WO2018123805A1 - 発光素子およびそれを用いた画像表示素子 - Google Patents
発光素子およびそれを用いた画像表示素子 Download PDFInfo
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- WO2018123805A1 WO2018123805A1 PCT/JP2017/045920 JP2017045920W WO2018123805A1 WO 2018123805 A1 WO2018123805 A1 WO 2018123805A1 JP 2017045920 W JP2017045920 W JP 2017045920W WO 2018123805 A1 WO2018123805 A1 WO 2018123805A1
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- VPKHBJJEEGVQDL-UHFFFAOYSA-O CCC1[NH+](C)C=CC1C Chemical compound CCC1[NH+](C)C=CC1C VPKHBJJEEGVQDL-UHFFFAOYSA-O 0.000 description 1
- UXVSONSREFNCNN-HSZRJFAPSA-N CN1c(cccc2)c2N(Cc(c(F)cc(F)c2)c2[IH]N/C2=N\C(C(F)(F)F)=C)[C@H]1N1C2=CC=CC1 Chemical compound CN1c(cccc2)c2N(Cc(c(F)cc(F)c2)c2[IH]N/C2=N\C(C(F)(F)F)=C)[C@H]1N1C2=CC=CC1 UXVSONSREFNCNN-HSZRJFAPSA-N 0.000 description 1
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- C09K11/54—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing zinc or cadmium
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- C09K11/56—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing sulfur
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- C09K11/70—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus
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- G02B5/201—Filters in the form of arrays
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- G—PHYSICS
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- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
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- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
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- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
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- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/125—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/30—Devices specially adapted for multicolour light emission
- H10K59/35—Devices specially adapted for multicolour light emission comprising red-green-blue [RGB] subpixels
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- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/30—Devices specially adapted for multicolour light emission
- H10K59/38—Devices specially adapted for multicolour light emission comprising colour filters or colour changing media [CCM]
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- G—PHYSICS
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- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
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- H10K2102/301—Details of OLEDs
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Definitions
- the present invention relates to a light emitting element and an image display element using the light emitting element.
- FPD flat panel display
- CRT CRT
- the FPD includes a liquid crystal display, an organic electroluminescence (organic EL) display, a plasma display, an FED (field emission display), and the like, and recently, an organic EL and a liquid crystal have been particularly actively developed.
- organic EL organic electroluminescence
- plasma display plasma display
- FED field emission display
- EL elements typified by organic EL elements are self-luminous, do not require a backlight, can be thin and lightweight, have fewer members, and are easily foldable, but display due to deterioration of the light-emitting members
- problems such as defects. That is, there is a need to solve problems such as high cost due to poor yield during device manufacture, device burn-in due to lifetime, and display unevenness.
- full-color organic EL elements it is necessary to emit red, green, and blue colors independently, and the above problems are likely to occur especially in high-energy rays of short-wavelength blue.
- the element is yellowed due to fading of blue.
- JP 2011-209754 A Japanese Patent Laid-Open No. 10-12383 JP2015-125994A JP 2013-137931 A
- the characteristics of the fluorescent material having quantum dots used as the material of the wavelength conversion layer and the characteristics of the light emitting layer serving as the primary light source optimization of the respective characteristics is indispensable in order to obtain an optimal color reproduction range, There is a problem that it is difficult to select a material for that purpose.
- the wavelength conversion layer cannot sufficiently absorb light from the light emitting layer that is the primary light source, and light that cannot be absorbed by the wavelength conversion layer. Is transparent.
- the light converted by the wavelength conversion layer and the light from the primary light source that is the light emitting layer are mixed, resulting in a problem that the color reproducibility is lowered or a problem of coloring due to the deterioration of the wavelength conversion layer.
- blue light or ultraviolet light emitted from the light emitting layer is used as a primary light source, and light emitted from this light source is irradiated to a wavelength conversion layer made of a fluorescent material or the like, thereby obtaining three primary colors as a secondary light source.
- a display device having a configuration optimization of a primary light source and a wavelength conversion layer is required.
- the problem to be solved by the present invention is to provide a light emitting element capable of suppressing or preventing deterioration of the light conversion layer while achieving both high luminous efficiency and color reproducibility, and an image display element using the light emitting element. .
- Another problem to be solved by the present invention is to provide a light emitting element capable of suppressing or preventing color mixing of light from the light emitting layer and light transmitted through the light conversion layer, and an image display element using the light emitting element. It is in.
- the inventors of the present application have provided a pair of electrodes in which the first electrode and the second electrode are opposed to each other, and the first electrode and the second electrode.
- An electroluminescence layer, and a light conversion layer that includes a plurality of pixels and that converts light emitted from the electroluminescence layer having a blue emission spectrum into a different wavelength, and the light conversion layer is red (R) Any one of red (R), green (G), and blue (B) depending on light from the electroluminescent layer that has pixels of three primary colors of green (G) and blue (B) and is incident on at least one of the three primary colors
- the light emitting device of the present invention is excellent in transmittance and maintains a color reproduction region for a long time.
- the light emitting device of the present invention can suppress / prevent color mixing between light from the light emitting layer and light transmitted through the light conversion layer.
- the image display element of the present invention is not easily deteriorated by high-energy light such as short-wavelength visible light or ultraviolet light, and maintains the color reproduction region for a long time.
- the image display element of the present invention can suppress / prevent color mixing between light from the light emitting layer and light transmitted through the light conversion layer.
- FIG. 1 is a schematic view showing a cross section of a light emitting device of the present invention.
- FIG. 2 is an example of an enlarged schematic view of the light conversion layer according to the present invention.
- FIG. 3 is another example of an enlarged schematic view of the light conversion layer according to the present invention.
- FIG. 4 is a schematic view showing a cross section of another embodiment of the light emitting device of the present invention.
- FIG. 5 is another example of an enlarged schematic view of the light conversion layer according to the present invention.
- FIG. 6 is a schematic view showing a cross section of another embodiment of the light emitting device of the present invention.
- FIG. 7 is a schematic view showing a cross section of another embodiment of the light emitting device of the present invention.
- FIG. 1 is a schematic view showing a cross section of a light emitting device of the present invention.
- FIG. 2 is an example of an enlarged schematic view of the light conversion layer according to the present invention.
- FIG. 3 is another example of an enlarged schematic view of
- FIG. 8 is a schematic diagram of a circuit diagram showing a transistor layer according to the present invention.
- FIG. 9 is a schematic diagram of a circuit diagram showing a transistor layer according to the present invention.
- FIG. 10 is a schematic view showing a cross section of the image display element of the present invention.
- the first of the present invention comprises a pair of electrodes provided with a first electrode and a second electrode facing each other, an electroluminescence layer provided between the first electrode and the second electrode, and a plurality of pixels.
- a light conversion layer that converts light emitted from the electroluminescence layer having a blue emission spectrum into a different wavelength, and the light conversion layer includes red (R), green (G), and blue (B)
- R red
- G green
- B blue
- a light-emitting nanocrystal having three primary color pixels and having an emission spectrum in any of red (R), green (G), and blue (B) by light from the electroluminescence layer incident on at least one of the three primary colors It is a light emitting element characterized by containing.
- the light emitting device of the present invention is excellent in transmittance and maintains a color reproduction region for a long time.
- FIG. 1 is a schematic view showing a cross section of a light emitting device 100 of the present invention.
- the light-emitting element 100 of the present invention has a first electrode 2 and a second electrode 8 as a pair of opposed electrodes, an electroluminescence layer 12 between the electrodes, and a light conversion layer 9 on the second electrode 8. It has.
- the electroluminescent layer 12 according to the present invention only needs to have at least the light emitting layer 5, and the electroluminescent layer 12 according to the present invention includes the electron transport layer 6, the light emitting layer 5, the hole transport layer 4, and the hole injection. More preferably, layer 3 is provided.
- the electroluminescent layer 12 preferably has an electron injection layer 7, an electron transport layer 6, a light emitting layer 5, a hole transport layer 4 and a hole injection layer 3. Further, an electron blocking layer (not shown) may be provided between the light emitting layer 5 and the hole transport layer 4 in order to increase the external quantum efficiency and improve the light emission intensity. Similarly, a hole blocking layer (not shown) may be provided between the light emitting layer 5 and the electron transport layer 6 in order to increase the external quantum efficiency and improve the light emission intensity.
- the electroluminescent layer 12 has a hole injection layer 3 in contact with the first electrode 2, and a hole transport layer 4, a light emitting layer 5, and an electron transport layer 6 are sequentially stacked.
- the first electrode 2 is used as an anode and the second electrode 8 is used as a cathode for the sake of convenience.
- the configuration of the light emitting element 100 is not limited to this, and the first electrode 2
- the cathode may be used
- the second electrode 8 may be used as an anode, and the stacking order between these electrodes may be reversed.
- the hole injection layer 3, the hole transport layer 4, the electron blocking layer provided if necessary, the light emitting layer 5, the hole blocking layer provided if necessary, the electron transport layer 6 and The electron injection layer 7 may be stacked in this order.
- the light conversion layer 9 has a role of a so-called color layer, is provided with three primary color pixels of red (R), green (G), and blue (B), and contains light-emitting nanocrystals. Further, when light having a blue emission spectrum emitted from the electroluminescence layer 12 is irradiated to a pixel of at least one of the three primary colors, red (R), green (G), blue ( B) is converted into light having an emission spectrum.
- the light conversion layer 9 containing the nanocrystal NC for light emission is used as an alternative member for the color filter. Therefore, the light conversion layer 9 in the present invention includes three primary color pixels of red (R), green (G), and blue (B), and plays the same role as a so-called color filter.
- the light conversion layer 9 includes, for example, a red (R) pixel portion (red color layer portion) including a light conversion pixel layer (NC-Red) including a red light emitting nanocrystal, and a green (
- the pixel portion (green color layer portion) of R) includes a light conversion pixel layer (NC-Green) containing nanocrystals for green light emission, and the blue (R) pixel portion (blue color layer portion)
- An optical conversion pixel layer (NC-Blue) including a blue light emitting nanocrystal is provided.
- An example of such a single layer type light conversion layer 9 is shown in FIG.
- FIG. 2 shows an example of an enlarged schematic diagram of the light conversion layer 9 according to the present invention.
- the light conversion layer 9 includes a red color layer R, a green color layer G, and a blue color layer B.
- the red (R) pixel portion R (red color layer R) is composed of a light conversion pixel layer (NC-Red) including red light emitting nanocrystals.
- the green (G) pixel portion G (green color layer G) is composed of a light conversion pixel layer (NC-Green) containing green light emitting nanocrystals.
- the blue (B) pixel portion B blue color layer portion B (blue color layer portion B) includes a (light conversion pixel) layer (or a transparent resin layer) that optionally includes blue light emitting nanocrystals.
- the light conversion layer 9 is composed of one layer of the nanocrystal layer NCL including the red color layer R, the green color layer G, and the blue color layer B. Further, in order to prevent color mixture between the red color layer R, the green color layer G, and the blue color layer B, a black matrix BM is provided as a light shielding layer.
- the light conversion layer 9 can use the blue light as blue. Therefore, when the light emitted from the electroluminescence layer 12 as a light source is blue light, among the light conversion pixel layers (NC-Red, NC-Green, NC-Blue) of the respective colors, the light conversion pixel layer (NC-Blue) may be omitted, and the backlight for blue may be used as it is.
- the color layer displaying blue can be constituted by a transparent material or a color material layer (so-called blue color filter) containing a blue color material. Accordingly, in FIG. 1 and FIG. 2 and the like, since the blue light emitting nanocrystal can be an optional component, the blue light emitting nanocrystal is indicated by a one-dot broken line.
- the red color layer R, the green color layer G, and the blue color layer B may appropriately include color materials as necessary.
- the layer (NCL) including the light emitting nanocrystals NC may include color materials corresponding to the respective colors.
- a color layer (so-called “blue color filter”) containing a blue color material in a part of the light conversion layer 9 according to the wavelength of light emitted from the electroluminescent layer 12 or the electroluminescent layer 12 to be used. It is preferable to provide “)” between them in order to prevent the intrusion of unnecessary light from the outside and suppress the deterioration of the image quality.
- a structure of a modification of the light conversion layer 9 provided with such a blue color filter is shown in FIG.
- the nanocrystal layer NCL shown in FIG. 2 and a color material layer (so-called color filter) CFL containing a color material are laminated as one preferred embodiment of the light conversion layer.
- the light conversion layer does not visually recognize the remaining excitation light (blue light) by laminating a layer (NC) containing nanocrystals for light emission and a color layer (so-called color filter) CFL containing a color material. Is suppressed.
- the color layer (so-called color filter) CFL including a color material may be eliminated if necessary.
- a color layer including a blue color material is provided as the color filter layer CFL, assuming light having a main emission peak in a wavelength region of 420 nm or more and 480 nm or less as a light source (light emission by the electroluminescence layer).
- the type of the color layer is appropriately changed depending on the type of light source used.
- the image display element of the present invention can suppress / prevent color mixing between the light from the light emitting layer and the light transmitted through the light conversion layer.
- the light emitting device 100 shown in FIG. 1 when a voltage is applied between the first electrode 2 and the second electrode 8, electrons are injected from the second electrode 8 which is a cathode into the electroluminescence layer 12, and the anode From the first electrode 2, current flows as holes are injected into the electroluminescent layer 12.
- the injected electrons and holes recombine to form excitons. Accordingly, the light emitting material included in the light emitting layer 5 is excited, and light emission is obtained from the light emitting material. Thereafter, the light emitted from the light emitting layer 5 passes through the electron transport layer 6, the electron injection layer 7, and the second electrode and enters the surface of the light conversion layer 9.
- the light incident on the light conversion layer 9 is absorbed by the light-emitting nanocrystals and converted into an emission spectrum of red (R), green (G), or blue (B). ), Green (G), or blue (B).
- blue light is emitted from the light emitting layer 5 and the blue light incident on the light conversion layer 9 is absorbed by the light emitting nanocrystals, and is red (R), green (G), blue. It is a light-emitting element that displays any one of red (R), green (G), and blue (B) by being converted into one of (B).
- a color display method in an organic light emitting device is as follows: (1) a display format in which red, green, and blue light emitting materials are formed and coated separately; and (2) a light emitting layer that emits blue light. And a color conversion layer that converts blue light from the light emitting layer into green light, and a color conversion layer that converts blue light from the light emitting layer into red light, respectively, to develop three colors.
- Examples of the display method include (3) a method in which a light emitting layer that emits white light and a red, green, and blue color filter are combined.
