WO2018012223A1 - 塗布液、その製造方法、電子デバイス作製用インク、電子デバイス、有機エレクトロルミネッセンス素子、及び光電変換素子 - Google Patents

塗布液、その製造方法、電子デバイス作製用インク、電子デバイス、有機エレクトロルミネッセンス素子、及び光電変換素子 Download PDF

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WO2018012223A1
WO2018012223A1 PCT/JP2017/022768 JP2017022768W WO2018012223A1 WO 2018012223 A1 WO2018012223 A1 WO 2018012223A1 JP 2017022768 W JP2017022768 W JP 2017022768W WO 2018012223 A1 WO2018012223 A1 WO 2018012223A1
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organic
layer
coating liquid
carbon dioxide
compound
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PCT/JP2017/022768
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English (en)
French (fr)
Japanese (ja)
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北　弘志
田中　達夫
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コニカミノルタ株式会社
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Priority to CN201780042907.6A priority Critical patent/CN109479355B/zh
Priority to KR1020197000606A priority patent/KR102174806B1/ko
Priority to JP2018527474A priority patent/JP6844621B2/ja
Publication of WO2018012223A1 publication Critical patent/WO2018012223A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/36—Inkjet printing inks based on non-aqueous solvents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
    • H10K71/135—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing using ink-jet printing
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour

Definitions

  • the present invention relates to a coating liquid, a method for producing the same, an ink for producing an electronic device, an electronic device, an organic electroluminescence element, and a photoelectric conversion element, and in particular, effectively removes moisture, oxygen, and the like attached to an organic material, and is excellent.
  • the present invention relates to the provision of a coating liquid capable of producing an electronic device having a satisfactory performance, a method for producing the same, an ink for producing an electronic device, an electronic device, an organic electroluminescence element, and a photoelectric conversion element.
  • organic electroluminescence elements organic electrotechnologies disclosed in JP2010-272619A, JP2014-078742A, etc.
  • Various electronic devices such as organic light-emitting elements, organic photoelectric conversion elements, and organic transistors have been developed, and along with their technical progress, various industries have been developed. ⁇ The market is becoming popular.
  • organic EL elements which are typical examples of organic electronic devices, have begun to be used in various fields such as displays, lighting, and indicators, and have already entered the current life together with liquid crystal displays and light emitting diodes (LEDs). From now on, we are about to enter a period of dramatic expansion.
  • organic EL elements are already used in the main display of smartphones, and large displays exceeding 50 inches have become a product in the market.
  • the white element achieves a luminous efficiency of 139 Lm / W, approximately twice that of a fluorescent lamp, and the red half-life and the green phosphor have a luminance half life of 100. Since a long life of 10,000 hours has been achieved, and even the most difficult blue phosphorescent devices have resulted in over 100,000 hours, by applying a precise layer structure and meticulous film formation, It seems that it has already reached a level sufficient for practical use.
  • the RGB side-by-side display which is an advantage of the original organic EL element as described in detail later, has not reached mass production in a large display.
  • the manufacturing method based on the coating method developed for the purpose of reducing the production load has much room for improvement in the purification and handling of solvents and organic materials. That is, it can be said that solving the low productivity is a necessary condition for developing the organic EL element.
  • This is also considered to be the same for other organic electronic devices such as organic photoelectric conversion elements.
  • An organic EL element has an electron and a hole in a light emitting material (generally also referred to as “dopant”) present in a light emitting layer which is one of organic functional layers.
  • a light emitting material generally also referred to as “dopant”
  • the basic principle is that the exciton produced when the recombination occurs and emits light when returning to the ground state.
  • this exciton is a highly active chemical species that is in an excited state, so it easily reacts with water molecules and oxygen molecules, easily undergoes chemical changes or state changes such as decomposition and denaturation, and emits light. Will decrease. That is, it is one of the factors that reduce the light emission lifetime. That is, when forming an organic functional layer such as a light emitting layer, it is necessary to perform it in an environment where moisture and oxygen do not enter at all.
  • an organic EL element unlike an LED, the existence state of an organic compound constituting a light emitting layer is not a crystal but an amorphous (amorphous) condition for high efficiency light emission. Therefore, in order to form a homogeneous amorphous film, it is desired that the molecular state (amorphous state) of the organic compound and the surrounding environment are constant during the film formation. Therefore, the deposition method for the organic functional layer of the organic EL element that exhibits good performance so far is the vacuum deposition method, for the reasons such as prevention of the harmful effects caused by moisture and oxygen and the necessity of making the organic compound amorphous. It was due to. For organic EL displays for smartphones already mass-produced and organic EL displays used for large televisions, the vapor deposition method is employed as a method for forming the organic functional layer.
  • Organic electroluminescence is self-luminous, and the luminescent color is uniquely determined by the luminescent material constituting the luminescent layer, so basically red (Red: R), green (Green: G), blue (Blue: B)
  • red Red
  • Green Green
  • Blue B
  • a method RGB side-by-side method in which organic EL elements of respective emission colors are formed for each pixel and arrayed to form a display has been adopted.
  • each pixel is formed while shifting the shadow mask for each pixel.
  • the method is common.
  • the formation (film formation) method of the light emitting layer or the like is a vacuum vapor deposition method, there is a decisive problem that the shadow mask is thermally expanded by the radiant heat from the vapor deposition source and causes pixel displacement. Due to this critical problem, small to medium-sized displays for smartphones are produced in hundreds of millions of panels per year using the RGB side-by-side method. The production yield originated from the thermal deformation of the shadow mask is low, and large-scale production is not performed.
  • a method for reproducing full color a method (color filter method) for reproducing white light obtained from an organic EL element by color filtering into RGB by passing it through a color filter (color filter method) is adopted.
  • color filter method for reproducing white light obtained from an organic EL element by color filtering into RGB by passing it through a color filter (color filter method) is adopted.
  • Large-scale displays that have already been mass-produced are organic EL elements that emit white light for each pixel, and the organic EL elements that can emit high-contrast light with independent pixels in the color filter method. There is a problem that the advantages and features cannot be fully exhibited.
  • the organic functional layer constituting the organic EL element has a laminated structure of about 4 to 7 layers, and the total layer (film) thickness is about 100 to 200 nm. is there. If it is too thin, the anode and the cathode are partially short-circuited due to the surface roughness of the electrode serving as the underlayer, and a current leakage phenomenon occurs. If the thickness is larger than this, the charge conduction mechanism of the organic EL element is different from Ohm's law, and is a space charge limited current (SCLC) according to the child law. Since it is inversely proportional to the third power of, a significant drive voltage rise occurs, resulting in a problem of increased power consumption.
  • SCLC space charge limited current
  • the organic functional layer of an organic EL device is generally deposited by depositing a low molecular compound, but instead of the low molecular compound, a ⁇ -conjugated polymer such as polyphenylene vinylene or polyfluorene is used for carrier movement and light emission. There is also a method using a light emitting polymer (LEP) utilized for both. Since the polymer material cannot be formed by vapor deposition, the organic functional layer is produced by a wet coating method (wet film formation method, wet coating method) such as spin coating, die coating, flexographic printing, and ink jet printing.
  • a wet coating method such as spin coating, die coating, flexographic printing, and ink jet printing.
  • Minolta has announced a prototype of a phosphorescent white element that emits high-efficiency light by coating four layers of low-molecular compounds.
  • the present invention has been made in view of the above-described problems and situations, and a solution to that problem is to efficiently remove moisture, oxygen, and the like attached to an organic material, and to produce an electronic device with good performance. It is providing a coating liquid, its manufacturing method, ink for electronic device preparation, an electronic device, an organic electroluminescent element, and a photoelectric conversion element.
  • the present inventor is a coating liquid containing an organic compound and an organic solvent in the process of examining the cause of the above-mentioned problem, and It has been found that the concentration of dissolved carbon dioxide with respect to the solvent is within a specific range, thereby providing a coating liquid that can efficiently remove moisture, oxygen, and the like, and a method for producing the same. Further, by using this coating liquid, it is possible to provide an ink for producing an electronic device, an electronic device, an organic electroluminescence element, and a photoelectric conversion element with good performance. That is, the said subject which concerns on this invention is solved by the following means. In order to facilitate understanding of the present invention, the basic policy according to the present invention and the background of research and development will be described later.
  • a coating liquid containing an organic compound and an organic solvent A coating liquid, wherein a dissolved carbon dioxide concentration with respect to the organic solvent under a condition of 50 ° C. or less and atmospheric pressure is in a range of 1 ppm or more and a saturation concentration or less with respect to the organic solvent.
  • Item 5 The coating liquid according to Item 4, wherein the electronic device is a light emitting device.
  • Item 10 The method for producing a coating liquid according to Item 8 or 9, further comprising a step of separating a substance in the solution containing the organic compound using a supercritical fluid.
  • An ink for producing an electronic device comprising the coating liquid according to any one of items 1 to 7.
  • An electronic device comprising an organic functional layer formed using the coating liquid according to any one of items 1 to 7.
  • An organic electroluminescent device comprising an organic functional layer formed using the coating liquid according to any one of items 1 to 7.
  • Solvent in the coating solution is preferably a general-purpose solvent”, it is not sufficient to simply use a dehydration or deoxygenation solvent, and there is a special gas in the solution.
  • the gas is dissolved at a concentration close to saturation, and the robustness is increased with respect to moisture, oxygen, etc. mixed in later, which is very simple, but this is the present invention. It was found that it was the essence of The gas is carbon dioxide.
  • the coating solution is stored for a long time in a nitrogen atmosphere, and dissolved oxygen and nitrogen in the atmosphere are replaced by equilibrium, or nitrogen gas is bubbled or pressurized to expel oxygen, or
  • the coating solution was deoxygenated by using a similar method.
  • the coating process is exposed to the atmosphere even for a moment, the coating solution immediately absorbs oxygen and moisture, and the coating solution for dehydration and deoxygenation prepared with the utmost care is spoiled.
  • the characteristics of the device, particularly the light emission lifetime will be greatly degraded.
  • the phenomenon we have discovered is that water and oxygen are removed in the initial state of the coating solution, but by dissolving carbon dioxide close to the saturation concentration in the solution, the solution itself becomes difficult to absorb water and oxygen. That is.
  • the present inventors completely take dissolved oxygen out of the solution system together when supercritical carbon dioxide escapes from the solution as gaseous carbon dioxide, Also, trace amounts of water can be removed by hydrogen bonding with carbon dioxide, and carbon dioxide remaining at a concentration close to saturation can prevent oxygen and water from entering the solution system.
  • the eluent purified from supercritical HPLC was applied as it was, it was found that high performance, almost no variation in performance, and a stable and stable device could be produced.
  • the inventors have found that not only supercritical carbon dioxide but also a similar effect can be obtained by bubbling carbon dioxide gas or bringing it into contact with an organic solvent solution of an organic EL material that has been normally dissolved.
  • the present invention is constituted by the following technical elements.
  • the description so far has been a description of an organic EL device by a coating film forming method using a low molecular compound, but this is only one of the representative and most effective applications.
  • the same technique can also be applied to other electronic devices that are coated by coating, for example, organic thin film solar cells, organic transistors, and electrodes using organic compounds.
