WO2016072809A1 - Couche émettant de la lumière pour dispositif électroluminescent pérovskite, son procédé de fabrication et dispositif électroluminescent pérovskite l'utilisant - Google Patents

Couche émettant de la lumière pour dispositif électroluminescent pérovskite, son procédé de fabrication et dispositif électroluminescent pérovskite l'utilisant Download PDF

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WO2016072809A1
WO2016072809A1 PCT/KR2015/011963 KR2015011963W WO2016072809A1 WO 2016072809 A1 WO2016072809 A1 WO 2016072809A1 KR 2015011963 W KR2015011963 W KR 2015011963W WO 2016072809 A1 WO2016072809 A1 WO 2016072809A1
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organic
light emitting
emitting layer
nanoparticle
perovskite
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PCT/KR2015/011963
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English (en)
Korean (ko)
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이태우
임상혁
조힘찬
김영훈
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포항공과대학교 산학협력단
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Priority to US15/524,489 priority Critical patent/US10276807B2/en
Priority to JP2017524027A priority patent/JP6829682B2/ja
Priority claimed from KR1020150156173A external-priority patent/KR101724210B1/ko
Publication of WO2016072809A1 publication Critical patent/WO2016072809A1/fr
Priority to US16/398,230 priority patent/US10964896B2/en
Priority to US17/213,211 priority patent/US11730051B2/en
Priority to US18/223,431 priority patent/US20230363248A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • 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

Definitions

  • the present invention relates to a light emitting device, and more particularly, to a light emitting layer for an organic-inorganic hybrid perovskite or inorganic metal halide perovskite light emitting device, a method of manufacturing the same, and a light emitting device using the same and a method of manufacturing the same.
  • organic light emitters have the advantage of high efficiency, but the color spectrum is poor due to the broad spectrum.
  • Inorganic quantum dot light emitters have been known to have good color purity, but since the light emission is due to the quantum size effect, it is difficult to control the quantum dot size uniformly toward the blue side, and thus there is a problem that the color purity falls.
  • the two light emitters are expensive. Therefore, there is a need for a new type of organic / inorganic hybrid light emitting body that complements and maintains the disadvantages of organic and inorganic light emitting bodies.
  • Organic-inorganic hybrid materials have the advantages of organic materials, which are low in manufacturing cost, simple in manufacturing and device manufacturing process, easy to control optical and electrical properties, and inorganic materials having high charge mobility and mechanical and thermal stability. I can have it and am attracting attention academically and industrially.
  • the organic-inorganic hybrid perovskite material has high color purity, simple color control, and low synthesis cost, so there is great potential for development as a light-emitting body.
  • High color purity has a layered structure in which the 2D plane of the inorganic material is sandwiched between the 2D plane of the organic material, and the dielectric constant difference between the inorganic and organic material is large ( ⁇ organic ⁇ 2.4, ⁇ inorganic ⁇ 6.1)
  • the excitons are bound to the inorganic layer and are therefore formed because they have a high color purity (FWHMM ⁇ 20 nm).
  • the material having a conventional perovskite structure is an inorganic metal oxide.
  • Such inorganic metal oxides are generally oxides, such as Ti, Sr, Ca, Cs, Ba, Y, Gd, La, Fe, and Mn (alkali metals, alkalis) having different sizes at A and B sites.
  • Earth cations, transition metals and lanthanides) cations are located and oxygen anions are located at X site, and metal cations at B site are combined with oxygen anions at X site as corner-sharing octahedrons of 6-fold coordination.
  • Examples thereof include SrFeO 3 , LaMnO 3 , CaFeO 3, and the like.
  • the organic-inorganic hybrid perovskite has an organic ammonium (RNH 3 ) cation at the A site and an halides (Cl, Br, I) at the X site in the ABX 3 structure.
  • RNH 3 organic ammonium
  • Cl, Br, I halides
  • Inorganic metal oxide perovskite typically exhibits superconductivity, ferroelectricity, and colossal magnetoresistance, and thus, research has been conducted in general for sensors, fuel cells, and memory devices.
  • yttrium barium copper oxide has superconducting or insulating properties depending on oxygen contents.
  • organic-inorganic hybrid perovskite (or organometallic halide perovskite) has an organic plane (or an alkali metal plane) and an inorganic plane alternately stacked, similar to the lamellar structure, so that the exciton bonds in the inorganic plane. Because of this, it is essentially an ideal emitter that emits very high color purity light by the crystal structure itself rather than the size of the material.
  • the organic-inorganic hybrid perovskite even if the organic ammonium contains a chromophore (mainly containing conjugated structure) having a bandgap smaller than the central metal and halogen crystal structure (BX3), the emission from organic ammonium Because of this, the half color width of the emission spectrum becomes wider than 100 nm because it does not emit light of high color purity, making it unsuitable as a light emitting layer. Therefore, such a case is not very suitable for the high color purity illuminant emphasized in this patent.
  • a chromophore mainly containing conjugated structure having a bandgap smaller than the central metal and halogen crystal structure (BX3)
  • Korean Patent Laid-Open Publication No. 10-2001-0015084 discloses an electroluminescent device using a dye-containing organic-inorganic hybrid material as a light emitting layer by forming a thin film instead of particles. Luminescence does not come from the lobe-sky lattice structure.
  • organic / inorganic hybrid perovskite has a small exciton binding energy, it is possible to emit light at low temperatures, but at room temperature, the fundamental problem that excitons do not go into luminescence but is separated into free charges and disappears due to thermal ionization and delocalization of charge carriers. There is.
  • the free charge recombines again to form excitons, there is a problem that the excitons are dissipated by the surrounding layer having high conductivity, so that light emission does not occur. Therefore, in order to increase luminous efficiency and luminance of organic / inorganic hybrid perovskite-based LEDs, it is necessary to prevent quenching of exciton.
  • the problem to be solved by the present invention is to synthesize an organic-inorganic hybrid perovskite or inorganic metal halide perovskite into nanocrystals instead of forming a thin film directly to prevent thermal ionization, delocalization of charge carriers and quenching of excitons
  • the present invention provides a light emitting layer for an organic-inorganic hybrid EL device, a method of manufacturing the same, and a light emitting device using the same, and a method of manufacturing the same, which is formed by a thin film to improve luminous efficiency and durability.
  • One aspect of the present invention provides a method of manufacturing a light emitting layer.
  • the method of manufacturing the light emitting layer may include forming a nanoparticle first thin film by coating a solution including an organic / inorganic perovskite nanoparticle including an organic / inorganic perovskite nanocrystal structure on the light emitting layer coating member. Include.
  • the forming of the nanoparticle first thin film may use a solution process, and the solution process may include spin-coating, bar coating, slot-die coating, and gravure printing. Gravure-printing, nozzle printing, ink-jet printing, screen printing, electrohydrodynamic jet printing, and electrospray It may include at least one process.
  • the nanoparticle first thin film may have a thickness of 1 nm to 1 ⁇ m, and an average roughness of 0.1 nm to 50 nm.
  • the forming of the nanoparticle first thin film may include preparing an organic / inorganic perovskite nanoparticle solution including an anchoring solution and the organic / inorganic perovskite nanocrystal structure, and forming the nanoparticle on the light emitting layer coating member.
  • the method may further include forming a crosslinking agent layer on the anchoring light emitting layer, coating the organic-inorganic perovskite nanoparticle solution and the organic-inorganic layer
  • the thickness of the light emitting layer may be adjusted by alternately repeating forming the crosslinking agent layer on the layer coated with the robesky nanoparticle solution.
  • the forming of the first nanoparticle thin film may include preparing an organic-inorganic perovskite-organic semiconductor solution by mixing an organic semiconductor to a solution containing the organic-inorganic perovskite nanoparticles, and the organic-inorganic Coating the perovskite-organic semiconductor solution to form a light emitting layer.
  • the step of forming the light emitting layer by coating the organic-inorganic perovskite-organic semiconductor solution, the light emitting layer, the organic semiconductor layer and the organic-inorganic perovskite nanoparticles sequentially on the light emitting layer coating member It can be self-organized in a stacked form.
  • the forming of the nanoparticle first thin film may include forming a self-assembled monomolecular film on the light-emitting layer coating member, and coating the solution containing the organic-inorganic perovskite nanoparticles on the self-assembled monomolecular film. Forming the perovskite nanoparticle layer, and contacting the organic-inorganic perovskite nanoparticle layer using a stamp to remove the organic perovskite nanoparticle layer by a desired pattern, and then forming the second organic-inorganic perovskite nanoparticle layer. It may include the step of forming on the light emitting layer coating member.
  • the stamp is polyurethane (Polyurethane), PDMS (Polydimethylsiloxane) PEO (Polyethylene oxide), PS (Polystyrene), PCL (Polycaprolactone), PAN (Polyacrylonitrile), PMMA (Poly (methyl methacrylate)), Polyimide (Polyimide) ), At least one organic polymer selected from the group consisting of polyvinyllidene fluoride (PVDF), poly (n-vinylcarbazole) (PVK), and polyvinylchloride (PVC).
  • PVDF polyvinyllidene fluoride
  • PVK poly (n-vinylcarbazole)
  • PVC polyvinylchloride
  • the step of forming a nanoparticle first thin film by coating a solution containing the organic-inorganic perovskite nanoparticles including the organic-inorganic perovskite nanocrystal structure on the light emitting layer coating member a plurality of times
  • the thickness of the light emitting layer can be adjusted, and before or after the step of forming the nanoparticle first thin film, comprising an organic-inorganic perovskite nanocrystal structure on the light emitting layer coating member or the nanoparticle first thin film
  • Organic-inorganic perovskite microparticles or organic-inorganic perovskite second thin films can be formed.
  • the light emitting layer includes a light emitting layer coating member, and a nanoparticle first thin film disposed on the light emitting layer coating member and including the organic / inorganic perovskite nanocrystal structure manufactured by the above-described manufacturing method.
  • the nanoparticle first thin film may have a multi-layered structure, and may include an organic-inorganic perovskite nanocrystal structure between the light emitting layer coating member and the nanoparticle first thin film or on the nanoparticle first thin film.
  • the organic-inorganic perovskite microparticles or organic-inorganic perovskite second thin film may be further disposed.
  • the light emitting device includes a first electrode disposed on a substrate, a nanoparticle first thin film disposed on the first electrode, and including an organic-inorganic perovskite nanocrystal structure, which is prepared by the above-described manufacturing method.
  • an exciton buffer layer may be further disposed between the first electrode and the light emitting layer and may include a conductive material and a fluorine-based material having a lower surface energy than the conductive material.
  • the nanoparticle first thin film may have a multi-layer structure, and may include an organic-inorganic perovskite nanocrystal structure between the light emitting layer coating member and the nanoparticle first thin film or on the nanoparticle first thin film.
  • Organic-inorganic perovskite microparticles or organic-inorganic perovskite second thin films may be further disposed.
  • the method of manufacturing the light emitting layer may include preparing a light emitting layer coating member; And coating a solution including an inorganic metal halide perovskite nanoparticle including an inorganic metal halide perovskite nanocrystal structure on the light emitting layer coating member to form a nanoparticle first thin film.
  • the step of forming the nanoparticle first thin film is characterized in that using a solution process.
