CN117355364A

CN117355364A - Method for continuously purifying at least one functional material and device for continuously purifying at least one functional material

Info

Publication number: CN117355364A
Application number: CN202280036264.5A
Authority: CN
Inventors: 菲利普·施特塞尔
Original assignee: Merck Patent GmbH
Current assignee: Merck Patent GmbH
Priority date: 2021-05-21
Filing date: 2022-05-19
Publication date: 2024-01-05
Also published as: WO2022243403A1; KR20240012506A; EP4340969A1

Abstract

The invention describes a method for continuous purification of at least one functional material that can be used for producing functional layers of electronic devices, which functional layers involve charge injection or charge transport and/or light emission or light outcoupling. The invention also relates to a device for continuously purifying at least one functional material.

Description

Method for continuously purifying at least one functional material and device for continuously purifying at least one functional material

The invention describes a method for continuous purification of at least one functional material that can be used for producing functional layers of electronic devices, which involve charge injection or charge transport and/or light emission or light outcoupling. The invention also relates to a device for continuously purifying at least one functional material.

Electronic devices containing organic, organometallic and/or polymeric semiconductors are becoming increasingly important and are used in many commercial products for reasons of cost and their performance. Examples herein include organic-based charge transport materials in copiers (e.g., triarylamine-based hole transport materials), organic or polymer light emitting diodes (OLED or PLED) in readout and display devices, or organophotoreceptors in copiers. Organic solar cells (O-SCs), organic field effect transistors (O-FETs), organic thin film transistors (O-TFTs), organic integrated circuits (O-ICs), organic optical amplifiers and organic laser diodes (O-lasers) are in advanced stages of development and may have significant future significance.

In many cases, the fabrication of these devices involves the use of sublimable organic or organometallic-based functional materials. These materials must be used in very pure form to obtain good and durable electronic devices.

For this reason, these materials are generally sublimated and then condensed, thereby reliably removing byproducts and solvent residues.

Such methods and devices are described for performance in particular in publications WO2015/022043, KR2020/0123895, KR 2017/012563, CN109646987, KR 101835418B 1 and KR 2019/0125000.

For example, the claims according to publication WO2015/022043 do not allow continuous purification of the functional material, as the container has to be removed to extract the purified material. The same applies to claims in publications KR 2017/012563, CN109646987, KR 101835418B 1 and KR 2019/0125000, as here too the collection vessel or condensation plate needs to be taken out of the apparatus by opening the module.

In addition, publication KR 2020/0123995 suggests the use of ionic liquids condensed from functional materials. The ionic liquid loaded with functional material is directed out of the vacuum zone and treated with removal of the functional material.

KR 101918233B 1 describes a device for the continuous purification of functional materials, wherein the device has a common chamber between 200 and 300 according to the figures, which can be operated under reduced pressure.

DE 1130793B describes an apparatus for continuous vacuum sublimation of difficult sublimates.

Known methods and apparatus have useful performance characteristics. However, there remains a need to improve the performance of these methods and devices.

These properties include in particular the economic viability, reliability and complexity of the apparatus for the continuous purification of at least one functional material. In particular, the apparatus should be constructed in a very simple manner without reducing or changing the vacuum level for discharging the purified functional material. In addition, the use of recycle purification aids, such as ionic liquids, should be minimized. It should preferably not be used at all.

Another object may be considered to provide an apparatus for continuous purification of at least one functional material, which apparatus is inexpensive and continuously operated for a long time. Furthermore, the device should be efficient and easy to control. Furthermore, the device should be easy to scale up and construct in an environmentally friendly manner.

Furthermore, the method should result in high purity functional materials such that the lifetime of the electronic devices obtained with these materials and other properties thereof are not adversely affected.

It has been found that, surprisingly, the particular device described in detail hereinafter achieves these objects and eliminates the drawbacks of the prior art. An apparatus for purifying at least one functional material, which apparatus can be operated in particular in a low-cost and continuous manner if the apparatus comprises a discharge device comprising a discharge extruder unit, or the discharge device is a discharge extruder unit. Furthermore, the device can be constructed in a particularly simple manner. Furthermore, an improvement can be achieved in particular in terms of the purity of the material used for manufacturing the electronic device, wherein by means of the purification method very low thermal stresses are present in the purification of the material used for manufacturing the electronic device. Against this background, the use of such purified materials results in organic electronic devices, in particular organic electroluminescent devices, having very good properties, in particular in terms of lifetime, efficiency and operating voltage.

The invention therefore provides a method for purifying at least one functional material that can be used for producing a functional layer of an electronic device, the functional layer involving charge injection or charge transport and/or light emission or light outcoupling, characterized in that an apparatus is used, wherein the method comprises evaporating or sublimating and/or condensing the at least one functional material, and wherein the apparatus has:

a) At least one feeding device for the at least one functional material, wherein the at least one functional material is capable of being fed continuously via a feed opening provided in the feeding device;

b) At least one evaporation device disposed downstream of the feeding device, wherein the functional material is introduced into the evaporation device through the feeding device, and the functional material is continuously evaporated by the evaporation device;

c) At least one condensing device, wherein by means of the condensing device, the functional material can be continuously condensed after evaporation in the evaporating device;

d) At least one discharge device arranged downstream of the condensation device, wherein the functional material can be continuously introduced from the condensation device into the discharge device and can be discharged through a discharge opening present in the discharge device;

And wherein

The apparatus has an evaporation chamber in which at least a part of the evaporation means and at least a part of the condensation means are provided, wherein the evaporation chamber is connected or connectable to at least one evacuation apparatus, preferably at least one vacuum pump, and a reduced pressure, preferably a high vacuum, can be generated in the evaporation chamber when the continuous purification apparatus is operated, and the discharge means comprise or constitute a discharge extruder unit.

Accordingly, the present invention also provides an apparatus for continuous purification of at least one functional material, the apparatus comprising:

a) At least one feeding device for at least one functional material, wherein the at least one functional material is capable of being fed continuously via a feed opening provided in the feeding device;

b) At least one evaporation device arranged downstream of the feeding device, wherein the functional material can be introduced into the evaporation device through the feeding device and the functional material can be continuously evaporated by the evaporation device;

And wherein

The apparatus has an evaporation chamber in which at least a part of the evaporation means and at least a part of the condensation means are provided, wherein the evaporation chamber is connected or connectable to at least one evacuation apparatus and a reduced pressure, preferably a high vacuum, can be generated in the evaporation chamber when the continuous purification apparatus is operated, and the discharge means comprises or constitutes a discharge extruder unit, characterized in that the evaporation means at least partly encloses the condensation means.

A particularly surprising advantage is achieved in this connection that by liquefying/softening/solidifying at least one functional material in the discharge device, a reduced pressure, preferably a high vacuum, can be generated in the evaporation chamber. It is therefore preferably achieved that the device is sealed when the functional material is discharged via a discharge unit comprising or constituting a discharge extruder unit. The generation of reduced pressure, preferably high vacuum, in the evaporation chamber can be achieved in particular by means of the purification function material extruded out of the extruder unit, which purification function material can have a viscosity suitable for the purpose, i.e. can be extruded. In this way, a vacuum can be permanently maintained within the apparatus even when extracting the purified material.

A surprising advantage that can be achieved is that by liquefying/softening at least one functional material in the feed device and by increasing the viscosity, preferably solidifying, of at least one functional material in the discharge device, a reduced pressure, preferably a high vacuum, can be generated in the evaporation chamber. By this implementation, a vacuum can surprisingly be established and maintained without complicated and expensive technical measures.

In a preferred embodiment, it may be the case that the feeding means comprises grooved rolls and/or extruder screws, wherein the feeding means preferably comprises or constitutes a feeding extruder unit. This configuration allows for feeding functional material to the device in a particularly simple and reliable manner, wherein the configuration of the device may have a non-complex configuration. In this case, the amount of addition can be simply controlled, thereby achieving a controlled purification process. A feeding device comprising grooved rolls is described in detail in publication WO10/056325 (PCT/US 2009/006082); the description of the feeding device given in publication WO10/056325 is incorporated by reference into the present application. The feeding device using an extruder or extruder screw is also described in detail in the description of the prior art in publication WO 10/056325; these details in publication WO10/056325 are likewise incorporated into the present application by reference. These include publications US2006/0062918 and US2006/0177576.

Feeding means using an extruder or extruder screw are additionally described in WO 2006/118837; the description of the feeding device given in publication WO2006/118837 is incorporated into the present application by reference.

It may also be the case that the evaporation device has an evaporation material distributor system. It is also possible that the evaporation material distributor system comprises at least one scraper system, wherein the functional material is distributed by the scraper system on the evaporation unit of the evaporation device, wherein the scraper system is preferably configured as a rotary film, rolling scraper or wing scraper system. The evaporation unit is preferably configured as an evaporation surface over which the functional material to be purified is distributed by the evaporation material distributor system.

It may also be that the feed device comprises at least one vent through which the solvent is removable.

It is also possible that the evaporation device is electrically heatable or heatable by a fluid, preferably hot air or a heat transfer oil, more preferably electrically heatable or heatable by a heat transfer oil.

Furthermore, it may be the case that the temperature of the feeding means, preferably the feeding extruder unit, is controllable.

An apparatus for continuous purification of at least one functional material comprises an evaporation chamber, wherein at least a portion of an evaporation device and at least a portion of a condensation device are provided. At least one functional material is evaporated or sublimated and/or condensed in the evaporation chamber and purified by these steps. It is possible here for the evaporation device to have an evaporation unit, preferably an evaporation surface, by means of which at least one functional material can be evaporated and/or sublimated, and for the condensation device to comprise a condensation unit, preferably a condensation surface, by means of which the at least one functional material can be condensed, wherein the evaporation unit and the condensation unit are surrounded by an evaporation chamber. The evaporation chamber preferably encloses the evaporation surface of the evaporation means and the condensation surface of the condensation means.

In another configuration, it may be that the evaporation device has an evaporation surface through which the functional material can be evaporated, and the condensation device has a condensation surface through which the functional material can be condensed, wherein the evaporation surface is arranged parallel to the condensation surface. This design allows particularly low thermal stresses to be achieved on the functional material during purification, since the time interval between evaporation or sublimation and condensation can be kept very short.

In a preferred embodiment, it may be the case that the evaporation device has an evaporation unit, preferably an evaporation surface, wherein the evaporation unit has an evaporation cylinder, and preferably an evaporation cylinder, wherein at least a part of the surface of the evaporation cylinder may be regarded as the evaporation surface.

It may also be the case that the condensation device comprises a condensation unit, preferably a condensation surface, wherein the condensation unit has a condensation cylinder, and is preferably configured as a condensation cylinder, wherein at least a part of the surface of the condensation cylinder may be regarded as the condensation surface.

It is also possible that the condensing means is rotatable relative to the evaporating means. This configuration enables uniform condensation of the functional material on the condensation zone, thereby improving the efficiency of the process and reducing thermal stresses on the functional material during purification.

As the condensing device can be rotated by means of the drive unit, surprising advantages can be obtained with regard to the construction of the apparatus.

