JP2020004592A - Formation device of solid electrolyte membrane and formation method of solid electrolyte membrane - Google Patents

Abstract

To provide a formation device of solid electrolyte membrane and a formation method of the solid electrolyte membrane enabling stable feeding of raw materials.SOLUTION: A heating unit heats each part to satisfy following conditions: a temperature of a first crude storage tank 11 is not more than a melting point of a first raw material; a temperature of an upstream part 12A in a first piping 12 is higher than the temperature of the first crude storage tank 11; a temperature of a downstream part 12B in the first piping 12 is not lower than the temperature of the first crude storage tank 11 and is lower than the temperature of the upstream part 12A; and a temperature of a vacuum chamber 10 is not lower than the temperature of the first crude storage tank 11 and is lower than the temperature of the downstream part 12B.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a solid electrolyte membrane forming apparatus for forming a solid electrolyte membrane applied to a secondary battery, and a solid electrolyte membrane forming method.

  Lithium secondary batteries are known as batteries configured to be able to charge and discharge using a reversible battery reaction. In a lithium secondary battery, an electrolyte located between a positive electrode and a negative electrode functions as a lithium ion conduction path. Since a solid electrolyte membrane, which is a solid electrolyte, is required to cover a substrate having fine irregularities, a film formation method using a chemical vapor deposition method has been proposed (for example, Patent Documents 1 and 2). See).

JP 2013-125750 A JP 2014-500401 A

By the way, in the film forming method described above, after sublimating the raw material solid in the container containing the raw material solid, the raw material gas generated by the sublimation is sent from the container to the vacuum chamber through a pipe, and the raw material solid is sublimated. The gas is mixed with another gas and reacted. However, the gas of the raw material sublimated in the container is likely to be solidified again before reaching the vacuum chamber, which causes clogging of the piping and stagnation of the raw material, thereby hindering stable supply of the raw material.
An object of the present invention is to provide a solid electrolyte membrane forming apparatus and a solid electrolyte membrane forming method that enable stable supply of raw materials.

  An apparatus for forming a solid electrolyte membrane for solving the above-mentioned problem includes a raw material tank containing an organolithium compound as a raw material, a mixing chamber for mixing a raw material gas and a raw material gas other than the gas, and a substrate. A vacuum chamber in which a film forming chamber to be accommodated is separated by a shower plate, and a pipe for communicating the source tank and the mixing chamber to send the source gas sublimated in the source tank to the vacuum chamber by the communication. And a heating unit for separately heating the raw material tank, the vacuum chamber, and the piping. The heating unit may be configured such that the temperature of the raw material tank is equal to or lower than the melting point of the raw material, the temperature of the upstream portion of the pipe is higher than the temperature of the raw material tank, and the temperature of the downstream portion of the pipe is the raw material. Each part is heated so that the temperature of the tank is equal to or higher than the temperature of the upstream portion, and the temperature of the vacuum chamber is equal to or higher than the temperature of the raw material tank and lower than the temperature of the downstream portion.

  A method for forming a solid electrolyte membrane for solving the above-mentioned problem is to store an organic lithium compound in a raw material tank as a raw material, heat the organic lithium compound at a melting point or lower, and store a substrate in a film formation chamber. The communication between the source tank and the mixing chamber, and after the communication between the mixing chamber and the film forming chamber, maintaining the pressure in the film forming chamber at or below the vapor pressure of the raw material; Flowing the raw material gas from the raw material tank toward the mixing chamber while sublimating the raw material solid in the raw material tank by decompression of the raw material tank by communication with the mixing chamber; and After mixing the gas with another source gas other than the gas, flowing the source gas from the mixing chamber to the film forming chamber, and heating the substrate to reach the substrate By causing thermal reaction charge includes forming a lithium compound film is a solid electrolyte film on the substrate. A pipe connecting the raw material tank and the mixing chamber includes an upstream portion and a downstream portion located on the mixing chamber side with respect to the upstream portion. And, by flowing the gas of the raw material toward the mixing chamber, the temperature of the upstream portion is higher than the temperature of the raw material tank, the temperature of the downstream portion is higher than the temperature of the raw material tank, and Lowering the temperature of the film forming chamber and the mixing chamber from the temperature of the raw material tank and lowering the temperature of the downstream part than the temperature of the raw material tank.

  In a supply system in which the raw material gas generated by sublimation is sent from the raw material tank to the pipe, the cross-sectional area of the flow path through which the raw material gas flows narrows sharply from the raw material tank, thereby reducing the raw material gas generated by sublimation. Solidifies (sublimates) again in the piping. In this regard, according to each of the above configurations, since the temperature of the upstream portion of the pipe is higher than the temperature of the raw material tank, solidification of the raw material is suppressed when the raw material gas flows from the raw material tank to the pipe. As a result, a stable supply of the raw material becomes possible.

  In the solid electrolyte membrane forming apparatus, the raw material is a first raw material, the raw material tank is a first raw material tank, the pipe is a first pipe, and an organic phosphate compound is used as a second raw material. A second raw material tank to be housed, and a second pipe that communicates the second raw material tank with the mixing chamber and sends the second raw material gas to the vacuum chamber as the other raw material gas, The heating section may heat the second raw material to 0 ° C. or higher in the second raw material tank. According to the solid electrolyte membrane forming apparatus, a lithium phosphate compound can be formed as the solid electrolyte membrane.

