JP6517518B2 - Organic compound precipitation method and apparatus therefor - Google Patents

Description

  The present invention relates to a crystal growth method, purification method and apparatus of organic compounds such as organic semiconductors used for organic EL and the like.

  With respect to organic compounds such as organic semiconductors, various methods for producing crystals such as single crystals having higher purity have been studied in order to significantly reduce the performance when the incorporation of a small amount of impurities is utilized as an electronic device.

  Conventionally, in order to purify an organic compound, the organic compound is dissolved in a solvent, and the desired organic compound is utilized by utilizing the difference in solubility of the organic compound in the solvent using physical changes in the solvent such as temperature difference and evaporation of the solvent. Methods have been used to precipitate as crystals. Moreover, the purification method by sublimation which cools and collects after sublimating an organic compound under reduced pressure using a heat source is also performed.

  Non-Patent Document 1 discloses a vacuum deposition method via an ionic liquid in which an organic semiconductor compound is heated by a laser to be sublimated, and the sublimed organic semiconductor compound is precipitated as a single crystal in an ionic liquid.

Y. Matsumoto, APPLIED PHYSICS LETTERS 101, 083303 (2012)

  However, according to the vacuum evaporation method through an ionic liquid disclosed in Non-Patent Document 1, only the limited organic semiconductor compound irradiated with the laser is heated and sublimated, so that the obtained crystal is difficult to analyze by an analyzer. It was so trace amount.

  Therefore, the present invention provides a method and apparatus for efficiently obtaining a large amount of organic compounds for industrial production in the method of purifying organic compounds required to have high purity such as organic semiconductors. As an issue.

[1] Namely, the present invention is, upper lid provided with a cavity in each heart, a vaporizing chamber which is formed by interposing been connecting member between the lower cover and the lower cover and the upper cover, before Symbol A step of vaporizing the organic compound placed on the lower lid, the organic compound placed on the annularly disposed placement portion being heated under reduced pressure by the heating device covering the vaporization chamber, and the vaporized organic compound A process of transporting a substance by an inert gas to a discharge section projecting from a part of the vaporization chamber located inside the annular ring of the mounting section, and filling the ionic liquid with which the discharge section contacts. A method of depositing an organic compound, comprising: a deposition step of depositing the organic compound from the ionic liquid in a deposition vessel.

[2] Then, the upper lid which is provided with cavities in each heart, a vaporizing chamber which is formed by interposing been connecting member between the lower cover and the lower cover and the upper cover, the annular to said lower cover And an organic compound placed on the mounting portion provided in the form of a vapor is heated and vaporized in a reduced pressure state by a heating device covering the vaporization chamber, and the vaporized organic compound is placed as described above. A transfer step of transferring by inert gas to a discharge part projecting linearly straight downward from a part of the vaporization chamber located on the inner side of the ring of the part, and a predetermined distance from the discharge part And a deposition step of depositing the organic compound from the ionic liquid in the deposition container filled with the ionic liquid.

  [3] Then, the inert gas flows downward from above in the vertical direction into the vaporization chamber, and the discharge part is linearly projected from the vaporization chamber in the downward direction from above in the vertical direction. The method for depositing an organic compound according to the above [1] or [2], which flows toward the discharge port of the above.

  [4] Then, using the ionic liquid discharged from the deposition vessel, there is a regeneration step of extracting a compound contained in the ionic liquid by another solvent and liquid-liquid extraction method to regenerate the ionic liquid. The organic compound precipitation method according to any one of the above [1] to [3].

[5] Then, it is heated by a heating device, and is formed of an upper lid and a lower lid provided with a cavity in the central portion respectively and a connecting member interposed between the upper lid and the lower lid, and the organic compound is placed A vaporization chamber having a placement portion annularly provided on the lower lid, and a portion linearly projecting vertically downward from a part of the vaporization chamber located inside the annular ring of the placement portion, An organic compound deposition apparatus comprising: a discharge part through which the organic compound passes; and a deposition container filled with an ionic liquid which is in contact with the discharge part.

[6] The end portion of the discharge port of the discharge part is made of a member having a lower thermal conductivity than the base side of the discharge part, which is the organic compound deposition apparatus according to the above [5].