  • the solution process is spin-coating, bar coating, slot-die coating, gravure printing, nozzle printing, inkjet printing (ink) at least one process selected from the group consisting of -jet printing, screen printing, electrohydrodynamic jet printing, and electrospray.
  • the light emitting layer is a light emitting layer coating member; And a nanoparticle first thin film disposed on the light emitting layer coating member and including the inorganic metal halide perovskite nanocrystal structure described above.
  • Such a solar cell may be positioned between a first electrode, a second electrode, and the first electrode and the second electrode, and may include a photoactive layer including the above-described perovskite nanocrystalline particles.
  • Organic-inorganic hybrid perovskite or inorganic metal halide perovskite light emitting device according to the present invention and a method for manufacturing the same, and organic-inorganic hybrid perovskite or inorganic metal halide perovskite light emitting device using the same
  • An organic-inorganic hybrid perovskite or inorganic metal halide perovskite having a crystal structure combining FCC and BCC is formed in the light emitting body, and a lamellar structure in which an organic plane (or an alkali metal plane) and an inorganic plane are alternately stacked. And exciton is confined to the inorganic plane to produce high color purity.
  • the perovskite is made of nanoparticles and then introduced into the light emitting layer, light emission efficiency and luminance of the device may be improved.
  • FIG. 1 is a flow chart illustrating a method for preparing a solution including organic-inorganic perovskite nanoparticles including an organic-inorganic perovskite nanocrystal structure according to an embodiment of the present invention.
  • FIG. 2 is a cross-sectional view of a light emitting layer according to an embodiment of the present invention.
  • FIG 3 is a cross-sectional view of a light emitting layer according to another embodiment of the present invention.
  • 4A to 4D are cross-sectional views of a light emitting layer according to another embodiment of the present invention.
  • FIG. 5 is a schematic diagram illustrating a method of preparing the organic-inorganic hybrid perovskite nanoparticles according to an embodiment of the present invention through an inverse nano-emulsion method.
  • FIG. 6 is a schematic view showing an organic-inorganic hybrid perovskite nanocrystalline particle emitter and an inorganic metal halide perovskite nanocrystalline particle emitter according to an embodiment of the present invention.
  • FIG. 7 is a schematic diagram of a perovskite nanocrystal structure according to an embodiment of the present invention.
  • FIG. 8 is a schematic view showing a light emitting layer forming process through a spin-assembly process according to an embodiment of the present invention.
  • FIG. 9 is a schematic diagram showing a light emitting layer forming process through a floating process according to an embodiment of the present invention.
  • FIG. 10 is a schematic view showing a light emitting layer forming process through a dry contact printing process according to an embodiment of the present invention.
  • FIG. 11 is a schematic view showing a light emitting layer forming method through an organic-inorganic perovskite-organic host composite forming process according to an embodiment of the present invention.
  • 12A to 12D are cross-sectional views of light emitting devices illustrating a method of manufacturing a light emitting device according to an embodiment of the present invention.
  • FIG. 13 is a schematic diagram showing the effect of the exciton buffer layer 30 according to an embodiment of the present invention.
  • organic-inorganic perovskite nanoparticles including the organic-inorganic perovskite nanocrystal structure of Preparation Example 1 and ultraviolet in the organic-inorganic hybrid perovskite (OIP film) according to Comparative Examples 1 and 2 It is a fluorescent image taken by emitting light.
  • FIG. 15 is a schematic view of nanoparticles according to Preparation Example and Comparative Example 1.
  • FIG. 15 is a schematic view of nanoparticles according to Preparation Example and Comparative Example 1.
  • FIG. 17 is a graph showing photoluminescence of nanoparticles according to Preparation Example 1 and Comparative Example 1.
  • a layer is referred to herein as "on" another layer or substrate, it may be formed directly on the other layer or substrate, but a third layer may be interposed therebetween.
  • the directional expression of the upper part, the upper part, and the upper part may be understood as meanings of the lower part, the lower part, the lower part, and the like according to the criteria. That is, the expression of the spatial direction should be understood as a relative direction and should not be construed as limiting the absolute direction.
  • the method of forming the light emitting layer from the inorganic metal halide perovskite nanoparticles instead of the organic / inorganic hybrid perovskite nanoparticles is also the same. Therefore, the manufacturing method of the light emitting layer for organic-inorganic hybrid perovskite light emitting elements is demonstrated to an example.
  • the method for manufacturing the light emitting layer for the organic-inorganic hybrid perovskite light emitting device preparing a light emitting layer coating member and the organic-permeable perovskite nanocrystal structure on the light emitting layer coating member described above And coating a solution containing the organic-inorganic perovskite nanoparticles including the nanoparticles to form the first thin film.
  • the light emitting layer coating member is prepared.
  • the above-described light emitting layer coating member may be a substrate, an electrode, or a semiconductor layer.
  • a substrate, an electrode, or a semiconductor layer that can be used for the light emitting device can be used.
  • the light emitting layer coating member may have a form in which substrates / electrodes are sequentially stacked or a form in which substrates / electrodes / semiconductor layers are sequentially stacked.
  • the description of the above-described substrate, electrode, or semiconductor layer will refer to the contents of the 'organic-inorganic hybrid perovskite light emitting device' described later.
  • FIG. 1 is a flow chart illustrating a solution preparation method including organic-inorganic perovskite nanoparticles including an organic-inorganic perovskite nanocrystal structure according to an embodiment of the present invention.
  • a method of preparing a solution including organic-inorganic perovskite nanoparticles including an organic / inorganic perovskite nanocrystal structure includes a first solution in which an organic-inorganic hybrid perovskite is dissolved in a protic solvent. And preparing a second solution in which an alkyl halide surfactant is dissolved in an aprotic solvent (S100) and mixing the first solution with the second solution to form nanoparticles (S200).
  • the organic-inorganic hybrid perovskite nanoparticles according to the present invention can be prepared through an inverse nano-emulsion method.
  • a first solution in which an organic-inorganic hybrid perovskite is dissolved in a protic solvent and a second solution in which an alkyl halide surfactant is dissolved in an aprotic solvent are prepared (S100).
  • the protic solvent may include dimethylformamide, gamma butyrolactone or N-methylpyrrolidone, or dimethylsulfoxide, but is not limited thereto. It is not.
  • the organic-inorganic hybrid perovskite at this time may be a material having a two-dimensional crystal structure.
  • such organic-inorganic hybrid perovskite may be a structure of ABX 3 , A 2 BX 4 , ABX 4 or A n-1 B n X 3n + 1 (n is an integer between 2 and 6).
  • A is an organoammonium material
  • B is a metal material
  • X is a halogen element
  • A is (CH 3 NH 3 ) n , ((C x H 2x + 1 ) n NH 3 ) 2 (CH 3 NH 3 ) n, (RNH 3 ) 2 , (C n H 2n + 1 NH 3 ) 2 , (CF 3 NH 3 ), (CF 3 NH 3 ) n , ((C x F 2x + 1 ) n NH 3 ) 2 (CF 3 NH 3 ) n , ((C x F 2x + 1 ) n NH 3 ) 2 or (C n F 2n + 1 NH 3 ) 2 (n is an integer greater than or equal to 1, x is an integer greater than or equal to 1).
  • B may be a divalent transition metal, a rare earth metal, an alkaline earth metal, Pb, Sn, Ge, Ga, In, Al, Sb, Bi, Po, or a combination thereof.
  • the rare earth metal may be a divalent rare earth metal.
  • the alkaline earth metal may be, for example, Ca or Sr.
  • X may be Cl, Br, I or a combination thereof.
  • such perovskite can be prepared by combining AX and BX 2 in a certain ratio. That is, the first solution may be formed by dissolving AX and BX 2 in a proportion in a protic solvent.
  • a first solution in which A 2 BX 3 organic-inorganic hybrid perovskite is dissolved may be prepared by dissolving AX and BX 2 in a protic solvent in a 2: 1 ratio.
  • the aprotic solvent at this time is dichloroethylene, trichloroethylene, chloroform, chlorobenzene, dichlorobenzene, styrene, dimethylformamide, dimethyl sulfoxide, xylene, toluene, cyclohexene or isopropyl alcohol May be included but is not limited to this.
  • the alkyl halide surfactant may be of the structure of alkyl-X.
  • the halogen element corresponding to X may include Cl, Br, or I.
  • the alkyl structure includes primary alcohols and secondary alcohols having a structure such as acyclic alkyl having a structure of C n H 2n +1 , C n H 2n + 1 OH, and the like.
  • Tertiary alcohol, alkylamine having alkyl-N structure (ex.
  • carboxylic acid (COOH) surfactants may be used instead of alkyl halide surfactants.
  • the surfactant may be 4,4'-Azobis (4-cyanovaleric acid) (4,4'-Azobis (4-cyanovaleric acid)), acetic acid, 5-minano 5-Aminosalicylic acid, Acrylic acid, L-Aspentic acid, 6-Brohexahexanoic acid, Promoacetic acid ), Dichloro acetic acid, ethylenediaminetetraacetic acid, isobutyric acid, itaconic acid, maleic acid, r R-Maleimidobutyric acid, L-Malic acid, 4-nitrobenzoic acid, or 1-pyrenecarboxylic acid ), Such as oleic acid, but may contain carboxylic acid (COOH). It is not.
  • the first solution is mixed with the second solution to form nanoparticles (S200).
  • nanoparticles In the forming of the nanoparticles by mixing the first solution with the second solution, it is preferable to drop the first solution drop by drop into the second solution.
  • the second solution at this time may be stirred.
  • nanoparticles may be synthesized by slowly dropping a second solution in which an organic-inorganic perovskite (OIP) is dissolved into a second solution in which a strongly stirring alkyl halide surfactant is dissolved.
  • OIP organic-inorganic perovskite
  • the organic-inorganic perovskite (OIP) when the first solution is dropped into the second solution and mixed, the organic-inorganic perovskite (OIP) is precipitated in the second solution due to the difference in solubility.
  • the organic-inorganic perovskite (OIP) precipitated in the second solution generates an organic-inorganic perovskite nanocrystal (OIP-NC) that is well dispersed while the alkyl halide surfactant stabilizes the surface. Accordingly, a solution including organic-inorganic perovskite nanoparticles including organic-inorganic perovskite nanocrystals and a plurality of alkyl halide organic ligands surrounding the organic-inorganic perovskite nanocrystals can be prepared.
  • the solution containing the organic-inorganic perovskite nanoparticles is coated on the light emitting layer coating member to form a nanoparticle first thin film that is a light emitting layer.
  • FIG. 2 is a cross-sectional view of a light emitting layer according to an embodiment of the present invention.
  • the light emitting layer in the form of the nanoparticle first thin film 200a is formed on the light emitting layer coating member 100.
  • the forming of the nanoparticle first thin film may use a solution process.
  • a solution process a light emitting layer can be formed uniformly on the light emitting layer coating member.
  • the above-described solution process includes spin-coating, bar coating, slot-die coating, gravure printing, nozzle printing, inkjet printing and ink-jet printing. at least one process selected from the group consisting of jet printing, screen printing, electrohydrodynamic jet printing, and electrospray.
  • FIG 3 is a cross-sectional view of a light emitting layer according to another embodiment of the present invention.
  • the nanoparticle first thin film may be formed in a multilayer (N layer) structure.
  • 4A to 4D are cross-sectional views of a light emitting layer according to another embodiment of the present invention.
