KR101025046B1 - Sublimation refining apparatus and sublimation refining method using the same - Google Patents

Abstract

The present invention relates to a sublimation refining apparatus, which can more quickly obtain a purified material produced by a sublimation refining process to increase productivity, and to reduce the manufacturing cost by increasing the yield of the purified material. In addition, the phenomenon that occurs during the sublimation purification process can be effectively prevented.

Sublimation Refining Device, Outer Tube, Inner Tube, Heater, Connector, Separator

Description

Sublimation Purification Apparatus and Sublimation Purification Method Using the Apparatus {SUBLIMATION REFINING APPARATUS AND SUBLIMATION REFINING METHOD USING THE SAME}

The present invention relates to a sublimation refining apparatus and a sublimation refining method using the apparatus, and more particularly, to a sublimation refining apparatus and a sublimation refining method using the apparatus that can shorten the processing time and increase the yield in the sublimation refining process. .

In general, an organic light emitting diode (hereinafter referred to as an "organic EL element") is composed of a plurality of thin organic thin film layers between a large work function and a transparent anode and a low work function cathode metal. The emission principle of the organic EL device is that when a voltage is applied to the organic EL device in the forward direction, holes are injected into the organic layer from the anode electrode, electrons are injected from the cathode, and the holes and the electrons recombine in the emission layer to generate light. will be.

Such organic EL devices have all the characteristics of high-quality panels required in the information age, such as low power consumption, wide viewing angle, high speed response speed, and wide driving temperature range. In addition, the manufacturing process of the organic EL device is also relatively simple, which has the advantage of realizing a lower cost than the conventional flat panel display device.

By the way, the purity of the organic material is an important factor affecting the light emitting characteristics of the organic EL device. If impurities are mixed in the organic material, the impurities are trapped in the carrier or cause quenching, so that the luminescence intensity and luminous efficiency are lowered. Therefore, a process for reducing impurities by purifying organic materials is essential. As a method for purifying organic materials, a method of chemically recrystallization by a solvent and a method of purifying by sublimation using physical properties may be used.

The recrystallization method using the solvent has an advantage that the organic material can be purified in large quantities, but there is a problem that the solvent can penetrate into the organic crystal because the solvent is used. If a solvent enters into the organic crystal, the entered solvent acts as an impurity, which can lower the luminescence properties of the organic EL element.

The method of recrystallization by sublimation is a method of subliming and recrystallizing an organic material under vacuum, whereby most impurities in the organic material can be removed. Therefore, in recent years, the sublimation purification method is mainly used as a method for purifying organic materials for organic EL devices.

Sublimation purification method of the organic material as described above is "H. J. Wagner, el al., Jounal of Materials Science, 17, 2781, (1982). That is, a glass tube having a length of about 1 m is inserted into the copper tube for thermal conductivity, and a sample of the organic material to be purified is placed in one end region of the glass tube. Then, a heater is attached to surround the copper tube around the organic material sample, and the inside of the glass tube is maintained in a vacuum of about 200 Pa, and the sample in the glass tube is heated by the heater to sublimate the organic molecules of the sample. At this time, a temperature gradient is formed in the glass tube, and recrystallization proceeds while the vapor of organic molecules is cooled in the other end region of the glass tube. Thus, recrystallized organic crystals are generated in the other end region of the glass tube.

1 and 2 illustrate one example of a sublimation refining apparatus 50 according to the prior art. That is, the organic material (E) to be purified is introduced into one end of the glass tube 52 which is disposed horizontally with the ground, and the inside of the glass tube 52 is made into a vacuum, and the flowmeter 54 is partially opened to deactivate the inside of the glass tube 52. Create a flow of gas. The internal temperature of the glass tube 52 is heated to the sublimation temperature of the organic material E using the some heater 56. Then, a temperature gradient and a flow of an inert gas are formed in the glass tube 52, and the purified material sublimed from the organic material E to be purified is moved a predetermined distance toward the other end of the glass tube 52, and then the glass tube 52 Recrystallization proceeds by condensation at different locations in the furnace.

However, if the temperature of the condensed portion of the glass tube 52 corresponds to the melting point of the condensed purification material, the condensed purification material may be melted. As described above, when the purified material is melted with the condensation, it may flow down to the lower portion of the glass tube 52 and then flow to another portion of the glass tube 52. That is, the purified material of the organic material E is not generated in different portions of the glass tube 52 for each temperature region, but is highly likely to be mixed with each other inside the glass tube 52. Therefore, it is very difficult to obtain a desired refined material because the refined material of the organic material generated on one side of the glass tube 52 may be mixed with other materials generated on the other side of the glass tube 52, for example, impurities.

