KR20110107353A - Electro-form nozzle apparatus and method for solution coating - Google Patents

Abstract

Apparatus and method for liquid phase coating a layer onto a substrate of an electronic device. Electro-cast nozzles comprising a body and a disk are arranged in an array to effect multiple deposition on the substrate. The low solids mixture produces a very thin dry film of electronic material.

Description

ELECTROL-FORM NOZZLE APPARATUS AND METHOD FOR SOLUTION COATING}

Related application

This application claims 35 U.S.C. from U.S. Provisional Patent Application 61 / 140,945, filed Dec. 27, 2008, which is incorporated herein by reference in its entirety. Claim priority under § 119 (e).

The present invention generally relates to a method of manufacturing an electronic device. In particular, the present invention relates to a method and a nozzle apparatus for continuous coating of a liquid phase layer using a particular nozzle assembly for a liquid mixture with a low solids content.

Active organic molecules are increasingly used in electronic devices. These active organic molecules have electron or electroluminescent properties, including electroluminescence. Electronic devices comprising organic active materials can be used to convert electrical energy into radiation and can include light emitting diodes, light emitting diode displays, or diode lasers.

Two methods are commonly used to produce organic light emitting diode ("OLED") displays: vacuum deposition and liquid phase processing. (The latter is a true solution or suspension, including all forms of applying a layer from a fluid). Vacuum deposition equipment is typically very expensive to invest and inferior in material usage (higher operating costs), so liquid phase processing is desirable, especially for large area displays.

Liquid phase processing for the deposition of organic active layers includes a number of techniques for controlling the layer thickness on a substrate. Some of these techniques include self-regulating methods for controlling thickness, including spin coating, rod coating, dip coating, roll coating, gravure coating or printing, lithography or flexography printing, screen coating or printing, and the like. . Others of these techniques seek to control deposition thickness using controlled deposition techniques including inkjet printing, spray coating, nozzle coating, slot die coating, curtain coating, bar or slide coating, and the like.

Self-regulation techniques have many disadvantages. Fluids used in OLED display coatings are often applied over surfaces with topography—electrodes, contact pads, thin film transistors, pixel wells formed from photoresists, cathode separator structures, and the like. The uniformity of the wet layer deposited by the self-regulating technique depends on the coating gap and the resulting pressure distribution, so that a change in the substrate topography causes an undesirable change in the wet coating thickness. Self-regulating techniques generally present higher operating costs in that not all of the fluids provided on the substrate are deposited. Some fluids are recycled (eg, dip coating) in a fluid bath, or recycled (eg, roll or gravure coating) in an applicator, or discarded (eg, spin coating). The solvent evaporates from the recycled fluid and requires adjustment to maintain process stability. Disposal and recycling and adjustment of the materials adds cost.

Controlled technology can provide low operating costs. In some cases, however, wear of precision equipment such as nozzles results in inferior control over layers that are only nanometers thick when dried. Precision machined nozzles are expensive to produce, and providing an array of nozzles to cover a large substrate area would magnify control issues. Inconsistent formation of organic layers typically results in inferior device performance and inferior yields in the device fabrication process.

There is a continuing need for improved processes for the liquid phase deposition of organic materials for OLED applications.

In a controlled coating method, all fluid supplied to the coating nozzle is applied to the substrate or workpiece. The average wet coating thickness can be calculated a priori from the volume flow rate of the coating fluid, the coated width, and the rate at which the substrate moves past the nozzle. Fluid properties (eg, viscosity, surface tension) and external forces (eg, gravity) can affect the quality of the coating, but they do not affect the average wet thickness. A controlled coating method of particular interest is a continuous nozzle coating method, in particular an electro-cast method with a disk bonded to the recess of the distal end of the nozzle body.

Continuous nozzle operation has many variations, including the design of the nozzle itself, "patch coating" to "continuous coating", "stripe coating", and a method of generating pressure to force liquid out of the nozzle. Continuous nozzle coating is generally recognized as coating with a nozzle separated by a gap from the substrate or workpiece.

Typical thickness levels associated with nozzles are a few tenths of a micrometer when wet, and can be dried to a final film on the order of a few micrometers. In contrast, continuous nozzle coating of organic layers for making OLED displays generally produces a layer about 0.1 to 500 nanometers thick. Process improvements are needed to achieve acceptable layer performance at such thin dimensions.

Decomposition of the stream, also called the pillar, emitted from the nozzle, leads to unacceptable deposition and performance of organic material in the dried layer. When used in an array of nozzles, the decomposition of only one nozzle stream in an array of 16 nozzles can lead to unacceptable product loss, since many devices are coated during the array operation. In one embodiment of the present invention, the electro-cast disc may be attached to the nozzle body to facilitate easy exchange of the disc when the stream is broken beyond acceptable parameters. Instead of replacing the entire nozzle assembly, only the disc at the nozzle end needs to be replaced.

At least one embodiment provides a body comprising a recessed portion at the distal end, and

And a nozzle assembly comprising a disk having a centrally located opening. This opening has an opening diameter d _A and the disk has a diameter d _D. Also, the disk has a first side and a second side, wherein the first side is attached to the recessed area of the body and the second side has an opening located in the recessed area. This recessed area on the second side of the disc has a diameter d ₂ , where d _D is greater than d ₂ .

