(19)
(11)EP 3 709 773 A1

(12)EUROPEAN PATENT APPLICATION
published in accordance with Art. 153(4) EPC

(43)Date of publication:
16.09.2020 Bulletin 2020/38

(21)Application number: 18875190.3

(22)Date of filing:  07.11.2018
(51)Int. Cl.: 
H05B 33/14  (2006.01)
H01L 27/32  (2006.01)
H05B 33/02  (2006.01)
G09F 9/30  (2006.01)
H01L 51/50  (2006.01)
H05B 33/26  (2006.01)
(86)International application number:
PCT/JP2018/041259
(87)International publication number:
WO 2019/093345 (16.05.2019 Gazette  2019/20)
(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR
Designated Extension States:
BA ME
Designated Validation States:
KH MA MD TN

(30)Priority: 08.11.2017 JP 2017215800

(71)Applicant: NS Materials Inc.
Chikushino City Fukuoka 818-0042 (JP)

(72)Inventors:
  • MIYANAGA, Akiharu
    Chikushino-city Fukuoka 818-0042 (JP)
  • ITO, Tetsuji
    Chikushino-city Fukuoka 818-0042 (JP)
  • WATANABE, Mayuko
    Chikushino-city Fukuoka 818-0042 (JP)

(74)Representative: SSM Sandmair 
Patentanwälte Rechtsanwalt Partnerschaft mbB Joseph-Wild-Straße 20
81829 München
81829 München (DE)

  


(54)DISPLAY DEVICE


(57) Provided is a display device containing quantum dots. A display device (1) includes a display area. The display area has a light emitting device in which a first electrode (11), a layer (12) between the first electrode and an emitting layer, the emitting layer (13), a layer (14) between the emitting layer and a second electrode, and the second electrode (15) are stacked in this order on a substrate. The emitting layer is formed of an inorganic layer containing quantum dots, and the light emitting device is a bottom emission device. All the layers from the first electrode to the second electrode are preferably each formed of the inorganic layer.







Description

TECHNICAL FIELD



[0001] The present invention relates to a display device using quantum dots.

BACKGROUND ART



[0002] JP 2017-045650 A (PTL 1) discloses an invention relating to organic electro-luminescence (EL).

[0003] An organic EL device has a structure in which an anode, a hole injection layer, a hole transport layer, an emitting layer, an electron transport layer, an electron injection layer, and a cathode are stacked on a substrate. Such an organic EL device is formed from an organic compound and emits light from excitons formed by the recombination of electrons and holes injected into the organic compound.

CITATION LIST


Patent Literature



[0004] PTL 1: JP 2017-045650 A

SUMMARY OF INVENTION


(Technical Problem)



[0005] In recent years, light emitting devices using quantum dots are being developed. Quantum dots are nanoparticles made of around several hundreds to several thousands of atoms, each having a particle diameter of around several nanometers to several tens of nanometers. Quantum dots are also referred to as fluorescent nanoparticles, semiconductor nanoparticles, or nanocrystals. The emission wavelength of quantum dots may be variously changed depending on the particle diameter and the composition of the nanoparticles. As with an organic EL device, a light emitting device using quantum dots makes it possible to obtain a thinner device and surface emission.

[0006] However, the layered structure of bottom emission light emitting devices using quantum dots has not yet been established.

[0007] The present invention is made in consideration of the above, and seeks to provide a display device having a light emitting device that includes quantum dots.

(Solution to Problem)



[0008] A display device according to the present invention includes a display area. The display area has a light emitting device in which a first electrode, a layer between the first electrode and an emitting layer, the emitting layer, a layer between the emitting layer and a second electrode, and the second electrode are stacked in this order on a substrate. The emitting layer is formed of an inorganic layer containing quantum dots, and the light emitting device is a bottom emission device.

[0009] In an aspect of the present invention, all the layers from the first electrode to the second electrode are preferably each formed of an inorganic layer.

[0010] In another aspect of the present invention, the layer between the first electrode and the emitting layer, the emitting layer, and the layer between the emitting layer and the second electrode are preferably each constituted by the inorganic layer formed from nanoparticles.

[0011] In yet another aspect of the present invention, the display device is preferably flexible.

[0012]  In yet another aspect of the present invention, the quantum dots preferably have a structure in which a surface of a core is not covered by a shell.

[0013] In yet another aspect of the present invention, at least one of the layer between the first electrode and the emitting layer, the emitting layer, and the layer between the emitting layer and the second electrode is formed by an inkjet process.

[0014] In yet another aspect of the present invention, all the layers situated between the first electrode and the second electrode are preferably formed by coating.

(Advantageous Effects of Invention)



[0015] In a display device of the present invention, the layered structure of light emitting devices containing quantum dots, used in a display device can be optimized. Further, in the present invention, all the layers from the anode to the cathode can be formed of inorganic layers.

BRIEF DESCRIPTION OF DRAWINGS



[0016] In the accompanying drawings:

FIG. 1 is a partial plan view of a display device according to one embodiment;

FIG. 2 is a partial enlarged cross-sectional view illustrating one of display areas of the display device depicted in FIG. 1 that is enlarged;

FIG. 3 is a cross-sectional view illustrating the structure of a thin film transistor different from one in FIG. 2;

FIG. 4A is a cross-sectional view of a light emitting device of Embodiment 1, and FIG. 4B is an energy level diagram of each layer in a display device of Embodiment 1;

FIG. 5 is a schematic view of a quantum dot according to one embodiment;

FIGS. 6A to 6C are cross-sectional views each illustrating a light emitting device according to an embodiment different from that in FIG. 1;

FIG. 7A is an energy level diagram in the case of using quantum dots having a core-shell structure, and FIG. 7B is an energy level diagram in the case of using quantum dots having a structure in which a core is not covered by a shell;