In order to prevent the above problem, conventionally, the operation temperature of the heater 56 may be adjusted so that the temperature of the glass tube 52 is lower than the melting point of the purified material. In addition, since the heater temperature cannot be adjusted to match the melting point, the time required to raise and lower the internal temperature of the glass tube 52 is increased. Therefore, the processing speed of the sublimation purification process is slowed down, thereby increasing the processing time of the sublimation purification process.

In addition, since the conventional sublimation refining apparatus 50 is condensed in a state where some of the refined substances are mixed in a plurality of different positions of the glass tube 52, respectively, in order to obtain a high-purity desired purified substance, a considerable amount of the mixed portion must be arbitrarily removed. do. That is, the condensed purification materials may be condensed in a partially overlapped state without being condensed in a precisely separated state inside the glass tube 52.

In order to obtain the desired purified material among the condensed purified materials, some material loss is inevitable since it is necessary to remove the overlapping portions of other purified materials and take only the desired purified materials, thereby subliming purification apparatus ( The yield of 50) becomes very low. In addition, since the operation of removing the mixed portion of the desired refined substance and other refined substances is subjectively conducted according to the judgment of the operator, it is difficult to define a standard of process and quality. In addition, several sublimation purification steps may be repeatedly performed to obtain purified materials of desired purity.

On the other hand, Figure 2 shows an example of the glass tube 52 according to the prior art. As described above, when the sublimation direction of the organic material E, the vacuum direction of the glass tube 52, and the advancing direction of the inert gas coincide, the unsublimed organic material E exerts a driving force at the moment when the organic material E is sublimed. The shock phenomenon of moving at any distance may occur. For this reason, there arises a problem that the unsublimed organic material (E) is mixed with the sublimed and refined purified material normally. This phenomenon occurs in proportion to the temperature of the region containing the organic material (E). Therefore, in order to prevent the above phenomenon, the glass tube 52 should be heated at the lowest possible temperature. However, lowering the temperature causes a problem that the processing time of the sublimation purification process becomes long.

An embodiment of the present invention provides a sublimation refining apparatus and a sublimation refining method using the apparatus capable of shortening the processing time of the sublimation refining process by performing the sublimation refining process at a very high temperature. .

In addition, an embodiment of the present invention provides a sublimation purification apparatus and a sublimation purification method using the apparatus that can improve the yield by preventing the purification materials produced by the sublimation purification process to mix with each other.

In addition, an embodiment of the present invention provides a sublimation refining apparatus and a sublimation refining method using the apparatus that can obtain a high purity purified material by preventing the occurrence of sputtering phenomenon during the sublimation purification process.

According to an embodiment of the present invention, an inner tube is vacuumed and a flow of inert gas flowing from the lower portion to the upper portion is formed therein, and a plurality of the inner tubes are arranged to be stacked in a vertical direction and are disposed below Inner tubes for condensing material sublimed from water at different temperature ranges to collect purified materials, and a plurality of heaters are provided at positions corresponding to the inner tubes to heat the inside of the inner tube to different temperatures. And a coupling mechanism provided between the inner tubes to detachably connect the inner tubes in a vertical direction, and a circumference of any one of the connecting mechanisms disposed on the lower inner surface of the inner tube or the lower side of the inner tube. Is provided along, and comprises a separation mechanism for separating the purified material condensed inside the inner tube for each inner tube It provides a sublimation purification apparatus.
Here, the heaters heat the inner tubes to a temperature capable of melting in the liquid state the purified substances condensed inside the inner tubes, respectively, and the separation mechanisms are used to purify the purified substances respectively inside the inner tubes. It is formed into a receiving structure.

That is, since the purification material condensed on each of the inner tubes is separately accommodated in the inside of the inner tubes by the separating mechanism, the problem of arbitrarily mixing the condensed purification materials can be solved. In addition, even when the condensed purification materials are melted, the molten purification materials may be separately accommodated in the inner tubes by the separation mechanism. Thus, the operating temperature of the heaters can be raised to a temperature above the melting point of the purifying materials. As such, when the operating temperature of the sublimation refining process is increased and the starting operating temperature is increased, the sublimation treatment process can be accelerated and the sublimation treatment time can be shortened.

In the center of the connecting mechanism may be formed a through hole penetrating in the vertical direction. In addition, the separation mechanism may be formed in a ring shape along the through hole of the connection mechanism.

