WO2023234074A1 - Nanoparticules, liquide de dispersion, encre, couche mince, diode électroluminescente organique, affichage à boîtes quantiques et procédé de production de nanoparticules - Google Patents

Nanoparticules, liquide de dispersion, encre, couche mince, diode électroluminescente organique, affichage à boîtes quantiques et procédé de production de nanoparticules Download PDF

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WO2023234074A1
WO2023234074A1 PCT/JP2023/018779 JP2023018779W WO2023234074A1 WO 2023234074 A1 WO2023234074 A1 WO 2023234074A1 JP 2023018779 W JP2023018779 W JP 2023018779W WO 2023234074 A1 WO2023234074 A1 WO 2023234074A1
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nanoparticles
range
electrode
thin film
solution
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Japanese (ja)
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光 小林
暁 渡邉
晴彦 吉野
沙記 小澤
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Ａｇｃ株式会社
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    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating

Definitions

  • the present invention relates to nanoparticles, dispersions, inks, thin films, organic light emitting diodes and quantum dot displays comprising such thin films, and methods for producing nanoparticles.
  • OLEDs Organic light emitting diodes
  • QD quantum dot
  • a light-emitting layer is placed between two electrodes (anode and cathode).
  • a voltage is applied between both electrodes, holes and electrons are injected from each electrode into the light emitting layer.
  • holes and electrons are recombined within the luminescent layer, binding energy is generated, and the luminescent material in the luminescent layer is excited by this binding energy. Since light is emitted when the excited light-emitting material returns to its ground state, by utilizing this, light can be extracted to the outside.
  • a hole injection layer and/or hole transport layer is often installed between the anode and the emissive layer, and an electron injection layer and/or hole transport layer is installed between the emissive layer and the cathode. Or an electron transport layer is installed.
  • the hole injection layer and/or hole transport layer on the anode, as well as the light emitting layer placed on top of the layer are formed by a low-temperature process such as printing. It is proposed to do so.
  • the electron transport layer installed between the light emitting layer and the cathode is formed by a vapor deposition method. In order to further reduce manufacturing costs and simplify the process, it is considered effective to form the electron transport layer using a low-temperature process.
  • Patent Document 1 describes that an aggregate containing Zn-Si-O nanoparticles with a low work function can be produced by a thermal plasma treatment method, and that an ink containing such an aggregate of nanoparticles is applied. It is described that a thin film for an electron transport layer of an OLED can be formed by this method.
  • thermal plasma treatment methods tend to produce nanoparticles with relatively large particle diameters.
  • nanoparticles When such nanoparticles are applied to the electron transport layer of OLED and QD displays, there is a problem in that the surface of the electron transport layer becomes uneven. Irregularities on the surface of the electron transport layer can lead to scattering of light emitted from the light emitting layer. Further, at locations where the electron transport layer is thin, a problem may arise in that a current short circuit occurs between the light emitting layer and the cathode.
  • the present invention was made in view of this background, and provides nanoparticles that have a low work function, can be applied to low-temperature film formation processes, and have a significantly small particle size.
  • the purpose is to The present invention also aims to provide dispersions, inks, thin films containing such nanoparticles, organic light emitting diodes and quantum dot displays having such thin films, and methods for producing nanoparticles.
  • nanoparticles containing a metal oxide In the spectrum of the nanoparticles measured by infrared spectroscopy, the maximum intensity in the region of 400 cm -1 to 600 cm -1 derived from Zn-O-Zn bonds is defined as I 1 , and the maximum intensity derived from Zn-O-Si bonds is defined as I 1.
  • the peak intensity ratio I 2 /(I 1 +I 2 +I 3 ) is 0.28 or more
  • the atomic ratio Zn/(Zn+Si) in the nanoparticles is in the range of 0.3 to 0.95
  • Nanoparticles are provided in which the Scherrer diameter of the nanoparticles is in the range of 1 nm to 10 nm.
  • nanoparticles containing a metal oxide The average coordination number of the O atom closest to the Zn atom, determined by X-ray absorption fine structure (XAFS) analysis, is in the range of 3.0 to 4.5, and the X-ray absorption fine structure (XAFS) )
  • the average coordination number of the Zn atom closest to the Zn atom determined by analysis is in the range of 1.5 to 10
  • the atomic ratio Zn/(Zn+Si) in the nanoparticles is in the range of 0.3 to 0.95
  • Nanoparticles are provided in which the Scherrer diameter of the nanoparticles is in the range of 1 nm to 10 nm.
  • the present invention provides a dispersion liquid containing nanoparticles having the above-mentioned characteristics, a solvent, and a dispersant.
  • the present invention provides an ink that includes nanoparticles having the above characteristics, a solvent, a dispersant, a thickener, and a surfactant.
  • the present invention also provides a thin film containing nanoparticles having the above-mentioned characteristics.
  • an organic light-emitting diode comprising a first electrode, an organic light emitting layer, and a second electrode.
  • An organic light-emitting diode having an additional layer between the first electrode or the second electrode and the organic light-emitting layer, comprising a thin film having the above-mentioned characteristics.
  • a quantum dot display comprising an additional layer between the first electrode or the second electrode and the quantum dot emissive layer, comprising a thin film having the characteristics described above.
  • the present invention provides a method for producing nanoparticles containing metal oxides, comprising: (1) mixing raw materials containing zinc and silicon with a first solvent to prepare a first solution; (2) preparing a second solution containing an alkali; (3) mixing the first solution and the second solution using a flow reactor method to generate a third solution containing nanoparticles; (4) adding an additive that suppresses the growth of the nanoparticles to the third solution;
  • a method is provided having the following.