  • a coating solution containing carbon dioxide in a solution close to saturation in a solution in which a low molecular compound is dissolved (b) A coating solution in which carbon dioxide is brought into contact with the solution in a supercritical state (c) (A) to (c) can be achieved simultaneously by using a solution for coating dispersed in a solvent through adsorption-desorption equilibrium, that is, using a supercritical carbon dioxide HPLC-purified eluent without being completely concentrated to dryness.
  • the present invention is not a premise, and the method is not limited as long as it is dissolved in carbon dioxide and dispersed in a solvent (that is, completely dissolved) through adsorption-desorption equilibrium. There is nothing.
  • the coating solution of the present invention has a dissolved carbon dioxide concentration with respect to the organic solvent under a condition of 50 ° C. or less and atmospheric pressure within a range of 1 ppm or more and a saturation concentration or less with respect to the organic solvent.
  • the dissolved carbon dioxide escapes as gaseous carbon dioxide
  • the dissolved oxygen is taken out of the solution system together, and the water contained in a trace amount in the solution is also carbon dioxide. Is removed by hydrogen bonding.
  • carbon dioxide remaining at a concentration close to saturation can prevent oxygen and water from being mixed into the solution system.
  • the carbon dioxide in the present invention is dissolved in the coating solution for the purpose of preventing oxygen and water in the coating solution and preventing oxygen and water from being mixed into the coating solution. It is not used as a medium.
  • Comparison of deposited film and coated film results of particle size distribution analysis of organic compound fine particles in the film Comparison of deposited film and improved coating film: Results of particle size distribution analysis of organic compound fine particles in film
  • Schematic diagram of equipment using packed column in supercritical fluid chromatography Schematic diagram showing an example of a display device composed of organic EL elements
  • Schematic diagram of display part A Schematic showing the pixel circuit
  • Sectional drawing which shows the solar cell which consists of an organic photoelectric conversion element of a bulk heterojunction type
  • Sectional drawing which shows the solar cell which consists of an organic photoelectric conversion element provided with a tandem type bulk heterojunction layer
  • Schematic configuration diagram of organic EL full-color display device Schematic configuration diagram of organic EL full-color display device Schematic configuration diagram of organic EL full-color display device Schematic configuration diagram of organic EL full-color display device Schematic configuration diagram of organic EL full-color display device Schematic configuration diagram of organic EL full-color display device Schematic configuration diagram of organic EL full-color display device
  • the coating solution of the present invention is a coating solution containing an organic compound and an organic solvent, and a dissolved carbon dioxide concentration with respect to the organic solvent under a condition of 50 ° C. or lower and atmospheric pressure is 1 ppm or more and a saturated concentration with respect to the organic solvent. It is characterized by being within the following range. This feature is a technical feature common to or corresponding to the claimed invention.
  • the dissolved carbon dioxide concentration is in the range of 5 to 1000 ppm under the above conditions, from the viewpoint of manifesting the effects of the present invention.
  • the coating solution is a coating solution for producing an electronic device in that an electronic device having good performance can be produced, and the electronic device is preferably a light emitting device.
  • the organic compound is preferably an organic electroluminescent material from the viewpoint of the lifetime of the light emitting device and the luminous efficiency.
  • the coating liquid is an inkjet ink in terms of manufacturing various devices.
  • the manufacturing method of the coating liquid of this invention has the process of mixing the said organic compound and a carbon dioxide, It is characterized by the above-mentioned.
  • the coating solution is preferably produced using a solution containing the organic compound. That is, it is preferable in that carbon dioxide contained in the coating liquid can prevent air from being contacted with air in the film forming process and moisture adhering to the coating apparatus from being contaminated in the coating liquid. Further, there is no need to carry out a step of preparing a coating solution by concentrating and drying the purified organic compound and then redissolving it in a solvent suitable for coating film formation. It is preferable from the point of efficiency of a refinement
  • the coating liquid of the present invention is suitably contained in an electronic device production ink.
  • the coating liquid of this invention is used suitably for formation of each organic functional layer of an electronic device, an organic electroluminescent element, and a photoelectric conversion element.
  • ⁇ is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
  • ppm indicates “mass ppm”.
  • the coating solution of the present invention is a coating solution containing an organic compound and an organic solvent, and a dissolved carbon dioxide concentration with respect to the organic solvent under a condition of 50 ° C. or lower and atmospheric pressure is 1 ppm or more and a saturated concentration with respect to the organic solvent. It is characterized by being within the following range.
  • the organic EL compound is preferably a low molecular compound (a high molecular compound is not preferable).
  • the solvent in the coating solution is preferably a general-purpose solvent (an expensive dehydrated high-purity solvent is not preferred).
  • the solvent in the coating solution is preferably a general-purpose solvent (an expensive dehydrated high-purity solvent is not preferred).
  • Single molecule state is preferable for dissolution (microcrystal dispersion is not preferable)
  • Adsorption-desorption equilibrium is preferably used for the purification of compounds (thermal equilibrium is not preferred)
  • high-performance liquid chromatography HPLC
  • column chromatography with low purification efficiency low theoretical plate number
  • column chromatography can be used as a method for purifying low-molecular compounds.
  • the purification is performed by repeatedly performing a reprecipitation method using a good solvent and a poor solvent, and the low-molecular compound is more easily purified.
  • the polymer compound is a ⁇ -conjugated polymer compound, it is necessary to use a metal catalyst or a polymerization initiator for causing a polymerization reaction, and a reactive active substituent remains at the polymerization terminal. This is one of the reasons why low molecular weight compounds can be made more pure.
  • the light emitting polymer (LEP) is a ⁇ -conjugated polymer when the molecular weight is increased, a conjugated system is required to stabilize the molecule.
  • the energy level difference between the excited state of the singlet or triplet and the ground state (also referred to as “energy level gap” or “band gap”) becomes narrower, Blue light emission becomes difficult.
  • the light emitting polymer in blue phosphorescence requiring a higher energy level (large energy level difference) than fluorescent blue light emission, it is structurally difficult for the light emitting polymer to form a transition metal complex serving as the light emitting substance.
  • high T 1 compound a compound having high triplet energy
  • thermally activated delayed fluorescence (TADF) which has recently been attracting attention, has been achieved with a ⁇ -conjugated polymer, and thus it is difficult to use it for high-efficiency blue light emission with high market demand.
  • the low molecular weight compound there is no necessity to connect the ⁇ -conjugated system, and an aromatic compound residue that becomes a ⁇ -conjugated system unit is necessary. Therefore, in the low molecular weight compound, the highest occupied orbital (HOMO), the lowest unoccupied molecular orbital (LUMO), and the triplet (T 1 ) energy level can be adjusted intentionally. It is possible to make a blue phosphorescent substance, to use it as a host, and to construct a compound that causes the TADF phenomenon. In this way, the degree of expandability capable of intentionally designing and synthesizing an arbitrary electronic state and an arbitrary level is a factor of the second superiority of the low molecular weight compound.
  • HOMO highest occupied orbital
  • LUMO lowest unoccupied molecular orbital
  • T 1 triplet
  • the low molecular weight compound has no limitation on the molecular structure that can be synthesized compared to the light emitting polymer (LEP).
  • LEP light emitting polymer
  • the molecular structure can be used to add new functions and adjust physical properties (such as Tg, melting point, and solubility). Is relatively ready to accomplish this, which is the third advantage of low molecular weight compounds.
  • the equivalent circuit of the organic EL element includes a series connection of a diode and a resistor. Become. That is, it is also known that Joule heat is generated inside the organic EL element that is being energized and light emission, and that heat is actually generated at 100 ° C. or more inside the element, particularly in the light emitting layer where recombination occurs.
  • the organic layer thickness of the entire organic EL element is an extremely thin layer of about 200 nm, heat is conducted between layers (films), and not only the light emitting layer but also all layers continue to be in a high temperature state.
  • a state exceeds its own glass transition point (Tg)
  • Tg glass transition point
  • This crystal grows gradually, and when it exceeds several tens of nm, the thickness of the compound exceeds the thickness, and functional separation by the layer as the organic EL element becomes impossible, resulting in a decrease in luminous efficiency.
  • the low molecular weight compound of the organic EL element is a molecule that does not have a bulky non-aromatic substituent and has a glass transition point (Tg) exceeding 100 ° C. or higher (preferably 150 ° C. or higher). I have to.
  • the ⁇ -conjugated system is usually enlarged or the aromatic group is simply linked.
  • the compound formed in the usual case has extremely low solubility in a solvent, and coating Even if it cannot be made into a solution or can be applied, crystal precipitation, uneven distribution of substances, etc. will occur.
  • the number of components in the film by actively increasing geometric isomers or by causing multiple molecules (for example, host and dopant) in the same layer to interact in various shapes and forms Therefore, the entropy in the thin film state can be increased, and a stable amorphous film can be formed.
  • the inventors of the present invention have improved the molecular structure of low molecular weight compounds in accordance with the guidelines described above and optimized the drying conditions in the production of organic EL elements by a wet coating method. A dramatic improvement was achieved, with 95% of the device and 90% emission lifetime. As a result, even for devices using phosphorescent dopants, especially blue phosphorescent dopants, which are said to be the most difficult to improve their lifetime, the basic characteristics of coating film deposition methods are almost comparable to conventional deposition methods. Have found out that However, many problems still remain in the organic EL element with improved performance. Examples of such problems include removal of purity of low molecular weight compounds, trace moisture adhering to the surface of the compound, oxygen content of solvent used, water content, and the like.
  • purifying the compound A to be purified by recrystallization can be rationally explained by considering as follows.
  • A is dissolved at a high temperature in a solvent called B which can dissolve A
  • B which can dissolve A
  • entropy ( ⁇ S) is extremely large.
  • T ⁇ S applied with the absolute temperature T becomes smaller than before the cooling. At that time, in order to keep the cast free energy (- ⁇ G) constant before and after cooling, the enthalpy (- ⁇ H) must be increased.
  • the entropy term (T ⁇ S) first decreases with a decrease in temperature, and the enthalpy ( ⁇ H) increases due to crystallization to compensate for this, and the entropy term further decreases due to the decrease in the number of components. Recrystallization is accomplished by repeating the thermodynamic equilibrium in which ⁇ S decreases with decreasing ⁇ S and crystallization occurs accordingly. However, it is necessary to pay attention to the interaction between the solute A and the solvent B. Since the solute A dissolves by being solvated with the solvent B, A does not dissolve in B unless the interaction between AB is large.
  • the purification method by recrystallization can be applied only when the interaction force AA and the interaction force AB are adjusted to the conditions under which recrystallization occurs.
  • a large amount of purification of several hundred kg or more is possible at a time, and this method has been used for a long time in the chemical industry.
  • column chromatography (hereinafter also referred to as “chromatography”) will be considered.
  • the most typical column chromatography uses fine-particle silica gel as a stationary phase, adsorbs compound A therein, and gradually elutes it with a mobile phase (B) called an eluent. .
  • B mobile phase
  • A is an adsorption-desorption equilibrium between the silica and the mobile phase B.