Therefore, the sublimed material in the object to be processed may be elevated to the through hole and then flow into the inner tube disposed at the upper side through the separation mechanism. On the other hand, when the purified material condensed in each of the inner tube is collected in the liquid state, the purified material in the liquid state may be collected separately after flowing down to the site formed by the separation mechanism.

The separating mechanism may protrude obliquely upward from the lower inner surface of the inner tube or the connecting mechanism. In addition, a flow hole portion through which the material sublimated by the heaters may be formed in an upper portion of the separation mechanism. The separation mechanism as described above may be formed in any one shape of a conical protruding upward cone, a cone, a dome, or a funnel.

That is, the sublimed purification material may be guided to the flow hole along the inclined portion of the separation mechanism, and may be introduced into the inner tube through the flow hole. In addition, the molten purified material may be stably received between the inclined portion of the separation mechanism and the inner surface of the inner tube.

The workpiece is disposed in an inner tube of the lowest position among the inner tubes, and the heaters may be formed to provide a lower heating temperature to the inner tubes from the lower side to the upper side. Therefore, a temperature gradient may be formed inside the inner tubes to lower the internal temperature from the lower side to the upper side.

The heaters may heat the inner tube on which the workpiece is disposed to a temperature higher than the sublimation point of the refined substances, and heat the inner tubes above the melting temperature of the purified substances condensed on the inner tubes. Each can be heated. As described above, when the heating temperature of the heater is set to a high temperature at which the purified materials condensed on the inner tubes are melted, the sublimation in the inner tube may be actively performed, so that the progress of the sublimation purification process may be faster. have.

The inner tubes may include a first inner tube in which the object is disposed, a second inner tube communicatively stacked on an upper portion of the first inner tube, and a high temperature purified material condensed therein, the second inner tube A third inner tube communicatively stacked on an upper portion of the tube and condensed therein with a medium temperature purified material, and a fourth inner tube communicatively stacked on an upper portion of the third inner tube and a low temperature purified material condensed therein; It may include.

The to-be-processed object is an organic material, and the low temperature or the medium temperature purification material is at least one of a hole injection material, a hole transport material, an electron transport material, or a light emitting material. That is, the to-be-processed object may be an organic material serving as a main material of the organic EL device, and a medium-temperature purified material obtained from the third inner tube may be used for the organic EL device.

According to another aspect of the present embodiment, a first sublimation refining step of heating a to-be-processed object in a first inner tube to a first set temperature to sublimate a first sublimation material into a second inner tube in the to-be-processed object, wherein Heating the first sublimation material in a second inner tube to a second set temperature lower than the first set temperature to form a second sublimed material having a sublimation point lower than the second set temperature among the first sublimed materials. A second sublimation refining step of subliming the inside of the tube and condensing a high temperature purified material having a sublimation point higher than the second set temperature among the first sublimation material in a liquid state inside the second inner tube, the third Heating the second sublimation material in the inner tube to a third set temperature lower than the second set temperature to thereby produce a third sublimed material having a sublimation point lower than the third set temperature among the second sublimed materials. A third sublimation refining step of subliming into an inside of the secondary pipe and condensing a medium-temperature purified material having a sublimation point higher than the third set temperature among the second sublimation materials in a liquid state inside the third inner pipe, wherein the third sublimation purification step is performed. 4 The low temperature purifying material having a sublimation point higher than the fourth set temperature among the third sublimation materials by heating the third sublimation material in the inner tube to a fourth set temperature lower than the third set temperature. A fourth sublimation purification step of condensing in a liquid state inside the tube, and separating the second inner tube, the third inner tube and the fourth inner tube to remove the high temperature purified material, the medium temperature purified material, and the low temperature. It may include a sublimation purification method of the sublimation purification apparatus comprising a collection step of collecting each of the purified material of.

The first set temperature is a temperature above the sublimation point of the high, medium and low temperature purified material. The second set temperature is a temperature below the sublimation point of the hot purified material, and is a temperature above the sublimation point of the medium and low temperature purified materials. The third set temperature is a temperature equal to or lower than the melting point of the medium temperature purified material, and is equal to or higher than the sublimation point of the low temperature purified material. The fourth set temperature is a temperature below the melting point of the low temperature purified material.

Therefore, in the second inner tube, the third inner tube and the fourth inner tube, the purification materials corresponding to the temperature ranges of the heaters may be separated from each other in a molten state, whereby the second inner tube and the The internal temperature of the third inner tube and the fourth inner tube can be set sufficiently high to the melting point temperature of the purified material.