  • the present invention has a low work function, can be applied to a low-temperature film formation process, and can provide nanoparticles having a significantly small particle size.
  • the present invention can also provide dispersions, inks, thin films containing such nanoparticles, organic light emitting diodes and quantum dot displays having such thin films, and methods for producing nanoparticles.
  • FIG. 2 is a diagram showing an example of an infrared spectrum of nanoparticles according to an embodiment of the present invention.
  • FIG. 3 is a diagram showing an example of a Raman spectrum of nanoparticles according to an embodiment of the present invention.
  • 1 is a diagram schematically showing an example of a flow of a method for manufacturing nanoparticles according to an embodiment of the present invention.
  • 1 is a cross-sectional view schematically showing a configuration example of an OLED including nanoparticles according to an embodiment of the present invention.
  • 1 is a cross-sectional view schematically showing a configuration example of a QD display including nanoparticles according to an embodiment of the present invention.
  • nanoparticles comprising a metal oxide
  • I 1 the maximum intensity in the region of 400 cm -1 to 600 cm -1 derived from Zn-O-Zn bonds
  • I 1 the maximum intensity derived from Zn-O-Si bonds
  • the peak intensity ratio I 2 /(I 1 +I 2 +I 3 ) is 0.28 or more
  • the atomic ratio Zn/(Zn+Si) in the nanoparticles is in the range of 0.3 to 0.95
  • Nanoparticles are provided in which the Scherrer diameter of the nanoparticles is in the range of 1 nm to 10 nm.
  • the particles provided are in the form of nanoparticles, so that the nanoparticles are dispersed to prepare a dispersion, such as an ink, to form a film in a low-temperature process such as a printing method. Can be formed into a film.
  • Patent Document 1 describes Zn--Si--O nanoparticles produced by a thermal plasma method. It is described that these nanoparticles have a low work function, and that an electron transport layer of an OLED can be formed by applying an ink in which such nanoparticles are dispersed and forming a thin film.
  • the nanoparticles described in Patent Document 1 are manufactured by a thermal plasma method.
  • the thermal plasma method has a problem in that the size of the nanoparticles produced, especially the upper limit of the particle diameter, is relatively large.
  • the surface roughness of the electron transport layer can have a significant impact on the properties of the device. Therefore, it is preferable that the particle diameter of the nanoparticles be as small as possible.
  • nanoparticles according to an embodiment of the present invention are produced by a method other than the thermal plasma method, for example, a liquid phase synthesis method.
  • the liquid phase synthesis method can provide nanoparticles whose Scherrer diameter is controlled within a microscopic range of 10 nm or less. Therefore, in one embodiment of the present invention, it is possible to form a thin film with significantly suppressed surface irregularities when applied as an electron transport layer of OLED and QD displays.
  • liquid phase synthesis methods have a problem in that it is difficult to control the morphology of nanoparticles, especially the composition distribution within the particles.
  • a general liquid phase synthesis method zinc oxide and silicon oxide separate, and the zinc oxide core Nanoparticles with silicon oxide surrounding them (core-shell structure) tend to be produced.
  • the peak intensity ratio I 2 / (I 1 +I 2 + I 3 ) is 0.28 or more.
  • the maximum intensity I 1 corresponds to the Zn-O-Zn bond
  • the maximum intensity I 2 corresponds to the Zn-O-Si bond
  • the maximum intensity I 3 corresponds to the Si-O-Si bond.
  • the Zn--O--Si bond corresponding to the double oxide of zinc and silicon is significantly increased. Therefore, in one embodiment of the present invention, the work function of nanoparticles can be significantly reduced.
  • one embodiment of the present invention has a low work function, can be applied to a low-temperature film formation process, and can provide nanoparticles having a significantly small particle size.
  • nanoparticles containing a metal oxide The average coordination number of the O atom closest to the Zn atom, determined by X-ray absorption fine structure (XAFS) analysis, is in the range of 3.0 to 4.5, and the X-ray absorption fine structure (XAFS) )
  • the average coordination number of the Zn atom closest to the Zn atom determined by analysis is in the range of 1.5 to 10
  • the atomic ratio Zn/(Zn+Si) in the nanoparticles is in the range of 0.3 to 0.95
  • Nanoparticles are provided in which the Scherrer diameter of the nanoparticles is in the range of 1 nm to 10 nm.
  • Si is introduced into the nanoparticles.
  • the average coordination number of the O atom closest to the Zn atom is set in the range of 3.0 to 4.5, and the average coordination number of the Zn atom closest to the Zn atom is set in the range of 1.5 to 10.
  • a suitable electron transport layer can be obtained by adjusting the amount within this range.
  • the average coordination number of the O atom closest to the Zn atom and the average coordination number of the Zn atom closest to the Zn atom can be evaluated as described below using the XAFS analysis method.
  • the average coordination number of the O atom that is closest to the Zn atom is preferably 3.2 or more, from the viewpoint of suppressing coloring due to the generation of oxygen vacancies. It is more preferably .4 or more, and even more preferably 3.6 or more. Further, for example, the average coordination number of the O atom closest to the Zn atom is 4.4 or less, preferably 4.3 or less, from the viewpoint of increasing the band gap and obtaining high transparency.
  • the average coordination number of the Zn atom closest to the Zn atom is preferably 2.0 or more, and 2.5 or more, from the viewpoint of obtaining sufficient electrical conductivity. More preferably, it is 3.0 or more.
