LIGHT EMITTING ELEMENT, QUANTUM DOT-CONTAINING COMPOSITION, AND LIGHT EMITTING ELEMENT MANUFACTURING METHOD
20230313029 · 2023-10-05
Inventors
Cpc classification
B82Y20/00
PERFORMING OPERATIONS; TRANSPORTING
H05B33/10
ELECTRICITY
B82Y40/00
PERFORMING OPERATIONS; TRANSPORTING
H05B33/12
ELECTRICITY
C09K11/88
CHEMISTRY; METALLURGY
H10K50/115
ELECTRICITY
C09K11/61
CHEMISTRY; METALLURGY
C09K11/025
CHEMISTRY; METALLURGY
H05B33/14
ELECTRICITY
International classification
Abstract
A light-emitting element includes a light-emitting layer including the following: a quantum dot including a core and a shell covering the core; and a perovskite compound covering the quantum dot, wherein the shell includes a semiconductor or an insulator containing a zinc element, and the perovskite compound contains a halogen element.
Claims
1. A light-emitting element comprising a light-emitting layer including a quantum dot including a core having a surface exposed, or a quantum dot including the core and a shell covering the core, and a perovskite compound covering the quantum dot, wherein the surface of the core or the shell includes a semiconductor or an insulator containing a zinc element, and the perovskite compound contains a halogen element, wherein the perovskite compound includes a compound that is expressed by a chemical formula ABX.sub.3, an element A in the chemical formula includes at least one element selected from the group consisting of Na, K, Rb, Cs and La, an element B in the chemical formula includes at least one element selected from the group consisting of Na, K, Mg, Ca, Sr, Ba, Y, Mn, Fe, Co, Ni, Cu, Zn, Al, Ga, In, Ge, Sn, As, Sb, Bi and lanthanoid, an element X in the chemical formula includes at least one element selected from the group consisting of F, Cl, Br and I, and the element B includes Zn.
2. The light-emitting element according to claim 1, wherein the surface of the core or the shell includes a semiconductor or an insulator containing at least a zinc element and one or more elements selected from group 16 elements.
3. The light-emitting element according to claim 1, wherein the surface of the core or the shell contains at least one kind selected from the group consisting of ZnS, ZnSe, ZnSSe, ZnTe, ZnSTe, ZnSeTe and Zn.sub.2-xSi.sub.xO.sub.2, where 0≤X≤1 is satisfied.
4-5. (canceled)
6. The light-emitting element according to claim 1, wherein the perovskite compound includes at least one compound selected from the group consisting of CsZnF.sub.3, CsZnCl.sub.3, CsZnBr.sub.3, CsZnI.sub.3, RbZnF.sub.3, RbZnCl.sub.3, RbZnBr.sub.3, RbZnI.sub.3, CsZnF.sub.x1Cl.sub.3-x1, CsZnCl.sub.x1Br.sub.3-x1, CsZnBr.sub.x1I.sub.3-x1, RbZnF.sub.x1Cl.sub.3-x1, RbZnCl.sub.x1Br.sub.3-x1, and RbZnBr.sub.x1I.sub.3-x1, where 0<X1<3 is satisfied.
7. (canceled)
8. The light-emitting element according to claim 1, further comprising: an anode; and a cathode disposed to face the anode, wherein the light-emitting layer is provided between the anode and the cathode.
9. The light-emitting element according to claim 1, further comprising a light source, wherein the light-emitting layer is formed as a wavelength converting layer disposed in a location closer to a light taking surface of the light-emitting element than the light source.
10. The light-emitting element according to claim 1, wherein a weight ratio between the quantum dot and the perovskite compound is a value that falls within a range of 1:100 to 10:1.
11. The light-emitting element according to claim 1, wherein the quantum dot is disposed dispersedly within a group of crystals of the perovskite compound.