  In the solid electrolyte membrane forming apparatus, the raw material is a first raw material, the raw material tank is a first raw material tank, the pipe is a first pipe, and contains an organic lanthanum compound as a second raw material. A second raw material tank, a second pipe that communicates the second raw material tank with the mixing chamber and sends the second raw material gas to the vacuum chamber as the other raw material gas, and a third raw material tank. A third raw material tank containing an organic zirconium compound, and the third raw material tank and the mixing chamber being communicated with each other to send the third raw material gas as the other raw material gas to the vacuum chamber. Piping. The heating unit may be configured such that the temperature of the second raw material tank is equal to or lower than the melting point of the second raw material, the temperature of the third raw material tank is equal to or lower than the melting point of the third raw material, and the temperature of an upstream portion in the second pipe. Is higher than the temperature of the second raw material tank, the temperature of the upstream portion of the third pipe is higher than the temperature of the third raw material tank, and the temperature of the downstream portion of the second pipe is the second temperature. The temperature of the raw material tank is higher than the temperature of the upstream part of the second pipe, and the temperature of the downstream part of the third pipe is higher than the temperature of the third raw material tank and the upstream of the third pipe. Each part may be heated so as to satisfy the temperature below the part. According to the solid electrolyte membrane forming apparatus, a Li-La-Zr-O-based solid electrolyte membrane can be formed as the solid electrolyte membrane.

  The apparatus for forming a solid electrolyte membrane may further include an inert gas supply unit for flowing an inert gas together with the raw material gas from the upstream portion to the film forming chamber. According to the solid electrolyte membrane forming apparatus, since the addition of the inert gas for transporting the raw material is performed in the upstream portion, the raw material gas sublimated in the raw material tank is suppressed from being solidified again in the piping, and In addition, a stable flow rate of the raw material gas can be secured.

  The above-mentioned apparatus for forming a solid electrolyte membrane may further include an additional gas supply unit for directly flowing an additional gas into the film formation chamber for reforming the solid electrolyte membrane. According to the solid electrolyte membrane forming apparatus, the contact between the raw material gas and the additive gas before being mixed is suppressed, so that the mixing step and the reaction step for forming the solid electrolyte membrane are performed by the solid electrolyte. It can also be executed in an order suitable for film formation.

  In the solid electrolyte membrane forming apparatus, the upstream portion of the pipe may include a valve located at a boundary with a downstream portion of the pipe. The valve located at the boundary between the upstream portion and the downstream portion is opened when the temperature of the raw material tank is constant, so that the raw material gas before the raw material tank temperature becomes constant flows into the mixing chamber, and thus, Avoid excessive consumption of raw materials. Further, maintenance of each component such as a vacuum chamber and a pipe usually requires a valve to isolate the component from other components. It is preferable to provide two or more valves between the raw material tank and the vacuum chamber. A heat-resistant valve having a larger heat capacity than a pipe and a smaller cross-sectional area of a flow path than the pipe is preferably kept at a high temperature from the viewpoint of preventing the raw material gas from solidifying again. In this regard, in the above configuration, since the upstream portion having a higher temperature than the downstream portion is provided with a valve for separating the upstream portion and the downstream portion, the gas of the raw material sublimated in the raw material tank is further suppressed from solidifying again in the pipe. It will be possible.

FIG. 1 is a configuration diagram illustrating an apparatus configuration of a first embodiment of a solid electrolyte membrane forming apparatus. FIG. 4 is a configuration diagram illustrating a device configuration of a second embodiment of a solid electrolyte membrane forming device. The block diagram which shows the apparatus structure in the example of a change of the solid electrolyte membrane formation apparatus.

[First Embodiment]
Hereinafter, a first embodiment that embodies a solid electrolyte membrane forming apparatus and a solid electrolyte membrane forming method will be described with reference to FIG.

[Solid electrolyte membrane forming device]
As shown in FIG. 1, the apparatus for forming a solid electrolyte membrane includes a vacuum chamber 10, a first raw material tank 11, a second raw material tank 21, a first pipe 12, a second pipe 22, and a controller 50. The vacuum chamber 10 includes a film forming chamber 10A, a mixing chamber 10B, a mixing chamber heater 10C, and a film forming chamber heater 10F. The shower plate 10D divides the inside of the vacuum chamber 10 into a film forming chamber 10A and a mixing chamber 10B in a state where the film forming chamber 10A and the mixing chamber 10B communicate with each other.

  The film forming chamber 10A includes a stage heater 10E. The stage heater 10E mounts the substrate S carried into the vacuum chamber 10 so that the substrate S can be heated. The film forming chamber 10A is connected to a turbo pump P2. The exhaust port of the turbo pump P2 is connected to the rotary pump P1. The controller 50 drives the turbo pump P2 to cause the vacuum chamber 10 to reach a predetermined pressure. The pressure reached by the film forming chamber 10A and the mixing chamber 10B is lower than the lowest vapor pressure among the raw materials stored in the raw material tanks 11 and 21. The lowest vapor pressure of the raw materials stored in each of the raw material tanks 11 and 21 is, for example, 1 Pa.