  • the average coordination number of the Zn atom that is closest to the Zn atom is, for example, 9.0 from the viewpoint of reducing the spatial overlap between adjacent Zn4s orbitals and reducing the electron affinity and work function of the nanoparticle. It is preferably 8.0 or less, more preferably 7.0 or less, and even more preferably 6.0 or less.
  • the average coordination number of the O atom closest to the Zn atom is 4, and the average coordination number of the Zn atom closest to the Zn atom is 12.
  • Nanoparticles according to an embodiment of the present invention (hereinafter also simply referred to as "ZSO nanoparticles of the present invention”) have a Zn--Si--O based oxide as a metal oxide.
  • the ZSO nanoparticles of the present invention have an atomic ratio of Zn/(Zn+Si) in the range of 0.3 to 0.95.
  • Zn/(Zn+Si) becomes lower than 0.3, the conductivity of the nanoparticles decreases.
  • Zn/(Zn+Si) exceeds 0.95 the work function of the nanoparticles increases.
  • the lower limit of Zn/(Zn+Si) is preferably 0.6 or 0.7.
  • Zn/(Zn+Si) is preferably in the range of 0.80 to 0.92.
  • the Zn content in the ZSO nanoparticles of the present invention is 10% to 50% in terms of atomic concentration, preferably 31% to 47%, and more preferably 36% to 45%.
  • the Si content in the ZSO nanoparticles of the present invention is 1% to 30% in terms of atomic concentration, preferably 2% to 13%, and more preferably 3% to 9%.
  • the content of O in the ZSO nanoparticles of the present invention is 40% to 70% in terms of atomic concentration, preferably 50% to 62%, and more preferably 51% to 54%. If the contents of Zn, Si and O are within the above ranges, the nanoparticles will have high transparency and the display will have good light emitting characteristics.
  • the ZSO nanoparticles of the present invention may contain additives.
  • the additive at least one selected from the group consisting of Al, Ga, Mg, Li, Ti, In, and N is preferable. By including such additives, the conductivity of the nanoparticles can be adjusted.
  • the content of additives in the ZSO nanoparticles of the present invention is 1% to 20%, preferably 5% to 15%, and more preferably 8% to 10% in terms of atomic concentration. If the content of the additive is within the above range, the composition in the nanoparticles will be homogeneous and the dispersibility will be good when dispersed in a solvent.
  • the ZSO nanoparticles of the present invention have a Scherrer diameter in the range of 1 nm to 10 nm.
  • the Scherrer diameter is preferably in the range of 1 nm to 7 nm, more preferably in the range of 2 nm to 6 nm, even more preferably in the range of 3 nm to 5 nm.
  • the Scherrer diameter is 10 nm or less, deterioration in flatness when forming a film is suppressed. Moreover, if the Scherrer diameter is 1 nm or more, the stability of the work function and electrical properties of the film increases.
  • ⁇ is the peak half width.
  • the ZSO nanoparticles of the present invention have a band gap in the range of 3.1 eV to 3.9 eV.
  • the band gap is in the range of 3.2 eV to 3.8 eV.
  • the electron transport layer will have high transparency. Moreover, if the band gap is 3.9 eV or less, the electrical conductivity of the ZSO nanoparticles will be sufficient.
  • the band gap of ZSO nanoparticles can be determined from the light transmission spectrum obtained using an ultraviolet-visible spectrophotometer.
  • the ZSO nanoparticles of the present invention have an ionization potential in the range of 6.0 eV to 8.0 eV.
  • the ionization potential is in the range of 6.5 eV to 7.5 eV.
  • the ZSO nanoparticles will have sufficient electrical conductivity. Moreover, if the ionization potential is 8.0 eV or less, electron injection into the light emitting layer will be good.
  • the ionization potential of ZSO nanoparticles can be determined by ultraviolet photoelectron spectroscopy (UPS).
  • the ZSO nanoparticles of the present invention have an electron affinity in the range of 2.5 eV to 4.0 eV.
  • the electron affinity is in the range of 3.0 eV to 3.8 eV.
  • the electron affinity is 2.5 eV or more, the ZSO nanoparticles will have sufficient electrical conductivity. Further, if the electron affinity is 4.0 eV or less, the electron injection property into the light emitting layer will be good.
  • the electron affinity of the ZSO nanoparticles can be determined by subtracting the band gap value from the ionization potential value.
  • FIG. 1 shows an example of an infrared spectrum of ZSO nanoparticles of the present invention.
  • the spectrum of the SiO 2 sample, the spectrum of the ZnO sample, and the spectrum of the ZnSi 2 O 4 sample are shown simultaneously. Note that in FIG. 1, the intensity on the vertical axis increases toward the bottom.
  • a large absorption peak (referred to as "Zn--O--Zn bond peak”) appears at a wave number of approximately 410 cm.sup. -1 .
  • a large absorption peak (referred to as "Zn--O--Si bond peak”) appears at a wave number of about 920 cm -1 .
  • Si-O-Si bond peak appears at a wave number of approximately 1070 cm -1 .
  • the infrared spectra occurring in the wavenumber range of 400 cm -1 to 600 cm -1 are Zn-O-Zn
  • the infrared spectra generated in the range of wave numbers 870 cm -1 to 970 cm -1 correspond to the Zn-O-Si bond peak and wave numbers 1050 cm -1 to 1150 cm - It can be said that the infrared spectra generated in the range Q1 (referred to as region Q3 ) corresponds to the Si-O-Si bond peak.