The sublimation purification apparatus according to the embodiment of the present invention and the sublimation purification method using the apparatus can set the internal temperature of the inner tube up to the melting point of the purified material condensed in each inner tube, so that the sublimation purification process is very high. It can be done at temperature. As described above, when the operating temperature of the sublimation refining process is increased, the processing speed of the sublimation refining process is increased, thereby shortening the processing time of the sublimation refining process and maximizing the productivity of the purified material.

In addition, the sublimation purification apparatus according to an embodiment of the present invention and the sublimation purification method using the apparatus, since the purified substances produced in the sublimation purification process is separated from each other inside the inner tube, the desired purification material is mixed with other unnecessary purification material The phenomenon can be fundamentally prevented. Therefore, the yield for the purified material of high purity can be greatly improved, thereby significantly reducing the number of treatments in the sublimation purification process, thereby reducing the manufacturing cost.

In addition, the sublimation purification apparatus according to the embodiment of the present invention and the sublimation purification method using the apparatus, because the inner tubes are arranged vertically in the vertical direction and the separation mechanism is disposed between the inner tubes, respectively, during the sublimation purification process It is possible to prevent the unsublimed material from the object to be boiled up to the upper inner tube. If the occurrence of the above-described phenomena is prevented, the phenomenon that the unsublimed material is optionally mixed with the purified material and lowers the purity of the purified material can be prevented.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention is not limited or limited by the embodiments. Like reference numerals in the drawings denote like elements.

3 is a schematic view showing a sublimation refining apparatus according to an embodiment of the present invention, Figure 4 is a view showing the main part of the sublimation purification apparatus shown in Figure 3, Figure 5 is a sublimation shown in Figure 4 A perspective view showing an inner tube, a connection mechanism, and a separation mechanism of a purification device. And, Figure 6 is a side view schematically showing the separation mechanism shown in Figure 5, Figure 7 is a state diagram showing the internal state of the inner tube when the sublimation purification apparatus shown in FIG.

4 and 5, the sublimation refining apparatus 100 according to an embodiment of the present invention includes an outer tube 110, an inner tube 120, 122, 124, 126, and a heater 130 ( 132, 134, 136, coupling mechanisms 140, 142, 144, and separation mechanisms 150, 152, 154.

The outer tube 110 is a hollow cylindrical member inside, it may be formed long in the vertical direction. A door (not shown) may be formed at a side of the outer tube 110 to insert or withdraw the inner tube 120, 122, 124, 126.

An inert gas inlet 110a through which an inert gas flows may be formed below the outer tube 110, and an inert gas outlet 110b through which the inert gas is discharged may be formed above the outer tube 110. Nitrogen gas is used as the inert gas, but is not limited thereto, and various inert gases may be used.

A gas supplier (not shown) may be connected to the inert gas inlet 110a to supply an inert gas to an external tube. A valve assembly may be provided between the inert gas inlet 110a and the gas supplier to regulate the supply and flow rate of the inert gas.

The inert gas outlet 110b may be connected to a vacuum pump 112 for forming the inside of the outer tube 110 in a vacuum state. A trap 114 may be provided between the inert gas outlet 110b and the vacuum pump 112 to remove impurities. That is, the trap 114 may prevent foreign substances from flowing into the vacuum pump 112 by removing the foreign substances from the inert gas discharged through the inert gas outlet 110b.

That is, the vacuum pump 112 may make the inside of the outer tube 110 into a vacuum state, and the gas supply and the valve assembly supply the inert gas to the inside of the outer tube 110 so that the lower side of the outer tube 110 is lowered. It is possible to form a fine pressure gradient upwards. Therefore, the sublimed material of the to-be-processed object E mentioned later can be raised from the lower side to the upper side along the flow of inert gas.

3 to 7, the inner tubes 120, 122, 124 and 126 are tubular members having an upper and a lower opening and a hollow inside, and a plurality of inner tubes 120, 122, 124 and 126. May be arranged to be stacked in the vertical direction. That is, the inner tubes 120, 122, 124 and 126 are vertically disposed in the vertical direction so that the opened upper and lower portions are connected in communication with each other.

Specifically, for example, the inner tubes 120, 122, 124, 126, the first inner tube 120, the upper portion of the first inner tube 120, the object (E) is disposed therein. The second inner tube 122, which is communicatively stacked on the second inner tube 122, and the high temperature purified substance A is condensed therein. It may include a third inner tube 124 to be condensed in, the fourth inner tube 126 is communicatively stacked on the upper portion of the third inner tube 124 and the low-temperature purified material C is condensed therein. .

The material (E) may be any material that can be purified by a sublimation refining process, and among them, organic materials and amine compounds used in organic EL devices are representative. Hereinafter, the to-be-processed object E is limited to the organic material used for organic electroluminescent element, and it demonstrates.

