Source: https://patents.google.com/patent/WO2009099425A2/en
Timestamp: 2018-11-21 00:36:37
Document Index: 675755901

Matched Legal Cases: ['Application No. 61', 'Application No. 60', 'Application No. 08', 'Application No. 10', 'Application No. 11', 'Application No. 60', 'Application No. 60', 'Application No. 60', 'Application No. 11']

WO2009099425A2 - Flexible devices including semiconductor nanocrystals, arrays, and methods - Google Patents
Flexible devices including semiconductor nanocrystals, arrays, and methods Download PDF
WO2009099425A2
WO2009099425A2 PCT/US2008/013504 US2008013504W WO2009099425A2 WO 2009099425 A2 WO2009099425 A2 WO 2009099425A2 US 2008013504 W US2008013504 W US 2008013504W WO 2009099425 A2 WO2009099425 A2 WO 2009099425A2
PCT/US2008/013504
WO2009099425A3 (en )
Peter T. Kazlas
Ioannis Kymissis
H01L51/502—Electroluminescent [EL] layer comprising active inorganic nanostructures, e.g. luminescent quantum dots
H01L51/5246—Sealing arrangements having a self-supporting structure, e.g. containers characterised by the peripheral sealing arrangements, e.g. adhesives, sealants
The present invention relates to flexible devices including semiconductor nanocrystals, arrays including such devices, systems including the foregoing, and related methods. In one embodiment, a flexible light-emitting device includes a flexible substrate including a first electrode, an emissive layer comprising semiconductor nanocrystals disposed over the substrate, and second electrode disposed over the emissive layer comprising semiconductor nanocrystals, wherein, when the device is curved, the emissive layer comprising semiconductor nanocrystals lies substantially in the neutral plane of the device. In another embodiment, a light-emitting device includes an emissive layer comprising semiconductor nanocrystals disposed between two flexible substrates, a first electrode disposed over the emissive layer comprising semiconductor nanocrystals, and a second electrode disposed under the emissive layer comprising semiconductor nanocrystals. In certain preferred embodiments, at least one charge transport layer is disposed between one of the electrodes and the layer comprising semiconductor nanocrystals.
FLEXIBLE DEVICES INCLUDING SEMICONDUCTOR NANOCRYST ALS,
ARRAYS, AND METHODS
This application claims priority to U.S. Application No. 61/026,967 filed 7 February 2008, which is hereby incorporated herein by reference in its entirety.
This invention was made with Government support under FA9550-06-C-128 awarded by the United States Air Force. The Government has certain rights in the invention.
The present invention relates to the technical field of devices including semiconductor nanocrystals.
The present invention relates to devices including semiconductor nanocrystals, arrays including such devices, systems including the foregoing, and related methods. In certain embodiments, the devices comprise light-emitting devices.
In accordance with one aspect of the invention, there is provided a light-emitting device including an emissive layer comprising semiconductor nanocrystals disposed between two flexible substrates, a first electrode disposed over the emissive layer comprising semiconductor nanocrystals, and a second electrode disposed under the emissive layer comprising semiconductor nanocrystals. In certain preferred embodiments, at least one charge transport layer is disposed between one of the electrodes and the layer comprising semiconductor nanocrystals. In certain embodiments, the emissive layer is patterned. In certain embodiments, the emissive layer is unpatterned.
In accordance with another aspect of the invention, there is provided a light- emitting device including an emissive layer comprising semiconductor nanocrystals disposed between two flexible substrates, a first electrode disposed over the emissive layer comprising semiconductor nanocrystals, a second electrode disposed under the emissive layer comprising semiconductor nanocrystals, and a third electrode layer disposed on the outside surface of either flexible substrate making electrical contact with either or both interior electrodes through a substrate via or external connection. In certain preferred embodiments, at least one charge transport layer is disposed between one of the electrodes and the layer comprising semiconductor nanocrystals. In certain embodiments, the emissive layer is patterned. In certain embodiments, the emissive layer is unpatterned.
In accordance with another aspect of the invention, there is provided a flexible light-emitting device including: a flexible substrate, a first electrode disposed over a portion of the flexible substrate, an emissive layer comprising semiconductor nanocrystals disposed over the first electrode, and second electrode disposed over the emissive layer comprising semiconductor nanocrystals, wherein, when the device is curved, the emissive layer comprising semiconductor nanocrystals lies substantially in the neutral plane of the device. In certain embodiments, the emissive layer is patterned. In certain embodiments, the emissive layer is unpatterned. In certain embodiments, the device further includes a third electrode layer disposed on the outside surface of the flexible substrate making electrical contact with either or both interior electrodes through a substrate via or external connection.
In accordance with another aspect of the invention, there is provided a flexible light-emitting device including an emissive layer comprising semiconductor nanocrystals disposed between two flexible substrates, a first electrode disposed over the emissive layer comprising semiconductor nanocrystals and a second electrode disposed under the emissive layer comprising semiconductor nanocrystals, wherein, when the device is curved, the emissive layer comprising semiconductor nanocrystals lies substantially in the neutral plane of the device. In certain embodiments, the emissive layer is patterned. In certain embodiments, the emissive layer is unpatterned. In certain embodiments, the device further includes a third electrode layer disposed on the outside surface of either flexible substrate making electrical contact with either or both interior electrodes through a substrate via or external connection.
In certain embodiments of a flexible light-emitting device in accordance with certain aspects of the invention, the moduli of the various components or parts of the device are such that, when the device is curved, the neutral axis or neutral plane (i.e., the axis or plane in which no compression or tension exists) lies substantially in the plane of the emissive layer. In certain embodiments, the neutral axis or neutral plane does not deviate from the plane of the emissive layer by more than about 25 percent. In certain embodiments, the neutral axis or neutral plane does not deviate from the plane of the emissive layer by more than about 20 percent. In certain embodiments, the neutral axis or neutral plane does not deviate from the plane of the emissive layer by more than about 15 percent. In certain embodiments, the neutral axis or neutral plane does not deviate from the plane of the emissive layer by more than about 10 percent. In certain embodiments, the neutral axis or neutral plane does not deviate from the plane of the emissive layer by more than about 5 percent. In certain embodiments, the neutral axis or neutral plane does not deviate from the plane of the emissive layer by more than about 1 percent.
In accordance with another aspect of the invention, there is provided a method for making a light-emitting device. The method comprises depositing a layer of flexible sealant over exposed (e.g., top and side) surfaces of device layers disposed on a surface of a substrate, and disposing a protective layer over the sealant. In certain embodiments, the layer of flexible sealant and/or protective layer also covers a portion of the substrate surface not covered by the device layers. In certain embodiments, the layer of flexible sealant and/or protective layer comprises a continuous layer over the exposed surfaces of the device layers and the portion of the substrate surface not covered by the device layers. In certain embodiments, the protective layer provides mechanical protection, e.g., against abrasion, handling, other external factors, etc. In certain embodiments, gettering material is associated with (e.g., disposed on, over, under, adjacent, etc.) the device layers before the sealant is disposed thereover. In certain embodiments, gettering material is disposed over at least a portion of an exposed surface of the device layers. In certain embodiments, gettering material is disposed over at least a portion of the substrate between the bottom device layer and the substrate. In certain embodiments, the gettering material comprises a layer. In certain embodiments, the gettering material comprises moisture gettering material. In certain embodiments, the gettering material comprises oxygen gettering material. In certain embodiments, the gettering material comprises moisture and oxygen gettering material. In certain embodiments, the gettering material comprises a mixture of two or more gettering materials. In certain embodiments, the emissive layer is patterned. In certain embodiments, the emissive layer is unpatterned. In certain embodiments, the substrate is flexible.
In accordance with another aspect of the invention, there is provided a light- emitting device comprising a layer of flexible sealant disposed over exposed (e.g., top and side) surfaces of device layers disposed on surface of a substrate, and a protective layer disposed over the sealant. In certain embodiments, the layer of flexible sealant and/or protective layer also covers a portion of the substrate surface not covered by the device layers. In certain embodiments, the layer of flexible sealant and/or protective layer comprises a continuous layer over at least the exposed surfaces of the device layers and the portion of the substrate surface not covered by the device layers. In certain embodiments, the protective layer provides mechanical protection, e.g., against abrasion, handling, other external factors, etc. In certain embodiments, gettering material is associated with (e.g., disposed on, over, under, adjacent, etc.) the device layers before the sealant is disposed thereover. In certain embodiments, gettering material is disposed over at least a portion of an exposed surface of the device layers. In certain embodiments, gettering material is disposed over at least a portion of the substrate between the bottom device layer and the substrate. In certain embodiments, the gettering material comprises a layer. In certain embodiments, the gettering material comprises moisture gettering material. In certain embodiments, the gettering material comprises oxygen gettering material. In certain embodiments, the gettering material comprises moisture and oxygen gettering material. In certain embodiments, the gettering material comprises a mixture of two or more gettering materials. In certain embodiments, the light-emitting device comprises one of the devices taught herein. In certain embodiments, the emissive layer is patterned. In certain embodiments, the emissive layer is unpatterned. In certain embodiments, the substrate is flexible.
In accordance with another aspect of the invention, there is provided a method for making a light-emitting device. The method comprises depositing a layer of flexible sealant over a substrate including device layers thereon, and disposing a protective layer over the sealant. In certain embodiments, the protective layer provides mechanical protection, e.g., against abrasion, handling, other external factors, etc. In certain embodiments, gettering material is associated with (e.g., disposed on, over, under, adjacent, etc.) the device layers before the sealant is disposed over the device layers. In certain embodiments, gettering material is disposed over at least a portion of an exposed surface of the device layers. In certain embodiments, gettering material is disposed on at least a portion of the substrate between the substrate and the bottom device layer. In certain embodiments, the gettering material comprises a layer. In certain embodiments, the gettering material comprises moisture gettering material. In certain embodiments, the gettering material comprises oxygen gettering material. In certain embodiments, the gettering material comprises moisture and oxygen gettering material. . In certain embodiments, the gettering material comprises a mixture of two or more gettering materials. In certain embodiments, the emissive layer is patterned. In certain embodiments, the emissive layer is unpatterned. In certain embodiments, the substrate is flexible.
In accordance with another aspect of the invention, there is provided a light- emitting device including a layer of flexible sealant over a substrate including device layers thereon, and a protective layer disposed over the sealant. In certain embodiments, the protective layer provides mechanical protection, e.g., against abrasion, handling, other external factors, etc. In certain embodiments, gettering material associated with (e.g., disposed on, over, under, adjacent, etc.) the device layers before the sealant layer is disposed over the substrate including device layers thereon. In certain embodiments, gettering material is disposed over at least a portion of an exposed surface of the device layers. In certain embodiments, gettering material is disposed over at least a portion of the substrate between the substrate and the bottom device layer. In certain embodiments, gettering material comprises a layer. In certain embodiments, the gettering material comprises moisture gettering material. In certain embodiments, the gettering material comprises oxygen gettering material. In certain embodiments, the gettering material comprises moisture and oxygen gettering material. In certain embodiments, the gettering material comprises a mixture of two or more gettering materials. In certain embodiments, the light-emitting device comprises one of the devices taught herein. In certain embodiments, the emissive layer is patterned. In certain embodiments, the emissive layer is unpatterned. In certain embodiments, the substrate is flexible. In accordance with another aspect of the invention, there is provided a method for making a light-emitting device. The method comprises forming a sealant dam around the perimeter of device layers on a substrate to form a defined area, depositing a flexible sealant over the defined area, and disposing a protective layer over at least the uppermost surface of the sealant dam and sealant. In certain embodiments, the protective layer provides mechanical protection, e.g., against abrasion, handling, other external factors, etc. In certain embodiments, gettering material is associated with (e.g., disposed on, over, under, adjacent, etc.) the device layers before the sealant is deposited over the defined area. In certain embodiments, gettering material is disposed over at least a portion of an exposed surface of the device layers. In certain embodiments, gettering material is disposed over at least a portion of the substrate between the substrate and the bottom device layer. In certain embodiments, the gettering material comprises a layer. In certain embodiments, the gettering material comprises moisture gettering material. In certain embodiments, the gettering material comprises oxygen gettering material. In certain embodiments, the gettering material comprises moisture and oxygen gettering material. In certain embodiments, the gettering material comprises a mixture of two or more gettering materials. In certain embodiments, the emissive layer is patterned. In certain embodiments, the emissive layer is unpatterned. In certain embodiments, the substrate is flexible.
