Solid material supplying device and solid material supplying method

Abstract

To provide a solid material supply device that can supply a material that is a solid in a normal state, stably for a long time, without using a carrier gas.SOLUTION: A solid material supply device 500 is adopted so as to supply a gas of a material that is solid at a normal temperature and a normal pressure (25°C, 1 atm), the material volatilized or sublimated according to a vapor pressure. The solid material supply device has a container set 1, crossover piping 100, a first pressure measurement device P100, a first heater H100 and a first regulator. The container set 10 has solid material containers 11, 12, 13 filled with the material S, a pair of connection pipes 11a, 11b, a piping set 10, a second pressure measurement device P10, a second heater H10, a second regulator, third pressure measurement devices P11a, P11b, third heaters H11a, H11b, a third regulator, fourth heaters H11, H12, H13, a fourth regulator, temperature measurement devices T11, T12, T13 and weight measurement devices W11, W12, W13.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a solid material supplying device and a solid material supplying method. [Background technology]

[0002] In recent years, in order to solve problems caused by miniaturization and high integration of semiconductor devices, new film formation techniques using precursors that have not been used in the past are required. Conventionally, gaseous materials and liquid materials that are relatively easy to handle have been widely used as precursor materials. On the other hand, some of the inorganic metal compounds and organometallic compounds such as aluminum, hafnium, indium, molybdenum, tantalum, titanium, tungsten, yttrium, and zirconium used in cutting-edge 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 a chamber for a film formation process. These solid materials generally have high melting points and low vapor pressures, so the solid materials need to be sublimated prior to being introduced into the film formation chamber.

[0003] For example, Patent Document 1 discloses a technology in which a solid material is placed on a tray inside a container, the solid material is heated to generate saturated vapor, and a carrier gas containing solid material components (sublimation gas) is brought into contact with the solid material to supply the carrier gas as a raw material gas. Furthermore, Patent Document 2 discloses a technique in which a solid material is vaporized in a container and then accompanied by a carrier gas, thereby transporting a constant concentration of solid material vapor into a chamber. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2013-028854 A [Patent Document 2] JP 2019-007073 A Summary of the Invention [Problem to be solved by the invention]

[0005] However, in the techniques disclosed in Patent Documents 1 and 2, the sublimation gas of the solid material is supplied to a film-forming process chamber (reactor) together with a carrier gas, so that the concentration of the precursor is rate-limited by the vapor pressure of the solid material, and the supply pressure and supply flow rate of the carrier gas. Furthermore, as the solid material is consumed, the filling height of the solid material in the source container decreases, so that the flow path where the carrier gas and the solid material come into contact becomes shorter. In other words, the contact time between the carrier gas and the solid material becomes shorter, so that the concentration of the solid material entrained in the carrier gas gradually decreases. Therefore, the conventional techniques have the problem that a film with uniform properties cannot be formed.

[0006] The present invention has been made in consideration of the above circumstances, and an object of the present invention is to provide a solid material supplying device and a solid material supplying method that can stably supply solid material under standard conditions for a long period of time without using a carrier gas. [Means for solving the problem]

[0007] In order to solve the above problems, the present invention has the following aspects. [1] A solid material supplying device that supplies a gas produced by vaporization or sublimation of a solid material at room temperature and pressure (25°C, 1 atm) according to the vapor pressure, One or more collection containers; A connecting pipe connected to each of the one or more collecting vessels; A first pressure measuring device located in the connecting pipe; A first heater for heating the connecting pipe; A first regulator that controls a temperature of the first heater; The collection vessel comprises one or more solid material vessels filled with the material therein; A pair of connecting pipes communicating with the solid material container; a collecting pipe connected to one or more of the solid material containers via a pair of the connecting pipes; A second pressure measuring device located in the collecting pipe; a second heater for heating the collecting pipe; a second regulator for controlling a temperature of the second heater; a third pressure measuring device located in each of the pair of connecting pipes; a third heater for heating each of the pair of connecting pipes; a third regulator that controls a temperature of the third heater; a fourth heater for heating the solid material container; a fourth regulator that controls a temperature of the fourth heater; a temperature measuring device for monitoring an internal temperature of the solid material container; and a weight measuring device for monitoring the weight of the solid material container. [2] The solid material supplying device according to [1], further comprising a controller capable of transmitting and receiving electrical signals to and from the first to third pressure measuring devices, the first to fourth heaters, the first to fourth regulators, the temperature measuring device, and the weight measuring device. [3] An on-off valve is located in each of the pair of connecting pipes, The solid material supplying apparatus according to [1] or [2], wherein, of the pair of pipes, one of the pipes in which the on-off valve is in a closed state is an upstream connecting pipe that does not supply the gas, and the other pipe in which the on-off valve is in an open state is a downstream connecting pipe that supplies the gas. [4] A method for supplying a solid material, comprising the steps of: using the solid material supplying device according to any one of [1] to [3]; and supplying a gas produced by volatilization or sublimation of a solid material at room temperature and atmospheric pressure (25°C, 1 atm) in accordance with the vapor pressure of the solid material, a pressure value of the third pressure measuring device located on the upstream connecting pipe and a pressure value of the third pressure measuring device located on the downstream connecting pipe in the solid material container that supplies the gas, and when a difference between the pressure values ​​reaches a predetermined threshold, a set temperature of the pair of connecting pipes is increased. [5] The method for supplying a solid material according to [4], further comprising: comparing a pressure value of a second pressure gauge in the collecting vessel for supplying the gas with a pressure value of a third pressure gauge located in the downstream connecting pipe; and increasing a set temperature of the collecting pipe when a difference between the pressure values ​​reaches a predetermined threshold value. [6] The method for supplying a solid material described in [4] or [5], further comprising: comparing a pressure value of the first pressure measuring device with a pressure value of the second pressure measuring device in the collection vessel that supplies the gas; and increasing a set temperature of the connecting pipe when a difference between the pressure values ​​reaches a predetermined threshold value. [7] The method for supplying a solid material according to any one of [4] to [6], further comprising increasing a set temperature of the solid material container for supplying the gas when any one or more of the following (a) to (f) is met: (a) In the solid material container supplying the gas, the measurement value of the temperature measuring device is compared with the measurement value of the third regulator, and a temperature difference reaches a predetermined threshold value. (b) When the measurement value of the temperature measuring device in the solid material container supplying the gas becomes smaller than a predetermined set value. (c) When the rate of decrease in the measurement value of the temperature measuring device in the solid material container supplying the gas becomes greater than a predetermined set value. (d) In the solid material container supplying the gas, either the pressure value of the third pressure measuring instrument located on the upstream connecting pipe or the pressure value of the third pressure measuring instrument located on the downstream connecting pipe becomes smaller than a predetermined set value. (e) In the solid material container supplying the gas, when either the pressure decrease rate of the third pressure measuring device located on the upstream connecting pipe or the pressure decrease rate of the third pressure measuring device located on the downstream connecting pipe becomes greater than a predetermined set value. (f) When the rate of decrease in the measurement value of the weight measuring device in the solid material container supplying the gas becomes smaller than a predetermined set value. [8] A solid material supply method according to any one of [4] to [7], further comprising: comparing the measurement value of the temperature measuring device with the measurement value of the third regulator in the solid material container for supplying the gas; and lowering the set temperature of the solid material container for supplying the gas when the temperature difference becomes smaller than a predetermined set value. [9] A solid material supply method according to any one of [4] to [8], wherein when any one or more of the following (g) to (k) apply, the set temperatures of the solid material container having the lowest temperature, the solid material container having the fastest rate of temperature decrease, the solid material container having the lowest pressure, the solid material container having the fastest rate of pressure decrease, and the solid material container having the slowest rate of weight decrease are increased among the collection containers for supplying the gas. (g) In the collection vessel supplying the gas, the temperatures in all the solid material vessels are compared, and the difference between the lowest and highest temperatures is greater than a predetermined set value. (h) In the collection vessel for supplying the gas, the temperature decrease rates of all the solid material vessels are compared, and the difference between the largest temperature decrease rate and the smallest temperature decrease rate is greater than a predetermined set value. (i) In the collection vessel supplying the gas, the measurement values ​​of the third pressure measuring devices of all the solid material vessels are compared, and the difference between the lowest pressure value and the highest pressure value is greater than a predetermined set value. (j) In the collection vessel for supplying the gas, the pressure reduction rates are compared for all the solid material vessels, and the difference between the largest pressure reduction rate and the smallest pressure reduction rate is greater than a predetermined set value. (k) In the collection vessel for supplying the gas, the weight loss rates of all the solid material vessels are compared, and the difference between the largest weight loss rate and the smallest weight loss rate is greater than a predetermined set value. Effect of the Invention

