JP7610430B2 - Solid material supplying device and solid material supplying method - Google Patents

Description

The present invention relates to a solid material supply device and a solid material supply method.

In recent years, new film formation techniques using precursors that have not been used before are required to solve problems caused by the miniaturization and high integration of semiconductor devices. Conventionally, gaseous 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 pressure. Precursor materials that are solid at standard temperature and 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 must be sublimated prior to being introduced into the film formation chamber.

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, thereby supplying 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.

JP 2013-028854 A JP 2019-007073 A

However, in the technology disclosed in Patent Documents 1 and 2, the sublimation gas of the solid material is supplied to the film formation process chamber (reactor) together with the carrier gas, so 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, and 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 the concentration of the solid material entrained in the carrier gas gradually decreases. Therefore, the conventional technology had the problem of being unable to form a film with uniform properties.

The present invention has been made in consideration of the above circumstances, and aims to provide a solid material supplying device and a solid material supplying method that can stably supply solid materials under standard conditions for long periods of time without using a carrier gas.

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 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.
[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 normal 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 according to [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 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, when 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.
[8] The method for supplying a solid material 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] The method for supplying a solid material according to any one of [4] to [8], wherein, when any one or more of the following (g) to (k) apply, among the collection containers for supplying the gas, 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.
(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 gauges 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.

The solid material supply device and method of the present invention can stably supply solid materials under standard conditions for long periods of time without using a carrier gas.

1 is a system diagram showing a solid material supplying device according to an embodiment of the present invention; FIG. 2 is a block diagram for explaining the operation of a controller constituting the solid material supplying device of the present embodiment. FIG. 1 is a diagram showing the results of Comparative Example 1. FIG. 1 shows the results of Example 1. FIG. 13 is a diagram showing the results of Comparative Example 2. FIG. 13 is a diagram showing the results of Comparative Example 2. FIG. 13 is a diagram showing the results of Comparative Example 2. FIG. 13 shows the results of Example 2. FIG. 13 shows the results of Example 2. FIG. 13 shows the results of Example 2.

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.

<Solid material supply device>
First, a solid material supplying apparatus 500 shown in FIG. 1 will be described as an 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.

As shown in FIG. 1, the solid material supply device 500 of this embodiment is a device that supplies 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 pressure (25°C, 1 atm) according to the vapor pressure to a reactor.

The solid material supply device 500 of this embodiment includes collection containers 1 and 2, a transition pipe 100 that is connected to the collection containers 1 and 2, a first pressure measuring device P100 located in the transition pipe 100, a first heater H100 that heats the transition pipe 100, a first regulator (not shown) that controls the temperature of the first heater H100, and a controller (not shown).

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, it is preferable that the number of collection containers is three or less.

The collection vessel 1 has three solid material vessels 11, 12, and 13 filled with solid material S, a pair of connecting pipes 11a, 11b, 12a, 12b, and 13a, 13b that are connected to each solid material vessel, and a collection pipe 10 that is connected to the solid material vessels 11, 12, and 13 via each connecting pipe.

In the solid material supply device 500 of this embodiment, an example is described in which the collection container 1 has three solid material containers, but this is not limiting. The number of solid material containers may be one, or three or more. From the standpoint of controllability and the effects of malfunctions, it is preferable that the number of solid material containers be nine or less.

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.

The solid material S may include organic compounds, organometallic compounds, metal halides, metal oxyhalides, and compounds thereof, more specifically, inorganic metal compounds 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.

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 inside. 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.

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 top surface that is the opening of the container body.

The material of the solid material container 11 is not particularly limited, but a material with high thermal conductivity is preferable to improve the efficiency of heat transfer to the solid material S. Such materials include stainless steel, aluminum, silicon carbide, aluminum nitride, aluminum oxide, and silicon nitride.

In addition to heat transfer efficiency, the solid material container 11 may also require corrosion resistance and strength. If multiple properties are required for the solid material container 11, it may be configured by stacking multiple materials.

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.

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

The solid material container 11 is provided with a pair of connecting pipes 11a, 11b. The pair of connecting pipes 11a, 11b are also provided with on-off valves V11a, V11b, which can be adjusted to any opening degree from fully open (100% opening) to fully closed (0% opening) and can be remotely operated.

Of these pair of connecting pipes 11a, 11b, the one with the on-off valve V11a in the open state is the downstream connecting pipe 11a that supplies gas. In contrast, the other pipe with the on-off valve V11b in the closed state is the upstream connecting pipe 11b that is intended for pressure monitoring and does not supply gas.

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 instrument 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.

In the solid material supply device 500 of this embodiment, a configuration has been described in which a pair of connecting pipes provided in the solid material container each has a heater (third heater), but this is not limited to this. The pair of connecting pipes may also share one heater (third heater).

The collective pipe 10 is provided with a second pressure measuring device P10, a second heater H10 that heats the entire collective pipe 10, a second regulator (not shown) that controls the temperature of the second heater H10, and purging ports K and L.