In accordance with another aspect of the invention, there is provided a light- emitting device including a sealant dam around the perimeter or device layers on a substrate to form a defined area, and a flexible sealant covering the defined area and at least the uppermost surface of the sealant dam. In certain embodiments, gettering material is associated with (e.g., disposed on, over, under, adjacent, etc.) the device layers before the sealant is included. In certain embodiments, gettering material is disposed over at least a portion of an exposed surface of the device layers. In certain embodiments, gettering material is disposed over at least a portion of the substrate between the substrate and the bottom device layer. In certain embodiments, the gettering material comprises a layer. In certain embodiments, the gettering material comprises moisture gettering material. In certain embodiments, the gettering material comprises oxygen gettering material. In certain embodiments, the gettering material comprises moisture and oxygen gettering material. In certain embodiments, the gettering material comprises a mixture of two or more gettering materials. In certain embodiments, the light-emitting device comprises one of the devices taught herein. In certain embodiments, the emissive layer is patterned. In certain embodiments, the emissive layer is unpatterned. In certain embodiments, the substrate is flexible.
In accordance with another aspect of the invention, there is provided an array comprising two or more of one of the devices taught herein, wherein the devices are in electrical connection (e.g., direct or indirect). In certain preferred embodiments, the two or more devices are mounted on a flexible printed circuit board. In certain preferred embodiments, the two or more devices are electrically connected by way of the flexible printed circuit board. In certain embodiments, the flexible circuit board is further laminated to a surface.
In accordance with another aspect of the invention, there is provided a system including a light-emitting device taught herein and a sensor, wherein the sensor is in electrical connection (e.g., direct or indirect) with an electronic circuit which is also in electrical connection (e.g., direct or indirect) with the light-emitting device. In certain embodiments, the sensor is in close proximity to the light-emitting device.
In certain embodiments, the sensor comprises an optical sensor. In certain embodiments, the sensor comprises a temperature sensor. In certain embodiments, the sensor comprises a photoconductor. In certain embodiments, the sensor comprises a radio frequency sensor. In certain embodiments, the sensor comprises a capacitive sensor. In certain embodiments, the sensor is a color sensor. In certain embodiments, the sensor comprises a chemical sensor. In certain embodiments, the sensor comprises a biological sensor. In certain embodiments, the sensor comprises an acoustic sensor.
In certain embodiments, the sensor comprises more than one sensor.
In certain embodiments, the sensor comprises more than one type of sensor.
In certain embodiments, the sensor is on the same surface of the flexible substrate as the light-emitting device. In certain of such embodiments wherein the sensor is optically sensitive, the sensor can collect light from the same surface of the flexible substrate as the light-emitting device.
In certain embodiments, the sensor is on the opposite side of the substrate from the light-emitting device. In certain of such embodiments wherein the sensor is optically sensitive, the sensor can collect light from the opposite side of the substrate from the light- emitting device. In certain embodiments, the sensor is adjacent to the light-emitting device. In certain of such embodiments wherein the sensor is optically sensitive, the sensor collects light adjacent to the light-emitting device.
In certain embodiments, the sensor is located remotely from the light-emitting device, and communicates with the light-emitting device electronically. Such embodiment can be useful, for example, when an opaque body is located between the light-emitting device and the sensor.
In certain embodiments wherein the sensor is optically sensitive, the sensor includes a narrow-band optical filter. In certain embodiments, the sensor includes a wideband optical filter. In certain embodiments wherein the sensor is optically sensitive, the sensor may include more than one optical sensor, each of which can include a different optical filter that is either narrow- or wide-band to sense the color of the light being monitored. In certain embodiments, each optical sensor can includes the same optical filter, which can be narrow-band or wide-band to sense the color of the light being monitored. In certain embodiments, ambient light is being monitored.
In certain embodiments, the electronic circuit controls the brightness level of the light-emitting device. In certain embodiments, the electronic circuit controls the color of the light-emitting device. In certain embodiments, the electronic circuit controls both the brightness level and color of the light-emitting device.
In certain embodiments, the electronic circuit comprises an amplifier that controls light-emitting device brightness. In certain embodiments, the electronic circuit comprises one or more transistors. In certain embodiments, the electronic circuit comprises one or more passive elements such as a resistor, capacitor or inductor.
In certain embodiments, the system further includes a controller coupled to the light-emitting device and at least one sensor, the controller being configured to process information acquired by the sensor to control the light-emitting device to generate a light output with at least one predetermined characteristic. In certain embodiments, a predetermined characteristic can comprise color, brightness, or other light characteristic.
In certain embodiments, the system is associated with a product or other item. In certain embodiments, a system can be fixedly or removable mounted or attached to a product or other item.
In accordance with another aspect of the invention, there is provided a tile comprising one of the devices taught herein. In certain embodiments, the tile is flexible. In certain preferred embodiments, a tile comprises one or more of the devices taught herein mounted on a flexible printed circuit board. In certain preferred embodiments, the one or more devices are electrically connected by way of the flexible printed circuit board. In certain embodiments, the flexible circuit board is further laminated to a surface. Such tile can further be included in the above-described system.
In accordance with another aspect of the invention, there is provided an array comprising two or more of one of the tiles taught herein, wherein the tiles are in electrical connection. In certain embodiments, the array can be a two-dimensional array of such tiles. In certain embodiments, the array can be a one-dimensional array of such tiles. In certain embodiments, the array can be completely populated with tiles, e.g., the array of tiles is completely filled. In certain embodiments, the array can be incompletely filled with tiles and contiguous, the array can be incompletely filled with tiles and not contiguous.
Such array can further be included in the above-described system.
As used herein, "light" refers to electromagnetic radiation of any wavelength, whether visible or not.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention as claimed. Other embodiments will be apparent to those skilled in the art from consideration of the description and drawings, from the claims, and from practice of the invention disclosed herein.
Figure 1 schematically illustrates the cross-section of an example of an unpackaged light-emitting device structure useful in embodiments of the inventions taught herein.
Figure 2 displays an example of a functioning flexible, white light-emitting display tile embodiment of the invention operating at 9 Volts.
Figure 3 displays the spectra of the functional flexible, white light-emitting display tile example shown in Figure 2. Figure 4 schematically illustrates an example of an embodiment of the invention including device encapsulation using "dam and fill" technique described herein.
Figure 5 schematically illustrates an example of an embodiment of the invention including device encapsulation using a laminated back-side barrier film.
The attached figures are simplified representations presented for purposes of illustration only; the actual structures may differ in numerous respects, including, e.g., relative scale, etc.
FIG. 1 schematically depicts the cross-section of an example of an embodiment of a light-emitting device structure useful in various embodiments of the inventions taught herein. The depicted example is not packaged (e.g., is not encapsulated). The illustrated example includes a transparent flexible substrate. The depicted example includes a bottom light-emitting device architecture. In other embodiments in which the light is to be emitted from the top, the substrate may optionally be non-transparent.
In certain embodiments, a light-emitting device can further include a second flexible substrate over the device layers.
In certain embodiments, there is provided a flexible light-emitting device including: a flexible substrate, a first electrode disposed over a portion of the flexible substrate, an emissive layer comprising semiconductor nanocrystals disposed over the first electrode, and second electrode disposed over the emissive layer comprising semiconductor nanocrystals, wherein, when the device is curved, the emissive layer comprising semiconductor nanocrystals lies substantially in the neutral plane of the device.
Examples of suitable flexible substrate materials include, but are not limited to, polyethylene terephthalate (PET), polyethylene naphthalate (PEN) and polyethersulfone (PES), Flexible glass, polyetherketone (PEK), polycarbonate (PC), polypropylene (PP), polyamide (PA), polyacrylate (PAC), aliphatic cyclic polyolefin, and norbornene thermoplastic transparent resin. In certain embodiments, a flexible substrate can comprise a layered structure made of suitable flexible materials. Other suitable flexible substrate materials, transparent or non-transparent, can be readily ascertained by one of ordinary skill in the art. Examples of nontransparent, flexible substrates materials include, but are not limited to metal backed plastic substrates and polymide. A preferred substrate material is polyethylene terephthalate (PET) with an incorporated inorganic barrier layer such as such as an aluminum film (for example, AlON, AlN, or AlO), a carbon film (such as a DLC (diamond-like carbon) film), or a silicon nitride or silicon oxide film in a single- layer structure or a multilayer structure over a surface of the flexible substrate or over the surface and a rear surface thereof.
In the depicted example, a first electrode (shown as an anode comprising indium tin oxide (ITO)) is disposed over the substrate. Other suitable anode materials include, e.g., other high work function (e.g., greater than 4.0 eV) hole-injecting conductors. Examples include, but not limited to, tungsten, nickel, cobalt, platinum, palladium and their alloys, gallium indium tin oxide, zinc indium tin oxide, titanium nitride, polyaniline, or other high work function hole-injection conducting polymers.
ITO is an example of a preferred electrode material for a bottom light emitting device due to its light-transmisive properties. In addition to ITO, examples of other light- transmissive electrode materials include conducting polymers, and other metal oxides, low or high work function metals, conducting epoxy resins, or carbon nanotubes/polymer blends or hybrids that are at least partially light transmissive. An example of a conducting polymer that can be used as an electrode material is poly(ethlyendioxythiophene), sold by Bayer AG under the trade mark PEDOT. Other molecularly altered polythiophenes are also conducting and could be used, as well as emaraldine salt form of polyaniline.
A substrate including a first electrode (e.g., an anode) disposed thereon may be obtained or fabricated using any suitable technique. For example, commercially available transparent conducting films from Delta Technologies and TetoLight (Japan) are particularly well-suited for use in fabricating devices in accordance with the invention. Such commercially available films exhibit moderate flexure and show no visible cracking after device fabrication.
In certain embodiments, a light-emitting device can optionally include additional layers, e.g., charge transport layers, hole blocking layers, hole injection layers, etc. The depicted example shows optional charge transport layers over and under the emissive layer and also an optional hole blocking layer between the emissive layer and cathode.
The emissive layer includes semiconductor nanocrystals.
The emissive layer can comprise one or more separate layers. In certain other embodiments, the emissive material can be included in a layer comprising a matrix material.
In certain embodiments, semiconductor nanocrystals included in the emissive layer can be excited by electrical excitation to generate light (electroluminescent (EL) mode). In certain other embodiments, the emissive layer may include semiconductor nanocrystals and a second light-emitting material (including, for example, but not limited to, a light- emitting polymer (e.g., an organic light-emitting polymer such as those used in fabricating organic light emitting devices (OLEDs), a light emitting small organic molecule composition, or other light-emitting material (organic or inorganic)), wherein the second light emitting material generates light upon electrical excitation. The light generated by the second light emitting material can then optically excite the semiconductor nanocrystals to generate light (photoluminescent (PL) mode) of a predetermined wavelength, which is preferably different from the wavelength generated by the second light-emitting material. For example, when a blue emitting organic light emitting polymer (e.g., Lumation BP105 and Lumation BP361 polymer material from Sumation Co., Ltd.) is used, a full or partial layer of semiconductor nanocrystals can be disposed thereover to convert at least a portion of the blue light to light of a predetermined color. In certain embodiments, the emissive layer can comprise a full or partial layer of semiconductor nanocrystals. Such layer can be patterned or unpatterned. In certain embodiments, the pattern comprises an arrangement which permits converted and unconverted light to be emitted. In certain embodiments, the semiconductor nanocrystals can be dispersed in the second light-emitting material. In certain embodiments, a charge transport material can comprise the second light-emitting material.
