KR20240002867A - Apparatus and method to deliver organic material via organic vapor jet printing (ovjp) - Google Patents

Abstract

Embodiments of the disclosed subject matter provide apparatus having a device having an array of micronozzles disposed on a micromachined fluid die. The device may include a first gas distribution plate and a second opposing plate, wherein the micromachined fluid die is disposed between the first gas distribution plate and the second opposing plate, and the first gas distribution plate is hermetically sealed to form a micronozzle. Irreversibly coupled to the array, the first gas distribution plate includes a plurality of sealed flow paths. The manifold can be reversibly coupled to the first gas distribution plate, and the micromachined fluid die and the first gas distribution plate and the second opposing plate are disposed between the manifolds. The thermally conductive plate may have one or more windows that provide a clearance fit for the device over a range of motion relative to the thermally conductive plate.

Description

Apparatus and method for delivering organic materials via organic vapor jet printing (OVJP) {APPARATUS AND METHOD TO DELIVER ORGANIC MATERIAL VIA ORGANIC VAPOR JET PRINTING (OVJP)}

Cross-reference to related applications

This application is a continuation-in-part of U.S. Patent Application No. 17/224,240, filed on November 11, 2021, which claims priority to U.S. Patent Application No. 63,022,631, filed on May 11, 2020, each of which The entire contents of are incorporated herein by reference.

Field

The present invention provides high temperature, low profile, bondable gas distribution plates and counter plates for coupling a jet head to a larger gas delivery system for delivering organic materials via organic vapor jet printing (OVJP), and devices comprising the same, and It's about technique.

Optoelectronic devices using organic materials are becoming increasingly important for several reasons. Because many of the materials used to fabricate such devices are relatively inexpensive, organic optoelectronic devices have the potential for a cost advantage over inorganic devices. Additionally, the unique properties of organic materials, such as their flexibility, may make them well suited for certain applications, such as fabrication on flexible substrates. Examples of organic optoelectronic devices include organic light-emitting diodes/devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. In the case of OLEDs, organic materials can have performance advantages over conventional materials. For example, the wavelength at which an organic light-emitting layer emits light can generally be easily adjusted with an appropriate dopant.

OLEDs use organic thin films that emit light when a voltage is applied across the device. OLED is an increasingly important technology for applications such as flat panel displays, lighting and backlighting. Various OLED materials and configurations are described in US Pat. Nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety.

One application for phosphorescent emitting molecules is full color displays. Industry standards for such displays require pixels to be tuned to emit specific colors, referred to as “saturated” colors. In particular, these criteria require saturated red, green, and blue pixels. Alternatively, OLEDs can be designed to emit white light. In a typical liquid crystal display, emission from a white backlight is filtered using an absorption filter to produce red, green, and blue light emissions. The same technique can be used for OLED. White OLEDs can be single EML devices or stacked structures. Color can be measured using CIE coordinates, which are well known in the art.

As used herein, the term “organic” includes small molecule organic materials as well as polymeric materials that can be used to fabricate organic optoelectronic devices. “Small molecule” refers to any organic material that is not a polymer, and “small molecules” can actually be quite large. Small molecules may contain repeat units in some circumstances. For example, using a long chain alkyl group as a substituent does not exclude the molecule from the “small molecule” category. Small molecules can also be incorporated into the polymer, for example as pendant groups on or as part of the polymer backbone. Small molecules can also act as the core moiety of dendrimers, which consist of a series of chemical shells built on the core moiety. The core moiety of the dendrimer may be a fluorescent or phosphorescent small molecule emitter. Dendrimers can be “small molecules,” and all dendrimers currently used in the OLED field are believed to be small molecules.

As used herein, “top” means furthest from the substrate and “bottom” means closest to the substrate. When a first layer is described as being “disposed on top” of a second layer, the first layer is disposed at a distance from the substrate. There may be other layers between the first and second layers unless it is specified that the first layer is “in contact” with the second layer. For example, the cathode may be described as being “disposed on top” of the anode, even though various organic layers exist between the cathode and the anode.

As used herein, “solution processable” means capable of being dissolved, dispersed or transported in and/or deposited from a liquid medium in the form of a solution or suspension.

If the ligand is believed to contribute directly to the photoactive properties of the luminescent material, the ligand may be referred to as “photoactive.” A ligand may be referred to as “auxiliary” if the ligand is not believed to contribute to the photoactive properties of the luminescent material, although the accessory ligand may alter the properties of the photoactive ligand.

As used herein, and as generally understood by those skilled in the art, a first “highest occupied molecular orbital” (HOMO) or “lowest unoccupied molecular orbital” when the first energy level is closer to the vacuum energy level. The (LUMO) energy level is “larger than” or “higher than” the second HOMO or LUMO energy level. Since the ionization potential (IP) is measured as a negative energy relative to the vacuum level, higher HOMO energy levels correspond to IPs with smaller absolute values (less negative IPs). Likewise, higher LUMO energy levels correspond to electron affinities (EA) with smaller absolute values (less negative EA). In a conventional energy level diagram with the vacuum level at the top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. “Higher” HOMO or LUMO energy levels appear closer to the top of the diagram than “lower” HOMO or LUMO energy levels.

As used herein, and as generally understood by those skilled in the art, a first work function is “greater than” or “higher” than a second work function if the absolute value of the first work function is greater. Work functions are usually measured as negative numbers relative to the vacuum level, so a “higher” work function is more negative. In a typical energy level diagram with the vacuum level at the top, the “higher” work function is illustrated as being farther down from the vacuum level. Therefore, the definition of HOMO and LUMO energy levels follows a different convention than the work function.

Layers, materials, regions, and devices may be described herein in terms of the color of light they emit. Generally, as used herein, a light-emitting region described as producing a particular color of light may include one or more light-emitting layers disposed on top of each other in a stack.

As used herein, a “red” layer, material, region, or device refers to one that emits light in the range of about 580 to 700 nm or has the highest peak of the emission spectrum in this region. Likewise, a “green” layer, material, region, or device refers to one that emits or has an emission spectrum with a peak wavelength in the range of about 500 to 600 nm; A “blue” layer, material, or device refers to one that emits or has an emission spectrum with a peak wavelength in the range of about 400 to 500 nm; A “yellow” layer, material, region, or device refers to one that has an emission spectrum with a peak wavelength in the range of about 540 to 600 nm. In some arrangements, separate regions, layers, materials, regions, or devices may provide separate “deep blue” and “light blue” light. As used herein, in an arrangement providing distinct “light blue” and “dark blue” colors, the “dark blue” component is defined as having a peak emission wavelength that is at least about 4 nm less than the peak emission wavelength of the “light blue” component. refers to Typically, the “light blue” component has a peak emission wavelength in the range of about 465 to 500 nm, and the “dark blue” component has a peak emission wavelength in the range of about 400 to 470 nm, although these ranges may vary depending on some configurations. there is. Likewise, a color change layer refers to a layer that converts or changes light of a different color into light with a wavelength specified for that color. For example, a “red” color filter refers to a filter that produces light with a wavelength in the range of about 580 to 700 nm. Generally, there are two classes of color changing layers: color filters, which alter the spectrum by removing unwanted wavelengths of light, and color changing layers, which convert high energy photons into low energy photons. A “colored” component refers to a component that, when activated or used, produces or emits light having a specific color as previously described. For example, “a first light-emitting region of a first color” and “a second light-emitting region of a second color different from the first color” mean that, when activated within a device, they emit two different colors as described above. Describe the luminous area of the dog.

As used herein, light-emitting materials, layers, and regions refer to each other and different structures based on the light initially produced by the materials, layers, or regions, as opposed to the light ultimately emitted by the same or different structures. can be distinguished from Typically, initial light generation is the result of an energy level change that causes the emission of a photon. For example, an organic light-emitting material may initially produce blue light, which is converted to red or green light by color filters, quantum dots, or other structures, such that a complete light-emitting stack or subpixel can emit red or green light. In this case the initial emitting material or layer may be referred to as the “blue” component, while the subpixels are the “red” or “green” component.

In some cases, it may be desirable to describe the colors of components such as emissive regions, subpixels, color changing layers, etc. in 1931 CIE coordinates. For example, a yellow emitting material may have multiple peak emission wavelengths, one at or near the edge of the "green" region and one at or near the edge of the "red" region, as previously described. It is in Accordingly, as used herein, each color term also corresponds to a form of the 1931 CIE coordinate color space. The shape of the 1931 CIE color space is constructed along a trajectory between two color points and an arbitrary additional interior point. For example, the internal shape parameters for red, green, blue, and yellow can be defined as shown below.