- the display format (2) is preferable.
- the electroluminescent layer 12 has the purpose of lowering the potential barrier of hole or electron injection, the purpose of increasing the transport property of holes or electrons, the purpose of inhibiting the transport property of holes or electrons, or the electrode.
- a layer exhibiting various effects may be formed as a single layer or a plurality of layers as necessary.
- an overcoat layer 10 may be provided as a protective film so as to cover the light conversion layer 9, and a substrate 11 such as glass may be bonded over the entire surface of the overcoat layer 10 as necessary.
- a known adhesive layer for example, thermosetting or ultraviolet curable resin
- the overcoat layer 10 and the substrate 11 are preferably made of a transparent material.
- the overcoat layer 10 and the substrate 11 are not particularly limited.
- FIG. 1 shows a form in which the first electrode 2 is formed on the substrate 1, and the substrate includes the first electrode 2, the electroluminescence layer 12, the second electrode 8, and the light conversion layer 9. It is a support body which supports a laminated body, A well-known thing can be used.
- FIG. 4 is a schematic view showing a cross section of another embodiment of the light emitting device 100 of the present invention.
- the configuration other than the light conversion layer 9 is the same as that of FIG.
- the red color layer portion includes a light conversion pixel layer (NC-Red) containing red light emitting nanocrystals and a red color layer portion.
- a color material layer containing a color material (so-called red color filter) (CF-Red) has a two-layer structure
- the green color layer portion contains green light emitting nanocrystals that emit green light. It has a two-layer structure in which a light conversion pixel layer (NC-Green) and a color material layer containing a green color material (so-called green color filter) (CF-Green) are laminated.
- the two-layer structure of such a color layer is a color layer for the purpose of absorbing the remaining excitation light without transmitting it when all of the light emitted from the electroluminescence layer 12 cannot be converted by the light conversion pixel layer containing nanocrystals.
- a filter (CFL) and color material layers of each color are laminated. More specifically, the light conversion layer 9 has a red color layer portion, a green color layer portion, and a blue color layer portion, and the red (R) pixel portion (red color layer portion) is red.
- a light conversion pixel layer (NC-Red) including a light emitting nanocrystal and a color material layer (CF-Red) including a red color material are configured as a two-layer structure.
- the green (R) pixel portion (green color layer portion) includes a light conversion pixel layer (NC-Green) including a green light emitting nanocrystal and a color material layer (CF-Green) including a green color material. Configured as a layered structure.
- the green color layer portion includes a light conversion pixel layer (NC-Green) including a green light emitting nanocrystal and a yellow color material in order to perform color correction in consideration of transmission of excitation light. It may be combined with a color material layer (CF-Yellow) containing
- the blue (R) pixel portion (blue color layer portion) is composed of a color layer (NC-Blue) that optionally includes blue light emitting nanocrystals.
- a preferable form of the color layer (NC-Blue) to be included is the same as that of the embodiment shown in FIG. In FIG. 4, the red color layer portion, the green color layer portion, and the blue color layer portion are shown as being in contact with each other. However, in order to prevent color mixing, a light shielding layer is provided between them. A black matrix may be arranged.
- a color material layer containing a blue color material is interposed between them. It is preferable to provide it on one side from the viewpoint that unnecessary light can be prevented from entering from the outside and deterioration in image quality can be suppressed.
- An example of the layer structure including the two-layer light conversion layer 9 and the blue color filter as essential components is the structure shown in FIG.
- FIG. 5 shows an example of an enlarged schematic diagram of the light conversion layer 9 according to the present invention.
- the light conversion layer 9 includes a red color layer R, a green color layer G, and a blue color layer B.
- the red (R) pixel portion R is a light conversion pixel layer (NC) including a color material layer (so-called red color filter) CF-Red including a red color material and a red light emitting nanocrystal.
- a color material layer CFL blue color filter CF-Blue
- the green (G) pixel portion includes a color material layer containing a green color material (so-called green color filter) CF-Green and a light conversion pixel layer (NC) containing green light emitting nanocrystals. It is composed of a color material layer CFL (blue color filter CF-Blue) containing a blue color material.
- the blue (R) pixel portion includes a transparent resin layer and / or a color layer CFL (so-called blue color filter) containing a blue color material and a layer containing light-emitting nanocrystals (optional). NC) and a color layer CFL (blue color filter) containing a blue color material. Further, a black matrix is disposed as a light shielding layer between the red color layer, the green color layer, and the blue color layer.
- the light conversion layer 9 includes a (blue) color filter layer CFL, a layer (NCL) including the nanocrystal NC for light emission, and three primary color pixels of red (R), green (G), and blue (B).
- the red (R), green (G), and blue (B) color filters are sequentially stacked, and have a three-layer structure.
- the color filter layer CFL may be omitted if necessary.
- a color material layer (so-called yellow color filter) including a yellow color material may be used for color adjustment instead of the color material layer (so-called green color filter) CF-Green including the green color material.
- the red color layer R, the green color layer G, and the blue color layer B may appropriately include color materials as necessary.
- the layer (NCL) including the light emitting nanocrystals NC may include color materials corresponding to the respective colors.
- the color filter layer CFL is provided with a blue color filter layer assuming light having a main peak near 450 nm (light having a blue emission spectrum) as light from the electroluminescence layer 12.
- the color type of the color filter layer is appropriately changed depending on the type of light source used.
- FIG. 6 is a schematic view showing a cross section of another embodiment of the light emitting device 100 of the present invention.
- the configuration other than the light conversion layer 9 is the same as that of FIG.
- the light conversion layer 9 shown in the embodiment of FIG. 6 has two layers in which a layer containing nanocrystals for light emission and a color filter are laminated.
- the light conversion layer 9 includes a red (R) pixel portion (red color layer portion) of a layer (NCL) including a light emitting nanocrystal and a color material layer including a red color material.
- the green (R) pixel portion (green color layer portion) is composed of a two-layer structure of a layer (NC) containing a light emitting nanocrystal and a color material layer containing a green color material.
- the blue (R) pixel portion (blue color layer portion) has a two-layer structure of a layer (NC) containing nanocrystals for light emission and a color material layer containing a blue color material.
- the light-emitting nanocrystal in the layer including the light-emitting nanocrystal NC absorbs incident light (light from the light source, preferably blue light) and emits blue light, and incident light (from the light source). Of light emission, preferably blue light) and emits green light, and green light emission nanocrystals that emit incident light (light from a light source, preferably blue light) and emit red light. It is preferable that 1 type or 2 types selected from a group are included. In the present embodiment, a black matrix may be provided for the purpose of preventing color mixing between the color layers.
- a blue color filter on one side so as to be adjacent to the light emitting layer side of the light conversion layer 9 from the viewpoint of preventing unnecessary light from entering and suppressing deterioration in image quality.
- the structure of a modification of the light conversion layer 9 provided with such a blue color filter can be shown in FIG.
- FIG. 7 is a schematic view showing a cross section of another embodiment of the light emitting device 100 of the present invention.
- the embodiment of FIG. 7 differs from the embodiment of FIG. 6 in that a color material layer containing a blue color material (so-called blue color filter) is provided on one side, and the other embodiment is the embodiment shown in FIG. Are omitted here.
- a color material layer containing a blue color material so-called blue color filter
- the light conversion layer, the electron injection layer, the electron transport layer, the light emitting layer, the hole transport layer, and the hole injection layer which are main components of the light emitting device according to the present invention, will be described in detail.
- the constituent elements of the pixel portion include a light-emitting nanocrystal as an essential component, and have an affinity for the resin component and, if necessary, the light-emitting nanocrystal. Molecules, known additives, and other coloring materials. Further, as described above, it is preferable from the viewpoint of contrast that the boundary portion of each pixel layer has a black matrix.
- the light conversion layer according to the present invention contains light-emitting nanocrystals.
- the term “nanocrystal” preferably refers to a particle having at least one length of 100 nm or less.
- the shape of the nanocrystal may have any geometric shape and may be symmetric or asymmetric. Specific examples of the shape of the nanocrystal include an elongated shape, a rod shape, a circle shape (spherical shape), an ellipse shape, a pyramid shape, a disk shape, a branch shape, a net shape, or any irregular shape.
- the nanocrystals are preferably quantum dots or quantum rods.
- the light-emitting nanocrystal preferably has a core including at least one first semiconductor material and a shell that covers the core and includes a second semiconductor material that is the same as or different from the core.
- the light-emitting nanocrystal includes at least a core including the first semiconductor material and a shell including the second semiconductor material, and the first semiconductor material and the second semiconductor material may be the same or different. Further, the core and / or the shell may contain a third semiconductor material other than the first semiconductor and / or the second semiconductor. In addition, what is necessary is just to coat
- the light-emitting nanocrystal further includes a core including at least one first semiconductor material, a first shell covering the core and including a second semiconductor material that is the same as or different from the core, and It is preferable to have a second shell that covers the first shell and includes a third semiconductor material that is the same as or different from the first shell.
- the nanocrystal for light emission according to the present invention has a form having a core containing a first semiconductor material and a shell covering the core and containing the same second semiconductor material as the core, that is, one type or two
- core-only structure also referred to as core structure
- core structure also referred to as core structure
- the light-emitting nanocrystal according to the present invention preferably includes three forms of a core structure, a core / shell structure, and a core / shell / shell structure.
- the core has two or more kinds of semiconductors.
- a mixed crystal containing a material may be used (for example, CdSe + CdS, CIS + ZnS, etc.).
- the shell may also be a mixed crystal containing two or more semiconductor materials.
- the light emitting nanocrystal may have a molecule (so-called ligand) having an affinity for the light emitting nanocrystal in contact with the light emitting nanocrystal.
- the above-mentioned molecules having affinity are low molecules and polymers having a functional group having affinity for the nanocrystals for light emission, and the functional group having affinity is not particularly limited. And a group containing one element selected from the group consisting of oxygen, sulfur and phosphorus. Examples include organic sulfur groups, organic phosphate groups pyrrolidone groups, pyridine groups, amino groups, amide groups, isocyanate groups, carbonyl groups, and hydroxyl groups.
- the semiconductor material according to the present invention is one selected from the group consisting of II-VI group semiconductors, III-V group semiconductors, I-III-VI group semiconductors, IV group semiconductors, and I-II-IV-VI group semiconductors. Or it is preferable that they are 2 or more types.
- Preferable examples of the first semiconductor material, the first semiconductor material, and the third semiconductor material according to the present invention are the same as the semiconductor materials described above.
- the semiconductor material according to the present invention includes CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTTe, HgSeS, HgSeS, HgSe CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, CdHgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe AlSb, InN, InP, InAs, InSb, GaNP, GANAS, GaNSb, GaP s, GaPSb, AlNP, AlNA
- the light emitting nanocrystal according to the present invention is at least selected from the group consisting of a red light emitting nanocrystal that emits red light, a green light emitting nanocrystal that emits green light, and a blue light emitting nanocrystal that emits blue light. It preferably contains one kind of nanocrystal.
- the emission color of a light-emitting nanocrystal depends on the particle size according to the Schrodinger wave equation of the well-type potential model, but also depends on the energy gap of the light-emitting nanocrystal. The emission color is selected by adjusting the crystal and its particle size.
- the upper limit of the wavelength peak of the fluorescence spectrum of the red light emitting nanocrystal emitting red light is 665 nm, 663 nm, 660 nm, 658 nm, 655 nm, 653 nm, 651 nm, 650 nm, 647 nm, 645 nm, 643 nm, 640 nm, 637 nm, 635 nm. 632 nm or 630 nm
- the lower limit of the wavelength peak is preferably 628 nm, 625 nm, 623 nm, 620 nm, 615 nm, 610 nm, 607 nm or 605 nm.
- the upper limit of the wavelength peak of the fluorescence spectrum of the green light emitting nanocrystal emitting green light is 560 nm, 557 nm, 555 nm, 550 nm, 547 nm, 545 nm, 543 nm, 540 nm, 537 nm, 535 nm, 532 nm or 530 nm.
- the lower limit of the wavelength peak is preferably 528 nm, 525 nm, 523 nm, 520 nm, 515 nm, 510 nm, 507 nm, 505 nm, 503 nm or 500 nm.
- the upper limit of the wavelength peak of the fluorescence spectrum of the blue light emitting nanocrystal emitting blue light is 480 nm, 477 nm, 475 nm, 470 nm, 467 nm, 465 nm, 463 nm, 460 nm, 457 nm, 455 nm, 452 nm or 450 nm.
- the lower limit of the wavelength peak is 450 nm, 445 nm, 440 nm, 435 nm, 430 nm, 428 nm, 425 nm, 422 nm or 420 nm.
- the semiconductor material used for the red light emitting nanocrystal emitting red light has a peak wavelength of light emission in the range of 635 nm ⁇ 30 nm.
- the semiconductor material used for the green light emitting nanocrystal that emits green light preferably has a light emission peak wavelength in the range of 530 nm ⁇ 30 nm, and is used for the blue light emitting nanocrystal that emits blue light.
- the semiconductor material to be used preferably has a light emission peak wavelength in the range of 450 nm ⁇ 30 nm.
- the lower limit of the fluorescence quantum yield of the luminescent nanocrystal according to the present invention is preferably in the order of 40% or more, 30% or more, 20% or more, 10% or more.
- the upper limit of the half-value width of the fluorescence spectrum of the luminescent nanocrystal according to the present invention is preferably in the order of 60 nm or less, 55 nm or less, 50 nm or less, and 45 nm or less.
- the upper limit of the particle diameter (primary particle) of the red light emitting nanocrystal according to the present invention is preferably in the order of 50 nm or less, 40 nm or less, 30 nm or less, and 20 nm or less.
- the upper limit value of the peak wavelength of the nanocrystal for red light emission according to the present invention is 665 nm, and the lower limit value is 605 nm, and the compound and its particle size are selected so as to match this peak wavelength.
- the upper limit value of the peak wavelength of the green light emitting nanocrystal is 560 nm
- the lower limit value is 500 nm
- the upper limit value of the peak wavelength of the blue light emitting nanocrystal is 420 nm
- the lower limit value is 480 nm. Select the compound and its particle size.
- the light emitting element or the image display element according to the present invention includes at least one pixel.