  • the infrared spectra of the ZSO nanoparticles of the present invention have the maximum intensity in region Q 1 as I 1 , the maximum intensity in region Q 2 as I 2 , and the maximum intensity in region Q 3 .
  • the intensity is I 3
  • the peak intensity ratio I 2 /(I 1 +I 2 +I 3 ) is characterized by being 0.28 or more.
  • the ZSO nanoparticles of the present invention have a high proportion of Zn--O--Si bonds corresponding to the double oxide of zinc and silicon, and therefore the work function can be significantly reduced.
  • the peak intensity ratio I 2 /(I 1 +I 2 +I 3 ) is preferably 0.29 or more, more preferably 0.30 or more, and even more preferably 0.31 or more.
  • the work function of the ZSO nanoparticles of the present invention can be further reduced.
  • the work function of the ZSO nanoparticles of the present invention is 3.9 eV or less.
  • the work function is preferably 3.8 eV or less.
  • FIG. 2 shows an example of the Raman spectrum of the ZSO nanoparticles of the present invention.
  • the spectrum of the SiO 2 sample, the spectrum of the ZnO sample, and the spectrum of the Zn 2 SiO 4 sample are shown simultaneously for comparison. Note that in FIG. 2, the intensity on the vertical axis increases toward the top.
  • the ZSO nanoparticles of the present invention exist in the state of a double oxide in which zinc oxide and silicon oxide are mixed at the atomic level.
  • Nanoparticles according to an embodiment of the present invention can be produced, for example, by a liquid phase synthesis method.
  • FIG. 3 schematically shows an example of a flow of a method for producing nanoparticles according to an embodiment of the present invention.
  • the method for producing nanoparticles according to one embodiment of the present invention is as follows: (1) mixing raw materials containing zinc and silicon with a first solvent to prepare a first solution (step S110); (2) preparing a second solution containing an alkali (step S120); (3) mixing the first solution and the second solution using a flow reactor method to generate a third solution containing nanoparticles (step S130); (4) adding a particle growth inhibitor to the third solution (step S140); has.
  • Step S110 First, raw materials containing a zinc source and a silicon source are prepared.
  • the raw materials may be prepared in liquid form.
  • the zinc source may be a zinc compound, such as, for example, zinc oxide, zinc acetate, zinc nitrate, zinc carbonate, zinc chloride, zinc sulfate, and zinc alkoxide.
  • a zinc compound such as, for example, zinc oxide, zinc acetate, zinc nitrate, zinc carbonate, zinc chloride, zinc sulfate, and zinc alkoxide.
  • the silicon source may also be silicon compounds such as H 2 SiO 3 (silicic acid) and silicates.
  • the silicon source may be, for example, a silicon oxide or hydroxide, other silicates, silicon compounds such as alkoxides, or hydrates thereof.
  • Alkoxysilane silicon sources include dimethyldimethoxysilane (DMDMS), methyltrimethoxysilane (MTMS), tetramethoxysilane (TMOS), dimethyldiethoxysilane (DMDES), methyltriethoxysilane (MTES), and tetraethoxysilane. Examples include silane (TEOS). Also, oligomeric condensates of TEOS, such as ethyl silicate, may be used.
  • the raw material is mixed with a first solvent to prepare a first solution.
  • the first solvent is not particularly limited as long as it can sufficiently dissolve and mix the raw materials.
  • the first solvent may be, for example, a dimethyl sulfoxide (DMSO) solvent.
  • DMSO dimethyl sulfoxide
  • the first solution is prepared so that the atomic ratio of zinc and silicon contained is Zn/(Zn+Si) of 0.3 to 0.95.
  • Step S120 Next, a second solution is prepared.
  • the second solution is an alkaline solution, such as at least one selected from lithium hydroxide, sodium hydroxide, potassium hydroxide, tetramethylammonium (TMAH), tetraethylammonium (TEAH), and ammonia ( NH3 ). It may have one. Alternatively, the second solution may be a metal alkoxide such as sodium ethoxide.
  • Step S130 Next, the first solution and the second solution are mixed. This causes a reaction in which zinc and silicon bond together in the liquid, forming a third solution containing nanoparticles.
  • a flow reactor method is used in order to form a double oxide in which zinc oxide and silicon oxide are sufficiently mixed with each other.
  • the flow reactor method two disks are stacked one above the other, and a minute reaction field (thickness on the order of ⁇ m) is provided between the two disks. Further, the first liquid and the second liquid are respectively supplied from different ports provided on the upper disk.
  • At least one of the two discs is rotating at high speed, and the supplied first liquid and second liquid are supplied to a reaction field rotating at high speed, where a reaction occurs.
  • reaction products are discharged from the system of the apparatus together with the residual liquid due to the centrifugal force of the rotation of the disk.
  • the first liquid and the second liquid can be sufficiently mixed within a narrow reaction field by increasing the rotational speed of the circular disk.
  • the plurality of generated phases becomes difficult to separate, and more homogeneous fine particles can be obtained.
  • the supply temperatures of the first liquid and the second liquid are not particularly limited.
  • the temperature of the first liquid and the second liquid is, for example, in the range of 20°C to 120°C, preferably in the range of 50°C to 90°C.
  • step S130 a third solution containing nanoparticles is generated.
  • the third solution may be filtered to recover the nanoparticles, if necessary.
  • Step S140 In the first method, desired nanoparticles can be manufactured in the process of steps S110 to S130 described above.
  • step S130 a particle growth inhibitor is added to the third solution.
  • the type of particle growth inhibitor is not particularly limited as long as it is a substance that can suppress the grain growth of nanoparticles.