FIG. 8A is a cross-sectional view of a light emitting device different from one in FIG. 4, and FIG. 8B is an energy level diagram of each layer in the light emitting device of FIG. 8A;

FIGS. 9A to 9C are cross-sectional views each illustrating a light emitting device according to an embodiment different from that in FIG. 8;

FIG. 10A is an energy level diagram in the case of using quantum dots having a core-shell structure, and FIG. 10B is an energy level diagram in the case of using quantum dots having a structure in which a core is not covered by a shell;

FIG. 11 is a schematic view illustrating a step of forming an inorganic layer by the inkjet process;

FIG. 12 is a photograph showing an application in Examples;

FIG. 13 shows PYS measurement data of Cd-based green quantum dots;

FIG. 14 shows PYS measurement data;

FIG. 15 is an energy level diagram of each layer in the light emitting device used in an experiment;

FIG. 16 is a graph illustrating the relationship between the current value and the EQE of an EL emitter and a PL emitter using green quantum dots;

FIG. 17 shows plots illustrating the relationship between the current value and the EQE of an EL emitter and a PL emitter using red quantum dots; and a plot illustrating the relationship between the current value and the EQE of an EL emitter using blue quantum dots;

FIG. 18 presents a graph illustrating the energy band gap Eg of each layer in the light emitting device used in an experiment, the energy ECB at the bottom of the conduction band, and the energy EVB at the top of the conduction band, and an energy level diagram of the layers;

FIG. 19 shows the UV data of ZnOx(Li) and ZnOx(K) used in an electron transport layer (ETL);

FIG. 20 shows the PL data of ZnOx(Li) and ZnOx(K) used in an electron transport layer (ETL);

FIG. 21 shows the PYS data of ZnOx(Li) and ZnOx(K) used in an electron transport layer (ETL); and

FIG. 22A and FIG. 22B are schematic views illustrating the structures for improving the outcoupling efficiency of bottom emission devices.


DESCRIPTION OF EMBODIMENTS



[0017] Embodiments of the present invention (hereinafter simply referred to as "embodiments") will now be described in detail. Note that the present invention is not limited to the following embodiments, and various modifications may be made without departing from the spirit of the present invention.

[0018] As illustrated in FIG. 1, a plurality of display areas 2 are arranged in a matrix in the display device 1. The display areas 2 fall into three types: red emission regions 2a emitting red light, green emission regions 2b emitting green light, and blue emission regions 2c emitting blue light. These three emission regions 2a, 2b, and 2c are for example arranged in a row direction to form a set constituting one pixel for color display.

[0019] In each of the emission regions 2a, 2b, and 2c, a light emitting device 3 is formed. The layer structure of the light emitting device 3 will be described below. A thin film transistor (TFT) 4 is connected to each light emitting device 3. The light emitting devices 3 are bottom emission devices.

[0020] As illustrated in FIG. 2, the thin film transistor 4 is built in such a manner that a gate electrode 4a, a channel layer 4b, a gate insulating film (not shown), a drain electrode 4c, a source electrode 4d, etc. are stacked on a substrate 5. The channel layer 4b is formed from a P-type semiconductor, for example, amorphous silicon; however, the material of the layer is not limited to this. The thin film transistor 4 depicted in FIG. 2 has a top-contact bottom-gate configuration; alternatively, the thin film transistor 4 may have a bottom-contact bottom-gate configuration.

[0021] The source electrode 4d is connected to a power supply line, and the drain electrode 4c is connected to the light emitting device 3.

[0022] Further, the thin film transistor 4 may have a top-gate configuration depicted in FIG. 3. As illustrated in FIG. 3, the channel layer 4b is formed on the substrate 5, and the surface of the channel layer 4b is covered with the gate insulating film 4e. The gate electrode 4a is formed on the surface of the gate insulating film 4e. As illustrated in FIG. 3, the surface of the gate electrode 4a is covered with an insulating film 4f. Further, a plurality of through holes extending through the gate insulating film 4e and the insulating film 4f to reach the channel layer 4b, and the drain electrode 4c and the source electrode 4d are formed in the respective through holes. Further, the surfaces of the drain electrode 4c and the source electrode 4d are covered with a protective film 7. Further, a transparent electrode connected to the drain electrode 4c and the source electrode 4d is formed on the surface of the protective film 7. The transparent electrode 8 depicted in FIG. 3 is connected to the drain electrode 4c.

[0023] The channel layer 4b of the thin film transistor 4 shown in FIG. 3 is formed from, for example, P-Si.

[0024] As illustrated in FIG. 2, the display device 1 has a structure in which the thin film transistor 4 and the light emitting device 3 are interposed between a pair of substrates 5 and 6, and, although not shown, sealing resin is provided in a frame pattern between the substrates 5 and 6 so that the substrates 5 and 6 are connected with the sealing resin therebetween.

[0025]  Hereinafter, the structure of the light emitting device 3 will be described. FIG. 4A is a cross-sectional view of a light emitting device of Embodiment 1, and FIG. 4B is an energy level diagram of each layer in a display device of Embodiment 1.

[0026] As shown in FIG. 4A, the light emitting device 3 is configured to have a substrate 10, an anode 11 formed on the substrate, a hole transport layer (HTL) 12 formed on the anode 11, an emitting layer (EML) 13 formed on the hole transport layer 12, an electron transport layer (ETL) 14 formed on the emitting layer 13, and a cathode 15 formed on the electron transport layer 14. In this embodiment, the anode 11 is built as a first electrode, and the cathode 15 is built as a second electrode.

[0027] When a voltage is applied to between the electrodes of the light emitting device 3 in this embodiment, holes are injected from the anode 11, and electrons are injected from the cathode 15. FIG. 4B shows the energy level models of the hole transport layer 12, the emitting layer 13, and the electron transport layer 14. As shown in FIG. 4B, holes transported through the hole transport layer 12 are injected from the HOMO level of the hole transport layer 12 into the HOMO level of the emitting layer 13. On the other hand, electrons transported through the electron transport layer 14 are injected from the LUMO level of the electron transport layer 14 into the LUMO level of the emitting layer 13. The holes and electrons are recombined in the emitting layer 13, which promotes quantum dots in the emitting layer 13 to the excited state, thus light emission from the excited quantum dots can be achieved.