- the color constituting the pixel is obtained by three adjacent pixels, and each pixel is red (for example, CdSe light-emitting nanocrystal, CdSe rod-shaped light-emitting nanocrystal, and rod-shaped light-emitting device having a core-shell structure)
- red for example, CdSe light-emitting nanocrystal, CdSe rod-shaped light-emitting nanocrystal, and rod-shaped light-emitting device having a core-shell structure
- the shell portion is CdS
- the inner core portion is ZnSe
- the core shell for example, CdSe light-emitting nanocrystal, CdSe rod-shaped light-emitting nanocrystal, and rod-shaped light-emitting device having a core-shell structure
- nanocrystals for light emission, light-emitting nanocrystal having a core-shell structure, the shell portion is ZnSe, the inner core portion is ZnS, and the rod-shaped light-emitting nanocrystal having a core-shell structure
- a use nanocrystals comprises a core portion inside of the shell portion is a ZnSe is ZnS, light emitting nanocrystals CdS, different nanocrystals that emit in the CdS rod light emitting nanocrystals).
- Other colors for example, yellow
- the average particle diameter (primary particles) of the luminescent nanocrystal according to the present invention can be measured by TEM observation.
- examples of the method for measuring the average particle size of nanocrystals include a light scattering method, a sedimentation type particle size measurement method using a solvent, and a method of actually observing particles with an electron microscope and measuring the average particle size.
- any number of crystals are directly observed with a transmission electron microscope (TEM) or a scanning electron microscope (SEM), and the length of the nanocrystals for light emission is reduced by projection two-dimensional images.
- TEM transmission electron microscope
- SEM scanning electron microscope
- a method is preferred in which the particle diameters are calculated from the diameter ratio and the average is obtained. Therefore, in the present invention, the average particle diameter is calculated by applying the above method.
- the primary particle of the light emitting nanocrystal is a single crystal having a size of several to several tens of nanometers or a crystallite close thereto, and the size and shape of the primary particle of the light emitting nanocrystal is the primary particle. It is considered that it depends on the chemical composition, structure, manufacturing method and manufacturing conditions.
- the light conversion layer in the present invention preferably contains a resin component for appropriately dispersing and stabilizing the light-emitting nanocrystals in addition to the light-emitting nanocrystals described above.
- Such a resin component is preferably a polymer of a photopolymerizable compound and alkali-developable, since the light conversion layer is mainly produced by a photolithography method.
- a resin component is preferably a polymer of a photopolymerizable compound and alkali-developable, since the light conversion layer is mainly produced by a photolithography method.
- Polymer of bifunctional monomer trimethylol propaton triacrylate, pentaerythritol triacrylate, tris [2- (meth) acryloyloxyethyl) isocyanurate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacyl Polymers of relatively low molecular weight small polyfunctional monomers rate, etc., polyester acrylate, polyurethane acrylate, a polymer of a large multi-functional monomer of relatively low molecular weight such as polyether acrylate.
- thermoplastic resins may be used in combination with these polymers.
- examples of the thermoplastic resins include urethane resins, acrylic resins, polyamide resins, polyimide resins, and styrene maleic acid resins. And styrene maleic anhydride resin.
- a polymerization initiator in addition to the transparent resin and the luminescent nanocrystal, a polymerization initiator, a catalyst, alumina, silica, titanium oxide beads, a scattering agent such as zeolite or zirconia, Known additives may be included.
- the light conversion layer according to the present invention includes three-color pixel portions of red (R), green (G), and blue (B), and may include a color material as necessary.
- a color material for example, a diketopyrrolopyrrole pigment and / or an anionic red organic dye in the red (R) pixel portion, and a copper halide phthalocyanine pigment, phthalocyanine-based in the green (G) pixel portion.
- the preferred colorant optionally added together with the luminescent nanocrystals in the red color layer according to the present invention preferably contains a diketopyrrolopyrrole pigment and / or an anionic red organic dye.
- a diketopyrrolopyrrole pigment include C.I. I. One or more selected from Pigment Red 254, 255, 264, 272, Orange 71 and 73 are preferred, and one or more selected from Red 254, 255, 264 and 272 Is more preferred, and C.I. I. Pigment Red 254 is particularly preferable.
- Specific examples of the anionic red organic dye include C.I. I. One or more selected from Solvent Red 124, Acid Red 52 and 289 are preferred. I. Solvent Red 124 is particularly preferred.
- Preferred colorants optionally added together with the light emitting nanocrystals in the green color layer according to the present invention are metal halide phthalocyanine pigments, phthalocyanine green dyes and mixtures of phthalocyanine blue dyes and azo yellow organic dyes. It is preferable to contain at least one selected from the group consisting of Examples of the metal halide phthalocyanine pigment include the following two groups of metal halide phthalocyanine pigments.
- (First group) It has a metal selected from the group consisting of Al, Si, Sc, Ti, V, Mg, Fe, Co, Ni, Zn, Ga, Ge, Y, Zr, Nb, In, Sn and Pb as a central metal, and phthalocyanine
- a metal selected from the group consisting of Al, Si, Sc, Ti, V, Mg, Fe, Co, Ni, Zn, Ga, Ge, Y, Zr, Nb, In, Sn and Pb as a central metal
- phthalocyanine A halogenated metal phthalocyanine pigment in which 8 to 16 halogen atoms per molecule are bonded to the benzene ring of the phthalocyanine molecule.
- the central metal When the central metal is trivalent, the central metal contains one halogen atom, hydroxyl group Or when a sulfonic acid group (—SO 3 H) is bonded and the central metal is a tetravalent metal, the central metal has one oxygen atom or two halogens which may be the same or different.
- a halogenated metal phthalocyanine pigment to which any one of an atom, a hydroxyl group and a sulfonic acid group is bonded.
- Halogen having molecules as structural units and each central metal of these structural units bonded through a divalent atomic group selected from the group consisting of oxygen atom, sulfur atom, sulfinyl (—SO—) and sulfonyl (—SO 2 —)
- a pigment comprising a metal halide phthalocyanine dimer.
- all the halogen atoms bonded to the benzene ring may be the same or different. Different halogen atoms may be bonded to one benzene ring.
- the halogenated metal phthalocyanine pigment used in the present invention in which 9 to 15 bromine atoms out of 8 to 16 halogen atoms per phthalocyanine molecule are bonded to the benzene ring of the phthalocyanine molecule is yellowish. It exhibits a bright green color and is optimal for use in the green pixel portion of the color filter.
- the metal halide phthalocyanine pigment used in the present invention is insoluble or hardly soluble in water or an organic solvent.
- the halogenated metal phthalocyanine pigment used in the present invention includes both a pigment that has not been subjected to a finishing treatment described later (also referred to as a crude pigment) and a pigment that has been subjected to a finishing treatment.
- halogenated metal phthalocyanine pigments belonging to the first group and the second group can be represented by the following general formula (PIG-1).
- the halogenated metal phthalocyanine pigment belonging to the first group is as follows in the general formula (PIG-1).
- X 1 to X 16 each represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom.
- the four X atoms bonded to one benzene ring may be the same or different.
- 8 to 16 are chlorine, bromine or iodine atoms.
- M represents a central metal.
- a pigment having a total of less than 8 chlorine atoms, bromine atoms and iodine atoms out of 16 X 1 to X 16 is blue.
- Y bonded to the central metal M is a monovalent atomic group selected from the group consisting of a halogen atom of any one of fluorine, chlorine, bromine or iodine, an oxygen atom, a hydroxyl group and a sulfonic acid group, and m is bonded to the central metal M. Represents the number of Y to be represented, and is an integer of 0-2.
- m The value of m is determined by the valence of the central metal M.
- One of the groups is attached to the central metal.
- the central metal M is divalent like Mg, Fe, Co, Ni, Zn, Zr, Sn, and Pb, Y does not exist.
- the halogenated metal phthalocyanine pigment belonging to the second group is as follows in the general formula (PIG-1).
- X 1 to X 16 are as defined above, and the central metal M represents a trivalent metal selected from the group consisting of Al, Sc, Ga, Y and In, m represents 1. Y represents the following atomic group.
- the central metal M has the same definition as described above, and X 17 to X 32 have the same definition as X 1 to X 16 in the general formula (PIG-1).
- A represents a divalent atomic group selected from the group consisting of an oxygen atom, a sulfur atom, sulfinyl (—SO—) and sulfonyl (—SO 2 —).
- M in the general formula (PIG-1) and M in the atomic group Y are bonded via the divalent atomic group A.
- the halogenated metal phthalocyanine pigment belonging to the second group is a halogenated metal phthalocyanine dimer in which two molecules of metal halide phthalocyanine are structural units and these are bonded via the divalent atomic group.
- metal halide phthalocyanine pigment represented by the general formula (PIG-1) include the following (1) to (4).
- Mainly divalent metals selected from the group consisting of Mg, Fe, Co, Ni, Zn, Zr, Sn, and Pb, such as halogenated tin phthalocyanine pigment, halogenated nickel phthalocyanine pigment, and halogenated zinc phthalocyanine pigment.
- a halogenated metal phthalocyanine pigment which is a metal and has 8 to 16 halogen atoms bonded to 4 benzene rings per phthalocyanine molecule.
- chlorinated brominated zinc phthalocyanine pigments include C.I. I. Pigment Green 58, which is particularly preferable.
- a trivalent metal selected from the group consisting of Al, Sc, Ga, Y and In, such as a halogenated chloroaluminum phthalocyanine, has one halogen atom, hydroxyl group or sulfonic acid as the central metal.
- a halogenated metal phthalocyanine pigment having any of the groups and having 8 to 16 halogen atoms bonded to 4 benzene rings per phthalocyanine molecule.
- a central metal is a tetravalent metal selected from the group consisting of Si, Ti, V, Ge, Zr and Sn, such as halogenated oxytitanium phthalocyanine and halogenated oxyvanadium phthalocyanine. 8 to 16 halogen atoms bonded to four benzene rings per one phthalocyanine molecule, having one oxygen atom or two halogen atoms which may be the same or different, a hydroxyl group or a sulfonic acid group Halogenated metal phthalocyanine pigment.
- a halogenated ⁇ -oxo-aluminum phthalocyanine dimer and a halogenated ⁇ -thio-aluminum phthalocyanine dimer.
- the valence metal is the central metal
- the halogenated metal phthalocyanine is composed of two molecules of 8-16 halogen atoms bonded to 4 benzene rings per phthalocyanine molecule. Each central metal of these structural units is an oxygen atom.
- a pigment comprising a metal halide phthalocyanine dimer bonded through a divalent atomic group selected from the group consisting of sulfur atom, sulfinyl and sulfonyl.
- C.I. in the green color layer I. Solvent Blue 67 and C.I. I. A mixture with Solvent Yellow 162, or C.I. I.
- Pigment Green 7 and / or 36 are optionally contained.
- the preferred colorant optionally added together with the light emitting nanocrystals in the blue color layer according to the present invention preferably contains an ⁇ -type copper phthalocyanine pigment and / or a cationic blue organic dye.
- the ⁇ -type copper phthalocyanine pigment is C.I. I. Pigment Blue 15: 6.
- Specific examples of the cationic blue organic dye include C.I. I. Solvent Blue 2, 3, 4, 5, 6, 7, 23, 43, 72, 124, C.I. I. Basic Blue 7 and 26 are preferred, and C.I. I. Solvent Blue 7 and Basic Blue 7 are more preferable, and C.I. I. Solvent Blue 7 is particularly preferable.
- C.I. I. Pigment Blue 1 C.I. I. Pigment Violet 23, C.I. I. Basic Blue 7, C.I. I. Basic Violet 10, C.I. I. Acid Blue 1, 90, 83, C.I. I. It is preferable to contain at least one organic dye / pigment selected from the group consisting of Direct Blue 86.
- the light conversion layer according to the present invention includes a yellow (Y) pixel portion (yellow color layer), C.I. I. Pigment Yellow 150, 215, 185, 138, 139, C.I. I. It is also preferable to contain at least one yellow organic dye / pigment selected from the group consisting of Solvent Yellow 21, 82, 83: 1, 33, 162.
- the upper limit of the content of the light-emitting nanocrystals with respect to the transparent resin is preferably 80 parts by mass, 70 parts by mass, 60 parts by mass, or 50 parts by mass with respect to 100 parts by mass of the transparent resin.
- the minimum of content of the nanocrystal for light emission 1.0 mass part, 3.0 mass part, 5.0 mass part, and 10.0 mass parts are preferable with respect to 100 mass parts of transparent resin.
- the above content represents the total amount.
- the light conversion layer according to the present invention is preferably a laminate in which a layer (NC) containing nanocrystals for light emission and a color filter (CF) are laminated (for example, FIG. 19). More specifically, the light conversion layer preferably has a red color layer R, a green color layer G, and a blue color layer B.
- the red (R) pixel portion R includes a layer (NC) including a red light emitting nanocrystal and a color material layer (CF-Red) including a red color material.
- the green (R) pixel portion includes a layer (NC) including a green light emitting nanocrystal and a color material layer (CF-Green) including a green color material or a yellow color material. It is preferably composed of a color material layer (yellow color layer).
- the blue (R) pixel portion includes a color material layer containing a blue color material (CF-Blue color layer containing layer) and / or a transparent resin layer, and optionally emitting blue light. And a layer (NC) containing nanocrystals for use.
- a color filter containing a color material such as a blue color filter (CF-Blue) can be used as appropriate.
- the color filter is preferably formed using the above color material.
- diketopyrrolopyrrole pigment and / or anionic red organic dye in red (R) color filter copper halide phthalocyanine pigment, phthalocyanine green dye, phthalocyanine blue dye in green (G) color filter
- R red
- G green
- at least one selected from the group consisting of a mixture of an azo-based yellow organic dye contains an ⁇ -type copper phthalocyanine pigment and / or a cationic blue organic dye in a blue (B) color filter.
- the color filter may contain the above-described transparent resin, a photocurable compound described later, a dispersant, and the like, if necessary, and the color filter can be produced by a known photolithography method or the like.
- the light conversion layer can be formed by a conventionally known method.
- a typical method for forming the pixel portion is a photolithography method, which is a light-emitting nanocrystal-containing photocurable composition to be described later and a black matrix of a transparent substrate for a conventional color filter.
- pre-baking After applying to the surface on the side, heating and drying (pre-baking), pattern exposure is performed by irradiating ultraviolet rays through a photomask to cure the photocurable compound at the location corresponding to the pixel portion, and then unexposed
- the portion is developed with a developing solution, the non-pixel portion is removed, and the pixel portion is fixed to the transparent substrate.
- a pixel portion composed of a cured colored film of a light-emitting nanocrystal-containing photocurable composition is formed on a transparent substrate.