Further details and the preceding definition of OLED can be found in U.S. Patent No. 7,279,704, which is incorporated herein by reference in its entirety.

According to an embodiment, an organic light emitting diode/device (OLED) is also provided. An OLED may include an anode, a cathode, and an organic layer disposed between the anode and the cathode. According to embodiments, the organic light emitting device is included in one or more devices selected from consumer products, electronic component modules, and/or lighting panels.

According to embodiments, an apparatus may include a device having an array of micronozzles disposed on a micromachined fluid die. The device may include a first gas distribution plate and a second opposing plate, where a micromachined fluid die is disposed between the first gas distribution plate and the second opposing plate. The first gas distribution plate may be single crystal silicon, columnar silicon, and/or polycrystalline silicon, and may be irreversibly coupled to the micronozzle array in a hermetic seal, wherein the first gas distribution plate has a plurality of Contains a sealed flow path. The manifold can be reversibly coupled to the first gas distribution plate, wherein the micromachined fluid die and the first gas distribution plate and the second opposing plate can be disposed between the manifold. The device may include a thermally conductive plate in thermal contact with the active cooling source, wherein the thermally conductive plate has one or more windows passing through its entire thickness, through which the first gas distribution plate and the second opposing plate of the device are connected. , a portion of the micromachined fluid die, and the micronozzle array protrude so that the shortened cross-section of the window provides a clearance fit for the device over a range of motion relative to the thermally conductive plate. The device can include one or more thermal evaporation sources in fluid communication with a first gas distribution plate, where the manifold can be in fluid communication with the micronozzle array through a plurality of sealed flow paths in the first gas distribution plate.

The device's micronozzle array can be placed on the edge of a micromachined fluid die. A micronozzle array can be placed on one side of a micromachined fluid die.

The micromachined fluid die of the device may include one or more of silicon, quartz, and/or metal.

The second opposing plate of the device may be a second gas distribution plate, where the manifold is coupled to the first gas distribution plate in an airtight seal.

One or more of the plurality of sealed flow paths of the device may be configured to convey a mixture of organic vapor and an inert carrier gas.

The first gas distribution plate of the device may have a segment adjacent to the micronozzle array through which all flow paths pass, the aspect ratio of the depth of the segment being less than or equal to 10% of the width or height of the segment. As used generally, depth may be in a direction perpendicular to one side of the micronozzle array.

The thermally conductive plate of the device can protect the manifold and the object on which the micronozzle array acts from heat generated by the plurality of evaporation sources.

The seal of the device may be a gasket or joint. The micronozzle array of the device is irreversibly bonded to the first gas distribution plate and the second opposing plate using glass frit, ceramic adhesive, bonding, and/or solder or soldering compound with a reflow temperature of greater than 350°C or greater than 500°C. They can be combined to form a seal. The first gas distribution plate of the device may comprise a material having an average coefficient of thermal expansion of less than 4×10 ⁻⁶ K ⁻¹ between room temperature and the reflow temperature of the solder.

The first gas distribution plate and second opposing plate of the device may be fabricated from one or more of monocrystalline silicon, columnar silicon, and polycrystalline silicon.

The device may include a heater thermally coupled to the micronozzle array, where the heater is configured to heat the micronozzle array. The micronozzle array can direct a convective jet of gas to the surface of the substrate.

The device's micronozzle array and substrate can be configured to move relative to each other.

The device's micromachined fluid die and micronozzle array may be comprised of silicon, and the micromachined fluid die may be coupled to the first gas distribution plate.

The thermally conductive plate may have a window lined with an insulating material. The micronozzle array and the first gas distribution plate may include at least a portion of the device protruding through a window of the thermally conductive plate such that a normal plane of the device is parallel to a depth dimension of the first gas distribution plate.

The first gas distribution plate and second opposing plate of the device may include a resistive heater. The first gas distribution plate and the second opposing plate of the device may include one or more thermal insulating materials selected from monocrystalline silicon, columnar silicon, and polycrystalline silicon. One or more of the first gas distribution plate and the second opposing plate of the device may be configured to have gas supplied therethrough.

The device may include a deformable metal gasket, and the first gas distribution plate is sealed to the manifold using the deformable metal gasket. The deformable metal gasket can be reversibly sealed to the device. The deformable metal gasket may be comprised of a material that is integrated with the manifold.

The first gas distribution plate of the device may be comprised of a plurality of etched or milled layers of material bonded together using a formation temperature greater than the reflow temperature of the material used to join the micronozzle array to the first gas distribution plate. You can.

According to embodiments, the apparatus may include a device having a micronozzle array. The device may include a first gas distribution plate that is monocrystalline silicon, columnar silicon, and/or polycrystalline silicon and is irreversibly coupled to the micronozzle array in a hermetic seal, wherein the first gas distribution plate is a plurality of sealed gas distribution plates. Includes euros. One or more thermal evaporation sources of the device may be in fluid communication with the first gas distribution plate. The device can include a manifold, and the first gas distribution plate is reversibly coupled to the manifold. The manifold may be in fluid communication with the micronozzle array through a plurality of sealed flow paths in the first gas distribution plate. One or more of these flow paths may carry a mixture of organic vapor and an inert carrier gas. The first gas distribution plate may have a segment adjacent the micronozzle array through which all flow paths pass, the depth of the segment being no wider than the depth of the micronozzle array at the point of attachment, and the depth being in a direction perpendicular to the plane of the micronozzle array. You can. The device may include a thermally conductive plate, wherein the first gas distribution plate and the thermally conductive plate are in thermal contact with an active cooling source. The thermally conductive plate may have one or more windows passing through its entire thickness, through which a device protrudes so that a shortened cross-section of the window provides a clearance fit for at least the micronozzle array of the device over the range of motion of the device relative to the thermally conductive plate. whereby the thermally conductive plate protects the manifold and the object on which the micronozzle array acts from heat generated by one or more thermal evaporation sources.

The seal of the device may be a gasket or joint. The micronozzle array of the device is irreversibly bonded and/or attached to the device using, for example, a glass frit, ceramic adhesive, bonding, and/or a solder or soldering compound having a reflow temperature greater than 350° C., or greater than 500° C. It can be. The first gas distribution plate may comprise a material having an average coefficient of thermal expansion of less than 4×10 ^-6 K ^-1 between room temperature and the reflow temperature of the solder. The device may include one or more of molybdenum, tungsten, Khovar, aluminum nitride, silicon nitride, single crystalline silicon, columnar silicon, and/or polycrystalline silicon.

The device may include a heater thermally coupled to the micronozzle array, where the heater is configured to heat the micronozzle array.

The device's micronozzle array can direct a convective jet of gas toward the surface of the substrate. The micronozzle array and the substrate are configured to move relative to each other. The micronozzle array may be made of silicon.

The thermally conductive plate of the device may include a window lined with an insulating material.

The device may include a deformable metal gasket, and the first gas distribution plate is sealed to the manifold using the deformable metal gasket. The deformable metal gasket can be reversibly sealed to the device. In some embodiments, the deformable metal gasket is comprised of a material that is integrated with the manifold.

Figure 1 shows an organic light emitting device.
Figure 2 shows an inverted structure organic light emitting device without a separate electron transport layer.
Figure 3 shows an OVJP jet head with a micronozzle array positioned on the edge of a micromachined die.
4A shows an OVJP jet head with a micronozzle array positioned on the edge of a micromachined die comprising a gas distribution plate and an opposing plate according to an embodiment of the disclosed subject matter.
4B shows an OVJP jet head with a micronozzle array positioned on the edge of a micromachined die including a gas distribution plate with both supply and exhaust piped from the same side of the assembly according to an embodiment of the disclosed subject matter.
5A shows an OVJP jet head with a micronozzle array positioned on the edge of a micromachined die comprising an opposing plate and a gas distribution plate with additional insulation surrounding a window of the cooling plate according to an embodiment of the disclosed subject matter. .
5B shows a micronozzle array positioned on the edge of a micromachined die comprising a gas distribution plate and opposing plates with additional thermal insulation forming a sheath around the gas distribution plate and opposing plates according to an embodiment of the disclosed subject matter. An OVJP jet head with .
6 illustrates the thermal load applied to a substrate by an OVJP jet head according to an embodiment of the disclosed subject matter.
Figure 7 shows an alternative embodiment of an OVJP jet head, where the micronozzle array is located on the face of the micromachined die.
8 shows an alternative embodiment of an OVJP jet head, in accordance with an embodiment of the disclosed subject matter, wherein the micronozzle array is located on the face of a micromachined die comprising a gas distribution plate and an opposing plate.