[0028] In this embodiment, the emitting layer 13 is formed of an inorganic layer containing quantum dots.

(Quantum dot)



[0029] For example, quantum dots in this embodiment are nanoparticles having a particle diameter of around several nanometers to several tens of nanometers; however, the structure and the material of the quantum dots are not limited to those.

[0030] For example, quantum dots are formed from CdS, CdSe, ZnS, ZnSe, ZnSeS, ZnTe, ZnTeS, InP, (Zn)AgInS2, (Zn)CuInS2, etc. Because of the toxicity of Cd, the use of Cd is restricted in many countries; thus, quantum dots are preferably free of Cd.

[0031] As shown in FIG. 5A, many organic ligands 21 are preferably placed on the surface of a quantum dot 20. This can inhibit aggregation of quantum dots 20, resulting in the target optical properties. The ligands available for the reaction are not particularly limited; for example, the following ligands can be given as typical examples.
Aliphatic primary amines: oleylamine: C18H35NH2, stearyl(octadecyl)amine: C18H37NH2, dodecyl(lauryl)amine: C12H25NH2, decylamine: C10H21NH2, octylamine: C8H17NH2
Aliphatic acids: oleic acid: C17H33COOH, stearic acid: C17H35COOH, palmitic acid: C15H31COOH, myristic acid: C13H27COOH, lauric (dodecanoic) acid: C11H23COOH, decanoic acid: C9H19COOH, octanoic acid: C7H15COOH
Thiols: octadecanethiol: C18H37SH, hexadecanethiol: C16H33SH, tetradecanethiol: C14H29SH, dodecanethiol: C12H25SH, decanethiol: C10H21SH, octanethiol: C8H17SH
Phosphines: trioctylphosphine: (C8H17)3P, triphenylphosphine: (C6H5)3P, tributylphosphine: (C4H9)3P
Phosphine oxides: trioctylphosphine oxide: (C8H17)3P=O, triphenylphosphine oxide: (C6H5)3P=O, tributylphosphine oxide: (C4H9)3P=O

[0032] A quantum dot 20 depicted in FIG. 5B has a core-shell structure having a core 20a and a shell 20b covering the surface of the core 20a. As shown in FIG. 5B, many organic ligands 21 are preferably placed on the surface of the quantum dot 20. The core 20a of the quantum dot 20 shown in FIG. 5B is the nanoparticle shown in FIG. 5A. Accordingly, the core 20a is formed for example from the materials listed above. The shell 20b is formed from, for example, zinc sulfide (ZnS); however, the material of the shell 20b is not limited to this. As with the core 20a, the shell 20b is preferably free of cadmium (Cd).

[0033] The shell 20b may be in a condition of being a solid solution on the surface of the core 20a. In FIG. 5B, the boundary between the core 20a and the shell 20b is indicated by a dotted line, and this means that the boundary between the core 20a and the shell 20b may or may not be identified by an analysis.

(Emitting layer 13)



[0034] The emitting layer 13 may be formed from the above-mentioned quantum dots alone; alternatively, the emitting layer 13 may contain the quantum dots and another luminescent material other than the quantum dots. Further, the emitting layer 13 may be formed by applying quantum dots dissolved in a solvent, for example, by the inkjet process. Here, a slight amount of the solvent component may be left in the emitting layer 13.

[0035] Red quantum dots emitting red light are contained in the emitting layer 13 of the light emitting devices 3 formed in the red emission regions 2a depicted in FIG. 1. Further, green quantum dots emitting green light are contained in the emitting layer 13 in the light emitting devices 3 formed in the green emission regions 2b depicted in FIG. 1. Further, blue quantum dots emitting blue light are contained in the emitting layer 13 in the light emitting devices 3 formed in the blue emission regions 2c depicted in FIG. 1.

[0036] Note that the wavelength of blue emission is preferably around 450 nm. Thus, health risks can be reduced by adjustments such that light of a wavelength shorter than 450 nm is not emitted can.

[0037]  The emitting layer 13 can be formed by an existing thin film formation method such as the inkjet process and vacuum deposition mentioned above.

(Hole transport layer 12)



[0038] The hole transport layer 12 is made from an inorganic material or an organic material having hole transporting functions. The hole transport layer 12 is preferably made from an inorganic material, for example, is preferably formed from an inorganic oxide such as NiO or WO3. In particular, the hole transport layer 12 is preferably formed from nanoparticles of NiO. Further, for use in the hole transport layer 12, for example, Al2O3 or the like may be mixed in NiO. And, a metal oxide may be doped with Li, Mg, Al, etc. Further, the hole transport layer 12 may be of an inorganic material other than inorganic oxides.

[0039] As with the emitting layer 13, the hole transport layer 12 can be formed by a printing process such as the inkjet process, or may be formed by an existing thin film technique such as vacuum deposition.

(Electron transport layer 14)



[0040] The electron transport layer 14 is made from an inorganic material or an organic material having electron transporting functions. The electron transport layer 14 is preferably made from an inorganic material, for example, is preferably formed from an inorganic oxide such as ZnOx, Ti-O, Zn-O, Sn-O, V-O, or Mo-O. Two or more of these materials may be selected as materials. In particular, the electron transport layer 14 is preferably formed from nanoparticles of ZnOx. And, a metal oxide may be doped with Li, Mg, Al, Mn, etc. Further, the electron transport layer 14 may be made of an inorganic material (for example, CsPbBr3 etc.) other than inorganic oxides. X is, but not limited to, around 0.8 to 1.2.

