first pressure measuring means 4. For example, a blockage of the first branch valve 2A may be determined to be an abnormality. (S7) Latest First Remaining W r1When the value is less than the third threshold Th3, it is determined that the replenishment limit level has been reached, and the system switches from the first solid material container 1A to the second solid material container 1B. The first branch valve 2A is closed, and the second branch valve 2B is opened. As a result, sublimation gas is sent from the second solid material container 1B to the buffer tank 13. While sublimation gas is being replenished from the second solid material container 1B, the first solid material container 1A is replaced with a new solid material container. By repeating the above steps, continuous supply becomes possible. Furthermore, in S6-1, the latest first remaining amount W r1 This refers to the latest second remaining capacity W, which will be described later. r2 You may use either the mean or the mean, or the average of both, or the weighted mean.

[0037] (Another method for measuring remaining amount) Another method for measuring the remaining amount focuses on the point at which the sublimation gas is transferred from the solid material container to the buffer tank 13 and calculates the remaining amount. Figure 2B shows the operation flow. (S100) The first branch valve 2A is open, and the second valve 10 is closed. The second solid material container 1B is a spare for switching, and the second branch valve 2B is closed. The third valve 15 is closed. Here, the buffer tank 13 may or may not contain sublimation gas. (S101) With the third valve 15 closed, the pressure inside the buffer tank 13 (P close_1 ) Measure. (S102) Open the second valve 10. Replenish the buffer tank 13 with sublimation gas from the first solid material container 1A. (S103) The pressure in the buffer tank 13 reaches the first threshold Th1 (measured by the second pressure measuring means 11). The second valve 10 is closed and replenishment is stopped. (S104) Pressure P measured by the second pressure measuring means 11 _full Measure. (S105) Calculate the second differential pressure ΔP2 (ΔP2 = (P _full )-(P close_1 )) (S106) Volume V of buffer tank 13 buffer, the second differential pressure ΔP2, the density d of the sublimation gas, and the second correction coefficient C2 to calculate the second consumption (Consumption _2 ) of the sublimation gas sent to the buffer tank 13. Consumption _2 [kg] = V buffer [m 3 × ΔP2 [Pa] / 0.1013 [MPa] × d [kg / m 3 × C2(4) The second correction coefficient C2 may not be necessary. The second correction coefficient C2 is a coefficient obtained from the verification data after the installation of the device and may be selected from, for example, the range of 0.8 to 1.2. (S107) Subtract the second consumption (Consumption _2 ) calculated in S106 from the initial weight W0 of the solid material contained in the first solid material container 1A. Thereby, the second remaining amount W r2 of the solid material contained in the first solid material container 1A can be obtained from the transfer amount to the buffer tank 13. The second remaining amount W r2 [kg] = initial weight (W0) - Consumption _2 [kg] (5) (S108) After closing the second valve 10, open the third valve 15. Thereby, the sublimation gas is sent from the buffer tank 13 to the subsequent process. When the supply to the subsequent process stops, S10l to S108 are repeated during the downtime. (S109 - 1) It is judged whether or not the supply to the subsequent process has stopped. (S109 - 2) When the supply stops, close the third valve 15. During the downtime, repeat S101 to S108. When obtaining the next second remaining amount W r2 in S107, use the second remaining amount W r2 obtained immediately before instead of the initial weight W0. The second remaining amount (W r2 ) [kg] = the previous second remaining amount (W r2 ) - Consumption _2 [kg] The remaining amount is calculated by repeating the process as described above, and is equivalent to the following formula. Second remaining capacity (W r2 )[kg] = Initial weight (W0) - ΣConsumption _2 [kg] (6)