- a photocurable composition to be described later is prepared for each of other color pixels such as a red (R) pixel, a green (G) pixel, a blue (B) pixel, and a yellow (Y) pixel as necessary, By repeating these operations, a light conversion layer having colored pixel portions of red (R) pixels, green (G) pixels, blue (B) pixels, and yellow (Y) pixels at a predetermined position can be manufactured.
- Examples of a method for applying a light-emitting nanocrystal-containing photocurable composition to be described later on a transparent substrate such as glass include a spin coating method, a roll coating method, and an inkjet method.
- the drying conditions of the coating film of the light-emitting nanocrystal-containing photocurable composition applied to the transparent substrate vary depending on the type of each component, the blending ratio, etc., but usually at 50 to 150 ° C. for about 1 to 15 minutes. is there.
- light used for photocuring of the light-emitting nanocrystal-containing photocurable composition it is preferable to use ultraviolet rays or visible light in a wavelength range of 200 to 500 nm. Various light sources that emit light in this wavelength range can be used.
- Examples of the developing method include a liquid filling method, a dipping method, and a spray method.
- the transparent substrate on which the necessary color pixel portion is formed is washed with water and dried.
- the color filter thus obtained is subjected to a heat treatment (post-baking) at 90 to 280 ° C. for a predetermined time by a heating device such as a hot plate or an oven, thereby removing volatile components in the colored coating film and simultaneously emitting light.
- the unreacted photocurable compound remaining in the cured colored film of the photocurable composition containing the nanocrystals for use is thermally cured to complete the light conversion layer.
- the light-emitting layer color material and resin of the present invention together with the light-emitting nanocrystal of the present invention, deterioration due to blue light or ultraviolet light, an increase in ion density (ID) can be prevented, and display defects such as white spots can be prevented. It is possible to provide an image display device that solves the above problem.
- a dispersion for forming the pixel portion of the light conversion layer is prepared, and then a photocurable compound and A method of forming a light-emitting nanocrystal-containing photocurable composition containing a light-emitting nanocrystal by adding a thermoplastic resin, a photopolymerization initiator, or the like as necessary is common.
- organic solvent used here examples include aromatic solvents such as toluene, xylene, methoxybenzene, ethyl acetate, propyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol methyl ether acetate.
- aromatic solvents such as toluene, xylene, methoxybenzene, ethyl acetate, propyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol methyl ether acetate.
- Acetate solvents such as diethylene glycol ethyl ether acetate, diethylene glycol propyl ether acetate, diethylene glycol butyl ether acetate, propionate solvents such as ethoxyethyl propionate, alcohol solvents such as methanol and ethanol, butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl Ether, diethylene glycol dimethyl ether Ether solvents such as tellurium, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, aliphatic hydrocarbon solvents such as hexane, N, N-dimethylformamide, ⁇ -butyrolactam, N-methyl-2-pyrrolidone, aniline And nitrogen compound solvents such as pyridine, lactone solvents such as ⁇ -butyrolactone, and carbamate esters such as a 48:52 mixture of
- Dispersants used here include, for example, Big Chemie's Dispersic 130, Dispersic 161, Dispersic 162, Dispersic 163, Dispersic 170, Dispersic 171, Dispersic 174, Dispersic 180, Dispersic 182, Dispersic 183, Dispersic 184, Dispersic 185, Dispersic 2000, Dispersic 2001, Dispersic 2020, Dispersic 2050, Dispersic 2070, Dispersic 2096, Dispersic 2150, Dispersic LPN21116, Dispersic LPN6919 Efka EFKA 46, EFKA 47, EFKA 452, EFKA LP4008, EFKA 009, Efka LP4010, Efka LP4050, LP4055, Efka400, Efka401, Evka402, Efka403, Efka450, Efka451, Efka453, Evka4540, Efka4550, EfkaLP4560, Efka120, Efka150, Evka
- rosin such as acrylic resin, urethane resin, alkyd resin, wood rosin, gum rosin, tall oil rosin, polymerized rosin, disproportionated rosin, hydrogenated rosin, oxidized rosin, modified rosin such as maleated rosin, Rosin derivatives such as rosinamine, lime rosin, rosin alkylene oxide adduct, rosin alkyd adduct, rosin modified phenol
- a synthetic resin that is liquid and water-insoluble at room temperature can be contained. Addition of these dispersants and resins also contributes to reduction of flocculation, improvement of pigment dispersion stability, and improvement of viscosity characteristics of the dispersion.
- organic pigment derivatives such as phthalimidomethyl derivatives, sulfonic acid derivatives, N- (dialkylamino) methyl derivatives, N- (dialkylaminoalkyl) sulfonic acid amide derivatives, etc. You can also. Of course, two or more of these derivatives can be used in combination.
- thermoplastic resin used in the preparation of the light-emitting nanocrystal-containing photocurable composition examples include urethane resins, acrylic resins, polyamide resins, polyimide resins, styrene maleic acid resins, and styrene maleic anhydride resins. Examples thereof include resins.
- Examples of the photocurable compound containing nanocrystals for light emission include 1,6-hexanediol diacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, bis (acryloxyethoxy) bisphenol A, 3 -Bifunctional monomers such as methylpentanediol diacrylate, trimethylol propaton triacrylate, pentaerythritol triacrylate, tris [2- (meth) acryloyloxyethyl) isocyanurate, dipentaerythritol hexaacrylate, dipentaerythritol penta Polyfunctional monomers with relatively low molecular weight such as acrylate, polyester acrylate, polyurethane acrylate, polyether acrylate, etc. Large multifunctional monomers comparatively molecular weight and the like.
- photopolymerization initiator examples include acetophenone, benzophenone, benzyldimethylketanol, benzoyl peroxide, 2-chlorothioxanthone, 1,3-bis (4′-azidobenzal) -2-propane, 1,3-bis (4 ′ -Azidobenzal) -2-propane-2'-sulfonic acid, 4,4'-diazidostilbene-2,2'-disulfonic acid, and the like.
- photopolymerization initiators include, for example, “Irgacure (trade name) -184”, “Irgacure (trade name) -369”, “Darocur (trade name) -1173” manufactured by BASF, “Lucirin- "TPO”, Nippon Kayaku Co., Ltd. "Kayacure (trade name) DETX”, “Kayacure (trade name) OA”, Stofer “Bicure 10", “Bicure 55", Akzo "Trigonal PI”, Sand “Sandray 1000" manufactured by Upjohn, “Deep” manufactured by Upjohn, and “Biimidazole” manufactured by Kurokin Kasei.
- a known and commonly used photosensitizer can be used in combination with the photopolymerization initiator.
- the photosensitizer include amines, ureas, compounds having a sulfur atom, compounds having a phosphorus atom, compounds having a chlorine atom, nitriles or other compounds having a nitrogen atom. These can be used alone or in combination of two or more.
- the blending ratio of the photopolymerization initiator is not particularly limited, but is preferably in the range of 0.1 to 30% with respect to the compound having a photopolymerizable or photocurable functional group on a mass basis. If it is less than 0.1%, the photosensitivity at the time of photocuring tends to decrease, and if it exceeds 30%, crystals of the photopolymerization initiator are precipitated when the pigment-dispersed resist coating film is dried. May cause deterioration of film properties.
- the materials as described above on a mass basis, 300 to 100,000 parts of an organic solvent and 1 to 500 parts of an affinity molecule or dispersant per 100 parts of the light-emitting nanocrystal of the present invention.
- the dye / pigment solution can be obtained by stirring and dispersing so as to be uniform.
- an organic solvent is further added, and the light-curable nanocrystal-containing photocurable composition for forming a pixel portion by stirring and dispersing so as to be uniform can be obtained.
- the developer a known and commonly used organic solvent or alkaline aqueous solution can be used.
- the photocurable composition contains a thermoplastic resin or a photocurable compound, and at least one of them has an acid value and exhibits alkali solubility
- the color filter can be washed with an alkaline aqueous solution. It is effective for forming the pixel portion.
- the manufacturing method of the colored pixel part of R pixel, G pixel, B pixel, and Y pixel by the photolithography method was described in detail, the pixel part prepared by using the nanocrystal-containing composition for light emission of the present invention Forming each color pixel portion by other electrodeposition method, transfer method, micellar electrolysis method, PVED (Photovoltaic Electrodeposition) method, ink jet method, reversal printing method, thermosetting method, etc. to produce a light conversion layer Also good.
- the material used for the electron injection layer according to the present invention can be a substance having a small work function, such as an alkali metal such as lithium or cesium or an oxide thereof, a halide thereof or a carbonate thereof, calcium or the like. Examples thereof include alkaline earth metals or oxides thereof, halides thereof or carbonates thereof, Lewis base lithium aluminum alloys such as magnesium silver and magnesium oxide, and the like. These materials are considered to be able to reduce a potential barrier generated when electrons are injected from one electrode. Furthermore, a composite material that exhibits an electron donating property (donor) with respect to a material used for the electron transporting layer may be used.
- a composite material that exhibits an electron donating property (donor) with respect to a material used for the electron transporting layer may be used.
- Examples of the electron donating material include lithium fluoride (LiF) and cesium fluoride (CsF).
- Alkali metal compounds such as calcium fluoride (CaF 2 ) and lithium oxide (LiOx), or alkaline earth metal compounds thereof, and rare earth metal compounds such as erbium fluoride (ErF 3 ).
- a composite material in which an organic compound (acceptor) and an electron donor (donor) are mixed may be used.
- the electron donor may be any substance that exhibits an electron donating property with respect to the acceptor organic compound, and is preferably an alkali metal, an alkaline earth metal, or a rare earth metal, and a compound containing these. Examples include cesium, magnesium, calcium, erbium or ytterbium and compounds containing these, alkali metal oxides and alkaline earth metal oxides being preferred, Lewis bases such as lithium oxide, calcium oxide, magnesium oxide, or barium oxidation A thing etc. are more preferable. Further, an organic material such as tetrathiafulvalene may be used.
- an organic compound (acceptor) an electron is imparted to the organic compound by an electron donor (donor). Therefore, a composite material in which an organic compound (acceptor) and an electron donor (donor) are mixed has an electron injecting property. In addition, it has excellent electron transport properties.
- the organic compound (acceptor) is preferably an electron transporting material described later.
- the material used for the electron transport layer according to the present invention is preferably a material having a higher electron transport property than holes, such as a ⁇ -electron deficient heteroaromatic compound such as a nitrogen-containing heteroaromatic compound or a metal complex.
- a ⁇ -electron deficient heteroaromatic compound such as a nitrogen-containing heteroaromatic compound or a metal complex.
- metal complexes having quinoline ligand, perylene ligand, benzoquinoline ligand, oxazole ligand, or thiazole ligand, fullerene, oxadiazole derivative, triazole derivative, phenanthroline derivative examples thereof include pyridine derivatives, bipyridine derivatives, and pyrimidine derivatives.
- Alq tris (8-quinolinolato) aluminum (III)
- Almq3 tris (4-methyl-8-quinolinolato) aluminum (III)
- bis (10-hydroxybenzo [h] quinolinato) beryllium II
- bis (2-methyl-8-quinolinolato) (4-phenylphenolato) aluminum III
- bis (8-quinolinolato) zinc II
- bis [2- (2-benzoxazolyl) phenolato Zinc II
- 2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole 1,3-bis [5- (p-tert-butylphenyl) -1,3,4-oxadiazol-2-yl] benzene, 9- 4- (5-phenyl-1,3,4-oxadiazol-2-yl) phenyl
- poly (2,5-pyridinediyl), poly [(9,9-dihexylfluorene-2,7-diyl) -co- (pyridine-3,5-diyl)], poly [(9,9-dioctyl) Polymers such as fluorene-2,7-diyl) -co- (2,2′-bipyridine-6,6′-diyl)] may also be used.
- the average film thickness of the electron transport layer according to the present invention is preferably 7 nm to 300 nm.
- the electron transport layer is not limited to a single layer, and a plurality of layers made of the above-described substances may be stacked as necessary, and the electron transport can be controlled between the electron transport layer and the light emitting layer.
- a functional layer such as a hole blocking layer may be provided.
- the light emitting layer 5 preferably has an emission spectrum peak in the blue wavelength region.
- the light-emitting layer may include not only a single layer but also a plurality of layers including two or more layers including a light-emitting material described later.
- a mode including three light emitting layers one of the light emitting layers emits light in a blue (420 nm to 480 nm) wavelength region, and one of the light emitting layers has a green (500 to 560 nm) wavelength region.
- An example is a mode in which light is emitted and one of the light emitting layers emits light in a red (620 to 650 nm) wavelength region.
- a buffer layer may be provided between the blue light-emitting layer, the green light-emitting layer, and the red light-emitting layer in contact with the green light-emitting layer.
- one of the light emitting layers emits light in a blue (420 nm to 480 nm) wavelength region, and one of the light emitting layers has a yellow (570 to 590 nm) wavelength region. The form which light-emits is mentioned.
- a buffer layer may be provided between the blue light-emitting layer and the yellow light-emitting layer as necessary.
- the light emitting layer is a single layer, a light emitting layer that emits light in the blue (420 nm to 480 nm) wavelength region is preferable, and a light emitting layer that emits light in the blue (430 nm to 470 nm) wavelength region is more preferable.
- a light emitting layer that emits light in a blue (440 nm to 460 nm) wavelength region is more preferable.
- a particularly preferable embodiment of the present invention is a single layer in which the light emitting layer emits light in a blue (420 nm or more and 480 nm or less) wavelength region.
- the color display system of the present invention includes a light emitting layer that emits blue light, a light conversion layer that converts blue light from the light emitting layer into green light, and blue light from the light emitting layer into red light.
- a display method in which three colors are developed in combination with a light conversion layer that performs color conversion for conversion is preferable. Blue uses blue of the blue light-emitting layer, and green and red display three colors using light-emitting nanocrystals having different particle diameters and materials.
- the light emitting layer according to the present invention is formed by a physical vapor deposition method (PVD method) such as a vacuum deposition method, a printing method such as a screen printing method and an ink jet printing method, a coating method such as a laser transfer method and a spin coating method, or the like.
- PVD method physical vapor deposition method
- the blue light emitting layer which is the above preferred form can be formed by, for example, a vapor deposition method.
- CBP blue luminescent host material: 4,4′-N, N′-dicarbazolylbiphenyl
- CzC blue luminescent host material: 9- (4-tert-butylphenyl) -3,6-ditrityl-9H-carbazole
- mCP blue light-emitting host material: 1,3-Di-9-carbazolylbenzene
- BD102 blue fluorescent light-emitting material as a blue light-emitting dopant: Idemitsu Kosan Co., Ltd.