It may also be that the feed device comprises or constitutes a feed extruder unit and the discharge device comprises or constitutes a discharge extruder unit, wherein the extruder screw of the feed extruder unit is connected to the extruder screw of the discharge extruder unit such that the extruder screw of the feed extruder unit and the extruder screw of the discharge extruder unit are rotatable by the drive unit.

It is also possible that the condensation device has a condensation cylinder connected to the extruder screw of the feed extruder unit and the extruder screw of the discharge extruder unit, so that the extruder screw of the feed extruder unit, the condensation cylinder and the extruder screw of the discharge extruder unit can be rotated by at least one, preferably exactly one drive unit.

In another embodiment, it may be that the feed device comprises or constitutes a feed extruder unit and the discharge device comprises or constitutes a discharge extruder unit, wherein the extruder screw of the feed extruder unit is rotatable by the drive unit and the extruder screw of the discharge extruder unit is rotatable by the second drive unit such that the extruder screw of the feed extruder unit is rotatable independently of the extruder screw of the discharge extruder unit.

The second embodiment is somewhat more complex in construction but has the advantage of being able to control the feed device independently of the discharge. This advantage is particularly advantageous for the start-up of the plant.

It is also possible that the condensing device has a condensing cylinder which is connected to the extruder screw of the feed extruder unit or the extruder screw of the discharge extruder unit such that the condensing cylinder can be rotated together with the extruder screw of the feed extruder unit or the extruder screw of the discharge extruder unit. The apparatus herein may comprise at least two drive units, one of which is connected to the extruder screw of the feed extruder unit and the second of which is connected to the extruder screw of the discharge extruder unit. It is also possible that the condensation cylinder can be driven by a separate drive unit, so that the condensation cylinder can be rotated independently of the extruder screw feeding the extruder unit or the extruder screw exiting the extruder unit.

In a particularly preferred embodiment, it may be that the evaporation device encloses the condensation device.

A surprising advantage that can be achieved with regard to the construction of the device is that the condensation device has a condensate collector, by means of which condensed functional material can be collected in the discharge device.

It is also possible that the condensate collector may be of funnel-like configuration, in which case the funnel opening is directed towards the discharge device.

It is also possible that the condensation device has a moving unit, in which case the condensation function material can be peeled off from a part of the surface of the condensation device by means of the moving unit. Thus, the moving unit facilitates the transfer of the condensed functional material into the discharge device. Such a mobile unit is not absolutely necessary. For example, the moving unit may be dispensed with, in particular in the case of low-viscosity condensation function materials which are liable to flow from the condensation device into the discharge device.

In a particularly preferred embodiment, the displacement unit may be configured as a stripper or scraper system.

It is also possible that the temperature of the discharge means, preferably the discharge extruder unit, is controllable.

In a preferred embodiment, a temperature gradient may be produced between the evaporator and the condenser, wherein the temperature of the evaporator is selectable at a level higher than the temperature of the condenser.

Preferably, the evaporation device and/or the evaporation chamber comprise at least one opening through which the residue collection container can be connected or connected. This embodiment allows the device to be operated over a particularly long period of time without having to interrupt the process. In another configuration, residues can be collected within the apparatus, in which case the method must be interrupted here after a long time. It should be emphasized here that these residues are generally present only in small amounts in the starting material to be purified, so that in any case an improvement over the prior art can be achieved.

In a further development, it may be that the evaporation device and/or the evaporation chamber comprise at least two openings, through each of which a residue collection container can be connected or connected. This further development enables a further improvement of the method, since the residue collection container can be replaced and cleaned even during operation. The residue collection container is preferably designed to be inert and/or evacuable.

It is also possible that the apparatus is vertically aligned in which case the feed means is arranged above the evaporation means and the evaporation means is arranged above the discharge means. Preferably, the apparatus is operable in vertical alignment, in which case the functional material may be transferred from the feed device to the vaporising device under gravity.

In a preferred configuration, it may be that the apparatus is vertically alignable, wherein the functional material may be introduced into the discharge means from the condensing means under gravity.

The discharge device is provided with a discharge hole through which the purified functional material can be discharged. It is possible here for the discharge opening to be connected to a granulation unit, in which case the resulting granular material can preferably be introduced into a discharge vessel.

A surprising advantage that can be achieved is that the device has at least one rotational coupling arranged between rotatable constructional parts of the device, in which case the rotational coupling is selected from a ferrofluid-tight rotational bushing or a double-or triple-acting slip ring seal. In particular, as described above, the condensing device may be configured to be rotatable relative to the evaporating device. The discharge device further comprises a discharge extruder unit. Furthermore, the feeding device may comprise a feeding extruder unit. These assemblies comprise components of rotatable construction, wherein the rotational coupling is preferably constructed in the manner described in detail above.

It may also be the case that the device comprises a camera through which evaporation and/or condensation of the functional material can be observed.

The apparatus for continuously purifying at least one functional material is connected or connectable to an evacuation apparatus. The connection to the evacuation device causes a reduced pressure to be generated within the evaporation chamber, which is suitable for achieving evaporation or sublimation. Systems suitable for the purpose are known in the art and these systems generally comprise or are constructed as at least one vacuum pump, preferably a vacuum pump system.

In a preferred embodiment, the device may comprise at least one vacuum pump system, which is preferably formed by a multistage system comprising a feed pump, in particular an oil pump or a dry-running scroll pump, a rotary piston pump.

The above preferred embodiments can be combined with each other as required as long as the conditions specified in claim 1 are satisfied. In a particularly preferred embodiment of the invention, the above-described preferred embodiments are applied simultaneously.

The invention also provides a method for purifying at least one functional material as described above.

Functional materials for the production of functional layers for electronic components, which involve charge injection or charge transport and/or light emission or light outcoupling, are well known in the art. It may be preferable that the functional material that can be used for manufacturing the functional layer of the electronic device is selected from a fluorescent light emitter, a phosphorescent light emitter, a light emitter exhibiting TADF (thermally activated delayed fluorescence), a light emitter exhibiting superfluorescence or superphosphorescence, a host material, an exciton blocking material, an electron injection material, an electron transport material, an electron blocking material, a hole injection material, a hole conducting material, a hole blocking material, an n-type dopant, a p-type dopant, a wide bandgap material, a charge generating material, or a combination thereof. These materials, which can be used for the fabrication of the functional layer of the electronic device as described above, can be used in the method of the invention either alone or as a mixture of two, three, four, five or more materials. It is possible here for the mixture to be composed of exactly two, exactly three, exactly four or exactly five functional materials which can be used for producing functional layers of electronic components and which involve charge injection or charge transfer and/or light emission or light outcoupling, and to be purified according to the invention.

As mentioned above, at least one, preferably at least two, more preferably all functional materials that can be used for the fabrication of the functional layers of the electronic device are/are preferably organic materials or comprise organic compounds. The organic compound contains a carbon atom, and preferably contains a hydrogen atom.

As mentioned above, at least one, preferably at least two, more preferably all functional materials to be purified which can be used for the manufacture of functional layers of electronic devices can be provided in the form of, for example, powder/granular materials or plexiglas. Furthermore, however, the method of the invention can in particular be carried out as a step in the production of functional materials. The free-flowing composition of the functional material is preferably provided as described above and introduced into the feed means of the apparatus of the present invention.

Preferably, the at least one functional material is meltable without decomposition at a temperature above 50 ℃, preferably above 100 ℃.

Furthermore, it may be preferable that, as mentioned, the at least one functional material is present at a temperature of from 1 to 10 at a temperature of above 30 ℃, preferably at a temperature of above 50 ℃, more preferably at a temperature of above 100 DEG C ⁴ [1/s]Preferably 10 to 10 ³ [1/s]More preferably 100[1/s ]]Viscosity at shear rate in the range of 1 to 10 ²⁰ [mPa s]Preferably 10 ³ To 10 ¹⁸ [mPa s]More preferably 10 ⁶ To 10 ¹⁴ [mPa s]. The preferred method of viscosity measurement is set forth below.

It may also be that the at least one functional material in the molten state at the processing temperature exhibits no more than 0.1% by weight degradation during 10 hours of storage. The treatment temperature here may be in the range of 50 ℃ to 500 ℃. The treatment temperature refers to the temperature at which extrusion is performed in the discharge extruder unit. Preferably, at least one, preferably at least two and more preferably all functional materials used at the melting temperature exhibit no more than 0.1% by weight degradation during 10 hours of storage, as described above.

In a preferred configuration of the method according to the invention, the sublimable material is preferably purified. Thus, preferably, at least one, more preferably at least two and especially preferably all functional materials to be purified are sublimable. As described below, the sublimable material preferably has a low molecular weight.

In the discharge extruder unit, the purified functional material is extruded. Furthermore, the feeding device may comprise a feeding extruder unit. The term "extrusion" is well known in the art and refers to extruding a curable body through an opening. For this purpose, an extruder is used. Extruders are also known in the art and are commercially available. The term "extruder" refers to a conveying device for performing extrusion. For the purpose of disclosure, the description of publication EP 2 381 B1, in particular of the extruder contained therein, is incorporated by reference into the present application.

For example, a single screw or twin screw extruder may be used. The selection and adjustment of the appropriate extruder screw, in particular its geometry, based on the respective processing functions such as suction, delivery, homogenization, softening and compression form part of the common general knowledge of the person skilled in the art.

In the inlet region of the extruder, preferably a screw extruder, a barrel temperature is established, preferably in the range of 50 ℃ to 450 ℃, preferably 80 ℃ to 350 ℃, depending on the nature of the functional material. For example, in the suction zone, the functional material described above and below may be fed in the form of powder, free-flowing substances and/or granular material. This is especially true if the feeding device comprises a feeding extruder unit. The apparatus of the present invention comprises an exit extruder unit into which the condensed material is introduced. The material may be introduced into the inlet area of the discharge extruder unit as a free flowing substance, optionally in the form of a liquid with a low viscosity, which is cooled within the discharge extruder unit so that a reduced pressure, preferably a high vacuum, may be created within the evaporation chamber. Furthermore, the condensation material may be introduced in the form of a condensed solid into the inlet area of the discharge extruder unit, in which case the solid can first be gently heated to obtain a viscous mass by means of which a reduced pressure, preferably a high vacuum, can be generated in the evaporation chamber.

The temperature profile used here varies depending on the functional material used. The temperature distribution established in the softening range is preferably in the range from 80 ℃ to 450 ℃, preferably from 90 ℃ to 350 ℃, more preferably from 100 ℃ to 300 ℃, particularly preferably from 120 ℃ to 250 ℃ and particularly preferably from 130 ℃ to 230 ℃. This is especially true if the feeding device comprises a feeding extruder unit. The temperature in the discharge zone is preferably in the range from 80 ℃ to 450 ℃, preferably from 90 ℃ to 350 ℃, more preferably from 100 ℃ to 300 ℃, particularly preferably from 120 ℃ to 250 ℃ and particularly preferably from 130 ℃ to 230 ℃. Here, each extruder may have a temperature distribution that increases or decreases with temperature. When a feed extruder unit is used, the temperature may be raised in the direction of the evaporation device such that the powder or granular material liquefies, while the liquid or substance with a relatively low viscosity is solidified by cooling in the discharge extruder unit such that a reduced pressure, preferably a high vacuum, is created in the evaporation chamber. If condensation in the condensing device results in a solid, the solid can first be melted slightly and then solidified, so that a reduced pressure, preferably a high vacuum, can be created in the evaporation chamber. The temperatures specified here are related to the cylinder temperature and can be measured by thermocouples such as FeCuNi L-type or J-type, pt 100 thermometers or IR thermometers.