  • the organic-inorganic perovskite microparticles comprising an organic-inorganic perovskite nanocrystalline structure on the light emitting layer coating member or the nanoparticle first thin film or
  • the method may further include forming the organic / inorganic perovskite second thin film.
  • the aforementioned organic-inorganic perovskite microparticles or the organic-inorganic perovskite second thin film include the organic-inorganic perovskite nanoparticles that mix the first solution and the second solution. Unlike solution preparation, it can be formed by coating using only the first solution.
  • the organic-inorganic perovskite microparticles having a micro range or Sunano to water An organic-inorganic perovskite second thin film containing an organic-inorganic perovskite crystal structure having a micro range can be formed.
  • the organic-inorganic perovskite microparticles 200b described above are disposed on the nanoparticle first thin film 200a as described above with reference to FIG. 4A on the light emitting layer coating member 100.
  • 4 is a form in which the aforementioned nanoparticle first thin film 200a is formed on the organic-inorganic perovskite microparticle 200b described above with reference to FIG. 4B, and the nanoparticle first described above with reference to FIG. 4C.
  • the organic-inorganic perovskite second thin film 200c described above is disposed on the thin film 200a, or the organic-inorganic perovskite second thin film 200c described above as illustrated in FIG. 4 (d).
  • the nanoparticle first thin film 200a may be formed.
  • organic-inorganic perovskite microparticles described above may be formed in various shapes such as spherical and polygonal.
  • the thickness of the above-described nanoparticle first thin film may be 1 nm to 1 ⁇ m, and the average roughness may be 0.1 nm to 50 nm.
  • the band gap energy of the above-mentioned organic-inorganic hybrid perovskite nanocrystalline particles may be 1 eV to 5 eV.
  • the emission wavelength of the organic-inorganic hybrid perovskite nanoparticles described above may be 200nm to 1300nm.
  • the size of the organic-inorganic perovskite nanocrystals can be controlled by adjusting the length or shape factor of the alkyl halide surfactant.
  • shape factor adjustment can control the size through a linear, tapered or inverted triangular surfactant.
  • the size of the organic-inorganic perovskite nanocrystals thus produced may be 1 to 900nm. If the size of the organic-inorganic perovskite nanocrystals exceeds 900 nm, the fundamental problem is that excitons do not go into luminescence due to thermal ionization and delocalization of charge carriers in large nanocrystals. There may be.
  • FIG. 5 is a schematic diagram illustrating a method of preparing the organic-inorganic hybrid perovskite nanoparticles according to an embodiment of the present invention through an inverse nano-emulsion method.
  • a first solution in which an organic-inorganic hybrid perovskite is dissolved in a protic solvent is added dropwise to a second solution in which an alkyl halide surfactant is dissolved in an aprotic solvent.
  • the protic solvent may include dimethylformamide, gamma butyrolactone or N-methylpyrrolidone, or dimethylsulfoxide, but is not limited thereto. It is not.
  • the inorganic hybrid perovskite is ABX 3 , A 2 BX 4 , ABX 4 Or A n- 1 B n X 3n +1 (n is an integer between 2 and 6).
  • A is an organoammonium material
  • B is a metal material
  • X is a halogen element.
  • A is (CH 3 NH 3 ) n , ((C x H 2x + 1 ) n NH 3 ) 2 (CH 3 NH 3 ) n, (RNH 3 ) 2 , (C n H 2n + 1 NH 3 ) 2 , (CF 3 NH 3 ), (CF 3 NH 3 ) n , ((C x F 2x + 1 ) n NH 3 ) 2 (CF 3 NH 3 ) n , ((C x F 2x + 1 ) n NH 3 ) 2 or (C n F 2n + 1 NH 3 ) 2 (n is an integer greater than or equal to 1, x is an integer greater than or equal to 1).
  • B may be a divalent transition metal, a rare earth metal, an alkaline earth metal, Pb, Sn, Ge, Ga, In, Al, Sb, Bi, Po, or a combination thereof.
  • the rare earth metal 2 at this time may be a rare earth metal, for example Ge, Sn, Pb, Eu or Yb.
  • the alkaline earth metal may be, for example, Ca or Sr.
  • X may be Cl, Br, I or a combination thereof.
  • the structure of the perovskite at this time may be formed by a ratio-specific combination of AX and BX 2 .
  • a first solution in which A 2 BX 3 organic-inorganic hybrid perovskite is dissolved may be prepared by dissolving AX and BX 2 in a protic solvent in a 2: 1 ratio.
  • organic-inorganic hybrid perovskite when the first solution is added to the second solution, organic-inorganic hybrid perovskite is precipitated in the second solution due to the difference in solubility, and the precipitated organic-inorganic hybrid perovskite is deposited. While the alkyl halide surfactants surround and stabilize the surface, the organic-inorganic hybrid perovskite nanoparticles 100 including the organic-inorganic hybrid perovskite nanocrystal structure are well dispersed. At this time, the surface of the organic-inorganic hybrid perovskite nanocrystals are surrounded by organic ligands, which are alkyl halides.
  • the protic solvent including the organic-inorganic hybrid perovskite nanoparticles 100 dispersed in the aprotic solvent in which the alkyl halide surfactant is dissolved is selectively evaporated by heating, or the aprotic solvent and aprotic solvent
  • the organic-inorganic hybrid perovskite nanoparticles can be obtained by selectively extracting a protic solvent including nanoparticles from the aprotic solvent by adding a magnetic solvent and co-solvent that can be dissolved in both.
  • Figure 6 is a schematic diagram showing a perovskite nanoparticles according to an embodiment of the present invention.
  • FIG. 6 shows the organic-inorganic hybrid perovskite nanocrystalline particles.
  • the light emitter is an organic-inorganic hybrid perovskite (or inorganic metal halide perovskite) nanoparticle, in which an organic plane (or an alkali metal plane) and an inorganic plane are alternated. And a two-dimensional organic-inorganic hybrid perovskite nanocrystal 110 having a lamellar structure stacked with a.
  • These two-dimensional organic-inorganic hybrid perovskite is ABX 3 , A 2 BX 4 , ABX 4 Or A n- 1 B n X 3n +1 (n is an integer between 2 and 6).
  • A is an organoammonium material
  • B is a metal material
  • X is a halogen element.
  • A is (CH 3 NH 3 ) n , ((C x H 2x + 1 ) n NH 3 ) 2 (CH 3 NH 3 ) n, (RNH 3 ) 2 , (C n H 2n + 1 NH 3 ) 2 , (CF 3 NH 3 ), (CF 3 NH 3 ) n , ((C x F 2x + 1 ) n NH 3 ) 2 (CF 3 NH 3 ) n , ((C x F 2x + 1 ) n NH 3 ) 2 or (C n F 2n + 1 NH 3 ) 2 (n is an integer greater than or equal to 1, x is an integer greater than or equal to 1).
  • B may be a divalent transition metal, a rare earth metal, an alkaline earth metal, Pb, Sn, Ge, Ga, In, Al, Sb, Bi, Po, or a combination thereof.
  • the rare earth metal at this time may be a divalent rare earth metal, for example Ge, Sn, Pb, Eu or Yb.
  • the alkaline earth metal may be, for example, Ca or Sr.
  • X may be Cl, Br, I or a combination thereof.
  • the organic-inorganic hybrid perovskite nanoparticle 100 may further include a plurality of organic ligands 120 surrounding the organic-inorganic hybrid perovskite nanocrystal 110 described above.
  • the organic ligands 120 may include an alkyl halide as a material used as a surfactant. Therefore, the alkyl halide used as a surfactant to stabilize the surface of the organic-inorganic hybrid perovskite precipitated as described above becomes an organic ligand surrounding the surface of the organic-inorganic hybrid perovskite nanocrystals.
  • the size of the nanocrystals to be formed may be larger than 900 nm can be formed, in this case for thermal ionization and delocalization of the charge carriers in the large nanocrystals There may be a fundamental problem that the excitons do not go to the light emission but are separated by the free charge and disappear.
  • the size of the organic-inorganic hybrid perovskite nanocrystals formed is inversely proportional to the length of the alkyl halide surfactant used to form these nanocrystals.
  • the size of the organic-inorganic hybrid perovskite nanocrystals formed by using an alkyl halide of a predetermined length or more as a surfactant can be controlled to a predetermined size or less.
  • octadecyl-ammonium bromide may be used as an alkyl halide surfactant to form organic-inorganic hybrid perovskite nanocrystals having a size of 900 nm or less.
  • the inorganic metal halide perovskite having a two-dimensional crystal structure may be a structure of A 2 BX 4 , ABX 4 or A n-1 Pb n I 3n + 1 (n is an integer between 2 and 6).
  • A is an alkali metal
  • B is a divalent transition metal, a rare earth metal, an alkaline earth metal, Pb, Sn, Ge, Ga, In, Al, Sb, Bi, Po, or a combination thereof
  • X is Cl , Br, I or a combination thereof.
  • the rare earth metal may be Ge, Sn, Pb, Eu or Yb.
  • the alkaline earth metal may be, for example, Ca or Sr.
  • the inorganic metal halide perovskite nanocrystalline particles having the two-dimensional structure according to the present invention may further include a plurality of organic ligands surrounding the inorganic metal halide perovskite nanocrystal structure described above.
  • organic ligands may include alkyl halides.
  • FIG. 7 is a schematic diagram of a perovskite nanocrystal structure according to an embodiment of the present invention.
  • FIG. 7 shows the structures of the organic-inorganic hybrid perovskite nanocrystals and the inorganic metal halide perovskite nanocrystals together.
  • the organic-inorganic hybrid perovskite (or inorganic metal halide perovskite) nanocrystal structure includes organic ammonium (or alkali metal) and halides. have.
  • FIG. 8 is a schematic view showing a light emitting layer forming process through a spin-assembly process according to an embodiment of the present invention.
  • an organic-inorganic perovskite nanoparticle solution including the anchoring solution and the organic perovskite nanocrystal structure is prepared.
  • the above-mentioned anchoring solution is a solution containing a resin imparting tack that exhibits an anchoring effect.
  • a resin imparting tack that exhibits an anchoring effect.
  • 3-mercaptopropionic acid ethanilic solution may be used.
  • the anchoring solution described above is preferably in a concentration of 7wt% to 12wt%.
  • the anchoring solution is coated on the light emitting layer coating member to form an anchoring agent layer.
  • the coating speed is preferably 1000 rpm to 5000 rpm, the coating time is preferably 15 seconds to 150 seconds. If the coating speed is lowered below 1000 rpm, or the coating time is shortened to less than 15 seconds, the thin film may become uneven or the solvent may not evaporate.
  • the organic-inorganic perovskite nanoparticle solution is coated on the aforementioned anchoring agent layer to form an anchoring light emitting layer.
  • a denser nanocrystal layer may be formed.
  • a crosslinking agent layer may be formed on the anchoring light emitting layer.
  • a denser perovskite nanocrystal layer can be formed, and the ligand length is shortened, so that charge injection into the nanocrystal is more smooth, thereby increasing the luminous efficiency and luminance of the light emitting device. It works.
  • the crosslinking agent is preferably a crosslinking agent having an X-R-X structure.
  • 1,2-ethanedithiol may be used.
  • the crosslinking agent is mixed with a soluble solvent to prepare a solution, followed by spin coating.