[7] The organic compound deposition apparatus according to [5] or [6], further comprising an extraction device for mixing the ionic liquid discharged from the deposition container with another solvent.

  According to the present invention, it is possible to efficiently obtain a large amount of organic compounds such as organic semiconductors which are required to have high purity in order to industrially produce them in a purification method.

It is a conceptual diagram showing the organic compound precipitation device of a first embodiment of the present invention. It is a conceptual diagram which shows the organic compound precipitation apparatus of 2nd embodiment of this invention.

  Hereinafter, embodiments of the method for depositing an organic compound and the apparatus according to the present invention will be described in detail with reference to the attached drawings. Note that although the embodiments described below are specific examples preferable for practicing the present invention, various technical limitations have been made, but the present invention is intended to particularly limit the invention in the following description. It is not limited to this form unless otherwise specified. Moreover, the vertical up-down direction in description is the left-right direction in FIG. In addition, the notation showing a numerical range includes an upper limit and a lower limit.

  As shown in FIG. 1, the organic compound deposition apparatus E of the first embodiment of the present invention is a space formed by being surrounded by the upper lid 6, the lower lid 7 and the connecting member 8 heated by the heating device 2. The chamber 1, the discharge unit 3 protruding from the vaporization chamber 1, and the deposition container 4 filled with the ionic liquid IL in contact with the discharge unit 3 are provided.

  The vaporization chamber 1 is a space having a wall surface of a member heated by the heating device 2 and a mounting portion 71 on which the organic compound OC is mounted. In the first embodiment shown in FIG. 1, the vaporization chamber 1 is a space formed by interposing an annular coupling member 8 between the upper lid 6 and the lower lid 7 having a cavity at the center. The upper lid 6, the lower lid 7 and the connecting member 8 are members heated by the heating device 2, and the boundary between the upper lid 6, the lower lid 7 and the connecting member 8 with the vaporization chamber 1 corresponds to the wall surface of the vaporization chamber 1.

  The upper lid 6, the lower lid 7 and the connecting member 8 are provided so as to be separable. The upper lid 6 is provided with a substantially cylindrical cavity at the center, and a through hole for connecting a gas supply pipe P1 for supplying the gas supplied from the gas cylinder GB is provided on the upper surface thereof. The supplied gas can be sent to the central cavity. The lower lid 7 is provided with a cavity at its central portion, and on the upper surface thereof, a placement portion 71 for placing the organic compound OC as a raw material is provided in an annular recessed shape. In another embodiment, the mounting portion 71 may be a container of a separate member from the lower lid 7 if it does not fill the hollow of the central portion that opens to the vaporization chamber 1 and continues to the discharge portion 3. . A hollow discharge part 3 is connected to the hollow of the central part of the lower lid 7, and the organic compound OC as the raw material vaporized in the vaporization chamber 1 can be sent to the discharge part 3 by the gas from the gas cylinder GB. . The connecting member 8 is an annular member having a thickness in the vertical direction, and is connected to the upper lid 6 and the lower lid 7 so as to keep a constant distance between the lower surface side of the upper lid 6 and the upper surface side of the lower lid 7. Thus, the vaporization chamber 1 of a predetermined size is formed. The upper lid 6, the lower lid 7 and the connecting member 8 are preferably made of a material excellent in heat conduction, and specifically, preferably are inorganic materials such as metals such as stainless steel and copper, and glass. Although not shown, in order to maintain the airtightness of the vaporization chamber 1, it is preferable that a gasket having heat resistance be provided at the connecting portion such as the upper lid 6, the lower lid 7 and the connecting member 8.

  The heating device 2 is a member for heating the vaporization chamber 1 and the deposition container 4. In the first embodiment, the heating device 2 is formed of an electric heating member or the like whose temperature is separately controlled by a temperature control device (not shown), and is embedded in the heat retaining portion 5 made of a heat insulating material.