[0008] The solid material supplying device and the solid material supplying method of the present invention can stably supply a solid material under standard conditions for a long period of time without using a carrier gas. [Brief description of the drawings]

[0009] [Figure 1] 1 is a system diagram showing a solid material supplying device according to an embodiment of the present invention; [Diagram 2]FIG. 2 is a block diagram for explaining the operation of a controller constituting the solid material supplying device of the present embodiment. [Diagram 3] FIG. 1 is a diagram showing the results of Comparative Example 1. [Figure 4] FIG. 1 shows the results of Example 1. [Diagram 5] FIG. 13 is a diagram showing the results of Comparative Example 2. [Figure 6] FIG. 13 is a diagram showing the results of Comparative Example 2. [Figure 7] FIG. 13 is a diagram showing the results of Comparative Example 2. [Figure 8] FIG. 1 shows the results of Example 2. [Figure 9] FIG. 1 shows the results of Example 2. [Figure 10] FIG. 1 shows the results of Example 2. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Hereinafter, an embodiment of the present invention will be described in detail with reference to the drawings. In the drawings used in the following description, the dimensions of the components may be shown at different scales to make each component easier to see, and the dimensional ratios of each component may not necessarily be the same as in reality. Furthermore, the materials, dimensions, etc. exemplified in the following description are merely examples, and the present invention is not necessarily limited to them, and may be appropriately modified and implemented within the scope of the present invention.

[0011] <Solid material supply device> First, a solid material supplying apparatus 500 shown in FIG. 1 will be described as one embodiment of the present invention. FIG. 1 is a system diagram that illustrates a configuration of a solid material supplying apparatus 500 according to one embodiment of the present invention.

[0012] As shown in FIG. 1, a solid material supplying apparatus 500 of the present embodiment is an apparatus for supplying a gas (gas, hereinafter sometimes simply referred to as "solid material vapor") produced by volatilization or sublimation of a solid material (hereinafter sometimes simply referred to as "solid material vapor") S at room temperature and normal pressure (25°C, 1 atm) according to vapor pressure to a reactor.

[0013] The solid material supplying device 500 of this embodiment includes collection containers 1 and 2, a connecting pipe 100 connected to the collection containers 1 and 2, a first pressure measuring device P100 located in the connecting pipe 100, a first heater H100 for heating the connecting pipe 100, a first regulator (not shown) for controlling the temperature of the first heater H100, and a controller (not shown).

[0014] The connecting pipe 100 is a pipe that connects each of the collection vessels 1, 2 with the reactor. The solid material supplying device 500 of the present embodiment will be described as having two collection containers 1 and 2 as an example, but is not limited thereto. The number of collection containers may be one or three or more. From the viewpoint of controllability and the influence of malfunctions, the number of collection containers is preferably three or less.

[0015] The collection container 1 has three solid material containers 11, 12, and 13 filled with solid material S, a pair of connecting pipes 11a, 11b, 12a, 12b, 13a, and 13b connected to each solid material container, and a collection pipe 10 connected to the solid material containers 11, 12, and 13 via each connecting pipe.

[0016] In the solid material supplying device 500 of this embodiment, an embodiment in which the collection container 1 has three solid material containers will be described as an example, but is not limited to this. The number of solid material containers may be one or three or more. From the viewpoint of controllability and the influence of the occurrence of a malfunction, the number of solid material containers is preferably nine or less.

[0017] The solid material S is not particularly limited as long as it is a material that is in a solid state at room temperature and normal pressure (25°C, 1 atm). The solid material S may be in a crystalline or powdered state, or may be supported on a support or the like. The solid material S may be in a solid state when filled, may be in a solid state during transportation, or may be in a liquid state when filled or heated.