  • the step of coating the organic-inorganic perovskite nanoparticle solution and the step of forming a cross-linking agent layer on the layer coated with the organic-inorganic perovskite nanoparticle solution are alternately repeated to reduce the thickness of the light emitting layer I can regulate it.
  • the coating speed is preferably 1000 rpm to 5000 rpm, the coating time is preferably 15 seconds to 150 seconds. If the coating speed is lowered below 1000 rpm, or the coating time is shortened to less than 15 seconds, the thin film may become uneven or the solvent may not evaporate.
  • FIG. 9 is a schematic diagram showing a light emitting layer forming process through a floating process according to an embodiment of the present invention.
  • a solution containing trioctyl phosphine (TOP) and trioctyl phosphine oxide (TOPO) is added to a solution containing the organic-inorganic perovskite nanoparticles described above.
  • TOP trioctyl phosphine
  • TOPO trioctyl phosphine oxide
  • the ligand comprises a triphenyl diamine (TPD) compound in a solution containing organic-inorganic perovskite nanoparticles substituted with trioctyl phosphine (TOP) and trioctyl phosphine oxide (TOPO).
  • TPD triphenyl diamine
  • TOP trioctyl phosphine
  • TOPO trioctyl phosphine oxide
  • the aforementioned triphenyldiamine compound may be N, N'-diphenyl-N, N'-bis (3-methylphenyl)-(1,1'-biphenyl) -4, 4'diamine.
  • TPD triphenyl diamine
  • the above-described TPD-inorganic hybrid perovskite nanoparticle solution is coated on the light-emitting layer coating member to form a light-emitting layer for an organic-inorganic hybrid perovskite light emitting device.
  • the light emitting layer described above may simplify the process as the organic semiconductor layer and the organic-inorganic perovskite nanoparticles are sequentially stacked on the light emitting layer coating member and self-organized. .
  • the coating speed is preferably 1000 rpm to 5000 rpm, the coating time is preferably 15 seconds to 150 seconds. If the spin coating speed is lowered below 1000 rpm, or the coating time is shortened to within 15 seconds, the thin film may become uneven or the solvent may not evaporate.
  • FIG. 10 is a schematic view showing a light emitting layer forming process through a dry contact printing process according to an embodiment of the present invention.
  • a self-assembled monolayer may be formed on the light emitting layer coating member.
  • a member made of silicon may be used as the light emitting layer coating member. More specifically, an ODTS-treated wafer may be used in which a silicon native wafer is dipped in an octadecyltrichlorosilane (ODTS) solution.
  • ODTS octadecyltrichlorosilane
  • organic-inorganic perovskite nanoparticles coated on the aforementioned self-assembled monolayer to form an organic-inorganic perovskite nanoparticle layer.
  • organic-inorganic perovskite nanoparticle layer is contacted with the organic-inorganic perovskite nanoparticle layer using a stamp, and then separated by a desired pattern to form the organic-inorganic perovskite nanoparticle layer on the second light emitting layer coating member.
  • the stamps described above include polyurethane, Polydimethylsiloxane (PDMS) Polyethylene oxide (PEO), Polystyrene (PS), Polycaprolactone (PCL), Polyacrylonitrile (PAN), Poly (methyl methacrylate) (PMMA), Polyimide, It may include at least one organic polymer selected from the group consisting of polyvinyllidene fluoride (PVDF), poly (n-vinylcarbazole) (PVK), and polyvinylchloride (PVC).
  • PDMS Polydimethylsiloxane
  • PEO Polyethylene oxide
  • PS Polystyrene
  • PCL Polycaprolactone
  • PAN Polyacrylonitrile
  • PMMA Poly (methyl methacrylate)
  • Polyimide It may include at least one organic polymer selected from the group consisting of polyvinyllidene fluoride (PVDF), poly (n-vinylcarbazole) (PVK), and polyvinylchlor
  • the substrate sensitivity and the large-area assembly which are problematic in the conventional wet process, are formed by forming the organic-inorganic perovskite nanoparticle layer through a stamping process.
  • the difficulty of large-area assembly and layer-by-layer deposition processes can be solved.
  • FIG. 11 is a schematic view showing a light emitting layer forming method through an organic-inorganic perovskite-organic host composite forming process according to an embodiment of the present invention.
  • the organic-inorganic perovskite-organic semiconductor solution may be mixed by first mixing an organic semiconductor with the above-described solution containing organic / inorganic perovskite nanoparticles. To prepare.
  • the aforementioned organic semiconductors include tris (8-quinolinorate) aluminum (Alq3), TAZ, TPQ1, TPQ2, Bphen (4,7-diphenyl-1,10-phenanthroline (4,7-diphenyl-1,10 -phenanthroline)), BCP, BeBq2, BAlq, CBP (4,4'-N, N'-dicarbazole-biphenyl), 9,10-di (naphthalen-2-yl) anthracene (ADN), TCTA (4 , 4 ', 4 "-tris (N-carbazolyl) triphenylamine), TPBI (1,3,5-tris (N-phenylbenzimidazol-2-yl) benzene (1,3,5-tris ( N-phenylbenzimidazole-2-yl) benzene)), TBADN (3-tert-butyl-9,10-di (naphth-2-yl) anthracene)
  • the organic-inorganic perovskite-organic semiconductor solution described above is coated to form a light emitting layer.
  • the coating speed is preferably 1000 rpm to 5000 rpm, the coating time is preferably 15 seconds to 150 seconds. If the spin coating speed is lowered below 1000 rpm, or the coating time is shortened to within 15 seconds, the thin film may become uneven or the solvent may not evaporate.
  • the organic-inorganic perovskite nanoparticles including the organic-inorganic perovskite nanocrystal structure are formed on the light-emitting layer coating member.
  • an organic-inorganic hybrid perovskite having a crystal structure of FCC and BCC combined is formed in the nanoparticle light emitter, and a lamellar structure in which an organic plane and an inorganic plane are alternately stacked is formed, and excitons are formed on the inorganic plane. It can be constrained to produce high color purity.
  • the perovskite is made of nanoparticles and then introduced into the light emitting layer, light emission efficiency and luminance of the device may be improved.
  • 12A to 12D are cross-sectional views of light emitting devices illustrating a method of manufacturing a light emitting device according to an embodiment of the present invention.
  • first a first electrode 20 is formed on a substrate 10.
  • the substrate 10 described above serves as a support of the organic light emitting device, and is made of a transparent material.
  • the above-described substrate 10 may be used both a flexible material and a hard material, it is more preferably configured of a flexible material.
  • the material of the substrate 10 described above having transparent and flexible properties may be PET, PS, PI, PVC, PVP or PE.
  • the first electrode 20 described above is an electrode into which holes are injected, and is made of a conductive material.
  • the material constituting the above-described first electrode 20 may be a metal oxide, and in particular, it is preferable that the material is a transparent conductive metal oxide.
  • the above-described transparent conductive metal oxide may include ITO, AZO (Al-doped ZnO), GZO (Ga-doped ZnO), IGZO (In, Ga-dpoed ZnO), MZO (Mg-doped ZnO), Mo-doped ZnO, Al-doped MgO, Ga-doped MgO, F-doped SnO 2 , Nb-dpoed TiO 2 or CuAlO 2 and the like.
  • Deposition processes for forming the above-described first electrode 20 include physical vapor deposition (PVD), chemical vapor deposition (CVD), sputtering, pulsed laser deposition. PLD), thermal evaporation, electron beam evaporation, atomic layer deposition (ALD), molecular beam epitaxy (MBE), and the like.
  • an exciton buffer layer 30 including a conductive material and a fluorine-based material having a lower surface energy than the aforementioned conductive material is formed on the first electrode 20 described above.
  • the above-described exciton buffer layer 30 may have a form in which a conductive layer 31 including a conductive material and a surface buffer layer 32 including a fluorine-based material having a lower surface energy than the conductive material are sequentially stacked.
  • the conductive layer 31 described above comprises a conductive material.
  • the aforementioned conductive material may include at least one selected from the group consisting of a conductive polymer, metallic carbon nanotubes, graphene, reduced graphene oxide, metal nanowires, semiconductor nanowires, metal grids, metal nanodots, and conductive oxides. Can be.
  • the conductive polymers described above may include polythiophene, polyaniline, polypyrrole, polystyrene, sulfonated polystyrene, poly (3,4-ethylenedioxythiophene), self-doped conductive polymers, derivatives thereof, or combinations thereof. have.
  • the above-mentioned derivative may mean that it may further include various sulfonic acids and the like.
  • the above-mentioned conductive polymer may include Pani: DBSA (Polyaniline / Dodecylbenzenesulfonic acid: polyaniline / dodecylbenzenesulfonic acid, see the following formula), PEDOT: PSS (Poly (3,4-ethylenedioxythiophene) / Poly (4-styrenesulfonate): Poly (3,4-ethylenedioxythiophene) / poly (4-styrenesulfonate), see formula below), Pani: CSA (Polyaniline / Camphor sulfonicacid: polyaniline / camphorsulfonic acid) and PANI: PSS (Polyaniline) / Poly ( 4-styrenesulfonate): polyaniline) / poly (4-styrenesulfonate)) may include at least one selected from the group consisting of, but is not limited thereto.
  • DBSA Polyaniline / Dodecylbenzen
  • the conductive polymer may be Pani: DBSA (Polyaniline / Dodecylbenzenesulfonic acid, see Chemical Formula), PEDOT: PSS (Poly (3,4-ethylenedioxythiophene) / Poly (4-styrenesulfonate)), See Formula: Polyaniline / Camphor sulfonicacid (CSA) or PANI: PSS (Polyaniline) / Poly (4-styrenesulfonate) and the like, but are not limited thereto.
  • DBSA Polyaniline / Dodecylbenzenesulfonic acid, see Chemical Formula
  • PEDOT PSS (Poly (3,4-ethylenedioxythiophene) / Poly (4-styrenesulfonate))
  • CSA Camphor sulfonicacid
  • PANI PSS (Polyaniline) / Poly (4-styrenesulfonate) and the like, but are not limited thereto.
  • R may be H or a C1-C10 alkyl group.
  • the self-doped conductive polymer may have a polymerization degree of 13 to 10,000,000, and may have a repeating unit represented by Formula 21 below:
  • At least one of R 1 , R 2 , R 3 , R ' 1 , R' 2 , R ' 3 and R' 4 contains an ionic group, and A, B, A ', and B' are each independently C , Si, Ge, Sn, or Pb;
  • R 1 , R 2 , R 3 , R ' 1 , R' 2 , R ' 3 and R' 4 are each independently hydrogen, halogen, nitro group, substituted or unsubstituted amino group, cyano group, substituted or unsubstituted Substituted C 1 -C 30 alkyl group, substituted or unsubstituted C 1 -C 30 alkoxy group, substituted or unsubstituted C 6 -C 30 aryl group, substituted or unsubstituted C 6 -C 30 arylalkyl group, substituted or Unsubstituted C 6 -C 30 aryloxy group, substituted or unsubstituted C 2 -C 30 heteroaryl group, substituted or unsubstituted C 2 -C 30 heteroarylalkyl group, substituted or unsubstituted C 2 -C 30 heteroaryloxy group, substituted or unsubstituted C 5 -C 30 cycloalky
  • R 4 consists of a conjugated conductive polymer chain
  • X and X ' are each independently a simple bond, O, S, a substituted or unsubstituted C 1 -C 30 alkylene group, a substituted or unsubstituted C 1 -C 30 heteroalkylene group, a substituted or unsubstituted C 6 -C 30 arylene group, substituted or unsubstituted C 6 -C 30 arylalkylene group, substituted or unsubstituted C 2 -C 30 heteroarylene group, substituted or unsubstituted C 2 -C 30 heteroarylalkyl
  • a ylene group, a substituted or unsubstituted C 5 -C 20 cycloalkylene group, and a substituted or unsubstituted C 5 -C 30 heterocycloalkylene group arylester group, optionally selected from carbon in the formula Hydrogen or halogen elements may be bonded.