Preferably the semiconductor nanocrystals comprise a substantially monodisperse population of nanocrystals. An emissive layer comprising semiconductor nanocrystals can be included in a device by spin-casting a dispersion including semiconductor nanocrystals and a volatilizable liquid on an layer of the device. Other techniques, including, but not limited to, e.g., phase separation, drop-casting, Langmuir-Blodgett techniques, contact printing, screen-printing, and other techniques known or readily identified by one skilled in the relevant art, may also be used for forming the emissive layer in the device. Examples of semiconductor nanocrystals and other related information are included below.
Other optional layers (e.g., charge transport layer (e.g., comprising a material capable of transporting holes or electrons), hole blocking layers, hole injection layers, etc.) may be deposited using any suitable technique. Examples of such layers and materials that can be included therein are discussed below. In certain embodiments, layers can be patterned. In certain embodiments, layers can be unpatterned.
In certain embodiments, layers can be disposed over a predetermined region of the substrate.
The second electrode can be, for example, a cathode comprising a low work function (e.g., less than 4.0 eV), electron-injecting, metal, such as Al, Ba, Yb, Ca, a lithium-aluminum alloy (Li:Al), a magnesium-silver alloy (Mg:Ag), or lithium fluoride - aluminum (LiFrAl). The second electrode, such as Mg:Ag, can optionally be covered with an opaque protective metal layer, for example, a layer of Ag for protecting the cathode layer from atmospheric oxidation, or a relatively thin layer of substantially transparent ITO. The second electrode can be sandwiched, sputtered, or evaporated onto the exposed surface of the solid layer.
Non-polymeric electrode materials can be deposited by, for example, sputtering or evaporating. Polymeric electrode materials can be deposited by, for example, spin- casting.
One or both of the electrodes can be patterned. Electrode material, including light- transmittable electrode material, can be patterned by, for example, a chemical etching method such as a photolithography or a physical etching method using laser, etc. Also, the electrode may be patterned by vacuum vapor deposition, sputtering, etc. while masking.
The electrodes of the device can be connected to a voltage source by electrically conductive pathways. Upon application of the voltage, light is generated from the device. In certain embodiments, the first electrode may be patterned. In certain embodiments, a blanket first electrode may be used. In certain embodiments, the second electrode may be patterned. In certain embodiments, a blanket second electrode may be used.
In a device structure such as that shown in FIG. 1, for example, the first electrode can have a thickness of about 500 Angstroms to 4000 Angstroms. The first optional charge transport layer can have a thickness of about 50 Angstroms to about 1000 Angstroms. The second optional charge transport layer can have a thickness of about 50 Angstroms to about 1000 Angstroms. The second electrode can have a thickness of about 5 Angstroms to greater than about 10,000 Angstroms.
As discussed above, in the example shown in FIG. 1, light is emitted from the bottom of the structure. If an adequately light transmissive top electrode is used, the structure could emit light from the top of the structure.
Alternatively, the structure of FIG. 1 can be inverted, in which case light can be emitted from the top.
In certain embodiments in which the substrate and all other device materials are transparent, the light-emitting device can be transparent.
Functional light-emitting devices may be achieved by combining the various layers described in different ways, or layers may 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 of the examples provided herein describe various layers as comprising a single material, it is understood that combinations of materials, such as a mixture of host and dopant, or more generally a mixture, may be used. Also, the layers may have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. Optionally, one or more of the layers can be patterned. For example, patterned layers (other than the emissive layer) can be deposited by vapor deposition using shadow masks or other masking techniques.
Optionally a desiccant or other moisture absorptive material and/or other moisture and/or oxygen gettering material can be included in the device before it is sealed, e.g., with an epoxy, such as a UV curable expoxy. Desiccants or moisture absorptive materials and other moisture and/or oxygen gettering materials suitable for inclusion in a device can be readily identified by one of ordinary skill in the relevant art.
In certain embodiments, for example, a flexible light-emitting device comprises a an emissive layer comprising semiconductor nanocrystals disposed between a first electrode and a second electrode, supported by a flexible substrate, wherein the emissive material comprises semiconductor nanocrystals capable of emitting light of a predetermined wavelength, wherein, when the device is curved, the emissive layer comprising semiconductor nanocrystals lies substantially in the neutral plane of the device. In certain embodiments of a flexible light-emitting device in accordance with certain aspects of the invention, the moduli of the various components or parts of the device are such that, when the device is curved, the neutral axis or neutral plane (i.e., the axis or plane in which no compression or tension exists) lies substantially in the plane of the emissive layer. In certain embodiments, the neutral axis or neutral plane does not deviate from the plane of the emissive layer by more than about 25 percent. In certain embodiments, the neutral axis or neutral plane does not deviate from the plane of the emissive layer by more than about 20 percent. In certain embodiments, the neutral axis or neutral plane does not deviate from the plane of the emissive layer by more than about 15 percent. In certain embodiments, the neutral axis or neutral plane does not deviate from the plane of the emissive layer by more than about 10 percent. In certain embodiments, the neutral axis or neutral plane does not deviate from the plane of the emissive layer by more than about 5 percent. In certain embodiments, the neutral axis or neutral plane does not deviate from the plane of the emissive layer by more than about 1 percent.
In certain embodiments, a device can further includes a third electrode layer disposed on the outside surface of a flexible substrate making electrical contact with either or both interior electrodes through a substrate via or external connection.
The color of the light output of a light-emitting device can be precisely controlled by the selection of the composition, structure, and size of the various semiconductor nanocrystals included in the emissive layer. In certain embodiments, two or more different semiconductor nanocrystals (having different compositions, structures, and/or sizes) can be included.
Light-emitting devices in accordance with embodiments of the invention may be incorporated into a wide variety of products or associated with a wide variety of items, including, but not limited to, large area displays, billboards, lights for interior or exterior illumination and/or signaling, heads up displays, fully transparent displays, a large area wall, theater or stadium screen, sign, ceilings, or other surfaces (e.g., and without limitation, vehicles (such as cars, aircraft, etc.), buildings, etc.) and other objects. Various control mechanisms may be used to control devices fabricated in accordance with the present invention, including passive matrix and active matrix.
A flexible substrate can be opaque, light transmissive, or transparent. In certain embodiments, a flexible substrate can comprise, for example, and without limitation, flexible plastic, metal foil, fiberglass, or semiconductor (e.g., silicon). In some applications, the substrate can include a backplane. Most preferably, the backplane is flexible. The backplane includes active or passive electronics for controlling or switching power to individual pixels or light-emitting devices. Including a backplane can be useful for applications such as displays, sensors, or imagers. In particular, the backplane can be configured as an active matrix, passive matrix, fixed format, direct drive, or hybrid. The display can be configured for still images, moving images, or lighting. A display including an array of light emitting devices can provide white light, monochrome light, or color-tunable light.
Preferably, a light-emitting device including an emissive material comprising a plurality of semiconductor nanocrystals is processed in a controlled (oxygen-free and moisture-free) environment, preventing the quenching of luminescent efficiency during the fabrication process.
In another embodiment, a light-emitting device includes a sealant dam around the perimeter or device layers on a substrate to form a defined area, and a flexible sealant covering the defined area and at least the uppermost surface of the sealant dam. In certain embodiments, gettering material is associated with (e.g., disposed on, over, under, adjacent, etc.) the device layers before the sealant is included. In certain embodiments, gettering material is disposed over at least a portion of an exposed surface of the device layers. In certain embodiments, gettering material is disposed over at least a portion of the substrate between the substrate and the bottom device layer. In certain embodiments, the gettering material comprises a layer. In certain embodiments, the gettering material comprises moisture gettering material. In certain embodiments, the gettering material comprises oxygen gettering material. In certain embodiments, the gettering material comprises moisture and oxygen gettering material. In certain embodiments, the gettering material comprises a mixture of two or more gettering materials. In certain embodiments, the light-emitting device comprises one of the devices taught herein. In certain embodiments, the substrate is flexible.
FIG. 4 depicts an example of an embodiment of a flexible light-emitting device of the invention including a sealant dam around the perimeter of device layers on a flexible substrate to form a defined area. In the depicted example, a flexible sealant covers the defined area and at least the uppermost surface of the sealant dam.
In certain embodiments, such light-emitting device can be prepared by a method comprising forming a sealant dam around the perimeter of device layers on a substrate to form a defined area, depositing a flexible sealant over the defined area, and disposing a protective layer over at least the uppermost surface of the sealant dam and sealant. In certain embodiments, the protective layer provides mechanical protection, e.g., against abrasion, handling, other external factors, etc. In certain embodiments, gettering material is associated with (e.g., disposed on, over, under, adjacent, etc.) the device layers before the sealant is deposited over the defined area. In certain embodiments, gettering material is disposed over at least a portion of an exposed surface of the device layers. In certain embodiments, gettering material is disposed over at least a portion of the substrate between the substrate and the bottom device layer. In certain embodiments, the gettering material comprises a layer. In certain embodiments, the gettering material comprises moisture gettering material. In certain embodiments, the gettering material comprises oxygen gettering material. In certain embodiments, the gettering material comprises moisture and oxygen gettering material. In certain embodiments, the gettering material comprises a mixture of two or more gettering materials. In certain embodiments, the substrate is flexible.
In a preferred embodiment, a "dam and fill" technique includes first printing a patterned dam of semi-rigid epoxy around the display perimeter to be sealed and then coats or prints a flexible sealant to fill the defined area.
A sealant dam preferably comprises a UV- or thermally-activated resin material. Sealants preferably comprising at least one material from a group consisting of photoresist, spin-on glass, polyimide, polybenzoxazole, polyglutarimide, benzocyclobutene, polyethylene, polystyrene, polypropylene, silicon nitride and aluminum oxide. Examples of adhesives and resins that may be useful in various aspect and embodiments of the inventions taught herein include Advanced UV adhesive UV Resin T- 470/UR7117LV, UV Resin T-470/UR7117SLV, and UV Resin XNR5516ZHV, available from Nagase ChemteX Corporation, electronics & Structural Materials Department, Hyogo, Japan.
In certain embodiments of the light-emitting devices taught herein, the entire back of a light-emitting device/substrate assembly can optionally be coated with a metallization vapor barrier to further protect the device layers. Examples of such barriers include, for example, commercial OLED encapsulants from companies such as Nagase Chemtex and Epoxy Technology as well as development-grade materials from National Starch. In another embodiment, a light-emitting device comprises a layer of flexible sealant disposed over exposed (e.g., top and side) surfaces of device layers disposed on surface of a substrate, and a protective layer disposed over the sealant. In certain embodiments, the layer of flexible sealant and/or protective layer also covers a portion of the substrate surface not covered by the device layers. In certain embodiments, the layer of flexible sealant and/or protective layer comprises a continuous layer over the exposed surfaces of the device layers and the portion of the substrate surface not covered by the device layers. In certain embodiments, the protective layer provides mechanical protection, e.g., against abrasion, handling, other external factors, etc. In certain embodiments, gettering material is associated with (e.g., disposed on, over, under, adjacent, etc.) the device layers before the sealant is disposed over the device layers. In certain embodiments, gettering material is disposed over at least a portion of an exposed surface of the device layers. In certain embodiments, gettering material is disposed over at least a portion of the substrate between the bottom device layer and the substrate. In certain embodiments, the gettering material comprises a layer. In certain embodiments, the gettering material comprises moisture gettering material. In certain embodiments, the gettering material comprises oxygen gettering material. In certain embodiments, the gettering material comprises moisture and oxygen gettering material. In certain embodiments, the gettering material comprises a mixture of two or more gettering materials. In certain embodiments, the light-emitting device comprises one of the devices taught herein. In certain embodiments, the substrate is flexible.