[0041] As with the emitting layer 13, the electron transport layer 14 can be formed by applying a solvent containing nanoparticles by a printing process such as the inkjet process, or may be formed by an existing thin film technique such as vacuum deposition.

(Anode 11)



[0042] In this embodiment, the material for forming the anode 11, is preferably for example, but not limited to, a compound oxide of indium-tin (ITO), a metal such as Au, a conductive transparent material such as CuISnO2, or ZnOx. Of those, the anode 11 is preferably formed from ITO. The anode 11 can be formed as a thin film of the electrode material on the substrate 10 by a method such as vapor deposition or sputtering.

[0043] In this embodiment, since a structure in which light is given off from the substrate 10 side is used, the anode 11 needs to be a transparent electrode, and is preferably one of the metal oxides mentioned above or an extremely thin metal film.

(Cathode 15)



[0044] In this embodiment, for example, a metal, an alloy, an electrically conductive compound, and a mixture of those can be used as an electrode material of the cathode 15; however, the material of the cathode 15 is not limited to those. Examples of the electrode material include Al, Mg, Li, and mixtures of these. Of those, the cathode 15 is preferably formed from Al.

[0045] The cathode 15 can be formed as a thin film of the electrode material by a method such as vapor deposition or sputtering.

(Substrate 10)



[0046] In this embodiment, the substrate 10 can be formed of, for example, glass or plastic; however, the material of the substrate 10 is not limited to these. In this embodiment, since a structure in which light is given off from the substrate 10 side (thin film transistor side) is used, the substrate 10 is preferably a transparent substrate. Examples of the transparent substrate include, for example, glass, quartz, and transparent resin films.

[0047] The substrate 10 may either be a rigid substrate or a flexible substrate; when a flexible substrate is used, a flexible device can be obtained. Examples of the material of the transparent film include, for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyester, polyethylene, polypropylene, cellophane, cellulose diacetate, and cellulose triacetate (TAC).

[0048] In the display device 1 in FIG. 2, using flexible substrates for the substrates 5 and 6, the display device 1 can be flexible. Note that the substrates 5 and 6 can also be formed using a similar material to that of the substrate 10. The substrate 5 can also serve as the substrate 10.

[0049] In this embodiment, all the layers from the anode 11 to the cathode 15, that is, all the anode 11, the hole transport layer 12, the emitting layer 13, the electron transport layer 14, and the cathode 15 can each be formed of an inorganic layer. Forming all the layers from inorganic layers allow all the layers to be formed using the same coating/drying apparatuses, etc. and facilitates the production process. Further, the high-low relationships of the HOMO levels of the anode 11, the hole transport layer 12, and the emitting layer 13 can be optimized; the high-low relationships of the LUMO levels of the cathode 15, the electron transport layer 14, and the emitting layer 13 can be optimized. This improves the carrier balance as compared with the case of using organic compounds.

[0050] In Embodiment 1 illustrated in FIG. 4, a hole injection layer and an electron injection layer are not formed separately from the transport layers, thus the number of the layers can be reduced. Namely, the transport layers also serve as injection layers. Note however that in this embodiment, a hole injection layer and an electron injection layer made of an inorganic material may be interposed between the electrodes and the transport layers.

[0051] FIG. 6A is a cross-sectional view of a light emitting device of Embodiment 2. In FIG. 6A, the anode 11, a hole injection layer (HIL) 16, the hole transport layer 12, the emitting layer 13, the electron transport layer 14, and the cathode 15 are stacked in this order on the substrate 10. Unlike in FIG. 4A, in FIG. 6A, the hole injection layer 16 is placed between the anode 11 and the hole transport layer 12.

[0052] FIG. 6B is a cross-sectional view of a light emitting device of Embodiment 3. In FIG. 6B, the anode 11, the hole transport layer 12, the emitting layer 13, the electron transport layer 14, an electron injection layer (EIL) 18, and the cathode 15 are stacked in this order on the substrate 10. Unlike in FIG. 4A, in FIG. 6B, the electron injection layer 18 is placed between the electron transport layer 14 and the cathode 15.

[0053] FIG. 6C is a cross-sectional view of a light emitting device of Embodiment 4. In FIG. 6C, the anode 11, the hole injection layer 16, the hole transport layer 12, the emitting layer 13, the electron transport layer 14, the electron injection layer 18, and the cathode 15 are stacked in this order on the substrate 10. Unlike in FIG. 4A, in FIG. 6C, the hole injection layer 16 is placed between the anode 11 and the hole transport layer 12, and in addition, the electron injection layer 18 is placed between the electron transport layer 14 and the cathode 15.

[0054] The material of the hole injection layer 16 and the electron injection layer 18 may be either an inorganic material or an organic material. Forming the hole injection layer 16 and the electron injection layer 18 from inorganic layers is preferred because all the layers from the anode 11 to the cathode 15 can each be formed of an inorganic layer. However, the material of the injection layers is not limited to this. The material of the hole injection layer 16 and the electron injection layer 18 is selected from various kinds of materials depending on the energy level models.

[0055] In this embodiment, the layer between the anode 11 and the emitting layer 13 is preferably a layer serving as the hole transport layer 12, the hole injection layer 16, or both the hole injection layer and the hole transport layer; or a layer in which the hole transport layer 12 and the hole injection layer 16 are stacked.

[0056] In this embodiment, the layer between the cathode 15 and the light emitting layer 13 is preferably a layer serving as the electron transport layer 14, the electron injection layer 18, or both the electron injection layer and the electron transport layer; or a layer in which the electron transport layer 14 and the electron injection layer 18 are stacked.

[0057] Note that in the structure of the display device 1 depicted in FIG. 2, the thin film transistor 4 has, for example, a bottom-gate configuration, and the drain electrode 4c is connected to the anode 11 of the light emitting device 3. Here, the drain electrode 4c can be made to serve as the anode 11 without forming the anode 11 superposed on the drain electrode 4c. This allows the light emitting device 3 to be suitably connected with the thin film transistor 4 and the ground line.