Typically, OLEDs include one or more organic layers disposed between and electrically connected to an anode and a cathode. When current is applied, the anode injects holes into the organic layer(s) and the cathode injects electrons. The injected holes and electrons each move toward oppositely charged electrodes. When an electron and a hole become localized on the same molecule, an “exciton” is created, which is a localized electron-hole pair with an excited energy state. When excitons relax through a photoemission mechanism, light is emitted. In some cases, excitons may localize to excimers or exciplexes. Non-radiative mechanisms, such as thermal relaxation, may also occur, but are generally considered undesirable.

Early OLEDs used luminescent molecules that emit light (“fluorescence”) from a singlet state, as disclosed, for example, in U.S. Pat. No. 4,769,292, which is incorporated by reference in its entirety. Fluorescence emission typically occurs in a time frame of less than 10 nanoseconds.

More recently, OLEDs have been presented with luminescent materials that emit light from the triplet state (“phosphorescence”). Baldo et al., “Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices,” Nature, vol. 395, 151-154, 1998; (“Baldo-I”)] and Baldo et al., “Very high-efficiency green organic light-emitting devices based on electrophosphorescence,” Appl. Phys. Lett., vol. 75, no. 3, 4-6 (1999) (“Baldo-II”)] is incorporated by reference in its entirety. Phosphorescence is described more specifically in U.S. Patent No. 7,279,704 at columns 5-6, which is incorporated by reference.

1 shows an organic light emitting device 100. The drawings are not necessarily drawn to scale. The device 100 includes a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, a light emitting layer 135, a hole blocking layer 140, and an electron transport layer ( 145), an electron injection layer 150, a protective layer 155, a cathode 160, and a barrier layer 170. The cathode 160 is a compound cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 may be fabricated by depositing the layers in the order described. The properties and functions of these various layers, as well as example materials, are described in more detail in U.S. Pat. No. 7,279,704 at columns 6-10, which is incorporated by reference.

More examples for each of these layers are also available. For example, a flexible, transparent substrate-anode combination is disclosed in U.S. Pat. No. 5,844,363, which is incorporated by reference in its entirety. One example of a p-doped hole transport layer is m-MTDATA doped with F ₄ -TCNQ at a molar ratio of 50:1, as disclosed in US Patent Application Publication No. 2003/0230980, which describes The full text is incorporated by reference. Examples of luminescent and host materials are disclosed in U.S. Pat. No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a 1:1 molar ratio, as disclosed in US Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. U.S. Patent Nos. 5,703,436 and 5,707,745, incorporated by reference in their entirety, disclose examples of cathodes, including compound cathodes with thin layers of metals, such as Mg:Ag, with a laminated transparent, electrically conductive sputter-deposited ITO layer. It is done. The theory and use of the barrier layer is described in more detail in U.S. Patent No. 6,097,147 and U.S. Patent Application Publication No. 2003/0230980, which are incorporated by reference in their entirety. An example of an injection layer is provided in US Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of the protective layer can be found in US Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety.

Figure 2 shows an inverted structure OLED 200. The device includes a substrate 210, a cathode 215, a light emitting layer 220, a hole transport layer 225, and an anode 230. Device 200 can be fabricated by depositing the layers in the order described. Since the most common OLED configuration is with the cathode disposed above the anode, and device 200 has cathode 215 disposed below the anode 230, device 200 may be referred to as an “inverted” OLED. You can. Materials similar to those described with respect to device 100 may be used in that layer of device 200. Figure 2 provides an example of how some layers may be omitted from the structure of device 100.

The simple stacked structures shown in Figures 1 and 2 are provided as non-limiting examples, and it is understood that embodiments of the invention may be used in connection with a variety of other structures. The specific materials and structures described are illustrative in nature; other materials and structures may be used. Functional OLEDs can be achieved by combining the various layers described in different ways, or layers can be omitted entirely based on design, performance and cost factors. Other layers not specifically described may also be included. Materials other than those specifically described may be used. Although many examples provided herein describe various layers as comprising a single material, it is understood that combinations of materials may be used, such as mixtures of hosts and dopants, or more generally mixtures. Additionally, the layer may have various sublayers. The names given for the various layers herein are not intended to be strictly limiting. For example, in device 200, hole transport layer 225 transports holes and injects holes into emissive layer 220, and may be described as a hole transport layer or a hole injection layer. In one embodiment, an OLED can be described as having an “organic layer” disposed between the cathode and anode. This organic layer may comprise a single layer, or may further comprise a plurality of layers of different organic materials, for example as described in connection with Figures 1 and 2.

OLEDs (PLEDs) composed of structures and materials not specifically described, such as polymer materials disclosed in U.S. Pat. No. 5,247,190 (Friend et al.), which is incorporated by reference in its entirety, may also be used. As a further example, OLEDs with a single organic layer can be used. OLEDs can be laminated, for example, as described in U.S. Pat. No. 5,707,745 to Forrest et al., which is incorporated herein by reference in its entirety. OLED structures can deviate from the simple stacked structures shown in FIGS. 1 and 2. For example, the substrate may have an out-coupling (mesa) structure described in U.S. Patent No. 6,091,195 (Forrest et al.) and/or a pit structure described in U.S. Patent No. 5,834,893 (Bulovic et al.). may include an angled reflective surface to improve out-coupling, and these patent documents are incorporated herein by reference in their entirety.

In some embodiments disclosed herein, light-emitting layers or materials, such as light-emitting layer 135 and light-emitting layer 220 shown in Figures 1-2, may each include quantum dots. A “light-emitting layer” or “light-emitting material” disclosed herein may include an organic light-emitting material and/or a light-emitting material comprising quantum dots or equivalent structures, unless otherwise explicitly or context indicates, according to the understanding of those skilled in the art. This light-emitting layer may include only a separate light-emitting material or quantum dot material that converts light emitted by another emitter, or may also include a separate light-emitting material or other emitter, or may emit light directly from the application of a current. You can. Likewise, color changing layers, color filters, up-conversion or down-conversion layers or structures may include materials containing quantum dots, but such layers may not be considered “emissive layers” as disclosed herein. Typically, the "emissive layer" or material is the one that emits the initial light, although this can be altered by other layers within the device, such as color filters or other color changing layers that do not themselves emit the initial light. Based on the light, it is possible to re-emit altered light of different spectral contents.

Unless explicitly stated to the contrary, any layer of the various embodiments may be deposited by any suitable method. For the organic layer, preferred methods include thermal evaporation as described in U.S. Pat. Nos. 6,013,982 and 6,087,196 (which are incorporated by reference in their entirety), ink-jet, U.S. Pat. No. 6,337,102 (Forrest et al.) Organic Vapor Deposition (OVPD), as described in U.S. Patent No. 7,431,968, which is incorporated by reference in its entirety, and Organic Vapor Jet Printing (OVJP), which is incorporated by reference in its entirety. Deposition by . Other suitable deposition methods include spin coating and other solution-based processes. The solution-based process is preferably carried out in nitrogen or an inert atmosphere. For other layers, preferred methods include thermal evaporation. Preferred pattern formation methods include deposition through a mask, cold welding as described in U.S. Pat. Includes pattern formation. Other methods may also be used. The material to be deposited can be modified to be compatible with a particular deposition method. For example, substituents such as alkyl groups and aryl groups, branched or unbranched, preferably containing three or more carbons, can be used in small molecules to improve their solution processing ability. Substituents having 20 or more carbons can be used, and the preferred range is 3 to 20 carbons. Because asymmetric materials may have a lower tendency to recrystallize, materials with an asymmetric structure may have better solution processability than materials with a symmetric structure. Dendrimer substituents can be used to improve the solution processing ability of small molecules.