  • the purification efficiency by the chromatographic method is proportional to the length of the stationary phase and also to the passing speed of the mobile phase. Proportional to the surface area of the stationary phase. This is achieved by high-performance liquid chromatography, which is widely used for component analysis and quality assurance of organic compounds. It is a rare technique that can realize a high number of theoretical plates backed by this theory. This is due to the fact that
  • the interaction between A and the mobile phase B ′ is greater than the interaction between A and the silica gel. If the action is strong, the number of reciprocations of adsorption-desorption equilibrium is drastically reduced and the purification effect is lowered. That is, in order to enhance the purification effect, it is necessary to mix a large excess of the poor solvent C in addition to the good solvent B ′ to increase the number of reciprocations of adsorption-desorption equilibrium.
  • the solution of Compound A purified and fractionated contains a large excess of C, and the biggest problem is that it must be concentrated.
  • the mixing ratio of the good solvent B ′ and the poor solvent C needs to be about 1:99 to 10:90, and generally the poor solvent C of about 10 L to 100 L is required. It becomes necessary. For this reason, HPLC fractionation is applied to research and development but is not used for mass production.
  • a means for solving the problem of poor solvent concentration is HPLC using supercritical carbon dioxide.
  • Supercritical carbon dioxide is a supercritical fluid made of carbon dioxide at high temperature and high pressure, and other substances can be made into such a supercritical fluid. Therefore, carbon dioxide is used exclusively in chromatography and extraction.
  • This supercritical carbon dioxide has different characteristics from ordinary fluids and liquids. That is, by changing the temperature and pressure, the polarity can be continuously changed in accordance with the polarity of the one to be dissolved.
  • this supercritical carbon dioxide is used to selectively extract docosahexaenoic acid contained in fish heads, and sebum dissolves and adheres to cleaning special clothing that uses adhesives.
  • the agent is achieved by making supercritical carbon dioxide, which does not dissolve, under temperature and pressure control.
  • supercritical carbon dioxide can have various polarities as described above, the polarity of supercritical carbon dioxide formed at a relatively low temperature and pressure is about cyclohexane or heptane. In the supercritical HPLC currently on the market, this degree of polar supercritical carbon dioxide is produced in the apparatus, mixed with a good solvent, and entered into the column. Purification is performed.
  • the compounds constituting each layer are basically formed by vacuum deposition. It lands on a substrate or an organic layer in the state of vaporized isolated single molecule, which is formed into a solid thin film. Therefore, a film is basically formed by a random assembly of single molecules, and an ideal amorphous film is obtained.
  • the coating film forming method if the coating solution is a dispersion of fine crystals of organic EL compound, it seems that it is completely dissolved, but the actual state of the obtained thin film is The thin film is a collection of microcrystals.
  • the level of HOMO or LUMO is not that of a single molecule, but that of a stacked aggregate (crystalline state), which can cause performance degradation.
  • the microcrystals become nuclei and grow into coarse crystals, which not only makes it impossible to separate the functions between layers, but if the crystals become large crystals that short-circuit the anode and cathode, There is a big problem of generating spots.
  • coating film-forming elements using low molecules how to approximate the coating solution in the initial state to a monomolecular dispersion state based on the above-mentioned studies over many years, first of all, to achieve the same performance as the vapor deposition method It is clear that this is a necessary condition.
  • FIG. 1 is a particle size distribution curve (horizontal axis: particle size (nm), vertical axis: frequency distribution) of fine particles of a compound constituting a thin film produced by a vapor deposition method, and a solid line is a thin film produced by a coating method. It is a particle size distribution of fine particles of a constituent compound. Since both use the same compound, they can be directly compared.
  • the particle size at the position corresponding to the maximum peak is about 2 nm, and the particle size is close to monodispersion. Since this is the size of one molecule or two molecules, this means that an amorphous film is formed by arranging almost single molecules at random in vapor deposition.
  • the particle size at the position corresponding to the maximum peak is about 4.5 nm, which is wider than the particle size distribution in the vapor deposition film formation.
  • FIG. 2 shows the result of examining the particle size distribution of the coating thin film prepared with the coating solution used for the prototype in which the compound is improved and the method for adjusting the coating solution is improved by the same analysis.
  • the process such as the dissolution method and the storage method, is very laborious even though the coating method should be excellent in productivity.
  • the organic EL element has a basic function of a phenomenon in which light is emitted when the light emitting material in an excited state returns to the ground state. Further, it is necessary to transport electrons and holes through the hopping phenomenon between the electrode and the light emitting layer.
  • an excited state for example, in the case of an organic EL element doped with a light emitting material having a concentration of 5%, in order to continuously emit light at a luminance of 1000 cd / m 2 , simply calculate, One dopant needs to be about 1 billion excitons. At this time, if the exciton reacts with the water molecule only once, it becomes a compound different from the original molecule. In addition, when excitons react with oxygen molecules, some kind of oxidation reaction or oxidative coupling reaction occurs. This is the most typical phenomenon of a chemical change that causes a decrease in the function of the organic EL element.
  • the radical state is almost the same number of times, and both the radical anion state and the cation radical state are active species compared to the ground state, which causes a decrease in the function of the organic EL element.
  • chemical changes will occur. That is, water molecules and oxygen molecules should not be present at all in the coating solution, and that is the premise.
  • a high purity anhydrous solvent is very expensive and difficult to handle. Therefore, after all, in order to reduce the cost by the coating method, it is important how to use a general-purpose solvent as a consumable agent.
  • the coating solution of the present invention is a coating solution containing an organic compound and an organic solvent, and a dissolved carbon dioxide concentration with respect to the organic solvent under a condition of 50 ° C. or lower and atmospheric pressure is 1 ppm or more and a saturated concentration with respect to the organic solvent. It is characterized by being within the following range.
  • the dissolved carbon dioxide concentration is preferably in the range of 5 to 1000 ppm under the above conditions.
  • the coating solution may contain the dissolved carbon dioxide concentration within the range of 1.0 to 100,000 times the dissolved oxygen concentration under the above conditions. It is preferable from the viewpoint of the stability of the device produced by using it.
  • the dissolved carbon dioxide concentration can be measured, for example, by gas chromatography.
  • the coating solution of the present invention is preferably a coating solution for producing an electronic device or an inkjet ink.
  • the electronic device is preferably a light-emitting device such as an organic EL element, a photoelectric conversion element (solar cell), or a liquid crystal display element.
  • the organic compound used in the present invention is not limited to a compound of a specific type and a specific structure, but is preferably a compound used for various electronic devices from the viewpoint of manifesting the effects of the present invention.
  • the organic compound is preferably an organic electroluminescent material (hereinafter also referred to as “organic EL material”).
  • organic EL material refers to a compound that can be used for an organic electroluminescence layer (hereinafter also referred to as “organic functional layer” or “organic EL layer”) formed between an anode and a cathode described later.
  • an organic EL element a light-emitting element composed of an anode, a cathode, and an organic EL layer using an organic EL material. Examples of compounds used as the organic EL material will be described later.
  • an organic compound is a p-type organic-semiconductor material or a n-type organic-semiconductor material. Examples of compounds used as these p-type organic semiconductor materials and n-type organic semiconductor materials will be described later.
  • an organic solvent means the medium which consists of an organic compound which can melt
  • the liquid medium for dissolving or dispersing the organic EL device material according to the present invention include ketones such as methylene chloride, methyl ethyl ketone, tetrahydrofuran, and cyclohexanone, fatty acid esters such as ethyl acetate, isopropyl acetate, and isobutyl acetate, chlorobenzene, dichlorobenzene, Halogenated hydrocarbons such as 2,2,3,3-tetrafluoro-1-propanol (TFPO), aromatic hydrocarbons such as toluene, xylene, mesitylene, and cyclohexylbenzene, aliphatics such as cyclohexane, decalin, and dodecane Examples include hydrocarbons, n-butanol, s-butan
  • the manufacturing method of the coating liquid of this invention has the process (henceforth a mixing process) which mixes the said organic compound and the said carbon dioxide, It is characterized by the above-mentioned. After the mixing step, it is preferable to manufacture the coating solution using a solution containing the organic compound. Moreover, the manufacturing method of the coating liquid of this invention is also called the process (henceforth a separation process) which isolate
  • the mixing step is a step of mixing an organic compound and carbon dioxide. Specifically, it is sufficient that carbon dioxide can be dissolved in an organic compound. For example, carbon dioxide gas is bubbled into a mixed solution of an organic solvent and an organic compound to mix the organic compound and carbon dioxide, or It is mentioned that an organic compound and carbon dioxide are mixed using a supercritical fluid chromatography method.
  • the coating liquid of this invention can be manufactured using the solution obtained by bubbling of a carbon dioxide gas, ie, the solution of the organic solvent and organic compound in which the carbon dioxide was mixed by the mixing process. That is, the solution obtained by the mixing step can be used as it is as the coating solution of the present invention.
  • a packed column, an open column, or a capillary column can be used.
  • the temperature of the column 15 is adjusted in a column oven 16.
  • the filler can be appropriately selected from silica used in conventional chromatography methods or surface-modified silica.
  • the manufacturing method of the coating liquid of this invention has a process (separation process) which isolate
  • the coating liquid of this invention can be manufactured using the solution containing the isolate
  • the supercritical fluid is a substance in a supercritical state.
  • the supercritical state will be described.
  • Substances change between three states of gas, liquid, and solid due to changes in environmental conditions such as temperature, pressure (or volume), and this is determined by the balance between intermolecular force and kinetic energy.
  • a phase diagram shows the transition of the gas-liquid solid state with temperature on the horizontal axis and pressure on the vertical axis.
  • the three phases of gas, liquid, and solid coexist in this state.
  • the point at is called the triple point.
  • the pressure at this time is a saturated vapor pressure and is represented by an evaporation curve (vapor pressure line).
  • a fluid that is above the critical temperature and above the critical pressure is called a supercritical fluid, and a temperature / pressure region that gives the supercritical fluid is called a supercritical region.
  • Supercritical fluids can be understood as high-density fluids with high kinetic energy, and exhibit liquid behavior in terms of dissolving solutes and gaseous characteristics in terms of density variability. Although there are various solvent properties of supercritical fluids, it is important to have low viscosity, high diffusivity, and excellent permeability to solid materials.
  • the supercritical state is carbon dioxide
  • the critical temperature hereinafter also referred to as Tc
  • the critical pressure hereinafter also referred to as Pc
  • C, Pc 43.4 ⁇ 10 5 Pa
  • Pc 52.2 ⁇ 10 5 Pa
  • the fluid has a large diffusion coefficient and low viscosity. Since movement and concentration equilibrium are reached quickly and the density is high like a liquid, efficient separation becomes possible.
  • the recovery is quickened by using a substance that becomes a gas at normal pressure and normal temperature, such as carbon dioxide.
  • the solvent used as the supercritical fluid carbon dioxide, dinitrogen monoxide, ammonia, water, methanol, ethanol, 2-propanol, ethane, propane, butane, hexane, pentane and the like are preferably used. Can be preferably used.
  • the solvent used as the supercritical fluid can be used alone, or a so-called modifier or entrainer for adjusting the polarity can be added.