[0058] In this embodiment, the hole transport layer 12, the emitting layer 13, and the electron transport layer 14 can all be inorganic layers formed from nanoparticles. In such a case, each layer can be formed by printing by the inkjet process or the like, thus the layers can be formed easily and formed to be uniform in thickness. This can effectively improve emission efficiency.

[0059] When the quantum dots used in the emitting layer 13 of this embodiment have a core-shell structure, the energy level diagram presented in FIG. 7A is obtained, and the energy level of the shell would be as a barrier to the recombination of holes and electrons. Accordingly, a quantum dot of which surface is not covered with a shell (the surface of the core is exposed, or the material forming the quantum dot is uniform from the center of the quantum dot to the surface thereof) as shown in FIG. 7B is preferably used. Using such quantum dots eliminates the energy barrier to the recombination of hole and electrons, and allows holes and electrons to be efficiently recombined, thus the light emission efficiency can be improved. With a view to improving the electron transportation efficiency and the hole transportation efficiency, the organic ligands 21 are preferably placed on the surface of each quantum dot 20 as illustrated in FIG. 5A.

[0060] Further, in this embodiment, as illustrated in FIG. 8A, the light emitting device 3 may be configured to have the substrate 10, the cathode 15 formed on the substrate, the electron transport layer (ETL) 14 formed on the cathode 15, the emitting layer (EML) 13 formed on the electron transport layer 14, the hole transport layer (HTL) 12 formed on the light emitting layer 13, and the anode 11 formed on the hole transport layer 12.

[0061] The materials of the layers are as described above. Note that in FIG. 8A, the anode 11 forms a second electrode, and the cathode 15 forms a first electrode. Since the light emitting device 3 of this embodiment is a bottom emission device, the cathode 15 is preferably formed as a transparent electrode of ITO etc., and the anode 11 is preferably made of an opaque material such as Al that can reflect light. This allows light to be reflected at the anode 11 and light to be given off from the cathode 15 side (thin film transistor side).

[0062] FIG. 9A is a cross-sectional view of a light emitting device according to a different embodiment from FIG. 8A. In FIG. 9A, the cathode 15, the electron transport layer 14, the emitting layer 13, the hole transport layer 12, the hole injection layer (HIL) 16, and the anode 11 are stacked in this order on the substrate 10. Unlike in FIG. 8A, in FIG. 9A, the hole injection layer 16 is placed between the anode 11 and the hole transport layer 12.

[0063] FIG. 9B is a cross-sectional view of a light emitting device according to a different embodiment from FIG. 8A. In FIG. 9B, the cathode 15, the electron injection layer (EIL) 18, the electron transport layer 14, the emitting layer 13, the hole transport layer 12, and the anode 11 are stacked in this order on the substrate 10. Unlike in FIG. 8A, in FIG. 9B, the electron injection layer 18 is placed between the electron transport layer 14 and the cathode 15.

[0064] FIG. 9C is a cross-sectional view of a light emitting device according to a different embodiment from FIG. 8A. In FIG. 9C, the cathode 15, the electron injection layer 18, the electron transport layer 14, the emitting layer 13, the hole transport layer 12, the hole injection layer 16, and the anode 11 are stacked in this order on the substrate 10. Unlike in FIG. 8A, in FIG. 9C, the hole injection layer 16 is placed between the anode 11 and the hole transport layer 12, and in addition, the electron injection layer 18 is placed between the electron transport layer 14 and the cathode 15.

[0065] When the quantum dots used in the emitting layer 13 of this embodiment in FIG. 8A to FIG. 9C have a core-shell structure, the energy level diagram presented in FIG. 10A is obtained, and the energy level of the shell would be as a barrier to the recombination of holes and electrons. Accordingly, using quantum dots in which the surface of the core is not covered with a shell as depicted in FIG. 10B eliminates the energy barrier to the recombination of hole and electrons, and allows holes and electrons to be efficiently recombined, thus the light emission efficiency can be improved. With a view to improving the electron transportation efficiency and the hole transportation efficiency, the organic ligands 21 are preferably placed on the surface of each quantum dot 20 as illustrated in FIG. 5A.

[0066] The light emitting devices of the embodiments shown in FIG. 8A to FIG. 9C are inverted EL devices having a layered structure opposite to ones in FIGS. 4A and 4B and FIGS. 6A to 6C. The thin film transistor is preferably an n-ch TFT, and an In-Ga-Zn-O-based semiconductor can be preferably used in the channel layer. Alternatively, Poly-Si can also be preferably used.

[0067] As described above, since the light emitting device 3 of this embodiment is a bottom emission device, the first electrode on the substrate 10 side is a transparent electrode, and the second electrode away from the substrate 10 is preferably formed from an opaque material (preferably a metal) that is excellent in the light reflectivity.

[0068] In this embodiment, at least one of the layer between the anode 11 and the emitting layer 13, the emitting layer 13, and the layer between the emitting layer 13 and the cathode 15 can be formed by the inkjet process. As illustrated in FIG. 11, a mask 30 is placed on the substrate 10, and an inorganic layer 31 is printed in a plurality of application regions 30a provided in the mask 30 by the inkjet process. Here, the surfaces of the sidewalls 30b of the rises of the mask 30 are, for example, subjected to fluorination to impart water repellency to the sidewalls 30b. This can reduce the affinity of the surface of the sidewalls 30b for ink and prevents defects such as dents in the surface of the printed inorganic layer 31, and thus can increase the flatness of the surface of the inorganic layer 31.