The mixing chamber heater 10C heats the mixing chamber 10B to a predetermined temperature. The temperature of the film forming chamber 10A, the temperature of the mixing chamber 10B, and the temperature of the shower plate 10D may be different from each other or may be equal to each other.
The film forming chamber heater 10F is provided to suppress the unreacted source gas from being deposited in the vacuum chamber 10, and sets the temperature of the inner surface (wall) in the film forming chamber 10A to 50 ° C. or more and 300 ° C. or less, for example. Heat to 200 ° C.

  The film forming chamber 10A is connected to the additive gas pipe L5. The additional gas pipe L5 sends the additional gas directly to the film formation chamber 10A without passing the additional gas through the mixing chamber 10B. The additive gas is used to improve the membrane characteristics of the solid electrolyte membrane. The additive gas is, for example, ammonia gas. The valve V5 is located in the middle of the additive gas pipe L5. The controller 50 drives the valve V5 to supply and stop the additional gas.

  The stage heater 10E is a hot plate in which a sheath heater is embedded, and includes a temperature control sensor. The controller 50 supplies power to the stage heater 10E from a power supply to heat the substrate S to a reaction temperature. The reaction temperature promotes decomposition of the raw materials and promotes a reaction for forming a solid electrolyte membrane. The reaction temperature promotes the reaction between the organolithium compound and the organophosphate compound, for example. The reaction temperature is from 300 ° C. to 700 ° C., for example, 550 ° C. The heater 10F for heating the film formation chamber is provided to prevent the deposition of unreacted source gas, and the temperature is 50 ° C. or more and 300 ° C. or less, for example, 200 ° C.

  The first raw material tank 11 stores a solid of the first raw material. The solid of the first raw material is, for example, a solid of an organolithium compound. The organolithium compound contained in the first raw material tank 11 is solid in a standard state. The organic lithium compound contained in the first raw material tank 11 has, for example, a vapor pressure at 170 ° C. of 1 Pa or less. The controller 50 drives the first tank heater 13 to heat the first raw material stored in the first raw material tank 11.

  Examples of the organolithium compound include dipivaloylmethanathium lithium (Li (dpm): CAS registration number 22441-13-0), tertiary butoxylithium (LiOtBu: CAS registration number 1907-33-1), and trimethylsilyl amide lithium ( Li (tmSa): CAS registration number 4039-321).

  The vapor pressure of dipivaloylmethanatolithium is about 300 Pa at 230 ° C., about 20 Pa at 200 ° C., and about 1 Pa at 170 ° C. The melting point of dipivaloyl methanato lithium is 280 ° C. The vapor pressure of tertiary butoxylithium is about 10 Pa at 110 ° C. The melting point of tertiary butoxylithium is from 170 ° C to 205 ° C. The vapor pressure of lithium trimethylsilylamide is about 1 Pa at 82 ° C. The melting point of lithium trimethylsilylamide is 72 ° C.

  The first raw material tank 11 is connected to the first pipe 12. The introduction valve V12 is located near the entrance of the downstream portion of the first pipe 12. The derived heat-resistant valve V13 is located near the outlet of the first pipe 12.

  The first pipe 12 is connected to the mixing chamber 10B. The first pipe 12 is divided into an upstream portion 12A and a downstream portion 12B with the introduction valve V12 as a boundary. The upstream portion 12A includes an introduction valve V12. The controller 50 drives the introduction valve V12 to switch between the communication between the upstream portion 12A and the downstream portion 12B and the cutoff thereof.

  The inert gas pipe L1 is connected to the middle of the upstream portion 12A via the valve V11. The inert gas sends the gas of the first raw material sublimated in the first raw material tank 11 toward the mixing chamber 10B. The inert gas is, for example, nitrogen. The controller 50 drives the valve V11 to introduce and stop the inert gas.

  The apparatus for forming a solid electrolyte membrane includes a first upstream heater 14A and a first downstream heater 14B. The controller 50 constitutes a heating unit. The controller 50 drives the first upstream heater 14A to heat the upstream portion 12A. The controller 50 drives the first downstream heater 14B to heat the downstream portion 12B. The controller 50 raises the temperature of the upstream portion 12A higher than the temperature of the downstream portion 12B.

  The second raw material tank 21 stores the liquid of the second raw material. The liquid of the second raw material is, for example, a liquid of an organic phosphoric acid compound. The organic phosphoric acid compound contained in the second raw material tank 21 is a liquid in a standard state. The organic phosphoric acid compound is triethyl phosphate (TEP). The controller 50 drives the second tank heater 23 to heat the liquid of the second raw material stored in the second raw material tank 21 to 0 ° C. or higher and lower than the boiling point of the second raw material.

  The second raw material tank 21 is connected to the second pipe 22. The introduction valve V22 is located near the entrance of the downstream portion of the second pipe 22. The derived heat-resistant valve V23 is located near the outlet of the second pipe 22.

  The second pipe 22 is connected to the mixing chamber 10B. The second pipe 22 is divided into an upstream portion 22A and a downstream portion 22B with the introduction valve V22 as a boundary. The upstream portion 22A includes an introduction valve V22. The controller 50 drives the introduction valve V22 to switch between the communication between the upstream portion 22A and the downstream portion 22B and the cutoff thereof.