[0018] The solid material S may include organic compounds, organometallic compounds, metal halides, metal oxyhalides, and compounds thereof, more specifically inorganic and organometallic compounds of aluminum, hafnium, indium, molybdenum, tantalum, titanium, tungsten, yttrium, zirconium, and the like. The solid material S may contain any one of these compounds or may contain two or more of them.

[0019] The solid material container 11 is not particularly limited as long as it is a container capable of being filled with the solid material S. Specifically, the solid material container 11 can be used repeatedly by supplying the solid material S filled inside in a gaseous state and then filling the inside with the solid material S again.

[0020] The solid material container 11 is not particularly limited, but from the viewpoint of filling the inside with the solid material S, it is preferable that the solid material container 11 is a cylindrical container having a bottomed cylindrical container body and a lid that closes the upper surface, which is the opening of the container body.

[0021] The material of the solid material container 11 is not particularly limited, but is preferably a material with high thermal conductivity in order to improve the efficiency of heat transfer to the solid material S. Examples of such materials include stainless steel, aluminum, silicon carbide, aluminum nitride, aluminum oxide, and silicon nitride.

[0022] In addition to the heat transfer efficiency, the solid material container 11 may be required to have corrosion resistance and strength. When multiple properties are required for the solid material container 11, the solid material container 11 may be configured by laminating multiple materials.

[0023] The solid material container 11 is provided with a fourth heater H11 for heating the solid material S filled inside the solid material container 11, a fourth regulator (not shown) for controlling the temperature of the fourth heater H11, a temperature measuring device T11 for monitoring the internal temperature of the solid material container 11, and a weight measuring device W11 for monitoring the weight of the solid material container 11.

[0024] The fourth heater H11 is not particularly limited, but may be appropriately selected from a type that heats the solid material container 11 from the outside (e.g., a mantle heater, a thermostatic bath, a high-frequency heating device, etc.) and a type that heats the solid material container 11 from the inside (e.g., a rod heater, etc.). These types may also be used in combination.

[0025] A pair of connecting pipes 11a and 11b are provided in the solid material container 11. In addition, the pair of connecting pipes 11a and 11b are provided with on-off valves V11a and V11b, respectively, which can be adjusted to any opening degree from fully open (100% opening) to fully closed (0% opening) and can be remotely controlled.

[0026] Of the pair of connecting pipes 11a, 11b, the one in which the on-off valve V11a is open is the downstream connecting pipe 11a that supplies gas, whereas the other pipe in which the on-off valve V11b is closed is the upstream connecting pipe 11b that is used for pressure monitoring and does not supply gas.

[0027] The connecting pipe 11a is provided with a third pressure measuring device P11a, a third heater H11a for heating the connecting pipe 11a, a third regulator (not shown) for controlling the temperature of the third heater H11a, and purge ports A and B. Similarly, the connecting pipe 11b is provided with a third pressure measuring device P11b, a third heater H11b for heating the connecting pipe 11b, a third regulator (not shown) for controlling the temperature of the third heater H11b, and purging ports C and D. The same applies to the solid material containers 12 and 13.

[0028] In the present embodiment, the solid material supplying device 500 has been described as an example in which the pair of connecting pipes provided in the solid material container each have a heater (third heater), but is not limited thereto. The pair of connecting pipes may share one heater (third heater).

[0029] The collecting pipe 10 is provided with a second pressure measuring device P10, a second heater H10 for heating the entire collecting pipe 10, a second regulator (not shown) for controlling the temperature of the second heater H10, and purging ports K and L.

[0030] The controller can transmit and receive electrical signals to and from all the pressure measuring devices (first to third pressure measuring devices), all the heaters (first to fourth heaters), all the temperature regulators (first to fourth regulators), all the temperature measuring devices T11, T12, T13, and all the weight measuring devices W11, W12, W13 by wired or wireless communication. The controller also has a function of taking in received signals, a function of performing calculations described below, and a function of changing the set temperature of each temperature regulator based on the calculation results.

[0031] The controller performs feedback control of the overall operation of the solid material supplying apparatus 500 of this embodiment. Specifically, as shown in Fig. 2, the controller is used to transmit control signals to all heaters (first to fourth heaters) and all temperature regulators (first to fourth regulators) individually provided in the connecting pipes, the collecting pipes, and the connecting pipes located between each of the solid material containers 11, 12, and 13 and the reactor, and to set each part to a predetermined temperature.

[0032] <Solid material supply method> Next, a method for supplying a solid material using the solid material supplying apparatus 500 of this embodiment will be described.

[0033] (Normal operation) First, the connecting pipe 100 of the solid material supplying device 500 is connected to a reactor which is a point of use. Next, in order to vaporize the solid material S, the fourth heaters H11, H12, and H13 of the collection vessel 1 for supplying solid material vapor are started to operate, and heating of the solid material vessels 11, 12, and 13 is started.

[0034] 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 predetermined stabilization time has elapsed, the on-off valves installed in each pipe can be opened by remote control, thereby supplying the solid material vapor to the use point.

[0035] Next, after the supply of the solid material S is completed, the solid material vapor remaining in the piping of all collection vessels 1 is discharged and purged. Finally, the on-off valves installed in each piping are closed by remote control to terminate the supply of the solid material.

[0036] In addition to the above-described normal operation control, the solid material supplying method of the present embodiment performs the following controls (1) to (6) by a controller (not shown) when predetermined conditions are satisfied.

[0037] (1) Measures to prevent blockage of connecting pipes In the solid material supply method of the present embodiment, in a solid material container supplying solid material vapor (gas), the pressure value of a third pressure gauge located in an upstream connecting pipe is compared with the pressure value of a third pressure gauge located in a downstream connecting pipe, and when the difference in the pressure values ​​reaches a predetermined threshold, the set temperatures of the pair of connecting pipes are increased to heat them. This makes it possible to prevent clogging of the connecting pipes in the solid material container supplying gas. The predetermined threshold value is not particularly limited, and can be appropriately selected depending on the type of solid material, the size (volume) of the solid material container, and the like.