  • Particle growth inhibitors include, for example, ethyl acetate, butyl acetate, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, diethyl ether, methyl tert-butyl ether (MTBE), It may be selected from diisopropyl ether, diphenyl ether, 1,4-dioxane, tetrahydrofuran (THF).
  • THF tetrahydrofuran
  • the nanoparticles may be classified if necessary.
  • the ZSO nanoparticles of the present invention can be manufactured.
  • Nanoparticles according to one embodiment of the invention can be provided, for example, in the form of a dispersion.
  • a dispersion can be prepared by dispersing nanoparticles in a solvent containing a dispersant.
  • polar solvent it makes it difficult to dissolve the organic light-emitting layer of the OLED and reduces damage to the interface.
  • polar solvents that can be used include water, alcohols, glycols, glycol ethers, glycerin, and/or ethers.
  • Alcohols, glycols, glycol ethers, or ethers include, for example, the following compounds: (i) Alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-ethyl-1-butanol, isoamyl alcohol, 2-methyl-1 -butanol, 2-methyl-2-butanol, 3-methyl-2-butanol, 3-methoxybutanol, pentyl alcohol, 1-hexanol, 1-octanol, 1-pentanol, tert-pentyl alcohol and the like.
  • Glycols include ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, triethylene glycol, dimethyldiethylene glycol, dipropylene glycol, and the like.
  • Glycol ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monophenyl ether, ethylene glycol butyl ethyl ether, and ethylene glycol Butyl methyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol mono t-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether
  • N-methylformamide N-methylpyrrolidone
  • dimethyl sulfoxide fluorinated alcohol-based solvents
  • glycol dialkyl ether-based solvents may be used.
  • solvents may be used alone or in combination.
  • a nonpolar solvent such as water, acetone, benzene, toluene, xylene, and/or hexane can also be used as the solvent.
  • the amount of nanoparticles contained in the dispersion may range, for example, from 0.01% to 50% by weight, and the amount of solvent may range from 50% to 99.9% by weight, for example. .
  • the dispersant is not particularly limited, but a polymeric dispersant, a surfactant type (low molecular type) dispersant, an inorganic type dispersant, etc. can be used.
  • polymer dispersants include polycarboxylic acid polymer dispersants, polyamine polymer dispersants, acrylic polymer dispersants, urethane polymer dispersants, acrylic block copolymer polymer dispersants, and polyether polymer dispersants.
  • Examples include a similar dispersant, a polyester polymer dispersant, polyethyleneimine, polyethyleneimine ethoxylate, and the like.
  • surfactant-type dispersants examples include anionic surfactants such as carboxylates, sulfonates, sulfuric acid ester salts, and phosphoric acid ester salts, cationic surfactants such as amine salts and quaternary ammonium, and fatty acid esters. Any of the nonionic surfactants can be used.
  • aminoethanols such as monoethanolamine, diethanolamine, triethanolamine, 2-amino 1,3-propanediol, thiols, organic sulfur compounds such as disulfides, methoxyacetic acid (MA), 2-methoxyethoxy Acetates such as acetic acid (MEA), 2-(2-methoxyethoxy)ethoxyacetic acid, (MEEA), and 2-ethoxyacetic acid can also be suitably used.
  • silane coupling agents, titanate coupling agents, aluminum coupling agents, etc. can also be used.
  • the amount of dispersant contained in the dispersion is, for example, in the range of 1.0% by mass to 4.0% by mass.
  • nanoparticles according to an embodiment of the invention may be prepared in the form of an ink.
  • the ink is prepared by dispersing nanoparticles in one or more solvents that include a dispersant, an image tackifier, and a surfactant.
  • One or more solvents may be selected from the candidates listed as solvents for the dispersion liquid described above.
  • the solvent is preferably one that is difficult to volatilize at the nozzle portion and has a boiling point of 180° C. or higher.
  • solvents include, for example, ethylene glycol, diethylene glycol (DEG), propylene glycol, and dipropylene glycol (DPG).
  • the above-mentioned dispersants can be used.
  • Thickeners may include propylene glycol, terpineol and ethylcellulose. Further, as another additive, a transparent conductor (indium tin oxide) for adjusting the conductivity of the ink, aluminum-doped zinc oxide (AZO), and/or carbon black may be used.
  • a transparent conductor indium tin oxide
  • AZO aluminum-doped zinc oxide
  • carbon black may be used as another additive.
  • the dispersant, image tackifier, and surfactant may be contained in the entire ink at a concentration of 10% by mass or less, for example.
  • the viscosity of the ink is preferably 1 to 50 mPa ⁇ s (CP).
  • the viscosity of the ink is preferably 5 to 20 mPa ⁇ s (CP).
  • the ink has a viscosity of 8 to 15 mPa ⁇ s (CP).
  • the ink preferably has a low water content, and therefore it is preferable to dehydrate the ink before use.
  • the dehydration method is not particularly limited, but molecular sieves, anhydrous sodium sulfate, and/or calcium hydroxide can be used.
  • the moisture content of the ink is preferably 0.1% by mass or less.
  • the ink may contain an alkali metal complex, an alkali metal salt, an alkaline earth metal complex, or an alkaline earth metal salt.
  • an electron injection layer/electron transport layer containing an alkali metal or alkaline earth metal complex or salt can be formed by a printing process.
  • electron injection efficiency can be further improved.
  • alkali metal or alkaline earth metal complex or salt is soluble in the solvent of the ink.
  • Alkali metals include lithium, sodium, potassium, rubidium, and cesium.