  • entrainers include hydrocarbon solvents such as hexane, cyclohexane, benzene, and toluene, halogenated hydrocarbon solvents such as methyl chloride, dichloromethane, dichloroethane, and chlorobenzene, alcohol solvents such as methanol, ethanol, propanol, and butanol, Ether solvents such as diethyl ether and tetrahydrofuran, acetal solvents such as acetaldehyde diethyl acetal, ketone solvents such as acetone and methyl ethyl ketone, ester solvents such as ethyl acetate and butyl acetate, carboxylic acids such as formic acid, acetic acid and trifluoroacetic acid Solvent, nitrogen compound solvent such as acetonitrile, pyridine, N, N-dimethylformamide, sulfur compound solvent such as carbon disulfide, dimethyl sulfoxide,
  • the temperature at which the supercritical fluid is used is basically not particularly limited as long as it is equal to or higher than the temperature at which the organic compound of the present invention is dissolved, but if the temperature is too low, the solubility of the organic compound in the supercritical fluid becomes poor. In some cases, and when the temperature is too high, the organic compound may be decomposed. Therefore, the operating temperature range is preferably 20 to 600 ° C.
  • the working pressure of the supercritical fluid is basically not limited as long as it is higher than the critical pressure of the substance to be used, but if the pressure is too low, the solubility of the organic compound in the supercritical fluid may be poor. If the pressure is too high, problems may occur in terms of durability of the production apparatus, safety during operation, and the like. Therefore, the working pressure is preferably 1 to 100 MPa.
  • the apparatus using the supercritical fluid is not limited as long as the organic compound has a function of dissolving in the supercritical fluid in contact with the supercritical fluid.
  • the supercritical fluid is closed in a closed system. It is possible to use a batch method to be used, a distribution method in which a supercritical fluid is circulated, a composite method in which the batch method and the distribution method are combined, or the like.
  • the ink for producing an electronic device of the present invention is characterized by containing the above coating liquid. That is, the ink for producing an electronic device of the present invention is derived from the coating solution.
  • the electronic device is preferably a light emitting device, and more preferably an organic EL element or a photoelectric conversion element.
  • Each layer which comprises the said electronic device can be formed with the inkjet method using the ink for electronic device preparation containing the coating liquid of this invention.
  • the electronic device of the present invention has an organic functional layer formed using the coating solution. That is, the electronic device of the present invention is characterized by having an organic functional layer derived from the coating solution, in other words, having an organic functional layer formed by coating the coating solution.
  • the electronic device is preferably a light emitting device, and more preferably an organic EL element or a photoelectric conversion element.
  • the organic EL device of the present invention has an organic functional layer formed using the coating solution. That is, the organic EL element of the present invention is characterized by having an organic functional layer derived from the coating liquid, in other words, having an organic functional layer formed by coating the coating liquid. Details of the organic EL element will be described below. As described above, the organic EL device of the present invention has an anode and a cathode on the substrate, and one or more organic functional layers (also referred to as “organic compound layer” or “organic EL layer”) between these electrodes. It has the structure.
  • substrate Although it does not specifically limit as a board
  • the glass substrate include alkali-free glass, low alkali glass, and soda lime glass.
  • alkali-free glass is preferable from the viewpoint of low moisture adsorption, but any of these may be used as long as it is sufficiently dried.
  • the resin film used as the base material of the plastic substrate is not particularly limited.
  • polyester such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate (TAC) ), Cellulose acetates such as cellulose acetate butyrate, cellulose acetate propionate (CAP), cellulose acetate phthalate, cellulose nitrate, or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate , Norbornene resin, polymethylpentene, polyetherketone, polyimide, polyethersulfone PES), polyphenylene sulfide, polysulfones, polyetherimides, poly
  • organic / inorganic hybrid resin examples include those obtained by combining an organic resin and an inorganic polymer (for example, silica, alumina, titania, zirconia, etc.) obtained by a sol-gel reaction.
  • an organic resin for example, silica, alumina, titania, zirconia, etc.
  • norbornene (or cycloolefin-based) resins such as Arton (manufactured by JSR) or Apel (manufactured by Mitsui Chemicals) are particularly preferable.
  • Arton manufactured by JSR
  • Apel manufactured by Mitsui Chemicals
  • the plastic substrate that is normally produced has a relatively high moisture permeability and may contain moisture inside the substrate. Therefore, when using such a plastic substrate, it is preferable to provide a film (hereinafter referred to as “barrier film” or “water vapor sealing film”) that suppresses intrusion of water vapor, oxygen, or the like on the resin film.
  • a film hereinafter referred to as “barrier film” or “water vapor sealing film” that suppresses intrusion of water vapor, oxygen, or the like on the resin film.
  • the material constituting the barrier film is not particularly limited, and an inorganic film, an organic film, a hybrid of both, or the like is used.
  • a film may be formed, and the water vapor transmission rate (25 ⁇ 0.5 ° C., relative humidity (90 ⁇ 2)% RH) measured by a method according to JIS K 7129-1992 is 0.01 g / ( m 2 ⁇ 24 h) or less, and the oxygen permeability measured by a method according to JIS K 7126-1987 is preferably 1 ⁇ 10 ⁇ 3 mL / (m 2 ⁇ 24 h ⁇ atm), and a water vapor permeability of 1 ⁇ 10 ⁇ 5 g / (m 2 ⁇ 24 h) or less is preferable.
  • the material constituting the barrier film is not particularly limited as long as it has a function of suppressing the intrusion of elements that cause deterioration of elements such as moisture and oxygen.
  • An inorganic material, an organic material, a hybrid material of both, or the like can be used.
  • Metal oxide, metal oxynitride or metal nitride includes silicon oxide, titanium oxide, indium oxide, tin oxide, metal oxide such as indium tin oxide (ITO), aluminum oxide, metal nitride such as silicon nitride And metal oxynitrides such as silicon oxynitride and titanium oxynitride.
  • the barrier membrane had a water vapor permeability (25 ⁇ 0.5 ° C., relative humidity (90 ⁇ 2)% RH) of 0.01 g / (m 2 ⁇ 24 h) measured by a method according to JIS K 7129-1992.
  • the following barrier film is preferable, and further, the oxygen permeability measured by a method according to JIS K 7126-1987 is 10 ⁇ 3 mL / (m 2 ⁇ 24 h ⁇ atm) or less, and the water vapor permeability.
  • the film has a high barrier property of 10 ⁇ 5 g / (m 2 ⁇ 24 h) or less.
  • the method of providing the barrier film on the resin film is not particularly limited, and any method may be used.
  • Vapor deposition method sputtering method, reactive sputtering method, molecular beam epitaxy method, cluster ion beam method, ion plating method, plasma polymerization method, atmospheric pressure plasma
  • a polymerization method, a CVD method chemical vapor deposition: for example, a plasma CVD method, a laser CVD method, a thermal CVD method, etc.
  • a coating method for example, a sol-gel method, or the like
  • the method by plasma CVD treatment at or near atmospheric pressure is preferable from the viewpoint that a dense film can be formed.
  • the opaque substrate examples include metal plates such as aluminum and stainless steel, films, opaque resin substrates, ceramic substrates, and the like.
  • anode As the anode of the organic EL element, a material having a work function (4 eV or more) metal, alloy, metal electrically conductive compound, or a mixture thereof is preferably used.
  • the “metal conductive compound” refers to a compound of a metal and another substance having electrical conductivity, and specifically, for example, a metal oxide, a halide or the like. That has electrical conductivity.
  • an electrode substance examples include a conductive transparent material such as a metal such as Au, CuI, indium tin oxide (ITO), SnO 2 , and ZnO.
  • a conductive transparent material such as a metal such as Au, CuI, indium tin oxide (ITO), SnO 2 , and ZnO.
  • the anode can be produced by forming a thin film made of these electrode materials on the substrate by a known method such as vapor deposition or sputtering.
  • a pattern having a desired shape may be formed on the thin film by a photolithography method, and when the pattern accuracy is not so high (about 100 ⁇ m or more), a desired shape can be formed at the time of vapor deposition or sputtering of the electrode material.
  • a pattern may be formed through a mask.
  • the transmittance is larger than 10%.
  • the sheet resistance as the anode is several hundred ⁇ / sq. The following is preferred. Further, although the film thickness of the anode depends on the material constituting it, it is usually selected in the range of 10 nm to 1 ⁇ m, preferably 10 nm to 200 nm.
  • the organic functional layer (also referred to as “organic EL layer” or “organic compound layer”) includes at least a light-emitting layer.
  • the light-emitting layer is a current flowing through an electrode composed of a cathode and an anode. Specifically, it refers to a layer containing an organic compound that emits light when an electric current is passed through an electrode composed of a cathode and an anode.
  • the organic EL device used in the present invention may have a hole injection layer, an electron injection layer, a hole transport layer, and an electron transport layer in addition to the light emitting layer as necessary, and these layers are cathodes. And the anode.
  • a cathode buffer layer (for example, lithium fluoride) may be inserted between the electron injection layer and the cathode, and an anode buffer layer (for example, copper phthalocyanine) may be inserted between the anode and the hole injection layer. ) May be inserted.
  • anode buffer layer for example, copper phthalocyanine
  • the light emitting layer according to the present invention is a layer that emits light by recombination of electrons and holes injected from the electrode, the electron transport layer, or the hole transport layer, and the light emitting portion is within the layer of the light emitting layer. May be the interface between the light emitting layer and the adjacent layer.
  • the light emitting layer may be a layer having a single composition, or may be a laminated structure including a plurality of layers having the same or different compositions.
  • the light emitting layer itself may be provided with functions such as a hole injection layer, an electron injection layer, a hole transport layer, and an electron transport layer. That is, (1) an injection function capable of injecting holes from an anode or a hole injection layer and applying electrons from a cathode or an electron injection layer when an electric field is applied to the light emitting layer, and (2) injection At least one of a transport function that moves electric charges (electrons and holes) by the force of an electric field, and (3) a light-emitting function that provides a recombination field of electrons and holes inside the light-emitting layer and connects it to light emission.
  • a function may be added.
  • the light emitting layer may have a difference in the ease of hole injection and the ease of electron injection, and the transport function represented by the mobility of holes and electrons may be large or small. The one having a function of moving at least one of the charges is preferable.
  • the type of the light emitting material used for the light emitting layer is not particularly limited, and conventionally known light emitting materials for organic EL elements can be used.
  • a light-emitting material is mainly an organic compound, and has a desired color tone, for example, Macromol. Symp. 125, pages 17 to 26, and the like.
  • the light emitting material may be a polymer material such as p-polyphenylene vinylene or polyfluorene, and a polymer material in which the light emitting material is introduced into a side chain or a polymer material having the light emitting material as a main chain of the polymer. May be used. Note that, as described above, since the light emitting material may have a hole injection function and an electron injection function in addition to the light emission performance, most of the hole injection material and the electron injection material described later may be used as the light emitting material. Can be used.
  • the main component when the layer is composed of two or more organic compounds, the main component is called a host, the other components are called dopants, and the host and dopant are used in combination in the light emitting layer of this patent.
  • the mixing ratio of the light-emitting layer dopant (hereinafter also referred to as light-emitting dopant) to the host compound as the main component is preferably 0.1 to less than 30% by mass.
  • the dopants used in the light emitting layer are roughly classified into two types: fluorescent dopants that emit fluorescence and phosphorescent dopants that emit phosphorescence.