12. A quantum-dot-containing composition comprising: a quantum dot including a core having a surface containing a zinc element, or a quantum dot including a shell provided so as to cover the core, the shell including a semiconductor or an insulator containing a zinc element; and a perovskite precursor containing a solvent, a negative ion of a halogen element, and at least two kinds of combinations of univalent to trivalent positive ions, wherein the two kinds of combinations of univalent to trivalent positive ions include at least any one of a first combination of a first positive ion of univalence and a second positive ion of trivalence, a second combination of a first positive ion of trivalence and a second positive ion of univalence, and a third combination of a first positive ion of bivalence and a second positive ion of bivalence, the first positive ion includes at least one positive ion selected from the group consisting of Na.sup.+, K.sup.+, Rb.sup.+, Cs.sup.+, Mg.sup.2+, Ca.sup.2+, Sr.sup.2+, Ba.sup.2+, Y.sup.3+ and La.sup.3+, the second positive ion includes at least one positive ion selected from the group consisting of Mn.sup.2+, Fe.sup.2+, Co.sup.2+, Ni.sup.2+, Cu.sup.2+, Zn.sup.2+, Al.sup.3+, Ga.sup.3+, In.sup.3+, Ge.sup.2+, Sn.sup.2+, As.sup.3+, Sb.sup.3+ and Bi.sup.3+, the negative ion includes at least one negative ion selected from the group consisting of F.sup.−, Cl.sup.−, Br.sup.− and I.sup.−, and the second positive ion is Zn.sup.2+.
13. The quantum-dot-containing composition according to claim 12, wherein the quantum dot is dispersed within the solvent.
14. The quantum-dot-containing composition according to claim 12, wherein the negative ion of the halogen element attaches to a surface of the shell.
15-18. (canceled)
19. The quantum-dot-containing composition according to claim 12, wherein the surface of the core or the shell includes a semiconductor or an insulator containing at least a zinc element and one or more elements selected from group 16 elements.
20. The quantum-dot-containing composition according to claim 12, wherein the surface of the core or the shell contains at least one kind selected from the group consisting of ZnS, ZnSe, ZnSSe, ZnTe, ZnSTe, ZnSeTe and Zn.sub.2-xSi.sub.xO.sub.2, where 0≤X≤1 is satisfied.
21-24. (canceled)
25. A light-emitting element comprising a light-emitting layer including a quantum dot including a core having a surface exposed, or a quantum dot including the core and a shell covering the core, and a perovskite compound covering the quantum dot, wherein the surface of the core or the shell includes a semiconductor or an insulator containing a zinc element, and the perovskite compound contains a halogen element, wherein the perovskite compound includes a compound that is expressed by a chemical formula ABX.sub.3, an element A in the chemical formula includes at least one element selected from the group consisting of Na, K, Rb, Cs and La, an element B in the chemical formula includes at least one element selected from the group consisting of Na, K, Mg, Ca, Sr, Ba, Y, Mn, Fe, Co, Ni, Cu, Zn, Al, Ga, In, Ge, Sn, As, Sb, Bi and lanthanoid, and an element X in the chemical formula includes at least one element selected from the group consisting of F, Cl, Br and I, and the perovskite compound includes at least one compound selected from the group consisting of Cs.sub.2NaYCl.sub.6, Cs.sub.2NaBiCl.sub.6, Cs.sub.2NaInCl.sub.6, Cs.sub.2NaCeCl.sub.6, Cs.sub.2NaY.sub.x2Ce.sub.1-x2 Cl.sub.6, Cs.sub.2Na.sub.x2K.sub.1-x2YCl.sub.6 and Cs.sub.2Zn.sub.x2Na.sub.(1-x2)Bi.sub.(1-x2)Cl.sub.6, where 0<X2<1 is satisfied.
26. The light-emitting element according to claim 25, wherein the surface of the core or the shell includes a semiconductor or an insulator containing at least a zinc element and one or more elements selected from group 16 elements.
27. The light-emitting element according to claim 25, wherein the surface of the core or the shell contains at least one kind selected from the group consisting of ZnS, ZnSe, ZnSSe, ZnTe, ZnSTe, ZnSeTe and Zn.sub.2-xSi.sub.xO.sub.2, where 0≤X≤1 is satisfied.
28. The light-emitting element according to claim 25, further comprising: an anode; and a cathode disposed to face the anode, wherein the light-emitting layer is provided between the anode and the cathode.
29. The light-emitting element according to claim 25, further comprising a light source, wherein the light-emitting layer is formed as a wavelength converting layer disposed in a location closer to a light taking surface of the light-emitting element than the light source.
30. The light-emitting element according to claim 25, wherein a weight ratio between the quantum dot and the perovskite compound is a value that falls within a range of 1:100 to 10:1.
31. The light-emitting element according to claim 25, wherein the quantum dot is disposed dispersedly within a group of crystals of the perovskite compound.
Description
BRIEF DESCRIPTION OF DRAWINGS
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DESCRIPTION OF EMBODIMENTS
[0043] A light-emitting element, a quantum-dot-containing composition and a method for manufacturing the same according to the embodiments of the present disclosure will be described with reference to the drawings. It is noted that identical or equivalent components will be denoted by the same signs throughout the drawings, and the description of redundancies about the identical or equivalent components will not be repeated.