In one embodiment, the diameter d _A of the opening is 0.05 mm or less. In another embodiment, d _A is 0.01 mm or less. In yet another embodiment, d _A varies between the first side of the disc and the second side of the disc. In another embodiment, d _A is greater in the first face than in the second face. In another embodiment, the radius r _A defines the surface of the opening between the first side and the second side. In one embodiment, the radius is less than 0.05 mm. In another embodiment, the radius r _A is less than 0.04 mm. In another embodiment, the radius r _A is less than 0.03 mm.

At least one embodiment includes a liquid phase coating method comprising several steps, such as providing a body comprising a recessed region at the distal end of the body. In the case of providing a disk with a centrally located opening, the opening has an opening diameter d _A and the disk has a diameter d _D , a first side and a second side. The second side of the disk has an opening located in a recessed region having a diameter d ₂ , where the disk diameter d _D is greater than d ₂ . The first side of the disk is attached to the recessed area of the body to form a nozzle assembly, and a mixture is provided that includes a liquid and a solid. This mixture is directed to create a layer through the nozzle assembly. In one embodiment the liquid is an organic solvent. In another embodiment the liquid is water. In one embodiment the mixture is a solution with a solids content of less than 10%, and in another embodiment the mixture is a suspension with a solids content of less than 10%.

In one embodiment, the workpiece includes a substrate (eg, glass) useful for organic electronic devices. The term "organic electronic device" or sometimes only "electronic device" is intended to mean a device comprising one or more organic semiconductor layers or materials. Organic electronic devices include (1) devices that convert electrical energy into radiation (e.g., light emitting diodes, light emitting diode displays, diode lasers, or lighting panels), and (2) devices that detect signals using electronic processes (e.g., For example, photodetectors, photoconductive cells, photoresistors, optical switches, phototransistors, phototubes, infrared ("IR") detectors, or biosensors, (3) devices that convert radiation into electrical energy (e.g., Photovoltaic devices or solar cells), and (4) devices (eg, transistors or diodes) comprising one or more electronic components, including one or more organic semiconductor layers, or devices of items (1)-(4). And any combination of these.

<Figure 1>
1 illustrates an electronic device.
<FIG. 2>
2 is an illustration of one embodiment of a disk with an opening located in the center of the invention.
3,
Figure 3 is a view of the edge taken along line 3-3 of the disk of Figure 2 of the present invention.
<Figure 4>
4 is a view of one embodiment of a recessed region of a distal end of the nozzle body of the present invention.
<Figure 5>
5 is a diagram of one embodiment of a nozzle arrangement of the present invention.

One example of an electronic device including an organic light emitting diode (“OLED”) is shown in FIG. 1 and indicated at 100. The device has an anode layer 110, a buffer layer 120, a photoactive layer 130, and a cathode layer 150. An optional electron injection / transport layer 140 is adjacent to the cathode layer 150. Between the buffer layer 120 and the photoactive layer 130, there is an optional hole injection / transport layer (not shown).

As used herein, the term "buffer layer" or "buffer material" is intended to mean an electrically conductive or semiconducting material, and in organic electronic devices, the planarization, charge transport and / or charge injection properties, oxygen of the underlying layer, Or removal of impurities such as metal ions, and other aspects that enhance or improve the performance of the organic electronic device. The buffer material may be a polymer, oligomer or small molecule and may be in the form of a solution, dispersion, suspension, emulsion, colloidal mixture or other composition. When referring to a layer, material, member, or structure, the term “hole transport” refers to the transfer of positive charge through the thickness of such layer, material, member, or structure. To promote relatively efficient and low charge losses. When referring to a layer, material, member, or structure, the term "electron transport" promotes the transfer of negative charges through such layer, material, member, or structure to another layer, material, member, or structure. Or to promote such layers, materials, members, or structures. When referring to a layer, material, member, or structure, the term "hole-injection" refers to the injection of a positive charge through the thickness of such layer, material, member, or structure. It is intended to mean that the movement and transport is relatively efficient and the charge loss is promoted small. The term "electron injection", when referring to a layer, material, member, or structure, allows the layer, material, member, or structure to be relatively efficient and to reduce the thickness of such layer, material, member, or structure with little charge loss. Through this means to promote the injection and movement of negative charge.

The device may include a support or substrate (not shown) that may be adjacent to the anode layer 110 or the cathode layer 150. Most often, the support is adjacent to the anode layer 110. The support can be flexible or rigid, organic or inorganic. Generally, glass or flexible organic films are used as the support. The anode layer 110 is an electrode that is more efficient in hole injection than the cathode layer 150. The anode may comprise a material comprising a metal, mixed metal, alloy, metal oxide or mixed oxide. Suitable materials include mixed oxides of Group 11 elements, elements within Groups 4, 5 and 6, Groups 8-10 transition elements and Group 2 elements (ie Be, Mg, Ca, Sr, Ba, Ra). In order for the anode layer 110 to be light transmissive, mixed oxides of Group 12, 13 and 14 elements, for example indium-tin-oxide, may be used. As used herein, the phrase “mixed oxide” refers to an oxide having at least two different cations selected from Group 2 elements or Group 12, 13 or 14 elements. Some non-limiting examples of materials for anode layer 110 include, but are not limited to, indium tin oxide (“ITO”), aluminum tin oxide, gold, silver, copper, and nickel. The anode may also include an organic material such as polyaniline, polythiophene, or polypyrrole. The IUPAC numbering system is used throughout, and the family of the periodic table is numbered 1 to 18 from left to right (CRC Handbook of Chemistry and Physics, 81 ^st Edition, 2000).