  • fluorescent dopants include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, perylene dyes. Stilbene dyes, polythiophene dyes, rare earth complex phosphors, and other known fluorescent compounds.
  • At least one light emitting layer contains a phosphorescent compound.
  • a phosphorescent compound is a compound in which light emission from an excited triplet is observed, and is a compound having a phosphorescence quantum yield of 0.001 or more at 25 ° C.
  • the phosphorescence quantum yield is preferably 0.01 or more, more preferably 0.1 or more.
  • the phosphorescence quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of Experimental Chemistry Course 4 of the 4th edition. Although the phosphorescence quantum yield in a solution can be measured using various solvents, the phosphorescence quantum yield used in the present invention only needs to achieve the above phosphorescence quantum yield in any solvent.
  • the phosphorescent dopant is a phosphorescent compound, and a typical example thereof is preferably a complex compound containing a group 8-10 metal in the periodic table of elements, more preferably an iridium compound or an osmium compound. , Rhodium compounds, palladium compounds, or platinum compounds (platinum complex compounds). Among them, iridium compounds, rhodium compounds, and platinum compounds are preferable, and iridium compounds are most preferable.
  • dopants are compounds described in the following documents or patent publications. J. et al. Am. Chem. Soc. 123, 4304-4312, International Publication Nos. 2000/70655, 2001/93642, 2002/02714, 2002/15645, 2002/44189, 2002/081488, JP 2002-280178, 2001. No. 18616, No. 2002-280179, No. 2001-181617, No. 2002-280180, No. 2001-247859, No. 2002-299060, No. 2001-313178, No. 2002-302671. No. 2001, No. 2001-345183, No. 2002-324679, No. 2002-332291, No. 2002-50484, No. 2002-332292, No.
  • Only one kind of light emitting dopant may be used, or a plurality of kinds may be used. By simultaneously taking out light emitted from these dopants, a light emitting element having a plurality of light emission maximum wavelengths can be configured. For example, both a phosphorescent dopant and a fluorescent dopant may be added.
  • the light emitting dopants contained in each layer may be the same or different, may be a single type, or may be a plurality of types. .
  • a polymer material in which the light emitting dopant is introduced into a polymer chain or the light emitting dopant is used as a polymer main chain may be used.
  • the host compound examples include those having a basic skeleton such as a carbazole derivative, a triarylamine derivative, an aromatic borane derivative, a nitrogen-containing heterocyclic compound, a thiophene derivative, a furan derivative, and an oligoarylene compound. Materials and hole transport materials are also suitable examples.
  • the host compound When applied to a blue or white light emitting element, a display device, and a lighting device, the host compound preferably has a maximum fluorescence wavelength of 415 nm or less. When a phosphorescent dopant is used, the phosphorescence of the host compound is 0- More preferably, the 0 band is 450 nm or less.
  • a compound having a hole transporting ability and an electron transporting ability, preventing emission light from being increased in wavelength, and having a high Tg (glass transition temperature) is preferable.
  • the luminescent dopant may be dispersed throughout the layer containing the host compound or may be partially dispersed. A compound having another function may be added to the light emitting layer.
  • a light emitting layer can be formed by using the above-mentioned materials to form a thin film by a known method such as vapor deposition, spin coating, casting, LB, ink jet transfer, or printing.
  • the light emitting layer formed is particularly preferably a molecular deposited film.
  • the molecular deposition film refers to a thin film formed by deposition from the gas phase state of the compound or a film formed by solidification from the molten state or liquid phase state of the compound.
  • this molecular deposited film and a thin film (molecular accumulation film) formed by the LB method can be distinguished from each other by a difference in aggregated structure and higher order structure and a functional difference resulting therefrom.
  • the phosphorescent dopant and host compound which are said luminescent materials as an organic compound of this invention. That is, it is preferable to form a light emitting layer by applying a solution containing the phosphorescent dopant and host compound and an organic solvent by spin coating or the like because a light emitting layer composed of a molecular volume film can be formed. .
  • the coating solution containing the phosphorescent dopant, the host compound, and the organic solvent the dissolved carbon dioxide concentration with respect to the organic solvent under an atmospheric pressure condition of 50 ° C. or less is set to 1 ppm to a saturated concentration with respect to the organic solvent. Is preferred.
  • a method of bubbling carbon dioxide gas in a solution containing a phosphorescent dopant and a host compound and an organic solvent, or containing an organic solvent and carbon dioxide And supercritical fluid chromatography using a supercritical fluid As the means for setting the dissolved carbon dioxide concentration in the above range, as described above, a method of bubbling carbon dioxide gas in a solution containing a phosphorescent dopant and a host compound and an organic solvent, or containing an organic solvent and carbon dioxide And supercritical fluid chromatography using a supercritical fluid.
  • the hole injection material used for the hole injection layer has either a hole injection property or an electron barrier property.
  • the hole transport material used for the hole transport layer has an electron barrier property and a function of transporting holes to the light emitting layer. Therefore, in the present invention, the hole transport layer is included in the hole injection layer.
  • These hole injection material and hole transport material may be either organic or inorganic.
  • triazole derivatives for example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives , Hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline copolymers, porphyrin compounds, thiophene oligomers and other conductive polymer oligomers.
  • arylamine derivatives and porphyrin compounds are preferred.
  • aromatic tertiary amine compounds and styrylamine compounds are preferable, and aromatic tertiary amine compounds are more preferable.
  • aromatic tertiary amine compound and styrylamine compound include N, N, N ′, N′-tetraphenyl-4,4′-diaminophenyl; N, N′-diphenyl-N, N ′.
  • the hole transport material of the hole transport layer preferably has a fluorescence maximum wavelength at 415 nm or less. That is, the hole transport material is preferably a compound that has a hole transport ability, prevents the emission of light from becoming longer, and has a high Tg.
  • the above-described hole injection material and hole transport material are known from, for example, a vacuum deposition method, a spin coating method, a casting method, an LB method, an ink jet method, a transfer method, and a printing method. This method can be formed by thinning the film.
  • the hole injection material or hole transport material described above it is preferable to use the hole injection material or hole transport material described above as the organic compound of the present invention.
  • the hole transport layer is preferably formed by applying a solution containing the hole transport material (or hole injection material) and an organic solvent by spin coating or the like.
  • the dissolved carbon dioxide concentration with respect to the organic solvent under an atmospheric pressure condition at 50 ° C. or lower is set to 1 ppm to a saturated concentration with respect to the organic solvent.
  • a means for setting the dissolved carbon dioxide concentration in the above range as described above, a method of bubbling carbon dioxide gas in a solution containing a hole transport material and an organic solvent, or a supercritical containing an organic solvent and carbon dioxide. Examples include supercritical fluid chromatography using a fluid.
  • the thickness of the hole injection layer and the hole transport layer is not particularly limited, but is usually about 5 nm to 5 ⁇ m.
  • the hole injection layer and the hole transport layer may each have a single-layer structure composed of one or more of the above materials, or a laminated structure composed of a plurality of layers having the same composition or different compositions. Also good.
  • a positive hole injection layer and a positive hole transport layer although a different material is normally used among said materials, you may use the same material.
  • the electron injecting layer only needs to have a function of transmitting electrons injected from the cathode to the light emitting layer, and any material can be selected from conventionally known compounds.
  • Examples of materials used for this electron injection layer include heterocyclic tetracarboxylic acid anhydrides such as nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, naphthalene perylene, and carbodiimides. , Fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives and the like.
  • a series of electron transfer compounds described in Japanese Patent Application Laid-Open No. 59-194393 is disclosed as a material for forming a light emitting layer in the publication, but as a result of investigations by the present inventors, electron injection is performed. It was found that it can be used as a material.
  • a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, or a quinoxaline derivative having a quinoxaline ring known as an electron-withdrawing group can also be used as an electron injection material.
  • metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (abbreviated as Alq 3 ), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8- Quinolinol) aluminum, tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), etc.
  • Alq 3 8-quinolinol aluminum
  • metal-free or metal phthalocyanine or those whose terminal is substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron injection material.
  • an inorganic semiconductor such as n-type-Si or n-type-SiC can also be used as the electron injection material.
  • the preferred compound used for the electron transport layer preferably has a fluorescence maximum wavelength at 415 nm or less. That is, the compound used for the electron transport layer is preferably a compound that has an electron transport ability, prevents emission of longer wavelengths, and has a high Tg.
  • the electron injection layer is formed by thinning the electron injection material by a known method such as a vacuum deposition method, a spin coating method, a casting method, an LB method, an ink jet method, a transfer method, or a printing method. Can do.
  • the above electron injection material is preferably used as the organic compound of the present invention. That is, the electron injection layer is preferably formed by applying a solution including the electron injection material and the organic solvent by spin coating or the like. In the coating liquid including the electron injection material and the organic solvent, the electron injection layer is 50 ° C. or less.
  • the dissolved carbon dioxide concentration with respect to the organic solvent under atmospheric pressure conditions is preferably 1 ppm to a saturated concentration with respect to the organic solvent.
  • the thickness of the electron injection layer is not particularly limited, but is usually selected in the range of 5 nm to 5 ⁇ m.
  • This electron injection layer may have a single layer structure composed of one or more of these electron injection materials, or may have a laminated structure composed of a plurality of layers having the same composition or different compositions.
  • an electron carrying layer is contained in an electron injection layer.
  • the electron transport layer is also referred to as a hole blocking layer (hole block layer).
  • a hole blocking layer hole block layer
  • examples thereof include, for example, International Publication No. 2000/70655, Japanese Patent Laid-Open No. 2001-313178, Japanese Patent Laid-Open No. 11-204258, No. 11-204359 and “Organic EL devices and their industrialization front line (November 30, 1998, issued by NTS, Inc.)”, page 237, and the like.
  • a buffer layer may be present between the anode and the light emitting layer or hole injection layer and between the cathode and the light emitting layer or electron injection layer.
  • the buffer layer is a layer that is provided between the electrode and the organic layer in order to lower the driving voltage and improve the light emission efficiency. “The organic EL element and the forefront of its industrialization (issued on November 30, 1998 by NTS Corporation) ) ”, Chapter 2, Chapter 2,“ Electrode Materials ”(pages 123 to 166), which includes an anode buffer layer and a cathode buffer layer.
  • anode buffer layer represented by copper phthalocyanine And an oxide buffer layer typified by vanadium oxide, an amorphous carbon buffer layer, and a polymer buffer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene.
  • a phthalocyanine buffer layer represented by copper phthalocyanine And an oxide buffer layer typified by vanadium oxide, an amorphous carbon buffer layer, and a polymer buffer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene.
  • cathode buffer layer The details of the cathode buffer layer are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like, specifically, metals represented by strontium, aluminum and the like.
  • examples thereof include a buffer layer, an alkali metal compound buffer layer typified by lithium fluoride, an alkaline earth metal compound buffer layer typified by magnesium fluoride, and an oxide buffer layer typified by aluminum oxide.
  • the buffer layer is desirably a very thin film, and depending on the material, the thickness is preferably in the range of 0.1 to 100 nm. Furthermore, in addition to the basic constituent layers, layers having other functions may be appropriately laminated as necessary.
  • the cathode of the organic EL device generally uses a metal having a low work function (less than 4 eV) (hereinafter referred to as an electron injecting metal), an alloy, a metal electroconductive compound, or a mixture thereof as an electrode material. Things are used.