[0038] Next, we will show a method for determining the timing of the changeover and any abnormalities based on the remaining amount of solid material in the solid material container. In (S200)S102, if the pressure in the buffer tank 13 does not exceed the first threshold Th1 (pressure measured by the second pressure measuring means 11 > first threshold Th1) within a predetermined period (downtime), it is determined whether the pressure value in the first solid material container 1A (measured by the first pressure measuring means 4) has decreased from the pressure value when the second valve 10 was opened (at S102) (for example, by more than a predetermined value, within a predetermined range, or by 10% to 20% or more pressure) (i.e., the pressure measured by the first pressure measuring means 4 when the second valve 10 is closed is compared with the pressure measured by the first pressure measuring means 4 when the second valve 10 is open to determine whether it has decreased), or whether the pressure value in the first solid material container 1A (measured by the first pressure measuring means 4) exceeds the second threshold Th2. The determination is made with the second valve 10 open. (S201) If the pressure has not decreased or exceeds the second threshold Th2 in S200, it is determined that there is an abnormality in the sublimation gas piping 5 downstream of the first pressure measuring means 4. For example, it is determined that there is an abnormality such as blockage of the second valve 10. (S202) In S200, if the amount has decreased or has not exceeded the second threshold Th2, the latest second remaining amount (W) determined in S107 r2 This determines whether the third threshold Th3 is smaller than or equal to the third threshold. (S203) Latest (calculated immediately before) second remaining amount W r2 If the pressure is not less than the third threshold Th3, it is determined that there is an abnormality in the sublimation gas piping 5 or the first branch pipe 3A upstream of the first pressure measuring means 4. For example, it is determined that there is an abnormality such as blockage of the first branch valve 2A. (S204) Latest second remaining W r2If the value is less than the third threshold Th3, the system switches from the first solid material container 1A to the second solid material container 1B. The first branch valve 2A is closed, and the second branch valve 2B is opened. This allows the sublimation gas from the second solid material container 1B to be sent to the buffer tank 13. While sublimation gas is being replenished from the second solid material container 1B, the first solid material container 1A is replaced with a new solid material container. By repeating the above steps, continuous supply becomes possible. Also, in S202, the latest second remaining capacity (W r2 ) is the latest remaining amount (W) r1 You may use ) or the average of both, or a weighted average.

[0039] Figure 3 shows a schematic diagram of the ALD apparatus incorporating the first sublimation gas supply system. The ALD apparatus may include the sublimation gas supply system, a chamber, an introduction pipe 14 connected to the chamber via valve 22, a purge line for sublimation gas (precursor) connected via valve 21, an oxidizer or reducing agent supply unit connected to the chamber via valves 23 and 25, a purge line for oxidizer or reducing agent connected to the chamber via valves 24 and 25, and another material supply system connected to the chamber via valve 26.

[0040] (Embodiment 2) Figure 4 shows a schematic of the second sublimation gas supply system. Unlike Embodiment 1, Embodiment 2 replaces the first pressure measuring means 4 with a first sub-pressure measuring means 4A and a second sub-pressure measuring means 4B directly provided in the first solid material container 1A and the second solid material container 1B, respectively. In addition, the first switching determination unit 131 is replaced with a second switching determination unit 132. When sublimation gas is sent from any solid material container to the buffer tank 13, the second switching determination unit 132 determines whether the pressure value in the solid material container has decreased from the pressure value when the second valve 10 was open (for example, by more than a predetermined value, within a predetermined range, or by 10% to 20% or more) if the pressure in the buffer tank 13 has not exceeded the first threshold Th1 within a preset period (i.e., it compares the pressure measured by the first pressure measuring means 4 when the second valve 10 is closed with the pressure measured by the first pressure measuring means 4 when the second valve 10 is open to determine whether it has decreased), or whether the pressure value in the solid material container exceeds the second threshold Th2. If the pressure value in the solid material container has not decreased from the pressure value when the second valve 10 was open, or if the pressure value in the solid material container exceeds the second threshold Th2, it is determined that there is an abnormality in the sublimation gas piping 5 downstream of the solid material container. If the pressure value inside the solid material container has decreased from the pressure value when the second valve 10 was opened, or if the pressure value inside the solid material container does not exceed the second threshold Th2, it is determined to switch to a different solid material container.