[0038] In the following, the case of the solid material container 11 will be described as an example. Specifically, when the value (Pd) of the pressure gauge (P11a) provided on the downstream connecting pipe 11a connected to the solid material container 11 becomes 30% or more smaller than the value (Pu) of the pressure gauge (P11b) provided on the upstream connecting pipe 11b connected to the same solid material container 11, the set temperature of the third regulator that controls the temperature of the third heaters H11a, H11b that heat the connecting pipes 11a, 11b is increased by 5° C. This makes it possible to prevent clogging of the connecting pipes 11a, 11b in the solid material container 11. The solid material container 12 and the solid material container 13 are controlled in a similar manner.

[0039] (2) Measures to prevent blockage of collective piping In the solid material supply method of this embodiment, in a collecting vessel supplying solid material vapor (gas), the pressure value of the second pressure gauge is compared with the pressure value of a third pressure gauge located in the downstream connecting pipe, and when the difference between the pressure values ​​reaches a predetermined threshold, the set temperature of the collecting pipe is increased to heat it. This makes it possible to prevent clogging of the collecting pipe in the collecting vessel supplying gas. The predetermined threshold value is not particularly limited, and can be appropriately selected depending on the type of solid material, the size (volume) of the solid material container, and the like.

[0040] The following description will be given taking the collection container 1 as an example. Specifically, when the value (Ps) of the second pressure gauge (P10) provided in the collecting pipe 10 becomes 30% or more smaller than the value (Pd) of the pressure gauge (P11a) provided in the downstream connecting pipe 11a of the solid material container 11 connected to the collecting pipe 10, the set temperature of the second regulator that controls the temperature of the second heater H10 that heats the collecting pipe 10 is increased by 5° C. This makes it possible to prevent the collecting pipe 10 from being blocked in the collecting container 1. The solid material container 12 and the solid material container 13 are controlled in a similar manner.

[0041] (3) Measures to prevent blockage of connecting pipes In the solid material supply method of this embodiment, the pressure value of the first pressure measuring device P100 is compared with the pressure value of the second pressure measuring device P10 in the collection vessel that supplies the solid material vapor (gas), and when the difference between the pressure values ​​reaches a predetermined threshold, the set temperature of the connecting pipe 100 is increased to heat it. This makes it possible to prevent the connecting pipe 100 from being blocked. The predetermined threshold value is not particularly limited, and can be appropriately selected depending on the type of solid material, the size (volume) of the solid material container, and the like.

[0042] The following description will be given taking the collection container 1 as an example. Specifically, when the value (Pw) of the first pressure gauge P100 provided in the connecting pipe 100 is 30% or more smaller than the value (Ps) of the second pressure gauge P10 provided in the collecting pipe 10, the set temperature of the first regulator that controls the temperature of the first heater H100 that heats the connecting pipe 100 is increased by 5° C. This makes it possible to prevent the connecting pipe 100 from being blocked. The same control is performed for collection container 2.

[0043] (4) Measures to secure steam pressure In the solid material supplying method of this embodiment, when any one or more of the following conditions (a) to (f) is met (i.e., when the supplying capacity of the solid material supplying device 500 is reduced), the set temperature of the solid material container that supplies the solid material vapor (gas) is increased for heating. This ensures the vapor pressure in the solid material container, and the supplying capacity of the solid material supplying device 500 can be restored. (a) In a solid material container supplying gas, the measurement value of the temperature measuring device is compared with the measurement value of the third regulator, and the temperature difference reaches a predetermined threshold value. (b) If the temperature measuring instrument reading in a solid material container supplying gas falls below the specified set value. (c) In a solid material container supplying gas, if the rate of decrease in the temperature measuring instrument reading becomes greater than the specified set value. (d) In a solid material container supplying gas, if either the pressure value of the third pressure measuring device located on the upstream connecting pipe or the pressure value of the third pressure measuring device located on the downstream connecting pipe becomes smaller than the specified set value. (e) In a solid material container supplying gas, if either the pressure decrease rate of the third pressure measuring device located on the upstream connecting pipe or the pressure decrease rate of the third pressure measuring device located on the downstream connecting pipe becomes greater than the specified set value. (f) In a solid material container supplying gas, if the rate of decrease in the measurement value of a weight measuring device becomes slower than the specified set value.

[0044] In the above (a) to (f), the predetermined threshold value and the predetermined set value are not particularly limited and can be appropriately selected depending on the type of solid material, the size (capacity) of the solid material container, etc.

[0045] The following describes an example of controlling the solid material container 11 in the collection container 1. The solid material containers 12 and 13 are also controlled in the same manner. Specifically, the following controls (a) to (f) are performed.

[0046] (a) When the temperature (material temperature inside the container: Tm) measured by the temperature measuring device T11 installed in the solid material container 11 becomes smaller by 15 degrees or more compared with the temperature (downstream connecting pipe temperature: Td) measured by the third regulator (not shown) of the downstream connecting pipe 11a connected to the same solid material container 11, the set temperature of the fourth regulator (not shown) that controls the temperature of the fourth heater H11 that heats the solid material container 11 is increased by 5 degrees.

[0047] (b) When the temperature (Tm) measured by the temperature measuring device T11 provided in the solid material container 11 becomes smaller than a predetermined set value by 5% or more, the set temperature of the fourth regulator (not shown) that controls the temperature of the fourth heater H11 that heats the solid material container 11 is increased by 5°C.

[0048] (c) When the rate of decrease (ΔTm) of the temperature inside the container measured by the temperature measuring device T11 installed in the solid material container 11 becomes 5% or more greater than a predetermined set value, the set temperature of the fourth regulator (not shown) that controls the temperature of the fourth heater H11 that heats the solid material container 11 is increased by 5°C.

[0049] (d) When the value (Pu) of the third pressure gauge P11b provided on the upstream connecting pipe 11b connected to the solid material container 11, or the value (Pd) of the third pressure gauge P11a provided on the downstream connecting pipe 11a, becomes smaller than a predetermined set value by 5% or more, the set temperature of the fourth regulator (not shown) that controls the temperature of the fourth heater H11 that heats the solid material container 11 is increased by 5°C.

[0050] (e) When the rate of decrease in the value of the third pressure gauge P11b provided on the upstream connecting pipe 11b connected to the solid material container 11 (upstream connecting pipe pressure decrease rate: ΔPu) or the rate of decrease in the value of the third pressure gauge P11a provided on the downstream connecting pipe 11a (downstream connecting pipe pressure decrease rate: ΔPd) becomes 5% or more greater than a predetermined set value, the set temperature of the fourth regulator (not shown) that controls the temperature of the fourth heater H11 that heats the solid material container 11 is increased by 5°C.