  • Electrode materials include sodium, magnesium, lithium, aluminum, indium, rare earth metals, sodium-potassium alloys, magnesium / copper mixtures, magnesium / silver mixtures, magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / Aluminum oxide (Al 2 O 3 ) mixture, lithium / aluminum mixture and the like.
  • the cathode may contain a Group 13 metal element. preferable. That is, in the present invention, as described later, the surface of the cathode is oxidized with oxygen gas in a plasma state to form an oxide film on the cathode surface, thereby preventing further oxidation of the cathode and improving the durability of the cathode. Can be made.
  • the electrode material of the cathode is preferably a metal having a preferable electron injecting property required for the cathode and capable of forming a dense oxide film.
  • the cathode electrode material containing the Group 13 metal element examples include aluminum, indium, a magnesium / aluminum mixture, a magnesium / indium mixture, and an aluminum / aluminum oxide (Al 2 O 3 ) mixture. And lithium / aluminum mixtures.
  • the mixing ratio of each component of the said mixture can employ
  • the cathode can be produced by forming a thin film on the organic compound layer (organic EL layer) using the electrode material described above by a method such as vapor deposition or sputtering.
  • the sheet resistance as a cathode is several hundred ⁇ / sq.
  • the film thickness is usually selected from the range of 10 nm to 1 ⁇ m, preferably 50 to 200 nm.
  • Method for producing organic EL element As an example of the method for producing the organic EL device of the present invention, a method for producing an organic EL device comprising an anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode will be described.
  • a thin film made of a desired electrode material for example, an anode material is formed on a suitable substrate by a method such as vapor deposition or sputtering so as to have a thickness of 1 ⁇ m or less, preferably 10 to 200 nm, thereby producing an anode.
  • a method such as vapor deposition or sputtering so as to have a thickness of 1 ⁇ m or less, preferably 10 to 200 nm, thereby producing an anode.
  • the vacuum deposition method or the spin coating method is preferable.
  • the spin coating method is particularly preferable in that the coating liquid of the present invention can be used.
  • Different film formation methods may be applied for each layer.
  • the vapor deposition conditions vary depending on the type of compound used, but generally the boat heating temperature is 50 to 450, the degree of vacuum is 10 ⁇ 6 to 10 ⁇ 2 Pa, and the vapor deposition rate is 0.01. It is desirable to select appropriately within the range of ⁇ 50 nm / second, the substrate temperature of ⁇ 50 to 300 ° C., and the thickness of 0.1 nm to 5 ⁇ m.
  • a thin film made of a cathode material is formed thereon by a method such as vapor deposition or sputtering so as to have a thickness of 1 ⁇ m or less, preferably in the range of 50 to 200 nm, and a cathode is provided.
  • a desired organic EL element can be obtained.
  • the organic EL element is preferably manufactured from the hole injection layer to the cathode consistently by a single evacuation, but may be taken out halfway and subjected to different film forming methods. At that time, it is necessary to consider that the work is performed in a dry inert gas atmosphere.
  • the organic EL element sealing means is not particularly limited. For example, after sealing the outer periphery of the organic EL element with a sealing adhesive, a sealing member is provided so as to cover the light emitting region of the organic EL element. The method of arranging is mentioned.
  • sealing adhesive examples include photocuring and thermosetting adhesives having reactive vinyl groups such as acrylic acid oligomers and methacrylic acid oligomers, and moisture curing adhesives such as 2-cyanoacrylates. Can be mentioned. Moreover, heat
  • a polymer film and a metal film can be preferably used from the viewpoint of reducing the thickness of the organic EL element.
  • inert gases such as nitrogen and argon, fluorinated hydrocarbons, and silicon oil are used. Inert liquids can also be injected. Further, the gap between the sealing member and the display area of the organic EL element can be evacuated, or a hygroscopic compound can be sealed in the gap.
  • the multicolor display device using the organic EL element of the present invention is provided with a shadow mask only at the time of forming a light emitting layer, and the other layers are common, so patterning such as a shadow mask is unnecessary, vapor deposition method, casting method, A film can be formed by a spin coating method, an inkjet method, a printing method, or the like.
  • the method is not limited, but is preferably a vapor deposition method, an inkjet method, or a printing method. In the case of using a vapor deposition method, patterning using a shadow mask is preferable.
  • a DC voltage When a DC voltage is applied to the multicolor display device thus obtained, light emission can be observed by applying a voltage of about 2 to 40 V with the positive polarity of the anode and the negative polarity of the cathode. Further, even when a voltage is applied with the opposite polarity, no current flows and no light emission occurs. Further, when an AC voltage is applied, light is emitted only when the anode is in the + state and the cathode is in the-state.
  • the alternating current waveform to be applied may be arbitrary.
  • the multicolor display device can be used as a display device, a display, and various light sources.
  • a display device or display full-color display is possible by using three types of organic EL elements of blue, red, and green light emission.
  • Display devices and displays include televisions, personal computers, mobile devices, AV devices, teletext displays, information displays in automobiles, and the like. In particular, it may be used as a display device for reproducing still images and moving images, and the driving method when used as a display device for reproducing moving images may be either a simple matrix (passive matrix) method or an active matrix method.
  • Light sources include home lighting, interior lighting, clock and liquid crystal backlights, billboard advertisements, traffic lights, light sources for optical storage media, light sources for electrophotographic copying machines, light sources for optical communication processors, light sources for optical sensors, etc. For example, but not limited to.
  • organic EL element according to the present invention may be used as an organic EL element having a resonator structure.
  • Examples of the purpose of use of the organic EL element having such a resonator structure include a light source of an optical storage medium, a light source of an electrophotographic copying machine, a light source of an optical communication processing machine, and a light source of an optical sensor. It is not limited. Moreover, you may use for the said use by making a laser oscillation.
  • the organic EL device of the present invention may be used as a kind of lamp such as an illumination or exposure light source, a projection device that projects an image, or a display device that directly recognizes a still image or a moving image. (Display) may be used.
  • the driving method when used as a display device for moving image reproduction may be either a simple matrix (passive matrix) method or an active matrix method. Alternatively, it is possible to produce a full-color display device by using two or more organic EL elements of the present invention having different emission colors.
  • FIG. 4 is a schematic view showing an example of a display device composed of organic EL elements. It is a schematic diagram of a display such as a mobile phone that displays image information by light emission of an organic EL element.
  • the display 41 includes a display unit A having a plurality of pixels, a control unit B that performs image scanning of the display unit A based on image information, and the like.
  • the control unit B is electrically connected to the display unit A, and sends a scanning signal and an image data signal to each of the plurality of pixels based on image information from the outside.
  • the pixels for each scanning line are converted into image data signals by the scanning signal. In response to this, light is sequentially emitted and image scanning is performed to display image information on the display unit A.
  • FIG. 5 is a schematic diagram of the display unit A.
  • the display unit A includes a wiring unit including a plurality of scanning lines 55 and data lines 56, a plurality of pixels 53, and the like on a substrate.
  • the main members of the display unit A will be described below.
  • FIG. 5 shows a case where the light emitted from the pixel 53 is extracted in the direction of the white arrow (downward).
  • the scanning lines 55 and the plurality of data lines 56 in the wiring portion are each made of a conductive material, and the scanning lines 55 and the data lines 56 are orthogonal to each other in a lattice shape and are connected to the pixels 53 at the orthogonal positions (details are shown in FIG. Not shown).
  • the pixel 53 receives an image data signal from the data line 56, and emits light according to the received image data.
  • Full color display is possible by appropriately arranging pixels in the red region, the green region, and the blue region that emit light on the same substrate.
  • FIG. 6 is a schematic diagram of a pixel.
  • the pixel includes an organic EL element 60, a switching transistor 61, a driving transistor 62, a capacitor 63, and the like.
  • a full color display can be performed by using red, green, and blue light emitting organic EL elements as the organic EL elements 60 for a plurality of pixels, and juxtaposing them on the same substrate.
  • an image data signal is applied to the drain of the switching transistor 61 from the control unit B (not shown in FIG. 6 but shown in FIG. 4) via the data line 56.
  • a scanning signal is applied from the control unit B to the gate of the switching transistor 61 through the scanning line 55, the driving of the switching transistor 61 is turned on, and the image data signal applied to the drain is supplied to the capacitor 63 and the driving transistor 62. Is transmitted to the gate.
  • the capacitor 63 is charged according to the potential of the image data signal, and the drive of the drive transistor 62 is turned on.
  • the drive transistor 62 has a drain connected to the power supply line 67 and a source connected to the electrode of the organic EL element 60, and the power supply line 67 changes to the organic EL element 60 according to the potential of the image data signal applied to the gate. Current is supplied.
  • the driving of the switching transistor 61 is turned off. However, even if the driving of the switching transistor 61 is turned off, the capacitor 63 holds the potential of the charged image data signal, so that the driving of the driving transistor 62 is kept on and the next scanning signal is applied. Until then, the organic EL element 60 continues to emit light.
  • the driving transistor 62 is driven according to the potential of the next image data signal synchronized with the scanning signal, and the organic EL element 60 emits light.
  • the organic EL element 60 emits light by providing a switching transistor 61 and a driving transistor 62 as active elements for the organic EL elements 60 of the plurality of pixels, and a plurality of pixels 53 (not shown in FIG. 6). FIG. 5)) Each organic EL element 60 emits light.
  • Such a light emitting method is called an active matrix method.
  • the light emission of the organic EL element 60 may be light emission of a plurality of gradations by a multi-value image data signal having a plurality of gradation potentials, or on / off of a predetermined light emission amount by a binary image data signal. But you can.
  • the potential of the capacitor 63 may be held continuously until the next scanning signal is applied, or may be discharged immediately before the next scanning signal is applied.
  • the present invention not only the active matrix method described above, but also a passive matrix light emission drive in which an organic EL element emits light according to a data signal only when a scanning signal is scanned.
  • FIG. 7 is a schematic view of a passive matrix display device.
  • a plurality of scanning lines 55 and a plurality of image data lines 56 are provided in a lattice shape so as to face each other with the pixel 53 interposed therebetween.
  • the scanning signal of the scanning line 55 is applied by sequential scanning, the pixel 53 connected to the applied scanning line 55 emits light according to the image data signal.
  • the passive matrix method there is no active element in the pixel 53, and the manufacturing cost can be reduced.
  • the photoelectric conversion element of this invention has an organic functional layer formed using the said coating liquid. That is, the photoelectric conversion element of the present invention is characterized by having an organic functional layer derived from the coating liquid, in other words, having an organic functional layer formed by coating the coating liquid.
  • FIG. 8 is a cross-sectional view showing an example of a solar cell having a single configuration (a configuration having one bulk heterojunction layer) composed of a bulk heterojunction type organic photoelectric conversion element.
  • a bulk heterojunction type organic photoelectric conversion element 200 has a transparent electrode (anode) 202, a hole transport layer 207, a bulk heterojunction layer photoelectric conversion unit 204, an electron transport layer (or an electron transport layer) on one surface of a substrate 201. 208 and a counter electrode (cathode) 203 are sequentially stacked.