First Embodiment
[0044]
[0045] It is noted that an electron transport layer (not shown) may be provided between the light-emitting layer EML and the anode 10, and that a hole transport layer (not shown) may be provided between the light-emitting layer EML and the cathode 20.
[0046] The principal component of the core C of the quantum dot QD may be a group II-VI semiconductor or group n-V semiconductor, a binary semiconductor, a ternary semiconductor, or a quaternary semiconductor or may be any semiconductor of, but not limited to, Cd, Se, Zn, Te, Ga, In, P or S that can be used as the core of a quantum dot.
[0047] The shell S includes a semiconductor or an insulator containing a zinc element. The principal component of the shell S of the quantum dot QD is made of a material, such as ZnS, ZnSe, ZnSSe, ZnTe or Zn.sub.2-xSi.sub.xO.sub.2 (0≤X≤1). Zinc silicate (Zn.sub.2-xSi.sub.xO.sub.2) is a semiconductor when x stands at 0.3 or smaller and is an insulator when x stands at 0.3 to 1.
[0048] However, the light-emitting layer EML may include the quantum dots QD each consisting of only the core C. The surface of the core C in this case needs to include a semiconductor or an insulator containing a zinc element. The principal component of the surface of the core C is made of a material, such as ZnS, ZnSe or ZnTe.
[0049] The quantum dots QD may have any particle diameter that falls within a range recognized as a quantum dot. The quantum dots QD thus may have any particle diameter that can achieve the following effect.
[0050] The quantum dots QD are used as a constituent of the light-emitting layer EML of a quantum light-emitting diode (QLED). However, the quantum dots QD may be used as a constituent of a wavelength converting layer.
[0051] When the quantum dots QD are used as a constituent of a wavelength converting layer, the quantum dots QD having different particle diameters involve different differences between the wavelength of light that is input to the wavelength converting layer and the wavelength of light that is output from the wavelength converting layer. This enables at least one of the wavelength of light not yet converted by the wavelength converting layer and the wavelength of light converted by the wavelength converting layer to be adjusted to a necessary value. A specific example of this wavelength converting layer will be detailed in a third embodiment.
[0052] The light-emitting layer EML according to this embodiment includes perovskite compounds covering the quantum dots QD. The perovskite compounds contain a halogen element.
[0053] To be more specific, the light-emitting element 1 according to this embodiment is configured such that each quantum dot QD containing Zn in its outermost layer is covered with a halogenation metal (chemical formula ABX.sub.3) having a perovskite structure composed of Zn or an element X of a Lewis acid harder than Zn. As such, the quantum dot QD is covered with a halogenation metal (chemical formula ABX.sub.3) containing no Pb. This can stabilize the quantum dot QD. It is noted that all of metals (elements A and B) constituting perovskite crystals contained in a perovskite compound Pe are preferably zinc or a Lewis acid harder than zinc.
[0054] This is because that a chemical reaction is less likely to occur at the interface between ZnS or ZnSe and the perovskite compound Pe if a metal identical to or harder than Zn of the shell S containing ZnS or ZnSe is used as an ingredient of the perovskite compound. It is noted that the perovskite compound Pe will be detailed later on.
[0055] The shell S may be anything containing a zinc element; in particular, the shell S preferably contains at least one of zinc sulfide and zinc selenide. This configuration improves the light emission efficiency of the light-emitting element 1 with more certainty. However, the shell S may be not only a semiconductor containing a zinc element, but also an insulator containing a zinc element.
[0056] Further, the shell S may be composed of, as other examples of the semiconductor or insulator containing a zinc element, a semiconductor or an insulator containing ZnS, ZnO, InP/ZnSe or CdS/ZnSe.
[0057] Further, the surface of the core C or the shell S may include, as other examples, a semiconductor or an insulator containing at least a zinc element and one or more elements selected from the group 16 elements. The group 16 elements are O, S, Se, Te, and Po.
[0058] Further, few of quantum dots containing PbS in their outermost layers emit visible light, as those in a comparative example described later on. However, the quantum dots QD according to this embodiment containing Zn in their outermost layers emit visible light.
[0059] The foregoing configuration of the light-emitting layer EML according to this embodiment can improve the light emission efficiency of the light-emitting element 1 that emits visible light. To be more specific, voltage necessary for driving the light-emitting element 1 lowers. Further, the endurance of the light-emitting element 1 enhances.