It is also possible that at least one functional material is transferred from the feed device to the evaporation device at a temperature of at least 5 ℃, preferably at least 10 ℃, above the glass transition temperature of the respective functional material.

In a preferred configuration, it may be that the feeding means of the apparatus comprises a feed extruder unit by means of which at least one functional material is extruded, wherein the extrusion is performed using a substance having a viscosity in the range of 1 to 50000[ mpas ], preferably 10 to 10000[ mpas ] and more preferably 20 to 1000[ mpas ], as measured by a rotary flat plate method under a shear rate of 100[1/s ] and a temperature in the range of 150 to 450 ℃.

Viscosity values as described above and below were determined by the spin plate method. Here, rheological measurements can be carried out using a Discovery mixing rheometer HR-3 (equipped with an ETC heating unit) from Waters GmbH-UM TA Instruments D-65760Eschborn, germany. The calibration can be performed with reference. For example, the following oils may be used for this purpose:

in many cases, viscosity is measured as a function of temperature at three different shear rates (10/s, 100/s and 500/s); the respective conditions are set forth above and below in more detail. The shear rate is preferably 100s ^-1 . The viscosity number is preferably measured in accordance with DIN 53019, in particular DIN 53019-1:2008-09, DIN 53019-2:2001-02, DIN 53019-3:2008-09.

Preferably, at least one functional material to be purified according to the invention, which can be used for the production of the functional layer of an electronic device as described above, has a melting temperature in the range from 150 ℃ to 500 ℃, preferably from 180 ℃ to 400 ℃, more preferably from 220 ℃ to 380 ℃ and particularly preferably from 250 ℃ to 350 ℃, said melting temperatures being measured according to DIN EN ISO 11357-1 and DIN EN ISO 11357-2. The melting temperature here is obtained by measuring the glass transition temperature in the form of a DSC signal; further details of the melting temperature measurement are related to the determination of the glass transition temperature.

With the current methods, the material does not have to have a melting point. In general, it is sufficient for the material used to soften at a sufficiently high viscosity.

Thus, the at least one functional material to be purified may have no melting point.

It may be preferable that at least one functional material to be purified is sublimable.

It may therefore be the case that the sublimation temperature of the at least one functional material to be purified, measured according to DIN 51006, is in the range from 150 ℃ to 500 ℃, preferably from 180 ℃ to 400 ℃, more preferably from 220 ℃ to 380 ℃ and particularly preferably from 250 ℃ to 350 ℃. The sublimation temperature can be found here from vacuum TGA measurements, in which the material sublimates or evaporates in a controlled manner. The TG 2099f1 Libra instrument of Netzsch can be used to make measurements under the following measurement conditions:

Sample weight: 1mg of

Crucible: open type aluminum crucible

Rate of temperature rise: 5K/min

Temperature range: 105-550 DEG C

Atmosphere: vacuum 10 ^-2 mbar (Regulation)

Evacuation time before starting measurement: about 30 minutes.

The sublimation temperature used is the temperature at which a 5% weight loss occurs.

It is also possible that the breakdown temperature of the at least one functional material to be purified is higher than 340 ℃, preferably higher than 400 ℃, more preferably higher than 500 ℃. The decomposition temperature, i.e. the temperature at which material destruction is detected, is determined here by DSC or TGA measurements. The decomposition temperature is considered to be the temperature at which 50% of the substance is detected in the heating operation at a rate of 5K per minute (about 1mg of sample amount). The process according to the invention should always be carried out below the breakdown temperature of the at least one functional material.

In a preferred embodiment, it may be the case that the glass transition temperature of the at least one functional material to be purified is in the range from 80 ℃ to 400 ℃, preferably from 90 ℃ to 300 ℃, more preferably from 100 ℃ to 250 ℃, particularly preferably from 120 ℃ to 220 ℃ and particularly preferably from 130 ℃ to 200 ℃, said glass transition temperature being measured according to DIN EN ISO 11357-1 and DIN EN ISO 11357-2. Details of determining the glass transition temperature are known to those skilled in the art from the standard; the glass transition temperature is preferably determined after the first heating and cooling operation. For many substances, an appropriate glass transition temperature can be obtained at a heating rate of 20K/min for the first and second heating operations and a cooling rate of 20K/min for the first and second cooling operations, and is determined as a signal in the second or third heating operation, preferably in the second heating operation. In a particularly preferred embodiment, the glass transition temperature is determined using a sample prepared by a first heating operation at a heating rate of 20K/min and by a quenching operation of directly cooling the heated sample in liquid nitrogen, and the glass transition temperature is determined by subjecting the thus pretreated sample to a second heating operation at a heating rate of 50K/min. By these measures, the glass transition temperature can be reliably determined even for a substance having a glass transition masked by the recrystallization temperature in other processes. The test method, in which the first cooling operation is performed by the quenching operation and the second heating operation is performed at a heating rate of 50K/min, is particularly superior to other working methods, for example, working methods employing lower cooling rates or lower heating rates. If the melting temperature is below 300 ℃, the heating range is preferably in the range of 0 ℃ to 350 ℃. In the case of substances with a higher melting point, the heating range is correspondingly enlarged at the upper end, but must still remain below the decomposition temperature. Preferably, the upper temperature in the heating range is at least 5 ℃ lower than the decomposition temperature.

The sample amount is preferably in the range of 10mg to 15 mg. Further information about the determination of the glass transition temperature can be found in the examples. The examples give details of particularly preferred measuring devices.

It is also possible to use at least one functional material to be purified in the form of a mixture, wherein the mixture preferably comprises at least two functional materials, as described above. In this case, the materials used in the mixture have similar sublimation and/or softening properties. The more similar these properties are, the better the quality of the resulting purified material mixture. It may thus be preferable to use at least two functional materials in a mixture which are particularly useful for the manufacture of functional layers of electronic devices and which have substantially similar softening, evaporation and/or sublimation properties.

In a preferred embodiment, it may be that at 10 ^-3 mbar to 10 ^-7 mbar, preferably 10 ^-4 mbar to 10 ^- ⁶ The evaporation or sublimation and/or condensation of the at least one functional material is carried out at a pressure in the range of mbar.

In another configuration, the at least one functional material to be purified, which is particularly useful for manufacturing an electronic device functional layer involving charge injection or charge transport and/or light emission or light outcoupling, is chosen from: benzene, fluorene, indenofluorene, spirobifluorene, carbazole, indenocarbazole, indole Carbazoles, spirocarbazoles, pyrimidines, triazines, quinazolines, quinoxalines, pyridines, quinolines, isoquinolines, lactams, triarylamines, dibenzofurans, diazadibenzofurans, dibenzothiophenes, diazadibenzothiophenes, imidazoles, benzimidazoles, benzofuransAzole, benzothiazole, 5-arylphenanthridine-6-one, 9, 10-dihydrophenanthrene, fluoranthene, naphthalene, phenanthrene, anthracene, benzanthracene, indeno [1,2,3-jk]Fluorene, pyrene, perylene,>borazine, boroxine, borole, azaborole, ketones, phosphine oxides, arylsilanes, siloxanes, biphenyls, triphenyls, terphenyls, triphenylenes, arylgermanium, bismuth aryl iodide, metal complexes, chelate complexes, transition metal complexes, metal clusters, and combinations thereof, wherein the metal complexes, chelate complexes, transition metal complexes, metal clusters preferably contain element Li, na, K, cs, be, mg, B, al, ga, in, ge, sn, bi, se, te, sc, ti, zr, mo, W, re, ru, os, rh, ir, pd, pt, cu, ag, au, zn.

Functional materials that can be used to fabricate functional layers of electronic devices are in many cases organic compounds that provide the functions described above and below. Thus, the terms "functional compound" and "functional material" are in many cases to be understood as synonyms.

Examples of suitable functional materials that can be purified according to the invention are described below.

A compound having hole injection properties, also referred to herein as a hole injection material, facilitates or enables the transfer of holes, i.e. positive charges, from the anode into the organic layer.

Compounds having hole transporting properties, also referred to herein as hole transporting materials, are capable of transporting holes, i.e., positive charges, that are typically injected from an anode or an adjacent layer, such as a hole injection layer.

Preferred compounds having hole injection and/or hole transport propertiesIncluding, for example, triarylamine derivatives, benzidine derivatives, tetraaryl p-phenylenediamine derivatives, triarylphosphine derivatives, phenothiazine derivatives, phenonesOxazine derivatives, dihydrophenazine derivatives, thianthrene derivatives, dibenzop-di +.>English derivatives, pheno->A thia derivative, a carbazole derivative, an azulene derivative, a thiophene derivative, a pyrrole derivative and a furan derivative.

The following compounds having hole injection and/or hole transport properties should be mentioned in particular: phenylenediamine derivatives (US 3615404), arylamine derivatives (US 3567450), amino-substituted chalcone derivatives (US 3526501), styreneanthracene derivatives (JP-A-56-46234), polycyclic aromatic compounds (EP 1009041), polyarylalkane derivatives (US 3615402), fluorenone derivatives (JP-A-54-110837), hydrazone derivatives (US 3717462), acylhydrazones, stilbene derivatives (JP-A-61-210363), silazane derivatives (US 4950950), polysilanes (JP-A-2-204996), aniline copolymers (JP-A-2-282263), thiophene oligomers (JP Heisei 1 (1989) 211399), polythiophenes, poly (N-vinylcarbazole) (PVK), polypyrroles, polyanilines and other conductive macromolecules, porphyrin compounds (JP-A-63-2956965, US 20432), aromatic dimethylene type compounds, such as CDBP, CBP, mCP, aromatic tertiary amines and styrylamine compounds (US 4127412), for example triphenylamine, triphenylamine type and triphenylamine type diamine. It is also possible to use arylamine dendrimers (JP Heisei 8 (1996) 193191), monomeric triarylamines (US 3180730), triarylamines having one or more vinyl groups and/or at least one functional group having active hydrogen (US 3567450 and US 3658520) or tetraaryldiamines (two tertiary amine units are linked by an aryl group). Even more triarylamino groups may be present in the molecule. Also suitable are phthalocyanine derivatives, naphthalocyanine derivatives, butadiene derivatives and quinoline derivatives such as bipyrazino [2,3-f:2',3' -h ] quinoxaline hexacarbonitriles.