Devices fabricated according to embodiments of the present invention may optionally further include a barrier layer. One purpose of the barrier layer is to protect the electrode and organic layer from damage due to exposure to harmful species in environments containing moisture, vapors and/or gases, etc. The barrier layer may be deposited on any other part of the device, including the edge, or on, under, or next to the electrode or substrate. The barrier layer may include a single layer or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques and may include compositions having a single phase as well as compositions having multiple phases. Any suitable material or combination of materials can be used in the barrier layer. The barrier layer may include inorganic or organic compounds or both. Preferred barrier layers include mixtures of polymeric and non-polymeric materials described in U.S. Pat. No. 7,968,146 and PCT patent applications PCT/US2007/023098 and PCT/US2009/042829, which are incorporated herein by reference in their entirety. . To be considered a “mixture,” the polymeric and non-polymeric materials described above, including the barrier layer, must be deposited simultaneously and/or under the same reaction conditions. The weight ratio of polymeric to non-polymeric materials may range from 95:5 to 5:95. Polymeric and non-polymeric materials can be produced from the same precursor material. In one example, the mixture of polymeric and non-polymeric materials consists substantially of polymeric silicon and inorganic silicon.

In some embodiments, at least one of the anode, cathode, or new layers disposed over the organic emissive layer functions as a reinforcement layer. The enhancement layer includes a plasmonic material that non-radiatively couples to the emitter material and exhibits a surface plasmon resonance that transfers excited state energy from the emitter material to a non-radiative mode of surface plasmon polaritons. The enhancement layer is provided within a critical distance from the organic emitting layer, wherein the emitter material has a total non-radiative decay rate constant and a total radioactive decay rate constant due to the presence of the enhancement layer, and the critical distance is such that the total non-radioactive decay rate constant is the total radioactive decay rate. It is the same place as the constant. In some embodiments, the OLED further includes an outcoupling layer. In some embodiments, the outcoupling layer is disposed over the reinforcement layer on the opposite side of the organic emissive layer. In some embodiments, the outcoupling layer is disposed on the opposite side of the emissive layer from the enhancement layer but still outcouples energy from the surface plasmon mode of the enhancement layer. The outcoupling layer scatters energy from the surface plasmon polaritons. In some embodiments this energy is scattered into free space as photons. In other embodiments, energy is scattered from the surface plasmon mode to other modes of the device, such as, but not limited to, organic guided modes, substrate modes, or other guided modes. If energy is scattered into the non-free space modes of the OLED, another outcoupling scheme can be incorporated to extract that energy into free space. In some embodiments, one or more intervening layers may be disposed between the reinforcement layer and the outcoupling layer. Examples of intervening layer(s) may be dielectric materials, including organic, inorganic, perovskite, oxides, and may include stacks and/or mixtures of these materials.

The reinforcement layer modifies the effective properties of the medium in which the emitter material resides, leading to any or all of the following: lower emission rate, change in emission line shape, change in emission intensity with angle, or change in stability of the emitter material. , changes in efficiency of OLED, and reduced efficiency roll-off of OLED devices. Placing a reinforcement layer on the cathode side, anode side, or both creates an OLED device that utilizes any of the previously mentioned effects. In addition to the specific functional layers described in the various OLED examples mentioned herein and shown in the figures, OLEDs according to the present disclosure may include any other functional layers commonly provided in OLEDs.

The enhancement layer may be composed of plasmonic materials, optically active metamaterials, or hyperbolic metamaterials. The plasmonic material used herein is a material whose real part of the dielectric constant intersects 0 in the visible or ultraviolet region of the electromagnetic spectrum. In some embodiments, the plasmonic material includes at least one metal. In this embodiment the metal may be Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, Ca, or alloys of these materials. or mixtures, and stacks of these materials. In general, a metamaterial is a medium composed of different materials, in which the entire medium acts differently than the sum of its material parts. In particular, the present applicant defines an optically active metamaterial as a material that has both negative dielectric constant and negative transmittance. Meanwhile, hyperbolic metamaterials are anisotropic media whose permittivity or transmittance have different signs for different spatial directions. Optically active metamaterials and hyperbolic metamaterials are strictly distinct from many other photonic structures, such as Distributed Bragg Reflectors (“DBRs”), in that the medium must appear uniform in the direction of propagation across the wavelength length scale of light. do. Using terms understandable to those skilled in the art: The dielectric constant of the metamaterial in the direction of propagation can be described by the effective medium approximation. Plasmonic materials and metamaterials provide a way to control the propagation of light that can improve OLED performance in a variety of ways.

In some embodiments, the reinforcement layer is provided as a planar layer. In other embodiments, the reinforcement layer has wavelength-sized features that are arranged periodically, quasi-periodically, or randomly, or sub-wavelength-sized features that are arranged periodically, quasi-periodically, or randomly. In some embodiments, wavelength-sized features and sub-wavelength-sized features have sharp edges.

In some embodiments, the outcoupling layer has wavelength-sized features that are arranged periodically, quasi-periodically, or randomly, or sub-wavelength-sized features that are arranged periodically, quasi-periodically, or randomly. In some embodiments, the outcoupling layer may be comprised of a plurality of nanoparticles and in other embodiments the outcoupling layer may be comprised of a plurality of nanoparticles disposed over the material. In these embodiments, outcoupling includes changing the size of the plurality of nanoparticles, changing the shape of the plurality of nanoparticles, changing the material of the plurality of nanoparticles, adjusting the thickness of the material, It may be adjustable by at least one of changing the refractive index of the material or additional layer disposed on the plurality of nanoparticles, changing the thickness of the reinforcing layer, and/or changing the material of the reinforcing layer. The plurality of nanoparticles of the device may be a metal, a dielectric material, a semiconductor material, an alloy of a metal, a mixture of dielectric materials, a stack or layer of one or more materials, and/or a core of one material, coated with a shell of a different type of material. It may be formed by at least one of the cores. In some embodiments, the outcoupling layer is a metal such as Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, It consists of at least one metal nanoparticle selected from the group consisting of Ca, alloys or mixtures of these materials, and stacks of these materials. The plurality of nanoparticles may have additional layers disposed thereon. In some embodiments, the polarization of light emission can be adjusted using an outcoupling layer. By varying the dimensionality and periodicity of the outcoupling layer, the type of polarization that is preferentially outcoupled to air can be selected. In some embodiments the outcoupling layer also acts as an electrode of the device.

It is believed that the internal quantum efficiency (IQE) of fluorescent OLEDs can exceed the 25% spin statistical limit through delayed fluorescence. As used herein, there are two types of delayed fluorescence: P-type delayed fluorescence and E-type delayed fluorescence. P-type delayed fluorescence is generated from triplet-triplet annihilation (TTA).

On the other hand, E-type delayed fluorescence does not depend on the collision of two triplets, but on the thermal population between the triplet state and the singlet excited state. Compounds that can produce E-type delayed fluorescence must have a very small singlet-triplet gap. Thermal energy can activate the transition from the triplet state to the singlet state. This type of delayed fluorescence is also known as thermally activated delayed fluorescence (TADF). A distinctive feature of TADF is that as the temperature increases, the delay component increases due to the increase in thermal energy. If the rate of intersystem crossing is fast enough to minimize non-radiative decay in the triplet state, the fraction of back populated singlet excited states can potentially reach 75%. The total singlet fraction can be 100%, which far exceeds the spin statistical limit for electrically generated excitons.

Type E delayed fluorescence properties can be found in exciplex systems or single compounds. Without being bound by theory, it is believed that E-type delayed fluorescence requires the emitting material to have a small singlet-triplet energy gap (ΔES-T). Organic, non-metal containing donor-acceptor luminescent materials can achieve this. Luminescence from these materials is usually characterized as donor-acceptor charge transfer (CT) type emission. The spatial separation of HOMO and LUMO in these donor-acceptor type compounds usually leads to a small ΔES-T. These conditions may include CT conditions. In many cases, donor-acceptor luminescent materials are constructed by linking an electron donor moiety, such as an amino or carbazole derivative, with an electron acceptor moiety, such as an N-containing six-membered aromatic ring.