At least one of a high temperature refinement | purification substance (A), a medium temperature refinement | purification substance (B), or a low temperature refinement | purification substance (C) is a high purity organic material used for an organic EL element. Hereinafter, in the present embodiment, it will be described that the purified material (B) of medium temperature is a high purity organic material used for the organic EL device. The middle temperature refining material (B) is any one of a hole injection material, a hole transport material, an electron transport material or a light emitting material.

Meanwhile, since the inner tubes 120, 122, 124, and 126 are vertically disposed vertically and the flow of inert gas is formed in a direction opposite to gravity, the unsublimed material is removed from the object E. 튐 phenomena flowing into the upper inner tubes 120, 122, 124, 126 may be limited by the effect of gravity. Therefore, while the degree of vacuum in the inner tubes 120, 122, 124 and 126 is kept constant, contamination of the purification material (A) (B) (C) caused by the spalling phenomenon can be significantly reduced and high A large amount of the workpiece E can be sublimed and purified in a short time at temperature.

3 and 4, the heaters 130, 132, 134, and 136 correspond to the inner tubes 120, 122, 124, and 126 on the outside of the outer tube 110, respectively. It is provided with a plurality. These heaters 130, 132, 134, 136 may be formed to provide a lower heating temperature to the inner tubes 120, 122, 124, 126 from the lower side to the upper side. Therefore, a temperature gradient may be formed inside the inner tubes 120, 122, 124, and 126, the inner temperature of which decreases from the lower side to the upper side, and the temperature distribution formed is formed in the shape of a normal distribution curve. do.

Specifically, for example, the heaters 130, 132, 134, and 136 are disposed at positions corresponding to the first inner tube 120 to move the inside of the first inner tube 120 to the first set temperature. A second heater 132 and a third interior disposed at a position corresponding to the first heater 130 to heat the second inner tube 122 and heating the inside of the second inner tube 122 to a second set temperature; A third heater 134 disposed at a position corresponding to the tube 124 and heating the inside of the third inner tube 124 to a third set temperature, and disposed at a position corresponding to the fourth inner tube 126. And a fourth heater 136 that heats the inside of the fourth inner tube 126 to a fourth set temperature.

The first set temperature is set to a temperature higher than the sublimation point of the high-temperature purified material (A), the medium-temperature purified material (B), and the low-temperature purified material (C). The second set temperature is a temperature below the sublimation point of the high temperature purified material (A) and is a temperature above the sublimation point of the medium and low temperature purified materials, and the third set temperature is below the melting point of the medium temperature purified material (B). The temperature is equal to or higher than the sublimation point of the low temperature purified material, and the fourth set temperature is set to a temperature equal to or lower than the melting point of the low temperature purified material (C).
That is, the high temperature purification material (A), the medium temperature purification material (B), and the low temperature purification material (C) are formed of the first inner tube 120, the second inner tube 122, and the third inner tube 124. It is produced in the molten liquid state or in the sublimed solid state, respectively. In particular, the second set temperature, the third set temperature and the fourth set temperature are set such that the high-temperature purified material (A), the medium-temperature purified material (B), and the low-temperature purified material (C) are produced in the molten liquid state, respectively. It is desirable to be. Therefore, since the internal temperature of the inner tubes 120, 122, 124, and 126 can be set higher than that of the conventional sublimation refining apparatus, the sublimation action can be more actively performed, so that the progress of the sublimation purification process can be faster. .

Between the heaters 130, 132, 134, 136 and the outer tube 110, a conductor for conducting heat from the heaters 130, 132, 134, 136 to the outer tube 110 ( Not shown) can be deployed. In the conductor, a temperature sensor (not shown) for measuring the temperature of the outer tube 110 may be disposed, and a cooler 116 for cooling the conductor may be installed.

3 to 7, the connecting mechanisms 140, 142, and 144 are provided between the inner tubes 120, 122, 124, and 126, respectively, and the inner tubes 120 and 122. 124, 126 is a member that detachably connects in the vertical direction. In the center of the connection mechanism 140, 142, 144, a through hole 140a may be formed to penetrate in the vertical direction. That is, the connection mechanisms 140, 142 and 144 may be formed in a ring shape. In addition, the connection mechanisms 140, 142, 144 may be provided in a state coupled with any one of the inner tube (120) 122, 124, 126 disposed on the upper side and the lower side.

The connecting mechanisms 140, 142, 144 and the inner tubes 120, 122, 124, 126 may be detachably connected in various ways. For example, it may be connected by a screw fastening method, fastened by a separate fastening member, or connected by a hook fastening method.