Aromatic tertiary amines having at least two tertiary amine units are preferred (US 2008/0102311, US4720432 and US 5061569), for example NPD (α -npd=4, 4' -bis [ N- (1-naphthyl) -N-phenylamino)]Biphenyl) (US 5061569), TPD 232 (=n, N ' -bis (N, N ' -diphenyl-4-aminophenyl) -N, N-diphenyl-4, 4' -diamino-1, 1' -biphenyl) or MTDATA (MTDATA or m-mtdata=4, 4',4 "-tris [3- (methylphenyl) phenylamine)]Triphenylamine) (JP-A-4-308688), TBDB (=N, N, N ', N' -tetra (4-biphenyl) diaminodiphenylene), TAPC (=1, 1-bis (4-di-p-tolylaminophenyl) cyclohexane), TAPPP (=1, 1-bis (4-di-p-tolylaminophenyl) -3-phenylpropane), BDTAPVB (=1, 4-bis [2- [4- [ N, N-di (p-tolyl) amino group)]Phenyl group]Vinyl group]Benzene), TTB (=n, N ' -tetra-p-tolyl-4, 4' -diaminobiphenyl), TPD (=4, 4' -bis [ N-3-methylphenyl)]-N-phenylamino) biphenyl), N, N, N ', N' -tetraphenyl-4, 4 '-diamino-1, 1',4', 1',4', 1' -tetraphenyl and tertiary amines likewise having carbazole units, for example TCTA (=4- (9H-carbazol-9-yl) -N, N-bis [4- (9H-carbazol-9-yl) phenyl)]Aniline). Also preferred are hexaazatriphenylene compounds and phthalocyanine derivatives (e.g. H) according to US2007/0092755 ₂ Pc, cuPc (=copper phthalocyanine), coPc, niPc, znPc, pdPc, fePc, mnPc, clAlPc, clGaPc, clInPc, clSnPc, cl ₂ SiPc、(HO)AlPc、(HO)GaPc、VOPc、TiOPc、MoOPc、GaPc-O-GaPc)。

Triarylamine compounds of the following formulae (TA-1) to (TA-14) are particularly preferred, which are described in documents EP 1162193B1, EP 650 9555B 1, synth.metals 1997,91 (1-3), 209, DE19646119, WO2006/122630, EP1860097, EP1834945, JP08053397, US6251531, US2005/0221124, JP08292586, US7399537, US2006/0061265, EP1661888 and WO 2009/04635. The compounds of formulae (TA-1) to (TA-14) may also be substituted:

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other hole injection materials, hole transport materials or electron blocking materials that can be purified according to the invention are described in EP0891121, EP1029909, US2004/0174116, WO2013/120577, WO2013/087142, WO2014/067614, WO2014/072017, WO2014/015937, WO2014/015935, WO2015/022051, WO2016/078747, WO2016/087017, WO2017/041874, WO2017/016632, WO2017/148564, WO 2018/083053.

In principle, any known electron blocking material may be used. Suitable electron blocking materials are, among others described elsewhere in this application, transition metal complexes, such as Ir (ppz) ₃ (US2003/0175553)。

Compounds having electron-injecting and/or electron-transporting properties are, for example, pyridine, pyrimidine, pyridazine, pyrazine,Diazole, quinoline, quinoxaline, anthracene, benzanthracene, pyrene, perylene, benzimidazole, triazine, ketone, phosphine oxide and phenazine derivatives, but also triarylboranes.

Particularly suitable compounds for the electron transport and electron injection layer are metal chelates of 8-hydroxyquinoline (e.g. LiQ, alQ ₃ 、GaQ ₃ 、MgQ ₂ 、ZnQ ₂ 、InQ ₃ 、ZrQ ₄ ) BAlQ, ga hydroxyquinoline complexes, 4-azaphenanthren-5-ol-Be complexes (US 5529853A, see formula ET-1), butadiene derivatives (US 4356429), heterocyclic optical brighteners (US 4539507), benzimidazole derivatives (US 2007/0273272) such as TPBI (US 5766779, see formula ET-2), 1,3, 5-triazines such as spirobifluorene-triazine derivatives (e.g. according to DE 102008064200), pyrene, anthracene, tetracene, fluorene, spirobifluorene, dendrimers, tetracene (e.g. rubrene derivatives), 1, 10-phenanthroline derivatives (JP 2003-115387, JP 2004-311184, JP 2001-267080, WO 2002/043449), silacyclopentadiene derivatives (EP 1480280, EP 1478032, EP 1469533), borane derivatives such as Si-containing triarylborane derivatives (US 2007/0087219A1, see formula ET-3), pyridinesDerivatives (JP 2004-200162), phenanthrolines, in particular 1, 10-phenanthroline derivatives such as BCP and Bphen, including various phenanthrolines linked by biphenyl or other aromatic groups (US 2007-0252517) or phenanthrolines linked by anthracene (US 2007-012656, see formulas ET-4 to ET-6), and pyrimidines or triazines, as described for example in formulas ET-7 and ET-8. The compounds of the formulae (ET-1) to (ET-8) may also be substituted:

Also suitable are heterocyclic organic compounds, for example thiopyranodidioxide,Oxazole, triazole, imidazole or +.>Diazoles are described. Examples of the use of five-membered rings containing N are e.g.>Azole, preferably 1,3,4->Diazoles, for example compounds of the formulae ET-6, ET-7, ET-8 and ET-9, which are described in particular in detail in U.S. Pat. No. 6,0273272 A1, thiazole,/o>Diazoles, thiadiazoles, triazoles, see in particular US2008/0102311 A1 and Y.A.Levin, M.S.Skorobogatova, khimiya Geterotsiklicheskikh Soedinenii 1967 (2), 339-341, preferably compounds of formula ET-10, silacyclopentadiene derivatives. Preferred compounds are the following compounds of formulae (ET-9) to (ET-10):

organic compounds such as fluorenone, fluorenylmethylene, perylene tetracarboxylic acid, anthraquinone-dimethane, dibenzoquinone, anthrone and anthraquinone-diethylenediamine derivatives can also be used.

2,9,10-substituted anthracene (substituted with 1-or 2-naphthyl and 4-or 3-biphenyl) or molecules containing two anthracene units are preferred (US 2008/0193796 A1, see formula ET-11). Also very advantageous are compounds of 9, 10-substituted anthracene units with benzimidazole derivatives (U.S. Pat. No. 3,182A and EP 1551206 A1, see formulae ET-12 and ET-13).

Other electron injecting or electron transporting materials that can be purified according to the invention are described in WO2005/053055, WO2010/072300, WO 2014/023288, WO2015/049030, WO 2016/012675, WO2017/178311, WO2017/016630, WO2018/060307, WO 2018/060218.

The functional material used in the method of the invention may comprise a light emitter. The term "luminophore" refers to a material that upon excitation, which can occur by the transfer of any type of energy, causes a radiative transition to the ground state under the conditions of light emission. Generally, two types of luminophores are known: fluorescent light emitters and phosphorescent light emitters. The term "fluorescent emitter" refers to a material or compound in which a radiative transition from an excited singlet state to a ground state occurs. The term "phosphorescent emitter" preferably refers to a luminescent material or compound comprising a transition metal.

If the dopant causes the above-mentioned properties in the system, the light emitter is also generally referred to as a dopant. The dopant in the system comprising the host material and the dopant is understood to mean a smaller proportion of the components in the mixture. Accordingly, a host material in a system comprising the host material and a dopant is understood to mean a component in a mixture in a greater proportion. Thus, the term "phosphorescent emitter" can also be understood to mean, for example, phosphorescent dopants.

Compounds capable of emitting light include fluorescent and phosphorescent emitters. These compounds include compounds having stilbene, stilbene amine, styrylamine, coumarine, rubrene, rhodamine, thiazole, thiadiazole, cyanine, thiophene, p-phenylene, perylene, phthalocyanine, porphyrin, ketone, quinoline, imine, anthracene, and/or pyrene structures. Particularly preferred are compounds that are capable of efficiently emitting light from the triplet state, i.e. exhibit electrophosphorescence instead of electrofluorescence, even at room temperature, which often leads to an increase in energy efficiency. First, compounds containing heavy atoms with an atomic number greater than 36 are suitable for this purpose. Preferred compounds are those containing d-or f-transition metals satisfying the above conditions. Particular preference is given here to corresponding compounds which contain elements of groups 6 to 10, preferably 8 to 10 (Mo, W, re, cu, ag, au, zn, ru, os, rh, ir, pd, pt, preferably Ru, os, rh, ir, pd, pt). Functional compounds useful herein include, for example, the various complexes described in, for example, WO 02/068435A1, WO 02/081488A1, EP 1239526 A2 and WO 04/026886 A2.

Preferred compounds that can be used as fluorescent emitters are described in detail below by way of example. Preferred fluorescent emitters are selected from the group consisting of monostyrylamines, distyrylamines, tristyrylamines, tetrastyrylamines, styrylphosphines, styrylethers and arylamines.

Monostyrylamine is understood to mean a compound containing one substituted or unsubstituted styryl group and at least one amine, preferably an aromatic amine. Distyrylamine is understood to mean a compound containing two substituted or unsubstituted styryl groups and at least one amine, preferably an aromatic amine. Tristyrylamine is understood to mean a compound containing three substituted or unsubstituted styryl groups and at least one amine, preferably an aromatic amine. Tetraphenylvinylamine is understood to mean a compound containing four substituted or unsubstituted styryl groups and at least one amine, preferably an aromatic amine. The styryl group is more preferably stilbene, which may also be further substituted. In a similar manner to amines, the corresponding phosphines and ethers are defined. At the position ofAryl amine or aromatic amine in the sense of the present invention is understood to mean a compound containing three substituted or unsubstituted aromatic or heteroaromatic ring systems directly bonded to the nitrogen. Preferably, at least one of these aromatic or heteroaromatic ring systems is preferably a fused ring system, preferably having at least 14 aromatic ring atoms. Preferred examples thereof are aromatic anthraceneamines, aromatic anthracenediamines, aromatic pyrenamines, aromatic pyrenediamines, aromatic Amine or aromatic->A diamine. Aromatic anthraceneamines are understood to mean compounds in which the diarylamino group is directly bonded to the anthracene group, preferably in the 9-position. Aromatic anthracenediamine is understood to mean a compound in which two diarylamino groups are directly bonded to the anthracene group, preferably in the 2, 6-or 9, 10-position. In a similar manner thereto, aromatic pyrenamines, pyrenediamines, (-) -are defined>Amine and->Diamines in which the diarylamino group is bonded to pyrene preferably in the 1-position or in the 1, 6-position.

Also preferred are fluorescent emitters selected from: indenofluorene amine or indenofluorene diamine, which is described in detail in particular in document WO 06/122630; benzindene fluorenamines or benzindene fluorendiamines, which are described in detail in particular in document WO 2008/006449; and dibenzoindenofluorene amines or dibenzoindenofluorene diamines, which are described in detail, inter alia, in document WO 2007/140847.