[0060]
[0061] As illustrated in
[0062] The element A in the chemical formula ABX.sub.3 preferably contains at least one element selected from the group consisting of Na, K, Rb, Cs and La.
[0063] The element B in the chemical formula ABX.sub.3 contains at least one element selected from the group consisting of Na, K, Mg, Ca, Sr, Ba, Y, Mn, Fe, Co, Ni, Cu, Zn, Al, Ga, In, Ge, Sn, As, Sb, Bi and lanthanoid. However, the element B is further preferably Zn. Lanthanoid is any of 15 elements consisting of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu.
[0064] The element X in the chemical formula ABX.sub.3 preferably contains at least one element selected from the group consisting of F, Cl, Br and I. It is noted that negative ions of halogen elements such as F, Cl, Br, and I have the property of easily coordinating with Zn contained in the quantum dots QD.
[0065] Such a perovskite compound Pe as described above can improve the light emission efficiency of the light-emitting element 1 with more certainty.
[0066] To be more specific, the perovskite compound Pe further preferably includes at least one compound selected from the group consisting of CsZnF.sub.3, CsZnCl.sub.3, CsZnBr.sub.3, CsZnI.sub.3, RbZnF.sub.3, RbZnCl.sub.3, RbZnBr.sub.3, RbZnI.sub.3, CsZnF.sub.x1Cl.sub.3-x1, CsZnCl.sub.x1Br.sub.3-x1, CsZnBr.sub.x1I.sub.3-x1, RbZnF.sub.x1C.sub.3-x1, RbZnCl.sub.x1Br.sub.3-x1 and RbZnBr.sub.x1I.sub.3-x1, and the condition 0<X1<3 is further preferably satisfied. This configuration improves the light emission efficiency of the light-emitting element 1 with more certainty.
[0067] Although the perovskite compound Pe is CsMX.sub.3 for instance, where M is a bivalent metal that is a Lewis acid as hard as or harder than zinc, a plurality of kinds of MM′ may be used instead of M. In this case, X is a halogen element, and M′ is a metal that is a Lewis acid different from M and as hard as or harder than zinc. The perovskite compound Pe may be thus, for instance, a double perovskite like Cs2MM′X.sub.6.
[0068] Further, the perovskite compound Pe, when being a double perovskite, further preferably contains at least one compound selected from Cs.sub.2NaYC.sub.6, Cs.sub.2NaBiCl.sub.6, Cs.sub.2NaInCl.sub.6, Cs.sub.2NaCeCl.sub.6, Cs.sub.2KYCl.sub.6, Cs.sub.2KBiCl.sub.6, Cs.sub.2KInCl.sub.6, Cs.sub.2NaCeCl.sub.6, Cs.sub.2Na.sub.x2K.sub.1-x2YCl.sub.6, Cs.sub.2NaY.sub.x2Ce.sub.1-x2Cl.sub.6 and Cs.sub.2Zm.sub.x2Na.sub.(1-x2)Bi.sub.(1-x2)Cl.sub.6, and the condition 0<X2<1 is further preferably satisfied. This configuration improves the light emission efficiency of the light-emitting element 1 with more certainty.
[0069] The light-emitting element 1 is preferably configured such that the weight ratio between the quantum dot QD and the perovskite compound Pe is a value that falls within a range of 1:100 to 10:1. This configuration further improves the light emission efficiency of the light-emitting element 1. This is because that if the weight ratio of the quantum dot QD to the perovskite compound Pe is smaller than 1/100, the probability of exciton generation within the quantum dot QD reduces, and that if the weight ratio of the quantum dot QD to the perovskite compound Pe is larger than 10, the number of quantum dots QD that are not covered with the perovskite compound Pe increases.
[0070] The quantum dots QD are preferably disposed dispersedly within a group of crystals of the perovskite compounds Pe. This configuration also further improves the light emission efficiency of the light-emitting element 1.
[0071]
[0072]
[0073] The quantum-dot-containing composition 50 includes the quantum dots QD and perovskite precursors PePr. Each quantum dot QD includes the shell S provided so as to cover the core C and including a semiconductor or an insulator containing a zinc element. The perovskite precursors PePr are ion crystals and contain a solvent SO, negative ions X.sup.− of a halogen element and two kinds of combinations of univalent to trivalent positive ions.