In one embodiment, the buffer layer 120 comprises a hole transport material. Examples of hole transport materials for layer 120 are described, for example, in Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, Vol. 18, p. 837-860, 1996, by Y. Wang. Both hole transport molecules and polymers can be used. Commonly used hole transport molecules include, but are not limited to, 4,4 ', 4 "-tris (N, N-diphenyl-amino) -triphenylamine (TDATA); 4,4', 4 "-tris (N-3-methylphenyl-N-phenyl-amino) -triphenylamine (MTDATA); N, N'-diphenyl-N, N'-bis (3-methylphenyl)-[1,1'-biphenyl] -4,4'-diamine (TPD); 1,1-bis [(di-4-tolylamino) phenyl] cyclohexane (TAPC); N, N'-bis (4-methylphenyl) -N, N'-bis (4-ethylphenyl)-[1,1 '-(3,3'-dimethyl) biphenyl] -4,4'-dia Min (ETPD); Tetrakis- (3-methylphenyl) -N, N, N ', N'-2,5-phenylenediamine (PDA); α-phenyl-4-N, N-diphenylaminostyrene (TPS); p- (diethylamino) benzaldehyde diphenylhydrazone (DEH); Triphenylamine (TPA); Bis [4- (N, N-diethylamino) -2-methylphenyl] (4-methylphenyl) methane (MPMP); 1-phenyl-3- [p- (diethylamino) styryl] -5- [p- (diethylamino) phenyl] pyrazoline (PPR or DEASP); 1,2-trans-bis (9H-carbazol-9-yl) cyclobutane (DCZB); N, N, N ', N'-tetrakis (4-methylphenyl)-(1,1'-biphenyl) -4,4'-diamine (TTB); N, N'-bis (naphthalen-1-yl) -N, N'-bis- (phenyl) benzidine (α-NPB); And porphyrinic compounds such as copper phthalocyanine. Commonly used hole transporting polymers include polyvinylcarbazole, (phenylmethyl) polysilane, poly (9,9, -dioctyl-fluorene-co-N- (4-butylphenyl) diphenylamine) and the like. Dioxythiophene), polyaniline, and polypyrrole. Hole transport polymers may also be obtained by doping hole transport molecules such as those mentioned above into polymers such as polystyrene and polycarbonate.

Photoactive layer 130 may typically be any organic electroluminescent (“EL”) material, including but not limited to small molecule organic fluorescent compounds, fluorescent and phosphorescent metal complexes, conjugated polymers, and mixtures thereof. . Examples of fluorescent compounds include, but are not limited to, pyrene, perylene, rubrene, coumarin, derivatives thereof and mixtures thereof. Examples of metal complexes include metal chelated oxynoid compounds such as tris (8-hydroxyquinolato) aluminum (Alq 3); Cyclometalated iridium and platinum electroluminescent compounds such as iridium and phenyl as disclosed in US Pat. Nos. 6,670,645 to Petrov et al. And International Patent Publications WO 03/063555 and WO 2004/016710 Pyridine, phenylquinoline, or complexes of phenylpyrimidine ligands, and organometallic complexes disclosed in, for example, WO 03/008424, WO 03/091688, and WO 03/040257, and mixtures thereof. But it is not limited to this. Electroluminescent emissive layers comprising charge-carrying host materials and metal complexes are described in Burrows and Thompson in US Pat. No. 6,303,238 by Thompson et al. It is explained by Examples of conjugated polymers include but are not limited to poly (phenylenevinylene), polyfluorene, poly (spirobifluorene), polythiophene, poly (p-phenylene), copolymers thereof, and mixtures thereof. It is not limited.

The specific material selected may depend on the specific application, the potential used during operation, or other factors. The EL layer 130 including the electroluminescent organic material can be applied using any of a number of techniques, including liquid phase processing. In other embodiments, an EL polymer precursor can be applied and then converted to the polymer, typically by other sources of heat or external energy (eg, visible or UV radiation).

The selection layer 140 may function to facilitate both electron injection / transport and may also function as a confinement layer to prevent quenching reaction at the layer interface. More specifically, layer 140 promotes electron mobility and can reduce the likelihood of quenching reactions when layers 130 and 150 are in direct contact without it. Examples of materials for the selective layer 140 are metal chelate oxynoid compounds such as tris (8-hydroxyquinolato) aluminum (Alq3), bis (2-methyl-8-quinolinolato) (para -Phenyl-phenollato) aluminum (III) (BAlQ), and tetrakis- (8-hydroxyquinolinato) zirconium (IV) (ZrQ); And azole compounds such as 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole (PBD), 3- (4-biphenylyl) 4-phenyl-5- (4-t-butylphenyl) -1,2,4-triazole (TAZ), and 1,3,5-tri (phenyl-2-benzimidazole) benzene (TPBI); Quinoxaline derivatives such as 2,3-bis (4-fluorophenyl) quinoxaline; Phenanthrolines such as 4,7-diphenyl-1,10-phenanthroline (DPA) and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (DDPA) and mixtures thereof Including but not limited to. Alternatively, the selection layer 140 may be an inorganic layer and may include BaO, LiF, Li ₂ O, or the like.

Cathode layer 150 is an electrode that is particularly efficient for the injection of electron or negative charge carriers. Cathode layer 150 may be any metal or nonmetal having a lower work function than the first electrical contact layer (in this case anode layer 110). The term "lower work function" as used herein is intended to mean a material having a work function of about 4.4 eV or less. As used herein, "higher work function" is intended to mean a material having a work function of at least approximately 4.4 eV.