  • Alkaline earth metals include magnesium, calcium, strontium, and barium.
  • Complexes include ⁇ -diketone complexes, and salts include alkoxides, phenoxides, carboxylates, carbonates, and hydroxides.
  • complexes or salts of alkali metals and alkaline earth metals include sodium acetylacetonate, cesium acetylacetonate, calcium bisacetylacetonate, barium bisacetylacetonate, sodium methoxide, sodium phenoxide, and sodium tert-butoxide. , sodium tert-pentoxide, sodium acetate, sodium citrate, cesium carbonate, cesium acetate, sodium hydroxide, and cesium hydroxide.
  • Nanoparticles according to an embodiment of the present invention can be used in thin films of various devices and the like.
  • nanoparticles according to an embodiment of the present invention can be applied to the electron injection layer/electron transport layer of an OLED.
  • FIG. 4 schematically shows a cross section of an OLED to which nanoparticles according to an embodiment of the present invention are applied.
  • the OLED 100 includes a substrate 110, a bottom electrode (anode) 120, a hole injection layer/hole transport layer 130, an organic light emitting layer 140, an additional layer 150, and a top electrode (cathode) 160. , and an insulating layer 170.
  • the OLED 100 when the substrate 110 and the bottom electrode 120 are made of a transparent material, the OLED 100 becomes a bottom emission type in which the substrate 110 side becomes the light extraction surface.
  • the OLED 100 when the upper electrode 160 is made of a transparent material or a semi-transparent material and the lower side of the bottom electrode 120 is made of a reflective layer, the top emission type in which the upper electrode 160 side becomes the light extraction surface. becomes.
  • the substrate 110 has the role of supporting each layer installed thereon.
  • the bottom electrode 120 is made of a conductive metal oxide such as indium tin oxide (ITO), for example.
  • the upper electrode 160 is made of metal or semiconductor, for example.
  • the hole injection layer/hole transport layer 130 is made of a hole transporting compound.
  • the hole transporting compound is preferably a compound having an ionization potential of 4.5 eV to 6.0 eV from the viewpoint of a charge injection barrier from the anode to the hole injection layer.
  • hole-transporting compounds include aromatic amine compounds, phthalocyanine compounds, porphyrin compounds, oligothiophene compounds, polythiophene compounds, benzylphenyl compounds, compounds in which tertiary amines are linked with fluorene groups, and hydrazone compounds. compounds, silazane-based compounds, quinacridone-based compounds, and the like.
  • aromatic amine compounds are preferred, and aromatic tertiary amine compounds are particularly preferred, in terms of amorphousness and visible light transparency.
  • the aromatic tertiary amine compound is a compound having an aromatic tertiary amine structure, and also includes a compound having a group derived from an aromatic tertiary amine.
  • the type of aromatic tertiary amine compound is not particularly limited, but a polymeric compound with a weight average molecular weight of 1,000 or more and 1,000,000 or less (a polymeric compound with a series of repeating units) is preferred, since it is easy to obtain uniform light emission due to the surface smoothing effect. It is preferable to use
  • the organic light-emitting layer 140 is made of an organic substance that emits red, green, and/or blue light, for example.
  • the organic light emitting layer 140 is a functional layer that has the function of emitting light (including visible light).
  • the organic light emitting layer 140 is usually composed of an organic material that mainly emits at least one of fluorescence and phosphorescence, or this organic material and a dopant that assists the organic material.
  • a dopant is added, for example, to improve luminous efficiency or change the emission wavelength.
  • the organic substance may be a low molecular compound or a high molecular compound.
  • the thickness of the emissive layer may be, for example, about 2 nm to 200 nm.
  • the insulating layer 170 is made of, for example, a photosensitive resin such as a fluororesin or a polyimide resin.
  • the hole injection layer/hole transport layer 130 and/or the organic light emitting layer 140 can be formed, for example, by a printing process.
  • Additional layer 150 includes ZSO nanoparticles of the present invention.
  • additional layer 150 may include a thin film comprising ZSO nanoparticles of the present invention.
  • additional layer 150 has a relatively low work function and adequate electrical conductivity.
  • the work function of additional layer 150 is 3.9 eV or less.
  • the electrical conductivity of the additional layer 150 is, for example, 10 ⁇ 8 Scm ⁇ 1 or more, for example, 10 ⁇ 5 Scm ⁇ 1 or more.
  • the additional layer 150 can function as an electron injection layer and/or an electron transport layer.
  • the additional layer 150 can be formed using a low-temperature process such as a printing process. That is, the additional layer 150 can be formed on the organic light emitting layer 140 by preparing an ink as described above and performing a printing process using the ink.
  • the printing process for example, an inkjet printing method, a screen printing method, etc. can be used.
  • the thickness can be more easily controlled than when the additional layer 150 is formed by a conventional vapor deposition method.
  • the Scherrer diameter of the nanoparticles included in the additional layer 150 is in the range of 1 nm to 10 nm. When such fine nanoparticles are used, unevenness on the surface of the additional layer 150 can be significantly suppressed.
  • the surface roughness RMS (root mean square height) of the additional layer 150 is 5 nm or less.
  • the hole injection layer/hole transport layer 130 to the additional layer 150 can be formed by a printing process.
  • the conventional vapor deposition equipment for forming the electron injection layer/electron transport layer is not required, and the equipment cost can be reduced. Therefore, OLED 100 can be easily manufactured at relatively low cost.
  • additional layer 150 includes nanoparticles having characteristics as described above. Therefore, the upper electrode 160 disposed on the additional layer 150 can be formed using a heat generation process such as sputtering, for example.