[0074] The quantum dots QD are preferably dispersed within the solvent SO. The halogen-element negative ions X.sup.− preferably attach to the surface of the shell S.
[0075] The two kinds of combinations of univalent to trivalent positive ions preferably include any one of three combinations listed below.
[0076] The first combination is a combination of a first positive ion A.sup.+ of univalence and a second positive ion B.sup.+ of trivalence.
[0077] The second combination is a combination of a first positive ion A.sup.+ of trivalence and a second positive ion B.sup.+ of univalence.
[0078] The third combination is a combination of a first positive ion A.sup.+ of bivalence and a second positive ion B.sup.+ of bivalence.
[0079] The shell S preferably contains at least one of zinc sulfide (ZnS) and zinc selenide (ZnSe).
[0080] The two kinds of positive ions A.sup.+ and B.sup.+ are positive ions different from each other and are provided with three conditions (1) to (3) listed below.
[0081] (1) Each of the two kinds of positive ions exists stably in univalent, bivalent or trivalent form.
[0082] (2) Each of the two kinds of positive ions in the form of a Lewis acid is as hard as or harder than zinc. As such, the quantum dot QD and the perovskite compound Pe do not react chemically.
[0083] (3) The two kinds of positive ions A.sup.+ and B.sup.+ and the halogen negative ions X.sup.− can constitute a perovskite crystalline structure.
[0084] The light-emitting layer EML is formed from the foregoing quantum-dot-containing composition 50.
[0085]
[0086] As seen from
[0087] The reason why the positive ions A.sup.+ and the positive ions B.sup.+ are selected as a candidate is that mixing a quantum dot having ZnS or ZnSe in its outermost layer into the perovskite precursor PePr containing positive ions other than the foregoing positive ions causes a chemical reaction due to these positive ions. That is, the reason is that a mixture of a quantum dot having ZnS or ZnSe in its outermost layer and of a perovskite compound containing positive ions other than the positive ions provided with the foregoing three conditions (1) to (3) is not stable chemically.
[0088] In view of the foregoing, the first positive ions A.sup.+ according to this embodiment preferably include at least one positive ion selected from the group consisting of Na.sup.+, K.sup.+, Rb.sup.+, Cs.sup.+, Mg.sup.2+, Ca.sup.2+, Sr.sup.2+, Ba.sup.2+, Y.sup.3+ and La.sup.3+. Further, the second positive ions B.sup.+ preferably include at least one positive ion selected from the group consisting of Mn.sup.2+, Fe.sup.2+, Co.sup.2+, Ni.sup.2+, Cu.sup.2+, Zn.sup.2+, Al.sup.3+, Ga.sup.3+, In.sup.3+, Ge.sup.2+, Sn.sup.2+, As.sup.3+, Sb.sup.3+ and Bi.sup.3+.
[0089] Further, since the perovskite compound Pe and the Zn shell S are a favorable combination, the B-site in the chemical formula ABX.sub.3 of the perovskite compound Pe preferably has Zn negative ions. As such, the second positive ions B.sup.+ are Zn.sup.2+ in this embodiment. It is noted that the negative ions X.sup.− preferably include at least one negative ion selected from the group consisting of F.sup.−, Cl.sup.−, Br.sup.− and I.sup.−.
[0090] According to the hard and soft acids and bases (HSAB) principle, a hard base and a hard acid form a compound easily, and a soft base and a soft acid form a compound easily. Zinc is a somewhat hard Lewis acid, and sulfur and selenium are somewhat soft Lewis bases. Sulfur or selenium and a somewhat soft metal thus form a compound easily. As a result, the shell S containing sulfur or selenium is eroded. Consequently, the endurance of the shell S containing sulfur or selenium conceivably lowers. As such, a semiconductor or an insulator having the perovskite compound Pe is desirably made of zinc that is used for the shell S of the quantum dot QD or is desirably made of a metal kind that is a harder Lewis acid than zinc.
[0091]
[0092]
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[0094] However, the PLQY lowers when the quantum dot QD having the ZnS-containing shell S in its outermost layer and a metal ion having intermediate hardness are mixed together. Further, a mixture of the quantum dot QD having the ZnS-containing shell S in its outermost layer and a soft metal ion emits light little.