[0051] (f) When the weight loss rate (ΔWt) of the solid material container 11 becomes smaller than a predetermined set value by 5% or more, the set temperature of the fourth regulator (not shown) that controls the temperature of the fourth heater H11 that heats the solid material container 11 is increased by 5°C.

[0052] (5) Measures to prevent overheating of solid materials In the solid material supply method of this embodiment, in a solid material container that supplies solid material vapor (gas), the measured value of the temperature measuring device is compared with the measured value of the third regulator, and when the temperature difference becomes smaller than a predetermined set value, the set temperature of the fourth regulator that controls the temperature of the fourth heater that heats the solid material container that supplies gas is lowered. This makes it possible to suppress an excessive rise in temperature of the solid material in the solid material container. The predetermined set value is not particularly limited, and can be appropriately selected depending on the type of solid material, the size (volume) of the solid material container, and the like.

[0053] In the following, the case of the solid material container 11 will be described as an example. Specifically, when the difference (Td-Tm) between the temperature (Tm) measured by the temperature measuring device T11 provided in the solid material container 11 and the temperature (Td) measured by the third regulator that controls the temperature of the third heater H11a that heats the downstream connecting pipe 11a connected to the solid material container 11 becomes 5°C or less, the set temperature of the fourth regulator that controls the temperature of the fourth heater H11 that heats the solid material container 11 is lowered by 5°C. This makes it possible to prevent the solid material S in the solid material container 11 from overheating. The same control is performed for the solid materials 12 and 13.

[0054] (6) Measures to prevent uneven wear between solid material containers In the solid material supply method of this embodiment, when any one or more of the following (g) to (k) apply, among the collection vessels supplying solid material vapor (gas), the set temperatures of the solid material vessel with the lowest temperature, the solid material vessel with the fastest temperature decrease rate, the solid material vessel with the lowest pressure, the solid material vessel with the fastest pressure decrease rate, and the solid material vessel with the slowest weight decrease rate are raised and heated. This makes it possible to suppress uneven consumption between the solid material vessels connected to the same collection vessel. (g) In a gas supply collection vessel, the temperatures in all solid material vessels are compared and the difference between the lowest and highest temperatures is greater than a predetermined set value. (h) In a gas supply collection vessel, the temperature decrease rates of all solid material vessels are compared, and the difference between the highest and lowest temperature decrease rates is greater than a predetermined set value. (i) In a gas supply collecting vessel, the measurements of the third pressure gauges of all solid material vessels are compared and the difference between the lowest and highest pressure values ​​is greater than the specified set value. (j) In a gas supply collection vessel, the pressure reduction rates of all solid material vessels are compared and the difference between the highest and lowest pressure reduction rates is greater than a specified set value. (k) In a gas supply collection vessel, the weight loss rates of all solid material vessels are compared, and the difference between the highest and lowest weight loss rates is greater than a predetermined set value.

[0055] In the above (g) to (k), the predetermined set values ​​are not particularly limited, and can be appropriately selected depending on the type of solid material, the size (volume) of the solid material container, and the like.

[0056] The following describes the case where the collection container 1 is controlled as an example. Specifically, the following controls (g) to (k) are performed.

[0057] (g) For the solid material containers 11, 12, 13 connected to the collecting pipe 10, the temperatures measured by the temperature measuring devices T11, T12, T13 installed in each are compared, and if the difference (Tmh-Tml) between the highest container temperature (Tmh) and the lowest container temperature (Tml) is 5°C or more, the set temperature of the fourth regulator (not shown) that controls the temperature of the fourth heater that heats the solid material container showing the lowest temperature is increased by 5°C.

[0058] (h) The rates of temperature decrease measured by temperature measuring devices T11, T12, T13 installed in the solid material containers 11, 12, 13 connected to the collecting pipe 10 are compared, and if the difference (ΔTmh-ΔTml) between the largest temperature decrease rate (ΔTmh) and the smallest temperature decrease rate (ΔTml) is 5% or more larger, the set temperature of the fourth regulator (not shown) that controls the temperature of the fourth heater that heats the solid material container showing the largest temperature decrease rate is increased by 5°C.

[0059] (i) For the solid material containers 11, 12, 13 connected to the collecting pipe 10, the values ​​of the third pressure measuring devices P11a, P12a, P13a provided on the respective downstream connecting pipes 11a, 12a, 13a are compared, and if the difference (Pdh-Pdl) between the highest pressure (highest downstream connecting pipe pressure: Pdh) and the lowest pressure (lowest downstream connecting pipe pressure: Pdl) is greater than 30%, the set temperature of the fourth regulator (not shown) that controls the temperature of the fourth heater that heats the solid material container showing the lowest pressure is increased by 5°C.

[0060] (j) For the solid material containers 11, 12, 13 connected to the collecting pipe 10, the pressure decrease rates of the third pressure measuring devices P11a, P12a, P13a installed on the respective downstream connecting pipes 11a, 12a, 13a are compared, and if the difference (ΔPdh-ΔPdl) between the largest pressure decrease rate (ΔPdh) and the smallest pressure decrease rate (ΔPdl) is 30% or more larger, the set temperature of the fourth regulator (not shown) that controls the temperature of the fourth heater that heats the solid material container showing the largest pressure decrease rate is increased by 5°C.

[0061] (k) The weight loss rates of the weight measuring devices W11, W12, and W13 respectively installed on the solid material containers 11, 12, and 13 connected to the collecting pipe 10 are compared, and if the difference (ΔWth-ΔWtl) between the largest weight loss rate (ΔWth) and the smallest weight loss rate (ΔWtl) is 30% or more larger, the set temperature of the fourth regulator (not shown) that controls the temperature of the fourth heater that heats the solid material container showing the smallest weight loss rate is increased by 5°C.

[0062] In the solid material supplying method of this embodiment, the indices used when carrying out the above-mentioned controls (1) to (6) are shown in Table 1 below.

[0063] [Table 1]

[0064] Moreover, in the solid material supplying method of this embodiment, an example of threshold values ​​and set values ​​when performing the above-mentioned controls (1) to (6) is shown in Table 2 below.