Devices fabricated according to embodiments of the present invention may be incorporated into a wide variety of electronic component modules (or units) that may be incorporated into various electronic products or intermediate components. Examples of such electronic products or intermediate components include display screens, light-emitting devices such as individual light source devices or lighting panels, etc., which may be used by end-consumer product producers. These electronic component modules may optionally include drive electronics and/or power source(s). Devices fabricated in accordance with embodiments of the present invention may be incorporated into a wide variety of consumer products that include one or more electronic component modules (or units) therein. A consumer product comprising an OLED comprising a compound of the present disclosure in an organic layer within the OLED is disclosed. These consumer products may include any type of product that includes one or more light source(s) and/or one or more image displays of some type. Some examples of these consumer products include flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, indoor or outdoor lighting and/or signal lights, head-up displays, fully or partially transparent displays, flexible displays, and rollable displays. , foldable displays, stretchable displays, laser printers, phones, mobile phones, tablets, phablets, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, camcorders, viewfinders, and microdisplays with a diagonal of less than 2 inches. , 3D displays, virtual or augmented reality displays, vehicles, video walls containing multiple displays tiled together, theater or stadium screens, and signage. A variety of control mechanisms, including passive matrix and active matrix, can be used to control devices fabricated according to the present invention. Many devices are intended for use in a temperature range that is comfortable for humans, such as 18°C to 30°C, more preferably at room temperature (20°C to 25°C), but may also be used at temperatures outside this temperature range, such as -40°C to +80°C. It can also be used in

The materials and structures described herein may have applications in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors can use the materials and structures. More generally, organic devices, such as organic transistors, can use the materials and structures.

In some embodiments, the OLED has one or more properties selected from the group consisting of flexible, rollable, foldable, stretchable, and curved properties. In some embodiments, the OLED is transparent or translucent. In some embodiments, the OLED further includes a layer comprising carbon nanotubes.

In some embodiments, the OLED further includes a layer comprising a delayed fluorescent emitter. In some embodiments, the OLED includes an RGB pixel arrangement, or a white plus color filter pixel arrangement. In some embodiments, the OLED is a mobile device, handheld device, or wearable device. In some embodiments, an OLED is a display panel that is less than 10 inches diagonally or less than 50 square inches in area. In some embodiments, an OLED is a display panel that is at least 10 inches diagonally or at least 50 square inches in area. In some embodiments, an OLED is a lighting panel.

In some embodiments of the light-emitting region, the light-emitting region further comprises a host.

In some embodiments, the compound may be a luminescent dopant. In some embodiments, the compounds may produce luminescence via phosphorescence, fluorescence, heat-activated delayed fluorescence, i.e., TADF (also referred to as E-type delayed fluorescence), triplet-triplet quenching, or a combination of these processes. .

OLEDs disclosed herein may be included in one or more of consumer products, electronic component modules, and lighting panels. The organic layer can be an emissive layer and the compound can be a luminescent dopant in some embodiments, while the compound can be a non-luminescent dopant in other embodiments.

The organic layer may also include a host. In some embodiments, two or more hosts are preferred. In some embodiments, the host used may be a) an amphipathic, b) electron transporting, c) hole transporting, or d) wide band gap material that plays little role in charge transport. In some embodiments, the host can include a metal complex. The host may be an inorganic compound.

Combination with other substances

Materials described herein as useful for a particular layer in an organic light emitting device can be used in combination with a wide variety of other materials present in the device. For example, the luminescent dopants disclosed herein can be used in combination with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes, and other layers that may be present. The materials described or referenced below are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and those skilled in the art may readily consult the literature to identify other materials that may be useful in combination. .

A variety of materials can be used for the various emissive and non-emissive layers and arrangements disclosed herein. Examples of suitable materials are disclosed in US Patent Application Publication No. 2017/0229663, the entire contents of which are incorporated by reference.

Conductive dopant:

The charge transport layer can be doped with a conductive dopant to substantially change its charge carrier density, which will in turn change its conductivity. Conductivity is increased by creating charge carriers in the matrix material and, depending on the type of dopant, a change in the Fermi level of the semiconductor may be achieved. The hole transport layer can be doped with a p-type conductive dopant and an n-type conductive dopant is used in the electron transport layer.

HIL/HTL:

The hole injection/transport material to be used in the present invention is not specifically limited, and any compound can be used as long as the compound is commonly used as a hole injection/transport material.

EBL:

An electron blocking layer (EBL) can be used to reduce the number of electrons and/or excitons leaving the emissive layer. The presence of such a blocking layer in the device can lead to significantly higher efficiency and/or longer lifetime compared to similar devices without the blocking layer. Additionally, a blocking layer can be used to localize light emission to a desired area of the OLED. In some embodiments, the EBL material has a higher LUMO (closer to vacuum level) and/or a higher triplet energy than the emitter closest to the EBL interface. In some embodiments, the EBL material has a higher LUMO (closer to vacuum level) and/or a higher triplet energy than one or more of the hosts closest to the EBL interface. In one embodiment, the compound used in EBL contains the same molecule or functional group used as one of the hosts described below.

Host:

The light-emitting layer of the organic EL device of the present invention preferably contains at least a metal complex as a light-emitting material, and may contain a host material using the metal complex as a dopant material. Examples of the host material are not particularly limited, and any metal complex or organic compound can be used as long as the triplet energy of the host is greater than the triplet energy of the dopant. Any host material can be used with any dopant as long as it meets the triplet criteria.

HBL:

A hole blocking layer (HBL) can be used to reduce the number of holes and/or excitons leaving the emissive layer. The presence of such a blocking layer in the device can lead to significantly higher efficiency and/or longer lifetime compared to similar devices without the blocking layer. Additionally, a blocking layer can be used to localize light emission to a desired area of the OLED. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and/or a higher triplet energy than the emitter closest to the HBL interface. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and/or a higher triplet energy than one or more of the hosts closest to the HBL interface.

ETL:

The electron transport layer (ETL) may include a material capable of transporting electrons. The electron transport layer can be native (undoped) or doped. Doping can be used to improve conductivity. Examples of ETL materials are not particularly limited, and any metal complex or organic compound can be used as long as they are conventionally used to transport electrons.

Charge generation layer (CGL)

In tandem or stacked OLEDs, CGL plays an essential role in performance, and it consists of an n-doped layer and a p-doped layer for injecting electrons and holes, respectively. Electrons and holes are supplied from the CGL and electrodes. The electrons and holes consumed in the CGL are refilled by electrons and holes injected from the cathode and anode, respectively; After that, the bipolar current gradually reaches the steady state. Typical CGL materials include n and p conducting dopants used in the transport layer.

Embodiments of the disclosed subject matter provide high temperature, low profile, bondable gas distribution plates and opposing plates for coupling a jet head to a larger gas delivery system for delivering organic materials via organic vapor jet printing (OVJP). The bonded assembly allows efficient transfer of hot materials to the surface of the substrate with minimal thermal load to the substrate.

In the example OVJP system shown in FIG. 3, micromachined die 301 includes a micronozzle array 302 along its lower edge. Die 301 is typically made of silicon, but other materials may be used. Die 301 is clamped between two heated plates 303. One or more plates of the clamps direct organic vapors entrained in the inert carrier gas through run lines 305 extending from the manifold 304 through the plates 303 to one or more vias on the face of the die 301. It is connected to a heated manifold 304 that supplies the die. One or more plates 303 of the clamp have exhaust lines 306 that connect vias on die 301 with a low pressure reservoir to recover process gases and excess organic vapors from the printing zone. The heater 307 may be connected to one or more plates 303 of the clamp, as well as the manifold 304. The micromachined die 301 and the device that secures and connects it to the heated manifold 304 are referred to as jet heads.

The temperature of the substrate affects the morphology of the deposited film. To control the morphology, it is important to control the heat load on the surface. A temperature control plate, or cooling plate, is disposed between the print head and the substrate 308. The cooling plate has a thick portion (309) that allows efficient heat conduction to the coolant loop, and a thin portion (310) proximate the micronozzle array. Although this thin portion (310) is a less effective heat shield than the thick portion (309), the form factor of the clamp assembly allows material to be removed from the cooling plate to allow the micronozzle array to be in close proximity to the substrate (308). It is necessary to accept. The micronozzle array must be maintained at high temperatures, so the tip of the die can only protrude a short distance from the clamp. Requirements for thermal uniformity, hermetic sealing, and mechanical rigidity limit the extent to which clamps can be miniaturized. The window of the cooling plate should be wide enough to accommodate part of the clamp around die 301. The clamp is therefore only partially protected by the substrate 308, the protected section of which is only protected by a portion of the cooling plate that is thinner than optimal.

Embodiments of the disclosed subject matter reduce the thermal load applied to the substrate by the OVJP mechanism by providing a gas distribution plate that allows as much of the assembly as possible to remain protected by the thick cooling plate during operation.