  • the substrate 201 is a member that holds the transparent electrode 202, the photoelectric conversion unit 204, and the counter electrode 203 that are sequentially stacked. In the present embodiment, since light that is photoelectrically converted enters from the substrate 201 side, the substrate 201 can transmit the light that is photoelectrically converted, that is, with respect to the wavelength of the light to be photoelectrically converted. A transparent member is preferred.
  • the substrate 201 for example, a glass substrate or a resin substrate is used.
  • the substrate 201 is not essential.
  • the bulk heterojunction organic photoelectric conversion element 200 may be configured by forming the transparent electrode 202 and the counter electrode 203 on both surfaces of the photoelectric conversion unit 204.
  • the photoelectric conversion unit 204 is a layer that converts light energy into electrical energy, and includes a bulk heterojunction layer in which a p-type semiconductor material and an n-type semiconductor material are uniformly mixed.
  • the p-type semiconductor material functions relatively as an electron donor (donor)
  • the n-type semiconductor material functions relatively as an electron acceptor (acceptor).
  • the electron donor and the electron acceptor are “an electron donor in which, when light is absorbed, electrons move from the electron donor to the electron acceptor to form a hole-electron pair (charge separation state)”.
  • an electron acceptor which does not simply donate or accept electrons like an electrode, but donates or accepts electrons by a photoreaction.
  • the transport direction of electrons and holes can be controlled.
  • FIG. 9 is a cross-sectional view showing a solar cell composed of an organic photoelectric conversion element having a tandem bulk heterojunction layer.
  • the transparent electrode 202 and the first photoelectric conversion unit 209 are sequentially stacked on the substrate 201, the charge recombination layer (intermediate electrode) 205 is stacked, and then the second photoelectric conversion unit 206, Next, by stacking the counter electrode 203, a tandem structure can be obtained.
  • Examples of materials that can be used for the layer as described above include n-type semiconductor materials and p-type semiconductor materials described in paragraphs 0045 to 0113 of JP-A-2015-149483.
  • Examples of a method for forming a bulk heterojunction layer in which an electron acceptor and an electron donor are mixed include a vapor deposition method and a coating method (including a casting method and a spin coating method).
  • the coating method is preferable in order to increase the area of the interface where charges and electrons are separated from each other as described above and to produce a device having high photoelectric conversion efficiency.
  • the coating method is also excellent in production speed.
  • the n-type semiconductor material and the p-type semiconductor material constituting the bulk heterojunction layer can be used as the organic compound of the present invention.
  • the bulk heterojunction layer is preferably formed by coating a solution containing the n-type semiconductor material and the p-type semiconductor material and the organic solvent, and the n-type semiconductor material, the p-type semiconductor material, and the organic solvent
  • the dissolved carbon dioxide concentration with respect to the organic solvent under an atmospheric pressure condition of 50 ° C. or lower is preferably 1 ppm to a saturated concentration with respect to the organic solvent.
  • the bulk heterojunction layer can have an appropriate phase separation structure. As a result, the carrier mobility of the bulk heterojunction layer is improved and high efficiency can be obtained.
  • the photoelectric conversion portion (bulk heterojunction layer) 204 may be configured as a single layer in which an electron acceptor and an electron donor are uniformly mixed, but a plurality of the mixture ratios of the electron acceptor and the electron donor are changed. It may consist of layers. Next, the electrode which comprises an organic photoelectric conversion element is demonstrated.
  • the organic photoelectric conversion element positive and negative charges generated in the bulk heterojunction layer are taken out from the transparent electrode and the counter electrode via the p-type organic semiconductor material and the n-type organic semiconductor material, respectively, and function as a battery. To do.
  • Each electrode is required to have characteristics suitable for carriers passing through the electrode.
  • the counter electrode is preferably an electrode for taking out electrons.
  • the conductive material may be a single layer, or in addition to a conductive material, a resin that holds these may be used in combination.
  • counter electrode material for example, known cathode conductive materials described in JP2010-272619A, JP2014-078742A, and the like can be used.
  • counter electrode material for example, known cathode conductive materials described in JP2010-272619A, JP2014-078742A, and the like can be used.
  • the transparent electrode is preferably an anode having a function of taking out holes generated in the photoelectric conversion part.
  • an electrode that transmits light having a wavelength of 380 to 800 nm is preferable.
  • known anode materials described in JP2010-272619A, JP2014-078742A, and the like can be used.
  • intermediate electrode As a material of the intermediate electrode required in the case of a tandem configuration, a layer using a compound having both transparency and conductivity is preferable.
  • the material for example, known intermediate electrode materials described in JP2010-272619A, JP2014-078742A, and the like can be used.
  • the organic photoelectric conversion device of the present invention has a hole transport layer / electron block layer between the bulk heterojunction layer and the transparent electrode in order to more efficiently extract charges generated in the bulk heterojunction layer. It is preferable to have.
  • the material for the photoelectric conversion element constituting the hole transport layer for example, known materials described in JP2010-272619A, JP2014-078742A, and the like can be used.
  • the organic photoelectric conversion device of the present invention can more efficiently extract charges generated in the bulk heterojunction layer by forming an electron transport layer, a hole blocking layer, and a buffer layer between the bulk heterojunction layer and the counter electrode. Therefore, it is preferable to have these layers.
  • the electron transport layer for example, known materials described in JP 2010-272619 A, JP 2014-078742 A, and the like can be used.
  • the electron transport layer may be a hole blocking layer having a hole blocking function that has a rectifying effect so that holes generated in the bulk heterojunction layer do not flow to the counter electrode side.
  • a material for forming the hole blocking layer for example, a known material described in JP-A-2014-078742 can be used.
  • a structure having various intermediate layers in the element may be employed.
  • the intermediate layer include a hole block layer, an electron block layer, a hole injection layer, an electron injection layer, an exciton block layer, a UV absorption layer, a light reflection layer, and a wavelength conversion layer.
  • the substrate When light that is photoelectrically converted enters from the substrate side, the substrate is preferably a member that can transmit this photoelectrically converted light, that is, a member that is transparent to the wavelength of the light to be photoelectrically converted. .
  • the substrate for example, a glass substrate, a resin substrate and the like are preferably mentioned, but it is desirable to use a transparent resin film from the viewpoint of light weight and flexibility.
  • a transparent resin film There is no restriction
  • the organic photoelectric conversion element of the present invention may have various optical functional layers for the purpose of more efficient reception of sunlight.
  • the optical functional layer for example, a light condensing layer such as an antireflection film or a microlens array, or a light diffusing layer that can scatter the light reflected by the counter electrode and enter the bulk heterojunction layer again can be provided. Good.
  • antireflection layer examples include known antireflection layers, light collecting layers, and light scattering layers described in, for example, JP2010-272619A, JP2014-078742A, and the like. Can be used.
  • Electrode There is no particular limitation on the method and process for patterning the electrode, the power generation layer, the hole transport layer, the electron transport layer, and the like according to the present invention.
  • JP 2010-272619 A, JP 2014-078742 A, etc. The known methods described can be applied as appropriate.
  • dry air refers to dry air produced using a dry air generator (manufactured by Ikeda Rika Co., Ltd., AT35HS), and in the atmosphere is 25 ° C. in a laboratory set at 1 atm.
  • a nitrogen atmosphere refers to a nitrogen atmosphere using nitrogen gas supplied from a G1 grade nitrogen cylinder manufactured by Taiyo Nippon Sanso.
  • Example 1 In a high purity nitrogen atmosphere, a high purity carbon dioxide gas (Taiyo Nippon Oil, high purity carbon dioxide gas ( > 99.995 vol.%) was bubbled at a flow rate of 100 mL / min for 10 minutes and then degassed for 10 minutes to prepare solution s-5.
  • the amount of carbon dioxide contained in s-1 and s-5 was measured by gas chromatography. Specifically, the measurement was performed by an absolute calibration curve method using Porapack Type S GC Bulk Packing Material (Mesh 80-100) manufactured by Waters Corporation as a column packing material. The water content of s-1 and s-5 was measured by the Karl Fischer method. The results are shown in Table 1.
  • the various solvents used are as follows. Toluene (Kanto Chemical Co., Ltd., dehydrated toluene), isobutyl acetate (Kanto Chemical Co., Ltd., special grade isobutyl acetate), TFPO (Tokyo Chemical Industry Co., Ltd., 2,2,3,3-tetrafluoro-1-propanol)
  • Example 2 After storing s-1 to s-8 prepared in Example 1 for 1 hour under the conditions shown in Table 2, the dissolved oxygen concentration of each sample was measured by gas chromatography. The results are shown in Table 2.
  • Example 3 Transparent support provided with this ITO transparent electrode after patterning on a substrate (NH45 manufactured by NH Techno Glass Co., Ltd.) formed by depositing 100 nm of ITO (indium tin oxide) on a glass substrate of 100 mm ⁇ 100 mm ⁇ 1.1 mm The substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes. On this substrate, s-4 produced in Example 1 was formed by an inkjet method (film thickness of about 40 nm), and the mass (w (0)) before the start of drying was measured. Thereafter, the mass (w (t)) when dried at 60 ° C.
  • a substrate NH45 manufactured by NH Techno Glass Co., Ltd.
  • ITO indium tin oxide
  • Example 4 ⁇ Preparation of coating solution for hole transport layer (HT layer)>
  • a solution solution s-10) in which 600 mg of polyvinylcarbazole (PVK) was dissolved in 100 ml of chlorobenzene was divided into two parts, each treated by the following method, and one of them was designated as solution s-11.
  • the other was bubbled with carbon dioxide for 10 minutes in a groove box under a nitrogen atmosphere to obtain a solution s-12.
  • the carbon dioxide concentration of the solution s-12 was measured by the method of Example 1, and it was confirmed that the solution s-12 contained 200 ppm of carbon dioxide.
  • solution s-11 and the solution s-12 were each divided into three and treated by the following method to obtain the solutions shown in Table 4.
  • Treatment 1 Solution s-11 was prepared and stored for 30 minutes under a nitrogen atmosphere to obtain solution s-111.
  • Treatment 2 Solution s-11 was stored for 30 minutes in a dry air atmosphere to obtain Solution s-112.
  • Treatment 3 Solution s-11 was stored in the atmosphere for 30 minutes to obtain solution s-113.
  • Treatment 4 Solution s-12 was stored for 30 minutes under the prepared nitrogen atmosphere to obtain Solution s-121.
  • Treatment 5 The solution s-12 was stored for 30 minutes in a dry air atmosphere to obtain a solution s-122.
  • Process 6 The solution s-12 was stored in the atmosphere for 30 minutes to obtain a solution s-123.
  • ⁇ Preparation of coating solution for light emitting layer (EM layer)> In a glove box under a nitrogen atmosphere, a solution (solution s-20) in which 600 mg of CBP and 30.0 mg of compound Ir-12 were dissolved in 60 ml of toluene / isobutyl acetate (1/1) was divided into two parts. One was solution s-21 and the other was bubbled with carbon dioxide for 10 minutes in a groove box under a nitrogen atmosphere to obtain solution s-22. The carbon dioxide concentration of the solution s-22 was measured by the method of Example 1, and it was confirmed that the solution s-22 contained 250 ppm of carbon dioxide. Further, the solution s-21 and the solution s-22 were each divided into three parts and treated by the following method to obtain the solutions shown in Table 4.