Materials for the cathode layer include alkali metals of Group 1 (eg, Li, Na, K, Rb, Cs), Group 2 metals (eg, Mg, Ca, Ba, etc.), Group 12 metals, lanthanides ( For example, Ce, Sm, Eu, etc.) and actinides (eg, Th, U, etc.). Materials such as aluminum, indium, yttrium and combinations thereof may also be used. Specific non-limiting examples of materials for the cathode layer 150 include, but are not limited to, barium, lithium, cerium, cesium, europium, rubidium, yttrium, magnesium, samarium, and alloys and combinations thereof.

In other embodiments, additional layer (s) may be present in the organic electronic device. For example, a layer (not shown) between the buffer layer 120 and the EL layer 130 can promote positive charge transport, band gap matching of the layers, function as a protective layer, and the like. Similarly, an additional layer (not shown) between the EL layer 130 and the cathode layer 150 can promote negative charge transport, band gap matching between layers, function as a protective layer, and the like. Layers known in the art can be used. In addition, any of the layers described above may be made of two or more layers. Alternatively, some or all of the inorganic anode layer 110, buffer layer 120, EL layer 130, and cathode layer 150 may be surface treated to increase the charge carrier transport efficiency. The choice of material for each of the component layers can be determined by balancing the goal of providing devices with high device efficiency with manufacturing costs, manufacturing complexity, or other potential factors.

The different layers can have any suitable thickness. In one embodiment, the inorganic anode layer 110 is typically about 500 nm or less, for example about 10 to 200 nm; Buffer layer 120 is typically no greater than approximately 250 nm, for example approximately 50-200 nm; EL layer 130 is typically about 100 nm or less, for example about 50 to 80 nm; The selection layer 140 is typically about 100 nm or less, for example about 20 to 80 nm; And the cathode layer 150 is typically about 100 nm or less, for example about 1 to 50 nm. If the anode layer 110 or the cathode layer 150 needs to transmit at least some light, the thickness of such layer may not exceed approximately 100 nm.

In the organic light emitting diode (OLED), electrons and holes injected from the cathode layer 150 and the anode layer 110 into the EL layer 130 respectively form negatively charged polar ions and positively charged polar ions in the polymer. These polar ions migrate under the influence of an applied electric field, forming polar ion excitons with opposite charge species and then undergoing radiation recombination. Sufficient potential difference between the anode and the cathode, typically less than about 12 volts, and in many cases up to about 5 volts may be applied to the device. The actual potential difference may depend on the use of the device in the larger electronic element. In many embodiments, anode layer 110 is biased with a positive voltage and cathode layer 150 is substantially at ground potential or zero volts during operation of the electronic device. A battery or other power source (s) may be electrically connected to the electronic device as part of the circuit but is not shown in FIG. 1.

2 illustrates one embodiment of a disk 200. Disk 200 has a first side 202 (shown in FIG. 3) and a second side 204. The opening 206 passes through the disk 200 and exhibits an opening diameter d _A at the second face 204. The second face 204 additionally includes a recessed region 208. This recessed region 208 serves to shield the stream (not shown) from the wind generated during the relative movement between the substrate (not shown) and the nozzle assembly 502 (see FIG. 5). A stop zone is formed in the recessed region 208 to create more controlled deposition conditions. In one embodiment of the present invention, the diameter d _D of the disk may be 10 cm or less. In other embodiments, d _D can be 5 cm or less. In other embodiments, the opening diameter d _A can be 0.05 mm or less. In other embodiments, d _A can be 0.01 mm or less. In another embodiment, the diameter of the recessed region, d ₂ , may be 1.0 mm or less. In other embodiments, d ₂ can be 0.05 mm or less. The ratio of t _D / d ₂ is sufficient to create a stop zone in the recess region 208. In one embodiment, t _D May be 0.05 mm and d ₂ may be 0.5 mm.

FIG. 3 illustrates one embodiment of the edge of the disk 200, as shown by lines 3-3 in FIG. 2. The first surface 202 and the second surface 204 are separated by the thickness of the disk, as indicated by the disk thickness t _D , where t _D can be 0.1 mm or less. In one embodiment of the present invention, the disk thickness, t _D may be 0.05 mm or less. In other embodiments t _D can be 0.03 mm or less. In one embodiment, the thickness of the opening, t _A , may be 50 μm or less. In other embodiments t _A can be 10 μm or less. If the thin thickness opening causes a reduced pressure loss, the jet discharge rate is maintained, so that the stream is less likely to scatter into droplets. Such embodiments may be useful for depositing buffer layers, charge blocking layers, charge injection layers, charge transport layers, electroluminescent layers, or combinations thereof.

4 illustrates an embodiment of a body 400 having a recessed area that includes a shoulder 402 and a hole 404. Disc 200 is bonded to body 400, where first surface 202 is bonded to shoulder 402 to form nozzle assembly 502 (shown in FIG. 5). Bonding may include mechanical bonding, bonding, soldering, welding, fusing, etc., such as fasteners, clips, or other mechanical means. In one embodiment, the body 400 is aluminum and coated with nickel, and the disk 200 is soldered into the recessed area of the body 400. Other materials and methods can be used without changing the scope of the invention. For example, the distal end of body 400 may not contain a recess, and disk 200 may be bonded directly to the distal surface of body 400 (not shown).