  • the additional layer 150 may be composed of a multilayer of a thin film containing the ZSO nanoparticles of the present invention and other layers.
  • Nanoparticles according to an embodiment of the present invention can be applied to the electron injection layer/electron transport layer of a QD display.
  • FIG. 5 schematically shows a cross section of a QD display to which nanoparticles according to an embodiment of the present invention are applied.
  • the QD display 200 includes a substrate 210, a bottom electrode (anode) 220, a hole injection layer/hole transport layer 230, a quantum dot (QD) light emitting layer 240, an additional layer 250, and a top It has an electrode (cathode) 260.
  • the description in the above-mentioned OLED 100 can be referred to for the substrate 210, the bottom electrode (anode) 220, the hole injection layer/hole transport layer 230, and the upper electrode (cathode) 260. Therefore, detailed explanation will be omitted here.
  • the QD light emitting layer 240 is composed of nanoparticles such as CdSe, ZnSe, InP, PbS, perovskite (CsPbX3; X is Cl, Br, or I).
  • the additional layer 250 includes ZSO nanoparticles of the present invention.
  • additional layer 250 has a relatively low work function and adequate electrical conductivity.
  • the work function of additional layer 250 is 3.9 eV or less.
  • the electrical conductivity of the additional layer 250 is, for example, 10 ⁇ 8 Scm ⁇ 1 or more, for example, 10 ⁇ 5 Scm ⁇ 1 or more.
  • the additional layer 250 can function as an electron injection layer and/or an electron transport layer.
  • the additional layer 250 can be deposited using a low temperature process such as a printing process. That is, the additional layer 250 can be formed on the QD light emitting layer 240 by preparing an ink as described above and performing a printing process using the ink.
  • the printing process for example, an inkjet printing method, a screen printing method, etc. can be used.
  • the additional layer 250 is deposited by a printing process, the thickness can be more easily controlled than when deposited by a conventional vapor deposition method.
  • the Scherrer diameter of the nanoparticles included in the additional layer 250 is in the range of 1 nm to 10 nm. When such fine nanoparticles are used, unevenness on the surface of the additional layer 250 can be significantly suppressed.
  • the surface roughness RMS (root mean square height) of the additional layer 250 is 5 nm or less.
  • the hole injection layer/hole transport layer 230 to the additional layer 250 can be formed by a printing process.
  • the QD display 200 can be easily manufactured at relatively low cost.
  • the additional layer 250 includes nanoparticles having the characteristics described above. Therefore, the upper electrode 260 disposed on the additional layer 250 can be formed using a heat generation process such as a sputtering method.
  • Examples 1 to 3 are examples, and Examples 11 to 13 are comparative examples.
  • Nanoparticles were produced by the first method described above.
  • TEOS tetraethoxysilane
  • the concentration of zinc acetate in the first solution was 0.1 mol/L, and the concentration of TEOS was 0.038 mol/L. Therefore, the atomic ratio Zn/(Zn+Si) in the first solution is 0.725.
  • TEAH tetraethylammonium hydroxide
  • the temperature of the first solution supplied was set in the range of 60°C to 70°C.
  • the supply flow rate of the first solution was 43.6 mL/min, and the supply pressure was 0.1 to 0.2 MPaG.
  • the temperature of the second solution supplied was set in the range of 60°C to 70°C.
  • the supply flow rate of the second solution was 26.4 mL/min, and the supply pressure was 0.1 to 0.2 MPaG.
  • the rotation speed of the disk was 5000 rpm.
  • reaction solution discharged from the flow reactor device was immediately poured into a container filled with ethyl acetate as a growth inhibitor to stop the reaction.
  • nanoparticles 1 were collected by collecting and filtering the third solution discharged from the flow reactor device.
  • the filtration method used a centrifuge to discard the supernatant liquid of the third solution and collect the precipitate. Further, the operation of diluting the precipitate with ethanol and then recovering the precipitate using a centrifuge was repeated three times.
  • Example 2 Nanoparticles were produced by a method similar to Example 1. However, in this Example 2, the flow rates of the first and second solutions supplied to the flow reactor device were changed. The supply flow rate of the first solution was 18.68 mL/min. The supply flow rate of the second solution was 11.32 mL/min.
  • nanoparticles 2 As a result, nanoparticles (hereinafter referred to as “nanoparticles 2”) were recovered.
  • Nanoparticles were produced by a method similar to Example 1. However, in this Example 3, the flow rates of the first and second solutions supplied to the flow reactor device were changed. The supply flow rate of the first solution was 31.14 mL/min. The feed flow rate of the second solution was 18.86 mL/min. As a result, nanoparticles (hereinafter referred to as “nanoparticles 3") were recovered.
  • Nanoparticles were produced using a beaker instead of a flow reactor device.
  • first solution and second solution were added into a beaker and thoroughly stirred at room temperature.
  • the compositions of the first solution and the second solution are the same as in Example 1. After 5 minutes, stirring was stopped and ethyl acetate was added to the beaker.
  • nanoparticles 11 were recovered by filtering the solution in the beaker.
  • Example 12 Nanoparticles were produced by a method similar to Example 1. However, in this Example 12, only zinc acetate and no tetraethoxysilane (TEOS) were added to the first solution.
  • TEOS tetraethoxysilane
  • nanoparticles 12 were recovered.
  • Nanoparticles were manufactured using a thermal plasma method as follows.
  • the raw material slurry was prepared by dispersing in alcohol a mixed powder obtained by mixing zinc oxide particles and silicon dioxide particles at a molar ratio of 60:40.