Embodiments of the disclosed subject matter provide high temperature, low profile, bondable gas distribution plates and opposing plates for connecting microfluidic devices made of silicon or other materials with larger gas delivery systems. The gas distribution plate and opposing plate may have a low profile in the depth direction, but are relatively large and wide. This arrangement can provide a minimal cross-sectional area of the heated jet head facing the substrate and allows a thick cooling plate to surround the gas distribution plate and opposing plate to thermally isolate the remainder of the heated OVJP component from the substrate.

When trying to seal a fluid connection at the interface of two components, operating at high temperatures in a high-purity vacuum environment can cause problems. The maximum operating temperature of conventional polymer seals is about 300° C., much lower. Even in high temperature grades of polymers, degassing can be a problem. Although metal seals can operate at higher temperatures, metal and polymer seals usually use additional fasteners for assembly, such as bolting, which increases the physical size of the gas distribution plate and opposing plate. Heat transfer within the OVJP mechanism can be controlled, as some components of the OVJP mechanism may be hot while other components may be heat sensitive. The additional size of the fixture increases the heat load on system components, which may be undesirable. The gas distribution plates and counter plates disclosed herein can serve as pass-through devices to move fluid from one thermal zone to another through windows in a cooling plate, reducing the thermal load on the system. there is. This ensures that the substrate is most effectively protected from the heat generated by the evaporation source and the connected manifold.

The gas distribution plates and counter plates disclosed herein may be useful in organic vapor jet printing (OVJP). OVJP is a system in which organic materials are transferred to a substrate via a high-temperature carrier gas, where an array of micronozzles need to be incorporated into a macroscopic assembly to heat the materials and entrain them in a vapor stream. The vapor stream may not be able to cool along its path, and the process equipment may not transfer excess heat to the substrate. By reducing the size of the portion of the printhead assembly exposed to the substrate and using a protective or cooled interface, the heat load can be more easily managed.

4A shows a device according to an embodiment of the disclosed subject matter. Micronozzle array 401 may be similar to a micronozzle array with a plane perpendicular to its aperture and may have one or more delivery apertures in fluid communication with a flow of inert carrier gas and organic vapor. The delivery aperture may be laterally bordered by an exhaust aperture in fluid communication with the exhaust line. The micronozzle array 401 may be disposed on the edge of the silicon die 402 disposed between the plates 403. Plate 403 may include a first gas distribution plate and a second opposing plate. The first gas distribution plate may be monocrystalline silicon, columnar silicon, and/or polycrystalline silicon. Micronozzle array 401, silicon die 402, and plate 403 may protrude through cooling plate 404. The micronozzle array 401 may be close to the substrate 410 on which deposition is targeted. Die 402 may be irreversibly sealed to one or more of the gas distribution plate and the opposing plate using methods such as glass frit, ceramic adhesive, bonding, soldering, or brazing. In some embodiments, die 402 can be attached to a gas distribution plate. The gas distribution plate of plate 403 may be mechanically attached to the interface manifold block 405 and may seal one or more flow paths 406 with a high temperature seal at a gland feature 407. One or more of the plates 403 have channels 408 through which organic vapor entrained in an inert carrier gas can be supplied to the die 402 from a manifold connected to one or more organic vapor sublimation sources 411. One or more of the plates 403 may include exhaust lines 409 that connect vias on die 402 with low pressure reservoir 412 to recover process gases and excess organic vapors from the printing zone.

FIG. 4B shows an alternative arrangement of FIG. 4A where the organic vapor channels 408 and exhaust lines 409 may exit through the same plate 403. The opposing plate 403a and manifold block 405a may not include any internal channels and therefore may not use an airtight seal at their interface.

Figure 5A shows an alternative arrangement to the embodiment shown in Figure 4A. The arrangement shown in FIG. 5A may include an insulating material 501, such as quartz or borosilicate glass, which may be attached to the perimeter of the window of the cooling plate 404. The insulation 501 is used to maintain a temperature gradient so that the plate 403 can be maintained at a hot temperature and the cooling plate 404 can be maintained at a cold temperature. In other words, plate 403 may have a predetermined high temperature that is higher than the predetermined low temperature of cooling plate 404. An alternative embodiment is shown in FIG. 5B in which an insulating sheet may wrap and/or cover the outer surface of the plate 403 and the micromachined die assembly. Among the embodiments shown in FIGS. 5A and 5B, the embodiment shown in FIG. 5A may be preferred because it reduces the cross-sectional dimension of the heated jet head proximate to the substrate 410.

Plate 403 may include stacked and bonded channels and/or holes. Bonding may be vacuum soldering, diffusion bonding, soldering, glass frit, ceramic adhesive, etc. Bonding can enable complex internal geometries that can reduce the profile of plate 403. The final bonded component may have a plurality of leak-tight fluid passages each connecting an inlet to an outlet orifice. If soldering, soldering, or welding techniques are used to fabricate one or more plates 403, the forming temperature is equal to that of the solder used to attach the plates 403 to the die 402 containing the micronozzle array 401. Or it may be higher than the solder temperature. The material used for plate 403 is tailored to the coefficient of thermal expansion (CTE) of silicon to avoid breakage of the silicon due to differential expansion of the combined materials. Some examples of materials that fit the CTE of silicon may include single crystalline silicon, columnar silicon, and/or polycrystalline silicon, etc. The average CTE between room temperature and the liquid of the material used to solder the micronozzle array 401 to the gas distribution plate and opposing plate may be less than 4×10 ^-6 K ^-1 . By adjusting the expansion, the silicon die 402 and plate 403 can be joined eliminating another sealing interface.

The acceptable thermal expansion mismatch may be a function of the soldering or sealing temperature and the size of the silicon die attached to the distribution plate (eg, first gas distribution plate). For small OVJP silicon MEMS dies used in research and development systems, less than 30 mm in length, a thermal expansion coefficient mismatch of 2×10 ^-6 K ^-1 may be acceptable. Metals such as tungsten or molybdenum, and ceramics such as aluminum nitride may fall within this range. For the large dies used in manufacturing-scale OVJP systems, which can be as long as 150 mm in length, these materials can exhibit cracks, spalling, and other damage due to the high stresses that arise from even these relatively small thermal expansion mismatches. It turns out. To reduce or prevent this damage, it was found that the thermal expansion coefficient mismatch in manufacturing scale systems should be less than 0.25×10 ^-6 K ^-1 . Thermal mismatch is eliminated by bonding the silicon die to the silicon distribution plate. The silicon distribution plate can be made of single crystal silicon, the material used in OVJP dies, columnar silicon, or polycrystalline silicon. The first gas distribution plate of columnar silicon and polycrystalline silicon can be fabricated by machining a block of material, while single crystal silicon can be fabricated using photolithography and acid etching.

The silicon die 402 containing the micronozzle array 401 is connected to a heater attached to the clamped plate, in a similar manner to the heater 307, which may be connected to one or more plates 303 of the clamp shown in FIG. It can be heated indirectly by Surface-to-surface metal contact may have a greater thermal resistivity than solder contact, so the clamp must be heated to a much higher temperature than the desired temperature at the tip of the silicon die 402. Embodiments of the disclosed subject matter can be offset by adjusting the heater to a higher temperature setpoint. A bonded interface between silicon die 402 and plate 403 may provide more efficient heat conduction and thus lower heater temperatures. This can further lower both the thermal load on the substrate 410 and the cooling requirements of the OVJP tool.

Heat transfer to the substrate may be limited by a temperature control plate mounted between the high temperature assembly and the substrate. Areas of the temperature control plate can be removed, allowing the micronozzle and its support structure to pass through and be closer to the substrate without exposing all hot components. Bonding can also reduce the overall size of these structures because they eliminate the fasteners needed to clamp and seal the silicon at its gas interface. Accordingly, smaller cutout windows can be created in the plate to further reduce heat load to the substrate.