  • the ionic group is PO 3 2-, SO 3 -, COO -, I -, CH 3 COO - anion group selected from the group consisting of and Na +, K +, Li + , Mg + 2, Zn + 2 And metal ions selected from Al + 3 , H + , NH 4 + , CH 3 (-CH 2- ) n O + (n is a natural number of 1 to 50) and selected from the group consisting of It may comprise a cationic group forming.
  • R 1 , R 2 , R 3 , R ' 1 , R' 2 , R ' 3 and R' 4 may be fluorine or substituted with fluorine. It may be, but is not limited to.
  • examples of the conductive polymer include, but are not limited to:
  • unsubstituted alkyl group herein include methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl and the like as the linear or branched alkyl group, and the aforementioned alkyl group
  • Heteroalkyl group herein means that at least one of the carbon atoms in the main chain of the alkyl group described above, preferably 1 to 5 carbon atoms is substituted with a hetero atom such as an oxygen atom, a sulfur atom, a nitrogen atom, a person atom and the like.
  • aryl group herein refers to a carbocycle aromatic system comprising one or more aromatic rings, wherein the rings described above may be attached or fused together in a pendant manner.
  • Specific examples of the aryl group may include aromatic groups such as phenyl, naphthyl, tetrahydronaphthyl, and the like, and one or more hydrogen atoms in the aforementioned aryl groups may be substituted with the same substituents as in the alkyl group described above.
  • Heteroaryl group herein refers to a ring aromatic system having 5 to 30 ring atoms containing 1, 2 or 3 heteroatoms selected from N, O, P or S, and the remaining ring atoms are C, and the aforementioned rings It can be attached or fused together in a pendant manner. At least one hydrogen atom of the heteroaryl group described above may be substituted with the same substituent as in the alkyl group described above.
  • Alkoxy groups herein refer to radicals —O-alkyl, wherein alkyl is as defined above. Specific examples include methoxy, ethoxy, propoxy, isobutyloxy, sec-butyloxy, pentyloxy, iso-amyloxy, hexyloxy, and the like.
  • One or more hydrogen atoms of the alkoxy group described above may be Substituents similar to those of the alkyl group can be substituted.
  • Heteroalkoxy groups which are substituents used in the present invention, have essentially the meaning of alkoxy described above except that one or more heteroatoms, for example oxygen, sulfur or nitrogen, may be present in the alkyl chain, for example CH 3 CH 2 OCH 2 CH 2 O-, C 4 H 9 OCH 2 CH 2 OCH 2 CH 2 O-, and CH 3 O (CH 2 CH 2 O) n H and the like.
  • An arylalkyl group herein means that some of the hydrogen atoms in the aryl group as defined above are substituted with radicals such as lower alkyl, for example methyl, ethyl, propyl and the like. For example benzyl, phenylethyl and the like. At least one hydrogen atom of the aforementioned arylalkyl group may be substituted with the same substituent as in the case of the aforementioned alkyl group.
  • heteroarylalkyl group used herein means that a part of the hydrogen atoms of the heteroaryl group is substituted with a lower alkyl group, and the definition of heteroaryl in the heteroarylalkyl group is as described above. At least one hydrogen atom of the aforementioned heteroarylalkyl group may be substituted with the same substituent as in the case of the aforementioned alkyl group.
  • aryloxy group herein refers to the radical -O-aryl, where aryl is as defined above. Specific examples include phenoxy, naphthoxy, anthracenyloxy, phenanthrenyloxy, fluorenyloxy, indenyloxy, and the like, and at least one hydrogen atom of the aryloxy group is substituted with the same substituent as in the case of the alkyl group described above. It is possible.
  • Heteroaryloxy group as used herein refers to the radical —O-heteroaryl, wherein heteroaryl is as defined above.
  • heteroaryloxy group of the present specification examples include a benzyloxy, a phenylethyloxy group, and the like, and at least one hydrogen atom in the heteroaryloxy group may be substituted with the same substituent as in the alkyl group described above.
  • cycloalkyl group herein is meant a monovalent monocyclic system having 5 to 30 carbon atoms. At least one hydrogen atom of the cycloalkyl group described above may be substituted with the same substituent as in the alkyl group described above.
  • Heterocycloalkyl group herein refers to a monovalent monocyclic system having 5 to 30 ring atoms containing 1, 2 or 3 heteroatoms selected from N, O, P or S, and the remaining ring atoms being C. At least one hydrogen atom of the cycloalkyl group described above may be substituted with the same substituent as in the alkyl group described above.
  • the alkyl ester group of the present specification means a functional group to which an alkyl group and an ester group are bonded, wherein the alkyl group is as defined above.
  • heteroalkyl ester group herein refers to a functional group having a heteroalkyl group and an ester group bonded thereto, and the aforementioned heteroalkyl group is as defined above.
  • the aryl ester group of the present specification means a functional group having an aryl group and an ester group bonded thereto, wherein the aryl group is as defined above.
  • the heteroaryl ester group of the present specification means a functional group having a heteroaryl group and an ester group bonded thereto, wherein the heteroaryl group is as defined above.
  • the amino group used in the present invention means -NH 2 , -NH (R) or -N (R ') (R “), R' and R" are independently an alkyl group having 1 to 10 carbon atoms.
  • Halogen herein is fluorine, chlorine, bromine, iodine or asstatin, among which fluorine is particularly preferred.
  • the metallic carbon nanotubes described above are carbon nanotubes that are purified metallic carbon nanotubes or carbon nanotubes having metal particles (eg, Ag, Au, Cu, Pt particles, etc.) attached to the inner and / or outer walls of the carbon nanotubes. It may be a tube.
  • the above-mentioned graphene is a graphene monolayer having a thickness of about 0.34 nm, a few layer graphene having a structure in which 2 to 10 graphene monolayers are stacked, or a larger number of graphenes than the above-described water layer graphene.
  • the pen monolayer may have a graphene multilayer structure having a stacked structure.
  • the metal nanowires and semiconductor nanowires described above are, for example, Ag, Au, Cu, Pt NiSi x (Nickel Silicide) nanowires and composites of two or more thereof, such as alloys or core-shells. shell) structure, etc.) may be selected from nanowires, but is not limited thereto.
  • the semiconductor nanowires described above may be Si nanowires doped with Si, Ge, B or N, Ge nanowires doped with B or N and composites of two or more of them (eg, alloys or core-shell structures, etc.). It may be selected from, but is not limited thereto.
  • the diameters of the metal nanowires and the semiconductor nanowires described above may be 5 nm to 100 nm or less, and the length may be 500 nm to 100 ⁇ m, which may vary depending on the manufacturing method of the metal nanowires and the semiconductor nanowires described above. Can be selected.
  • the above-described metal grid is formed of intersecting reticulated metal lines using Ag, Au, Cu, Al, Pt, and their alloys, and can have a line width of 100 nm to 100 ⁇ m, with a length limited. Do not receive.
  • the above-described metal grid may be formed to protrude above the first electrode or may be inserted into the first electrode to be recessed.
  • the aforementioned metal nanopoints may be selected from Ag, Au, Cu, Pt, and two or more of these composites (eg, alloys or core-shell structures, etc.) nanopoints, but are not limited thereto.
  • Z 100 , Z 101 , Z 102 , and Z 103 may each independently be bonded to hydrogen, a halogen atom, a substituted or unsubstituted C 1 -C 20 alkyl group, or a substituted or unsubstituted C 1 -C 20 alkoxy group).
  • At least one moiety represented by -S (Z 100 ) and -Si (Z 101 ) (Z 102 ) (Z 103 ) described above is a self-assembled moiety,
  • the bonding between the metal nanowires, the semiconductor nanowires, and the metal nanopoints or the metal nanowires, the semiconductor nanowires and the metal nanopoints, and the first electrode 210 may be strengthened. There is an effect that the mechanical strength is further improved.
  • the conductive oxide described above may be one of ITO (indium tin oxide), IZO (indium zinc oxide), SnO 2 and InO 2 .
  • Forming the above-described conductive layer 31 on the first electrode 20 described above may be carried out by coating, casting, Liangmuir-Blodgett (LB), ink-jet printing (ink-jet printing). ), Nozzle printing, slot-die coating, doctor blade coating, screen printing, dip coating, gravure printing Method of gravity printing, reverse-offset printing, physical transfer method, spray coating, chemical vapor deposition, or thermal evaporation method ) Process can be used.
  • LB Liangmuir-Blodgett
  • ink-jet printing ink-jet printing
  • Nozzle printing slot-die coating
  • doctor blade coating screen printing
  • dip coating gravure printing Method of gravity printing
  • reverse-offset printing physical transfer method
  • spray coating chemical vapor deposition
  • thermal evaporation method thermal evaporation method
  • the above-described conductive material may be mixed with a solvent to prepare a mixed solution, and then coated on the first electrode 10 and then heat treated to remove the aforementioned solvent.
  • the solvent described above may be a polar solvent, for example, water, alcohol (methanol, ethanol, n-propanol, 2-propanol, n-butanol, etc.), formic acid, nitromethane , Acetic acid, ethylene glycol, glycerol, normal methyl pyrrolidone (NMP, n-Methyl-2-Pyrrolidone), N-dimethyl acetamide, dimethyl With formamide (DMF, dimethylformamide), dimethyl sulfoxide (DMSO, dimethyl sulfoxide), tetrahydrofuran (THF, tetrahydrofuran), ethyl acetate (EtOAc, ethyl acetate), acetone, and acetonitrile (M
  • the metallic carbon nanotubes are grown on the aforementioned first electrode 20 or a solution-based printing method of carbon nanotubes dispersed in a solvent (eg, Spray coating method, spin coating method, dip coating method, gravure coating method, reverse offset coating method, screen printing method, slot-die coating method).
  • a solvent eg, Spray coating method, spin coating method, dip coating method, gravure coating method, reverse offset coating method, screen printing method, slot-die coating method.
  • a metal film is formed by vacuum depositing a metal on the above-described first electrode 20, and then patterned into various mesh shapes by photolithography, or a metal precursor or Metal particles may be dispersed in a solvent and formed by a printing method (eg, spray coating method, spin coating method, dip coating method, gravure coating method, reverse offset coating method, screen printing method, slot-die coating method).
  • a printing method eg, spray coating method, spin coating method, dip coating method, gravure coating method, reverse offset coating method, screen printing method, slot-die coating method.
  • the above-mentioned conductive layer 31 mainly serves to improve conductivity in the above-mentioned exciton buffer layer 30, and additionally controls scattering, reflection, and absorption to improve optical extraction, or gives flexibility to provide mechanical strength. Can play a role in improving
  • the surface buffer layer 32 described above includes a fluorine-based material.