[0041] Figure 5 shows the operation flow. The difference from Figure 2A is that steps S6-1 and S6-2 are omitted, and if the answer to S5-1 is "No", the process proceeds to S7. Also, although not shown, the flow corresponding to Figure 2B omits steps S202 and S203, and if the answer to S200 is "No", the process proceeds to S204.

[0042] In another embodiment, similar to Embodiment 1, the first pressure measuring means 4 may be provided in the sublimation gas piping 5. In this case, steps S6-1 and S6-2 may be operable.

[0043] (Embodiment 3) Figure 6 shows a schematic of the third sublimation gas supply system. Embodiment 3 is the same as Embodiment 1, but also includes a third solid material container 1C, a third branch valve 2C, and a third branch pipe 3C. Furthermore, fourth and fifth solid material containers, fourth and fifth branch valves, and fourth and fifth branch pipes may also be provided.

[0044] (Embodiment 4) Figure 7 shows a schematic of the fourth sublimation gas supply system. Embodiment 4 shows a configuration with two buffer tanks in Embodiment 1, but more than two may be provided. A first sublimation gas branch pipe 12A, branched from the sublimation gas piping 5, is connected to a first buffer tank 13A. A first inlet pipe 14A, leading from the first buffer tank 13A, is connected to the subsequent first process. A second valve 10A and a second pressure measuring means 11A are provided in the first sublimation gas branch pipe 12A. A third valve 15A is provided in the first inlet pipe 14A. A second sublimation gas branch pipe 12B, branched from the sublimation gas pipe 5, is connected to a second buffer tank 13B. A second inlet pipe 14B, leading from the second buffer tank 13B, is connected to the subsequent second process. The second sublimation gas branch pipe 12B is equipped with a second valve 10B and a second pressure measuring means 11B. The second inlet pipe 14B is equipped with a third valve 15B.

[0045] Figure 8 shows the operation flow of Embodiment 4. The difference from Figure 2A is that the amount of sublimation gas consumed when supplied to the subsequent process is calculated in both the first buffer tank 13A and the second buffer tank 13B. In essence, the operation is the same.

[0046] Figure 9 shows a schematic diagram of ALD apparatus A and ALD apparatus B, which incorporate the fourth sublimation gas supply system. ALD apparatus A may include the above-mentioned fourth sublimation gas supply system, a first chamber (Chamber-A), an introduction pipe 14A connected to the first chamber via valve 22, a purge line for sublimation gas (precursor) connected via valve 21, an oxidizer or reducing agent supply unit connected to the first chamber via valves 23 and 25, a purge line for oxidizer or reducing agent connected to the first chamber via valves 24 and 25, and another material supply system connected to the first chamber via valve 26. Furthermore, ALD apparatus B may include a second chamber (Chamber-B), an introduction pipe 14B connected to the second chamber via valve 28, a purge line for sublimation gas (precursor) connected via valve 27, an oxidizer or reducing agent supply unit connected to the second chamber via valves 29 and 31, a purge line for oxidizer or reducing agent connected to the second chamber via valves 30 and 31, and another material supply system connected to the second chamber via valve 32.

[0047] (Embodiment 5) Figure 10 shows a schematic of the fifth sublimation gas supply system. Unlike Embodiment 1, Embodiment 5 is provided with two buffer tanks, the first and second buffer tanks 13A and 13B. Furthermore, unlike Embodiment 4, Embodiment 5 integrates the inlet pipes 14A and 14B to form a single inlet pipe 16. The inlet pipe 16 is connected to one of the subsequent processes. The first buffer tank 13A and the second buffer tank 13B are configured such that valves 15A and 15B can be switched so that either one can supply sublimation gas to the subsequent process. For example, if the pressure in the first buffer tank 13A falls below a predetermined value and it becomes impossible to supply sublimation gas, valve 15A is closed, and valve 15B is opened instead to supply sublimation gas from the second buffer tank 13B. The replenishment of sublimation gas from the first and second solid material containers to the first and second buffer tanks 13A and 13B is the same as in Embodiment 4. The calculation of remaining volume, the detection of blockages in piping and valves, and the determination of when to replace the solid material containers are also the same as in Embodiment 4.