[0095]
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[0097] Tolerance Factor t
[0098] To be specific, when the ion radius of cesium, which is herein an A-site cation, stands at a value ranging from 1.30 to 0.68 Å, the quantum dot QD and any of the halogens constitute a perovskite crystal. To be specific, when the ion radius of rubidium, which is herein an A-site cation, stands at a value ranging from 1.16 to 0.58 Å, the quantum dot QD and any of the halogens constitute a perovskite crystal. For instance, CsZnBr.sub.3 made of zinc having an ion radius of 0.88 Å has a tolerance factor t of 0.95. It is thus estimated that an ideal perovskite crystal is formed in a perovskite compound CsZnBr.sub.3.
[0099] In the quantum-dot-containing composition 50, a combination of the foregoing first positive ions A.sup.+, second positive ions B.sup.+ and negative ions X.sup.− is preferably a combination that generates a crystal of at least one perovskite compound Pe selected from the group consisting of CsZnF.sub.3, CsZnCl.sub.3, CsZnBr.sub.3, CsZnI.sub.3, RbZnF.sub.3, RbZnC.sub.3, RbZnBr.sub.3, RbZnI.sub.3, CsZnF.sub.x1C.sub.3-x1, CsZnCl.sub.x1Br.sub.3-x1, CsZnBr.sub.x1I.sub.3-x1, RbZnF.sub.x1C.sub.3-x1, RbZnCl.sub.x1Br.sub.3-x1 and RbZnBr.sub.x1I.sub.3-x1, where 0<X1<3 is satisfied.
[0100]
[0101] As illustrated in
[0102] The mixture step S1 shown in
[0103] To be specific, the mixture step S1 is performed under a nitrogen atmosphere in the following procedure.
[0104] In the mixture step S1, firstly, cesium bromide (CsBr), zinc bromide (ZnBr.sub.2), and ammonium acetate are dissolved into 4 ml of N,N-dimethylformamide (DMF) solvent. That is, the halogenation substance of the element A is cesium bromide (CsBr), and the halogenation substance of the element B is zinc bromide (ZnBr.sub.2). Accordingly, a DMF solution is generated. Cesium bromide (CsBr) and zinc bromide (ZnBr.sub.2) are an example of two kinds of halogenation metals, which will be described later on. The DMF solvent is an example polar solvent. The generated DMF solution is the first mixed solution M1. The first mixed solution M1 contains Zn.sup.2+, Cs.sup.+, and Br.sup.−.
[0105] In the first mixed solution M1, the concentration of cesium bromide with respect to the DMF solution, the concentration of zinc bromide with respect to the DMF solution, and the concentration of ammonium acetate with respect to the DMF solution all stand at 0.01 mol/L.
[0106] The next is preparing 4 ml of octane solution containing the quantum dots QD having an organic modified base at 5 mg/ml in concentration. This octane solvent is an example first non-polar solvent.
[0107] The halogenation step S2 in
[0108] To be specific, the halogenation step S2 is performed under a nitrogen atmosphere in the following procedure.
[0109] In the halogenation step S2, 4 ml of octane solution containing the quantum dots QD having an organic modified base at 5 mg/ml in concentration, that is, the dispersed solution D, and a DMF solution containing Zn.sup.2+, Cs.sup.+ and Br.sup.−, that is, the first mixed solution M1, are mixed together. This generates the second mixed solution M2. In the second mixed solution M2, the first mixed solution M1, which is on the lower side, and the dispersed solution D, which is on the upper side, are separated into two layers, as illustrated in
[0110] Accordingly, the organic molecules L coordinating with the quantum dots QD disengage from the quantum dots QD and remain in the dispersed solution D, as illustrated in
[0111] To be specific, the quantum dots QD within the dispersed solution D on the upper side move to the DMF solution on the lower side, which is the first mixed solution M1. The next is discarding the octane solution on the upper side, where the ligands L remain, but no quantum dots QD remain, after confirming that almost all of the quantum dots QD have completely moved to the DMF solution. Accordingly, a solution FQD having the halogenated quantum dots QD and the DMF solvent remains.
[0112] In the second mixed solution M2, the octane solvent of the original dispersed solution D with the quantum dots QD dispersed, and the DMF solvent covered with the perovskite compounds Pe and containing the halogenated quantum dots QD are separated into two layers, as illustrated in
[0113] The next, i.e., the cleaning and separation step S3, is easily removing a supernatant liquid (octane solvent) containing no quantum dots QD from the second mixed solution M2, as illustrated in
[0114] Accordingly, zinc perovskite crystals, to be specific, the quantum dots QD covered with the perovskite compounds Pe and halogenated precipitate within the solution FQD, as illustrated in
[0115] The next, i.e., the film formation step S4, is dispersing a mixture of the precipitated CsZnBr.sub.3 crystals and quantum dots QD into 1 ml of DMF solvent, as illustrated in
[0116] As illustrated in
[0117] The following is a summary of the method for manufacturing the light-emitting element through the foregoing formation according to this embodiment.