5 illustrates one embodiment of a linear arrangement 500 of nozzle assemblies 502. Array 500 is a linear structure including sixteen total nozzle assemblies 502, but any number may be used and may be within the teachings of the present invention. The mixture is sent through a nozzle assembly to provide controlled deposition on the substrate. The mixture includes liquid and solid materials to produce solutions, suspensions, dispersions, emulsions, colloidal mixtures, or other compositions. The liquid may be an organic solvent or water, as discussed later herein. The solid is any one or more of the materials used for the buffer layer 120, the EL layer 130, or the selective layer 140.

Several variations are used in nozzle coating processes to improve the yield and final performance of electronic devices. Coating gap of 200 to 800 μm, coating speed of 2 to 10 m / s. Solids content of 2-15%, viscosity of 0.5-10 cp, and surface tension of 20-100 dyne / cm for the mixture.

In further embodiments, the viscosity of the liquid mixture is 5 centipoises or less. In yet another embodiment, the liquid mixture comprises a liquid solvent and the liquid solvent may comprise two or more solvents. In another embodiment, at least one of the solvents is water.

Additional equipment may be present in or used with the nozzle assembly 502, including a vessel and a supply line fluidly coupled to the nozzle assembly 502 to receive any number of components to form a liquid phase mixture. Other equipment may include any one or more stepper motors, pumps, filters, control electronics, other electrical, mechanical or electro-mechanical assemblies or subassemblies, facility connections, or any combination thereof.

During the coating operation, the pressure in the nozzle assembly 502 may range from approximately 100 to 500 KPa. In one embodiment, the pressure can be kept constant and the flow is controlled by a mass flow controller. The flow rate of the liquid mixture from the nozzle assembly 502 can range from 50 to 600 microliters per minute. In other embodiments, high or low pressures, high or low flow rates, or any combination thereof may also be used. After reading the specification, those skilled in the art will be able to adjust or modify the coating operation to achieve pressures and flow rates for their particular application.

3. Liquid composition

The nozzle assembly 502 can be used to deposit various different materials, including liquid solutions. The following paragraphs include only some but not all of the materials that may be used. In one embodiment, one or more materials for the organic layer in the electronic device are formed using the nozzle assembly 502.

The nozzle assembly 502 is well suited for printing liquid compositions. The nozzle assembly 502 allows a wider range of operating parameters and liquid compositions to be used compared to conventional inkjet printers. In one embodiment, one or more parameters may affect the flow characteristics of the liquid composition. Viscosity is a parameter that can affect the flow characteristics. Viscosity can be influenced by the choice of the liquid medium, the solids content in the liquid medium, the temperature of the liquid composition, or potentially one or more other factors, or any combination thereof. Viscosity can be determined by temperature directly (the viscosity of the liquid medium increases with temperature or decreases with temperature increase) or indirectly (ie, with a low or high boiling point) by changing the rate of evaporation of the liquid medium in the liquid composition. Or change the temperature of the liquid composition, or a combination thereof). After reading this specification, those skilled in the art will understand that they have many different ways to allow for a significantly larger selection of liquid media, a larger range of solids concentrations of liquid compositions used, or combinations thereof.

The liquid mixture may be in the form of a solution, dispersion, emulsion, or suspension. In the following paragraphs, non-limiting examples of solid materials and liquid media are given. The solid material (s) may then be selected based on the electron or electron emission properties for the layer to be formed. The liquid medium may be selected based on the criteria described later herein.

When using the nozzle assembly 502, the liquid composition may have more than approximately 2.0 weight percent solids (s) without having to worry about clogging. In one embodiment, the solid (s) content is in the range of approximately 2.0 to 3.0 weight percent. Thus, the nozzle assembly 502 can use a liquid composition having a higher viscosity or lower boiling point compared to conventional inkjet printers. In addition, the nozzle assembly 502 may use a liquid composition having a low viscosity or a high boiling point compared to a conventional inkjet printer. In addition, the liquid medium in the liquid composition does not need to be degassed before printing. For example, conventional inkjet printers used to dispense conductive organic materials in aqueous solutions require degassing of the aqueous solutions. However, the nozzle assembly 502 allows for more processing margin, so degassing of the liquid medium is not required for proper operation of the nozzle assembly 502.

The organic layer printed using the nozzle assembly 502 may be an organic active layer (eg, a radiation emitting organic active layer or a radiation responsive organic active layer), a filter layer, a buffer layer, a charge injection layer, a charge transport layer, a charge blocking layer, or any thereof. It can include a combination of. The organic layer can be used as part of a resistor, transistor, capacitor, diode, or the like.

For radiation emitting organic active layers, suitable radiation emitting materials include one or more small molecule materials, one or more polymeric materials, or combinations thereof. Small molecule materials are described, for example, in US Pat. No. 4,356,429 ("Tang"); U.S. Patent 4,539,507 ("Van Slyke"); US Patent Application Publication No. 2002/0121638 ("Grushin"); Or any one or more of those described in US Pat. No. 6,459,199 (“Kido”). Alternatively, polymeric materials may include US Pat. No. 5,247,190 (“Friend”); U.S. Patent 5,408,109 ("Heeger"); Or any one or more of those described in US Pat. No. 5,317,169 ("Nakano"). Exemplary materials are semiconducting conjugated polymers. Examples of such polymers include poly (paraphenylenevinylene) (PPV), PPV copolymer, polyfluorene, polyphenylene, polyacetylene, polyalkylthiophene, poly (n-vinylcarbazole) (PVK), and the like. Include. In one specific embodiment, a radiation emitting active layer free of any guest material may emit blue light.