[0048] (Embodiment 6) Figure 11 shows a schematic of the sixth sublimation gas supply system. This sublimation gas supply system is an example of a configuration that can be incorporated into a CVD apparatus. Unlike embodiment 4 (Figure 7), embodiment 6 has the first buffer tank 13A and the second buffer tank 13B arranged in series. Sublimation gas piping 5 is connected to the first buffer tank 13A. The first inlet piping 14A (connecting piping) leading out from the first buffer tank 13A is introduced to the subsequent second buffer tank 13B. Sublimation gas piping 5 is provided with a second valve 10 and a second pressure measuring means 11A for the first buffer tank. The first inlet piping 14A (connecting piping) is provided with a third valve 15A for the first buffer tank 13A and a second pressure measuring means 11B for the second buffer tank. The second inlet piping 14B leading out from the second buffer tank 13B is connected to the subsequent process. The second inlet piping 14B is provided with a third valve 15B for the second buffer tank.

[0049] Figure 12 shows the operation flow of Embodiment 6. The second valve 10 and the third valve 15A for the first buffer tank 13A are in the closed state. (S1201) Open the third valve 15B for the second buffer tank from its closed position. Sublimation gas is supplied to the subsequent process. (S1202) Determine whether the pressure value measured by the second pressure measuring means 11B for the second buffer tank exceeds the first threshold Th1. Repeat this determination as long as it exceeds the threshold. (S1203) If the pressure value does not exceed the first threshold Th1, the third valve 15A for the first buffer tank 13A is opened. Supply to the subsequent process continues. (S1204) It is determined whether the pressure value measured by the second pressure measuring means 11B for the second buffer tank exceeds the first threshold Th1 during a predetermined period. (S1204-1) If the limit is not exceeded, close the third valve 15B for the second buffer tank. Stop supplying the process to the subsequent stage. (S1205) If the limit is exceeded, the third valve 15A for the first buffer tank 13A is closed. (S1206) Next, the second valve 10 is opened. Sublimation gas is supplied from the first solid material container 1A to the first buffer tank 13A. (S1207) It is determined whether the pressure measured by the second pressure measuring means 11A for the first buffer tank exceeds the first threshold Th1. (S1207-1) If the value exceeds this, close the second valve 10. Then return to S1202. (S1208) It is determined whether the pressure inside the first solid material container 1A has not decreased below the pressure when the second valve 10 was opened, and whether the pressure value inside the first solid material container 1A exceeds the second threshold Th2. This is the same operation as in S5-1 or S200. (S1208-1) If the value does not decrease or exceeds the second threshold, it is determined that there is a malfunction in the second valve 10. This is the same operation as in S5-2 or S201. (S1209) Latest remaining amount (W r1 This determines whether the value is below the third threshold, Th3. This is the same operation as in S6-1 or S202. (S1209-1) Latest remaining amount (W r1 If the pressure is not below the third threshold Th3, it is determined that there is an abnormality, such as blockage of the first branch valve 2A upstream of the first pressure measuring means 4. This is the same operation as in S6-2 or S203. (S1210) Latest First Remaining W r1 If the value is less than the third threshold Th3, it is determined that the replenishment limit level has been reached, and the system switches from the first solid material container 1A to the second solid material container 1B. This is the same operation as in S7 or S204. In Embodiment 6, the first consumption amount of Embodiment 1 (Consumption _1 ) and the first remaining amount W r1 The same calculation is performed.

[0050] (Another embodiment) (1) In embodiments 1 to 5, the valves provided in each pipe are not limited to the positions shown in the figures, nor are their number limited. (2) Each valve may be a gate valve or a flow control valve. (3) A mass flow controller, mass flow meter, thermometer, etc. may be installed on each pipe. (4) The sublimation gas supply system of each embodiment 1 to 5 may be incorporated into any of the ALD apparatus, CVD apparatus, or etching apparatus.