[0065] [Table 2]

[0066] As described above, the solid material supplying apparatus 500 and the solid material supplying method of this embodiment are configured to include the solid material containers 11, 12, and 13 filled with the solid material S, the piping (connecting piping 11a, 11b, 12a, 12b, 13a, and 13c, the collecting piping 10, and the connecting piping 100) connecting these solid material containers to the reactor, the first to fourth heaters and the first to fourth regulators for keeping them at predetermined temperatures, measuring instruments for measuring the temperature, pressure, and weight at each location, and a controller for feedback control of the entire operation. The pressure difference, temperature difference, and weight change rate at each location are calculated, and the heaters at each location are appropriately controlled based on the results. Therefore, a predetermined flow rate of vapor (gas) of the solid material S can be stably supplied for a long time without causing problems such as solidification in any of the piping, and without using a carrier gas.

[0067] Furthermore, according to the solid material supplying apparatus 500 and the solid material supplying method of the present embodiment, precursor materials that are solid at standard temperature and standard pressure, such as inorganic metal chlorides and inorganic metal oxychlorides of germanium, gallium, aluminum, hafnium, tungsten, molybdenum, etc., can be stably supplied in a gaseous state to a reactor for a long period of time without using a carrier gas.

[0068] In the solid material supply device 500 of this embodiment, a pair of connecting pipes are provided in each solid material container, and each connecting pipe is further provided with an on-off valve, so that one connecting pipe can be used as a supply pipe for solid material gas by opening the on-off valve, and the other connecting pipe can be used as a reference pipe for comparison with the supply pipe by closing the on-off valve, thereby making it possible to prevent problems such as solidification of the solid material in the supply pipe.

[0069] The technical scope of the present invention is not limited to the above-described embodiment, and various modifications can be made without departing from the spirit of the present invention. EXAMPLES

[0070] The present invention will be described in more detail below using examples and comparative examples, but the present invention is not limited to these examples.

[0071] [Supply evaluation of molybdenum oxychloride] Using solid material supplying apparatus 500 shown in FIG. 1, the amount of gas supply by sublimation of molybdenum oxychloride powder as a solid material was evaluated. For the evaluation of the gas supply amount, a mass flow controller (hereinafter, referred to as "MFC") was installed at the end of the solid material supply device 500, and the supply of the solid material was stopped when the measured actual gas flow rate fell below the set value of the MFC. The duration of the supply of the solid material from the point at which the supply was stopped was defined as the supplyable time. Furthermore, the weight loss of each solid material container was measured, and the material consumption rate relative to the total supply amount and the total filled amount was calculated.

[0072] <Comparative Example 1> In the solid material supplying apparatus 500 shown in FIG. 1, the fourth heater H11 of the solid material container 11 was operated "without feedback control" to evaluate the gas supply amount. The details of the supply conditions are as follows:

[0073] (Supply conditions) Filling material: Molybdenum oxychloride Total filling amount: 1000g Heater temperature: solid material container 11: 145°C, connecting pipes 11a and 11b: 155°C, collecting pipe 10: 155°C ·MFC setting flow rate: 200sccm Exhaust pressure: 20 torr -Fourth heater: No feedback control

[0074] (Process) First step: The solid material supply container 11 and the pipes 11a, 11b, 10, and 100 are evacuated to a vacuum. Second step: The solid material supply container 11 and the pipes 11a, 11b, 10, and 100 are heated. Third step: Set the MFC supply flow rate to 200 sccm. · Fourth step: The exhaust pressure is controlled at 20 Torr. Fifth step: Transport of solid material vapor from the solid material supply vessel 11 is started. · Sixth step: When the flow rate of the MFC falls below 190 sccm, the supply of solid material vapor is stopped.

[0075] (Evaluation Results) ·Supply time: 280min Total supply: 497g ·Material consumption rate: 50%

[0076] Table 3 shows the details of the supply conditions and the evaluation results.

[0077] [Table 3]

[0078] FIG. 3 is a diagram showing the relationship between the temperature (Tm) measured by the temperature measuring device T11 and the flow rate in the solid material supply container 11 of Comparative Example 1, and the relationship between the value (Pu) of the third pressure measuring device P11b provided in the upstream connecting pipe 11b and the value (Pd) of the third pressure measuring device P11a provided in the downstream connecting pipe 11a and the flow rate.

[0079] 3, in Comparative Example 1, immediately after the start of the test, the temperature Tm in the solid material supply container 11 dropped rapidly, and the pressures Pu and Pd in ​​the connecting pipes 11a and 11b also dropped accordingly. After that, both the temperature and pressure in the solid material supply container 11 continued to decrease and did not stabilize.

[0080] In Comparative Example 1, as the solid material S sublimated, the material temperature decreased due to the latent heat of sublimation. However, the heat input from the fourth heater H11 that heats the solid material supply container 11 was insufficient, which caused the temperature and supply pressure of the solid material S to decrease, which is thought to have led to a decrease in the flow rate at an early stage.

[0081] <Example 1> In the solid material supplying apparatus 500 shown in FIG. 1, the fourth heater H11 of the solid material container 11 was operated with "feedback control" and the gas supply amount was evaluated. Other supply conditions and process details are the same as those in Comparative Example 1.

[0082] (Feedback control) The contents of the feedback control in the first embodiment are shown in Tables 4 and 5.

[0083] [Table 4]

[0084] [Table 5]

[0085] (Evaluation Results) Supply time: 535min Total supply: 950g ·Material consumption rate: 95%

[0086] Table 6 shows details of the supply conditions and evaluation results.

[0087] [Table 6]

[0088] FIG. 4 is a diagram showing the relationship between the temperature (Tm) measured by the temperature measuring device T11 and the flow rate in the solid material supply container 11 of Example 1, and the relationship between the value (Pu) of the third pressure measuring device P11b provided in the upstream connecting pipe 11b, and the value (Pd) of the third pressure measuring device P11a provided in the downstream connecting pipe 11a and the flow rate.