In certain embodiments, such device can be prepared by a method comprising depositing a layer of flexible sealant over exposed (e.g., top and side) surfaces of device layers disposed on a surface of a substrate, and disposing a protective layer over the sealant. In certain embodiments, the layer of flexible sealant and/or protective layer also covers a portion of the substrate surface not covered by the device layers. In certain embodiments, the layer of flexible sealant and/or protective layer comprises a continuous layer over the exposed surfaces of the device layers and the portion of the substrate surface not covered by the device layers. In certain embodiments, the protective layer provides mechanical protection, e.g., against abrasion, handling, other external factors, etc. In certain embodiments, gettering material is associated with (e.g., disposed on, over, under, adjacent, etc.) the device layers before the sealant is disposed over the device layers. In certain embodiments, gettering material is disposed over at least a portion of an exposed surface of the device layers. In certain embodiments, gettering material is disposed over at least a portion of the substrate between the bottom device layer and the substrate. In certain embodiments, the gettering material comprises a layer. In certain embodiments, the gettering material comprises moisture gettering material. In certain embodiments, the gettering material comprises oxygen gettering material. In certain embodiments, the gettering material comprises moisture and oxygen gettering material. In certain embodiments, the gettering material comprises a mixture of two or more gettering materials. In certain embodiments, the substrate is flexible.
FIG. 5 depicts an example of an embodiment of a device including a flexible sealant disposed over exposed (e.g., top and side) surfaces of device layers disposed on surface of a flexible substrate, and a protective layer disposed over the sealant.
In the example depicted in FIG. 5, a flexible barrier film such as Vitex' Barix film or a thin metal film is further laminated to the back side of a flexible light-emitting device assembly using a flexible sealant. Preferably, an air tight seal is achieved. For this package design, an additional encapsulant may be desired or required along the perimeter of the assembly to reduce gas permeation from the edges.
Examples of suitable flexible sealants include, but are not limited to, adhesives, such as a UV-curable epoxy and heat curable epoxies or acrylates. Other materials, techniques, methods, applications, and information that may be useful with the present invention are described in U.S. Patent No. 7,255,823, issued August 14, 2007, to Guenther, et al., for "Encapsulation For OLED Devices", the disclosure of which is hereby incorporated herein by reference in its entirety. The present invention will be further clarified by the following examples, which are intended to be exemplary of the present invention.
EXAMPLE Quantum Dot Device Fabricated on Flexible Substrate
A Flexible QD-LED was fabricated as follows:
A flexible substrate (50 mm x 50 mm) with patterned indium tin oxide (ITO, 100 Ω/sq.) electrode on one surface (obtained from Delta Tech) is cleaned in an oxygen plasma for about 30 seconds to remove contaminants and oxygenate the surface. The cleaning takes place in 100% oxygen under vacuum (0.1 - 1.5 torr). The substrate is placed on a water cooled plate to help control the increase in temperature during cleaning.
A layer of hole injection material (PEDOT, obtained from H.C. Starck, GmbH) (HIL) is spun onto the surface of the flexible substrate including the patterned electrode at a speed of 4000 RPM, to a thickness of about 750 Angstroms. This step is carried out under ambient conditions (i.e., not in a glove box). The PEDOT coated substrate is then heated on a 12O0C hot plate in a chamber (< 20 ppm water & < 10 ppm oxygen), in a HEPA filter environment (approx. Class 1), in a nitrogen atmosphere for > 20 minutes to dry the PEDOT. The PEDOT coated substrate is then allowed to cool to room temperature.
A mixture of hole transport material (N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)- spiro (spiro-TPD) (OLED grade, gradient sublimation purified) from Luminescent Technologies, Taiwan)) and Quantum Dots (a mixture of Red: CdSe/CdZnS (octadecylphosphonic acid (ODPA) and decylamine) and Green: CdZnSe/CdZnS (hexylphosphonic acid (HPA)) is created in Toluene (Sigma Aldrich, 99.8% anhydrous). (Red and green-emitting semiconductor nanocrystals are blended together such that when their emission is combined with blue emission from the underlying organic layer, the light output of the device appears white. In this device, the semiconductor nanocrystals are operating in EL mode.) The concentration of spiro-TPD in solution is 10mg/ml, the ratio of Red to Green quantum dots is 1 :2, and the optical densities in solvent/HTL are 0.0015 and 0.003 at first peak for red and green respectively. This material is then spun-coat on the flexible substrate at a speed of 3000 RPM, forming a layer approximately 55nm thick, which phase separates upon drying to form a distinct layer of HTL (~50nm) below a distinct layer of QDs (~5nm). This layer is then baked on a hot plate at 50C for 15 minutes before being loaded into a vacuum chamber (an AMOD chamber, obtained from Angstrom Engineering, Ottawa, Canada) for thermal deposition after the chamber is pumped down to 10"6 torr or better. (In the figures, spiro-TPD is referred to as E 105.) (The Red and Green semiconductor nanocrystals were prepared by methods similar to those described in International Application No. PCT/US2007/013152, filed 06/04/2007, of Coe-Sullivan, et al., for "Light-Emitting Devices And Displays With Improved Performance", the disclosure of which is hereby incorporated herein by reference in its entirey.) A layer of 2,2',2"-(l,3,5-Benzinetriyl)-tris(l-phenyl-l-H-benziniidazole) (TPBi) (OLED grade, gradient sublimation purified) from Luminescent Technologies, Taiwan) is deposited.
Each of the vapor deposited layers is patterned with use of shadow masks. After deposition of the electron transport material layer, the mask is changed before deposition of the metal cathode, which consists of 5 A of LiF followed by IOOOA of Al.
The details of the materials and layer thickness for the flexible QD-LED of this Example are set forth below in Table 1 :
Flexible Vacuum Thickness
OD-LED (torr) Material ("Angstroms)
HIL 0.1-1.5 PEDOT 75θA
HTL 1 Atm E105 5OθA
QD 1 Atm Nanocrystals 50-lOθA
ETL <10"6 TPBi 5OθA
CATHODE <10"6 LiF 5A
LAYER <10"6 Al ioooA
FIG. 2 illustrates an example of an embodiment of a device in accordance with the present invention. The device depicted in FIG. 2 is a functional unpackaged, flexible, white light-emitting light emitting display tile including semiconductor nanocrystals. The tile has an overall substrate dimension is 50 x 50 mm with an optically active area of 34 x 34 mm. Table 2 below summarizes the performance data for two devices. The color coordinates were within 9% and 18% percent of the X and Y target specifications, respectively. The EL spectrum of the device shown in FIG. 2 is given in FIG. 3. As mentioned above, in this device, green and red quantum semiconductor nanocrystal (also referred to herein as "quantum dot" or "QD") EL emissions along with blue organic emission provide the white color. In certain embodiments blue-emitting semiconductor nanocrystals may be employed to generate the blue emission to improve the color coordinates.
Table 2. Performance data for flexible, white QD-LED display tile
As discussed above, devices of the invention can be tiled into a large array or display. In a tiled display, additional interconnects can be printed or patterned after QD-LED deposition, before or after encapsulation. Alternatively, interconnects can be patterned prior to the thin film deposition of the transparent conductor and the QD-LED device.
In accordance with another embodiment of the invention, there is provided a system including one or more light-emitting devices or an array of devices taught herein and a sensor, wherein the sensor is in electrical connection with an electronic circuit which is also in electrical connection with the light-emitting device(s). In certain embodiments, the sensor is in close proximity to the light-emitting device. In certain embodiments, the system includes one or more tiles or an array of tiles taught herein and a sensor, wherein the sensor is in electrical connection with an electronic circuit which is also in electrical connection with the tile(s)
In certain embodiments, the sensor comprises an optical sensor. In certain embodiments, the sensor comprises a temperature sensor. In certain embodiments, the sensor comprises a photoconductor. In certain embodiments, the sensor comprises a radio frequency sensor. In certain embodiments, the sensor comprises a capacitive sensor. In certain embodiments, the sensor is a color sensor. In certain embodiments, the sensor comprises a chemical sensor. In certain embodiments, the sensor comprises a biological sensor. In certain embodiments, the sensor comprises an acoustic sensor. In certain embodiments, the sensor comprises more than one sensor.
In certain embodiments, the sensor is on the opposite side of the substrate from the light-emitting device. In certain of such embodiments wherein the sensor is optically sensitive, the sensor can collect light from the opposite side of the substrate from the light- emitting device.
In certain embodiments, the sensor is adjacent to the light-emitting device. In certain of such embodiments wherein the sensor is optically sensitive, the sensor collects light adjacent to the light-emitting device.
In certain embodiments wherein the sensor is optically sensitive, the sensor includes a narrow-band optical filter. In certain embodiments, the sensor includes a wideband optical filter. In certain embodiments wherein the sensor is optically sensitive, the sensor may include more than one optical sensor, each of which can include a different optical filter that is either narrow-band or wide-band to sense the color of the light being monitored. In certain embodiments, each optical sensor can includes the same optical filter, which can be narrow-band or wide-band to sense the color of the light being monitored. In certain embodiments, ambient light is being monitored.
In certain embodiments, the system further includes a controller coupled to the light-emitting device and at least one sensor, the controller being configured to process information acquired by the at least one sensor to control the light-emitting device to generate a light output with a predetermined characteristic. In certain embodiments, a predetermined characteristic can comprise color, brightness, or other light characteristic.
The above-described system can be incorporated into a wide variety of products or associated with a wide variety of items, including, but not limited to, large area displays, billboards, lights for interior or exterior illumination and/or signaling, heads up displays, fully transparent displays, a large area wall, theater or stadium screen, sign, ceilings, or other surfaces (e.g., and without limitation, vehicles (such as cars, aircraft, etc.), buildings, etc.) and other objects. Various control mechanisms may be used to control devices fabricated in accordance with the present invention, including passive matrix and active matrix.
Other materials, techniques, methods, applications, and information that may be useful with the system of the present invention are described in U.S. Patent No. 7,132,635 of Dowling, granted 7 November 2006; U.S. Patent No. 7,199,344 of Blake, granted 3 April 2007; and U.S. Patent No. 6,459,076 of Schlenker, granted 1 October 2002, each of foregoing being hereby incorporated herein by reference in its entirety.
Semiconductor nanocrystals include, for example, inorganic crystallites between about 1 ran and about 1000 nm in diameter. In certain embodiments the diameter is from about 2 nm and about 50 nm. In certain embodiments, the diameter is from about 5 nm to about 20 nm (such as about 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 nm).
The semiconductor forming the semiconductor nanocrystals can comprise a Group IV element, a Group II-VI compound, a Group H-V compound, a Group III-VI compound, a Group III-V compound, a Group IV-VI compound, a Group I-III-VI compound, a Group II-IV-VI compound, a Group II-IV-V compound, an alloy including any of the foregoing, and/or a mixture including any of the foregoing, including ternary and quaternary mixtures or alloys. A non-limiting list of examples include ZnO, ZnS, ZnSe, ZnTe, CdO, CdS, CdSe, CdTe, MgS, MgSe, GaAs, GaN, GaP, GaSe, GaSb, HgO, HgS, HgSe, HgTe, InAs, InN, InP, InSb, AlAs, AlN, AlP, AlSb, TIN, TIP, TlAs, TlSb, PbO, PbS, PbSe, PbTe, Ge, Si, an alloy including any of the foregoing, and/or a mixture including any of the foregoing, including ternary and quaternary mixtures or alloys.