[0051] From the above description, many improvements and other embodiments of the disclosure will be apparent to those skilled in the art. Therefore, the above description should be construed as illustrative only and is provided for the purpose of teaching those skilled in the art the best mode of carrying out the disclosure. The details of its structure and / or function can be substantially modified without departing from the spirit of the disclosure. [Explanation of Symbols]

[0052] 1. Sublimation gas supply system 1A First solid material container 1B Second solid material container 2A First Branch Valve 2B Second branch valve 3A First branch pipe 3B Second branch pipe 4. First pressure measuring means 5 Sublimation gas piping 10 Second valve 11. Second pressure measuring means 12 Buffer tank introduction piping 14. Inlet piping 15 Third valve 121 First remaining amount calculation unit 122 Second remaining amount calculation unit 131 First Change Judgment Department 132 Second switching determination unit

Claims

1. The method of supplying sublimation gas is: A supply step of supplying sublimation gas from a buffer tank to a subsequent process, A supply stop step that stops the supply of sublimation gas from the buffer tank to the subsequent process, The supply cessation step includes a sublimation gas replenishment step of replenishing sublimation gas to the buffer tank during the aforementioned supply cessation step, The aforementioned sublimation gas replenishment step is, A first remaining amount calculation step involves calculating the remaining amount of solid material by subtracting the total amount of sublimation gas consumed from the buffer tank to the subsequent process from the initial weight of the solid material, and / or A second remaining amount calculation step involves calculating the remaining amount of solid material by subtracting the total amount of sublimation gas transferred from the solid material container to the buffer tank from the initial weight of the solid material, Includes a switching determination step that determines the switching timing and abnormalities for switching to a different solid material container based on the pressure inside the solid material container, or the pressure inside the solid material container and the remaining amount of solid material inside the solid material container, Sublimation gas supply method.

2. The first remaining amount calculation step is: The pressure (P ｏｐｅｎ ) in the buffer tank before opening the third valve for sending to the subsequent process, when the sublimated gas is stored in the buffer tank, and the pressure (P ｃｌｏｓｅ ) in the buffer tank when the third valve is closed after sending the sublimated gas from the buffer tank to the subsequent process. The first differential pressure ΔP １ , the volume (V ｂｕｆｆｅｒ ) of the buffer tank, the density (d) of the sublimated gas, and the first correction coefficient (C １ ), calculate the first consumption amount (Consumption ＿１ ) of the sublimated gas sent from the buffer tank. Subtract the total amount of the calculated first consumption amount (Consumption ０ ) from the initial weight (W ＿１ ) of the solid material contained in the solid material container that is actually supplying the sublimated gas to the buffer tank, and calculate the first remaining amount (W ｒ１ ) of the solid material contained in the solid material container. The sublimation gas supply method according to claim 1.

3. The second remaining amount calculation step is: With the third valve for sending to the next process closed, the pressure in the buffer tank (P ｃｌｏｓｅ＿１ ) and when sublimation gas is sent from one of the solid material containers to the buffer tank and the pressure in the buffer tank reaches the set pressure (P ＿ｆｕｌｌ The second differential pressure ΔP2 between ) and the volume of the buffer tank (V ｂｕｆｆｅｒ ), density of sublimation gas (d), second correction factor (C ２ From ) to the second consumption of sublimation gas sent to the buffer tank (Consumption ＿２ ) is calculated, and the initial weight (W) of the solid material contained in the solid material container that is currently supplying sublimation gas to the buffer tank is calculated. ０ From the above-calculated second consumption amount (Consumption ＿２ Subtracting the entire amount of the solid material contained in the solid material container, the second remaining amount (W ｒ２ ) calculates, The sublimation gas supply method according to claim 1 or 2.