In the case of a radiation responsive organic active layer, suitable radiation responsive materials may comprise conjugated polymers or electroluminescent materials. Such materials include, for example, conjugated polymers or electric and photoluminescent materials. Specific examples include MEH-PPV complexes with poly (2-methoxy, 5- (2-ethyl-hexyloxy) -1,4-phenylene vinylene) ("MEH-PPV") or CN-PPV do.

For hole injection layers, hole transport layers, electron blocking layers, or any combination thereof, suitable materials include polyaniline ("PANI"), poly (3,4-ethylenedioxythiophene) ("PEDOT"), polypyrrole, organic charge. Delivery compounds such as tetrathiafulvalene tetracyanoquinodimethane (“TTF-TCQN”), hole transport materials as described in Kido, or any combination thereof.

For electron injection layers, electron transport layers, hole blocking layers, or any combination thereof, suitable materials include metal-chelate oxynoid compounds (eg, Alq ₃ or aluminum (III) bis (2-methyl-8-quinolina). To) 4-phenylphenolate ("BAlq")); Phenanthroline based compounds (eg, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline ("DDPA") or 9,10-diphenylanthracene ("DPA")) ; Azole compounds (eg, 2-tert-butylphenyl-5-biphenyl-1,3,4-oxadiazole (“PBD”) or 3- (4-biphenyl) -4-phenyl-5- ( 4-t-butylphenyl) -1,2,4-triazole ("TAZ"); electron transport material as described in Kido; diphenylanthracene derivatives; dynaphthylanthracene derivatives; 4,4-bis ( 2,2-diphenyl-ethen-1-yl) -biphenyl ("DPVBI");9,10-di-beta-naphthylanthracene; 9,10-di- (napentyl) anthracene; 9,10- Di- (2-naphthyl) anthracene ("ADN");4,4'-bis (carbazol-9-yl) biphenyl ("CBP"); 9,10-bis- [4- (2,2 -Diphenylvinyl) -phenyl] -anthracene ("BDPVPA"); anthracene, N-arylbenzimidazole (eg "TPBI"); 1,4-bis [2- (9-ethyl-3-car Vazoyl) vinylenyl] benzene; 4,4'-bis [2- (9-ethyl-3-carbazoyl) vinylenyl] -1,1'-biphenyl; 9,10-bis [2,2- (9,9-fluorenylene) vinylenyl] anthracene; 1,4-bis [2,2- (9,9-fluorenylene) vinylenyl] benzene; 4,4'-bis [2,2- ( 9,9-fluorenylene) Nilenyl] -1,1'-biphenyl; perylene, substituted perylene; tetra-tert-butylperylene ("TBPe"); bis (3,5-difluoro-2- (2-pyridyl) ) Phenyl- (2-carboxypyridyl) iridium III ("F (Ir) Pic"); pyrene, substituted pyrene; styrylamine; fluorinated phenylene; oxidazole; 1,8-naphthalimide; Polyquinoline, one or more carbon nanotubes in PPV, or any combination thereof.

In the case of electronic components such as resistors, transistors, capacitors, etc., the organic layer may comprise one or more thiophenes (e.g., polythiophene, poly (alkylthiophene), alkylthiophene, bis (diethienethiophene), alkylanthradithiate). Offen, etc.), polyacetylene, pentacene, phthalocyanine, or any combination thereof.

Examples of organic dyes are 4-dicyanethylenemethylene-2-methyl-6- (p-dimethylaminostyryl) -4H-pyran (DCM), coumarin, pyrene, perylene, rubrene, derivatives thereof, or any thereof It includes a combination of.

Examples of organometallic materials include functionalized polymers comprising one or more functional groups coordinated to at least one metal. Exemplary functional groups contemplated for use include carboxylic acids, carboxylic acid salts, sulfonic acid groups, sulfonic acid salts, groups with OH moieties, amines, imines, diimines, N-oxides, phosphines, phosphine oxides, β -Dicarbonyl groups, or any combination thereof. Exemplary metals contemplated for use include lanthanide metals (eg, Eu, Tb), Group 7 metals (eg, Re), Group 8 metals (eg, Ru, Os), Group 9 metals ( For example, Rh, Ir), Group 10 metals (eg Pd, Pt), Group 11 metals (eg Au), Group 12 metals (eg Zn), Group 13 metals (eg Al), or any combination thereof. Such organometallic materials include metal chelate oxynoid compounds such as tris (8-hydroxyquinolato) aluminum (Alq ₃ ); Ring metal iridium or platinum electroluminescent compounds such as phenylpyridine, phenylquinoline, or a complex of phenylpyrimidine ligands and iridium as disclosed in published PCT International Patent Application Publication No. WO 02/02714, for example published US patents Organometallic composites as disclosed in Application Publication No. 2001/0019782, European Patent Application Publication No. 1119,512, International Patent Publications WO 02/15645 and WO 02/31896, and European Patent Application Publication EP 1191614; Or any mixture thereof.

Examples of conjugated polymers include poly (phenylenevinylene), polyfluorene, poly (spirobifluorene), copolymers thereof, or any combination thereof.

The choice of liquid medium may also be an important factor in achieving one or more suitable characteristics of the liquid mixture. Factors considered when selecting a liquid medium include, for example, the viscosity of the resulting solution, emulsion, suspension or dispersion, the molecular weight of the polymeric material, the solids loading, the type of liquid medium, the boiling point of the liquid medium, the temperature of the underlying substrate, the guest material The thickness of the organic layer to accommodate, or any combination thereof.