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

The controller performs feedback control of the overall operation of the solid material supply device 500 of this embodiment. Specifically, as shown in FIG. 2, the controller is used to send control signals to all heaters (first to fourth heaters) and all temperature regulators (first to fourth regulators) individually provided in the connecting pipes, collective pipes, and crossover 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.

<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.

(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.

Next, when 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 are opened by remote control, so that the solid material vapor can be supplied to the use point.

Next, after the supply of 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 end the supply of solid material.

In addition to the normal operation control described above, the solid material supply method of this embodiment performs the following controls (1) to (6) using a controller (not shown) when certain conditions are met.

(1) Countermeasures against clogging of connecting pipes In the solid material supply method of this 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 for heating. 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.

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 the connecting pipes 11a, 11b from being blocked in the solid material container 11.
The solid material container 12 and the solid material container 13 are controlled in a similar manner.

(2) Countermeasures against clogging of the collecting pipe 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 the 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.

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.

(3) Measures against clogging of the connecting pipe In the solid material supply method of this embodiment, the pressure value of the first pressure gauge P100 is compared with the pressure value of the second pressure gauge 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 clogging of the connecting pipe 100.
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.

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 becomes 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 the collection container 2.

(4) Measures for Ensuring Vapor 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 supply 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 supply 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) In a solid material container supplying gas, the temperature measuring device reading becomes lower than the specified set value.
(c) In a solid material container supplying gas, the rate at which the temperature measurement value decreases becomes greater than a predetermined set value.
(d) In a solid material container supplying gas, when either the pressure value of a third pressure measuring device located on the upstream connecting pipe or the pressure value of a third pressure measuring device located on the downstream connecting pipe becomes smaller than a predetermined set value.
(e) In a solid material container supplying 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) In a solid material container supplying gas, if the rate of decrease in the measurement value of a weight measuring device becomes slower than a predetermined set value.

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.

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.

(a) If the temperature (material temperature inside the container: Tm) measured by the temperature measuring device T11 installed in the solid material container 11 is 15 degrees or more lower than 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.

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

(c) When the rate of decrease (ΔTm) of the temperature inside the solid material container 11 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.

(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 5% or more smaller 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.

(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.

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

(5) Measures against excessive temperature rise of solid material In the solid material supply method of this embodiment, in the solid material container that supplies the 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 the gas is lowered. This makes it possible to suppress excessive temperature rise 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.

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.

(6) Measures to prevent uneven consumption 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 collective containers supplying solid material vapor (gas), the set temperatures of the solid material container with the lowest temperature, the solid material container with the fastest temperature decrease rate, the solid material container with the lowest pressure, the solid material container with the fastest pressure decrease rate, and the solid material container with the slowest weight decrease rate are raised for heating. This makes it possible to prevent uneven consumption between solid material containers connected to the same collective container.
(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 largest and smallest temperature decrease rates is greater than a predetermined set value.
(i) In a gas supplying collection vessel, the measurement values of the third pressure measuring devices of all 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 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 predetermined 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 weight loss rate and the lowest weight loss rate is greater than a predetermined set value.

In the above (g) to (k), the predetermined set values are not particularly limited and can be selected appropriately depending on the type of solid material, the size (capacity) of the solid material container, etc.

The control of the collection container 1 will be described below as an example.
Specifically, the following controls (g) to (k) are performed.

(g) The temperatures measured by the temperature measuring devices T11, T12, and T13 installed in the solid material containers 11, 12, and 13 connected to the collective pipe 10 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), which controls the temperature of the fourth heater that heats the solid material container showing the lowest temperature, is increased by 5°C.

(h) The rate of temperature decrease measured by the temperature measuring devices T11, T12, T13 installed in each of the solid material containers 11, 12, 13 connected to the collecting pipe 10 is 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, the set temperature of the fourth regulator (not shown) that controls the temperature of the fourth heater that heats the solid material container that showed the largest temperature decrease rate is increased by 5°C.

(i) For the solid material containers 11, 12, 13 connected to the collective pipe 10, the values of the third pressure gauges P11a, P12a, P13a installed 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.

(j) For the solid material containers 11, 12, 13 connected to the collective pipe 10, the pressure reduction 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 reduction rate (ΔPdh) and the smallest pressure reduction rate (ΔPdl) is 30% or greater, the set temperature of the fourth regulator (not shown) that controls the temperature of the fourth heater that heats the solid material container that exhibits the largest pressure reduction rate is increased by 5°C.

(k) The weight loss rates of the weight measuring devices W11, W12, and W13 installed on the solid material containers 11, 12, and 13 connected to the collective 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 greater, the set temperature of the fourth regulator (not shown), which controls the temperature of the fourth heater that heats the solid material container that showed the smallest weight loss rate, is increased by 5°C.