- BD102 blue fluorescent light-emitting material as a blue light-emitting dopant: Idemitsu Kosan Co., Ltd.
- the light emitting layer according to the present invention preferably contains a light emitting material (also referred to as a guest material or a dopant) and a host material.
- a light emitting material also referred to as a guest material or a dopant
- the average thickness of the light emitting layer is 1 to 60 nm, and the mixing ratio (mass ratio) of the host material and the guest material is not particularly limited, and is, for example, 10: 1 to 300: 1. It is preferable to adjust to.
- Examples of the light emitting material according to the present invention include a light emitting material capable of converting singlet excitation energy into light emission or a light emitting material capable of converting triplet excitation energy into light emission.
- a luminescent material contained in the electroluminescent layer which concerns on this invention 1 type, or 2 or more types selected from the group which consists of an inorganic luminescent material, an organic low molecular fluorescent material, an organic high molecular fluorescent material, and an organic phosphorescent material is included. It is preferable to include.
- Examples of the light emitting material capable of converting the singlet excitation energy into light emission include low-molecular fluorescent materials or organic polymer fluorescent materials that emit fluorescence,
- the low molecular fluorescent material is preferably a compound having an anthracene structure, tetracene structure, chrysene structure, phenanthrene structure, pyrene structure, perylene structure, stilbene structure, acridone structure, coumarin structure, phenoxazine structure or phenothiazine structure.
- organic polymer fluorescent material examples include compounds represented by the following formulas (P-1) to (P-4).
- a phosphorescent material emitting phosphorescence is preferable.
- a metal complex containing at least one metal atom selected from the group consisting of iridium, rhodium, platinum, ruthenium, osmium, scandium, yttrium, gadolinium, palladium, silver, gold, and aluminum is preferable, iridium, More preferred is a metal complex containing at least one metal atom selected from the group consisting of rhodium, platinum, ruthenium, osmium, scandium, yttrium, gadolinium and palladium, and selected from the group consisting of iridium, rhodium, platinum and ruthenium.
- a metal complex containing at least one metal atom is more preferable, and an iridium complex or a platinum complex is particularly preferable.
- the compound having a blue emission peak for use in the light emitting layer according to the present invention is preferably an iridium metal complex or a platinum metal complex.
- the iridium metal complex together with the above compound include tris ⁇ 2- [5- (2 -Methylphenyl) -4- (2,6-dimethylphenyl) -4H-1,2,4-triazol-3-yl- ⁇ N2] phenyl- ⁇ C ⁇ iridium (III), tris (5-methyl-3,4 -Diphenyl-4H-1,2,4-triazolato) iridium (III), tris [4- (3-biphenyl) -5-isopropyl-3-phenyl-4H-1,2,4-triazolato] iridium (III) Tris [3- (5-biphenyl) -5-isopropyl-4-phenyl-4H-1,2,4-triazolate] iridium (III), Tris [3-Methy
- the following compounds can also be suitably used as compounds having an emission peak in blue for use in the light emitting layer according to the present invention.
- a known compound can be used, and tris (4-methyl-6-phenylpyrimidinato) iridium (III), tris (4-t-butyl-6-phenylpyrimidinato) iridium (III), (acetylacetonato) bis (6-methyl-4-phenylpyrimidinato) iridium (III), (acetylacetonato) bis (6 -Tert-butyl-4-phenylpyrimidinato) iridium (III), (acetylacetonato) bis [4- (2-norbornyl) -6-phenylpyrimidinato] iridium (III), (acetylacetonato) bis [5-Methyl-6- (2-methylphenyl) -4-phenylpyrimidinato] iridium (III), (acetone Ruacetonato) bis ⁇ 4,
- a known compound can be used, for example, (diisobutyrylmethanato) bis [4,6-bis (3-methyl).
- the host material of the light emitting layer As the host material of the light emitting layer according to the present invention, a known material can be used. In that case, the host material is preferably used by selecting one or more compounds having an energy gap larger than that of the light emitting material. In particular, when the light-emitting material is a phosphorescent material, the host material may select a compound having a triplet excitation energy larger than the triplet excitation energy (energy difference between the ground state and the triplet excited state) of the light-emitting material. preferable.
- Examples of the host material include tris (8-quinolinolato) aluminum (III), tris (4-methyl-8-quinolinolato) aluminum (III), bis (10-hydroxybenzo [h] quinolinato) beryllium (II), Bis (2-methyl-8-quinolinolato) (4-phenylphenolato) aluminum (III), bis (8-quinolinolato) zinc (II), bis [2- (2-benzoxazolyl) phenolato] zinc (II ), Bis [2- (2-benzothiazolyl) phenolato] zinc (II), 2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole, 1,3 -Bis [5- (p-tert-butylphenyl) -1,3,4-oxadiazol-2-yl] benzene, 3- (4-biphenyl) Enylyl) -4-phenyl-5- (4-tert-but
- Hole injection layer As the material used for the hole injection layer according to the present invention, a substance that prevents leakage current and improves the hole injection rate can be used. Transition metal oxide, phthalocyanine derivative, aromatic amine, or conductive polymer Compound etc. are mentioned.
- transition metal oxide examples include molybdenum oxide, vanadium oxide, ruthenium oxide, tungsten oxide, and manganese oxide.
- phthalocyanine derivative examples include metal phthalocyanines such as phthalocyanine or copper phthalocyanine.
- the conductive polymer compound examples include polythiophene, polyaniline, polypyrrole, polyphenylene vinylene, polythienylene vinylene, polyquinone, polyquinoxaline, poly (ethylenedioxythiophene) / poly (styrene sulfonic acid), and the like.
- aromatic amine examples include benzidine derivatives, phenylenediamine derivatives, and triarylamine derivatives.
- the hole injection layer according to the present invention may be a composite material in which an organic compound (acceptor) and an electron donor (donor) are mixed.
- the electron donor (donor) include a quinodimethane derivative, a chloranil derivative, and a hexaazatriphenylene derivative. Specifically, 7,7,8,8-tetracyano-2,3,5,6-tetrafluoroquino is used. Examples include dimethane, chloranil, or 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene.
- Examples of the electron donor (donor) include Group 4 to Group 8 metal oxides such as vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide, tungsten oxide, manganese oxide, or rhenium oxide. Is mentioned.
- the material used for the hole transport layer according to the present invention is preferably a material having a hole transport property higher than an electron transport property, such as an aromatic amine, a carbazole derivative or an aromatic hydrocarbon, a stilbene derivative, etc. And a ⁇ -electron rich heteroaromatic or aromatic amine can be suitably used.
- Materials used for the hole transport layer according to the present invention include N, N′-di (p-tolyl) -N, N′-diphenyl-p-phenylenediamine, 4,4′-bis [N- (4 -Diphenylaminophenyl) -N-phenylamino] biphenyl, N, N′-bis ⁇ 4- [bis (3-methylphenyl) amino] phenyl ⁇ -N, N′-diphenyl- (1,1′-biphenyl) -4,4'-diamine, 1,3,5-tris [N- (4-diphenylaminophenyl) -N-phenylamino] benzene, 3- [N- (4-diphenylaminophenyl) -N-phenylamino ] -9-phenylcarbazole, 3,6-bis [N- (4-diphenylaminophenyl) -N-phenylamino] -9-phenylc
- the layer containing a substance having a high hole-transport property is not limited to a single layer, and two or more layers containing the above compound may be stacked.
- the HOMO level of the compound of the hole transport layer is higher than the HOMO level of the compound of the electron transport layer
- the LUMO level of the compound of the hole transport layer is a compound of the electron transport layer It is preferably higher than the LUMO level.
- a thermally activated delayed fluorescent material may be used instead of the above light emitting material.
- the thermally activated delayed fluorescent material has a small difference between the singlet excitation energy level and the triplet excitation energy level, and plays a role in converting energy by reverse intersystem crossing from the triplet excited state to the singlet excited state. Have.
- the thermally activated delayed fluorescent material contains a metal containing at least one selected from the group consisting of fullerene and its derivatives, acridine derivatives (proflavine), magnesium, zinc, cadmium, tin, platinum, indium and palladium. Porphyrins or heterocyclic heat-activated delayed fluorescent materials.
- porphyrin examples include a protoporphyrin-tin fluoride complex (SnF 2 (Proto IX)), a mesoporphyrin-tin fluoride complex (SnF 2 (Meso IX)), and a hematoporphyrin-tin fluoride complex (SnF 2 (Hemato IX)).
- heterocyclic heat-activated delayed fluorescent material examples include compounds represented by the following formulas (II-1) to (II-7).
- Another heterocyclic type heat activated delayed fluorescent material is 2- (biphenyl-4-yl) -4,6-bis (12-phenylindolo [2,3-a] carbazol-11-yl)- 1,3,5-triazine, 2- ⁇ 4- [3- (N-phenyl-9H-carbazol-3-yl) -9H-carbazol-9-yl] phenyl ⁇ -4,6-diphenyl-1,3 , 5-triazine, 2- [4- (10H-phenoxazin-10-yl) phenyl] -4,6-diphenyl-1,3,5-triazine, 3- [4- (5-phenyl-5,10 -Dihydrophenazin-10-yl) phenyl] -4,5-diphenyl-1,2,4-triazole, 3- (9,9-dimethyl-9H-acridin-10-yl) -9H-xanthen-9-one Bis [4- (9,9-di Chill
- the thermally activated delayed fluorescent material may be a single compound or a plurality of two or more compounds.
- the electroluminescence layer (light emitting layer, hole injection layer, hole transport layer, electron transport layer, and electron injection layer) according to the present invention can be formed by a known production method, for example, a vapor deposition method or a vacuum deposition method. Method, inkjet method, coating method, and gravure printing.
- a second aspect of the present invention is an image display element having a light emitting element and a transistor layer.
- an image display element includes a pair of electrodes provided with a first electrode and a second electrode facing each other, an electroluminescence layer provided between the first electrode and the second electrode, and a plurality of electrodes
- a light conversion layer that includes pixels and converts light emitted from the electroluminescence layer having a blue emission spectrum to a different wavelength; and a transistor layer that is electrically connected to the first electrode or the second electrode.
- the light conversion layer includes three primary color pixels of red (R), green (G), and blue (B), and red (R) by light from the electroluminescence layer incident on at least one of the three primary colors.
- Green (G), or blue (B) contains a light-emitting nanocrystal having an emission spectrum.
- An image display element includes a plurality of pixels provided in a grid pattern, and the pixel includes a light emitting element and a transistor layer having a pixel circuit for driving the light emitting element, and scanning line driving described later. Light emission is controlled by signals from the circuit and the signal line driver circuit.
- the transistor layer according to the present invention will be described with reference to FIGS.
- FIG. 8 is a schematic circuit diagram showing a transistor layer according to the present invention, and is an example showing a circuit configuration of a pixel in the image display element according to the present invention.
- each of R, G, and B regions corresponds to one pixel
- the transistor layer includes at least two of a switching transistor 708 and a driving transistor 702 for one pixel.
- the control circuit is a circuit that controls the scanning line driver circuit, the signal line driver circuit, and the image display unit (not shown), and outputs a signal voltage based on a video signal input from the outside. Output to the line drive circuit.
- the image display unit (not shown) includes a plurality of pixels (R, G, B) provided in a lattice shape, and displays an image on the image display unit based on the video signal.
- the scanning line driving circuit is a driving circuit that controls on / off of the switching transistor 708 included in the pixel by outputting a scanning signal to a scanning line 707 provided in the image display portion.
- the signal line driver circuit is connected to the signal line 706 and is a driver circuit having a function of outputting a signal voltage based on a video signal to a pixel.
- the signal line 706 has a function of connecting the signal line driver circuit and each pixel and supplying a signal voltage based on the video signal to each pixel.
- the scan line 707 has a function of connecting the scan line driver circuit and each light emitting pixel and supplying timing for writing the signal voltage.
- the pixel includes a driving transistor 702, a switching transistor 708, a capacitor 701, a light emitting element 100, a signal line 706, a scanning line 707, a power supply line 703, and a common electrode 705.
- the driving transistor 702 has a gate electrode connected to one electrode of the capacitor 701, a source electrode connected to the anode side electrode (anode first electrode) of the light emitting element 100, and a drain electrode connected to the other electrode of the capacitor 701 and the power supply line 703. Is a driving element connected to.
- the driving transistor 702 converts a voltage corresponding to the signal voltage applied between the gate electrode and the source electrode into a drain current corresponding to the signal voltage.
- the driving transistor 702 is preferably composed of a known thin film transistor or the like.
- the power supply line 703 is a wiring for applying a voltage to the drain electrode of the driving transistor 702, and the common electrode 705 is an electrode for applying a voltage to the cathode electrode of the light emitting element 100.
- the switching transistor 708 has a gate electrode connected to the scanning line 707, one of the source electrode and the drain electrode connected to the gate electrode of the driving transistor 702, and the other of the source electrode and the drain electrode connected to the signal line 706. It is an element.
- the capacitor 701 is a capacitive element in which one electrode is connected to the gate electrode of the driving transistor 702 and the other electrode is connected to the drain electrode of the driving transistor 702.
- the light emitting element 100 is a light emitting element in which the cathode side electrode (cathode, second electrode) is connected to the common electrode 705 and the anode side electrode (anode first electrode) is connected to the source electrode of the driving transistor 702. Then, light is emitted according to the current supplied from the driving transistor 702.
- the holes injected from the first electrode 2 and the electrons injected from the second electrode 8 are recombined in the light emitting layer 5 as described above with reference to FIGS.
- This is a top emission type light emitting element that displays the light emitted from the second electrode 8 side. Therefore, in the image display element 101 according to the present invention, the transistor layer including the transistor for driving the pixel circuit is preferably provided between the first electrode 2 and the substrate 1, for example, referring to FIG. 1. In that case, the transistor layer is preferably electrically connected to the first electrode 2.
- the substrate 11 and the overcoat layer are preferably transparent. Further, if necessary, a polarizing layer may be provided on the substrate 11 to block light entering from the outside.
- the light emitting element according to the present invention may be a bottom emission type in which light is extracted from the first electrode 2 side.
- FIG. 10 is a schematic diagram showing a cross section of the image display element 101 of the present invention.
- the image display element 101 of the present invention includes a light emitting element 100 and a transistor layer 20.