In some embodiments, the liquid medium comprises at least one solvent. Exemplary organic solvents are halogenated solvents, colloid-forming polymeric acids, hydrocarbon solvents, aromatic hydrocarbon solvents, ether solvents, cyclic ether solvents, alcohol solvents, glycol solvents, ketone solvents, nitrile solvents, sulfoxide solvents, amide solvents, or Any combination.

Exemplary halogenated solvents include carbon tetrachloride, methylene chloride, chloroform, tetrachloroethylene, chlorobenzene, bis (2-chloroethyl) ether, chloromethyl ethyl ether, chloromethyl methyl ether, 2-chloroethyl ethyl ether, 2-chloroethyl Propyl ether, 2-chloroethyl methyl ether, or any combination thereof.

Exemplary colloid forming polymer acids include fluorinated sulfonic acids (eg, fluorinated alkylsulfonic acids such as perfluorinated ethylenesulfonic acid), or any combination thereof.

Exemplary hydrocarbon solvents include pentane, hexane, cyclohexane, heptane, octane, decahydronaphthalene, petroleum ether, ligroin, or any combination thereof.

Exemplary aromatic hydrocarbon solvents include benzene, naphthalene, toluene, xylene, ethyl benzene, cumene (iso-propyl benzene) mesitylene (trimethyl benzene), ethyl toluene, butyl benzene, cymene (iso-propyl toluene), diethylbenzene , Iso-butyl benzene, tetramethyl benzene, sec-butyl benzene, tert-butyl benzene, anisole, 4-methylanisole, 3,4-dimethylanisole, or any combination thereof.

Exemplary ether solvents are diethyl ether, ethyl propyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, methyl t-butyl ether, glyme, diglyme, benzyl methyl ether, isochroman, 2-phenyl Ethyl methyl ether, n-butyl ethyl ether, 1,2-diethoxyethane, sec-butyl ether, diisobutyl ether, ethyl n-propyl ether, ethyl isopropyl ether, n-hexyl methyl ether, n-butyl methyl Ether, methyl n-propyl ether, or any combination thereof.

Exemplary cyclic ether solvents are tetrahydrofuran, dioxane, tetrahydropyran, 4 methyl-1,3-dioxane, 4-phenyl-1,3-dioxane, 1,3-dioxolane, 2-methyl-1,3- Dioxolane, 1,4-dioxane, 1,3-dioxane, 2,5-dimethoxytetrahydrofuran, 2,5-dimethoxy-2,5-dihydrofuran, or any combination thereof .

Exemplary alcohol solvents include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol (ie iso-butanol), 2-methyl-2-propanol (ie tert-butanol), 1-pentanol, 2-pentanol, 3-pentanol, 2,2-dimethyl-1-propanol, 1-hexanol, cyclopentanol, 3-methyl-1-butanol, 3- Methyl-2-butanol, 2-methyl-1-butanol, 2,2-dimethyl-1-propanol, 3-hexanol, 2-hexanol, 4-methyl-2-pentanol, 2-methyl-1- Pentanol, 2-ethylbutanol, 2,4-dimethyl-3-pentanol, 3-heptanol, 4-heptanol, 2-heptanol, 1-heptanol, 2-ethyl-1-hexanol, 2 , 6-dimethyl-4-heptanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 4-methylcyclohexanol, or any combination thereof.

Alcohol ether solvents may also be used. Exemplary alcohol ether solvents include 1-methoxy-2-propanol, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-butanol, ethylene glycol monoisopropyl ether, 1-ethoxy-2- Propanol, 3-methoxy-1-butanol, ethylene glycol monoisobutyl ether, ethylene glycol mono-n-butyl ether, 3-methoxy-3-methylbutanol, ethylene glycol mono-tert-butyl ether, or any thereof Combinations.

Exemplary glycol solvents include ethylene glycol, propylene glycol, propylene glycol monomethyl ether (PGME), dipropylene glycol monomethyl ether (DPGME), or any combination thereof.

Exemplary ketone solvents are acetone, methylethyl ketone, methyl iso-butyl ketone, cyclohexanone, isopropyl methyl ketone, 2-pentanone, 3-pentanone, 3-hexanone, diisopropyl ketone, 2-hexanone , Cyclopentanone, 4-heptanone, iso-amyl methyl ketone, 3-heptanone, 2-heptanone, 4-methoxy-4-methyl-2-pentanone, 5-methyl-3-heptanone, 2 -Methylcyclohexanone, diisobutyl ketone, 5-methyl-2-octanone, 3-methylcyclohexanone, 2-cyclohexen-1-one, 4-methylcyclohexanone, cycloheptanone, 4-tert -Butylcyclohexanone, isophorone, benzyl acetone, or any combination thereof.

Exemplary nitrile solvents include acetonitrile, acrylonitrile, trichloroacetonitrile, propionitrile, pivalonitrile, isobutyronitrile, n-butyronitrile, methoxyacetonitrile, 2-methylbutyronitrile, isovalle Ronitrile, N-valeronitrile, n-capronitrile, 3-methoxypropionitrile, 3-ethoxypropionitrile, 3,3'-oxydipropionitrile, n-heptanitrile, glycolonitrile, Benzonitrile, ethylene cyanohydrin, succinonitrile, acetone cyanohydrin, 3-n-butoxypropionitrile, or any combination thereof.