In the solid material supply method of this embodiment, the indices used when performing the above-mentioned controls (1) to (6) are shown in Table 1 below.

In addition, in the solid material supply method of this embodiment, an example of threshold values and setting values when performing the above-mentioned controls (1) to (6) is shown in Table 2 below.

As described above, the solid material supply device 500 and the solid material supply method of this embodiment are configured to include solid material containers 11, 12, and 13 filled with solid material S, piping (connecting piping 11a, 11b, 12a, 12b, 13a, and 13c, collective piping 10, and crossover piping 100) connecting these solid material containers to the reactor, first to fourth heaters and first to fourth regulators for maintaining these at predetermined temperatures, measuring instruments for measuring the temperature, pressure, and weight at each location, and a controller for feedback control of the overall 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 solid material S can be stably supplied for a long time without using a carrier gas, without causing problems such as solidification in any of the piping.

In addition, according to the solid material supply device 500 and solid material supply method of this embodiment, solid precursor materials 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 to the reactor in a gaseous state for a long period of time without using a carrier gas.

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. Therefore, 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. This makes it possible to prevent problems such as solidification of the solid material in the supply pipe.

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.

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.

[Supply evaluation of molybdenum oxychloride]
The solid material supplying apparatus 500 shown in FIG. 1 was used to evaluate the amount of gas supply by sublimation of molybdenum oxychloride powder as a solid material.
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.

<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:

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

(Process)
First step: The solid material supply container 11 and each of 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 supply flow rate of the MFC to 200 sccm.
Fourth step: The exhaust pressure is controlled to 20 Torr.
Fifth step: Transport of solid material vapor from the solid material supply container 11 is started.
Sixth step: When the MFC flow rate falls below 190 sccm, the supply of solid material vapor is stopped.

(Evaluation Results)
・Supply time: 280min
Total supply: 497g
・Material consumption rate: 50%

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

Figure 3 also shows 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, the value (Pd) of the third pressure measuring device P11a provided in the downstream connecting pipe 11a, and the flow rate.

As shown in Figure 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 an accompanying drop in the pressures Pu and Pd in the connecting pipes 11a and 11b was also observed. After that, both the temperature and pressure in the solid material supply container 11 continued to decrease and did not stabilize.

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, which heats the solid material supply container 11, was insufficient, causing 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.

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.

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

(Evaluation Results)
Supply time: 535 min
Total supply: 950g
・Material consumption rate: 95%

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

Figure 4 also shows 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, the value (Pd) of the third pressure measuring device P11a provided in the downstream connecting pipe 11a, and the flow rate.

As shown in Figure 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 subsequently stabilized by feedback control. The pressures Pu and Pd in the connecting pipes 11a and 11b also showed a similar trend to the temperature Tm in the solid material supply container 11, and feedback control enabled a stable flow rate to be supplied for a long period of time.

<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:

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

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

(Evaluation Results)
・Supply time: 192min
Total supply amount: 1022 g (container 11: 432 g, container 12: 208 g, container 13: 382 g)
・Material consumption rate: 34%

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

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 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 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.

As shown in Figures 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 an accompanying drop in the pressures Pu and Pd in each of the connecting pipes was also confirmed. After that, both the temperature and pressure in the solid material supply containers 11 to 13 continued to decrease and did not stabilize.

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 containers with lower temperatures inside the containers and lower pressures in the connecting pipes had higher material consumption rates, it is presumed that one-sided flow occurred between the containers, resulting in a lower material consumption rate than the single solid material supply container in Comparative Example 1.

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" to evaluate the gas supply amount.
Other supply conditions and process details are the same as those in Comparative Example 2.

(Feedback Control)
The contents of the feedback control in the second embodiment are shown in Tables 8 to 10.

(Evaluation Results)
・Supply time: 532min
Total supply amount: 2835 g (container 11: 945 g, container 12: 943 g, container 13: 946 g)
・Material consumption rate: 94%

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

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.

As shown in Figures 8 to 10, in Example 2, immediately after the start of the test, the temperature Tm inside each solid material supply container dropped, and the pressures Pu and Pd in each connecting pipe dropped accordingly, but feedback control stabilized the temperature Tm inside each container. The pressures Pu and Pd in the connecting pipes also showed a similar trend to the temperature Tm inside the container, and the material consumption rate of each container was also almost constant, so no one-sided flow occurred between the containers and the material could be supplied at a stable flow rate for a long period of time.

1, 2... Collecting vessel 10... Collecting pipe 11, 12, 13... Solid material supply vessel 11a, 11b, 12a, 12b, 13a, 13b... Connecting pipe 100... Transition pipe 500... Solid material supply device H10... Second heater H11, H12, H13... Fourth 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 instrument V11a, V11b, V12a, V12b, V13a, V13b: Opening and closing valves W11, W12, W13: Weight measuring device

Claims (8)

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 . The solid material supply 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. 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. 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. 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 . 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. 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. 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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