- the light-emitting element 100 includes a first electrode 2 and a second electrode 8 as a pair of opposed electrodes, includes an electroluminescence layer 12 between the electrodes, and performs light conversion on the other surface of the first electrode 2.
- Layer 9 is provided.
- a transistor layer 20 including a transistor for driving the pixel circuit is provided between the substrate 1 and the light conversion layer 9.
- the electroluminescent layer 12 only needs to have at least the light emitting layer 5, and the electroluminescent layer 12 according to the present invention includes the electron injection layer 3, the electron transport layer 4, the light emitting layer 5, the hole transport layer 6, and the positive layer. It is preferable to have the hole injection layer 7. Similarly, in the bottom emission type light emitting element and the image display element, an electron blocking layer may be provided between the light emitting layer 5 and the hole transport layer 6 as necessary. If necessary, a hole blocking layer may be provided therebetween.
- the light emitting layer 5 is preferably a light emitting layer that emits blue light.
- the electroluminescence layer 12 has the hole injection layer 3 in contact with the first electrode 2, and the hole transport layer 4, the light emitting layer 5, and the electron transport layer 6 are sequentially stacked. It is a configuration.
- the first electrode 2 is used as an anode and the second electrode 8 is used as a cathode for the sake of convenience.
- the configuration of the light emitting element 100 is not limited to this, and the first electrode 2
- the cathode may be used
- the second electrode 8 may be used as an anode, and the stacking order between these electrodes may be reversed.
- the second electrode 8 on the anode side may be laminated in the order of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.
- the second electrode 8 is a light reflection type electrode having a function of reflecting light (for example, Al, ITO / Ag / ITO). It is preferable that On the other hand, in the case of the top emission type, the second electrode 8 is preferably a transparent electrode.
- the image display element 101 shown in FIG. 10 when a voltage is applied between the first electrode 2 and the second electrode 8, electrons are injected from the cathode second electrode 8 into the electroluminescence layer 12. Then, holes are injected from the first electrode 2 of the anode into the electroluminescence layer 12, and a current flows. The injected electrons and holes recombine to form excitons. Accordingly, the light emitting material included in the light emitting layer 5 is excited, and light emission is obtained from the light emitting material. Thereafter, the light emitted from the light emitting layer 5 passes through the hole transport layer 4, the hole injection layer 3, the first electrode (first transparent electrode) 2, and the transistor layer 20, and is in the plane of the light conversion layer 9. Is incident on.
- the light incident on the light conversion layer 9 is absorbed by the light-emitting nanocrystals and converted into an emission spectrum of red (R), green (G), or blue (B). ), Green (G), or blue (B).
- red (R), green (G), or blue (B) Of the light emitted from the light emitting layer 5, the light traveling toward the second electrode 8 is reflected by the second electrode 8 (reflection type electrode), travels toward the first electrode 2, and is reflected by the light conversion layer 9.
- any one of red (R), green (G), and blue (B) can be displayed.
- the image display element according to the present invention includes a transistor layer electrically connected to the first electrode or the second electrode, and light emitted from the electroluminescence layer is displayed through the light conversion layer and the transistor layer. .
- a preferred configuration of the top emission type image display element is that the substrate 1, the transistor layer 20, the first electrode 2, the hole injection layer 3, the hole transport layer 4, the light emitting layer 5, the electron transport layer 6, and the electron injection.
- the layer 7, the second electrode 8, the light conversion layer 9, and the transparent substrate 11 are sequentially laminated. Therefore, the light emitted from the electroluminescence layer 12 is displayed without passing through the transistor layer 20.
- the light emitting layer 5 is preferably a light emitting layer that emits blue light.
- the polarizing layer according to the present invention is not particularly limited, and a known polarizing plate (polarizing layer) can be used. Examples thereof include a dichroic organic dye polarizer, a coating type polarizing layer, a wire grid type polarizer, or a cholesteric liquid crystal type polarizer.
- the wire grid polarizer is formed on the first substrate, the second substrate, and the color filter, and is formed by any one of nanoimprint method, block copolymer method, E-beam lithography method, and glansing angle deposition method. It is preferable.
- red light emitting nanocrystals CdSe / ZnS oleylamine ligand emission peak 620 nm
- KAYARAD trade name
- DPHA dipentaerystol hexaacrylate
- a polymerization initiator Irgacure
- the mixture was diluted with propylene glycol monomethyl ether acetate, stirred with a dispersion stirrer, and filtered with a filter having a pore size of 1.0 ⁇ m to obtain a red-emitting nanocrystal-containing composition 1.
- Trioctylphosphine oxide (TOPO) 5 g, indium acetate 1.46 g (5 mmol) and lauric acid 3.16 g (15.8 mmol) were added to the reaction flask to obtain a mixture.
- the mixture was heated at 160 ° C. for 40 minutes under a nitrogen (N 2 ) environment, and then heated at 250 ° C. for 20 minutes under vacuum. Subsequently, the reaction temperature (temperature of the mixture) was raised to 300 ° C. under a nitrogen (N 2 ) environment.
- the reaction mixture is cooled to room temperature, and the resulting white precipitate is removed by centrifugation, whereby a transparent nanocrystal particle dispersion (InP / ZnSeS) in which red light-emitting InP / ZnSeS / ZnS nanocrystal particles are dispersed is obtained. / ODE dispersion of ZnS nanocrystal particles).
- a ligand represented by the following formula (1A) is obtained from JEFAMINE M-1000 (manufactured by Huntsman) and JEFAMINE M-1000 and an equimolar amount of succinic anhydride (manufactured by Sigma-Aldrich). It was.
- nanocrystal particles (InP / ZnSeS / ZnS nanocrystal particles modified with the organic ligands) were obtained by decanting the supernatant and drying under vacuum.
- the content of the organic ligand in the total amount of the nanocrystal particles modified with the organic ligand was 30% by mass.
- the obtained nanocrystal particles (InP / ZnSeS / ZnS nanocrystal particles modified with the above-mentioned organic ligand) are dispersed in EOEOA so that the content in the dispersion is 34.5% by mass, thereby emitting red light.
- a nanocrystal dispersion 1 was obtained.
- the content of EOEOA in the dispersion was 65.5% by mass.
- thermosetting resin solution 1 nonvolatile content: 30% by mass
- the mixture was filtered with a filter having a pore size of 5 ⁇ m. By filtering, the nanocrystal containing composition 3 for red light emission was obtained.
- Green light emitting nanocrystal-containing composition 2 instead of the red light emitting nanocrystal CdSe / ZnS of the red light emitting nanocrystal-containing composition, a green light emitting nanocrystal (InP / ZnS oleylamine ligand light emission peak 620 nm) was used in the same manner as described above. A crystal-containing composition 2 was obtained.
- Trioctylphosphine oxide (TOPO) 5 g, indium acetate 1.46 g (5 mmol) and lauric acid 3.16 g (15.8 mmol) were added to the reaction flask to obtain a mixture.
- the mixture was heated at 160 ° C. for 40 minutes under a nitrogen (N 2 ) environment, and then heated at 250 ° C. for 20 minutes under vacuum. Subsequently, the reaction temperature (temperature of the mixture) was raised to 300 ° C. under a nitrogen (N 2 ) environment.
- InP core InP nanocrystal particles
- hexane dispersion liquid containing 5% by mass of InP nanocrystal particles
- the reaction temperature was maintained at 80 ° C. for 10 minutes. The temperature was then raised to 140 ° C. and held for 30 minutes.
- a ZnS precursor solution obtained by dissolving 69 mg of diethylzinc and 66 mg of hexamethyldisilathian in 2 ml of ODE was dropped to form a 2 monolayer ZnS shell.
- the reaction was stopped by removing the heater.
- reaction mixture is cooled to room temperature, and the resulting white precipitate is removed by centrifugation, whereby a transparent nanocrystal particle dispersion liquid (ODE dispersion liquid) in which green light-emitting InP / ZnSeS / ZnS nanocrystal particles are dispersed is obtained.
- ODE dispersion liquid transparent nanocrystal particle dispersion liquid
- nanocrystal particles (InP / ZnSeS / ZnS nanocrystal particles modified with the organic ligands) were obtained by decanting the supernatant and drying under vacuum.
- the content of the organic ligand in the total amount of the nanocrystal particles modified with the organic ligand was 35% by mass.
- the obtained nanocrystal particles (InP / ZnSeS / ZnS nanocrystal particles modified with the above-mentioned organic ligand) are dispersed in EOEOA so that the content in the dispersion is 30.0% by mass, thereby emitting green light.
- Nanocrystalline particle dispersion 1 was obtained.
- the content of EOEOA in the dispersion was 70.0% by mass.
- the green-emitting nanocrystal-containing composition is the same as the red-emitting nanocrystal-containing composition 3 except that the green-emitting nanocrystal particle dispersion 1 is used instead of the red-emitting nanocrystal particle dispersion 1. 3 was prepared.
- a blue coloring composition 1 was prepared by mixing propylene glycol monomethyl ether acetate, Dispersic LPN21116 (manufactured by Big Chemie Co., Ltd.), 0.3-0.4 mm ⁇ zirconia beads “ER-120S” manufactured by Saint-Gobain, and paint conditioner ( (Toyo Seiki Co., Ltd.) for 4 hours, and then filtered through a 1 ⁇ m filter to prepare a dispersion.
- Blue Coloring Composition 2 In the blue coloring composition, blue dye 1 (CI Solvent Blue 7) is put in a polybin, propylene glycol monomethyl ether acetate, Dispersic LPN21116 (manufactured by Big Chemie Co., Ltd.), 0.3-0. 4 mm ⁇ zirconia beads “ER-120S” was added and dispersed with a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) for 4 hours, followed by filtration with a 1 ⁇ m filter to obtain a pigment dispersion.
- a paint conditioner manufactured by Toyo Seiki Co., Ltd.
- (B) Manufacture of light conversion layer (B-1) Photolithographic method A spin-coated nanocrystal-containing composition for red light emission is formed to a thickness of 2 ⁇ m on a glass substrate provided with a TFT on which a black matrix has been formed in advance. It was applied as follows. After drying at 70 ° C. for 20 minutes, striped pattern exposure was performed using a photomask with ultraviolet rays using an exposure machine equipped with an ultrahigh pressure mercury lamp. Spray development with an alkali developer for 90 seconds, washing with ion exchange water, and air drying. Further, post-baking was performed at 180 ° C. for 30 minutes in a clean oven to form red pixels, which are striped colored layers, on a transparent substrate.
- the nanocrystal-containing composition for green light emission is similarly applied by spin coating so that the film thickness becomes 2 ⁇ m.
- the striped colored layer was exposed and developed at a place different from the above-mentioned red pixel by an exposure machine, thereby forming a green pixel adjacent to the above-mentioned red pixel.
- the light conversion layer 1 having stripe-shaped pixels of three colors of red, green, and blue, using the composition for coloring light-emitting nanocrystals or the composition for coloring so as to have the configuration shown in Table 1 below.
- a glass substrate on which a light conversion layer having 3 on the surface and a TFT were laminated was obtained.
- a blue color composition 2 is applied to the entire surface of the light conversion layer 1 and irradiated with ultraviolet rays to form a blue layer on the entire surface of the three-color stripe pixels of red, green, and blue.
- a glass substrate on which the light conversion layer and TFT provided on the surface were laminated was obtained.
- the design of the partition pattern thus created was a pattern having an opening corresponding to a sub-pixel of 100 ⁇ m ⁇ 300 ⁇ m, the line width was 20 ⁇ m, and the thickness was 8 ⁇ m.
- This BM substrate was used for producing a light conversion layer.
- a solid pattern was prepared by the same method, and the contact angle of the solvent (1,4-BDDA) used for the ink was measured. As a result, it was confirmed that it was 45 ° and showed liquid repellency with respect to the solvent.
- the nanocrystal-containing composition 3 for red light emission, the nanocrystal-containing composition 3 for green light emission, and the light-scattering composition ScB was discharged into the opening.
- 16 nozzles were formed in the head portion for ejecting ink of the ink jet printer, and the amount of ink composition used per ejection per nozzle was 10 pL.
- a black matrix (hereinafter also referred to as BM) is placed on the platen (base table) of DMP-2850, the black matrix pattern on the base is aligned with the scanning direction of the head, and alignment is performed. Ink was ejected to the opening at a speed of 6 m / sec.
- the ink was discharged and formed into a film until the thickness of the cured ink film reached 80% or more of the black matrix partition wall thickness.
- the thickness of the ink cured film printed and cured in the opening of the BM was measured with a light interference type film thickness meter (Vert Scan).
- the ink was dried and cured as follows.
- the ink was thermosetting, since it contained a solvent, it was dried under reduced pressure, then heated in a nitrogen atmosphere at 100 ° C. for 3 minutes, and then heated and cured at 150 ° C. for 30 minutes.
- blue light is applied to the BM substrate with a pixel portion that converts blue light into red light, a pixel portion that converts blue light into green light, and a light scattering agent-containing dispersion that does not contain luminescent nanocrystals. And a pixel portion to be transmitted (without color conversion).
- a patterned light conversion layer 4 having a plurality of types of pixel portions was obtained.
- the light emitting element 1 including the electroluminescence layer emitting blue light has the following configuration.
- the following TAPC was used as the hole transport layer of the light emitting device 1.
- mCP was used as the electronic block layer of the light-emitting element 1.
- the light emitting material uses the following compound,
- the following mCP was used as a host material for the first light emitting layer of the light emitting element 1.
- the light emitting material uses the following compound,
- the following UGH2 was used as a host material for the second light emitting layer of the light emitting element 1.
- the above UGH2 was used as the hole blocking layer of the light emitting element 1.
- the following compounds were used as the electron transport layer of the light emitting device 1.
- the hole transport layer, the electron blocking layer, the first light emitting layer, the second light emitting layer, the hole blocking layer, and the electron transport layer are arranged in this order. Patterning is performed to form a blue light-emitting layer by the method described in “Appl. Mater. Interfaces 2013, 5, 7341-7351”, and (LiF / Al) electrode as a cathode and a protective layer in this order.
- the image display elements 1A to 4A each having a light emitting element that emits blue light were produced by forming a solid film on the film and laminating the films.
- the light-emitting element 2 provided with the electroluminescence layer emitting blue light specifically has the following configuration.
- the following TAPC was used as the hole transport layer of the light emitting element 2.
- the light emitting material uses the following compounds,
- mCPPO1 was used as a host material for the light emitting layer of the light emitting element 2.
- the following compounds were used as the electron transport layer of the light emitting device 2.