  The inert gas pipe L2 is connected to the middle of the upstream portion 22A via the valve V21. The inert gas sends the gas of the second raw material flowing from the second raw material tank 21 toward the mixing chamber 10B. The inert gas is, for example, nitrogen. The controller 50 drives the valve V21 to introduce and stop the inert gas.

  The solid electrolyte membrane forming apparatus includes a second upstream heater 24A and a second downstream heater 24B. The controller 50 drives the second upstream heater 24A to heat the upstream portion 22A. The controller 50 drives the second downstream heater 24B to heat the downstream portion 22B. The controller 50 heats the upstream portion 22A and the downstream portion 22B to different temperatures or the same temperature.

  The controller 50 inputs a detection result of the temperature of the stage heater 10E from a sensor included in the stage heater 10E. The controller 50 inputs the detection result of each temperature from the temperature sensor 3S which separately detects the temperature of the film forming chamber 10A and the temperature of the mixing chamber 10B. The controller 50 inputs the detection result of each temperature from the sensor 12S that separately detects the temperature of the first raw material tank 11, the temperature of the upstream portion 12A of the first pipe 12, and the temperature of the downstream portion 12B of the first pipe 12. I do. The controller 50 inputs the detection result of each temperature from the sensor 22S that separately detects the temperature of the second raw material tank 21, the temperature of the upstream portion 22A of the second pipe 22, and the temperature of the downstream portion 22B of the second pipe 22. I do.

The controller 50 outputs a control signal for setting the detection result of the sensor to the set temperature to the drive unit of the stage heater 10E, and causes the drive unit to output a drive signal of the stage heater 10E. The controller 50 outputs a control signal for setting the detection result of the temperature sensor 3S to the set temperature to the heater driving unit 3D, and causes the heater driving unit 3D to output a driving signal for the mixing chamber heater 10C and the film forming chamber heater 10F. .
The controller 50 outputs a control signal for setting the detection result of the temperature sensor 12S to the set temperature to the heater driving unit 12D, and sends the driving signal of the first tank heater 13 and the control signal of the first upstream heater 14A to the heater driving unit 12D. A drive signal and a drive signal for the first downstream heater 14B are output.
The controller 50 outputs a control signal for setting the detection result of the temperature sensor 22S to the set temperature to the heater driving unit 22D, and the driving signal of the second tank heater 23 and the second upstream heater 24A are supplied to the heater driving unit 22D. A drive signal and a drive signal for the second downstream heater 24B are output.

The set temperature of each unit stored in the controller 50 is a temperature for sublimating the solid of the first raw material and sending it as a gas, and vaporizing the liquid of the second raw material and sending it as a gas. The set temperature of each unit stored in the controller 50 satisfies the following conditions 1 to 4 in order to send the solid of the first raw material as a gas.
[Condition 1] The set temperature of the film forming chamber 10A and the set temperature of the mixing chamber 10B are equal to or higher than the set temperature of the first raw material tank 11 and lower than the set temperature of the downstream portion 12B.
[Condition 2] The set temperature of the first raw material tank 11 is equal to or lower than the melting point of the raw material, and is a temperature at which the raw material sublimates due to the communication between the mixing chamber 10B and the first raw material tank 11.
[Condition 3] The set temperature of the upstream portion 12A is higher than the set temperature of the first raw material tank 11.
[Condition 4] The set temperature of the downstream portion 12B is equal to or higher than the set temperature of the first raw material tank 11 and lower than the set temperature of the upstream portion 12A.

[Method of forming solid electrolyte membrane]
First, the controller 50 lowers the pressure of the vacuum chamber 10 to the vapor pressure of each raw material or less. When the first raw material is an organic lithium compound, the pressure in the vacuum chamber 10 is, for example, 1E-3 Pa. The controller 50 drives each of the heaters 10C, 10E, 10F, 13, 14A, 14B, 23, 24A, and 24B to maintain each section at the set temperature. At this time, the controller 50 drives each of the heaters 10C, 10E, 10F, 13, and 14A so that the above conditions 1 to 4 are satisfied. The apparatus for forming a solid electrolyte membrane stands by in the idle state by the above operation until the substrate S is carried into the vacuum chamber 10.

  The controller 50 places the substrate S on the stage heater 10E with the valves V12, V13, V22, and V23 closed. The controller 50 drives the stage heater 10E to keep the substrate S at the film forming temperature.

  The controller 50 drives the valves V12 and V13 to communicate the mixing chamber 10B with the first raw material tank 11, and then drives the valve V11 to start supplying the inert gas. Further, the controller 50 drives the valves V22 and V23 to make the mixing chamber 10B communicate with the first raw material tank 11, and then drives the valve V21 to start supplying the inert gas. Further, the controller 50 drives the valve V5 to start supplying the additive gas to the film formation chamber 10A.

  The communication between the first raw material tank 11 and the mixing chamber 10B sublimates the solid of the first raw material and sends the gas of the first raw material to the mixing chamber 10B. The communication between the second raw material tank 21 and the mixing chamber 10B vaporizes the liquid of the second raw material and sends the gas of the second raw material to the mixing chamber 10B. The inert gas supplied from the inert gas pipe L1 sends the gas of the first raw material to the mixing chamber 10B to stabilize the supply amount of the first raw material. The inert gas supplied from the inert gas pipe L2 also sends the gas of the second raw material to the mixing chamber 10B to stabilize the supply amount of the second raw material. Then, after the gas of the first raw material and the gas of the second raw material are mixed in the mixing chamber 10B, the mixed gas and the additional gas reach the surface of the substrate S, and a solid state is formed by a thermal reaction. An electrolyte membrane is formed.