  The heating device 2 is provided to cover all or a part of the upper lid 6, the lower lid 7 and the connecting member 8 so as to cover the entire vaporization chamber 1. For this reason, when the organic compound OC which is a raw material in the vaporization chamber 1 is vaporized, it is deposited on and fixed to the wall of the vaporization chamber 1 without interfering with the flow of the vaporized organic compound OC. It is possible to suppress the decrease in the rate. The temperature control device 2 ′ is provided inside the heat insulating portion 5 made of a heat insulating material so as to cover the periphery of the deposition container 4, and the ionic liquid filled in the deposition container 4 via the deposition container 4. Temperature adjustments can be made to heat or cool the IL. By heating or cooling the ionic liquid IL, it is possible to control the solubility of the vaporized organic compound OC in the ionic liquid IL, so that the saturation degree and the deposition rate of the organic compound OC can be controlled. Depending on the type of organic compound to be purified, the contamination of impurities can be minimized. In addition, temperature control apparatus 2 'has only the function which only heats, and can also be provided integrally with the heating apparatus 2. As shown in FIG.

  The discharge part 3 is a member which is provided protruding from the vaporization chamber 1 and through which the vaporized organic compound OC passes. Since the discharge part 3 is hollow, the organic compound OC vaporized in the vaporization chamber 1 can pass through. In the first embodiment, the discharge unit 3 has a substantially cylindrical base 32 connected to the lower lid 7 and a substantially cylindrical discharge port 31 on the deposition container 4 side and smaller in diameter than the base 32. , Vertically downward from the vaporization chamber 1. The vaporized organic compound OC is discharged from the outlet 31 into the ionic liquid IL, dissolves, and becomes supersaturated to reach a dissolution equilibrium where repeated dissolution and precipitation occur. In this manner, the organic compound OC is precipitated as crystals such as single crystals, and the amount of precipitation increases inside the precipitation vessel 4. In the first embodiment, the discharge port 31 is embedded in and in contact with the ionic liquid IL, but in another embodiment, the end of the discharge port 31 and the liquid surface of the ionic liquid IL are in the same plane. It may be in contact so as to become, or a gap may be provided between the discharge port 31 and the liquid surface of the ionic liquid IL to separate a predetermined distance. When there is a gap between the outlet 31 and the liquid surface of the ionic liquid IL, the vaporized organic compound OC is crystallized and precipitated in the liquid surface or liquid of the ionic liquid IL.

  The discharge part 3 is preferably made of a material excellent in heat conduction, and specifically, is preferably a metal such as stainless steel or copper, or an inorganic material such as glass. Furthermore, in another embodiment, the end of the discharge port 31 in contact with the ionic liquid IL can be a member whose heat conduction is lower than that of the base 32 side. Thereby, even if the discharge part 3 is heated by the heating device 2 through the lower lid 7, the heat is hardly transmitted to the ionic liquid IL, so that the temperature of the ionic liquid IL can be controlled more precisely.

  The deposition container 4 is a member attached to the lower part of the lower lid 7 and filled with the ionic liquid IL. In the first embodiment, the deposition container 4 is a vertically long container having an opening at the top, the inside of which is filled with the ionic liquid IL, and the discharge port 31 of the discharge unit 3 is inserted. The deposition container 4 is preferably made of a material excellent in heat conduction, and specifically, preferably is an inorganic material such as a metal such as stainless steel or copper, or glass.

  The organic compound OC used in the present invention is an organic compound which sublimes from a solid to a gas, and an organic compound which evaporates from a liquid to a gas, and is an organic compound which can be vaporized by sublimation or evaporation. The organic compound OC is a raw material placed on the mounting portion 71 of the vaporization chamber 1 by being vaporized by being heated in the vaporization chamber 1 and deposited in the ionic liquid IL filled in the deposition vessel 4. The impurities contained in the organic compound OC are removed to increase its purity. Thus, as organic compound OC used for high purification, the organic semiconductor etc. which are used for organic EL, an organic field effect transistor, an organic solar cell, etc. are preferable. Specifically, as organic semiconductors, pentacene, anthracene, rubrene, tetracyanoquinodimethane <TCNQ>, oligothiophene compounds, phthalocyanine compounds, perylene compounds, tris (8-quinolinolato) aluminum <Alq3>, tetrathiafulvalene <TTF>, tetrathiafulvalene compounds, N, N′-diphenyl-N, N′-bis (3-methylphenyl) -1,1′-biphenyl-4,4′-diamine, bis (10-hydroxybenzo) [H] Quinolinato) beryllium complex, 1,3-bis [5- (p-tert-butylphenyl) -3,4-oxadiazol-2-yl] benzene and the like are preferable.