Examples of styrylamine-derived compounds which can be used as fluorescent emitters are substituted or unsubstituted trisilbene amines or the dopants described in WO 06/000388, WO 06/058737, WO 06/000389, WO 07/065549 and WO 07/115610. Distyrylbenzene and distyrylbiphenyl derivatives are described in US 5121029. Other styrylamine can be found in US 2007/012656 A1.

Particularly preferred styrylamine compounds are compounds of formula EM-1 as described in U.S. Pat. No. 2,50234 B2 and compounds of formula EM-2 as described in DE10 2005,058557A 1:

particularly preferred triarylamine compounds or groups or structural elements are compounds of the formulae EM-3 to EM-18 and derivatives thereof as detailed in documents CN1583691, JP08/053397 and U.S. Pat. No. 6251531, EP195760, U.S. Pat. No. 2008/013101, U.S. Pat. No. 2006/210830, WO08/006449 and DE 102008035413:

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further preferred compounds which can be used as fluorescent emitters are selected from the derivatives of: naphthalene, anthracene, naphthacene, benzanthracene, benzophenanthrene (DE 10 2009 005746), fluorene, fluoranthene, bisindenopyrene, indenopyrene, phenanthrene, perylene (US 2007/0252517 A1), pyrene,Decacyclic, hexabenzone, tetraphenylcyclopentadiene, pentaphenylcyclopentadiene, fluorene, spirofluorene, rubrene, coumarin (US 4769292, US 6020078, US2007/0252517 A1), pyran, -/->Azole, benzo->Oxazole, benzothiazole, benzimidazole, pyrazine, cinnamate, pyrrolopyrrole dione, acridone and quinacridone (US 2007/0252517 A1).

Among the anthracene compounds, anthracene substituted at 9,10 positions, such as 9, 10-diphenylanthracene and 9, 10-bis (phenylethynyl) anthracene, are particularly preferable. 1, 4-bis (9' -ethynylanthracenyl) benzene is also a preferred dopant.

Derivatives of the following are likewise preferred: rubrene, coumarin, rhodamine, quinacridones such as DMQA (=N, N' -dimethylquinacridone), dicyanomethylenepyrans such as DCM (=4- (dicyanoethylene) -6- (4-dimethylaminostyryl-2-methyl) -4H-pyran, thiopyran, polymethine, pyranAnd thiopyran->Salts, bisindenopyrenes and indenopyrenes.

Blue fluorescent emitters are preferably polycyclic aromatic compounds, such as 9, 10-bis (2-naphthylanthracene) and other anthracene derivatives, and derivatives of tetracenes, xanthenes, perylenes, such as 2,5,8, 11-tetra-tert-butylperylene, phenylene, such as 4,4 '-bis (9-ethyl-3-carbazolylenylene) -1,1' -biphenyl, fluorene, fluoranthene, arylpyrene (US 2006/0222886 A1), arylene vinylenes (US 5121029, US 5130603), bis (azinyl) imine boron compounds (US 2007/0092753 A1), bis (azinyl) methylene compounds and carbonyl styryl compounds.

Further preferred blue fluorescent emitters are described in the following documents: c.h.chen et al: "Recent developments in organic electroluminescent materials" macromol. Symp.125, (1997), 1-48, and "Recent progress of molecular organic electroluminescent materials and devices" Mat. Sci. And Eng. R,39 (2002), 143-222.

A further preferred blue fluorescent emitter is the hydrocarbon disclosed in DE 102008035413. Particular preference is also given to the compounds described in detail in WO2014/111269, in particular to compounds having a bis (indenofluorene) basic skeleton. For the purpose of disclosure, the above-mentioned documents DE102008035413 and WO2014/111269 are incorporated into the present application by reference.

Further preferred compounds that can be used as fluorescent emitters are described in WO2010/012328, WO2010/012330, WO2014/037077 and WO 2008/145239.

In the context of the present invention phosphorescence is understood to mean luminescence from an excited state having a higher spin multiplex state, i.e. a spin state >1, in particular luminescence from an excited triplet state. In the context of the present application, all luminescent complexes with transition metals or lanthanoids, in particular all iridium, platinum and copper complexes, should be regarded as phosphorescent compounds.

Suitable phosphorescent compounds (=triplet emitters) are in particular the compounds described below: when properly excited, emits light, preferably in the visible region; and also contains at least one atom having an atomic number greater than 20, preferably greater than 38 and less than 84, more preferably greater than 56 and less than 80, particularly metals having such an atomic number. Phosphorescent emitters which are preferably used are compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, in particular compounds containing iridium or platinum.

Examples of such emitters can be found in the following applications: WO 00/70655, WO2001/41512, WO2002/02714, WO2002/15645, EP1191613, EP1191612, EP1191614, WO05/033244, WO05/019373, US2005/0258742, WO2009/146770, WO2010/015307, WO2010/031485, WO2010/054731, WO2010/054728, WO2010/086089, WO2010/099852, WO2010/102709, WO2011/032626, WO2011/066898, WO2011/157339, WO 2012/0000086, WO2014/008982, WO 2014/0234377, WO2014/094961, WO2014/094960, WO 2012012012012012015, WO 2012016/117718, WO 015815, WO 2016/03304, WO 2016/03439, WO 2018/186, WO 2018/0010198, WO 201538/0198, WO 201538/2019/2010198, WO 2012019/2010198, WO 201201wo 2012012019/0199/2010592, WO 2012012012019/201wo 2012019/201052019, WO 2012012012019/2012019, WO 2012012012019/2019/201correctly, WO 2012019/2019, WO 2012012012019/2019, and WO 2012012012012012019. In general, all phosphorescent complexes known to those skilled in the art of phosphorescent electroluminescent devices and organic electroluminescence are suitable, and those skilled in the art will be able to use other phosphorescent complexes without inventive effort.

Preferred ligands are 2-phenylpyridine derivatives, 7, 8-benzoquinoline derivatives, 2- (2-thienyl) pyridine derivatives, 2- (1-naphthyl) pyridine derivatives, 1-phenylisoquinoline derivatives, 3-phenylisoquinoline derivatives or 2-phenylquinoline derivatives. All of these compounds may be substituted, for example for the blue color, with fluoro, cyano and/or trifluoromethyl substituents. The auxiliary ligand is preferably acetylacetone or picolinic acid.

Complexes of Pt or Pd of formula EM-19 with tetradentate ligands are particularly suitable for use as luminophores.

Compounds of formula EM-19 are described in more detail in US 2007/0087218 A1, which is incorporated herein by reference for the purpose of illustrating substituents and labels in the above formulae.

Also suitable are Pt-porphyrin complexes with an enlarged ring system (US 2009/0061681 A1) and Ir complexes, for example 2,3,7,8,12,13,17, 18-octaethyl-21 h,23 h-porphyrin-Pt (II), tetraphenyl-Pt (II) -tetrabenzoporphyrin (US 2009/0061681 A1), cis-bis (2-phenylpyridyl-N, C ² 'Pt (II), cis-bis (2- (2' -thienyl) pyridinato-N, C ³ 'Pt (II), cis-bis (2- (2' -thienyl) quinoline-N, C ⁵ ' Pt (II), (2- (4, 6-difluorophenyl) pyridino-N, C ² ') Pt (II) (acetylacetonate) or tris (2-phenylpyridino-N, C ² ' iridium (III) (=ir (ppy) ₃ Green), bis (2-phenylpyridino-N, C ² ) Ir (III) (acetylacetone) (=Ir (ppy) ₂ Acetylacetone, green, U.S. Pat. No. 2001/0053462 A1,Baldo,Thompson et al.Nature 403, (2000), 750-753), bis (1-phenylisoquinoline-N, C ² ') (2-phenylpyridino-N, C ² ') Ir (III), bis (2-phenylpyridino-N, C ² ') (1-phenylisoquinoline-N, C ² ')Ir(III)、Bis (2- (2' -benzothienyl) pyrido-N, C ³ ') Ir (III) (acetylacetonate), bis (2- (4 ',6' -difluorophenyl) pyridinato-N, C ² ') Ir (III) (picric acid) (FIrpic, blue), bis (2- (4 ',6' -difluorophenyl) pyridino-N, C ² ') Ir (III) (tetrakis (1-pyrazolyl) borate), tris (2- (biphenyl-3-yl) -4-t-butylpyridinato) Ir (III), (ppz) ₂ Ir(5phdpym)(US2009/0061681 A1)、(45ooppz) ₂ Derivatives of Ir (5 phdpym) (US 2009/0061681 A1), 2-phenylpyridino-Ir complexes such as PQIr (=ir (III) bis (2-phenylquinoline-N, C) ² ') acetylacetone), tris (2-phenylisoquinoline-N, C) Ir (III) (red), bis (2- (2' -benzo [4, 5-a)]Thienyl) pyridino-N, C ³ ) Ir (acetylacetonate) ([ Btp) ₂ Ir(acac)]Red, adachi et al appl. Phys. Lett.78 (2001), 1622-1624). The complexes described in detail in WO2016/124304 are also particularly suitable. For the purpose of this disclosure, the above-mentioned document, in particular WO2016/124304, is incorporated into the present application by reference.

Also suitable are trivalent lanthanides such as Tb ³⁺ And Eu ³⁺ Is a complex of (J.Kido et al Appl. Phys. Lett.65 (1994), 2124;Kido et al.Chem.Lett.657,1990;US 2007/0252517A 1) or of Pt (II), ir (I), rh (I) with a maleonitrile dithioester (Johnson et al, JACS105,1983,1795), re (I) -tricarbodiimide complex (Wright ton, JACS 96,1974,998inter alia), complexes of Os (II) with cyano ligands and bipyridyl or phenanthroline ligands (Ma et al, synth. Metals 94,1998,245).

Other phosphorescent emitters with tridentate ligands are described in US 6824895 and US 10/729238. Phosphorescent complexes that emit red light can be found in US6835469 and US 6830828.

Particularly preferred compounds for use as phosphorescent dopants include the compounds of formula EM-20 and derivatives thereof described in U.S. 2001/0053462 A1 and Inorg. Chem.2001,40 (7), 1704-1711, JACS2001,123 (18), 4304-4312.

Derivatives are described in US7378162, US6835469 and JP 2003/253145.

Furthermore, compounds of the formulae EM-21 to EM-28 and derivatives thereof described in US7238437, US2009/008607 and EP1348711 may be used as luminophores.

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Other luminophores which can be purified according to the invention are described in the following documents: WO 00/70655, WO2001/41512, WO2002/02714, WO2002/15645, EP1191613, EP1191612, EP1191614, WO05/033244, WO05/019373, US2005/0258742, WO2009/146770, WO2010/015307, WO2010/031485, WO2010/054731, WO2010/054728, WO2010/086089, WO2010/099852, WO2010/102709, WO2011/032626, WO2011/066898, WO2011/157339, WO 2012/0000086, WO2014/008982, WO 2014/0234377, WO2014/094961, WO2014/094960, WO 2012012012012012015, WO 2012016/117718, WO 015815, WO 2016/03304, WO 2016/03439, WO 2018/186, WO 2018/0010198, WO 201538/0198, WO 201538/2019/2010198, WO 2012019/2010198, WO 201201wo 2012012019/0199/2010592, WO 2012012012019/201wo 2012019/201052019, WO 2012012012019/2012019, WO 2012012012019/2019/201correctly, WO 2012019/2019, WO 2012012012019/2019, and WO 2012012012012012019.