  Here, when the gas of the first raw material generated by the sublimation is introduced from the first raw material tank 11 to the first pipe 12, the cross-sectional area of the flow path through which the gas of the first raw material flows is determined by the first raw material tank 11. Suddenly narrows. The first raw material gas generated by the sublimation is easily solidified in the upstream portion 12A of the first pipe 12. In this regard, if the configuration that satisfies the above condition 3, the temperature of the upstream portion 12A is higher than the temperature of the first raw material tank 11, that is, higher than the temperature at which the solid of the first raw material is sublimated. Therefore, in transporting the first raw material from the first raw material tank 11 to the first pipe 12, solidification of the first raw material is suppressed, and stable supply of the first raw material becomes possible.

Next, each test example using the solid electrolyte membrane forming apparatus will be described.
[Test Example 1]
Using dipivaloyl methanatolithium as the first raw material, triethyl phosphate as the second raw material, and setting the temperature of each part as follows so as to satisfy the above conditions 1 to 4, A film was formed. The film formation was repeated 10 times under the following conditions. As a result, the film formation rate was maintained at 100 nm / min, and a desired film structure was obtained as a solid electrolyte film in each case.
・ Set temperature of first raw material tank 11: 200 ° C
・ Set temperature of upstream section 12A: 260 ° C
・ Set temperature of downstream portion 12B: 240 ° C
・ Set temperature of the second raw material tank 21: 30 ° C
・ Set temperature of upstream section 22A: 50 ° C
・ Set temperature of downstream part 22B: 40 ° C
・ Set temperature of mixing chamber 10B: 200 ° C
・ Set temperature of film forming chamber 10A: 200 ° C
・ Set temperature of shower plate 10D: 200 ° C
・ Set temperature of substrate S: 550 ° C

[Test Example 2]
Film formation was performed under the same conditions as in Test Example 1 except that the following conditions in Test Example 1 were changed. That is, when a film was formed under the condition that the above conditions 3 and 4 were not satisfied, the film formation rate was 100 nm / min at the first time, but gradually decreased thereafter, and was 1 nm / min at the 50th time. . Further, solidification of the organolithium compound was recognized in the first pipe 12, and it was found that the first pipe 12 was clogged.
・ Set temperature of upstream section 12A: 180 ° C
・ Set temperature of downstream portion 12B: 160 ° C

[Test Example 3]
Film formation was performed under the same conditions as in Test Example 1 except that the following conditions in Test Example 1 were changed. That is, when the film was formed under the condition that the above condition 1 was not satisfied, the film formation rate was 100 nm / min at the first time, but gradually decreased thereafter, and was 1 nm / min at the 50th time. When the surface of the film structure was observed, it was confirmed that particles had adhered. In addition, solidification of the organolithium compound in the shower plate 10D was recognized, and it was recognized that the shower plate 10D was clogged.
・ Set temperature of shower plate 10D: 100 ° C

[Test Example 4]
Film formation was performed under the same conditions as in Test Example 1 except that the following conditions in Test Example 1 were changed. That is, when the film was formed under the condition that the above condition 1 was not satisfied, the film formation rate was 100 nm / min at the first time, but gradually decreased thereafter, and was 50 nm / min at the tenth time. Further, film formation of the lithium phosphate compound on the shower plate 10D was observed. It was recognized that the film was peeled off on the shower plate 10D, which caused the generation of particles.
・ Set temperature of shower plate 10D: 400 ° C

[Test Example 5]
Film formation was performed under the same conditions as in Test Example 1 except that the following conditions in Test Example 1 were changed. That is, when the film was formed under the condition that the above condition 4 was not satisfied, the film formation rate was 100 nm / min at the first time, but gradually decreased thereafter, and was 50 nm / min at the tenth time. Further, film formation of the lithium phosphate compound on the shower plate 10D was observed. It was recognized that the film was peeled off on the shower plate 10D, which caused the generation of particles.
・ Downstream part 12B: 300 ° C

As described above, according to the first embodiment, the following effects can be obtained.
(1) Since the heaters 10C, 10F, 13, 14A, 14B, 23, 24A, and 24B are driven so as to satisfy the above conditions 1 to 4, the gas of the raw material sublimated in the first raw material tank 11 is stable. Can be supplied.

  (2) When the temperature of the mixing chamber 10B is excessively high, the reaction between the gas of the first raw material and the gas of the second raw material proceeds in the mixing chamber 10B. On the other hand, when the temperature of the mixing chamber 10B is excessively low, the gas of the first raw material solidifies in the mixing chamber 10B. In this respect, if the configuration satisfies the above conditions 1 and 2, it is possible to suppress the reaction from proceeding in the mixing chamber 10B and the solidification of the first raw material in the mixing chamber 10B.

  (3) The addition of the inert gas for transporting the first raw material is performed in the upstream portion 12A. Therefore, it is possible to prevent the gas of the first raw material sublimated in the first raw material tank 11 from solidifying in the first pipe 12 and to secure a stable flow rate of the gas of the first raw material.