[0069] This embodiment involves bottom emission devices, and can improve the carrier balance in the conventional EL light emitting devices 3 depicted in FIGS. 4A and 4B and FIGS. 6A to 6C. Besides, all the layers situated between the anode 11 and the cathode 15 can be formed by coating (application). Specifically, in the structures in FIG. 4A and FIG. 8A, the hole transport layer 12, the emitting layer 13, and the electron transport layer 14 can all be formed by coating. Further, in the structures in FIG. 6A and FIG. 9A, the hole injection layer 16, the hole transport layer 12, the emitting layer 13, and the electron transport layer 14 can all be formed by coating. Further, in the structures in FIG. 6B and FIG. 9B, the hole transport layer 12, the emitting layer 13, the electron transport layer 14, and the electron injection layer 18 can all be formed by coating. This can facilitate the production process of the light emitting devices.

[0070] The display device 1 depicted in FIG. 1 is an example, and the arrangement of the red emission regions 2a, the green emission regions 2b, and the blue emission regions 2c may be different from that in FIG. 1. Further, of the red emission regions 2a, the green emission regions 2b, and the blue emission regions 2c, only the emission regions of one color or the emission regions of two colors may be included in the display device.

[0071] As in this embodiment, in a display device using quantum dots, the quantum dots can be used to build either a point light source or a surface light source, and a curved light source or a flexible product may also be obtained by selecting a suitable substrate.

[0072] Further, according to this embodiment, distinctive products such as lightings producing a mixture of colors comparable to that of sunlight which has been hardly obtained, lightings producing light easy on the eyes, and lightings optimized for plant factories can be developed.

[0073] Thus, display devices using quantum dots provide a high degree of flexibility in the design; for example, the devices can be formed to be thin, lightweight, and curved. Further, the devices can produce natural light not dazzling in the eyes that produces less shadows. In addition, the devices consume less power and have a long life. For example, display devices using quantum dots of this embodiment are superior to organic EL display devices in terms of color rendering properties, emission properties, product life, and product price.

[0074] A display device using quantum dots of this embodiment can be used as a PL emitter as well as an EL emitter. Further, for a display device using quantum dots, a hybrid light emitting device in which an EL emitter and a PL emitter are stacked can be obtained. For example, a PL emitter is superposed on a surface of an EL emitter, and the emission wavelength of the light emitted by excited quantum dots in the EL emitter can be changed using the quantum dots contained in the PL emitter. The EL emitter is a light emitting device having a layered structure described above, and the PL emitter is, for example, a sheet-like wavelength converting member in which a plurality of quantum dots are dispersed in a resin. Such a hybrid structure can be obtained with the use of quantum dots.

[0075]  Note that in this embodiment, in order to both increase the area of the display device using quantum dots and reduce the production cost, the inkjet printing process, the spin coating process, or the dispensing process is preferably used as a method for applying the quantum dots.

EXAMPLES



[0076] The effects of the present invention will be described using Examples of the present invention. Note that the embodiments of the present invention are not limited to the following examples in any way.

[0077] The samples shown in Table 1 below were prepared to investigate the drop characteristics in the inkjet process. Note that in Table 1, "Abs10" refers to a sample exhibiting an absorbance of 10 % with the quantum dots being dispersed, and "Abs20" refers to a sample exhibiting an absorbance of 20 % with the quantum dots being dispersed.
[Table 1]
SampleSolventSGViscosity (mPa·s)R.T. (°C)Ejection numberMass (g)Mass/drop (g)Volume/drop (pL)DropAdverse effect on EPDMNotes
Green QD Abs10 Cyclododecene 0.87   23.5 10 million 0.0407 4.07E-09 4.68 +    
Red QD Abs20 Cyclododecene 0.87   25.6 10 million 0.0397 3.97E-09 4.56 +    
Red QD Abs20 Tetradecane 0.77   26.1 10 million 0.0303 3.03E-09 3.94 + Cap deformation Head clogged
Green QD Abs10 Tetradecane       10 million Cancelled     +    
Green QD Abs10 Octadecene 0.79 3.12 25.0 10 million 0.0447 4.47E-09 5.66 +    
Red QD Abs20 Octadecene 0.79 2.97 26.7 10 million 0.0449 4.49E-09 5.68 +   Previous head replacement
Polyvinylcarbazole Dimethoxybenzene 1.08   26.7 10 million 0.0579 5.79E-09 5.34 + Head replacement twice Clogging after ethanol cleaning/ Clogging of damper filter
Polyvinylcarbazole Dimethoxybenzene: Cyclohexylbenzene 1:1               - Malformation of drops (2 drops)  
Polyvinylcarbazole Dimethoxybenzene: Cyclo he xylbenzene 2:1 1.13   26.5 10 million 0.0527 527E-09 4.66 +    
Zinc oxide nanoparticles IPA:Propylene glycol 1:1               - Defective drops Possibly high viscosity  
Solvent only Tetradecane 0.77 1.60 23.8 1 million 0.0040 4.00E-09 4.60 +    
Tetradecane 3 million 0.0126 420E-09 4.83 +    
Tetradecane 0.0109 3.63E-09 4.18 +    
Tetradecane 10 million 0.0362 3.62E-09 4.16 +    
Solvent only ODE(1-Octadecere 0.79 3.10 23.0 10 million 0.0385 3.85E-09 4.87 + Cap deformation  
Solvent only Decahydronaphthalene 0.88 2.20 23.0 10 million 0.0430 4.30E-09 4.89 + Affected  
Solvent only Cyclododecene 0.87 420 23.0 10 million 0.0514 5.14E-09 5.91 +    
Solvent only Ethylene glycol 1.10 20.50 21.7 Failed - - - - Not affected  
Solvent only Ethylene glycol 1 : IPA 1 0.94 7.40 25.0 10 million 0.0500 5.00E-09 5.32 + Not affected IPA specific gravity: 0.78
Solvent only Ethylene glycol 3 : IPA 1 1.02 12.80 22.7 10 million 0.0481 4.81E-09 4.72 + Not affected  
Solvent only Ethylene glycol 3 : IPA 2 0.97 10.30 22.3 10 million 0.0500 5.00E-09 5.15 + Not affected  
Solvent only Phenylcyclohexane 0.94 2.29 26.3 10 million 0.0444 4.44E-09 4.72 +    
Solvent only Dichlorobenzene 1.30 1.62 25.5 Failed - - - - Affected  
Solvent only n-Octane 0.70 Unmeasurable 24.3 Failed - - - - Cap deformation  


[0078] The "+" signs shown in the "drop" column in Table 1 correspond to the samples that had been appropriately dropped and the "-" signs correspond to the samples that were failed to be appropriately dropped.