  • Treatment 11 The solution s-21 was prepared and stored for 30 minutes in a nitrogen atmosphere to obtain a solution s-211.
  • Treatment 12 The solution s-21 was stored in a dry air atmosphere for 30 minutes to obtain a solution s-212.
  • Treatment 13 The solution s-21 was stored in the atmosphere for 30 minutes to obtain a solution s-213.
  • Process 14 Solution s-22 was stored for 30 minutes in the prepared nitrogen atmosphere to obtain solution s-221.
  • Process 15 The solution s-22 was stored in a dry air atmosphere for 30 minutes to obtain a solution s-222.
  • Treatment 16 The solution s-22 was stored in the atmosphere for 30 minutes to obtain a solution s-223.
  • ⁇ Coating solution for electron transport layer (ET layer)> In a glove box under a nitrogen atmosphere, a solution (solution s-30) in which 200 mg of bathocuproin (BCP) was dissolved in 60 ml of cyclohexane was divided into two parts, and each was treated by the following method. One side was bubbled with carbon dioxide for 10 minutes in a groove box under a nitrogen atmosphere to obtain a solution s-32. The carbon dioxide concentration of the solution s-32 was measured by the method of Example 1, and it was confirmed that the solution s-32 contained 180 ppm of carbon dioxide. Further, the solution s-31 and the solution s-32 were each divided into three and treated by the following method to obtain the solutions shown in Table 4.
  • solution s-31 and the solution s-32 were each divided into three and treated by the following method to obtain the solutions shown in Table 4.
  • Treatment 21 Solution s-31 was stored in the prepared nitrogen atmosphere for 30 minutes to obtain solution s-311.
  • Process 22 The solution s-31 was stored in a dry air atmosphere for 30 minutes to obtain a solution s-312.
  • Treatment 23 The solution s-31 was stored in the atmosphere for 30 minutes to obtain a solution s-313.
  • Treatment 24 The solution s-32 was stored for 30 minutes in the prepared nitrogen atmosphere to obtain a solution s-321.
  • Treatment 25 The solution s-32 was stored in a dry air atmosphere for 30 minutes to obtain a solution s-322.
  • Process 26 The solution s-32 was stored in the atmosphere for 30 minutes to obtain a solution s-323.
  • solution s-111 10 ml
  • solution s-211 6 ml
  • spin-coated at 1000 rpm for 30 seconds layer thickness: about 40 nm
  • vacuum-dried at 60 ° C. for 1 hour to obtain a light emitting layer.
  • solution s-311 6 ml
  • spin-coated under the condition of 1000 rpm for 30 seconds layer thickness of about 10 nm
  • vacuum-dried at 60 ° C. for 1 hour to form an electron transport layer that also serves as a hole blocking function.
  • this substrate was fixed to a substrate holder of a vacuum vapor deposition apparatus, and 200 mg of Alq 3 was put into a molybdenum resistance heating boat and attached to the vacuum vapor deposition apparatus.
  • the heating boat containing Alq 3 was energized and heated, and deposited on the electron transport layer at a deposition rate of 0.1 nm / second.
  • An electron injection layer having a thickness of 40 nm was provided.
  • the substrate temperature at the time of vapor deposition was room temperature.
  • the organic EL element 1 was produced.
  • the organic EL elements shown in Table 4 were prepared in the same manner as the organic EL element 1 except that the solutions s-111, s-211 and s-311 were replaced with the solutions shown in Table 4. Produced.
  • Example 5 ⁇ Purification of ink compounds> CBP was fractionated using the supercritical fluid chromatography system manufactured by JASCO Corporation under the following conditions.
  • Supercritical CO 2 pump SCF-Get Fully automatic pressure regulating valve: SFC-Bpg
  • Moving bed: carbon dioxide / toluene 9/1 Moving bed flow rate: 3ml / min
  • composition 1 This solution is referred to as composition 1.
  • Composition 2 Toluene solution containing 10% by mass of Ir-14 and 300 ppm of carbon dioxide
  • Composition 3 Toluene solution containing 10% by mass of Ir-1 and 300 ppm of carbon dioxide
  • Composition 4 10% by mass of Ir-15 Toluene solution containing 300 ppm of carbon dioxide
  • a TFPO solution containing 10% by mass of BCP and 300 ppm of carbon dioxide was obtained. .
  • This solution is designated as composition 5.
  • composition 1 9.5 parts by weight Composition 4 0.5 parts by weight Toluene 40 parts by weight Isobutyl acetate 50 parts by weight
  • FIG. 10 shows a schematic configuration diagram of an organic EL full-color display device. After patterning at a pitch of 100 ⁇ m on a substrate (NH45 manufactured by NH Techno Glass Co., Ltd.) having a 100 nm thick ITO transparent electrode (102) formed on a glass substrate 101 as an anode, non-between the ITO transparent electrodes on this glass substrate. A photosensitive polyimide partition 103 (width 20 ⁇ m, thickness 2.0 ⁇ m) was formed by photolithography.
  • the hole injection layer composition having the above composition is injected and injected using an inkjet head (“KM512L” manufactured by Konica Minolta), and a positive thickness of 40 nm is obtained by drying at 200 ° C. for 10 minutes.
  • the hole injection layer 104 was produced.
  • the blue light emitting layer composition, the green light emitting layer composition, and the red light emitting layer composition are similarly ejected and injected using an inkjet head, and the respective light emitting layers (105B, 105G, 105R) was formed.
  • the electron transport layer composition was similarly discharged and injected using an inkjet head, and an electron transport layer (106) that also served as a hole blocking function was formed on each layer of the light emitting layer 105.
  • Al (107) was vacuum-deposited as a cathode on the electron transport layer 106 to produce an organic EL device.
  • the produced organic EL element showed blue, green, and red light emission by applying a voltage to each electrode, and it was found that it can be used as a full-color display device.
  • Example 6 As a p-type material for the bulk heterojunction layer, a low band gap polymer described in Macromolecules 2007, 40, 1981, PCPDTBT, was synthesized and used with reference to non-patent literature (Nature Mat. Vol. 6 (2007), p497). Moreover, PCBM (purchased from Frontier Carbon Co.) was used as the n-type material.
  • a transparent electrode was formed by patterning an indium tin oxide (ITO) transparent conductive film deposited on a glass substrate to a width of 2 mm using a normal photolithography technique and hydrochloric acid etching.
  • the patterned transparent electrode was washed in the order of ultrasonic cleaning with a surfactant and ultrapure water, followed by ultrasonic cleaning with ultrapure water, dried with nitrogen blow, and finally subjected to ultraviolet ozone cleaning.
  • Baytron P4083 manufactured by Starck Vitec, which is a conductive polymer, was spin-coated with a film thickness of 60 nm, and then heat-dried at 140 ° C.
  • the substrate was brought into the glove box and operated under a nitrogen atmosphere.
  • the substrate was heat-treated at 140 ° C. for 10 minutes in a nitrogen atmosphere. Chlorobenzene obtained by bubbling carbon dioxide gas for 10 minutes was prepared, and the dissolved carbon dioxide concentration was measured by gas chromatography.
  • the substrate on which the bulk heterojunction layer was formed was placed in a vacuum deposition apparatus.
  • the element was set so that the shadow mask with a width of 2 mm was orthogonal to the transparent electrode, and the inside of the vacuum deposition apparatus was depressurized to 10 ⁇ 3 Pa or less, and then 0.5 nm of lithium fluoride and 80 nm of Al were evaporated.
  • the heating for 30 minutes was performed at 120 degreeC, and the organic photoelectric conversion element 1 was obtained.
  • the vapor deposition rate was 2 nm / second for all, and the size was 2 mm square.
  • the obtained organic photoelectric conversion element 1 was sealed using an aluminum cap and a UV curable resin in a nitrogen atmosphere.
  • the present invention can be used for an ink for producing an electronic device, an electronic device, an organic electroluminescence element, and an organic photoelectric conversion element.

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  • Electroluminescent Light Sources (AREA)
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PCT/JP2017/022768 2016-07-11 2017-06-21 塗布液、その製造方法、電子デバイス作製用インク、電子デバイス、有機エレクトロルミネッセンス素子、及び光電変換素子 WO2018012223A1 (ja)

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CN201780042907.6A CN109479355B (zh) 2016-07-11 2017-06-21 涂布液、其制造方法、电子设备制作用油墨、电子设备、有机电致发光元件和光电转换元件
KR1020197000606A KR102174806B1 (ko) 2016-07-11 2017-06-21 도포액, 그의 제조 방법, 전자 디바이스 제작용 잉크, 전자 디바이스, 유기 일렉트로루미네센스 소자, 및 광전 변환 소자
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JPH05115703A (ja) * 1991-10-30 1993-05-14 Mitsubishi Kakoki Kaisha Ltd 超臨界流体クロマト分離方法
WO2001038003A1 (fr) * 1999-11-26 2001-05-31 Asahi Glass Company, Limited Procede de fabrication de couche mince a partir d'une substance organique et appareil correspondant
JP2004524948A (ja) * 2000-12-06 2004-08-19 ウィルヘルム・テオドラス・ステファヌス・ハック 圧縮二酸化炭素を使用するパターン化付着
KR20150101956A (ko) * 2014-02-27 2015-09-04 주식회사 동진쎄미켐 습식 공정에 의해 형성된 유기 반도체 소자의 정제 방법
JP2016501430A (ja) * 2012-11-20 2016-01-18 メルク パテント ゲーエムベーハー 電子素子の製造のための高純度溶媒における調合物

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KR100461474B1 (ko) * 1998-12-28 2004-12-16 이데미쓰 고산 가부시키가이샤 유기 전기발광 소자
US7030168B2 (en) * 2001-12-31 2006-04-18 Advanced Technology Materials, Inc. Supercritical fluid-assisted deposition of materials on semiconductor substrates
JP4389494B2 (ja) * 2003-06-13 2009-12-24 コニカミノルタホールディングス株式会社 有機エレクトロルミネッセンス材料の精製方法
JP4195411B2 (ja) * 2004-04-12 2008-12-10 セイコーエプソン株式会社 有機エレクトロルミネッセンス装置の製造方法
JP5760779B2 (ja) * 2010-08-06 2015-08-12 株式会社リコー 発光素子及び表示装置

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JPH05115703A (ja) * 1991-10-30 1993-05-14 Mitsubishi Kakoki Kaisha Ltd 超臨界流体クロマト分離方法
WO2001038003A1 (fr) * 1999-11-26 2001-05-31 Asahi Glass Company, Limited Procede de fabrication de couche mince a partir d'une substance organique et appareil correspondant
JP2004524948A (ja) * 2000-12-06 2004-08-19 ウィルヘルム・テオドラス・ステファヌス・ハック 圧縮二酸化炭素を使用するパターン化付着
JP2016501430A (ja) * 2012-11-20 2016-01-18 メルク パテント ゲーエムベーハー 電子素子の製造のための高純度溶媒における調合物
KR20150101956A (ko) * 2014-02-27 2015-09-04 주식회사 동진쎄미켐 습식 공정에 의해 형성된 유기 반도체 소자의 정제 방법

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