Figure 6 shows a comparison of heat transfer to a substrate using the embodiment of the disclosed invention shown in Figure 4A and a jet head mounted on a conventional substrate. The temperature of the jet head can be displayed on the horizontal axis 601 in units of Celsius, and the heat transfer rate from the tip of the jet head to the substrate located 50 μm away from the micronozzle array can be displayed on the vertical axis 602 in units of watts. . The dashed gray line 603 may represent the heat transfer rate versus temperature for the OVJP jet head of the standard configuration shown in FIG. 3, and the solid gray line 604 may represent the heat transfer rate versus temperature for the OVJP jet head using the embodiment of the disclosed subject matter shown in FIG. 4A. can represent heat transfer rate versus temperature. The device shown in Figure 4A can reduce the thermal load on the substrate by approximately 12% over its operating range. This is due to the lower thermal mass and cross-section of the plate 303 compared to existing clamps, and the cooling plate 404 better shielding the substrate 410 from the heat generated by the sublimation source and the manifold connecting it to the plate 403. This may be due to the small window of the cooling plate 404 allowed by the plate 403, which may provide protection. The absence of milled recesses in the cooling plate 404 to accommodate the clamped hardware may improve thermal isolation between the substrate and the heated OVJP component. Lines 605 and 606 shown in Figure 6 are considered below in relation to the embodiment shown in Figure 8.

As shown in FIG. 7, the OVJP micronozzle array may have an aperture cut on a side other than the edge of the micromachined die. An aperture may be present on the bottom surface of die 701 connected to first gas distribution plate 702 via connection 703, which may include a solder connection, solder connection, bonding, glass frit, ceramic adhesive, Or it could be any other suitable connection. The face of the micronozzle array may be in a plane perpendicular to its aperture and may have one or more delivery apertures in fluid communication with a flow of inert carrier gas and organic vapor. The delivery aperture may be laterally bordered by an exhaust aperture in fluid communication with the exhaust line. In some implementations, the face of the micronozzle array can have different placements of delivery apertures and exhaust apertures. The micronozzle configuration may include a delivery aperture and an exhaust aperture as edges. The configuration shown in FIG. 7 may include a jet head with an increased cross-sectional area facing the substrate, which may provide a greater rate of heat transfer to the substrate. The greater heat transfer rate can be offset by the greater material deposition rate, so the amount of heat received per area of the substrate can be approximately the same or lower compared to the edge-on configuration considered previously. The first gas distribution plate 702 may be connected to the micronozzle array using solder or soldering techniques such as those disclosed in U.S. Pat. No. 9,700,901. The first gas distribution plate 702 may expose additional surface area to the substrate 706 for heat transfer and may require a substantial window through the cooling plate 707.

Figure 8 shows an edge-on configuration similar to that shown in Figure 3, but the configuration of Figure 8 could be fabricated such that the plate does not provide additional cross-sectional area to the substrate for heat transfer. Die 801 may be connected directly to plate 802 by seal 803, which may be a solder seal, solder seal, bonded, glass frit, ceramic adhesive seal, or other suitable seal. Plate 802 may include a first gas distribution plate and a second opposing plate. The first gas distribution plate may be monocrystalline silicon, columnar silicon, and/or polycrystalline silicon. Plate 802 may extend through a window cut through a thicker portion of cooling plate 804 that can better absorb heat from the evaporation source and the first gas distribution plate. The plate may include one or more transfer run lines 805 that transfer organic vapor entrained in an inert carrier gas from the evaporation source to the micronozzle array. The plate is at reduced pressure relative to the chamber and may include an exhaust line to recover gases beneath the die. A compact gas distribution plate and counter plate can significantly reduce the amount of heat transferred to the substrate compared to one of the previous configurations, such as that shown in Figure 3.

6 shows the jet head shown in FIG. 8 with a dashed line 605 for the jet head directly connected to the plate 802 and with a solid solid line 606 for the jet head configured to include a cooling plate 804. A plot of heat transferred to the substrate as a function of temperature is shown. Cooling plate 804 of FIG. 8 can reduce the heat load on the substrate by reducing the heated cross-sectional area to which the substrate is exposed. This configuration may allow for more thermal protection around the micronozzle array. An overall heat transfer reduction of 11% can be expected.

The first gas distribution plate and the second opposing plate can provide a solid surface that seals the flow path between the plate and the mating component or interface with a mechanical seal, such as a metal o-ring. The use of such seals on exposed silicon can lead to high stress concentrations and, in many cases, failure before the seal reaches maximum seating pressure. Some embodiments of the disclosed subject matter may include a soft, deformable metal disposable gasket material fused to a plate in a removable connection to an OVJP manifold.

In some printing and coating applications, it may be desirable to have an array of depositors that can match the width of the substrate to achieve full coverage in a single pass. Channels in the plates (e.g., gas distribution plates and counter plates) can be arranged in a linear pattern, creating long, thin gas distribution plates and counter plates that can be coupled to one or multiple microfluidic devices.

For example, the print head previously considered in relation to Figure 6 is modeled using the laminar flow and heat transfer package in COMSOL Multiphysics. A nitrogen atmosphere and room temperature heat bath were assumed for all cases, and a micronozzle array positioned 50 μm above the substrate and 1 mm below the fixture type was evaluated. The cooling plate and substrate platen were also at 20°C, and the platen used a glass substrate with a thickness of 0.7 mm. The cooling plate was 1 mm above the substrate. Four fixation devices were evaluated.

Embodiments of the disclosed subject matter may provide apparatus comprising a device having an array of micronozzles disposed on a micromachined fluid die. The device's micronozzle array can be placed on the edge of a micromachined fluid die. A micronozzle array can be placed on one side of a micromachined fluid die. The micromachined fluid die of the device may include one or more of silicon, quartz, and/or metal. The device may include a first gas distribution plate and a second opposing plate, with a micromachined fluid die disposed between the first gas distribution plate and the second opposing plate. The first gas distribution plate may be monocrystalline silicon, columnar silicon, and/or polycrystalline silicon. The first gas distribution plate may be irreversibly coupled to the micronozzle array in a hermetic seal, wherein the first gas distribution plate includes a plurality of sealed flow paths. The manifold can be reversibly coupled to the first gas distribution plate, wherein the micromachined fluid die and the first gas distribution plate and the second opposing plate can be disposed between the manifold. The device may include a thermally conductive plate in thermal contact with the active cooling source, wherein the thermally conductive plate has one or more windows passing through its entire thickness, through which the first gas distribution plate and the second opposing plate of the device are connected. , a portion of the micromachined fluid die, and the micronozzle array protrude so that the shortened cross-section of the window provides a clearance fit for the device over a range of motion relative to the thermally conductive plate. The device can include one or more thermal evaporation sources in fluid communication with a first gas distribution plate, where the manifold can be in fluid communication with the micronozzle array through a plurality of sealed flow paths in the first gas distribution plate.

In some embodiments, the device's micronozzle array can be placed on the edge of a micromachined fluid die. A micronozzle array can be placed on one side of a micromachined fluid die. The micromachined fluid die of the device may include one or more of silicon, quartz, and/or metal. The device's micronozzle array and substrate can be configured to move relative to each other. The device's micromachined fluid die and micronozzle array may be comprised of silicon, and the micromachined fluid die may be bonded to the first gas distribution plate.

The second opposing plate of the device may be a second gas distribution plate. The manifold can be coupled to the first gas distribution plate in an airtight seal.

One or more of the plurality of sealed flow paths of the device may be configured to convey a mixture of organic vapor and an inert carrier gas.

The first gas distribution plate of the device may have a segment adjacent to the micronozzle array through which all flow paths pass, the aspect ratio of the depth of the segment being less than or equal to 10% of the width or height of the segment, and the depth being on one side of the micronozzle array. It can be defined as a vertical direction.

The thermally conductive plate of the device can protect the manifold and the object on which the micronozzle array acts from heat generated by the plurality of evaporation sources. The thermally conductive plate may have a window lined with an insulating material such as quartz, borosilicate glass, etc. The micronozzle array and the first gas distribution plate may include at least a portion of the device protruding through a window of the thermally conductive plate such that a normal plane of the device is parallel to a depth dimension of the first gas distribution plate.

The seal of the device may be a gasket or joint. The micronozzle array of the device is irreversibly bonded to the first gas distribution plate and the second opposing plate using glass frit, ceramic adhesive, and/or solder or soldering compound having a reflow temperature of greater than 350 degrees Celsius or greater than 500 degrees Celsius. A seal can be formed. In other words, in some embodiments, non-metallic seals such as high temperature glass frit or ceramic adhesives may be used. The first gas distribution plate of the device may comprise a material having an average coefficient of thermal expansion of less than 4×10 ⁻⁶ K ⁻¹ between room temperature and the reflow temperature of the solder.