In a preferred configuration, suitable combinations of compounds preferably form a super-fluorescent and/or super-phosphorescent system. Such superfluorescent and/or superphosphorescent systems form a preferred embodiment of the functional material to be purified according to the invention.

Preferably, for this purpose, the fluorescent emitters are used in combination with one or more phosphorescent materials (triplet emitters) and/or compounds as TADF (thermally activated delayed fluorescence) host materials.

WO2015/091716 and WO2016/193243 disclose OLEDs comprising both phosphorescent compounds and fluorescent emitters in the light-emitting layer, wherein energy is transferred from the phosphorescent compounds to the fluorescent emitters (superphosphorescence). In this context, phosphorescent compounds correspondingly behave as host materials. As known to those skilled in the art, host materials have higher singlet and triplet energies than the emitters, so that energy from the host material will also be transferred to the emitters with maximum efficiency. The systems disclosed in the prior art are having such an energy relationship.

As described above, the fluorescent light-emitting body may be preferably used in combination with a TADF host material and/or a TADF light-emitting body.

For example, b.h. uoyama et al, nature 2012, vol.492,234 describe a process known as Thermally Activated Delayed Fluorescence (TADF). To achieve this, for example, less than about 2000cm is required in the illuminant ^-1 Is relatively small in singlet-triplet separation ΔE (S ₁ -T ₁ ). To turn on in principle spin-forbidden T ₁ →S ₁ The transitions, as well as the luminophores, may provide other compounds with strong spin-orbit coupling in the matrix, whereby intersystem crossing is achieved by spatial proximity and thus possible interactions between molecules, or spin-orbit coupling is produced by the metal atoms present in the luminophores.

Compounds used as host materials, particularly compounds used with emissive compounds, include various types of materials.

The host material typically has a larger band gap between the HOMO and LUMO than the emitter material used. In addition, preferred host materials exhibit the properties of hole or electron transporting materials. In addition, the host material may have electron or hole transport properties.

Host materials are also referred to as host materials in some cases, especially when the host materials are used in combination with phosphorescent emitters in OLEDs.

Preferred host materials or co-host materials particularly for use with fluorescent dopants are selected from the group consisting of: oligomeric arylene groups (e.g.2, 2', 7' -tetraphenylspirobifluorene or dinaphthyl anthracene according to EP 676861), in particular oligomeric arylene groups containing condensed aromatic groups, e.g.anthracene, benzanthracene, benzophenanthrene (DE 10 2009 005746, WO 09/06956) 6) Phenanthrene, naphthacene, hexabenzobenzene,Fluorene, spirofluorene, perylene, phthaloyl perylene, naphthaloyl perylene, decacyclic olefin, rubrene; oligomeric arylene vinylenes (e.g. dpvbi=4, 4 '-bis (2, 2-diphenylvinyl) -1,1' -biphenyl or spiro-DPVBi according to EP 676861); multipodal metal complexes (e.g. according to WO 04/081017), in particular metal complexes of 8-hydroxyquinoline such as Alq ₃ (=tris (8-hydroxyquinoline) aluminum (III) or bis (2-methyl-8-quinolinolato) -4- (phenylphenanthroline) aluminum, including imidazole chelates (US 2007/0092753 A1) and quinoline-metal complexes, aminoquinoline-metal complexes, benzoquinoline-metal complexes, hole-conducting compounds (e.g. according to WO 2004/058911), electron-conducting compounds, in particular ketones, phosphine oxides, sulfoxides, carbazole, spiro-carbazole, indenocarbazole etc. (e.g. according to WO05/084081 and WO 05/084082), atropisomers (e.g. according to WO 06/048268), boric acid derivatives (e.g. according to WO 06/117052) or benzanthracenes (e.g. according to WO 08/145239).

Particularly preferred compounds that can be used as host materials or co-host materials are selected from: oligomeric arylene groups including anthracene, benzanthracene, and/or pyrene; or atropisomers of these compounds. In the sense of the present invention, an oligomeric arylene group is understood to mean a compound in which at least three aryl or arylene groups are bonded to one another.

Preferably the host material is specifically selected from the group consisting of compounds of formula (H-100),

Ar ⁵ -(Ar ⁶ ) _p -Ar ⁷ (H-100)

wherein Ar is ⁵ 、Ar ⁶ 、Ar ⁷ An aryl or heteroaryl group which is identical or different in each case and has 5 to 30 aromatic ring atoms and which may be optionally substituted, and p is an integer in the range from 1 to 5; meanwhile, when p=1, ar ⁵ 、Ar ⁶ And Ar is a group ⁷ The sum of pi electrons in the electron pair is at least 30; when p=2, the sum of pi electrons is at least 36; and when p=3, the sum of pi electrons is at least42。

More preferably, in the compound of formula (H-100), the group Ar ⁶ Is anthracene and is a group Ar ⁵ And Ar is a group ⁷ Bonding in the 9 and 10 positions, where these groups may optionally be substituted. Most preferably, the group Ar ⁵ And/or Ar ⁷ At least one of which is a fused aryl group selected from the group consisting of: 1-or 2-naphthyl; 2-, 3-or 9-phenanthryl; or 2-, 3-, 4-, 5-, 6-or 7-benzanthracene. Anthracene-based compounds are described in US2007/0092753 A1 and US2007/0252517 A1, for example 2- (4-methylphenyl) -9, 10-bis- (2-naphthyl) anthracene, 9- (2-naphthyl) -10- (1, 1' -biphenyl) anthracene and 9, 10-bis [4- (2, 2-diphenylvinyl) phenyl ]]Anthracene, 9, 10-diphenylanthracene, 9, 10-bis (phenylethynyl) anthracene, and 1, 4-bis (9' -ethynylanthracenyl) benzene. Also preferred are compounds having two anthracene units (US 2008/0193796 A1), e.g. 10,10' -bis [1,1',4',1 ] " ]Terphenyl-2-yl-9, 9' -dianthracene.

Also preferred are derivatives of: aryl amines; styrylamine; fluorescein; diphenyl butadiene; tetraphenylbutadiene; cyclopentadiene; tetraphenyl cyclopentadiene; penta-phenylcyclopentadiene; coumarin;diazoles; dibenzo (dibenzo)An oxazoline; />An azole; pyridine; pyrazine; an imine; benzothiazole; benzo->An azole; benzimidazoles (US 2007/0092753 A1), for example 2,2' - (1, 3, 5-phenylene) tris [ 1-phenyl-1H-benzimidazole]The method comprises the steps of carrying out a first treatment on the surface of the Aldazines; stilbene; styrylarylene derivatives, e.g. 9, 10-bis [4- (2, 2-diphenylvinyl) phenyl ]]Anthracene and distyrylarylene derivatives (US 5121029); diphenylethylene; vinyl anthracene; diaminocarbazole; pyran; thiopyran; pyrrole compoundsAnd a diketopyrrolopyrrole; polymethine; cinnamic acid esters and fluorescent dyes.

Particular preference is given to derivatives of aryl amines and styrene amines, for example TNB (=4, 4' -bis [ N- (1-naphthyl) -N- (2-naphthyl) amino)]Biphenyl). Can be such as LiQ or AlQ ₃ The metal-quinoline complex of (2) is used as a co-host.

Preferred compounds with oligomeric arylene groups as matrix are described in detail in US2003/0027016, US7326371, US2006/043858, WO2007/114358, WO08/145239, JP3148176, EP1009044, US2004/018383, WO2005/061656, EP0681019, WO2004/013073, US5077142, WO2007/065678 and DE 102009005746, wherein particularly preferred compounds are described by the formulae H-101 to H-108. The compounds of the formulae H-101 to H-108 may also be substituted:

In addition, compounds that can be used as hosts or matrices include materials used with phosphorescent emitters. These compounds, which can also be used as structural elements in the polymer, include: CBP (N, N-dicarbazolyl biphenyl); carbazole derivatives (for example according to WO05/039246, US2005/0069729, JP2004/288381, EP1205527 or WO 08/086851); azacarbazoles (e.g. according to EP1617710, EP1617711, EP1731584, JP 2005/347160); ketones (for example according to WO 04/093207 or according to DE 102008033943); phosphine oxides; sulfoxides and sulfones (e.g. according to WO 05/003253); an oligophenylene group; aromatic amines (e.g. according to US 05/0069729); bipolar matrix materials (e.g. according to WO 07/137725); silanes (e.g.according to WO 05/111172); 9, 9-diaryl fluorene derivatives (e.g. according to DE 102008017591); azaboroles or borates (e.g. according to WO 06/117052); triazine derivatives (for example according to DE 102008036982); indolocarbazole derivatives (e.g. according to WO 07/063276 or WO 08/056746); indenocarbazole derivatives (e.g. according to DE 102009023155 and DE 102009031021); diazaphosphole derivatives (e.g. according to DE 102009022858); triazole derivatives, Azole and->Azole derivatives; imidazole derivatives; polyarylalkane derivatives; pyrazoline derivatives, pyrazolone derivatives; stilbene pyrazine derivatives; thiopyran dioxide derivatives; phenylenediamine derivatives; aromatic tertiary amines; styryl amines; amino-substituted chalcone derivatives; indoles; hydrazone derivatives; stilbene derivatives; silazane derivatives; aromatic dimethylene compounds; carbodiimide derivatives; metal complexes of 8-hydroxyquinoline derivatives such as Alq ₃ The 8-hydroxyquinoline complex may further contain triarylaminophenol ligands (US 2007/01345514 A1), metal complexes/polysilane compounds and thiophene, benzothiophene and dibenzothiophene derivatives.

Examples of preferred carbazole derivatives are mCP (=1, 3-N, N-dicarbazolylbenzene (=9, 9'- (1, 3-phenylene) bis-9H-carbazole)) (formula H-9), CDBP (=9, 9' - (2, 2 '-dimethyl [1,1' -biphenyl ] -4,4 '-diyl) bis-9H-carbazole), 1, 3-bis (N, N' -dicarbazolyl) benzene (=1, 3-bis (carbazol-9-yl) benzene), PVK (polyvinylcarbazole), 3, 5-bis (9H-carbazol-9-yl) biphenyl and CMTTP (formula H-10). Particularly preferred compounds (formulas H-111 and H-113) are described in detail in US 2007/0128767 A1 and US2005/0249976 A1.

Preferred tetraaryl-Si compounds are described in detail, for example, in documents US2004/0209115, US2004/0209116, US 2007/0087218A 1 and in Chemistry & Industry (London, united Kingdom), 1960,120 at H.Gilman, E.A.Zuech. Particularly preferred tetraaryl-Si compounds are described by the formulae H-114 to H-121.