Exemplary sulfoxide solvents include dimethyl sulfoxide, di-n-butyl sulfoxide, tetramethylene sulfoxide, methyl phenyl sulfoxide, or any combination thereof.

Exemplary amide solvents are dimethyl formamide, dimethyl acetamide, acylamide, 2-acetamidoethanol, N, N-dimethyl-m-toluamide, trifluoroacetamide, N, N-dimethyl Acetamide, N, N-diethyldodecanamide, epsilon-caprolactam, N, N-diethylacetamide, N-tert-butylformamide, formamide, pivalamide, N-butyamide, N, N -Dimethylacetoacetamide, N-methyl formamide, N, N-diethylformamide, N-formylethylamine, acetamide, N, N-diisopropylformamide, 1-formylpiperidine, N -Methylformanilide, or any combination thereof.

Crown ethers contemplated include any one or more crown ethers that can act to help reduce the chloride content of the epoxy compound starting material as part of the combination treated according to the invention. Exemplary crown ethers include benzo-15-crown-5; Benzo-18-crown-6; 12-crown-4; 15-crown-5; 18-crown-6; Cyclohexano-15-crown-5; 4 ', 4 "(5")-ditert-butyldibenzo-18-crown-6; 4 ', 4 "(5")-ditert-butyldicyclohexano-18-crown-6; Dicyclohexano-18-crown-6; Dicyclohexano-24-crown-8; 4'-aminobenzo-15-crown-5; 4'-aminobenzo-18-crown-6; 2- (aminomethyl) -15-crown-5; 2- (aminomethyl) -18-crown-6; 4'-amino-5'-nitrobenzo-15-crown-5; 1-aza-12-crown-4; 1-aza-15-crown-5; 1-aza-18-crown-6; Benzo-12-crown-4; Benzo-15-crown-5; Benzo-18-crown-6; Bis ((benzo-15-crown-5) -15-ylmethyl) pimelate; 4-bromobenzo-18-crown-6; (+)-(18-crown-6) -2,3,11,12-tetra-carboxylic acid; Dibenzo-18-crown-6; Dibenzo-24-crown-8; Dibenzo-30-crown-10; ar-ar'-di-tert-butyldibenzo-18-crown-6; 4'-formylbenzo-15-crown-5; 2- (hydroxymethyl) -12-crown-4; 2- (hydroxymethyl) -15-crown-5; 2- (hydroxymethyl) -18-crown-6; 4'-nitrobenzo-15-crown-5; Poly-[(dibenzo-18-crown-6) -co-formaldehyde]; 1,1-dimethylsila-11-crown-4; 1,1-dimethylsila-14-crown-5; 1,1-dimethylsila-17-crown-5; Cyclam; 1,4,10,13-tetrathia-7,16-diazacyclooctadecane; Porphine; Or any combination thereof.

In another embodiment, the liquid medium comprises water. The conductive polymer complexed with the water insoluble colloid forming polymer acid can be deposited on the substrate and used as the electron transport layer.

Many different classes of liquid media (eg, halogenated solvents, hydrocarbon solvents, aromatic hydrocarbon solvents, water, etc.) are described above. Mixtures of more than one of the liquid media from different classes may also be used.

The liquid mixture may also include inert materials such as binder materials, filler materials, or combinations thereof. In the context of a liquid mixture, the inert material does not significantly affect the electron, radiation emission, or radiation response properties of the layer formed by or receiving at least a portion of the liquid mixture.

It is to be understood that certain features of the invention described above in connection with separate embodiments can also be provided in a single embodiment in combination. Conversely, various features of the invention, which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any subcombination. In addition, reference to values stated in ranges includes each and every value within that range.

Claims (15)

A main body including a recessed region at the distal end of the main body; And
_A disk having an opening of a centrally located opening diameter d _A and an opening thickness t _A , the disk having a diameter d _D , the disk having a first side and a second side, wherein the first side is a retract of the body. And a second face having an opening located in a recessed area having a diameter d ₂ , wherein d _D is greater than d ₂ . The nozzle assembly of claim 1, wherein d _A is 0.05 mm or less. The nozzle assembly of claim 2, wherein d _A is 0.01 mm or less and t _A is 50 μm or less. (none) The nozzle assembly of claim 1, wherein d _A varies between the first side and the second side. 6. The nozzle assembly of claim 5, wherein d _A is larger at the first face than at the second face. 7. The nozzle assembly of claim 6, wherein radius r _A defines a surface of the opening between the first and second faces. 8. The nozzle assembly of claim 7, wherein radius r _A is less than 0.05 mm. 8. The nozzle assembly of claim 7, wherein the radius r _A is less than 0.04 mm. 8. The nozzle assembly of claim 7, wherein radius r _A is less than 0.03 mm. Providing a body comprising a recessed region at the distal end of the body;
Disc having a centrally located opening diameter d _A -the disk has a diameter d _D , the disk has a first side and a second side, the second side is located in a shallow recess area with a diameter d ₂ Having an opening, and d _D is greater than d ₂ ;
Attaching the first side of the disk to the recessed area of the body to form a nozzle assembly;
Providing a mixture comprising a liquid and a solid; And
Flowing the mixture through the nozzle assembly to produce a layer. The method of claim 11, wherein the liquid is an organic solvent. The method of claim 11, wherein the liquid is water. The method of claim 11, wherein the mixture is a solution having a solids content of less than 10%. The device of claim 11, wherein the mixture is a suspension having a solids content of less than 10%.

Images