[0079] In Table 1, the samples of "Red QD" and "Green QD" are used in emitting layers. Further, the samples of "polyvinylcarbazole" are used in hole injection layers. The sample of "Zinc oxide nanoparticles" is used in an electron transport layer or an electron injection layer.

[0080] Table 1 shows that IPA and propylene glycol were not preferred as the solvent for zinc oxide nanoparticles, and another solvent had to be used. The solvents corresponding to the "+" signs in the "drop" column shown in Table 1 can be appropriately used; however, hydrophilic solvents are preferred. For example, as a hydrophilic solvent, an alcohol-based solvent can be used.

[0081] FIG. 12 is a photograph showing a state where the application was performed by the inkjet process using ZnOx dissolved in ethoxyethanol:EG = 7:3 as a solvent. As shown in FIG. 12, a good application state was achieved.

[0082] Further, adverse effects on ethylene propylene diene monomer rubber (EPDM) inside an inkjet head was also investigated. As shown in Table 1, in some samples, cap deformation occurred or EPDM was adversely affected. This demonstrated that the effect on EPDM was preferably considered in the case of using EPDM.

(Experiment on shell thickness dependence of quantum dot)



[0083] In this experiment, quantum dots (green QDs) of the samples shown in Table 2 were prepared. For a bottom emission display device including the light emitting device using the quantum dots in FIG. 4A, the relationship between the shell thickness and the external quantum efficiency (EQE) was investigated.
[Table 2]
No.CoreCoating 1Coaring 2Coating 3Shell total (nm)CV (%)EQE (%)QY (%)FWHMQD layer thickness
1 GC_A I_A II_A III_ A Thick 1 1.8 17.2 - 86 38 -
2 GC_A I_A II_A III_ A Thick 2 2.4 18.8 4.5 80 39 37
3 GC_A I_A II_A III_ A Thick 3 3.1 15.2 0.9 43 39 23
4 GC_A I_A II_A - 1.2 12.4 0.5 85 30 15
5 GC_A I_A II_B - 1.8 21.9 2 88 32 25
6 GC_A I_A II_C - 2 18.9 1.2 82 38 27
7 GC_A - - - Reference 10.3 - 13 30  
8 GC_A I_B Thin - - 0.2 16.8   10 38  
9 GC_A I_B Thin - - 0.9 12.5   91 34  
10 GC_A I_B - - 1.3 12.9 6 86 33 36
11 GC_A I_B II_D - 1.4 14.5 6 93 33 31


[0084] As shown in Table 2, a correlation was found between the shell thickness and the EQE. The shell thickness was, but not limited to, 0.1 nm or more and 4.0 nm or less, preferably 0.5 nm or more and 3.5 nm or less, more preferably 1.0 nm or more and 3.0 nm or less, still more preferably 1.3 nm or more and 2.5 nm or less.

[0085] Further, the relationship between the quantum dot thickness (diameter) and the EQE was investigated, and the EQE was found to tend to be higher when the quantum dots had a certain level of thickness. The quantum dot thickness was, but not limited to, 5 nm or more and 50 nm or less, preferably 10 nm or more and 45 nm or less, more preferably 15 nm or more and 40 nm or less, still more preferably 20 nm or more and 40 nm or less, yet more preferably 25 nm or more and 40 nm or less.

[0086] Further, Cd-based green quantum dots were subjected to PYS measurements. In FIG. 13, the circle marks represent experimental data of the quantum dots each constituted by a core alone in Example 1, and the square marks represent experimental data of the quantum dots constituted by a core coated with a shell in Example 2.

[0087] The photo-electron yield spectroscopy (PYS) can measure the ionization potential. For example, the measurement can be performed using a system named AC-2/AC-3 manufactured by RIKEN KEIKI CO., LTD.

[0088] As shown in FIG. 13, the energy of the rising edge in Example 1 was found to be different from that in Example 2. The energy rose at approximately 6.1 eV in Example 1, and the energy rose at approximately 7.1 eV in Example 2.

[0089] FIG. 14 shows the PYS measurement results of the Cd-based green quantum dots with different shell thicknesses in Example 3 and Example 4. The shell thickness was larger in Example 4 than in Example 3. The energy of the rising edge in Example 3 was found to be different from that in Example 4. The energy rose at approximately 7.1 eV in Example 3, and the energy rose at approximately 8.1 eV in Example 4.

(Experiment on current dependence of EQE)



[0090] FIG. 15 is an energy level diagram of each layer in the light emitting device used in an experiment. FIG. 16 is a graph illustrating the relationship between the current value and the EQE of an EL emitter and a PL emitter using red quantum dots; Further, FIG. 17 shows plots illustrating the relationship between the current value and the EQE of an EL emitter and a PL emitter using red quantum dots; and a plot illustrating the relationship between the current value and the EQE of an EL emitter using blue quantum dots. The shell thicknesses in Example 5 and Example 6 in FIG. 16 were different. The shell thickness was larger in Example 5 than in Example 6. Further, in FIG. 17, the shell thickness was largest in Example 7, and the shell thickness was smaller in Example 8 and Example 9 in this order.