4. The aforementioned switching decision step is: When sublimation gas is introduced from any solid material container into a buffer tank, the pressure inside the buffer tank reaches a first threshold (Th) within a predetermined period. １ If the pressure value in the solid material container does not exceed the second threshold (Th ２ Determine whether it exceeds the second threshold (Th ２ If it exceeds the second threshold (Th ２ If it does not exceed the latest first remaining charge (W ｒ１ ), latest second remaining capacity (W ｒ２ ), the average or weighted average of both of them is the third threshold (Th ３ Determine whether it is smaller than ) and the latest remaining amount (W ｒ１ ), latest second remaining capacity (Wr ２ ), the average or weighted average of both of them is the third threshold (Th ３ If the value is not smaller than the first pressure measuring means, it is determined that there is an abnormality in the sublimation gas piping upstream of the first pressure measuring means or in any of the branch pipes, and the latest first remaining amount (Wr １ ), latest second remaining capacity (Wr ２ ), the average or weighted average of both of them is the third threshold (Th ３ If the value is smaller than the aforementioned solid material container, it is decided to switch to a different solid material container, or When sublimation gas is introduced from any solid material container into a buffer tank, the pressure inside the buffer tank reaches a first threshold (Th) within a predetermined period. １ If the pressure value in the solid material container does not exceed the second threshold (Th ２ Determine whether it exceeds the second threshold (Th ２ If the value exceeds the second threshold (Th ２ If the value does not exceed the aforementioned solid material container, it is determined to switch to a solid material container different from the aforementioned solid material container. A method for supplying sublimation gas according to any one of claims 1 to 3.

5. The sublimation gas supply system is A solid material container comprising at least two solid material containers containing solid material, A sublimation gas piping is formed by the convergence of branch pipes leading out from each of the solid material containers, At least one buffer tank connected to the sublimation gas piping, At least one introduction pipe for introducing sublimation gas from each of the at least one buffer tanks to at least one subsequent process, A first pressure measuring means provided in the sublimation gas piping or each branch pipe, A first valve provided between the solid material container and the first pressure measuring means, or each branch valve provided in each branch pipe, A first pressure measuring means and at least one buffer tank, or at least one second valve provided in each branch pipe branching from the sublimation gas piping to each buffer tank, At least one third valve provided in the aforementioned introduction piping, A second pressure measuring means is provided between the second valve and the third valve, A first remaining amount calculation unit calculates the remaining amount of solid material by subtracting the total amount of sublimation gas consumed from the buffer tank to the subsequent process from the initial weight of the solid material, and / or, A second remaining amount calculation unit calculates the remaining amount of solid material by subtracting the total amount of sublimation gas transferred from the solid material container to the buffer tank from the initial weight of the solid material, The system further includes a first switching determination unit that determines the switching timing and any abnormalities for switching to a different solid material container based on the pressure inside the solid material container and the remaining amount of solid material. Sublimation gas supply system.

6. The sublimation gas supply system is A solid material container comprising at least two solid material containers containing solid material, A sublimation gas piping is formed by the convergence of branch pipes leading out from each of the solid material containers, At least one buffer tank connected to the sublimation gas piping, At least one introduction pipe for introducing sublimation gas from each of the at least one buffer tanks to at least one subsequent process, Each of the solid material containers is provided with a first pressure measuring means, Each branch valve is provided in each branch pipe leading to the sublimation gas piping, A first pressure measuring means and at least one buffer tank, or at least one second valve provided in each branch pipe branching from the sublimation gas piping to each buffer tank, At least one third valve provided in the aforementioned introduction piping, A second pressure measuring means is provided between the second valve and the third valve, A first remaining amount calculation unit calculates the remaining amount of solid material by subtracting the total amount of sublimation gas consumed from the buffer tank to the subsequent process from the initial weight of the solid material, and / or, A second remaining amount calculation unit calculates the remaining amount of solid material by subtracting the total amount of sublimation gas transferred from the solid material container to the buffer tank from the initial weight of the solid material, The system further includes a second switching determination unit that determines the switching timing and any abnormalities for switching to a different solid material container based on the pressure inside the solid material container. Sublimation gas supply system.