  The ionic liquid IL used in the present invention is a salt which exists in a liquid state at normal temperature of about 25 to 30 ° C. The ionic liquid IL is a non-volatile organic solvent and does not evaporate even when heated under reduced pressure, so it is very useful as a solvent for purification by precipitation of the organic compound OC by recrystallization. Specifically, as the ionic liquid IL, 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide <Emin / TFSI>, 1-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide BMIM / TFSI>, 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide <EMIM / TFSI>, 1-octyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide <OMIM / TFSI> And 3-methyl-1-propylpyridinium bis (trifluoromethylsulfonyl) imide and the like are preferable.

  The gas cylinder GB is a cylinder in which an inert gas such as nitrogen or argon is sealed, and is supplied to the vaporization chamber 1 through the connected gas supply pipe P1. Then, the inert gas supplied to the vaporization chamber 1 is discharged together with the vaporized organic compound OC through the discharge unit 3 into the ionic liquid IL filled in the deposition container 4. Then, the inert gas released from the liquid surface of the ionic liquid IL is drawn into the vacuum pump VP through the through hole provided in the lower lid 7 and the gas discharge pipe P2.

  FIG. 2 shows a second embodiment of the present invention. In the first embodiment shown in FIG. 1, in order to take out the organic compound OC deposited in the deposition container 4, it is necessary to disassemble and take out the organic compound deposition apparatus E, which is laborious. However, in the second embodiment, since the organic compound OC deposited in the deposition container 4 can be taken out without decomposing the organic compound deposition apparatus E, purification can be performed continuously, which is efficient.

  In the second embodiment, a solid-liquid separator SLS, an extraction device EE, and a solvent tank ST are added to the organic compound deposition device E. A mixture of the organic compound OC and the ionic liquid IL discharged from the organic compound precipitation device E is transferred to the solid-liquid separator SLS and separated into the solid organic compound OC and the liquid ionic liquid IL. The separated ionic liquid IL is transferred to the extraction device EE, and is stored in the solvent tank ST, such as hexane, benzene, toluene, and other solvents that are not the ionic liquid IL and the extraction device EE by the liquid-liquid extraction method Compounds such as the organic compound OC and impurities contained in the liquid IL are extracted into another solvent so that the ionic liquid IL can be reused. Thus, the regenerated ionic liquid IL can be sent to the deposition container 4 of the organic compound deposition apparatus E. Since the ionic liquid IL is non-volatile, it is difficult to carry out distillation for purification, and it is preferable to carry out by a liquid-liquid extraction method. The other solvent used for extraction is discharged from the extraction device EE and discarded or reused by distillation or the like.

  The solid-liquid separator SLS can use various devices such as a filter that separates solid and liquid by a filter or the like, and a centrifuge that separates solid and liquid by centrifugal force. In addition, in the extraction device EE, a heater and an indirect cooling device may be provided so as to adjust the temperature of the contents.

  The approximate members of the organic compound deposition apparatus E are the same as in the first embodiment. A significant difference from the first embodiment is that the lower lid 7 is provided with a liquid transfer line through which the ionic liquid regenerated from the extraction device EE is fed, and the organic compound OC and the ionic liquid are provided at the bottom of the deposition container 4 It is the point provided with the member which can discharge the mixture of IL. For other members, the members in the first embodiment can be used.

  And the organic compound precipitation method of this invention has vaporization process S1, conveyance process S2, and precipitation process S3, and demonstrates it below.

The vaporization step S1 is a step in which the organic compound OC placed in the vaporization chamber 1 is heated and vaporized in a reduced pressure state by the heating device 2 covering the vaporization chamber 1. In the first embodiment and the second embodiment, the vaporization chamber 1 is heated by reducing the pressure of the vaporization chamber 1 by the vacuum pump VP and heating the upper lid 6, the lower lid 7 and the connecting member 8 by the heating device 2. The organic compound OC, which is a raw material placed on the placement unit 71, is vaporized by sublimation or evaporation. The degree of vacuum of the vaporization chamber 1 is preferably adjusted to 10 ⁻³ to 10 ⁻¹ Torr, since the inert gas appropriately flows from the gas cylinder GB into the vaporization chamber 1. If the degree of vacuum of the vaporization chamber 1 is within this range, the upper lid 6, the lower lid 7, the connecting member 8 and the like can be heated within a durable range, and a sufficient amount of the vaporized organic compound OC is transported An inert gas can be introduced into the vaporization chamber 1. The degree of vacuum of the vaporization chamber 1 can be measured by connecting a pressure gauge (not shown) to the vaporization chamber 1 or the like.