[0118] As illustrated in
[0119] The quantum dots QD that are used in the method for manufacturing the light-emitting element 1 according to this embodiment each include the core C having a surface exposed or each include the core C and the shell S covering the core C. The surface of the core C or the shell S includes a semiconductor or an insulator having a zinc element. The perovskite precursors PePr include two kinds of halogenation metals. The two kinds of halogenation metals will be detailed later on.
[0120] The next is preparing the first mixed solution M1, which is an example perovskite-precursor-dispersed solution, containing the DMF solvent, which is an example polar solvent, and the perovskite precursor PePr dispersed within the DMF solvent. The second mixed solution M2, which is an example mixed solution of the dispersed solution D and the first mixed solution M1, is generated.
[0121] Accordingly, the quantum dots QD within the dispersed solution D move to the first mixed solution M1 after the second mixed solution M2 is generated. The quantum dots QD are thereafter halogenated by the two kinds of halogenation metals within the mixed solution M1. The second mixed solution M2 is consequently turned into the solution FQD containing the halogenated quantum dots QD.
[0122] Thereafter, a processed solution with the second mixed solution M2 undergone a predetermined process is applied onto the substrate ST. The processed solution on the substrate ST undergoes burning.
[0123] The following describes the foregoing predetermined process and the foregoing processed solution.
[0124] The predetermined process includes a step of stirring the second mixed solution M2 for more than six hours, for 12 hours for instance, after generating the second mixed solution M2. This relatively long time stirring increases the possibility that the quantum dots QD come into contact with the two kinds of halogenation metals, thereby enabling the halogenated quantum dots QD to be generated at a high rate.
[0125] The octane solvent, which is an unnecessary non-polar solvent, is removed from the second mixed solution M2 after the foregoing stir step and before the foregoing step of applying the processed solution onto the substrate ST. This can generate the second mixed solution M2 containing the quantum dots QD and containing no octane solvent.
[0126] The forgoing predetermined process also includes a step of adding, after the step of removing the octane solvent, toluene, which is an example second non-polar solvent, to the solution FQD containing the halogenated quantum dots QD and the DMF solvent with the octane solvent removed from the second mixed solution M2. The solution FQD with toluene added thereto is centrifuged before the step of applying the processed solution, which is the solution FQD, onto the substrate ST.
[0127] The foregoing two kinds of halogenation metals are a combination that generates the perovskite compounds Pe incorporating the quantum dots QD through the step of burning the foregoing processed solution, which is the solution FQD. The perovskite compounds Pe include at least one compound selected from the group consisting of CsZnF.sub.3, CsZnCl.sub.3, CsZnBr.sub.3, CsZnI.sub.3, RbZnF.sub.3, RbZnC.sub.3, RbZnBr.sub.3, RbZnI.sub.3, CsZnF.sub.x1Cl.sub.3-x1, CsZnCl.sub.x1Br.sub.3-x1, CsZnBr.sub.x1I.sub.3-x1, RbZnF.sub.x1C.sub.3-x1, RbZnCl.sub.x1Br.sub.3-x1 and RbZnBr.sub.x1I.sub.3-x1, and the condition 0<X1<3 is satisfied.
[0128]
[0129]
[0130]
[0131]
[0132]
[0133]
[0134] The quantum dots QD are semiconductors. The quantum dots QD exist within the dispersing medium with their surfaces halogenated. The Lewis acid of the metal ions within the dispersing medium is as hard as or harder than Zn. A perovskite compound, which is a dispersing medium, has a band gap equal to or larger than that of the quantum dots QD. Thus for instance, CsPbX.sub.3 does not fall under the quantum dots QD according to this embodiment, whereas CsZnBr.sub.3 falls under the perovskite compounds according to this embodiment.
[0135]
[0136] To obtain the results shown in
[0137] In contrast, the first comparative example was conducted, where the quantum dots QD in the first example with their surfaces not yet brominated, that is, the quantum dots QD modified by octanethiol, were applied onto a glass substrate and were heated. The second comparative example was conducted, where the quantum dots QD used in the first example with their surfaces brominated were applied onto a glass substrate and were heated.