  • the above-described fluorine-based material is preferably a fluorine-based material having a lower surface energy than the above-described conductive material, it may have a surface energy of 30mN / m or less.
  • the aforementioned fluorine-based material may have a hydrophobicity greater than that of the conductive polymer described above.
  • the concentration of fluorine-based material described above is lower.
  • the work function of the second surface 32b of the surface buffer layer 32 may be 5.0 eV or more.
  • the work function measured on the second surface 32b of the surface buffer layer 32 described above may be 5.0 eV to 6.5 eV, but is not limited thereto.
  • the aforementioned fluorine-based material may be a perfluorinated ionomer or a fluorinated ionomer comprising at least one F.
  • the thickness of the buffer layer can be formed thick, and the phase separation of the conductive layer 31 and the surface buffer layer 32 can be prevented, thereby making it possible to form a more uniform exciton buffer layer 30. .
  • the aforementioned fluorine-based material may include at least one ionomer selected from the group consisting of ionomers having the structures of Formulas 1 to 12.
  • m is a number from 1 to 10,000,000
  • x and y are each independently a number from 0 to 10
  • M + is Na + , K + , Li + , H + , CH 3 (CH 2 ) n NH 3 + (n is an integer from 0 to 50)
  • m is a number from 1 to 10,000,000
  • m and n are 0 ⁇ m ⁇ 10,000,000, 0 ⁇ n ⁇ 10,000,000, x and y are each independently a number from 0 to 20,
  • M + is Na + , K + , Li + , H + , CH 3 (CH 2 ) n NH 3 + (n is an integer from 0 to 50),
  • m and n are 0 ⁇ m ⁇ 10,000,000, 0 ⁇ n ⁇ 10,000,000, x and y are each independently a number from 0 to 20, and M + is Na + , K + , Li + , H + , CH 3 (CH 2 ) n NH 3 + (n is an integer from 0 to 50), NH 4 + , NH 2 + , NHSO 2 CF 3 + , CHO + , C 2 H 5 OH + , CH 3 OH + , RCHO + (R is CH 3 (CH 2 ) n- ; n is an integer from 0 to 50);
  • m and n are 0 ⁇ m ⁇ 10,000,000, 0 ⁇ n ⁇ 10,000,000, z is a number from 0 to 20, and M + is Na + , K + , Li + , H + , CH 3 (CH 2 ) n NH 3 + (n is an integer from 0 to 50), NH 4 + , NH 2 + , NHSO 2 CF 3 + , CHO + , C 2 H 5 OH + , CH 3 OH + , RCHO + (R is CH 3 (CH 2 ) n- ; n is an integer from 0 to 50);
  • m and n are 0 ⁇ m ⁇ 10,000,000, 0 ⁇ n ⁇ 10,000,000, x and y are each independently a number from 0 to 20, Y is -COO - M + , -SO 3 - NHSO 2 CF 3 + , -PO 3 2- (M + ) 2 , M + is Na + , K + , Li + , H + , CH 3 (CH 2 ) n NH 3 + (n is an integer from 0 to 50 ), NH 4 + , NH 2 + , NHSO 2 CF 3 + , CHO + , C 2 H 5 OH + , CH 3 OH + , RCHO + (R is CH 3 (CH 2 ) n- ; n is an integer from 0 to 50);
  • m and n are 0 ⁇ m ⁇ 10,000,000, 0 ⁇ n ⁇ 10,000,000, and M + is Na + , K + , Li + , H + , CH 3 (CH 2 ) n NH 3 + (n is 0 To an integer of 50 to)), NH 4 + , NH 2 + , NHSO 2 CF 3 + , CHO + , C 2 H 5 OH + , CH 3 OH + , RCHO + (R is CH 3 (CH 2 ) n- ; n is an integer from 0 to 50);
  • n are 0 ⁇ m ⁇ 10,000,000, 0 ⁇ n ⁇ 10,000,000;
  • m and n are 0 ⁇ m ⁇ 10,000,000, 0 ⁇ n ⁇ 10,000,000, x is a number from 0 to 20, and M + is Na + , K + , Li + , H + , CH 3 (CH 2 ) n NH 3 + (n is an integer from 0 to 50), NH 4 + , NH 2 + , NHSO 2 CF 3 + , CHO + , C 2 H 5 OH + , CH 3 OH + , RCHO + (R is CH 3 (CH 2 ) n- ; n is an integer from 0 to 50);
  • n are 0 ⁇ m ⁇ 10,000,000, 0 ⁇ n ⁇ 10,000,000, x and y are each independently a number from 0 to 20, M + Silver Na + , K + , Li + , H + , CH 3 (CH 2 ) n NH 3 + (n is an integer from 0 to 50), NH 4 + , NH 2 + , NHSO 2 CF 3 + , CHO + , C 2 H 5 OH + , CH 3 OH + , RCHO + (R is CH 3 (CH 2 ) n -; n represents an integer of 0 to 50;
  • M + is Na +, K +, Li + , H +, CH 3 (CH 2)
  • n NH 3 + is an integer from 0 to 50
  • NH 4 + is CH 3 (CH 2 ) n- ; n is an integer from 0 to 50).
  • the aforementioned fluorine-based material may include at least one ionomer or fluorinated low molecule selected from the group consisting of ionomers or fluorinated low molecules having the structures of Formulas 13 to 19.
  • R 11 to R 14 , R 21 to R 28 , R 31 to R 38 , R 41 to R 48 , R 51 to R 58 and R 61 to R 68 are each independently of the other hydrogen, -F, C 1 -C 20 alkyl group, a C 1 -C 20 alkoxy group, at least one of -F substituted with a C 1 -C 20 alkyl group, at least one of -F substituted with C 1 -C 20 alkoxy group, Q 1, -O- (CF 2 CF (CF 3 ) -O) n- (CF 2 ) m -Q 2 , where n and m are, independently of each other, an integer from 0 to 20, where n + m is 1 or more; and-(OCF 2 CF 2 ) x -Q 3 , where x is an integer from 1 to 20,
  • the ionic group is an anionic group described above, and the cation, and the above-described anionic group PO 3 2-, SO 3 -, COO -, I -, CH 3 COO - and BO 2
  • the aforementioned cationic group comprises at least one of metal ions and organic ions, and the aforementioned metal ions are selected from Na + , K + , Li + , Mg +2 , Zn +2 and Al + 3
  • the aforementioned organic ions are H + , CH 3 (CH 2 ) n 1 NH 3 + , where n 1 is an integer from 0 to 50, NH 4 + , NH 2 + , NHSO 2 CF 3 + , CHO + , C 2 H 5 OH + , CH 3 OH + and RCHO + , wherein R is CH 3 (CH 2 ) n 2 — and n 2 is an integer from 0 to 50;
  • At least one of R 11 to R 14 , at least one of R 21 to R 28 , at least one of R 31 to R 38 , at least one of R 41 to R 48 , at least one of R 51 to R 58 and R 61 to R 68 At least one of -F, a C 1 -C 20 alkyl group substituted with at least one -F, a C 1 -C 20 alkoxy group substituted with at least one -F, -O- (CF 2 CF (CF 3 ) -O) n- (CF 2 ) m -Q 2 and-(OCF 2 CF 2 ) x -Q 3 is selected.)
  • X is a terminal group
  • M f represents a unit derived from a fluorinated monomer obtained from the condensation reaction of a perfluoropolyether alcohol, a polyisocyanate and an isocyanate reactive-non-fluorinated monomer;
  • M h represents a unit derived from a non-fluorinated monomer
  • M a represents a unit having a silyl group represented by -Si (Y 4 ) (Y 5 ) (Y 6 );
  • Y 4 , Y 5 and Y 6 described above independently of each other represent a substituted or unsubstituted C 1 -C 20 alkyl group, a substituted or unsubstituted C 6 -C 30 aryl group or a hydrolyzable substituent, and the aforementioned Y 4 At least one of Y 5 and Y 6 is the hydrolyzable substituent described above;
  • G is a monovalent organic group comprising residues of a chain transfer agent
  • n is a number from 1 to 100;
  • n is a number from 0 to 100;
  • r is a number from 0 to 100;
  • n + m + r is at least 5.
  • the thickness of the surface buffer layer 32 described above may be 20 nm to 500 nm, for example, 50 nm to 200 nm. When the thickness of the surface buffer layer 32 described above satisfies the above-described range, it is possible to provide excellent work function characteristics, transmittance and flexible characteristics.
  • the surface buffer layer 32 described above may be formed by preparing a mixed solution including the aforementioned fluorine-based material and a solvent on the conductive layer 31 and then heat-treating it.
  • the exciton buffer layer 30 thus formed may have a thickness of 50 nm to 1000 nm.
  • the above-described conductive layer 31 is formed, conductivity may be improved, and at the same time, the above-described surface buffer layer 32 may be formed to lower surface energy. Accordingly, the light emission characteristics can be maximized.
  • the surface buffer layer 32 described above is selected from the group consisting of carbon nanotubes, graphene, reduced graphene oxide, metal nanowires, metal carbon nanodots, semiconductor quantum dots, semiconductor nanowires, and metal nanodots. At least one additive may be further included. When further comprising the above-described additives, it is possible to maximize the conductivity improvement of the above-mentioned exciton buffer layer 30.
  • the surface buffer layer 32 described above may further include a crosslinking agent including a bisphenyl azide (Bis) material.
  • a crosslinking agent including a bisphenyl azide (Bis) material.
  • the bisphenyl azide (Bis) material described above may be a bisphenyl azide (Bis) material of Formula 20 below.
  • Forming the above-mentioned surface buffer layer 32 on the conductive layer 31 described above may be performed by spin coating, casting, Liangmuir-Blodgett (LB), ink-jet printing (ink-jet printing). ), Nozzle printing, slot-die coating, doctor blade coating, screen printing, dip coating, gravure printing Method of gravity printing, reverse-offset printing, physical transfer method, spray coating, chemical vapor deposition, or thermal evaporation method ) Process can be used.
  • LB Liangmuir-Blodgett
  • ink-jet printing ink-jet printing
  • Nozzle printing slot-die coating
  • doctor blade coating screen printing
  • dip coating gravure printing Method of gravity printing
  • reverse-offset printing physical transfer method
  • spray coating chemical vapor deposition
  • thermal evaporation method thermal evaporation method
  • the forming of the above-described exciton buffer layer 30 may sequentially deposit the above-described conductive layer 31 and the surface buffer layer 32 as described above, but may use the above-described conductive material and the above-described fluorine-based material as solvents. After mixing to prepare a mixed solution, it can be formed through the process of applying the above-described mixed solution on the above-described first electrode and heat treatment.
  • the conductive layer 31 and the surface buffer layer 32 are sequentially self-assembled on the first electrode 20 described above. Accordingly, there is an advantage that can simplify the process.
  • the aforementioned fluorine-based material may be a material having a solubility of at least 90%, for example at least 95%, with respect to the polar solvent.
  • the aforementioned polar solvents include water, alcohols (methanol, ethanol, n-propanol, 2-propanol, n-butanol, and the like), ethylene glycol, glycerol, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone And the like, but is not limited thereto.