  (4) The additional gas is supplied to the film forming chamber 10A without passing through the mixing chamber 10B. Therefore, contact between the gas of the raw material before mixing and the additional gas is suppressed, and the mixing step and the reaction step for forming the solid electrolyte membrane can be performed in an order suitable for the formation of the solid electrolyte membrane. Also.

(5) The valves connected to the vacuum chamber 10, the pipes 12, 22 and the like are usually arranged in the middle of the pipes 12, 22. The valves V12 and V22 having a larger heat capacity than the respective pipes 12 and 22 are components that are difficult to change the temperature, and are also portions where the cross-sectional area of the flow path through which the raw material gas passes decreases. Therefore, from the viewpoint of suppressing the solidification of the raw material gas, it is preferable to maintain the temperature at a high temperature. In this regard, in the above configuration, the upstream portion 12A having a higher temperature than the downstream portion 12B includes the valve V12 that separates the upstream portion 12A from the downstream portion 12B. Therefore, the solidification of the first raw material gas sublimated in the first raw material tank 11 in the first pipe 12 can be further suppressed.
(6) The valve located at the boundary between the upstream portion 12A and the downstream portion 12B is opened when the temperature of the first raw material tank 11 becomes constant, so that the valve before the temperature of the first raw material tank 11 becomes constant. The gas of one raw material is prevented from flowing into the mixing chamber 10B, and the excessive consumption of the first raw material is suppressed.

[Second embodiment]
Hereinafter, a second embodiment that embodies a solid electrolyte membrane forming apparatus and a solid electrolyte membrane forming method will be described with reference to FIG. In the solid electrolyte membrane forming apparatus according to the second embodiment, the second raw material tank 21 stores the solid of the second raw material, and connects the third raw material tank and the third raw material tank to the mixing chamber 10B. A third pipe is provided. Therefore, in the following, the same components as those of the solid electrolyte membrane forming apparatus of the first embodiment are denoted by the same reference numerals, and description thereof is omitted, and the configuration different from that of the solid electrolyte membrane forming apparatus of the first embodiment will be omitted. This will be described in detail.

  The second raw material tank 21 stores the solid of the second raw material. The solid of the second raw material is, for example, a solid of an organic lanthanum compound. The organic lanthanum compound contained in the second raw material tank 21 is solid in a standard state. The organic lanthanum compound contained in the second raw material tank 21 has, for example, a vapor pressure at 180 ° C. of 1 Pa or less. The controller 50 drives the second tank heater 23 to heat the second raw material stored in the second raw material tank 21. The controller 50 drives the second upstream heater 24A and the second downstream heater 24B to heat the upstream portion 22A and the downstream portion 22B to different temperatures.

  The third raw material tank 31 stores a solid of the third raw material. The solid of the third raw material is, for example, a solid of an organic zirconium compound. The organic zirconium compound contained in the third raw material tank 31 is solid in a standard state. The organic zirconium compound contained in the third raw material tank 31 has, for example, a vapor pressure at 200 ° C. of 1 Pa or less.

  The third raw material tank 31 is connected to a third pipe 32. The introduction valve V32 is located near the entrance of the downstream portion of the third pipe 32. The derived heat-resistant valve V33 is located near the outlet of the third pipe 32.

  The third pipe 32 is connected to the mixing chamber 10B. The third pipe 32 is divided into an upstream portion 32A and a downstream portion 32B with the introduction valve V32 as a boundary. The upstream portion 32A includes an introduction valve V32. The controller 50 drives the introduction valve V32 to switch between the communication between the upstream portion 32A and the downstream portion 32B and the cutoff thereof.

  The inert gas pipe L3 is connected in the middle of the upstream portion 32A via a valve V31. The inert gas sends the gas of the third raw material sublimated in the third raw material tank 31 toward the mixing chamber 10B. The inert gas is, for example, nitrogen. The controller 50 drives the valve V31 to introduce and stop the inert gas.

  The apparatus for forming a solid electrolyte membrane includes a third upstream heater 34A and a third downstream heater 34B. The controller 50 drives the third upstream heater 34A to heat the upstream portion 32A. The controller 50 drives the third downstream heater 34B to heat the downstream portion 32B. The controller 50 raises the temperature of the upstream portion 32A higher than the temperature of the downstream portion 32B.

  The controller 50 inputs the detection result of each temperature from the sensor 32S that separately detects the temperature of the third raw material tank 31, the temperature of the upstream portion 32A of the third pipe 32, and the temperature of the downstream portion 32B of the third pipe 32. I do. The controller 50 outputs a control signal for setting the detection result of the temperature sensor 32S to the set temperature to the heater driving unit 32D, and sends the driving signal of the third tank heater 33 and the control signal of the third upstream heater 34A to the heater driving unit 32D. A drive signal and a drive signal for the third downstream heater 34B are output.

  The set temperature of each unit stored in the controller 50 is a temperature for sublimating the solid of each raw material and sending it as a gas. The set temperature of each unit stored in the controller 50 satisfies the following conditions 1 to 4 in order to send the solid of each raw material as a gas.