[0089] 4, in Example 1, immediately after the start of the test, the temperature Tm in the solid material supply container 11 dropped, but it was stabilized thereafter by feedback control. The pressures Pu and Pd in ​​the connecting pipes 11a and 11b also showed the same tendency as the temperature Tm in the solid material supply container 11, and the feedback control enabled the supply of a stable flow rate for a long period of time.

[0090] <Comparative Example 2> In the solid material supplying apparatus 500 shown in FIG. 1, the fourth heaters H11, H12, and H13 of the collection vessel 1 (solid material vessels 11, 12, and 13) were operated "without feedback control" to evaluate the gas supply amount. The details of the supply conditions are as follows:

[0091] (Supply conditions) Filling material: Molybdenum oxychloride Total filling amount: 3000g (each solid material supply container filling amount: 1000g) Heater temperature: solid material containers 11, 12, 13... 145°C, connecting pipes 11a, 11b, 12a, 12b, 13a, 13b... 155°C, collective pipe 10... 155°C ·MFC setting flow rate: 600sccm Exhaust pressure: 20 torr -Fourth heater: No feedback control

[0092] (Process) First step: each solid material supply container and each pipe are evacuated. Second step: Each solid material supply container and each pipe are heated. Third step: Set the MFC supply flow rate to 600 sccm. · Fourth step: The exhaust pressure is controlled at 20 Torr. - Fifth step: Starting the transportation of solid material vapor from each solid material supply vessel. · Sixth step: When the flow rate of the MFC falls below 580 sccm, the supply of solid material vapor is stopped.

[0093] (Evaluation Results) ·Supply time: 192min Total supply: 1022g (Container 11: 432g, Container 12: 208g, Container 13: 382g) ·Material consumption rate: 34%

[0094] Table 7 shows details of the supply conditions and evaluation results.

[0095] [Table 7]

[0096] FIG. 5 is a diagram showing the relationship between the temperature (Tm) measured by the temperature measuring device T11 and the flow rate in the solid material supply container 11 of Comparative Example 2, and the relationship between the value (Pu) of the third pressure measuring device P11b provided in the upstream connecting pipe 11b, and the value (Pd) of the third pressure measuring device P11a provided in the downstream connecting pipe 11a and the flow rate. FIG. 6 is a graph showing the relationship between the temperature (Tm) measured by the temperature measuring device T12 and the flow rate in the solid material supply container 12 of Comparative Example 2, and the relationship between the value (Pu) of the third pressure measuring device P12b provided in the upstream connecting pipe 12b and the value (Pd) of the third pressure measuring device P12a provided in the downstream connecting pipe 12a and the flow rate. Furthermore, Figure 7 is a diagram showing the relationship between the temperature (Tm) measured by the temperature measuring device T13 and the flow rate in the solid material supply container 13 of Comparative Example 2, and the relationship between the value (Pu) of the third pressure measuring device P13b provided in the upstream connecting pipe 13b and the value (Pd) of the third pressure measuring device P13a provided in the downstream connecting pipe 13a and the flow rate.

[0097] 5 to 7, in Comparative Example 2, immediately after the start of the test, the temperature Tm in each of the solid material supply containers 11, 12, and 13 dropped rapidly, and the pressures Pu and Pd in ​​the connecting pipes also dropped accordingly. After that, both the temperature and pressure in the solid material supply containers 11 to 13 continued to decrease and did not stabilize.

[0098] In Comparative Example 2, the temperature inside each solid material supply container and the pressure in the connecting pipe also varied, and it is presumed that the amount of vaporization from each container was not uniform. In addition, since the container with the lower temperature inside the container and the lower pressure in the connecting pipe had a higher material consumption rate, it is presumed that the one-sided flow occurred between the containers, resulting in a lower material consumption rate than that of the single solid material supply container in Comparative Example 1.

[0099] <Example 2> In the solid material supplying apparatus 500 shown in FIG. 1, the fourth heaters H11, H12, and H13 of the collection vessel 1 (solid material vessels 11, 12, and 13) were operated with "feedback control" and the gas supply amount was evaluated. Other supply conditions and process details are the same as those in Comparative Example 2.

[0100] (Feedback control) The details of the feedback control in the second embodiment are shown in Tables 8 to 10.

[0101] [Table 8]

[0102] [Table 9]

[0103] [Table 10]

[0104] (Evaluation Results) ·Supply time: 532min Total supply: 2835g (Container 11: 945g, Container 12: 943g, Container 13: 946g) ·Material consumption rate: 94%

[0105] Table 11 shows details of the supply conditions and evaluation results.

[0106] [Table 11]

[0107] FIG. 8 is a diagram showing the relationship between the temperature (Tm) measured by the temperature measuring device T11 and the flow rate in the solid material supply container 11 of Example 2, and the relationship between the value (Pu) of the third pressure measuring device P11b provided in the upstream connecting pipe 11b, and the value (Pd) of the third pressure measuring device P11a provided in the downstream connecting pipe 11a and the flow rate. FIG. 9 is a diagram showing the relationship between the temperature (Tm) measured by the temperature measuring device T12 and the flow rate in the solid material supply container 12 of Example 2, and the relationship between the value (Pu) of the third pressure measuring device P12b provided in the upstream connecting pipe 12b, and the value (Pd) of the third pressure measuring device P12a provided in the downstream connecting pipe 12a and the flow rate. Furthermore, Figure 10 is a diagram showing the relationship between the temperature (Tm) measured by the temperature measuring device T13 and the flow rate in the solid material supply container 13 of Example 2, and the relationship between the value (Pu) of the third pressure measuring device P13b provided in the upstream connecting pipe 13b and the value (Pd) of the third pressure measuring device P13a provided in the downstream connecting pipe 13a and the flow rate.