  • FIG. 13 is a schematic diagram showing the effect of the exciton buffer layer 30 according to an embodiment of the present invention.
  • the exciton buffer layer 30 improves the hole injection efficiency, plays an electron blocking role, and suppresses quenching of the exciton.
  • the exciton buffer layer 30 described above may further include a crosslinking agent.
  • the above-mentioned crosslinking agent may include at least one functional group selected from the group consisting of an amine group (-NH 2 ), a thiol group (-SH), and a carboxyl group (-COO-).
  • the aforementioned crosslinking agent may be a bisphenyl azide (Bis) material, a diaminoalkane material, a dithiol material, a dicarboxylate, an ethylene glycol dimethacrylate (ethylene glycol di (meth) acrylate) derivatives, methylenebisacrylamide derivatives, and at least one selected from the group consisting of DVB.
  • a hole transport layer (not shown) may be formed on the exciton buffer layer 30 described above.
  • the hole transport layer described above may be formed according to a method arbitrarily selected from various known methods such as vacuum deposition, spin coating, casting, LB, and the like.
  • the deposition conditions is the desired compound, varies depending on the structure and thermal properties of the layer of interest, e.g., to the deposition temperature of 100 °C 500 °C, 10 -10 to 10 - 3 torr It can be selected within the vacuum degree range of, deposition rate range of 0.01 Pa / sec to 100 Pa / sec.
  • the coating conditions vary depending on the target compound, the structure and the thermal properties of the desired layer, but the coating speed range of 2000 rpm to 5000 rpm, heat treatment temperature of 80 °C to 200 °C (removing solvent after coating Heat treatment temperature).
  • the hole transport layer material may be selected from materials that can transport holes better than hole injection.
  • the hole transport layer described above may be formed using a known hole transport material, for example, may be an amine-based material having an aromatic condensed ring and may be a triphenyl amine-based material.
  • the above-described hole transporting material is 1,3-bis (carbazol-9-yl) benzene (1,3-bis (carbazol-9-yl) benzene: MCP), 1,3,5- Tris (carbazol-9-yl) benzene (1,3,5-tris (carbazol-9-yl) benzene: TCP), 4,4 ', 4 "-tris (carbazol-9-yl) triphenylamine (4,4 ', 4 "-tris (carbazol-9-yl) triphenylamine (TCTA), 4,4'-bis (carbazol-9-yl) biphenyl (4,4'-bis (carbazol-9- yl) biphenyl: CBP), N, N'-bis (naphthalen-1-yl) -N, N'-bis (phenyl) benzidine (N, N'-bis (naphthalen-1-yl) -N, N ' -bis (phenyl) benzidine
  • Di- [4,-(N, N-ditolyl-amino) -phenyl] cyclohexane Di- [4,-(N, N-ditolyl-amino) -phenyl] cyclohexane (Di- [4- (N, N-ditolyl-amino) -phenyl] cyclohexane (TAPC), N, N, N ' , N'-tetra-naphthalen-2-yl-benzidine (N, N, N ', N'-tetra-naphthalen-2-yl-benzidine: ⁇ -TNB) and N4, N4, N4', N4'-tetra (biphenyl-4-yl) biphenyl-4,4'-diamine (TPD15), poly (9,9-dioctylfluorene-co-bis-N, N '-(4-butylphenyl) -bis-N, N
  • the hole transport layer may have a thickness of about 5 nm to about 100 nm, for example, about 10 nm to about 60 nm.
  • excellent hole transporting properties can be obtained without increasing the driving voltage.
  • the above-described hole transport layer may be omitted.
  • the light emitting device including the exciton buffer layer 30 described above may have excellent efficiency, brightness, and lifespan characteristics without forming a hole injection layer. Therefore, there is an effect that can reduce the cost when manufacturing the above-described light emitting device.
  • the work function of the above-described hole transporting layer may be Z eV, but the aforementioned Z may be a real number of 5.2 to 5.6, but is not limited thereto.
  • the work function value Y 1 of the first surface 32a of the surface buffer layer 32 of the exciton buffer layer 30 described above may be in the range of 4.6 to 5.2, for example, 4.7 to 4.9.
  • Y 2 which is a work function value of the second surface 32b of the surface buffer layer 32 of the exciton buffer layer 30, may be the same as or smaller than the work function of the fluorine-based material included in the surface buffer layer 32.
  • Y 2 described above may range from 5.0 to 6.5, for example, 5.3 to 6.2, but is not limited thereto.
  • a light emitting layer including a first thin film of nanoparticles by coating a solution including organic / inorganic perovskite nanoparticles including an organic / inorganic perovskite nanocrystal structure on the aforementioned exciton buffer layer 30. 40 is formed.
  • the light emitting layer has the same structure and the same function as the above-mentioned ⁇ light emitting layer for organic-inorganic hybrid perovskite light emitting device>, the above description will be made.
  • the second electrode 50 is formed on the light emitting layer 40 described above.
  • the second electrode 50 described above is an electrode into which electrons are injected and is made of a conductive material.
  • the above-described second electrode 50 is preferably metal, and in particular, may be Al, Au, Ag, Cu, Pt, W, Ni, Zn, Ti, Zr, Hf, Cd or Pd.
  • Deposition processes for forming the above-described second electrode 50 include physical vapor deposition (PVD), chemical vapor deposition (CVD), sputtering, pulsed laser deposition. PLD), thermal evaporation, electron beam evaporation, atomic layer deposition (ALD), molecular beam epitaxy (MBE), and the like.
  • the light emitting device thus formed is disposed on the first electrode 20, the first electrode 20 described above, and the conductive layer 31 including the conductive material and the surface buffer layer 32 including the fluorine-based material are sequentially stacked. Disposed on the exciton buffer layer 30, the above-described exciton buffer layer 30, and disposed on the light emitting layer 40 including the organic-inorganic hybrid perovskite nanoparticle light-emitting body substituted with the organic ligand, and the above-described light emitting layer 40. And a second electrode 50.
  • the exciton buffer layer 30 described above it is possible to manufacture a light emitting device having a low work function and high conductivity, and including nanoparticles including an organic-inorganic hybrid perovskite nanocrystal structure.
  • an organic-inorganic hybrid perovskite having a crystal structure combining FCC and BCC is formed in the nanoparticle, and a lamellar structure in which an organic plane and an inorganic plane are alternately stacked.
  • the exciton is constrained to the inorganic plane and can give high color purity.
  • the light emitting device may be a laser diode or an LED.
  • the present invention may be applied to a solar cell using a photoactive layer including the organic-inorganic perovskite nanocrystalline particles or inorganic metal halide perovskite nanocrystalline particles.
  • a solar cell may be positioned between a first electrode, a second electrode, and the first electrode and the second electrode, and may include a photoactive layer including the above-described perovskite nanocrystalline particles.
  • a solution containing organic-inorganic perovskite nanoparticles including an organic-inorganic perovskite nanocrystal structure according to an embodiment of the present invention was formed. It was formed through the inverse nano-emulsion method.
  • a first solution was prepared by dissolving an organic-inorganic hybrid perovskite in a protic solvent.
  • Dimethylformamide was used as the protic solvent, and organic-inorganic hybrid perovskite (CH 3 NH 3 ) 2 PbBr 4 was used.
  • the (CH 3 NH 3 ) 2 PbBr 4 used was a mixture of CH 3 NH 3 Br and PbBr 2 in a 2: 1 ratio.
  • the first solution was slowly added dropwise to the second solution under vigorous stirring to form a solution containing the organic-inorganic perovskite nanoparticles including the organic-inorganic perovskite nanocrystal structure.
  • Chloroform spin coating (2500 rpm 20 s) removed perovskite nanocrystals that were not anchored.
  • 250 ⁇ L of 1 wt% 1,2-ethanedithiol (EDT) / ethanol solution was spin coated (2500 rpm 20s), followed by spin coating the perovskite nanocrystal solution. (2500 rpm 20s) was repeated to form a light emitting layer.
  • trioctylphosphine oxide (TOPO) and trioctylphosphine (TOP) solutions were added to the perovskite nanocrystal solution prepared in Example 1 to replace ligands of perovskite nanocrystals with TOPO and TOP.
  • N, N'-diphenyl, N'-bis (3-methylphenyl)-(1,1'-biphenyl) -4,4'-diamine (TPD) was added to the perovskite nanocrystal solution 100: TPD-perovskite nanocrystal solution was prepared by mixing at a ratio of 5 (w / w).
  • the TPD-perovskite nanocrystal solution was spin-coated (500 rpm 7s, 3000 rpm 90s) to form TPD and perovskite nanocrystal layers.
  • the TPD and the perovskite nanocrystals are phase-separated during the spin coating process, such that a nano thin film including the organic-inorganic hybrid perovskite nanoparticles including the perovskite nanocrystal structure is formed on the TPD layer. .
  • ODTS-treated wafers were fabricated by dipping Si native wafers in octadecyltrichlorosilane (ODTS) solution.
  • the perovskite nanocrystals were spin-coated (1500 rpm 60 s) on the ODTS-treated wafer to form a perovskite nanocrystal layer.
  • polydimethylsiloxane (PDMS) was poured on a flat silicon wafer and cured at 75 °C for 2 hours to prepare a PDMS stamp.
  • the PDMS stamp was tightly adhered to the perovskite nanocrystal layer, under sufficient pressure, and then quickly detached to separate the perovskite nanocrystals from the ODTS-treated wafer.
  • the separated perovskite nanocrystals were separated from PDMS by contact with a prepared indium tin oxide (ITO) / PEDOT: PSS substrate.
  • Tris (4-carbazoyl-9-ylphenyl) amine (TCTA), 1,3,5-tris (N-phenylbenzimidazole-2-yl) benzene (TPBi) was added to the perovskite nanocrystal solution 10: 10: 1 TCTA-TPBi-Perovskite nanocrystal solution was prepared by mixing at a (w / w) ratio.
  • the TCTA-TPBi-perovskite nanocrystal solution was spin coated (500 rpm 7s, 3000 rpm 90s) to form a TCTA-TPBi-perovskite nanocrystal layer.
  • a light emitting device according to an embodiment of the present invention was manufactured.
  • an ITO substrate (glass substrate coated with an ITO anode) is prepared, and then spin-coated a solution in which a conductive material, PEDOT: PSS (CLEVIOS PH from Heraeus) and a fluorine-based polymer 26, is mixed. After the heat treatment for 30 minutes at 150 °C to form an exciton buffer layer of 40nm thickness.
  • a conductive material PEDOT: PSS (CLEVIOS PH from Heraeus) and a fluorine-based polymer 26 is mixed.
  • a multilayer exciton buffer layer in which a conductive layer containing 50% or more of a conductive polymer and a surface buffer layer containing 50% or more of the aforementioned polymer 1 material are sequentially stacked on the aforementioned ITO anode is formed.
  • self-assembly forms a conductive layer and a surface buffer layer.
  • the weight ratio of the above-described conductive layer and the exciton buffer layer including the surface buffer layer is 1: 6: 25.4 for PEDOT: PSS: Polymer 1 and the work function is 5.95eV.
  • the CH 3 NH 3 PbBr 3 perovskite light emitting layer was formed on the exciton buffer layer described above using the light emitting layer manufacturing method described in Example 2.