3 to 7, the separation mechanism 150, 152, 154 may be any one of the inner tube 120, 122, 124, 126 or the connection mechanism 140, 142, 144. It is a member provided in one to separate the purification material (A) (B) (C) generated inside the inner tube (120) 122, 124, 126, respectively. At this time, if the purified materials (A) (B) (C) condensed inside the inner tubes 120, 122, 124, 126 are melted by the heaters 130, 132, 134, 136. The molten purified material (A) (B) (C) flows downward along the inner side of the inner tubes 120, 122, 124, 126, and inner tubes 120, 122, 124. Molten purification materials 150, 152, 154 provided under the 126 may be accommodated, respectively. Thus, the problem of the random mixing of the molten purified materials (A) (B) (C) inside the inner tubes 120, 122, 124, 126 can be essentially solved.

The separation mechanism 150, 152, 154 can accommodate the purification materials (A) (B) (C) melted inside the inner tubes 120, 122, 124, 126, respectively. The inner tube 120, 122, 124, 126 may be formed along the circumference of the inner surface of the inner tube 120, 122, 124, 126 or the through hole 140a of the connection mechanism 140, 142, 144. Hereinafter, in the present exemplary embodiment, the coupling mechanisms 140, 142, and 144 are provided with separation mechanisms 150, 152, and 154.

4 to 6, the separation mechanisms 150, 152, and 154 may protrude obliquely upward from the through-hole portions 140a of the connection mechanisms 140, 142, and 144. Separation mechanisms (150, 152, 154) may be formed in any one of a convex protruding upward, a cone, a dome, or a funnel. In addition, a flow hole 150a through which the sublimed material S1, S2, and S3 may pass through the separation mechanisms 150, 152, and 154 may be formed. Hereinafter, the separation mechanisms 150, 152 and 154 will be described as being formed in a funnel shape having a curved inclined surface 150b.

Therefore, the sublimated material (S1) (S2) (S3) is raised through the through-hole portion (140a), and then disposed on the upper side through the flow hole (150a) of the separation mechanism (150, 152, 154) May flow into the interior of the tubes 122, 124, 126. On the other hand, the purified material (A) (B) (C) condensed inside the inner tubes 122, 124, 126 is melted to form the inner surface of the inner tubes 122, 124, 126. As it flows down to the lower side, the inner surface of the inner tube 122, 124, 126 and the inclined surface 150b of the separation mechanism 150, 152, 154 can be collected to the site.

As described above, since the inner regions of the inner tubes 120, 122, 124, and 126 are separated by the separating mechanisms 150, 152 and 154, respectively, the inner tubes 120 and 122 are separated. Each of the purifying materials (A) (B) (C) formed inside of the 124, 126 can be prevented from moving to other inner tubes 120, 122, 124, 126. It is possible to sequester purified material (A) (B) (C) produced in the temperature range.

Referring to FIG. 1, a case 118 may be disposed outside the outer tube 110, the heaters 130, 132, 134 and 136 and the cooler 116. The case 118 serves to protect the internal parts of the sublimation refining apparatus 100.

Looking at the operation of the sublimation purification apparatus 100 according to an embodiment of the present invention configured as described above are as follows. 8 is a flowchart illustrating a sublimation purification method of a sublimation purification apparatus according to an embodiment of the present invention.

Sublimation purification method according to an embodiment of the present invention is a vacuum step (1), gas injection step (2), heating step (3), the first sublimation purification step (4), the second sublimation purification step (5), A third sublimation purification step (6), a fourth sublimation purification step (7), and a collection step (8).

In the vacuum step (1) to operate the vacuum pump 112 to make the interior of the outer tube 110 in a vacuum state. Therefore, it is possible to prevent a phenomenon in which impurities contained in the atmosphere penetrate into the purification material during the sublimation purification process or react with specific components of the atmosphere.

In the gas injection step 2, the gas supply is operated and the valve assembly is opened. That is, after the inert gas of the gas supplier passes through the valve assembly, the inert gas is injected into the outer tube 110 through the inert gas inlet 110a. The gas injected into the outer tube 110 flows upward, and then is discharged through the inert gas outlet 110b. Therefore, a flow of inert gas flowing from the lower side to the upper side is formed in the outer tube 110.

In the heating step (3), the heaters 130, 132, 134, 136 are operated to heat the inner space of the inner tubes 120, 122, 124, 126. At this time, the inner tubes 120, 122, 124 and 126 close to the object E are heated to a relatively high temperature, and the inner tube 120 far from the object E is disposed ( 122) 124 and 126 are heated to a relatively low temperature.