[0138] A third comparative example not shown was conducted, where a primary mixed solution was generated in such a manner that the ratio of CsBr and PbBr.sub.2 to a solvent stood at 0.4 mol/L. The quantum dots QD with their surfaces brominated were mixed into the primary mixed solution to generate a secondary mixed solution. The secondary mixed solution was applied onto a glass substrate and was heated. It was noted that the PLQY in the comparative example 3 was 7%.
Second Embodiment
[0139] The following describes a light-emitting element, a quantum-dot-containing composition and a method for manufacturing the light-emitting element according to a second embodiment. It is noted that the description of points similar to those in the first embodiment will not be repeated. The light-emitting element according to this embodiment is different from the light-emitting element according to the first embodiment in the following regard.
[0140]
[0141] As illustrated in
[0142] The light-emitting layer 18 according to this embodiment corresponds to the light-emitting layer EML according to the first embodiment. That is, the quantum-dot-containing composition 50 according to the first embodiment is used as raw materials for manufacturing the light-emitting layer 18 according to this embodiment. The light-emitting element 1 according to this embodiment improves the light emission efficiency of visible light.
Third Embodiment
[0143] The following describes a light-emitting element, a quantum-dot-containing composition and a method for manufacturing the light-emitting element according to a third embodiment. It is noted that the description of points similar to those in the first embodiment will not be repeated. The light-emitting element according to this embodiment is different from the light-emitting element according to the first embodiment in the following regard.
[0144]
[0145] The light-emitting element 1 illustrated in
[0146] The OLED is provided on the TFT unit 3. The OLED includes three first electrodes 5 in locations corresponding to respective color filters of three colors, which will be described later on. On the three first electrodes are three light-emitting layers 7. The light-emitting layers 7 emit white light.
[0147] On the light-emitting layers 7 is a second electrode 8. Furthermore, on the second electrode 8 is a sealing structure where a first sealing layer 9 and a second sealing layer 110 are stacked in this order. The second sealing layer 110 has a first adhesive layer 11, and an alpet 120 composed of a protective film 140 and aluminum foil 13.
[0148] In the OLED, a region consisting of the first electrodes 5, light-emitting layers 7 and second electrode 8 constitutes a light emission area LA.
[0149] A color filter unit 16A is disposed on a surface of the base 2 opposite to the surface where the OLED is disposed, with the second adhesive layer 15 interposed therebetween. The color filter unit 16A is configured such that a color filter layer 180 where a red color filter CFR1, a green color filter CFG1, and a blue color filter CFB1 are spaced from each other is disposed on a second base 17. The red color filter CFR1 contains a red coloring agent. The green color filter CFG1 contains a green coloring agent. The blue color filter CFB1 contains a blue coloring agent.
[0150] On the color filter layer 180 is a flattening layer 19, which is joined to the back surface of the first base 2 with the second adhesive layer 15 interposed therebetween. A polarizing plate is disposed outside the color filter unit 16A.
[0151] The light-emitting element 1 is configured such that the organic EL element is designed as a white-light emission type, and that white light passes through the individual color filters, thus taking out light LR that emits red, light LG that emits green, and light LB that emits blue in a bottom-emission form. Each of the color filters CFR1, CFG1 and CFB1 according to this embodiment is a wavelength converting layer and corresponds to the light-emitting layer EML according to the first embodiment. The quantum-dot-containing composition 50 according to the first embodiment is used as raw materials for manufacturing each of the color filters CFR1, CFG1 and CFB1.
[0152] The light-emitting element 1 according to this embodiment includes the light-emitting layers 7 as a light source corresponding to the light-emitting layer EML according to the first embodiment. Further in this embodiment, each of the color filters CFR1, CFG1 and CFB1, corresponding to the light-emitting layer EML, is formed as a wavelength converting layer disposed in a location closer to the light taking surface of the light-emitting element 1 than the light-emitting layers 7, serving as a light source. The light-emitting element 1 according to this embodiment improves the light emission efficiency of visible light.
[0153] Further, although the light-emitting element 1 according to this embodiment is a white-light-emitting organic EL element by way of example, the color of light emission in the light-emitting layers 7 is not limited to white; the light-emitting layers 7 may emit blue light. For instance, the light-emitting element 1 may be replaced with a blue-light-emitting organic electroluminescence (EL) element. When the light-emitting element 1 is a blue-light-emitting organic EL, the blue color filter CFB1 may be omitted. Furthermore, the light-emitting element 1 is not limited to an organic EL element; the light-emitting element 1 may be a micro light-emitting diode (LED).