[Condition 1] The set temperatures of the film forming chamber 10A and the mixing chamber 10B are equal to or higher than the set temperatures of the raw material tanks 11, 21, 31 and lower than the set temperatures of the downstream portions 12B, 22B, 32B.
[Condition 2] The set temperature of each raw material tank 11, 21, 31 is lower than the melting point of the raw material stored in the raw material tank, and the raw material is sublimated by the communication between the mixing chamber 10 B and each raw material tank 11, 21, 31. Temperature.
[Condition 3] The set temperature of each upstream portion 12A, 22A, 32A is higher than the set temperature of the raw material tank to which the upstream portion is connected.
[Condition 4] The set temperature of each downstream portion 12B, 22B, 32B is equal to or higher than the set temperature of the raw material tank to which the downstream portion is connected and lower than the set temperature of the upstream portion to which the downstream portion is connected.

[Method of forming solid electrolyte membrane]
The controller 50 drives each of the valves V12, V13, V22, V23, V32, and V33 to separately communicate the mixing chamber 10B with each of the raw material tanks 11, 21, and 31, and then controls each of the valves V11, V21, and V31. To start supplying inert gas. Further, the controller 50 drives the valve V5 to start supplying the additive gas to the film formation chamber 10A.

  The communication between the first raw material tank 11 and the mixing chamber 10B sublimates the solid of the first raw material and sends the gas of the first raw material to the mixing chamber 10B. The communication between the second raw material tank 21 and the mixing chamber 10B vaporizes the solid of the second raw material and sends the gas of the second raw material to the mixing chamber 10B. The communication between the third raw material tank 31 and the mixing chamber 10B vaporizes the solid of the third raw material and sends the third raw material gas to the mixing chamber 10B. After the gas of the first raw material, the gas of the second raw material, and the gas of the third raw material are mixed in the mixing chamber 10B, the mixed gas and the additional gas reach the surface of the substrate S, As the thermal reaction proceeds, a solid electrolyte membrane is formed.

Next, a test example using the solid electrolyte membrane forming apparatus will be described.
[Test Example 6]
Using dipivaloylmethanatolithium as the first raw material, trisdipivaloylmethanatantane as the second raw material, tetrakisdipivaloylmethanatozirconium as the third raw material, oxygen as the additive gas, and the above conditions. The set temperature of each part was set as follows so as to satisfy the conditions 1 to 4, and a solid electrolyte membrane was formed. When film formation was performed 10 times under the following conditions, the film formation rates were all 100 nm / min or more, and the desired film structures were obtained in each case.
・ Set temperature of first raw material tank 11: 110 ° C
・ Set temperature of upstream section 12A: 260 ° C
・ Set temperature of downstream portion 12B: 240 ° C
-Set temperature of the second raw material tank 21: 240 ° C
・ Set temperature of upstream section 22A: 300 ° C
・ Set temperature of downstream portion 22B: 280 ° C
・ Set temperature of the third raw material tank 31: 240 ° C
・ Set temperature of upstream section 32A: 300 ° C
・ Set temperature of downstream portion 32B: 280 ° C
・ Set temperature of mixing chamber 10B: 240 ° C
・ Set temperature of film forming chamber 10A: 240 ° C
・ Set temperature of shower plate 10D: 240 ° C
・ Set temperature of substrate S: 750 ° C

As described above, according to the second embodiment, the following effects can be obtained in addition to the effects according to the above (1) to (6).
(7) By using an organic lanthanum compound and an organic zirconium compound as a raw material, a Li-La-Zr-O-based solid electrolyte membrane can be obtained.

Note that each of the above embodiments can be modified and implemented as follows.
-The upstream part 12A, 22A, 32A and the downstream part 12B, 22B, 32B may be separated by components other than a valve. For example, the portion where the upstream heater is disposed is the upstream portion, the portion where the downstream heater is disposed is the downstream portion, and the element that separates the upstream portions 12A, 22A and 32A from the downstream portions 12B, 22B and 32B is the upstream portion. It is also possible to embody a heater and a downstream heater.

  At this time, the number of valves located in the upstream portions 12A, 22A, 32A may be two or more, or the valve may be embodied in a configuration in which no valves are located in the upstream portions 12A, 22A, 32A. . Further, each of the valves V12, V22, and V32 can be located in the middle of the upstream portions 12A, 22A, and 32A.

  -The connection destination of the inert gas pipes L1, L2, L3 can be changed to each raw material tank. Further, the inert gas pipes L1, L2, L3 can be connected to each raw material tank in addition to each upstream pipe.

  As shown in FIG. 3, the solid electrolyte membrane forming apparatus includes the above-described vacuum chamber 10 as an electrolyte membrane forming chamber 65, and includes a transfer chamber 61, a substrate housing chamber 62, a heating chamber 63, and an electrode forming chamber 64. Further provisions are possible.

  The transfer chamber 61 is connected to a substrate accommodation chamber 62, a heating chamber 63, an electrode formation chamber 64, and an electrolyte film formation chamber 65, respectively. The controller 50 carries the substrate S housed in the substrate housing chamber 62 into the transfer chamber 61. The controller 50 transports the substrate S loaded into the transport chamber 61 in the order of the heating chamber 63, the electrolyte film forming chamber 65, and the electrode forming chamber 64 through transport by the transport chamber 61. Then, the controller 50 performs the heating by the heating chamber 63, the formation of the electrolyte membrane by the electrolyte membrane formation chamber 65, and the formation of the electrodes by the electrode formation chamber 64 on the substrate S in order.