In the first sublimation refining step (4), the first heater 130 is a high-temperature purified material (A), a medium-temperature purified material (B) and a low temperature to be processed (E) in the first inner tube (120) It heats to the 1st set temperature higher than the sublimation point of refinement | purification substance (C). At this time, the first sublimation material S1 sublimated in the workpiece E rises upward toward the through hole portion 140a of the connection mechanism 140 and then through the flow hole portion 150a of the separation mechanism 150. The inside of the second inner tube 122 is moved. The inside of the first sublimation material S1 includes a high-temperature purified material A, a medium-temperature purified material B, and a low-temperature purified material C.

In the second sublimation refining step 5, the second heater 132 heats the first sublimation material S1 in the second inner tube 122 to a second set temperature lower than the first set temperature. The said 2nd set temperature is the temperature below the sublimation point of high temperature refinement | purification material (A), and is the temperature more than the sublimation point of the medium temperature refinement | purification substance (B) and low temperature refinement | purification substance (C). At this time, the second sublimation material S2 having the sublimation point lower than the second set temperature among the first sublimation material S1 is raised into the third inner tube 124. The high-temperature purified material A having a sublimation point higher than the second set temperature among the first sublimation material S1 is condensed in the molten state inside the second inner tube 122.

In the third sublimation refining step 6, the third heater 134 heats the second sublimation material S2 in the third inner tube 124 to a third set temperature lower than the second set temperature. The third set temperature is a temperature equal to or lower than the melting point of the medium-temperature purified material (B), and is equal to or higher than the sublimation point of the low-temperature purified material (C). At this time, the third sublimation material S3 having a sublimation point lower than the third set temperature among the second sublimation materials S2 is raised into the fourth inner tube 126. And the middle temperature refine | purified material B which has a sublimation point higher than a 3rd set temperature among the 2nd sublimation material S2 is condensed in the molten state inside the 3rd inner tube 124. FIG.

In the fourth sublimation purification step 7, the fourth heater 136 heats the third sublimation material S3 in the fourth inner tube 126 to a fourth set temperature lower than the third set temperature. The fourth set temperature is a temperature below the melting point of the low-temperature purified material (C). At this time, the low-temperature purified material C having the sublimation point higher than the fourth set temperature among the third sublimation material S3 is condensed in the molten state inside the fourth inner tube 126.

In the sublimation refining step 10, the purification materials (A) (B) (C) corresponding to different temperature ranges in the second, third, and fourth sublimation refining steps (4) (5) (6). Each of which is independently generated, is formed by the inner tubes 120, 122, 124, 126 and the separation mechanisms 150, 152, 154. And the low temperature purified material (C) are each separated.

In the collecting step (8), after the heaters 130, 132, 134, 136, the vacuum pump 112 and the gas supply is stopped, the door of the outer tube 110 is opened to open a second The inner tube 122, the third inner tube 124, and the fourth inner tube 126 are taken out. Then, the purified material (A) (B) (C) condensed in the second inner tube 122, the third inner tube 124 and the fourth inner tube 126 are collected, respectively, and the third inner tube 124 The medium temperature purified material (B) collected in the above) is used as the material for the organic EL device. The high temperature and low temperature refinement | purification substance (C) may be discarded or sublimed and refine | purified again, and the medium temperature refinement | purification substance (B) may be sublimated and refine | purified again as needed.

As described above, one embodiment of the present invention has been described by specific embodiments, such as specific components, and limited embodiments and drawings, but this is only provided to help a more general understanding of the present invention. The present invention is not limited thereto, and various modifications and variations can be made by those skilled in the art to which the present invention pertains. Accordingly, the spirit of the present invention should not be construed as being limited to the embodiments described, and all of the equivalents or equivalents of the claims, as well as the following claims, belong to the scope of the present invention .

1 is a view schematically showing an example of a sublimation refining apparatus according to the prior art,

FIG. 2 is a view showing a main part of the sublimation refining apparatus shown in FIG. 1;

3 is a schematic view showing a sublimation purification apparatus according to an embodiment of the present invention;

4 is a view showing the main part of the sublimation purification apparatus shown in FIG.

5 is a perspective view showing an inner tube, a connection mechanism, and a separation mechanism of the sublimation refining apparatus shown in FIG. 4;

Figure 6 is a side view schematically showing the separation mechanism shown in FIG.

7 is a state diagram showing an internal state of the inner tube when the sublimation refining apparatus shown in FIG. 3 is driven;

8 is a flowchart illustrating a sublimation purification method of a sublimation purification apparatus according to an embodiment of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS Fig.