Examples of the shape of the semiconductor nanocrystals include sphere, rod, disk, other shape or mixtures thereof.
Preferably, the semiconductor nanocrystals include a "core" of one or more first semiconductor materials, which may be surrounded by an overcoating or "shell" of one or more second semiconductor materials. A semiconductor nanocrystal core surrounded by a semiconductor shell is also referred to as a "core/shell" semiconductor nanocrystal.
For example, the semiconductor nanocrystal can include a core having the formula MX, where M is cadmium, zinc, magnesium, mercury, aluminum, gallium, indium, thallium, or mixtures thereof, and X is oxygen, sulfur, selenium, tellurium, nitrogen, phosphorus, arsenic, antimony, or mixtures thereof. Examples of materials suitable for use as semiconductor nanocrystal cores include, but are not limited to, ZnO, ZnS, ZnSe, ZnTe, CdO, CdS, CdSe, CdTe, MgS, MgSe, GaAs, GaN, GaP, GaSe, GaSb, HgO, HgS, HgSe, HgTe, InAs, InN, InP, InSb, AlAs, AlN, AlP, AlSb, TIN, TIP, TlAs, TlSb, PbO, PbS, PbSe, PbTe, Ge, Si, an alloy including any of the foregoing, and/or a mixture including any of the foregoing, including ternary and quaternary mixtures or alloys.
The shell can be a semiconductor material having a composition that is the same as or different from the composition of the core. The shell comprises an overcoat of a semiconductor material on a surface of the core semiconductor nanocrystal can include a Group IV element, a Group H-VI compound, a Group H-V compound, a Group III-VI compound, a Group III-V compound, a Group IV-VI compound, a Group I-III-VI compound, a Group II-IV-VI compound, a Group II-IV-V compound, alloys including any of the foregoing, and/or mixtures including any of the foregoing, including ternary and quaternary mixtures or alloys. Examples include, but are not limited to, ZnO, ZnS, ZnSe, ZnTe, CdO, CdS, CdSe, CdTe, MgS, MgSe, GaAs, GaN, GaP, GaSe, GaSb, HgO, HgS, HgSe, HgTe, InAs, InN, InP, InSb, AlAs, AlN, AlP, AlSb, TIN, TIP, TlAs, TlSb, PbO, PbS, PbSe, PbTe, Ge, Si, an alloy including any of the foregoing, and/or a mixture including any of the foregoing. For example, ZnS, ZnSe or CdS overcoatings can be grown on CdSe or CdTe semiconductor nanocrystals. An overcoating process is described, for example, in U.S. Patent 6,322,901. By adjusting the temperature of the reaction mixture during overcoating and monitoring the absorption spectrum of the core, over coated materials having high emission quantum efficiencies and narrow size distributions can be obtained. An overcoating may comprise one or more layers. An overcoating may comprise at least one semiconductor material which is the same as or different from the composition of the core. Preferably, an overcoating has a thickness from about one to about ten monolayers. An overcoating can also have a thickness greater than ten monolayers. In certain embodiments, more than one overcoating can be included on a core. In certain embodiments, the surrounding "shell" material can have a band gap greater than the band gap of the core material. In certain other embodiments, the surrounding shell material can have a band gap less than the band gap of the core material.
In certain embodiments, the shell can be chosen so as to have an atomic spacing close to that of the "core" substrate. In certain other embodiments, the shell and core materials can have the same crystal structure.
Examples of semiconductor nanocrystal (core)shell materials include, without limitation: red (e.g., (CdSe)ZnS (core)shell), green (e.g., (CdZnSe)CdZnS (core)shell, etc.), and blue (e.g., (CdS)CdZnS (core)shell.
Additional examples of core/shell semiconductor structures are described in U.S. Published Patent Application No. US 2004-0023010 Al, for "Light Emitting Device Including Semiconductor Nanocrystals" of Bulovic et al. The foregoing application is hereby incorporated herein by reference in its entirety.
Preparation and manipulation of semiconductor nanocrystals are described, for example, in U.S. Patent 6,322,901 and 6,576,291, and U.S. Patent Application No. 60/550,314, each of which is hereby incorporated herein by reference in its entirety. One example of a method of manufacturing a semiconductor nanocrystal is a colloidal growth process. Colloidal growth occurs by injection an M donor and an X donor into a hot coordinating solvent. One example of a preferred method for preparing monodisperse semiconductor nanocrystals comprises pyrolysis of organometallic reagents, such as dimethyl cadmium, injected into a hot, coordinating solvent. This permits discrete nucleation and results in the controlled growth of macroscopic quantities of semiconductor nanocrystals. The injection produces a nucleus that can be grown in a controlled manner to form a semiconductor nanocrystal. The reaction mixture can be gently heated to grow and anneal the semiconductor nanocrystal. Both the average size and the size distribution of the semiconductor nanocrystals in a sample are dependent on the growth temperature. The growth temperature necessary to maintain steady growth increases with increasing average crystal size. The semiconductor nanocrystal is a member of a population of semiconductor nanocrystals. As a result of the discrete nucleation and controlled growth, the population of semiconductor nanocrystals that can be obtained has a narrow, monodisperse distribution of diameters. The monodisperse distribution of diameters can also be referred to as a size. Preferably, a monodisperse population of particles includes a population of particles wherein at least about 60% of the particles in the population fall within a specified particle size range. A population of monodisperse particles preferably deviate less than 15% rms (root-mean-square) in diameter and more preferably less than 10% rms and most preferably less than 5%.
In certain embodiments, the preparation of semiconductor nanocrystals can be carried out in the presence of an amine. See, for example, U.S. Patent No. 6,576,291 for "Preparation of Nanocrsytallites" of Bawendi et al. issued 10 June 2003, which is hereby incorporated herein by reference in its entirety.
Alternatively, semiconductor nanocrystals can be prepared in a non-coordinating solvent.
The narrow size distribution of the semiconductor nanocrystals allows the possibility of light emission in narrow spectral widths. Monodisperse semiconductor nanocrystals have been described in detail in Murray et al. (J. Am. Chem. Soc, 115:8706 (1993)); in the thesis of Christopher Murray, "Synthesis and Characterization of II-VI Quantum Dots and Their Assembly into 3-D Quantum Dot Superlattices", Massachusetts Institute of Technology, September, 1995; and in U.S. Patent Application No. 08/969,302 for "Highly Luminescent Color-Selective Materials". The foregoing are hereby incorporated herein by reference in their entireties.
In processes involving a coordinating solvent, the process of controlled growth and annealing of the semiconductor nanocrystals in the coordinating solvent that follows nucleation can also result in uniform surface derivatization and regular core structures. As the size distribution sharpens, the temperature can be raised to maintain steady growth. By adding more M donor or X donor, the growth period can be shortened. The M donor can be an inorganic compound, an organometallic compound, or elemental metal. M is cadmium, zinc, magnesium, mercury, aluminum, gallium, indium or thallium. The X donor is a compound capable of reacting with the M donor to form a material with the general formula MX. The X donor can be a chalcogenide donor or a pnictide donor, such as a phosphine chalcogenide, a bis(silyl) chalcogenide, dioxygen, an ammonium salt, or a tris(silyl) pnictide. Suitable X donors include dioxygen, bis(trimethylsilyl) selenide ((TMS)2Se), trialkyl phosphine selenides such as (tri-noctylphosphine) selenide (TOPSe) or (tri-n-butylphosphine) selenide (TBPSe), trialkyl phosphine tellurides such as (tri-noctylphosphine) telluride (TOPTe) or hexapropylphosphorustriamide telluride (HPPTTe), bis(trimethylsilyl)telluride ((TMS)2Te), bis(trimethylsilyl)sulfide ((TMS)2S), a trialkyl phosphine sulfide such as (tri-noctylphosphine) sulfide (TOPS), an ammonium salt such as an ammonium halide (e.g., NH4C1), tris(trimethylsilyl) phosphide ((TMS)3P), tris(trimethylsilyl) arsenide ((TMS)3As), or tris(trimethylsilyl) antimonide ((TMS)3Sb). In certain embodiments, the M donor and the X donor can be moieties within the same molecule.
A coordinating solvent can help control the growth of the semiconductor nanocrystal. The coordinating solvent is a compound having a donor lone pair that, for example, has a lone electron pair available to coordinate to a surface of the growing semiconductor nanocrystal. Solvent coordination can stabilize the growing semiconductor nanocrystal. Examples of coordinating solvents include alkyl phosphines, alkyl phosphine oxides, alkyl phosphonic acids, or alkyl phosphinic acids, however, other coordinating solvents, such as pyridines, furans, and amines may also be suitable for the semiconductor nanocrystal production. Additional examples of suitable coordinating solvents include pyridine, tri-n-octyl phosphine (TOP), tri-n-octyl phosphine oxide (TOPO) and trishydroxylpropylphosphine (tHPP), tributylphosphine, tri(dodecyl)phosphine, dibutyl- phosphite, tributyl phosphite, trioctadecyl phosphite, trilauryl phosphite, tris(tridecyl) phosphite, triisodecyl phosphite, bis(2-ethylhexyl)phosphate, tris(tridecyl) phosphate, hexadecylamine, oleylamine, octadecylamine, bis(2-ethylhexyl)amine, octylamine, dioctylamine, trioctylamine, dodecylamine/laurylamine, didodecylamine tridodecylamine, hexadecylamine, dioctadecylamine, trioctadecylamine, phenylphosphonic acid, hexylphosphonic acid, tetradecylphosphonic acid, octylphosphonic acid, octadecylphosphonic acid, propylenediphosphonic acid, phenylphosphonic acid, aminohexylphosphonic acid, dioctyl ether, diphenyl ether, methyl myristate, octyl octanoate, and hexyl octanoate. In certain embodiments, technical grade TOPO can be used.
Size distribution during the growth stage of the reaction can be estimated by monitoring the absorption or emission line widths of the particles. Modification of the reaction temperature in response to changes in the absorption spectrum of the particles allows the maintenance of a sharp particle size distribution during growth. Reactants can be added to the nucleation solution during crystal growth to grow larger crystals. For example, for CdSe and CdTe, by stopping growth at a particular semiconductor nanocrystal average diameter and choosing the proper composition of the semiconducting material, the emission spectra of the semiconductor nanocrystals can be tuned continuously over the wavelength range of 300 ran to 5 microns, or from 400 ran to 800 nra.
The particle size distribution of the semiconductor nanocrystals can be further refined by size selective precipitation with a poor solvent for the semiconductor nanocrystals, such as methanol/butanol as described in U.S. Patent 6,322,901. For example, semiconductor nanocrystals can be dispersed in a solution of 10% butanol in hexane. Methanol can be added dropwise to this stirring solution until opalescence persists. Separation of supernatant and flocculate by centrifugation produces a precipitate enriched with the largest crystallites in the sample. This procedure can be repeated until no further sharpening of the optical absorption spectrum is noted. Size-selective precipitation can be carried out in a variety of solvent/nonsolvent pairs, including pyridine/hexane and chloroform/methanol. The size-selected semiconductor nanocrystal population preferably has no more than a 15% rms deviation from mean diameter, more preferably 10% rms deviation or less, and most preferably 5% rms deviation or less.
As discussed herein, semiconductor nanocrystals preferably have ligands attached thereto.