  The transport step S2 is a step in which the vaporized organic compound OC is transported by the inert gas to the discharge unit 3 provided protruding from the vaporization chamber 1. In the present embodiment, the inert gas flowing into the vaporization chamber 1 from the upper portion of the vaporization chamber 1 is vertically directed toward the discharge port 31 of the discharge portion 3 attached to the lower lid 7 while entraining the vaporized organic compound OC. The vaporized organic compound OC is transported to the discharge port 31 of the discharge unit 3 by flowing linearly from the upper side to the lower side of the direction. In the first embodiment and the second embodiment, an organic compound vaporized around the flow path of the inert gas in the vaporization chamber 1 to cause the inert gas to flow linearly from the vaporization chamber 1 to the ionic liquid IL, among others. It is possible to transport to the ionic liquid IL without stagnation at the discharge part 3 while uniformly engulfing OC.

  The deposition step S3 is a step in which the organic compound OC is deposited from the ionic liquid IL in the deposition container 4 filled with the ionic liquid IL in contact with the discharge part 3. That is, the vaporized organic compound OC dissolves in the ionic liquid IL and becomes supersaturated, and reaches a dissolution equilibrium in which repeated dissolution and precipitation occur. In this manner, the organic compound OC is precipitated as crystals such as single crystals, and the amount of precipitation increases inside the precipitation vessel 4. Thereby, it is easy to grow a single crystal, and the degree of purification can be further improved. In the first embodiment and the second embodiment, the vaporized organic compound OC transported into the ionic liquid IL through the discharge unit 3 by the inert gas is initially dissolved in the ionic liquid IL, but the vaporized organic Since the compound OC is continuously transported into the ionic liquid IL and dissolution thereof reaches saturation, the organic compound OC which can not be dissolved completely in the ionic liquid IL is precipitated in the precipitation vessel 4 in the form of crystals such as single crystals. . Alternatively, the organic compound OC may be dissolved in the ionic liquid IL to a saturated or nearly saturated state in advance, and the organic compound OC may be precipitated as soon as the vaporized organic compound OC is transported into the ionic liquid IL. . The solubility and the deposition rate of the organic compound OC can be controlled to minimize impurities by heating or cooling the ionic liquid IL by means of a temperature control device 2 'around the deposition vessel 4 and controlling the temperature. Crystals can be precipitated.

  Furthermore, in the second embodiment shown in FIG. 2, not only the vaporization step S1, the transport step S2, and the precipitation step S3 but also the regeneration step S4 can be included. That is, the regeneration step S4 is a step of extracting the compound contained in the ionic liquid IL by another solvent and liquid-liquid extraction method using the ionic liquid IL discharged from the deposition container 4 to regenerate the ionic liquid IL. is there. In the second embodiment, the ionic liquid IL separated by the solid-liquid separator SLS dissolves the organic compound OC and the impurities. This ionic liquid IL is transferred to the extractor EE, and is an organic compound OC contained in the ionic liquid IL by a liquid-liquid extraction method in the extractor EE and other solvents that are not the ionic liquid IL such as hexane, benzene, toluene, etc. Extract compounds such as and impurities into other solvents. As a result, the ionic liquid IL is sent to the deposition container 4 of the organic compound deposition apparatus E and reused, since compounds such as the organic compound OC and impurities are completely or almost completely removed from the ionic liquid IL. Become.

  Purification experiment of organic compound OC was performed using the organic compound precipitation apparatus E of 1st embodiment. 100.5 mg of pentacene as an organic compound OC (reagent made by Sigma-Aldrich), 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide as an ionic liquid <Emin / TFSI> 3.0 ml (reagent made by Kanto Chemical Co., Ltd.) And argon was used as an inert gas.