In particular, particularly preferred compounds for preparing phosphorescent dopant matrices are described in detail in DE 102009022858, DE 102009023155, EP 652273, WO 07/063276 and WO 08/056746, particularly preferred compounds being described by the formulae H-122 to H-125.

As the functional compound which can be used according to the present invention and can be used as a host material, a substance having at least one nitrogen atom is particularly preferable. These preferably include aromatic amines, triazine derivatives and carbazole derivatives. For example, carbazole derivatives in particular show surprisingly high efficiency. Triazine derivatives result in exceptionally long lifetimes of electronic devices comprising said compounds.

Other host materials that can be purified according to the invention are described in WO2010/136109, WO2011/057706, WO2011/160757, WO 2013/04176, WO2014/015931, WO2014/094963, WO2015/165563, WO2015/169412, WO2015/192939, WO2016/015810, WO 2016/18540, WO2017/025164, WO2017/071791 and WO 2018/050583.

In addition, compounds that improve transitions from singlet to triplet states and are used in support of functional compounds with emitter properties for improving the phosphorescent properties of these compounds can be purified. Useful units for this purpose are in particular carbazole and bridged carbazole dimer units, as described, for example, in WO 04/070772 and WO 04/113468. Also suitable for this purpose are ketones, phosphine oxides, sulfoxides, sulfones, silane derivatives and similar compounds, as are described, for example, in WO 05/040302.

The n-type dopant is herein considered to refer to a reducing agent, i.e. an electron donor. A preferred example of an n-type dopant is W (hpp) ₄ And other electron rich metal complexes according to WO 2005/086251, p=n compounds (e.g. WO 2012/175535, WO 2012/175219), naphthylene carbodiimides (e.g. WO 2012/168458), fluorenes (e.g. WO 2012/031735), radicals and diradicals (e.g. EP 1837926, WO 2007/107306), pyridines (e.g. EP 2452946, EP 2463927), N-heterocyclic compounds (e.g. WO 2009/000237), and acridines and phenazines (e.g. US 2007/145355).

Further, the functional material may be a wide bandgap material. Wide bandgap materials are considered to mean materials in the sense of the disclosure of US 7294849. These systems exhibit particularly advantageous performance data in electroluminescent devices.

In principle, any known hole blocking material may be used for purification. Suitable hole blocking materials are, among others described in detail elsewhere in this application, bis (2-methyl-8-quinolinato) (4-phenylphenol) aluminum (III) (BAlQ), fac-tris (1-phenyl-pyrazolato-N, C2) -iridium (III) (Ir (ppz) ₃ ) Phenanthroline derivatives such as BCP or phthalimides such as TMPP or hole blocking materials as described in WO 00/70655, WO 01/41512 and WO 01/93642.

Furthermore, preferred functional materials which can be used for the functional layer of the electronic device, if they are low molecular weight compounds, preferably have a molecular weight of 2000g/mol or less, more preferably 1500g/mol or less, particularly preferably 1200g/mol or less and most preferably 1000g/mol or less. The low molecular weight compounds are capable of sublimation or evaporation.

For the purpose of disclosure, the publications cited above for describing functional materials for the functional layers of the fabrication of electronic devices are incorporated by reference into the present application.

By the present process, a granular material is preferably obtained. The preferred particulate material may comprise all organic functional materials necessary for the manufacture of a particular functional layer of the electronic device. For example, if the hole transporting, hole injecting, electron transporting or electron injecting layer is formed specifically of two functional compounds, the particulate material thereby specifically contains these two compounds as organic functional materials. For example, if the luminescent layer comprises a combination of a luminescent body and a matrix or host material, the formulation specifically comprises a mixture of a luminescent body and a matrix or host material as an organic functional material, as explained in more detail elsewhere in the present application.

The functional material is typically an organic or inorganic material introduced between the anode and the cathode. Preferably, the organic functional material is selected from the group consisting of fluorescent emitters, phosphorescent emitters, emitters exhibiting TADF (thermally activated delayed fluorescence), emitters exhibiting superfluorescence or superphosphorescence, host materials, exciton blocking materials, electron injection materials, electron transport materials, electron blocking materials, hole injection materials, hole conducting materials, hole blocking materials, n-type dopants, p-type dopants, wide band gap materials, charge generating materials.

The purified functional material, preferably a particulate material, is preferably used in the manufacture of electronic devices.

An electronic device is understood to mean a device comprising an anode, a cathode and at least one intermediate functional layer comprising at least one organic or organometallic compound.

It should be noted that variations of the embodiments described in the present invention are included in the scope of the present invention. Any feature disclosed in this application may be replaced by an alternative feature serving the same, equivalent or similar purpose, unless expressly excluded. Thus, unless otherwise indicated, any feature disclosed in this specification should be considered as an example of a generic series or as an equivalent or similar feature.

All of the features of the invention may be combined with each other in any way unless the specific features and/or steps are mutually exclusive. This applies in particular to the preferred features of the invention. Also, features that are not necessarily combined may be used alone (and not in combination).

It should also be noted that many features, particularly of the preferred embodiments of the present invention, should be regarded as inventive in themselves and not just as some embodiments of the present invention. For these features, independent protection may be sought in addition to, or in place of, any of the presently claimed inventions.

The technical teachings disclosed in the present invention can be refined and combined with other examples.

Those skilled in the art will be able to use the details given to further fabricate the electronic device of the present invention without undue burden to implement the invention in the full scope of the claims.

The invention is illustrated below by means of schematic drawings. The drawings show:

FIG. 1 is a preferred embodiment of a continuous purification apparatus according to the present invention;

FIG. 2 is another embodiment of a continuous purification apparatus according to the present invention.

Fig. 1 shows a schematic view of an apparatus 10 according to the invention for continuous purification of at least one functional material. The illustrated apparatus 10 comprises a feed device 12, an evaporation device 14, a condensation device 16 and a discharge device 18 for at least one functional material.

The feeding device 12 for at least one functional material in the present invention is configured as a feeding extruder unit and comprises a reservoir vessel 20, which is preferably inert. The temperature of the feeding device 12 configured as a feeding extruder unit may be controlled by a temperature control unit 22, wherein the temperature control unit 22 is able to adjust the temperature of different areas of the feeding device 12 to different temperatures, whereby a temperature gradient may be created. Furthermore, the feed device 12 is provided with a vent 24, through which vent 24 solvent residues can be removed.

The evaporation apparatus 14 in the present invention comprises an evaporation material distributor system 26 that distributes the functional material to be purified over the surface of an evaporation unit 28. The vaporizing device 14 of the present invention may be heated using a fluid, wherein the fluid may be heated by a heating system 30 for the vaporizing device 14 and supplied to the vaporizing unit 28 via a heated fluid feed 32 and removed therefrom via a heated fluid outlet 34.

The evaporation device in the present invention comprises an opening connected to a residue collection container 38 via a residue outlet 36.

The vaporizing device 14 of the present invention forms with the feeding device 12 and the discharging device 18 a vaporizing chamber 40 that can be evacuated via a vacuum pump system 42.

The functional material to be purified is evaporated or sublimated in the evaporation device 14 and condensed in the condensation device 16.

The condensation device 16 is equipped with a condensate collector 44, wherein condensed functional material can be collected by the condensate collector 44 in the discharge device 18.

The condensed functional material is conducted through condensate collector 44 into discharge device 18. The discharge device 18 is configured to discharge the extruder unit and its temperature is controlled by a temperature controllable unit 46. In the discharge extruder unit, the condensed functional material solidifies and a reduced pressure, preferably a high vacuum, may be generated within the evaporation chamber 40.

The discharge device 18 comprises a discharge opening, which in the present case is connected to a discharge vessel 48, through which discharge vessel 48 purified functional material can be removed. In a preferred configuration, the discharge port is connected to a granulation unit and the obtained granular material is introduced into a discharge vessel 48.

Fig. 2 shows another embodiment of the apparatus for continuous purification according to the invention. This embodiment shows similarity to the apparatus for purifying at least one functional material described in detail in KR 2019/0125400. However, the apparatus detailed in KR 2019/0125400 does not have a discharge means to discharge the extruder unit, but instead uses a conventional collection vessel that must be removed to extract the purified material.

In a schematic fig. 2, an apparatus 110 for continuous purification of at least one functional material according to the present invention is shown. The illustrated apparatus 110 comprises a feed device 112, an evaporation device 114, a condensation device 116, an evaporation chamber 120 and a discharge device 118 for at least one functional material.

The embodiment detailed in fig. 2 is not preferred over the embodiment described in fig. 1 because the functional material to be purified is subjected to higher thermal stresses because of its longer duration.

In contrast to the prior art, what is important is the special configuration of the discharge device 118, which comprises the discharge extruder unit. Further details of the discharge extruder unit essentially correspond to the embodiment shown in fig. 1, so that it has a discharge opening through which the purified functional material can be removed. In a preferred configuration, the discharge port is connected to a granulation unit and the resulting granular material is introduced into a discharge vessel.

Details of other components of the embodiment detailed in fig. 2, in particular details of the feeding device 112, the evaporation device 114, the condensation device 116 and the evaporation chamber 120 for at least one functional material, can be found in the specification of KR 2019/0125000 (see KR 2019/0125000, fig. 5). These configurations are shown in particular in paragraphs 75 to 87 of pages 10 and 11, wherein figure 5 is described in detail, and for the purposes of this disclosure the detailed description given in publication KR 2019/0125000 regarding the feed device, evaporation device and condensation device is incorporated into this application by reference.

List of reference numerals

10. Continuous purification device

12. Feeding device for at least one functional material

14. Evaporation device

16. Condensing device

18. Discharge device

20. Reservoir container

22. Temperature control unit

24. Vent hole

26. Evaporated material dispenser system

28. Evaporation unit

30. Heating system

32. Heating fluid feeding device

34. Heating fluid outlet

36. Residue outlet

38. Residue collection container

40. Evaporation chamber

42. Vacuum pump system

44. Condensate collector

46. Temperature control unit

48. Discharge container

110. Continuous purification device

112. Feeding device for at least one functional material

114. Evaporation device

116. Condensing device

118. Discharge device

120. Evaporation chamber

A more detailed description of preferred extruders can be found in the prior art, for example in document EP 2 381 B1. These can be used in particular for the feeding and/or discharging of at least one functional material, as shown in particular in fig. 1 or fig. 2.

The determination of the glass transition temperature using a compound having a transition temperature which is difficult to determine is described in detail below.

Determination of the glass transition temperature (Tg) of bis-4, 4'- (N, N' -carbazolyl) biphenyls (CBP; CAS number 58328) 31-7)：

CBP has long been used as a host material in phosphorescent OLEDs (see, e.g., m.a. baldo et al, applied Physics Letters 1999,75 (1), 4-6).

The glass transition temperature of a material is difficult to determine, and thus this embodiment is particularly useful for providing evidence of the determinability of the glass transition temperature. A particularly preferred configuration measured shows that CBP has a glass transition temperature of about 115 ℃.