In certain embodiment, the ligands can be derived from the coordinating solvent used during the growth process. The surface can be modified by repeated exposure to an excess of a competing coordinating group to form an overlayer. For example, a dispersion of the capped semiconductor nanocrystal can be treated with a coordinating organic compound, such as pyridine, to produce crystallites which disperse readily in pyridine, methanol, and aromatics but no longer disperse in aliphatic solvents. Such a surface exchange process can be carried out with any compound capable of coordinating to or bonding with the outer surface of the semiconductor nanocrystal, including, for example, phosphines, thiols, amines and phosphates. The semiconductor nanocrystal can be exposed to short chain polymers which exhibit an affinity for the surface and which terminate in a moiety having an affinity for a liquid medium in which the semiconductor nanocrystal is suspended or dispersed. Such affinity improves the stability of the suspension and discourages flocculation of the semiconductor nanocrystal.
Organic ligands can be useful in facilitating large area, non-epitaxial deposition of highly stable inorganic nanocrystals within a device.
In certain embodiments, a coordinating ligand can have the formula:
(Y-) k-n -( XM-L)n wherein k is 2, 3 4, or 5, and n is 1, 2, 3, 4 or 5 such that k-n is not less than zero; X is O, O-S, O-Se, O-N, O-P, O-As, S, S=O, SO2, Se, Se=O, N, N=O, P, P=O, C=O As, or As=O; each of Y and L, independently, is H, OH, aryl, heteroaryl, or a straight or branched C2-18 hydrocarbon chain optionally containing at least one double bond, at least one triple bond, or at least one double bond and one triple bond. The hydrocarbon chain can be optionally substituted with one or more C 1-4 alkyl, C2-4 alkenyl, C2-4 alkynyl, C 1-4 alkoxy, hydroxyl, halo, amino, nitro, cyano, C3-5 cycloalkyl, 3-5 membered heterocycloalkyl, aryl, heteroaryl, C 1-4 alkylcarbonyloxy, C 1-4 alkyloxycarbonyl, C 1-4 alkylcarbonyl, or formyl. The hydrocarbon chain can also be optionally interrupted by -0-, -S-, -N(Ra)-, - N(Ra)-C(O)-O-, -0-C(O)-N(Ra)-, -N(Ra)-C(O)-N(Rb)-, -0-C(O)-O-, -P(Ra)-, or - P(O)(Ra)-. Each of Ra and Rb, independently, is hydrogen, alkyl, alkenyl, alkynyl, alkoxy, hydroxylalkyl, hydroxyl, or haloalkyl. An aryl group is a substituted or unsubstituted cyclic aromatic group. Examples include phenyl, benzyl, naphthyl, tolyl, anthracyl, nitrophenyl, or halophenyl. A heteroaryl group is an aryl group with one or more heteroatoms in the ring, for instance furyl, pyridyl, pyrrolyl, phenanthryl.
A suitable coordinating ligand can be purchased commercially or prepared by ordinary synthetic organic techniques, for example, as described in J. March, Advanced Organic Chemistry, which is hereby incorporated by reference in its entirety.
Other ligands are described in U.S. Patent Application No. 10/641,292 for "Stabilized Semiconductor Nanocrystals", filed 15 August 2003, which is hereby incorporated herein by reference in its entirety.
When an electron and hole localize on a semiconductor nanocrystal, emission can occur at an emission wavelength. The emission has a frequency that corresponds to the band gap of the quantum confined semiconductor material. The band gap is a function of the size of the semiconductor nanocrystal. Semiconductor nanocrystals having small diameters can have properties intermediate between molecular and bulk forms of matter. For example, semiconductor nanocrystals based on semiconductor materials having small diameters can exhibit quantum confinement of both the electron and hole in all three dimensions, which leads to an increase in the effective band gap of the material with decreasing crystallite size. Consequently, both the optical absorption and emission of semiconductor nanocrystals shift to the blue, or to higher energies, as the size of the crystallites decreases. The emission from a semiconductor nanocrystal can be a narrow Gaussian emission band that can be tuned through the complete wavelength range of the ultraviolet, visible, or infra-red regions of the spectrum by varying the size of the semiconductor nanocrystal, the composition of the semiconductor nanocrystal, or both. For example, CdSe can be tuned in the visible region and InAs can be tuned in the infra-red region. The narrow size distribution of a population of semiconductor nanocrystals can result in emission of light in a narrow spectral range. The population can be monodisperse preferably exhibits less than a 15% rms (root-mean-square) deviation in diameter of the semiconductor nanocrystals, more preferably less than 10%, most preferably less than 5%. Spectral emissions in a narrow range of no greater than about 75 run, preferably 60 nm, more preferably 40 nm, and most preferably 30 nm full width at half max (FWHM) for semiconductor nanocrystals that emit in the visible can be observed. IR-emitting semiconductor nanocrystals can have a FWHM of no greater than 150 nm, or no greater than 100 nm. Expressed in terms of the energy of the emission, the emission can have a FWHM of no greater than 0.05 eV, or no greater than 0.03 eV. The breadth of the emission decreases as the dispersity of semiconductor nanocrystal diameters decreases. Semiconductor nanocrystals can have high emission quantum efficiencies such as greater than about 10%, greater than about 20%, greater than about 30%, greater than about 40%, greater than about 50%, greater than about 60%, greater than about 70%, or greater than about 80%.
The narrow FWHM of semiconductor nanocrystals can result in saturated color emission. This can lead to efficient lighting devices even in the red and blue parts of the visible spectrum, since in semiconductor nanocrystal emitting devices no photons are lost to infra-red and UV emission. The broadly tunable, saturated color emission over the entire visible spectrum of a single material system is unmatched by any class of organic chromophores (see, for example, Dabbousi et al, J. Phys. Chem. 101, 9463 (1997), which is incorporated by reference in its entirety). A monodisperse population of semiconductor nanocrystals will emit light spanning a narrow range of wavelengths. A device including semiconductor nanocrystals of different compositions, sizes, and/or structures can emit light in more than one narrow range of wavelengths. The color of emitted light perceived by a viewer can be controlled by selecting appropriate combinations of semiconductor nanocrystal sizes and materials in the device as well as relative subpixel currents. The degeneracy of the band edge energy levels of semiconductor nanocrystals facilitates capture and radiative recombination of all possible excitons, whether generated by direct charge injection or energy transfer. The maximum theoretical semiconductor nanocrystal lighting device efficiencies are therefore comparable to the unity efficiency of phosphorescent organic light-emitting devices. The excited state lifetime (τ) of the semiconductor nanocrystal is much shorter (τ -10 ns) than a typical phosphor (τ > 0.1 μs), enabling semiconductor nanocrystal lighting devices to operate efficiently even at high current density and high brightness.
Transmission electron microscopy (TEM) can provide information about the size, shape, and distribution of the semiconductor nanocrystal population. Powder X-ray diffraction (XRD) patterns can provide the most complete information regarding the type and quality of the crystal structure of the semiconductor nanocrystals. Estimates of size are also possible since particle diameter is inversely related, via the X-ray coherence length, to the peak width. For example, the diameter of the semiconductor nanocrystal can be measured directly by transmission electron microscopy or estimated from X-ray diffraction data using, for example, the Scherrer equation. It also can be estimated from the UV/Vis absorption spectrum.
In certain embodiments, the emissive material can be deposited as one or more separate layers. In certain embodiments, a layer comprising emissive material can be disposed between any two layers of the device. For example, the layer comprising emissive material can be disposed between two hole transport layers and/or between two electron transport layers. In either case, each of the charge transport layers may further comprise one or more layers. In another embodiment, the emissive material can be deposited as one or more separate layers disposed between a hole transport layer and an electron transport layer. As discussed elsewhere herein, other layers may also be included between the electron transport layers and the hole transport layers. When included in the device as a separate layer, for example, an emissive layer comprising semiconductor nanocrystals can be disposed as a continuous or substantially continuous thin film or layer. When disposed as a separate layer, the layer can be patterned or unpatterned. Preferably, an emissive layer comprising semiconductor nanocrystals comprises a substantially monodisperse population of semiconductor nanocrystals.
In certain embodiments, an emissive layer comprising semiconductor nanocrystals is deposited at a thickness of multiple monolayers or less. For example, the thickness can be greater than three monolayers, three or less monolayers, two or less monolayers, a single monolayer, a partial monolayer, etc. The thickness of each deposited layer of semiconductor nanocrystals may vary. In certain embodiments, the variation of the thickness at any point of the deposited semiconductor nanocrystals is less than three monolayers. In certain embodiments, the variation of the thickness at any point of the deposited semiconductor nanocrystals is less than two monolayers. In certain embodiments, the variation of the thickness at any point of the deposited semiconductor nanocrystals is less than one monolayer. When deposited as a single monolayer, in certain embodiments at least about 60% of the semiconductor nanocrystals are at single monolayer thickness; in certain embodiments at least about 80% of the semiconductor nanocrystals are at single monolayer thickness; and in certain embodiments at least about 90% of the semiconductor nanocrystals are at single monolayer thickness. In a light- emitting device, a monolayer can provide the beneficial light emission properties of semiconductor nanocrystals while minimizing the impact on electrical performance.
Semiconductor nanocrystals show strong quantum confinement effects that can be harnessed in designing bottom-up chemical approaches to create complex heterostructures with electronic and optical properties that are tunable with the size and composition of the semiconductor nanocrystals.
As discussed herein, in certain embodiments, emissive material comprising a plurality of semiconductor nanocrystals can be deposited in a patterned arrangement. Patterned semiconductor nanocrystals can be used to form an array of light-emitting devices comprising, e.g., red, green, and blue, or alternatively, red, orange, yellow, green, blue-green, blue, violet, or other visible, infrared, or ultraviolet emitting, or other combinations of distinguishable wavelength emitting devices, that are energized to produce light of a predetermined wavelength.
A device or array of devices capable of emitting a variety of colors includes a pattern of emissive materials capable of emitting different colors.
When deposited in a patterned arrangement, the emissive layer can comprise a pattern comprising features having at least one dimension at a micron-scale (e.g., less than 1 mm, less than 500 μm, less than 200 μm, less than 100 μm or less, less than 50 μm or less, less than 20 μm or less). The emissive layer can also comprise a patterned arrangement comprising features at greater than micron-scale. The emissive layer can also comprise a patterned arrangement comprising features at less than micron-scale. A pattern comprising deposited emissive material having features on the micron scale may also be referred to herein as a micropattern. A micropattern can have features on the micron scale, such as less than 1 mm, less than 500 μm, less than 200 μm, less than 100 μm, less than 50 μm, or 20 μm or less in size. A 20 μm feature size or smaller is suitable for many light emitting devices.
The size of a display can have dimensions of > lmm, 1 cm or greater, 10 cm or greater, 100 cm or greater, or 1 ,000 cm or greater.
Optionally, devices can be stitched (or tiled) together, to expand display sizes from, e.g., 12" squares, to 'n x 12" squares' as is frequently done in the semiconductor lithography field.
Contact printing provides a method for applying a material to a predefined region on a surface to be printed. The predefined region is a region on a surface where the material is selectively applied. The material and substrate can be chosen such that the material remains substantially entirely within the predetermined area. By selecting a predefined region that forms a pattern, material can be applied to a surface such that the material forms a pattern. The pattern can be a regular pattern (such as an array, or a series of lines), or an irregular pattern. Once a pattern of material is formed on a surface, the surface can have a region including the material (the predefined region) and a region substantially free of material. In some circumstances, the material forms a monolayer on the surface. The predefined region can be a discontinuous region. In other words, when the material is applied to the predefined region of the surface, locations including the material can be separated by other locations that are substantially free of the material.