[0108] 8 to 10, in Example 2, immediately after the start of the test, the temperature Tm in each solid material supply container dropped, and the pressures Pu and Pd in ​​each connecting pipe dropped accordingly, but the temperature Tm in each container stabilized due to feedback control. The pressures Pu and Pd in ​​the connecting pipes also showed the same tendency as the temperature Tm in the container, and the material consumption rate of each container was almost constant, so that no one-sided flow occurred between the containers, and the material could be supplied at a stable flow rate for a long time. [Explanation of symbols]

[0109] 1,2...collection container 10 Collective piping 11,12,13...Solid material supply container 11a, 11b, 12a, 12b, 13a, 13b...Connecting piping 100···Crossover piping 500...Solid material feeding equipment H10: Second heater H11, H12, H13...4th heater H11a, H11b, H12a, H12b, H13a, H13b...Third heater H100: First heater P10: Second pressure measuring instrument P11a, P11b, P12a, P12b, P13a, P13b...Third pressure measuring instrument P100: First pressure measuring instrument S...Solid material T11,T12,T13...Temperature measuring device V11a, V11b, V12a, V12b, V13a, V13b...Shut-off valves W11,W12,W13...Weight measuring device

Claims

1. A solid material supplying device that supplies a gas produced by volatilization or sublimation of a solid material according to vapor pressure at room temperature and normal pressure (25°C, 1 atm), one or more collection containers; A connecting pipe that is connected to one or more of the collecting vessels, A first pressure measuring device located in the connecting pipe; A first heater that heats the connecting pipe; a first regulator that controls a temperature of the first heater; The collection vessel comprises one or more solid material vessels filled with the material therein; A pair of connecting pipes communicating with the solid material container; a collecting pipe connected to one or more of the solid material containers via a pair of the connecting pipes; A second pressure measuring device located in the collecting pipe; a second heater for heating the collecting pipe; a second regulator for controlling a temperature of the second heater; a third pressure measuring device located in each of the pair of connecting pipes; a third heater for heating each of the pair of connecting pipes; a third regulator that controls a temperature of the third heater; a fourth heater for heating the solid material container; a fourth regulator that controls a temperature of the fourth heater; a temperature measuring device for monitoring an internal temperature of the solid material container; and a weight measuring device for monitoring the weight of the solid material container. A solid material supply device, An on-off valve is located in each of the pair of connecting pipes, a solid material supplying device, wherein of the pair of pipes, one of the pipes in which the on-off valve is in a closed state is an upstream connecting pipe that does not supply the gas, and the other pipe in which the on-off valve is in an open state is a downstream connecting pipe that supplies the gas.

2. The solid material supplying device according to claim 1, further comprising a controller capable of transmitting and receiving electrical signals to and from the first to third pressure measuring devices, the first to fourth heaters, the first to fourth regulators, the temperature measuring device, and the weight measuring device.

3. A method for supplying a solid material, comprising the steps of: using the solid material supplying device according to claim 1 or 2; supplying a gas obtained by volatilizing or sublimating a solid material at room temperature and normal pressure (25° C., 1 atm) in accordance with a vapor pressure of the solid material; a pressure value of the third pressure gauge located on the upstream connecting pipe and a pressure value of the third pressure gauge located on the downstream connecting pipe in the solid material container that supplies the gas, and when a difference between the pressure values ​​reaches a predetermined threshold, a set temperature of the pair of connecting pipes is increased.

4. 4. The method for supplying a solid material according to claim 3, further comprising the steps of: comparing a pressure value of the second pressure gauge with a pressure value of the third pressure gauge located in the downstream connecting pipe in the collecting vessel for supplying the gas; and increasing a set temperature of the collecting pipe when a difference between the pressure values ​​reaches a predetermined threshold value.

5. 5. The method for supplying a solid material according to claim 3, further comprising the steps of: comparing a pressure value of the first pressure measuring device with a pressure value of the second pressure measuring device in the collection vessel that supplies the gas; and increasing a set temperature of the connecting pipe when a difference between the pressure values ​​reaches a predetermined threshold value.

6. The method for supplying a solid material according to any one of claims 3 to 5, further comprising increasing a set temperature of the solid material container for supplying the gas when any one or more of the following (a) to (f) is satisfied: (a) In the solid material container supplying the gas, the measurement value of the temperature measuring device is compared with the measurement value of the third regulator, and a temperature difference reaches a predetermined threshold value. (b) When the measurement value of the temperature measuring device in the solid material container supplying the gas becomes smaller than a predetermined set value. (c) When the rate of decrease in the measurement value of the temperature measuring device in the solid material container supplying the gas becomes greater than a predetermined set value. (d) In the solid material container supplying the gas, either the pressure value of the third pressure measuring device located on the upstream connecting pipe or the pressure value of the third pressure measuring device located on the downstream connecting pipe becomes smaller than a predetermined set value. (e) In the solid material container supplying the gas, when either the pressure decrease rate of the third pressure measuring device located on the upstream connecting pipe or the pressure decrease rate of the third pressure measuring device located on the downstream connecting pipe becomes greater than a predetermined set value. (f) When the rate of decrease in the measurement value of the weight measuring device in the solid material container supplying the gas becomes smaller than a predetermined set value.

7. 7. The method for supplying a solid material according to claim 3, further comprising the steps of: comparing the measurement value of the temperature measuring device with the measurement value of the third regulator in the solid material container for supplying the gas; and lowering the set temperature of the solid material container for supplying the gas when a temperature difference between the temperature measuring device and the third regulator becomes smaller than a predetermined set value.

8. The method for supplying a solid material according to any one of claims 3 to 7, wherein, when any one or more of the following (g) to (k) apply, the set temperatures of the solid material container having the lowest temperature, the solid material container having the highest rate of temperature decrease, the solid material container having the lowest pressure, the solid material container having the highest rate of pressure decrease, and the solid material container having the lowest rate of weight decrease are increased among the collection containers for supplying the gas. (g) In the collection vessel supplying the gas, the temperatures in all the solid material vessels are compared, and the difference between the lowest and highest temperatures is greater than a predetermined set value. (h) In the collection vessel for supplying the gas, the temperature decrease rates of all the solid material vessels are compared, and the difference between the largest temperature decrease rate and the smallest temperature decrease rate is greater than a predetermined set value. (i) In the collection vessel that supplies the gas, the measurement values ​​of the third pressure measuring devices of all the solid material vessels are compared, and the difference between the lowest pressure value and the highest pressure value is greater than a predetermined set value. (j) In the collection vessel supplying the gas, the pressure reduction rates are compared for all the solid material vessels, and the difference between the largest pressure reduction rate and the smallest pressure reduction rate is greater than a predetermined set value. (k) In the collection vessel that supplies the gas, the weight loss rates of all the solid material vessels are compared, and the difference between the largest weight loss rate and the smallest weight loss rate is greater than a predetermined set value.

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