  -The method of heating the vacuum chamber, the raw material tank, the upstream portion, and the downstream portion is not limited to the method of changing the power output to the heater based on the temperature detection result, for example, a predetermined power set for each unit. It can be embodied in a method of outputting to a heater.

  S: substrate, V5, V11, V12, V13, V21, V22, V23, V31, V32, V33 ... valve, 10 ... vacuum chamber, 10A ... film forming chamber, 10B ... mixing chamber, 10D ... shower plate, 11 ... 1 raw material tank, 12 ... first piping, 12A, 22A, 32A ... upstream portion, 12B, 22B, 32B ... downstream portion, 21 ... second raw material tank, 22 ... second piping, 31 ... third raw material tank, 32 ... Third pipe.

Claims (7)

A raw material tank containing an organic lithium compound as a raw material,
A mixing chamber for mixing a source gas and a source gas other than the gas, and a vacuum chamber in which a film formation chamber for accommodating the substrate is separated by a shower plate,
A pipe for communicating the raw material tank and the mixing chamber, and for sending the gas of the raw material sublimated in the raw material tank by the communication to the vacuum chamber,
The raw material tank, the vacuum chamber, and a heating unit for separately heating the piping,
The heating unit is
The temperature of the raw material tank is equal to or lower than the melting point of the raw material,
The temperature of the upstream portion of the pipe is higher than the temperature of the raw material tank,
The temperature of the downstream portion of the pipe is equal to or higher than the temperature of the raw material tank, and lower than the temperature of the upstream portion, and
An apparatus for forming a solid electrolyte membrane, wherein each part is heated so that the temperature of the vacuum chamber is equal to or higher than the temperature of the raw material tank and lower than the temperature of the downstream portion. The raw material is a first raw material,
The raw material tank is a first raw material tank,
The pipe is a first pipe,
A second raw material tank containing an organic phosphate compound as a second raw material,
A second pipe that communicates the second raw material tank with the mixing chamber and sends the second raw material gas to the vacuum chamber as the other raw material gas,
The heating unit is
The solid electrolyte membrane forming apparatus according to claim 1, wherein the second raw material is heated to 0 ° C or higher in the second raw material tank. The raw material is a first raw material,
The raw material tank is a first raw material tank,
The pipe is a first pipe,
A second raw material tank containing an organic lanthanum compound as a second raw material,
A second pipe that communicates the second raw material tank with the mixing chamber and sends the second raw material gas to the vacuum chamber including the second raw material gas as the other raw material gas;
A third raw material tank containing an organic zirconium compound as a third raw material,
A third pipe that communicates the third raw material tank and the mixing chamber and sends the third raw material gas to the vacuum chamber as the other raw material gas,
The heating unit is
The temperature of the second raw material tank is equal to or lower than the melting point of the second raw material,
The temperature of the third raw material tank is equal to or lower than the melting point of the third raw material,
The temperature of the upstream portion of the second pipe is higher than the temperature of the second raw material tank;
The temperature of the upstream portion of the third pipe is higher than the temperature of the third raw material tank;
The temperature of the downstream portion of the second pipe is equal to or higher than the temperature of the second raw material tank, and lower than the temperature of the upstream portion of the second pipe, and
The solid electrolyte membrane according to claim 1, wherein each part is heated such that a temperature of a downstream portion of the third pipe is equal to or higher than a temperature of the third raw material tank and lower than a temperature of an upstream portion of the third pipe. Forming equipment. The solid electrolyte membrane forming apparatus according to any one of claims 1 to 3, further comprising an inert gas supply unit configured to flow an inert gas together with the raw material gas from the upstream portion to the film forming chamber. The apparatus for forming a solid electrolyte membrane according to any one of claims 1 to 4, further comprising an additional gas supply unit configured to flow an additional gas that reacts thermally with the raw material directly into the film formation chamber. The solid electrolyte membrane forming apparatus according to any one of claims 1 to 5, wherein an upstream portion of the pipe includes a valve located at a boundary with a downstream portion of the pipe. Containing the organolithium compound as a raw material in a raw material tank, and heating the organolithium compound at a melting point or lower,
Accommodating the substrate in the film forming chamber;
After the communication between the raw material tank and the mixing chamber, and after the communication between the mixing chamber and the film forming chamber, to maintain the pressure in the film forming chamber below the vapor pressure of the raw material,
Flowing the gas of the raw material from the raw material tank toward the mixing chamber while sublimating the solid of the raw material in the raw material tank by decompression of the raw material tank by the communication between the raw material tank and the mixing chamber;
After mixing the raw material gas with a raw material gas other than the gas in the mixing chamber, flowing the raw material gas from the mixing chamber to the film forming chamber;
Forming a lithium compound film, which is a solid electrolyte film, on the substrate by heating the substrate to cause a thermal reaction of the raw material that has reached the substrate,
A pipe connecting the raw material tank and the mixing chamber includes an upstream portion, and a downstream portion located on the mixing chamber side with respect to the upstream portion,
By flowing the gas of the raw material toward the mixing chamber, the temperature of the upstream portion is higher than the temperature of the raw material tank, the temperature of the downstream portion is higher than the temperature of the raw material tank, and A temperature of the film forming chamber and the mixing chamber and a temperature of the raw material tank or higher and lower than a temperature of the downstream portion.

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