100: sublimation tablet device 110: outer tube

120,122,124,126: Inner tube 130,132,134,136: Heater

140, 142, 144: connection mechanism 150, 152, 154: separation mechanism

Claims (9)

An outer tube formed therein with a flow of inert gas flowing inside from the lower side to the upper side under vacuum; A plurality of inner tubes arranged inside the outer tube so as to be stacked in a vertical direction and condensing the material sublimed from the object disposed below at different temperature ranges to collect purified materials; A plurality of heaters provided at positions corresponding to the inner tubes to heat the inside of the inner tube to different temperatures; A coupling mechanism provided between the inner tubes to detachably connect the inner tubes in a vertical direction; And A separation mechanism provided along one of the lower inner surfaces of the inner tube or the connecting mechanism disposed below the inner tube and separating the purified substances condensed in the inner tubes by the inner tubes. ;; The heaters heat the inner tubes to a temperature capable of melting in a liquid state the purified materials condensed inside the inner tubes, respectively, The separation mechanism is a sublimation purification device formed of a structure for receiving the purification materials that are respectively melted in the inner tube. The method of claim 1, In the center of the connecting mechanism is formed a through hole penetrating in the vertical direction, The separation mechanism is a sublimation purification device formed in a ring shape along the through hole. The method of claim 1, The separating mechanism protrudes inclined upwardly from the lower inner surface of the inner tube or the connecting mechanism, Sublimation purification apparatus is formed in the upper portion of the separation mechanism flow hole for passing the sublimated material by the heaters. The method of claim 3, The separation mechanism is a sublimation purification device formed in any one of the shape of a polygonal pyramid, a cone, a dome, or a funnel projecting upwardly. The method according to any one of claims 1 to 4, The workpiece is disposed in an inner tube of the lowest position among the inner tubes, and the heaters are formed to provide a low heating temperature to the inner tubes from the lower side to the upper side, The heaters heat the inner tube on which the workpiece is disposed to a temperature higher than the sublimation point of the purified substances and heat the inner tubes above the melting temperature of the purified substances respectively condensed on the inner tubes. Sublimation tablet device, characterized in that. The method of claim 5, The inner tube may include a first inner tube in which the object is disposed; A second inner tube communicatively stacked on an upper portion of the first inner tube and configured to condense a high-temperature purified material therein; A third inner tube configured to be communicatively stacked on an upper portion of the second inner tube and to condense the purified material of medium temperature therein; And a fourth inner tube communicatively stacked on the third inner tube and condensed therein with a low temperature purified material. The method of claim 6, The to-be-processed object is an organic material, The sublimation refining apparatus is at least one of a hole injecting material, a hole transporting material, an electron transporting material, or a light emitting material. A first sublimation refining step of heating a to-be-processed object in a first inner tube to a first set temperature to sublimate a first sublimation material into a second inner tube in said to-be-processed object; Heating the first sublimation material in the second inner tube to a second set temperature lower than the first set temperature to form a second sublimation material having a sublimation point lower than the second set temperature among the first sublimed materials; A second sublimation refining step of subliming into an inner tube and condensing a high-temperature purified material having a sublimation point higher than the second set temperature among the first sublimation substances in a liquid state inside the second inner tube; Heating the second sublimation material in the third inner tube to a third set temperature lower than the second set temperature to produce a third sublimation material having a sublimation point lower than the third set temperature among the second sublimed materials. A third sublimation refining step of subliming the inside of the inner tube and condensing a medium-temperature purified material having a sublimation point higher than the third set temperature among the second sublimation substances in a liquid state inside the third inner tube; The third sublimation material in the fourth inner tube is heated to a fourth set temperature lower than the third set temperature to produce a low-temperature purified material having a sublimation point higher than the fourth set temperature among the third sublimed materials. A fourth sublimation purification step of condensing in a liquid state inside the inner tube; And And separating the second inner tube, the third inner tube and the fourth inner tube to collect the high temperature purified material, the medium temperature purified material and the low temperature purified material, respectively. The first set temperature is a temperature equal to or higher than the sublimation point of the high, medium and low temperature purified material, The second set temperature is a temperature below the sublimation point of the high temperature purified material and a temperature above the sublimation point of the medium and low temperature purified material, The third set temperature is a temperature equal to or lower than the melting point of the medium temperature purified material and a temperature equal to or more than the sublimation point of the low temperature purified material, The fourth preset temperature is a temperature below the melting point of the low-temperature purified material, sublimation purification method of the sublimation purification device. delete

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