- the hole transport layer, the electron blocking layer, the light emitting layer, the hole blocking layer, and the electron transport layer are patterned in this order to form a blue light emitting layer.
- a (LiF / Al) electrode as a cathode and a protective layer were sequentially formed and laminated in this order to produce image display elements 1B to 4B having light emitting elements that emit blue light.
- the color reproduction regions of the image display elements 1A to 4A and the image display elements 1B to 4B obtained above were measured. As a result, it was confirmed that the color reproduction region of the former was expanded in both the image display element having the light conversion layer and the conventional organic EL element not having the light conversion layer.
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Abstract
Description
なお、本発明に係るエレクトロルミネッセンス層12は、正孔若しくは電子の注入のポテンシャル障壁を低下させる目的、正孔若しくは電子の輸送性を上げる目的、正孔若しくは電子の輸送性を阻害する目的または電極による消光現象を抑制・防止する目的で、種々の効果を発現する層を、必要により単層または複数層形成してもよい。
次に、本発明における光変換層につき更に詳述すれば、その画素部の構成要素は、発光用ナノ結晶を必須成分として含み、樹脂成分、その他必要により当該発光用ナノ結晶に対して親和性のある分子、公知の添加剤、その他色材を含有してもよいものである。また、前記した通り、各画素層の境界部分にはブラックマトリックスを有することがコントラストの点から好ましい。
本発明に係る光変換層は、発光用ナノ結晶を含有する。本明細書における用語「ナノ結晶」は、好ましくは、100nm以下の少なくとも1つの長さを有する、粒子を指す。ナノ結晶の形状は、任意の幾何学的形状を有してもよく、対称または不対称であってよい。当該ナノ結晶の形状の具体例としては、細長、ロッド状の形状、円形(球状)、楕円形、角錐の形状、ディスク状、枝状、網状または任意の不規則な形状等を含む。一部の実施形態では、ナノ結晶は、量子ドットまたは量子ロッドであることが好ましい。
本発明に係る光変換層は、赤(R)、緑(G)、青(B)の三色画素部を備え、必要により色材を含んでもよく、当該色材としては、公知の色材を使用することができ、例えば、赤(R)の画素部中にジケトピロロピロール顔料及び/又はアニオン性赤色有機染料を、緑(G)の画素部中にハロゲン化銅フタロシニアン顔料、フタロシアニン系緑色染料、フタロシアニン系青色染料とアゾ系黄色有機染料との混合物からなる群から選ばれる少なくとも一種を、青(B)の画素部中にε型銅フタロシニアン顔料及び/又はカチオン性青色有機染料を含有することが好ましい。
Al、Si、Sc、Ti、V、Mg、Fe、Co、Ni、Zn、Ga、Ge、Y、Zr、Nb、In、Sn及びPbからなる群から選ばれる金属を中心金属として有し、フタロシアニン分子1個当たり8~16個のハロゲン原子がフタロシアニン分子のベンゼン環に結合したハロゲン化金属フタロシアニン顔料であり、その中心金属が三価の場合には、その中心金属には1つのハロゲン原子、水酸基又はスルホン酸基(-SO3H)のいずれかが結合しており、中心金属が四価金属の場合には、その中心金属には1つの酸素原子又は同一でも異なっていても良い2つのハロゲン原子、水酸基又はスルホン酸基のいずれかが結合しているハロゲン化金属フタロシアニン顔料。
Al、Sc、Ga、Y及びInからなる群から選ばれる三価金属を中心金属とし、フタロシアニン分子1個当たり8~16個のハロゲン原子がフタロシアニン分子のベンゼン環に結合したハロゲン化金属フタロシアニンの2分子を構成単位とし、これら構成単位の各中心金属が酸素原子、硫黄原子、スルフィニル(-SO-)及びスルホニル(-SO2-)からなる群から選ばれる二価原子団を介して結合したハロゲン化金属フタロシアニン二量体からなる顔料。
本発明に係る光変換層は、発光用ナノ結晶を含む層(NC)とカラーフィルタ(CF)とを積層させた積層体であることが好ましい(例えば、図19)。より詳細には、当該光変換層は、赤色の色層Rと、緑色の色層Gと、青色の色層Bと、を有することが好ましい。この場合、赤色(R)の画素部R(赤色の色層部R)は、赤色発光用ナノ結晶を含む層(NC)と赤色の色材を含む色材層(CF‐Red)とで構成されることが好ましい。緑色(R)の画素部(緑色の色層部G)は、緑色発光用ナノ結晶を含む層(NC)と緑色の色材を含む色材層(CF‐Green)または黄色の色材を含む色材層(黄色の色層)とで構成されることが好ましい。青色(R)の画素部(青色の色層部B)は、青色の色材を含む色材層(CF‐Blue 青色の色材を含む層)および/または透明樹脂層と、必要により青色発光用ナノ結晶を含む層(NC)とで構成されることが好ましい。本発明では、図4~図7における光変換画素層に積層される色材層(CF―Green、CF-Red)、図5~図7におけるカラーフィルタ(CFL)、図3、図5などにおける青色カラーフィルタ(CF-Blue)のように色材を含むカラーフィルタを適宜使用することができる。
光変換層は、従来公知の方法で形成することができる。画素部の形成方法の代表的な方法としては、フォトリソグラフィー法であり、これは、後記する発光用ナノ結晶含有光硬化性組成物を、従来のカラーフィルタ用の透明基板のブラックマトリックスを設けた側の面に塗布、加熱乾燥(プリベーク)した後、フォトマスクを介して紫外線を照射することでパターン露光を行って、画素部に対応する箇所の光硬化性化合物を硬化させた後、未露光部分を現像液で現像し、非画素部を除去して画素部を透明基板に固着させる方法である。この方法では、発光用ナノ結晶含有光硬化性組成物の硬化着色皮膜からなる画素部が透明基板上に形成される。
本発明に係る電子注入層に使用する材料は、仕事関数の小さい物質を用いることができ、リチウムやセシウム等のアルカリ金属若しくはこれらの酸化物、これらのハロゲン化物またはこれらの炭酸塩、カルシウム等のアルカリ土類金属若しくはこれらの酸化物、これらのハロゲン化物またはこれらの炭酸塩、マグネシウム銀、酸化マグネシウムのようなルイス塩基リチウムアルミニウム合金などが挙げられる。これらの材料は、一方の電極からの電子注入の際に生じるポテンシャル障壁を低減することができると考えられる。さらには、電子輸送層に用いる材料に対して電子供与性(ドナー)を示す複合材料を使用してもよく、当該電子供与性材料としては、フッ化リチウム(LiF)、フッ化セシウム(CsF)、フッ化カルシウム(CaF2)、及びリチウム酸化物(LiOx)等のようなアルカリ金属化合物、またはこれらのアルカリ土類金属化合物、フッ化エルビウム(ErF3)等の希土類金属化合物が挙げられる。
本発明に係る電子輸送層に使用する材料は、正孔よりも電子の輸送性の高い材料を使用することが好ましく、含窒素複素芳香族化合物等のπ電子不足型複素芳香族または金属錯体などが挙げられ、例えば、キノリン配位子、ペリレン配位子、ベンゾキノリン配位子、オキサゾール配位子、またはチアゾール配位子を有する金属錯体、フラーレン、オキサジアゾール誘導体、トリアゾール誘導体、フェナントロリン誘導体、ピリジン誘導体、ビピリジン誘導体またはピリミジン誘導体などが挙げられる。
本発明に係る発光層5は、青色の波長領域に発光スペクトルピークを有することが好ましい。また、発光層は、単層だけでなく、後述の発光材料を含む層が二層以上の複数層を有してもよい。例えば、発光層を3つ備える形態としては、発光層の一つが青色(420nm以上480nm以下)の波長領域の光を発光し、発光層の一つが緑色(500以上~560nm以下)の波長領域の光を発光し、発光層の一つが赤色(620以上~650nm以下)の波長領域の光を発光する形態が挙げられる。その場合、青色の発光層と、緑色の発光層および当該緑色の発光層と接する赤色の発光層との間にバッファー層を設けてもよい。また、発光層を2つ備える形態としては、発光層の一つが青色(420nm以上480nm以下)の波長領域の光を発光し、発光層の一つが黄色(570以上~590nm以下)の波長領域の光を発光する形態が挙げられる。その場合、青色の発光層と、黄色の発光層との間に必要によりバッファー層を設けてもよい。また発光層が単層の場合は、青色(420nm以上480nm以下)の波長領域の光を発光する発光層が好ましく、青色(430nm以上470nm以下)の波長領域の光を発光する発光層がより好ましく、青色(440nm以上460nm以下)の波長領域の光を発光する発光層がさらに好ましい。
当該低分子蛍光材料としては、アントラセン構造、テトラセン構造、クリセン構造、フェナントレン構造、ピレン構造、ペリレン構造、スチルベン構造、アクリドン構造、クマリン構造、フェノキサジン構造またはフェノチアジン構造を有する化合物が好ましく、例えば、5,6-ビス[4-(10-フェニル-9-アントリル)フェニル]-2,2’-ビピリジン、5,6-ビス[4’-(10-フェニル-9-アントリル)ビフェニル-4-イル]-2,2’-ビピリジン(、N,N’-ビス[4-(9H-カルバゾール-9-イル)フェニル]-N,N’-ジフェニルスチルベン-4,4’-ジアミン、4-(9H-カルバゾール-9-イル)-4’-(10-フェニル-9-アントリル)トリフェニルアミン、4-(9H-カルバゾール-9-イル)-4’-(9,10-ジフェニル-2-アントリル)トリフェニルアミン、N,9-ジフェニル-N-[4-(10-フェニル-9-アントリル)フェニル]-9H-カルバゾール-3-アミン、4-(10-フェニル-9-アントリル)-4’-(9-フェニル-9H-カルバゾール-3-イル)トリフェニルアミン、4-[4-(10-フェニル-9-アントリル)フェニル]-4’-(9-フェニル-9H-カルバゾール-3-イル)トリフェニルアミン、ペリレン、2,5,8,11-テトラ(tert-ブチル)ペリレン、N,N’-ジフェニル-N,N’-ビス[4-(9-フェニル-9H-フルオレン-9-イル)フェニル]ピレン-1,6-ジアミン、N,N’-ビス(3-メチルフェニル)-N,N’-ビス[3-(9-フェニル-9H-フルオレン-9-イル)フェニル]-ピレン-1,6-ジアミン、N,N’-ビス(ジベンゾフラン-2-イル)-N,N’-ジフェニルピレン-1,6-ジアミン、N,N’-ビス(ジベンゾチオフェン-2-イル)-N,N’-ジフェニルピレン-1,6-ジアミン、N,N’’-(2-tert-ブチルアントラセン-9,10-ジイルジ-4,1-フェニレン)ビス[N,N’,N’-トリフェニル-1,4-フェニレンジアミン]、N,9-ジフェニル-N-[4-(9,10-ジフェニル-2-アントリル)フェニル]-9H-カルバゾール-3-アミン、N-[4-(9,10-ジフェニル-2-アントリル)フェニル]-N,N’,N’-トリフェニル-1,4-フェニレンジアミン、N,N,N’,N’,N’’,N’’,N’’’,N’’’-オクタフェニルジベンゾ[g,p]クリセン-2,7,10,15-テトラアミン、クマリン30、N-(9,10-ジフェニル-2-アントリル)-N,9-ジフェニル-9H-カルバゾール-3-アミン、N-(9,10-ジフェニル-2-アントリル)-N,N’,N’-トリフェニル-1,4-フェニレンジアミン、N,N,9-トリフェニルアントラセン-9-アミン、クマリン6、クマリン545T、N,N’-ジフェニルキナクリドン、ルブレン、5,12-ビス(1,1’-ビフェニル-4-イル)-6,11-ジフェニルテトラセン、2-(2-{2-[4-(ジメチルアミノ)フェニル]エテニル}-6-メチル-4H-ピラン-4-イリデン)プロパンジニトリル、2-{2-メチル-6-[2-(2,3,6,7-テトラヒドロ-1H,5H-ベンゾ[ij]キノリジン-9-イル)エテニル]-4H-ピラン-4-イリデン}プロパンジニトリル、N,N,N’,N’-テトラキス(4-メチルフェニル)テトラセン-5,11-ジアミン、7,14-ジフェニル-N,N,N’,N’-テトラキス(4-メチルフェニル)アセナフト[1,2-a]フルオランテン-3,10-ジアミン、2-{2-イソプロピル-6-[2-(1,1,7,7-テトラメチル-2,3,6,7-テトラヒドロ-1H,5H-ベンゾ[ij]キノリジン-9-イル)エテニル]-4H-ピラン-4-イリデン}プロパンジニトリル、2-{2-tert-ブチル-6-[2-(1,1,7,7-テトラメチル-2,3,6,7-テトラヒドロ-1H,5H-ベンゾ[ij]キノリジン-9-イル)エテニル]-4H-ピラン-4-イリデン}プロパンジニトリル、2-(2,6-ビス{2-[4-(ジメチルアミノ)フェニル]エテニル}-4H-ピラン-4-イリデン)プロパンジニトリル、2-{2,6-ビス[2-(8-メトキシ-1,1,7,7-テトラメチル-2,3,6,7-テトラヒドロ-1H,5H-ベンゾ[ij]キノリジン-9-イル)エテニル]-4H-ピラン-4-イリデン}プロパンジニトリルまたは5,10,15,20-テトラフェニルビスベンゾ[5,6]インデノ[1,2,3-cd:1’,2’,3’-lm]ペリレンなどが挙げられる。
本発明に係る正孔注入層に使用する材料は、リーク電流の防止や正孔の注入率を向上させる物質を用いることができ、遷移金属酸化物、フタロシアニン誘導体、芳香族アミンまたは導電性高分子化合物などが挙げられる。
本発明に係る正孔輸送層に使用する材料は、電子の輸送性よりも正孔の輸送性の高い材料を使用することが好ましく、芳香族アミン、カルバゾール誘導体又は芳香族炭化水素、スチルベン誘導体などが挙げられ、π電子過剰型複素芳香族又は芳香族アミンなどを好適に用いることができる。
(光変換層またはカラーフィルタの製造)
(A)赤色発光用ナノ結晶含有組成物、緑色発光用ナノ結晶含有組成物および青色(発光用ナノ結晶含有)組成物の作製
[光拡散粒子分散液]
窒素ガスで満たした容器内で、酸化チタン(商品名:MPT141、石原産業株式会社製、平均粒子径(体積平均径):100nm)を2.4gと、高分子分散剤としてDISPERBYK-2164(BYK社製の商品名、「DISPERBYK」は登録商標)を0.4gと、1,4-ブタンジオールジアセテートを混合した後、得られた混合物にジルコニアビーズ(直径:1.25mm)を加え、ペイントコンディショナーを用いて2時間振とうさせることで混合物の分散処理し、ポリエステルメッシュフィルタにてジルコニアビーズを除去することで光拡散粒子分散液1(不揮発分:44質量%)を得た。