The first gas distribution plate and second opposing plate of the device may be fabricated from one or more of monocrystalline silicon, columnar silicon, or polycrystalline silicon.

The device may include a heater thermally coupled to the micronozzle array, where the heater is configured to heat the micronozzle array. The micronozzle array can direct a convective jet of gas to the surface of the substrate.

The first gas distribution plate and second opposing plate of the device may include a resistive heater. The first gas distribution plate and the second opposing plate of the device may include one or more thermal insulating materials selected from monocrystalline silicon, columnar silicon, and/or polycrystalline silicon. One or more of the first gas distribution plate and the second opposing plate of the device may be configured to have gas supplied therethrough.

The device may include a deformable metal gasket, and the first gas distribution plate is sealed to the manifold using the deformable metal gasket. The deformable metal gasket can be reversibly sealed to the device. The deformable metal gasket may be comprised of a material that is integrated with the manifold.

The first gas distribution plate of the device may be comprised of a plurality of etched or milled layers of material bonded together using a formation temperature greater than the reflow temperature of the material used to join the micronozzle array to the first gas distribution plate. You can.

Embodiments of the disclosed subject matter can provide apparatus comprising a device having a micronozzle array. The device can include a first gas distribution plate irreversibly coupled to the micronozzle array in a hermetic seal, where the first gas distribution plate includes a plurality of sealed flow paths. The first gas distribution plate may be monocrystalline silicon, columnar silicon, and/or polycrystalline silicon. One or more thermal evaporation sources of the device may be in fluid communication with the first gas distribution plate. The device can include a manifold, and the first gas distribution plate is reversibly coupled to the manifold. The manifold may be in fluid communication with the micronozzle array through a plurality of sealed flow paths in the first gas distribution plate. One or more of these flow paths may carry a mixture of organic vapor and an inert carrier gas. The first gas distribution plate may have a segment adjacent the micronozzle array through which all flow paths pass, the depth of the segment being no wider than the depth of the micronozzle array at the point of attachment. The device may include a thermally conductive plate, wherein the first gas distribution plate and the thermally conductive plate are in thermal contact with an active cooling source. The thermally conductive plate may have one or more windows passing through its entire thickness, through which a device protrudes so that a shortened cross-section of the window provides a clearance fit for at least the micronozzle array of the device over the range of motion of the device relative to the thermally conductive plate. whereby the thermally conductive plate protects the manifold and the object on which the micronozzle array acts from heat generated by one or more thermal evaporation sources.

The seal of the device may be a gasket or joint. The micronozzle array of the device may be irreversibly bonded to the device using a glass frit or ceramic adhesive, or a solder or brazing compound whose reflow temperature may be greater than 350°C or greater than 500°C. The first gas distribution plate may comprise a material having an average coefficient of thermal expansion of less than 4×10 ^-6 K ^-1 between room temperature and the reflow temperature of the solder. The device may include one or more of single crystalline silicon, columnar silicon, or polycrystalline silicon.

The device may include a deformable metal gasket, and the first gas distribution plate is sealed to the manifold using the deformable metal gasket. The deformable metal gasket can be reversibly sealed to the device. In some embodiments, the deformable metal gasket is comprised of a material that is integrated with the manifold.

The device may include a heater thermally coupled to the micronozzle array, where the heater is configured to heat the micronozzle array.

The device's micronozzle array can direct a convective jet of gas toward the surface of the substrate. The micronozzle array and the substrate are configured to move relative to each other. The micronozzle array may be made of silicon.

The thermally conductive plate of the device may include a window lined with an insulating material such as quartz, borosilicate glass, etc.

It should be understood that the various embodiments described herein are illustrative only and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein may be replaced with other materials and structures without departing from the spirit of the invention. Accordingly, the claimed invention may include variations resulting from the specific examples and preferred embodiments described herein, as will be apparent to those skilled in the art. It should be understood that there is no intention to limit the various theories as to why the present invention works.

Claims (15)

A micronozzle array disposed on a micromachined fluid die;
A first gas distribution plate and a second opposing plate, the first gas distribution plate comprising at least one member selected from the group consisting of single crystalline silicon, columnar silicon, and polycrystalline silicon, the micromachined fluid die comprising: disposed between a first gas distribution plate and a second opposing plate, wherein the first gas distribution plate is irreversibly coupled to the micronozzle array with an airtight seal, and the first gas distribution plate includes a plurality of sealed flow paths. a first gas distribution plate and a second opposing plate; and
A manifold reversibly coupled to a first gas distribution plate, wherein the micromachined fluid die and the first gas distribution plate and the second opposing plate are disposed between the manifolds.
A device including;
A thermally conductive plate in thermal contact with an active cooling source, the thermally conductive plate having one or more windows passing through its entire thickness, whereby the first gas distribution plate and the second opposing plate of the device, a portion of the micromachined fluid die, , and a micronozzle array projecting, such that the minor axis of the cross section of the window provides a clearance fit for the device over a range of motion relative to the thermally conductive plate; and
One or more thermal evaporation sources in fluid communication with the first gas distribution plate
A device comprising:
wherein the manifold is in fluid communication with the micronozzle array through a plurality of sealed flow paths in the first gas distribution plate. 2. The device of claim 1, wherein the micronozzle array is disposed on an edge of the micromachined fluid die. 2. The device of claim 1, wherein the micronozzle array is disposed on one side of the micromachined fluid die. 2. The apparatus of claim 1, wherein the second opposing plate is a second gas distribution plate and the manifold is coupled to the first gas distribution plate in a hermetic seal. 2. The apparatus of claim 1, wherein the first gas distribution plate comprises a material having an average coefficient of thermal expansion of less than 4×10 ^-6 K ^-1 between room temperature and the reflow temperature of the solder. 2. The device of claim 1, wherein the first gas distribution plate and the second opposing plate are made of at least one member selected from the group consisting of monocrystalline silicon, columnar silicon, and polycrystalline silicon. 2. The device of claim 1, wherein the micromachined fluid die and the micronozzle array are comprised of silicon, and the micromachined fluid die is coupled to the first gas distribution plate. 2. The device of claim 1, wherein the thermally conductive plate comprises a window lined with insulation. 2. The device of claim 1, wherein the first gas distribution plate and the second opposing plate are comprised of one or more insulating materials selected from the group consisting of monocrystalline silicon, columnar silicon, and polycrystalline silicon. According to paragraph 1,
Deformable metal gasket
A device further comprising:
Apparatus wherein the first gas distribution plate is sealed to the manifold using a deformable metal gasket. micronozzle array;
a first gas distribution plate irreversibly coupled to the micronozzle array with a hermetic seal, the first gas distribution plate comprising a plurality of sealed flow paths and comprising at least one member selected from the group consisting of single crystal silicon, columnar silicon, and polycrystalline silicon;
one or more thermal evaporation sources in fluid communication with the first gas distribution plate; and
Manifold to which the first gas distribution plate is reversibly coupled
A device comprising, and
thermal conductive plate
A device comprising:
The manifold is in fluid communication with the micronozzle array through a plurality of sealed flow paths in the first gas distribution plate,
One or more of these flow paths carry a mixture of organic vapor and an inert carrier gas,
The first gas distribution plate has a segment adjacent the micronozzle array through which all flow paths pass, the depth of the segment being no wider than the depth of the micronozzle array at the attachment point,
The first gas distribution plate and the thermally conductive plate are in thermal contact with the active cooling source,
The thermally conductive plate has one or more windows passing through its entire thickness, through which the device protrudes, such that the short axis of the cross section of the window provides a clearance fit for at least the micronozzle array of the device over the range of motion of the device relative to the thermally conductive plate. The device may have dimensions such that the thermally conductive plate protects the object on which the micronozzle array acts from heat generated by the manifold and one or more thermal evaporation sources. 12. The apparatus of claim 11, wherein the first gas distribution plate comprises a material having an average coefficient of thermal expansion between room temperature and the reflow temperature of the solder of less than 4×10 ^-6 K ^-1 . 12. The device of claim 11, wherein the device includes at least one selected from the group consisting of molybdenum, tungsten, kovar, aluminum nitride, silicon nitride, single crystal silicon, columnar silicon, and polycrystalline silicon. 12. The device of claim 11, wherein the micronozzle array is comprised of silicon. According to clause 11,
Deformable metal gasket
A device further comprising:
Apparatus wherein the first gas distribution plate is sealed to the manifold using a deformable metal gasket.