The exact procedure for this measurement is as follows:

1. repeating the manufacturing and purifying of the above materials; the preparation is carried out by a modified process according to BUCHWALD (see, e.g., buchwald et al, J.am.chem.Soc.1998,120 (37), 9722-9723). The improved process is based on patent application WO03/037844.

2. The material is subjected to secondary treatmentRepeated recrystallisation from alkanes is finally carried out by double "sublimation" (325 ℃ C.; 10) ^- ⁴ mbar; evaporating a liquid phase; solid state condensation).

3. The various materials were analyzed for purity by HPLC (instrument: agilent 1100; chromatographic column: agilent, sorbax SB-C18, 75X 4.6mm, particle size 3.5 μm; eluent mixture: 90% MeOH: THF (90:10, v/v) +10% water, residence time: 6.95 min); in each case, this is in the range of 99.9%, including all regioisomers obtained in the reaction.

4. By passing through ¹ H and ¹³ c NMR spectra test the identity and freedom of the material.

5. The determination of the glass transition temperature Tg is divided into two batches: batch a and batch B. Glass transition temperature Tg DSC 204/1/G with Netsch DSC instrumentAnd (5) determining. 10-15 mg of the sample was measured.

The glass transition temperature Tg was determined as described in Table 1 (batch A). For validation, the second batch (batch B) was used to make another reference measurement.

Table 1: determination of Tg of CBP

Table 1: tg determination of CBP (continuous)

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The data listed in table 1 show that glass transition temperatures can be reliably obtained even for difficult-to-determine compounds. Therefore, quenching is preferred after the first heating to obtain a clear glass transition temperature. Furthermore, one factor that has difficulty is recrystallization, which can occur in a temperature range between the glass transition temperature and the melting temperature. This can be reliably reduced by quenching and rapid reheating so that the glass transition temperature can be determined unambiguously and reliably.

Examples:

apparatus and method for controlling the operation of a device

The apparatus consisted of the following serially operated vacuum sealing components:

a feed extruder unit:

a) Inert melting vessels or vessels with heated feed valves

B)Thermo Scientific ^TM HAAKE ^TM MiniLab II micro-compounder with dedicated equipment for feeding, degassing, plasticizing and extrusion.

An evaporator unit:

UIC GmbH, modified KDl series model laboratory system.

High vacuum pump combination:

edwards, TSB4E1001, turbo pump station comprising a NEXT240D turbo pump with ISO100 flange and nXDS10i as booster pump, TAV5 vent valve and WRGSDN25KF pressure sensor, active wide range measurement tube.

Discharge extruder unit:

Thermo Scientific ^TM HAAKE ^TM mini Lab II micro-compounder with dedicated discharge and extrusion equipment.

Table 2 describes the functional material FM and the process conditions.

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Measurement conditions:

tg: the glass transition point from DSC, the first heating, the heating rate of 20K/min, the cooling rate of 20K/min, the measurement range of 0-350 ℃. Tm: for melting points in DSC, see Tg for description.

T sublimation evaporation TGA: the evaporation/sublimation temperature was measured by vacuum TGA as described above.

T sublimation process: process temperature during evaporation/sublimation.

T decomposition: decomposition temperature was obtained from a Duran glass ampoule melt-sealed in the dark at a specified temperature for 100 hours in a heat exposure test under high vacuum.

And (2) a P process: process pressure during evaporation/sublimation

Analysis:

by the method, by ¹ The functional material FM obtained by H NMR, HPLC and ICP-MS has the same purity characteristics as the material produced in a batch sublimation plant according to the prior art.

Application of functional materials FM1 to FM4 in OLED (organic light emitting diode) component

The functional materials FM1 to FM4 obtained by the above-described method are incorporated into the light-emitting layer of the phosphorescent OLED assembly, for example, as a hybrid host material.

The OLED is manufactured according to WO 2004/058911 by a general method, which is adapted to the environment described herein (variation of layer thickness, material used). The materials used are listed in table 3.

The OLED has the following layer structure:

substrate and method for manufacturing the same

Hole injection layer 1 (HIL 1), consisting of HTM1 doped with 5% NDP-9 (commercially available from Novaled), 20nm

Hole transport layer 1 (HTL 1) composed of HTM1, 40nm

Hole transport layer 2 (HTL 2), HTM2 20nm

Light emitting layer (EML), mixed host FM1:fm3 (40:60) (the numbers in brackets are the volume% of functional material in the mixture), doped with 15% dopant D

An electron transport layer (ETL 2) composed of ETL1, 5nm

An electron transport layer (ETL 1) composed of ETL1 (50%) ETL2 (50%) and 30nm

An Electron Injection Layer (EIL) composed of ETM2, 1nm

Cathode, composed of aluminum, 100nm

Table 3 summarizes the results:

table 4 shows the structural formulae of the materials used.

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Claims

1. A method of purifying at least one functional material that can be used for manufacturing a functional layer of an electronic device, the functional layer involving charge injection or charge transport and/or light emission or light outcoupling, characterized in that an apparatus (10, 110) is used, wherein the method comprises evaporating or sublimating and/or condensing the at least one functional material, and wherein the apparatus (10, 110) has:

a) At least one feed device (12, 112) for the at least one functional material, wherein the at least one functional material can be fed continuously via a feed opening provided in the feed device;

b) At least one evaporation device (14, 114) arranged downstream of the feeding device (12, 112), wherein the functional material is introduced into the evaporation device (14, 114) through the feeding device (12, 112) and is capable of being continuously evaporated by the evaporation device (14, 114);

c) At least one condensing device (16, 116), wherein by means of the condensing device (16, 116), the functional material is continuously condensable after evaporation in the evaporating device (14, 114);

D) At least one discharge device (18, 118) arranged downstream of the condensation device (16, 116), wherein the functional material can be continuously introduced from the condensation device (16, 116) into the discharge device (18, 118) and can be discharged through a discharge opening present in the discharge device (18, 118);

and wherein

The apparatus (10, 110) has an evaporation chamber (40, 120), at least a part of the evaporation means (14, 114) and at least a part of the condensation means (16, 116) are provided in the evaporation chamber (40, 120), wherein the evaporation chamber (40, 120) is connected or connectable to at least one evacuation apparatus and a reduced pressure, preferably a high vacuum, can be generated within the evaporation chamber (40, 120) when the continuous purification apparatus (10, 110) is operated, and the discharge means (18, 118) comprises or constitutes a discharge extruder unit.

2. The method of claim 1, wherein the at least one functional material is selected from the group consisting of fluorescent emitters, phosphorescent emitters, emitters that exhibit TADF (thermally activated delayed fluorescence), emitters that exhibit superfluorescence or superphosphorescence, host materials, exciton blocking materials, electron injection materials, electron transport materials, electron blocking materials, hole injection materials, hole conducting materials, hole blocking materials, n-type dopants, p-type dopants, wide bandgap materials, charge generating materials, or combinations thereof.

3. An apparatus (10, 110) for continuous purification of at least one functional material, the apparatus (10, 110) comprising:

e) At least one feed device (12, 112) for at least one functional material, wherein the at least one functional material can be fed continuously via a feed opening provided in the feed device;

f) At least one evaporation device (14, 114) arranged downstream of the feeding device (12, 112), wherein the functional material is introduced into the evaporation device (14, 114) through the feeding device (12, 112) and is capable of being continuously evaporated by the evaporation device (14, 114);

g) At least one condensing device (16, 116), wherein by means of the condensing device (16, 116), the functional material is continuously condensable after evaporation in the evaporating device (14, 114);

h) At least one discharge device (18, 118) arranged downstream of the condensation device (16, 116), wherein the functional material can be continuously introduced from the condensation device (16, 116) into the discharge device (18, 118) and can be discharged through a discharge opening present in the discharge device (18, 118);

and wherein

The apparatus (10, 110) has an evaporation chamber (40, 120), at least a part of the evaporation means (14, 114) and at least a part of the condensation means (16, 116) being provided in the evaporation chamber (40, 120), wherein the evaporation chamber (40, 120) is connected or connectable to at least one evacuation apparatus and a reduced pressure, preferably a high vacuum, can be generated within the evaporation chamber (40, 120) when the continuous purification apparatus (10, 110) is operated, and the evacuation means (18, 118) comprises or constitutes an evacuation extruder unit, characterized in that the evaporation means (14, 114) at least partly encloses the condensation means (16, 116).

4. An apparatus according to claim 3, characterized in that the feeding means (12, 112) comprise grooved rolls and/or extruder screws.

5. The apparatus according to claim 3 or 4, characterized in that the feed device (12, 112) comprises or constitutes a feed extruder unit and the discharge device (18, 118) comprises or constitutes a discharge extruder unit, wherein the extruder screw of the feed extruder unit is connected to the extruder screw of the discharge extruder unit such that the extruder screw of the feed extruder unit and the extruder screw of the discharge extruder unit are rotatable by a drive unit.

6. The apparatus according to claim 3 or 4, characterized in that the feeding means comprise or constitute a feeding extruder unit and the discharge means (18, 118) comprise or constitute a discharge extruder unit, wherein the extruder screw of the feeding extruder unit is rotatable by a drive unit and the extruder screw of the discharge extruder unit is rotatable by a second drive unit.

7. The apparatus according to any one of the preceding claims, characterized in that the evaporation device (14, 114) has an evaporation surface that can evaporate the functional material, and the condensation device (16, 116) has a condensation surface that can condense the functional material, wherein the evaporation surface is arranged in a parallel manner to the condensation surface.

8. The apparatus according to any one of the preceding claims, characterized in that the condensing means (16, 116) is rotatable relative to the evaporating means (14, 114).

9. The apparatus according to any one of the preceding claims, wherein the condensing means (16, 116) has a condensing cylinder connected to the extruder screw of the feed extruder unit and the extruder screw of the discharge extruder unit such that the extruder screw of the feed extruder unit, the condensing cylinder and the extruder screw of the discharge extruder unit are rotatable by a drive unit.

10. The apparatus according to any one of the preceding claims, characterized in that the evaporation device (14, 114) and/or the evaporation chamber (40, 120) comprise at least one opening through which a residue collection container (38) can be connected or connected.

11. The apparatus according to any of the foregoing claims, characterised in that a temperature gradient can be created between the evaporation means and the condensation means (16, 116), wherein the temperature of the evaporation means (14, 114) can be selected at a level higher than the temperature of the condensation means (16, 116).

12. The apparatus according to any one of the preceding claims, characterized in that the evaporation device (14, 114) has an evaporation material dispenser system (28).

13. The apparatus according to any one of the preceding claims, characterized in that the condensation device (16, 116) has a condensate collector (44), wherein condensed functional material can be collected in the discharge device (18, 118) by means of the condensate collector (44).

14. The apparatus according to any one of the preceding claims, wherein the apparatus is vertically alignable, wherein the feeding means (12, 112) is arranged above the evaporation means (14, 114) and the evaporation means (14, 114) is arranged above the discharge means (18, 118).

15. The apparatus according to any one of the preceding claims, wherein the apparatus (10, 110) is vertically alignable, wherein functional material is introducible from the condensing means (16, 116) into the discharging means (18, 118) under the influence of gravity.