赤色発光用ナノ結晶(CdSe/ZnS オレイルアミンリガンド 発光ピーク620nm)30質量部と、ジぺンタエリストールヘキサアクリレート(KAYARAD(商標名)DPHA、日本化薬株式会社製)30質量部と、重合開始剤(Irgacure-907(商標名) BASF社製)5質量部と、ポリエステルアクリレート樹脂(アロニックス(商標名)M7100、東亜合成化学工業株式会社製)30質量部とを混合して、固形分が20質量%となるようにプロピレングリコールモノメチルエーテルアセテートで希釈し、分散撹拌機で撹拌し、孔径1.0μmのフィルタで濾過し、赤色発光用ナノ結晶含有組成物1を得た。
上記赤色発光用ナノ結晶含有組成物の赤色発光用ナノ結晶CdSe/ZnSに代え、赤色発光用ナノ結晶(InP/ZnS オレイルアミンリガンド 発光ピーク530nm)を用いて、上記と同様にして、赤色発光用ナノ結晶含有組成物2を得た。
トリオクチルホスフィンオキサイド(TOPO)5g、酢酸インジウム1.46g(5mmol)及びラウリン酸3.16g(15.8mmol)を反応フラスコに添加し混合物を得た。窒素(N2)環境下において混合物を160℃にて40分間加熱した後、真空下で250℃にて20分間加熱した。次いで、反応温度(混合物の温度)を窒素(N2)環境の下で300℃に昇温した。この温度で、1-オクタデセン(ODE)3gとトリス(トリメチルシリル)ホスフィン0.25g(1mmol)との混合物を反応フラスコに迅速に導入し、反応温度を260℃に維持した。5分後、ヒーターの除去により反応を停止させ、得られた反応溶液を室温に冷却した。次いで、トルエン8ml及びエタノール20mlをグローブボックス中の反応溶液に添加した。続いて遠心分離を行いInPナノ結晶粒子を沈殿させた後、上澄みの傾瀉によってInPナノ結晶粒子を得た。次いで、得られたInPナノ結晶粒子をヘキサンに分散させた。これにより、InPナノ結晶粒子を5質量%含有する分散液(ヘキサン分散液)を得た。
上記赤色発光用ナノ結晶含有組成物の赤色発光用ナノ結晶CdSe/ZnSに代え、緑色発光用ナノ結晶(CdSe/ZnS オレイルアミンリガンド 発光ピーク530nm)を用いて、上記と同様にして、緑色発光用ナノ結晶含有組成物1を得た。
上記赤色発光用ナノ結晶含有組成物の赤色発光用ナノ結晶CdSe/ZnSに代え、緑色発光用ナノ結晶(InP/ZnS オレイルアミンリガンド 発光ピーク620nm)を用いて、上記と同様にして、緑色発光用ナノ結晶含有組成物2を得た。
トリオクチルホスフィンオキサイド(TOPO)5g、酢酸インジウム1.46g(5mmol)及びラウリン酸3.16g(15.8mmol)を反応フラスコに添加し混合物を得た。窒素(N2)環境下において混合物を160℃にて40分間加熱した後、真空下で250℃にて20分間加熱した。次いで、反応温度(混合物の温度)を窒素(N2)環境の下で300℃に昇温した。この温度で、1-オクタデセン(ODE)3gとトリス(トリメチルシリル)ホスフィン0.25g(1mmol)との混合物を反応フラスコに迅速に導入し、反応温度を260℃に維持した。5分後、ヒーターの除去により反応を停止させ、得られた反応溶液を室温に冷却した。次いで、トルエン8ml及びエタノール20mlをグローブボックス中の反応溶液に添加した。続いて遠心分離を行いInPナノ結晶粒子(InPコア)を沈殿させた後、上澄みの傾瀉によってInPナノ結晶粒子(InPコア)を得た。次いで、得られたInPナノ結晶粒子(InPコア)をヘキサンに分散させて、InPナノ結晶粒子(InPコア)を5質量%含有する分散液(ヘキサン分散液)を得た。
青色着色用組成物1は、プロピレングリコールモノメチルエーテルアセテート、ディスパービックLPN21116(ビックケミー株式会社製)、Saint-Gobain社製0.3-0.4mmφジルコニアビーズ「ER-120S」を混合し、ペイントコンディショナー(東洋精機株式会社製)で4時間分散した後、1μmのフィルタで濾過して分散液を調製した。次いで、当該分散液75質量部、ポリエステルアクリレート樹脂(アロニックス(商標名)M7100、東亜合成化学工業株式会社製)5.5質量部、ジぺンタエリストールヘキサアクリレート(KAYARAD(商標名)DPHA、日本化薬株式会社製)5質量部、ベンゾフェノン(KAYACURE(商標名)BP-100、日本化薬株式会社製)1質量部およびユーカーエステルEEP13.5質量部を分散撹拌機で撹拌し、孔径1.0μmのフィルタで濾過し、青色着色組成物1を得た。
青色着色組成物は、青色染料1(C.I.Solvent Blue 7)をポリビンに入れ、プロピレングリコールモノメチルエーテルアセテート、ディスパービックLPN21116(ビックケミー株式会社製)、Saint-Gobain社製0.3-0.4mmφジルコニアビーズ「ER-120S」を加え、ペイントコンディショナー(東洋精機株式会社製)で4時間分散した後、1μmのフィルタで濾過し顔料分散液を得た。
上記赤色発光用ナノ結晶分散体1(上記のInP/ZnSコアシェルナノ結晶(赤色発光性)を含む)の代わりに、1,4-ブタンジオールジアセテートを用い、赤色発光用ナノ結晶含有組成物3と同様にして光散乱性インク組成物ScBを得た。
(B-1)フォトリソグラフィー法
予めブラックマトリックスが形成されてあるTFTを設けたガラス基板上に、赤色発光用ナノ結晶含有組成物をスピンコートにより膜厚2μmとなるように塗布した。70℃で20分間乾燥の後、超高圧水銀ランプを備えた露光機にて紫外線をフォトマスクを介してストライプ状のパターン露光をした。アルカリ現像液にて90秒間スプレー現像、イオン交換水で洗浄し、風乾した。さらに、クリーンオーブン中で、180℃で30分間ポストベークを行い、ストライプ状の着色層である赤色画素を透明基板上に形成した。
無アルカリガラスからなるガラス基板(日本電気硝子社製の「OA-10G」)上に金属クロムをスパッタリング後、フォトリソグラフィー法にてパターン形成したのち、フォトレジストSU-8(日本化薬株式会社製)を塗布、露光、現像、ポストベークして、クロムパターン上に、SU-8パターンを形成した。
以上の操作により、複数種の画素部を備えるパターン付き光変換層4を得た。
(発光素子1及び画像表示素子1A~4Aの作製)
上記光変換層1~4が積層されたTFT積層ガラス基板の表面の光変換層上に対してITO電極を蒸着した後、当該ITO電極上に、「Appl. Mater. Interfaces 2013, 5, 7341-7351.」に記載の方法で青色発光するエレクトロルミネッセンス層を備えた発光素子1を設けた後、ITO電極とTFT層とをコンタクトホールを介して電気的に接続して、上記光変換層1~4に対応する画像表示素子1~4を作製した。当該青色発光するエレクトロルミネッセンス層を備えた発光素子1は具体的には以下の構成である。
上記光変換層1~4が積層されたTFT積層ガラス基板の表面の光変換層上に対してITO電極を蒸着した後、当該ITO電極上に、「J. Mater. Chem. C, 2014, 2, 6040-6047」に記載の方法で青色発光するエレクトロルミネッセンス層を備えた発光素子2を設けた後、ITO電極とTFT層とをコンタクトホールを介して電気的に接続して、上記光変換層1~4に対応する画像表示素子1B~3Bを作製した。
2 第一電極
3 正孔注入層
4 正孔輸送層
5 発光層
6 電子輸送層
7 電子注入層
8 第二電極
9 光変換層
10 オーバーコート層(保護層)
11 基板
10 トランジスタ層
100 発光素子
101 画像表示素子
701 コンデンサ
702 駆動トランジスタ
703 電源線
705 共通電極
706 信号線
707 走査線
708 スイッチングトランジスタ
Claims (11)
- 第一電極および第二電極が対向して設けられる一対の電極と、
前記第一電極と第二電極と間に設けられたエレクトロルミネッセンス層と、
複数の画素からなり、青色の発光スペクトルを有する前記エレクトロルミネッセンス層が発光した光を異なる波長に変換する光変換層と、を有し、
前記光変換層は、赤色(R)、緑色(G)および青色(B)の三原色画素を備え、前記三原色の内少なくとも一色に入射した前記エレクトロルミネッセンス層からの光により赤色(R)、緑色(G)、青色(B)の何れかに発光スペクトルを有する発光用ナノ結晶を含有することを特徴とする発光素子。 - 前記エレクトロルミネッセンス層は、無機発光材料、低分子蛍光材料、有機高分子蛍光材料、燐光材料および熱活性化遅延蛍光材料からなる群から選択される1種又は2種以上の発光材料を含む請求項1記載の発光素子。
- 前記低分子蛍光材料は、アントラセン構造、テトラセン構造、クリセン構造、フェナントレン構造、ピレン構造、ペリレン構造、スチルベン構造、アクリドン構造、クマリン構造、フェノキサジン構造及びフェノチアジン構造からなる群から選択される少なくとも1種を有する化合物である、請求項2記載の発光素子。
- 前記燐光材料は、イリジウム、ロジウム、白金、ルテニウム、オスミウム、スカンジウム、イットリウム、ガドリニウム、パラジウム、銀、金、アルミニウムからなる群から選択される少なくとも1種の金属原子を含む金属錯体である、請求項2記載の発光素子。
- 前記発光材料は、当該発光材料のエネルギーギャップより大きなエネルギーギャップを有するホスト材料を、一種又は2以上種選択して使用する、請求項2~4のいずれか1項に記載の発光素子。
- 前記青色の発光スペクトルを有する前記エレクトロルミネッセンス層が発光した光は、420nmから480nmにピークを有する請求項2記載の発光素子。
- 前記光変換層において、赤色(R)、緑色(G)及び青色(B)域の少なくとも一つの発光スペクトルの半値幅が20から50nmである請求項1記載の発光素子。
- 前記光変換層において発光用ナノ結晶が、第一の半導体材料を少なくとも1種又は2種以上含むコアと、
前記コアを被覆し、かつ前記コアと同一または異なる第二の半導体材料を含むシェルとを有する、請求項1~6のいずれか1項に記載の発光素子。 - 前記第一の半導体材料は、II-VI族半導体、III-V族半導体、I-III-VI族半導体、IV族半導体及びI-II-IV-VI族半導体からなる群から選択される1種又は2種以上である、請求項7記載の発光素子。
- 前記第一電極または前記第二電極と電気的に接続されたトランジスタ層を備え、前記エレクトロルミネッセンス層で発光した光は、前記光変換層および前記トランジスタ層を介して表示される、請求項1~9のいずれか1項に記載の画像表示素子。
- 前記第一電極または前記第二電極と電気的に接続されたトランジスタ層を備え、前記エレクトロルミネッセンス層で発光した光は、前記トランジスタ層を介することなく表示される、請求項1~9のいずれか1項に記載の画像表示素子。
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| JP2020015838A (ja) * | 2018-07-26 | 2020-01-30 | Dic株式会社 | インク組成物、光変換層及びカラーフィルタ |
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| JP2022191228A (ja) * | 2018-09-27 | 2022-12-27 | カティーバ, インコーポレイテッド | 量子ドットカラーフィルタインク組成物、および量子ドットカラーフィルタインク組成物を利用したデバイス |
| JP7522474B2 (ja) | 2018-09-27 | 2024-07-25 | カティーバ, インコーポレイテッド | 量子ドットカラーフィルタインク組成物、および量子ドットカラーフィルタインク組成物を利用したデバイス |
| JPWO2020111150A1 (ja) * | 2018-11-30 | 2021-02-25 | Dic株式会社 | カラーフィルタ |
| CN111435671A (zh) * | 2019-01-13 | 2020-07-21 | 群创光电股份有限公司 | 发光装置 |
| CN111435671B (zh) * | 2019-01-13 | 2024-01-09 | 群创光电股份有限公司 | 发光装置 |
| JP2020129535A (ja) * | 2019-02-06 | 2020-08-27 | 株式会社半導体エネルギー研究所 | 発光デバイス、発光装置、電子機器、表示装置および照明装置 |
| JP2024056985A (ja) * | 2019-02-06 | 2024-04-23 | 株式会社半導体エネルギー研究所 | 発光装置、表示装置及および電子機器 |
| WO2020161575A1 (en) * | 2019-02-06 | 2020-08-13 | Semiconductor Energy Laboratory Co., Ltd. | Light-emitting device, light-emitting apparatus, electronic device, display device, and lighting device |
| US12200952B2 (en) | 2019-02-06 | 2025-01-14 | Semiconductor Energy Laboratory Co., Ltd. | Light-emitting device, light-emitting apparatus, electronic device, display device, and lighting device |
| KR20220007002A (ko) * | 2020-07-09 | 2022-01-18 | 서울대학교산학협력단 | 나선광결정 기반 양자점 컬러 디스플레이 장치 및 이의 제조방법 |
| KR102689352B1 (ko) | 2020-07-09 | 2024-07-30 | 서울대학교산학협력단 | 나선광결정 기반 양자점 컬러 디스플레이 장치 및 이의 제조방법 |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI745519B (zh) | 2021-11-11 |
| KR102374025B1 (ko) | 2022-03-14 |
| CN110115106A (zh) | 2019-08-09 |
| US20190393273A1 (en) | 2019-12-26 |
| JPWO2018123805A1 (ja) | 2019-10-31 |
| KR20190094355A (ko) | 2019-08-13 |
| US11049911B2 (en) | 2021-06-29 |
| TW201838174A (zh) | 2018-10-16 |
| US20210366997A1 (en) | 2021-11-25 |
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