Microcontact printing and related techniques are described in, for example, U.S. Patent Nos. 5,512,131; 6,180,239; and 6,518,168, each of which is incorporated by reference in its entirety. In some circumstances, the stamp can be a featureless stamp having a pattern of ink, where the pattern is formed when the ink is applied to the stamp. See U.S. Patent Application No. 11/253,612, filed October 21, 2005, which is incorporated by reference in its entirety.
Other materials, techniques, methods, applications, and information that may be useful with the present invention are described in, International Application No. PCT/US2007/008873, filed 04/09/2007, of Coe-Sullivan et al., for "Composition Including Material, Methods Of Depositing Material, Articles Including Same And
Systems For Depositing Material"; International Application No. PCT/US2007/09255, filed 04/13/2007, of Anc, et al., for "Methods Of Depositing Material, Methods Of Making A Device, And System"; International Application No. PCT/US2007/003411, filed 02/08/2007, of Beatty, et al., for "Device Including Semiconductor Nanocrystals And A Layer Including A Doped Organic Material And Methods"; International Application No. PCT/US2007/14711, filed 06/25/2007, of Coe-Sullivan, for "Methods For Depositing Nanomaterial, Methods For Fabricating A Device, And Methods For Fabricating An Array Of Devices"; International Application No. PCT/US2007/ 14705, filed 06/25/2007, of Coe- Sullivan, et al., for "Methods For Depositing Nanomaterial, Methods For Fabricating A Device, Methods For Fabricating An Array Of Devices And Compositions"; International Application No. PCT/US2007/008705, filed 04/09/2007, of Coe-Sullivan, et al., for "Methods And Articles Including Nanomaterial"; International Application No. PCT/US2007/014706, filed 06/25/2007, of coe-sullivan, et al., for "Methods And Articles Including Nanomaterial"; International Application No. PCT/US2007/003525, filed 02/08/2007, of Coe-Sullivan, et al., for "Displays Including Semiconductor Nanocrystals And Methods Of Making Same"; International Application No. PCT/US2007/008721, filed 04/09/2007, of Cox, et al., for "Methods Of Depositing Nanomaterial & Methods Of Making A Device"; International Application No. PCT/US2007/019797, filed 09/12/2007, of Coe-Sullivan, et al., for "A Composite Including Nanoparticles, Methods, And Products Including A Composite"; International Application No. PCT/US2007/019796, of Coe- Sullivan, et al., filed 09/12/2007, for "Electroluminescent Display Useful For Displaying A Predetermined Pattern"; International Application No. PCT/US2007/24320, filed 1 1/21/2007, of Clough, et al., for "Nanocrystals Including A Group Ilia Element And A Group Va Element, Method, Composition, Device And Other Products"; U.S. Patent Application No. 60/971887, filed 09/12/2007, of Breen, et al., for "Functionalized Semiconductor Nanocrystals And Method"; U.S. Patent Application No. 60/992598, filed 12/05/2007, of Breen, et al., "Functionalized Semiconductor Nanocrystals And Method"; International Application No. PCT/US2008/010651, filed 9/12/2008, of Breen, et al., for "Functionalized Nanoparticles And Method"; International Application No. PCT/US2007/24305, filed 11/21/2007, of Breen, et al., for "Blue Light Emitting Semiconductor Nanocrystal And Compositions And Devices Including Same"; International Application No. PCT/US2007/24306, filed 11/21/2007, of Ramprasad, for "Semiconductor Nanocrystal And Compositions And Devices Including Same";
International Application No. PCT/US2007/013152, filed 06/04/2007, of Coe-Sullivan, et al., for "Light-Emitting Devices And Displays With Improved Performance"; International Application No. PCT/US2007/24750, of Coe-Sullivan, et al., filed 12/03/2007 "Improved Composites And Devices Including Nanoparticles"; International Application No. PCT/US2007/24310, filed 1 1/21/2007, of Kazlas, et al., for "Light-Emitting Devices And Displays With Improved Performance"; and International Application No. PCT/US2007/003677, filed 02/14/2007, of Bulovic, et al., for "Solid State Lighting Devices Including Semiconductor Nanocrystals & Methods". The disclosures of each of the foregoing listed patent documents are hereby incorporated herein by reference in their entireties.
Hole transport and electron transport layers mentioned above can be collectively referred to as charge transport layers. Either or both of these layers can comprise organic or inorganic materials. Examples of inorganic material include, for example, inorganic semiconductors. The inorganic material can be amorphous or polycrystalline. An organic charge transport material can be polymeric or non-polymeric.
An example of a typical organic material that can be included in an electron transport layer includes a molecular matrix. The molecular matrix can be non-polymeric. The molecular matrix can include a small molecule, for example, a metal complex. The metal complex of 8-hydoryquinoline can be an aluminum, gallium, indium, zinc or magnesium complex, for example, aluminum tris(8-hydroxyquinoline) (AIq3). In certain embodiments, the electron transport material can comprise LT-N820 or LT-N821 (1,3- Bis[2-(2,2'-bypyridine-6-yl)-l,3,4-oxadiazo-5-yl]benzene (also abbreviated as Bpy-OXD), available from Luminescent Technologies, Taiwan. For additional information relating to Bpy-OXD, see M. Ichikawa et al, J. Mater. Chem., 2006, 16, 221-25, the disclosure of which is hereby incorporated herein by reference in its entirety. Other classes of materials in the electron transport layer can include metal thioxinoid compounds, oxadiazole metal chelates, triazoles, sexithiophenes derivatives, pyrazine, and styrylanthracene derivatives. An electron transport layer comprising an organic material may be intrinsic (undoped) or doped. Doping may be used to enhance conductivity.
An example of a typical organic material that can be included in a hole transport layer includes an organic chromophore. The organic chromophore can include a phenyl amine, such as, for example, N,N'-diphenyl-N,N'-bis(3-mehtylphenyl)-(l,l '-biphenyl)- 4,4'-diamine (TPD). Other hole transport layer can include spiro-TPD, 4-4'-N,N'- dicarbazolyl-biphenyl (CBP), 4,4-. bis[N-(l-naphthyl)-N-phenylamino]biphenyl (NPD), etc., a polyaniline, a polypyrrole, a poly(phenylene vinylene), copper phthalocyanine, an aromatic tertiary amine or polynuclear aromatic tertiary amine, a 4,4'-bis(p-carbazolyl)- l,l '-biphenyl compound, or an N,N,N',N'-tetraarylbenzidine. A hole transport layer comprising an organic material may be intrinsic (undoped) or doped. Doping may be used to enhance conductivity.
Charge transport layers comprising organic materials and other information related to fabrication of organic charge transport layers are discussed in more detail in U.S. Patent Application Nos. 11/253,612 for "Method And System For Transferring A Patterned Material", filed 21 October 2005, and 11/253,595 for "Light Emitting Device Including Semiconductor Nanocrystals", filed 21 October 2005. The foregoing patent applications are hereby incorporated herein by reference in its entirety.
Organic charge transport layers may be disposed by known methods such as a vacuum vapor deposition method, a sputtering method, a dip-coating method, a spin- coating method, a casting method, a bar-coating method, a roll-coating method, and other film deposition methods. Preferably, organic layers are deposited under ultra-high vacuum (e.g., < 10"8 torr), high vacuum (e.g., from about 10"8 torr to about 10'5 torr), or low vacuum conditions (e.g., from about 10"5 torr to about 10"3 torr). Most preferably, the organic layers are deposited at high vacuum conditions from about 1 x 10'7 to about 5 x 10 torr. Alternatively, organic layers may be formed by multi-layer coating while appropriately selecting solvent for each layer. Examples of charge transport layers that can be solvent cast include but are not limited to fluorine-based polymers such as Poly(9,9'- dioctylfluorene-co-bis-N,N'-(4-butylphenyl)-bis-N,N'-phenyl-l,4-phenylene-diamine) (PFB) and poly(9,9'-dioctylfluorene-co-N-(4-butylphenyl)diphenylenediamine) (TFB).
Charge transport layers including inorganic materials and other information related to fabrication of inorganic charge transport layers are discussed further below and in more detail in U.S. Patent Application No. 60/653,094 for "Light Emitting Device Including Semiconductor Nanocrystals", filed 16 February 2005 and U.S. Patent Application No. 11/354,185, filed 15 February 2006, the disclosures of each of which are hereby incorporated herein by reference in their entireties.
Charge transport layers comprising an inorganic semiconductor can be deposited on a substrate at a low temperature, for example, by a known method, such as a vacuum vapor deposition method, an ion-plating method, sputtering, inkjet printing, etc. In addition to the charge transport layers, a device may optionally further include one or more charge-injection layers, e.g., a hole-injection layer (either as a separate layer or as part of the hole transport layer) and/or an electron-injection layer (either as a separate layer as part of the electron transport layer). Charge injection layers comprising organic materials can be intrinsic (un-doped) or doped. One or more charge blocking layers may still further optionally be included. For example, an electron blocking layer (EBL), a hole blocking layer (HBL), or an exciton blocking layer (eBL), can be introduced in the structure. A blocking layer can include, for example, 3-(4-biphenylyl)-4-phenyl-5-tert butylphenyl-l,2,4-triazole (TAZ), 3,4,5-triphenyl-l,2,4-triazole, 3,5-bis(4-tert- butylphenyl)- 4-phenyl-l,2,4-triazole, bathocuproine (BCP), 4,4',4"-tris{N-(3- methylphenyl)-Nphenylamino} triphenylamine (m-MTDATA), polyethylene dioxythiophene (PEDOT), 1,3- bis(5-(4-diphenylamino)phenyl-l,3,4-oxadiazol-2- yl)benzene, 2-(4-biphenylyl)-5-(4-tertbutylphenyl)- 1,3,4-oxadiazole, l,3-bis[5-(4-(l,l- dimethylethyl)phenyl)-l,3,4-oxadiazol-5,2-yl)benzene, l,4-bis(5-(4- diphenylamino)phenyl-l,3,4-oxadiazol-2-yl)benzene, l,3,5-tris[5- (4-(I9I- dimethylethyl)phenyl)-l,3,4-oxadiazol-2-yl)benzene, or 2,2',2"-(l,3,5-Benzinetriyl)- tris( 1 -phenyl- 1 -H-benzimidazole) (TPBi).
Charge blocking layers comprising organic materials can be intrinsic (un-doped) or doped.
The charge injection layers (if any), and charge blocking layers (if any) can be deposited on a surface of one of the electrodes by spin coating, dip coating, vapor deposition, or other thin film deposition methods. See, for example, M. C. Schlamp, et al., J. Appl. Phys., 82, 5837-5842, (1997); V. Santhanam, et al., Langmuir, 19, 7881-7887, (2003); and X. Lin, et al., J. Phys. Chem. B, 105, 3353-3357, (2001), each of which is incorporated by reference in its entirety.
Other multilayer structures may optionally be used to improve the performance (see, for example, U.S. Patent Application Nos. 10/400,907 and 10/400,908, filed March 28, 2003, each of which is incorporated by reference in its entirety) of the light-emitting devices and displays of the invention. The performance of light-emitting devices can be improved by increasing their efficiency, narrowing or broadening their emission spectra, or polarizing their emission. See, for example, Bulovic et al, Semiconductors and Semimetals 64, 255 (2000), Adachi et al, Appl. Phys. Lett. 78, 1622 (2001), Yamasaki et al., Appl. Phys. Lett. 76, 1243 (2000), Dirr et al, Jpn. J. Appl. Phys. 37, 1457 (1998), and D'Andrade et al, MRS Fall Meeting, BB6.2 (2001), each of which is incorporated herein by reference in its entirety.