After preparing pentacene and Emin / TFSI at predetermined positions, the pressure was adjusted to 10 ⁻² Torr by the vacuum pump VP. Then, argon is introduced into the vaporization chamber 1 at 1.0 mL / min, the upper lid 6, the lower lid 7 and the connecting member 8 are heated at 350 ° C. for 2 hours by the heating device 2, and the deposition container 4 is heated by the temperature control device 2 ′. Heated at 300 ° C. for 2 hours. Thereafter, the heating device 2 and the temperature control device 2 'were stopped and allowed to stand at room temperature.

  When the crystals deposited from the deposition vessel 4 were taken out, pentacene was recovered from the ionic liquid IL with a yield of 35%. Moreover, it adhered also to the discharge port 31 of the discharge part 3, and pentacene was collect | recovered from the discharge port 31 with 12.4% of yield. When the crystal structure of pentacene obtained from the ionic liquid IL is analyzed by XRD, only a single crystal is clearly purified as compared with the bulk phase pentacene as a raw material, and a crystal with high purity is obtained I found that.

DESCRIPTION OF SYMBOLS 1 ... Vaporization chamber 2 ... heating apparatus 2 '.. Temperature control apparatus 3 ... Discharge part 31 .. Discharge port 32 .. Base part 4 ... Deposition container 5 ... Thermal insulation part 6 ... Upper lid 7 lower lid 71 ··· Mounting portion 8 · · · Connecting member E · · · Organic compound deposition device OC · · organic compound IL · · ionic liquid VP · · vacuum pump GB · · · gas cylinder P1 · · · Supply pipe P2 · · · Gas discharge pipe SLS · solid-liquid separator EE · · extraction device ST · · solvent tank

Claims (7)

In a vaporization chamber formed of an upper cover, a lower cover, and a connecting member interposed between the upper cover and the upper cover and the lower cover each provided with a hollow in the central portion, the mounting being annularly provided on the lower cover A vaporizing step in which an organic compound placed in the mounting portion is heated and vaporized in a reduced pressure state by a heating device covering the vaporization chamber;
A conveying step in which the vaporized organic compound is conveyed by inert gas from a part of the vaporization chamber located inside the annular ring of the placing portion to a discharge portion projecting linearly downward vertically ;
And depositing the organic compound from the ionic liquid in the deposition container filled with the ionic liquid in contact with the discharge part. In a vaporization chamber formed of an upper cover, a lower cover, and a connecting member interposed between the upper cover and the upper cover and the lower cover each provided with a hollow in the central portion, the mounting being annularly provided on the lower cover A vaporizing step in which an organic compound placed in the mounting portion is heated and vaporized in a reduced pressure state by a heating device covering the vaporization chamber;
A conveying step in which the vaporized organic compound is conveyed by inert gas from a part of the vaporization chamber located inside the annular ring of the placing portion to a discharge portion projecting linearly downward vertically ;
2. A method of depositing an organic compound, comprising: a deposition container filled with an ionic liquid located at a predetermined distance from the discharge part, the deposition step of depositing the organic compound from the ionic liquid. The inert gas flows into the vaporization chamber downward from above in the vertical direction,
The organic compound deposition method according to claim 1, wherein the organic compound is deposited from the vertical direction from the upper side to the lower side toward the discharge port of the discharge part protruding linearly from the vaporization chamber. Using the ionic liquid discharged from the deposition container, the method includes a regeneration step of extracting a compound contained in the ionic liquid by another solvent and a liquid-liquid extraction method to regenerate the ionic liquid. The organic compound precipitation method in any one of Claim 1 to 3. It is heated by a heating device, and is formed of an upper lid, a lower lid, and a connecting member interposed between the upper lid and the upper lid and the lower lid each provided with a cavity in the central portion, an organic compound is placed and a circle is placed on the lower lid A vaporization chamber having a mounting portion provided annularly ;
A discharge portion which is vertically linearly protruded from a part of the vaporization chamber located inside the annular ring of the placing portion and through which the vaporized organic compound passes;
An organic compound deposition apparatus comprising: a deposition container filled with an ionic liquid with which the discharge unit comes in contact. The end portion of the discharge port of the said discharge part consists of a member whose heat conduction is lower than the base side of the said discharge part, The organic compound precipitation apparatus of Claim 5 characterized by the above-mentioned.   The organic compound deposition apparatus according to claim 5 or 6, further comprising an extraction device that mixes the ionic liquid discharged from the deposition container with another solvent.

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