  • TPBI 1,3,5-Tris (1-phenyl-1H-benzimidazol-2-yl) benzene
  • An organic / inorganic hybrid perovskite light emitting device was manufactured in the same manner as in Preparation Example 6, except that the light emitting layer was manufactured in the same manner as in Example 3.
  • the luminance of the fabricated light emitting device was 40 cd / m 2 , and the current efficiency was 0.015 cd / A.
  • An organic / inorganic hybrid perovskite light emitting device was manufactured in the same manner as in Preparation Example 6, except that the light emitting layer was manufactured in the same manner as in Preparation Example 4.
  • the luminance of the fabricated light emitting device was 45 cd / m 2 , and the current efficiency was 0.018 cd / A.
  • An organic / inorganic hybrid perovskite light emitting device was manufactured in the same manner as in Preparation Example 6, except that the light emitting layer was manufactured in the same manner as in Preparation Example 5.
  • the luminance of the fabricated light emitting device was 60 cd / m 2 , and the current efficiency was 0.03 cd / A.
  • An inorganic metal halide perovskite nanocrystalline particle was formed according to one embodiment of the present invention. It was formed through the inverse nano-emulsion method.
  • Cs2CO3 cesium carbonate
  • ODE Octadecene
  • PbBr2 oleic acid and oleylamine were added to an aprotic solvent, and a fourth solution was reacted at high temperature (120 ° C.) for one hour.
  • the third solution was slowly added dropwise to the strongly stirring fourth solution to form an inorganic metal halide perovskite (CsPbBr 3 ) nanocrystalline particle emitter having a three-dimensional structure.
  • a light emitting layer was prepared in the same manner as in Preparation Example 2, except that a solution containing the inorganic metal halide perovskite nanoparticles of Preparation Example 10 was used instead of the solution of Preparation Example 1.
  • a solar cell according to an embodiment of the present invention was prepared.
  • the organic-inorganic hybrid perovskite nanocrystalline particles according to Preparation Example 1 were mixed with Phenyl-C61-butyric acid methyl ester (PCBM) and coated on the hole extracting layer to form a photoactive layer, and immediately 100 nm thick on the photoactive layer. was deposited to prepare a perovskite nanocrystalline solar cell.
  • PCBM Phenyl-C61-butyric acid methyl ester
  • OIP film Organic-inorganic hybrid perovskite (OIP film) in the form of a thin film was prepared.
  • (CH 3 NH 3 ) 2 PbBr 4 is dissolved in dimethylformamide, a protic solvent, to prepare a first solution, followed by spin coating the first solution on a glass substrate (CH 3 NH 3 ) 2 PbBr 4 thin film was prepared.
  • OIP film Organic-inorganic hybrid perovskite (OIP film) in the form of a thin film was prepared.
  • a first solution is prepared by dissolving (CH 3 NH 3 ) 2 PbCl 4 in dimethylformamide, a protic solvent, and spin coating the first solution on a glass substrate (CH 3 NH 3 ) 2 PbCl 4 thin film was prepared.
  • organic-inorganic perovskite nanoparticles including the organic-inorganic perovskite nanocrystal structure of Preparation Example 1 and ultraviolet in the organic-inorganic hybrid perovskite (OIP film) according to Comparative Examples 1 and 2 It is a fluorescent image taken by emitting light.
  • FIG. 15 is a schematic view of nanoparticles according to Preparation Example and Comparative Example 1.
  • FIG. 15 is a schematic view of nanoparticles according to Preparation Example and Comparative Example 1.
  • Figure 15 (a) is a schematic diagram of the light emitting material according to Comparative Example 1
  • Figure 15 (b) is a schematic diagram of the organic-inorganic perovskite nanoparticles containing the organic-inorganic perovskite nanocrystal structure according to Preparation Example 1. to be.
  • the organic-inorganic perovskite nanoparticles including the organic-inorganic perovskite nanocrystal structure according to Comparative Example 1 is in the form of a thin film
  • Figure 15 (b) Preparation Example
  • the wavelength conversion particle according to 1 is in the form of a nanoparticle (110).
  • FIG. 16 (a) is an image taken at a low temperature (70 K) of the light emitting matrix of the organic-inorganic hybrid perovskite (OIP film) in the form of a thin film according to Comparative Example 1
  • Figure 16 (b) is shown in Comparative Example 1
  • the light-emitting matrix of the organic-inorganic hybrid perovskite (OIP film) in the form of a thin film is an image taken at room temperature.
  • FIG. 16 (c) is an image taken at a low temperature (70 K) of the photoluminescent matrix of the organic-inorganic perovskite nanoparticles including the organic-inorganic hybrid perovskite nanocrystal structure according to Preparation Example 1
  • FIG. 15 ( d) is an image taken at room temperature of the photoluminescent matrix of the organic-inorganic perovskite nanoparticles including the organic-inorganic hybrid perovskite nanocrystal structure according to Preparation Example 1.
  • the organic-inorganic perovskite nanoparticles including the organic-inorganic hybrid perovskite nanocrystal structure according to Preparation Example 1 in the thin film form according to Comparative Example 1 It shows photoluminescence at the same position as the organic-inorganic hybrid perovskite (OIP film), and it can be seen that the color purity is higher.
  • OIP-NC film according to the preparation example it shows a high color purity light emission at the same position as the low temperature at room temperature, it can be seen that the emission intensity does not decrease.
  • the organic-inorganic hybrid perovskite in the form of a thin film according to Comparative Example 1 differs in color purity and emission position at room temperature and low temperature, and excitons do not go into luminescence due to thermal ionization and delocalization of charge carriers at room temperature. It is separated and extinguished, showing low luminescence intensity.
  • FIG. 17 is a graph showing photoluminescence of nanoparticles according to Preparation Example 1 and Comparative Example 1.
  • Inorganic-inorganic hybrid perovskite nanocrystals having a crystal structure combining FCC and BCC are formed in the first nanoparticle-containing nanoparticles containing organic-inorganic perovskite nanoparticles, and the organic and inorganic planes alternate. It forms a lamellar structure that is laminated with a furnace, and excitons are constrained on the inorganic plane to produce high color purity.
  • the exciton diffusion length is reduced in the nanocrystals within the size of 10 nm to 300 nm or less, and the exciton binding energy is increased to excite the exciton due to thermal ionization and delocalization of the charge carriers. It can prevent the luminous efficiency at high room temperature.
  • Organic-inorganic perovskite nanoparticles comprising a scaled organic-inorganic hybrid perovskite nanocrystal structure of organic-inorganic hybrid perovskite nanocrystals can be synthesized.

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Abstract

L'invention concerne : une couche émettant de la lumière pour un dispositif électroluminescent pérovskite ; un procédé de fabrication de celle-ci ; un dispositif électroluminescent pérovskite utilisant celle-ci. Le procédé, selon la présente invention, de fabrication d'une couche émettant de la lumière pour un dispositif électroluminescent pérovskite hybride, organique et inorganique, comprend une étape de formation d'un premier film mince de nanoparticules par enduction, pour enduire un élément d'une couche émettant de la lumière, d'une solution comprenant des nanoparticules de pérovskite organique et inorganique comprenant une structure nanocristalline de pérovskite organique et inorganique. De cette manière, un corps émettant de la lumière comprenant des nanoparticules possède une pérovskite hybride, organique et inorganique, ayant une structure cristalline dans laquelle des cubiques à faces centrées (cF) et des cubiques centrés (cc) sont combinés ; ledit corps forme une structure lamellaire dans laquelle un plan organique et un plan inorganique sont empilés en alternance ; ledit corps peut présenter une grande pureté de couleur puisque les excitons sont confinés dans le plan inorganique. De plus, il est possible d'améliorer le rendement d'émission de lumière et la luminosité d'un dispositif par la mise de pérovskite sous forme de nanoparticules, puis par l'introduction de celles-ci dans une couche émettant de la lumière.
PCT/KR2015/011963 2014-11-06 2015-11-06 Couche émettant de la lumière pour dispositif électroluminescent pérovskite, son procédé de fabrication et dispositif électroluminescent pérovskite l'utilisant WO2016072809A1 (fr)

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US17/213,211 US11730051B2 (en) 2014-11-06 2021-03-25 Perovskite light-emitting device
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JP2019016772A (ja) * 2017-03-23 2019-01-31 国立大学法人電気通信大学 量子ドット、これを用いた光デバイス、及び量子ドットの作製方法
CN109830605A (zh) * 2019-01-31 2019-05-31 河北科技大学 一种双光电转换功能太阳能电池
CN109994655A (zh) * 2017-12-29 2019-07-09 Tcl集团股份有限公司 复合量子点、量子点固态膜及其应用
JP2020502769A (ja) * 2016-12-22 2020-01-23 トヨタ・モーター・ヨーロッパＴｏｙｏｔａ Ｍｏｔｏｒ Ｅｕｒｏｐｅ ２ｄ−ペロブスカイト活性層を有する光電子素子
KR102243623B1 (ko) 2020-03-11 2021-04-23 중앙대학교 산학협력단 페로브스카이트 나노입자 제조방법 및 이에 의해 제조된 페로브스카이트 나노입자를 포함하는 광전자소자
US11239429B1 (en) * 2015-06-08 2022-02-01 The Florida State University Research Foundation, Inc. Superluminescent halide perovskite light-emitting diodes with a sub-bandgap turn-on voltage
KR20220137445A (ko) 2021-04-02 2022-10-12 중앙대학교 산학협력단 페로브스카이트 양자점이 적용된 유기 발광 트랜지스터
US11730047B1 (en) 2016-05-27 2023-08-15 The Florida State University Research Foundation, Inc. Perovskite based charge transport layers for thin film optoelectronic devices and methods of making

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Cited By (9)

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US11239429B1 (en) * 2015-06-08 2022-02-01 The Florida State University Research Foundation, Inc. Superluminescent halide perovskite light-emitting diodes with a sub-bandgap turn-on voltage
US11730047B1 (en) 2016-05-27 2023-08-15 The Florida State University Research Foundation, Inc. Perovskite based charge transport layers for thin film optoelectronic devices and methods of making
JP2020502769A (ja) * 2016-12-22 2020-01-23 トヨタ・モーター・ヨーロッパＴｏｙｏｔａ Ｍｏｔｏｒ Ｅｕｒｏｐｅ ２ｄ−ペロブスカイト活性層を有する光電子素子
JP2019016772A (ja) * 2017-03-23 2019-01-31 国立大学法人電気通信大学 量子ドット、これを用いた光デバイス、及び量子ドットの作製方法
CN109994655A (zh) * 2017-12-29 2019-07-09 Tcl集团股份有限公司 复合量子点、量子点固态膜及其应用
CN109830605A (zh) * 2019-01-31 2019-05-31 河北科技大学 一种双光电转换功能太阳能电池
KR102243623B1 (ko) 2020-03-11 2021-04-23 중앙대학교 산학협력단 페로브스카이트 나노입자 제조방법 및 이에 의해 제조된 페로브스카이트 나노입자를 포함하는 광전자소자
KR20220137445A (ko) 2021-04-02 2022-10-12 중앙대학교 산학협력단 페로브스카이트 양자점이 적용된 유기 발광 트랜지스터
KR20240015132A (ko) 2021-04-02 2024-02-02 중앙대학교 산학협력단 페로브스카이트 양자점이 적용된 유기 발광 트랜지스터

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