The specific materials and structures described herein are exemplary in nature, and other materials and structures may be used. The present invention will be further clarified by the following examples, which are intended to be exemplary of the present invention.
As used herein, "top" and "bottom" are relative positional terms, based upon a location from a reference point. More particularly, "top" means furthest away from the reference point, while "bottom" means closest to the reference point. For example, for a light-emitting device that optionally includes two electrodes, if the substrate is selected as the reference point, the bottom electrode is the electrode closest to the substrate, and is generally the first electrode fabricated; the top electrode is the electrode that is more remote from the substrate, on the top side of the light-emitting material. The bottom electrode has two surfaces, a bottom surface closest to the substrate, and a top surface further away from the substrate. Where, e.g., a first layer is described as disposed or deposited "over" a second layer, the first layer is disposed further away from the substrate. There may be other layers between the first and second layer, unless it is otherwise specified. For example, a cathode may be described as "disposed over" an anode, even though there are various organic and/or inorganic layers in between.
As used herein, the singular forms "a", "an" and "the" include plural unless the context clearly dictates otherwise. Thus, for example, reference to an emissive material includes reference to one or more of such materials.
1. A light-emitting device including an emissive layer comprising semiconductor nanocrystals disposed between two flexible substrates, a first electrode disposed over the emissive layer comprising semiconductor nanocrystals and a second electrode disposed under the emissive layer comprising semiconductor nanocrystals.
2. A light-emitting device in accordance with claim 1 wherein the device further includes a charge transport layer disposed between one of the electrodes and the emissive layer comprising semiconductor nanocrystals.
3. A light-emitting device including an emissive layer comprising semiconductor nanocrystals disposed between two flexible substrates, a first electrode disposed over the emissive layer comprising semiconductor nanocrystals and a second electrode disposed under the emissive layer comprising semiconductor nanocrystals, wherein, when the device is curved, the emissive layer comprising semiconductor nanocrystals lies substantially in the neutral plane of the device.
4. A light-emitting device in accordance with claim 3 wherein the neutral plane does not deviate from the plane of the emissive layer comprising semiconductor nanocrystals by more than about 25 per cent of the total thickness of the device.
5. A light-emitting device in accordance with claim 3 wherein the neutral plane does not deviate from the plane of the emissive layer comprising semiconductor nanocrystals by more than about 20 per cent of the total thickness of the device.
6. A light-emitting device in accordance with claim 3 wherein the neutral plane does not deviate from the plane of the emissive layer comprising semiconductor nanocrystals by more than about 15 per cent of the total thickness of the device.
7. A light-emitting device in accordance with claim 3 wherein the neutral plane does not deviate from the plane of the emissive layer comprising semiconductor nanocrystals by more than about 10 per cent of the total thickness of the device.
8. A light-emitting device in accordance with claim 3 wherein the neutral plane does not deviate from the plane of the emissive layer comprising semiconductor nanocrystals by more than about 5 per cent of the total thickness of the device.
9. A light-emitting device in accordance with claim 3 wherein the neutral plane does not deviate from the plane of the emissive layer comprising semiconductor nanocrystals by more than about 1 per cent of the total thickness of the device.
10. A flexible light-emitting device including: a flexible substrate, a first electrode disposed over a portion of the flexible substrate, an emissive layer comprising semiconductor nanocrystals disposed over the first electrode, and a second electrode disposed over the emissive layer, wherein, when the device is curved, the emissive layer comprising semiconductor nanocrystals lies substantially in the neutral plane of the device.
11. A light-emitting device in accordance with claim 10 wherein the neutral plane does not deviate from the plane of the emissive layer comprising semiconductor nanocrystals by more than about 25 per cent of the total thickness of the device.
12. A light-emitting device in accordance with claim 10 wherein the neutral plane does not deviate from the plane of the emissive layer comprising semiconductor nanocrystals by more than about 20 per cent of the total thickness of the device.
13 A light-emitting device in accordance with claim 10 wherein the neutral plane does not deviate from the plane of the emissive layer comprising semiconductor nanocrystals by more than about 15 per cent of the total thickness of the device.
14. A light-emitting device in accordance with claim 10 wherein the neutral plane does not deviate from the plane of the emissive layer comprising semiconductor nanocrystals by more than about 10 per cent of the total thickness of the device.
15. A light-emitting device in accordance with claim 10 wherein the neutral plane does not deviate from the plane of the emissive layer comprising semiconductor nanocrystals by more than about 5 per cent of the total thickness of the device.
16. A light-emitting device in accordance with claim 10 wherein the neutral plane does not deviate from the plane of the emissive layer comprising semiconductor nanocrystals by more than about 1 per cent of the total thickness of the device.
17. A tile comprising a light-emitting device in accordance with claim 1.
18. A tile comprising a light-emitting device in accordance with claim 3.
19. A tile comprising a light-emitting device in accordance with claim 10.
20. An array comprising two or more light-emitting devices in accordance with claim 1 , wherein the devices are in electrical connection.
21. An array comprising two or more light-emitting devices in accordance with claim 3, wherein the devices are in electrical connection.
22. An array comprising two or more light-emitting devices in accordance with claim 10, wherein the devices are in electrical connection.
23. A method for making a light-emitting device comprising depositing a layer of flexible sealant over a substrate including device layers thereon, and disposing a protective layer over the sealant.
24. A device formed by the method of claim 23.
25. A method for making a light-emitting device comprising depositing a layer of flexible sealant at least over exposed surfaces of device layers disposed on a surface of a substrate, and disposing a protective layer over the sealant.
26. A method in accordance with claim 23 or 25 wherein the substrate is flexible and wherein the device layers comprise a first electrode disposed over a portion of the substrate, an emissive layer comprising semiconductor nanocrystals disposed over the first electrode, and a second electrode disposed over the emissive layer, wherein, when the device is curved, the emissive layer comprising semiconductor nanocrystals lies substantially in the neutral plane of the device.
27. A method in accordance with claim 23 or 25 wherein getter material is associated with the device layers before the sealant is deposited thereover.
28. A light-emitting device comprising a layer of flexible sealant disposed at least over exposed surfaces of device layers disposed on surface of a substrate, and a protective layer disposed over the sealant.
29. A light-emitting device in accordance with claim 28 wherein the substrate is flexible and wherein the device layers comprise a first electrode disposed over a portion of the substrate, an emissive layer comprising semiconductor nanocrystals disposed over the first electrode, and a second electrode disposed over the emissive layer, wherein, when the device is curved, the emissive layer comprising semiconductor nanocrystals lies substantially in the neutral plane of the device.
30. A light-emitting device in accordance with claim 24 or 28 wherein getter material is associated with the device layers before the sealant is deposited thereover.
31. A method for making a light-emitting device comprising forming a sealant dam around device layers on a substrate to form a defined area, depositing a flexible sealant over the defined area, and disposing a protective layer over the perimeter dam and sealant.
32. A method in accordance with claim 31 wherein the substrate is flexible and wherein the device layers comprises a first electrode disposed over a portion of the, an emissive layer comprising semiconductor nanocrystals disposed over the first electrode, and a second electrode disposed over the emissive layer, wherein, when the device is curved, the emissive layer comprising semiconductor nanocrystals lies substantially in the neutral plane of the device.
33. A method in accordance with claim 31 wherein getter material is associated with the device layers before the sealant is deposited thereover.
34. A device formed by the method of claim 31.
35. A light-emitting device including a sealant dam around the perimeter or device layers on a substrate to form a defined area, and a flexible sealant covering the defined area and at least the uppermost surface of the sealant dam.
36. A light-emitting device in accordance with claim 31 or 35 wherein the substrate is flexible and wherein the device layers comprises a first electrode disposed over a portion of the substrate, an emissive layer comprising semiconductor nanocrystals disposed over the first electrode, and a second electrode disposed over the emissive layer, wherein, when the device is curved, the emissive layer comprising semiconductor nanocrystals lies substantially in the neutral plane of the device.
37. A light-emitting device in accordance with claim 35 wherein getter material is associated with the device layers before the sealant is deposited thereover.
38. A light-emitting device including an emissive layer comprising semiconductor nanocrystals disposed between two flexible substrates, a first electrode disposed over the emissive layer comprising semiconductor nanocrystals, a second electrode disposed under the emissive layer comprising semiconductor nanocrystals, and a third electrode layer disposed on the outside surface of either flexible substrate making electrical contact with either or both interior electrodes through a substrate via or external connection.
39. A light-emitting device in accordance with claim 38 wherein the device further includes a charge transport layer disposed between one of the electrodes and the emissive layer comprising semiconductor nanocrystals.
40 . A light-emitting device in accordance with claim 38 wherein, when the device is curved, the emissive layer comprising semiconductor nanocrystals lies substantially in the neutral plane of the device.
41. A tile comprising a light-emitting device in accordance with claim 38.
42. An array comprising two or more light-emitting devices in accordance with claim 38, wherein the devices are in electrical connection.
43. A system including a light-emitting device in accordance with claim 1 and at least one sensor, wherein the at least one sensor is in electrical connection with an electronic circuit which is also in electrical connection with the light-emitting device.
44. A system in accordance with claim 1 further including a controller coupled to the light-emitting device and the at least one sensor, the controller being configured to process information acquired by the sensor to control the light-emitting device to generate a light output with at least one predetermined characteristic.
45. A system including a light-emitting device in accordance with claim 3 and at least one sensor, wherein the at least one sensor is in electrical connection with an electronic circuit which is also in electrical connection with the light-emitting device.
46. A system in accordance with claim 3 further including a controller coupled to the light-emitting device and the at least one sensor, the controller being configured to process information acquired by the sensor to control the light-emitting device to generate a light output with at least one predetermined characteristic.
47. A system including a light-emitting device in accordance with claim 10 and at least one sensor, wherein the at least one sensor is in electrical connection with an electronic circuit which is also in electrical connection with the light-emitting device.
48. A system in accordance with claim 10 further including a controller coupled to the light-emitting device and the at least one sensor, the controller being configured to process information acquired by the sensor to control the light-emitting device to generate a light output with at least one predetermined characteristic.
49. A system including a light-emitting device in accordance with claim 38 and at least one sensor, wherein the at least one sensor is in electrical connection with an electronic circuit which is also in electrical connection with the light-emitting device.
50. A system in accordance with claim 38 further including a controller coupled to the light-emitting device and the at least one sensor, the controller being configured to process information acquired by the sensor to control the light-emitting device to generate a light output with at least one predetermined characteristic.
51. A system in accordance with claim 43, 45, 47, or 49 wherein the light-emitting device is included on a tile.
52. A system in accordance with claim 43, 45, 47, or 49 wherein the system includes an array of light-emitting devices each of which is in electrical connection with the electronic circuit.
53. A system in accordance with claim 51 wherein the system includes an array of tiles, each of which includes one or more light-emitting devices, and wherein each light- emitting device is in electrical connection with the electronic circuit.
54. A light-emitting device in accordance with claim 10 further comprising a third electrode layer disposed on the outside surface of the flexible substrate making electrical contact with either or both interior electrodes through a substrate via or external connection.
PCT/US2008/013504 2008-02-07 2008-12-08 Flexible devices including semiconductor nanocrystals, arrays, and methods WO2009099425A3 (en)
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US12851336 Continuation US9431623B2 (en) 2008-02-07 2010-08-05 Flexible devices including semiconductor nanocrystals, arrays, and methods
WO2009099425A2 true true WO2009099425A2 (en) 2009-08-13
WO2009099425A3 true WO2009099425A3 (en) 2009-12-30
ID=40952585
PCT/US2008/013504 WO2009099425A3 (en) 2008-02-07 2008-12-08 Flexible devices including semiconductor nanocrystals, arrays, and methods
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