7. The first remaining amount calculation unit is: With sublimation gas stored in the buffer tank, the pressure inside the buffer tank before opening the third valve (P ｏｐｅｎ ) and the pressure inside the buffer tank (P) when the third valve is closed after the sublimation gas has been sent from the buffer tank to the subsequent process. ｃｌｏｓｅ ) First differential pressure ΔP １ And the volume of the buffer tank (V ｂｕｆｆｅｒ ), density of sublimation gas (d), first correction factor (C １ ) From the first consumption of sublimation gas sent from the buffer tank (Consumption ＿１ The first consumption amount (Consumption) is calculated from the initial weight (W0) of the solid material contained in the solid material container that is currently supplying sublimation gas to the buffer tank. ＿１ Subtracting the entire amount of the first remaining amount of solid material (W) contained in the solid material container, ｒ１ ) calculates, The sublimation gas supply system according to claim 6.

8. The second remaining amount calculation unit is: With the third valve closed, the pressure inside the buffer tank (P ｃｌｏｓｅ＿１ ) and when sublimation gas is sent from one of the solid material containers to the buffer tank and the pressure in the buffer tank reaches the set pressure (P ＿ｆｕｌｌ ) Second differential pressure ΔP ２ And the volume of the buffer tank (V ｂｕｆｆｅｒ ), density of sublimation gas (d), second correction factor (C ２ From ) to the second consumption of sublimation gas sent to the buffer tank (Consumption ＿２ ) is calculated, and the initial weight (W) of the solid material contained in the solid material container that is currently supplying sublimation gas to the buffer tank is calculated. ０ From the above-calculated second consumption amount (Consumption ＿２ Subtracting the entire amount of the solid material contained in the solid material container, the second remaining amount (W ｒ２ ) calculates, The sublimation gas supply system according to claim 6 or 7.

9. The first switching determination unit is When sublimation gas is introduced from any solid material container into a buffer tank, the pressure inside the buffer tank reaches a first threshold (Th) within a predetermined period. １ If the pressure value in the solid material container does not exceed the second threshold (Th ２ Determine whether it exceeds the second threshold (Th ２ If it exceeds the second threshold (Th ２ If it does not exceed the latest first remaining charge (W ｒ１ ), latest second remaining capacity (W ｒ２ ), the average or weighted average of both of them is the third threshold (Th ３ Determine whether it is smaller than ) and the latest remaining amount (W ｒ１ ), latest second remaining capacity (W ｒ２ ), the average or weighted average of both of them is the third threshold (Th ３ If the value is not smaller than the first pressure measuring means, it is determined that there is an abnormality in the sublimation gas piping upstream of the first pressure measuring means or in any of the branch pipes, and the latest first remaining amount (W) ｒ１ ), latest second remaining capacity (W ｒ２ ), the average or weighted average of both of them is the third threshold (Th ３ If the value is smaller than the aforementioned solid material container, it is decided to switch to a solid material container different from the aforementioned solid material container. The sublimation gas supply system according to claim 5.

10. The second switching determination unit described above is: When sublimation gas is introduced from any solid material container into a buffer tank, the pressure inside the buffer tank reaches a first threshold (Th) within a predetermined period. １ If the pressure value in the solid material container does not exceed the second threshold (Th ２ Determine whether it exceeds the second threshold (Th ２ If the value exceeds the second threshold (Th ２ If the value does not exceed the aforementioned solid material container, it is determined to switch to a solid material container different from the aforementioned solid material container. The sublimation gas supply system according to claim 6.

11. A method for measuring the remaining amount of solid material in a solid material container is: When replenishing the buffer tank with sublimation gas, A first remaining amount calculation step involves calculating the remaining amount of solid material by subtracting the total amount of sublimation gas consumed from the buffer tank to the subsequent process from the initial weight of the solid material, and / or A second remaining amount calculation step involves calculating the remaining amount of solid material by subtracting the total amount of sublimation gas transferred from the solid material container to the buffer tank from the initial weight of the solid material, Includes a switching determination step that determines the switching timing and abnormalities for switching to a different solid material container based on the pressure inside the solid material container, or the pressure inside the solid material container and the remaining amount of solid material inside the solid material container, Method for measuring remaining amount.

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