[0091] As shown in FIG. 16 and FIG. 17, for the EL emitter and the PL emitter, the EQE increased to the point around 20 mA. On the other hand, in the red emission device, the EQE increased even when the current value was 20 mA or more. As shown in FIG. 16 and FIG. 17, a larger shell thickness resulted in a larger increase in the EQE.

(Experiment on ZnOx synthesis)



[0092] FIG. 18 presents a graph illustrating the energy band gap Eg of each layer in the light emitting device used in an experiment, the energy ECB at the bottom of the conduction band, and the energy ECB at the top of the conduction band, and an energy level diagram of the layers. ZnOx(Li) was used as L1 or L2 in FIG. 18. Here, Li may or may not be added. X is, but not limited to, around 0.8 to 1.2. As shown in FIG. 18, it was found that use of ZnOx(Li) as ZnOx used for the electron injection layer (ETL) and the electron transport layer increased the band gap. ZnOx(Li) is presumed to have an effect of reducing the particle diameter. PVK shown in FIG. 18 corresponds to a hole injection layer; B1, B2, G(H), G(I3), and R(F) correspond to emitting layers (EL layers); and ZnOx, L2, and L4 correspond to electron injection layers. When B1 or B2 is used for the emitting layer, ZnOx can be used for the electron injection layer; however, it was found that when G(H), G(I3), or R(F) was used for the emitting layer, L2 or L4 was preferably used for the electron injection layer. L2 and L4 are ZnOx(Li).

[0093] In particular, when an emitting layer (EL layer) with a shallow conduction band is used, it is advantageous to use ZnOx(Li) for the electron injection layer or the electron transport layer.

[0094] ZnOx(Li) can be, but not exclusively, prepared by stirring a zinc acetate-ethanol solution at a predetermined temperature for a predetermined time, and then mixing and stirring a LiOH·4H2O-ethanol solution, followed by centrifugal separation, cleaning, etc.

[0095] FIG. 19 to FIG. 21 show the UV (band gap), the PL spectra, and the PYS data of ZnOx(Li) and ZnOx(K) used for the electron injection layer (ETL). ZnOx(K) was produced using KOH catalytically and was not doped with K or Li. ZnOx(Li) and ZnOx(K) were found to show differences in the UV data and the PL data. On the other hand, the PYS data of ZnOx(Li) and ZnOx(K) hardly differed, and the rising edge energies were almost the same.

[0096]  Thus, ZnOx of which band gap is controlled by selecting from different particle diameters to be used for an electron injection/transport layer of an EL device using quantum dots, and doped ZnOx for which defects are controlled and the band gap is controlled by adding doping species can be proposed.

[0097] When the recombination of electrons and holes for producing light cannot still be brought into balance, hole blocking functions are preferably added by interposing a thick insulating layer between the EL layer and the electron injection layer or integrating ZnOx with molecules thereby adjusting the balance. Here, the integrated layer involves the integration of, for example, ZnOx with T2T (2,4,6-tris(biphenyl-3-yl)-1,3,5-triazine). X is, but not limited to, around 0.8 to 1.2.

[0098] Further, ZnOx is known to have functions suitable for use in not only the electron injection/transport layer but also in a hole injection/transportation layer by performing ozone treatment or the like. Specifically, performing ozone treatment on ZnOx was found to improve the hole transporting performance.

(Consideration of outcoupling efficiency)



[0099] With a view to improving the outcoupling efficiency of a bottom emission device, the refractive index may be optimized to increase the outcoupling efficiency by a factor of approximately 1.5 to 2 as shown in FIG. 22. The numeric values given in FIG. 22A and FIG. 22B show the refractive indices of the layers.

[0100] In FIG. 22A, a glass substrate (refractive index: approximately 1.6) was placed on the underside of an ITO substrate (refractive index: 1.8 to 2.0), and a lens made of resin or the like with a refractive index of approximately 1.6 was placed on the underside of the glass substrate.

[0101] In particular, as illustrated in FIG. 22B, scattering effects can be obtained by placing one or more kinds of members having a high refractive index (higher than 1.5 and lower than 1.8), for example, a resin layer or glass is placed between the ITO electrode and the glass substrate, thus the outcoupling efficiency is expected to be further improved.

[0102] The EQE can be improved by improving the outcoupling efficiency.

INDUSTRIAL APPLICABILITY



[0103] According to the present invention, a light emitting device containing quantum dots can be used for a display device, and excellent emission properties can be obtained.

[0104] This application is based on Japanese patent application No. 2017-215800 filed on November 8, 2017, the content of which is hereby incorporated in its entirety.


Claims

1. A display device comprising a display area,
the display area having a light emitting device in which a first electrode, a layer between the first electrode and an emitting layer, the emitting layer, a layer between the emitting layer and a second electrode, and the second electrode are stacked in this order on a substrate,
wherein the emitting layer is formed of an inorganic layer containing quantum dots, and the light emitting device is a bottom emission device.
 
2. The display device according to Claim 1, wherein all the layers from the first electrode to the second electrode are each formed of an inorganic layer.
 
3. The display device according to Claim 1 or Claim 2, wherein the layer between the first electrode and the emitting layer, the emitting layer, and the layer between the emitting layer and the second electrode are each constituted by the inorganic layer formed from nanoparticles.
 
4. The display device according to any one of Claim 1 to Claim 3, which is flexible.
 
5. The display device according to any one of Claim 1 to Claim 4, wherein the quantum dots have a structure in which a surface of a core is not covered by a shell.
 
6. The display device according to any one of Claim 1 to Claim 5, wherein at least one of the layer between the first electrode and the emitting layer, the emitting layer, and the layer between the emitting layer and the second electrode is formed by an inkjet process.
 
7. The display device according to any one of Claim 1 to Claim 6, wherein all the layers situated between the first electrode and the second electrode are formed by coating.
 




Drawing


























































REFERENCES CITED IN THE DESCRIPTION



This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description