  • Thermal plasma was generated within the reaction chamber.
  • the temperature of the thermal plasma was about 10,000K.
  • N 2 :O 2 75:25
  • nanoparticles 13 were produced.
  • Table 1 summarizes the manufacturing conditions for nanoparticles in each example.
  • composition analysis The composition of each nanoparticle was analyzed using SEM-EDX.
  • a scanning electron microscope S4300 manufactured by Hitachi, Ltd. was used for the measurement. Further, as an EDX detector, an energy dispersive X-ray analyzer X-act manufactured by Oxford was used. At this time, the relative sensitivity coefficients of the measurement elements were calibrated in advance using standard samples, and measurement conditions were used in which the counts of each of O, Si, and Zn were 10,000 or more.
  • Samples for measurement were prepared according to the following procedure. First, the nanoparticles were diluted with an ethanol solvent, and then a dispersion containing the nanoparticles was prepared. The concentration of nanoparticles was 3 wt%. Next, about 10 ⁇ L of the dispersion liquid was dropped onto an Al sample stand for SEM. Thereafter, by drying the ethanol at room temperature, the nanoparticles were supported on the sample stage to form a measurement sample.
  • the atomic ratio Zn/(Zn+Si) was all in the range of 0.3 to 0.95.
  • the atomic ratio Zn/(Zn+Si) was approximately 1.
  • the atomic ratio Zn/(Zn+Si) was 0.75.
  • Nanoparticles 1 to 3 all had Scherrer diameters in the range of 1 nm to 10 nm.
  • Infrared spectroscopy Infrared spectroscopic analysis was performed using each nanoparticle. For the measurement, Nic-plan/Nicolet 6700 manufactured by Thermo Fisher Scientific was used.
  • FIG. 1 shows an infrared spectrum of nanoparticles 2.
  • I 2 /(I 1 +I 2 +I 3 ) in nanoparticle 2 was calculated.
  • I 1 is the maximum intensity in region Q 1
  • I 2 is the maximum intensity in region Q 2
  • I 3 is the maximum intensity in region Q 3 .
  • I 2 /(I 1 +I 2 +I 3 ) 0.383.
  • FIG. 2 shows the Raman spectrum of the nanoparticles 2.
  • XAFS analysis Perform XAFS measurement using nanoparticles 1 to 3 to determine the average coordination number of the O atom closest to the Zn atom and the average coordination number of the Zn atom closest to the Zn atom. Ta.
  • Aichi Synchrotron Optical Center BL11S was used.
  • a transmission step scan or QUICK XAFS method was used.
  • Each nanoparticle was diluted with boron nitride powder so that ⁇ t of the Zn K end was 1, and a pellet was produced by pressure molding.
  • the prepared pellets were sealed in a plastic film and set in a measuring device.
  • the XAFS measurement was performed at room temperature, and the EXAFS vibration in k-space was extracted from the obtained XAFS spectrum, and the FT-EXAFS (radial distribution function) in R-space was obtained by Fourier transformation.
  • the structural parameters of ZSO nanoparticles were calculated by EXAFS fitting analysis for R-space FT-EXAFS. Wurtzite type ZnO was used as the reference structure.
  • nanoparticles 1 to 3 had smaller particle sizes and relatively higher I 2 /(I 1 +I 2 +I 3 ) compared to nanoparticles 11 to 13. .
  • the average coordination number of the O atom closest to the Zn atom was found to be in the range of 3.0 to 4.5. Furthermore, it was found that in nanoparticles 1 to 3, the average coordination number of the Zn atom closest to the Zn atom was in the range of 1.5 to 10.
  • Thin film 1 A thin film was formed on a substrate using a dispersion containing nanoparticles 1.
  • the dispersion liquid was prepared as follows.
  • Nanoparticles 1 and monoethanolamine (MEA) were added to a propylene glycol solvent at room temperature, mixed thoroughly, and then treated with an ultrasonic homogenizer (manufactured by Nippon Seiki Seisakusho Co., Ltd.) at an output of 150 W for 30 minutes.
  • the concentration of nanoparticles 1 was 3 wt%, and the concentration of MEA was 3 wt%.
  • the obtained dispersion liquid was filtered using a filter with a hole diameter of 0.22 ⁇ m (Durapore manufactured by Merck & Co., Ltd.). As a result, a dispersion liquid (hereinafter referred to as "dispersion liquid 1”) was prepared.
  • Dispersion 1 was applied onto the substrate by a spin coating method to form a coating film. Thereafter, the coating film was baked at 150°C to form a thin film (hereinafter referred to as "thin film 1"). The thickness of the thin film 1 was targeted to be 40 nm.
  • a silica glass substrate and an indium tin oxide (ITO) substrate were used as the substrates.
  • Thin film 1 on the silica glass substrate was used for the flatness evaluation shown below, and thin film 1 on the ITO substrate was used for the work function evaluation.
  • Thin film 2 A dispersion containing nanoparticles 2 (hereinafter referred to as "dispersion 2") was prepared by diluting nanoparticles 2 with an ethanol solvent. The concentration of nanoparticles 2 was 3 wt%. A thin film was formed on an ITO substrate using Dispersion 2. The baking treatment temperature after spin coating was 100°C. The obtained thin film is referred to as "thin film 2.”
  • Thin film 3 A dispersion containing nanoparticles 3 (hereinafter referred to as "dispersion 3") was prepared by diluting nanoparticles 3 with an ethanol solvent. The concentration of nanoparticles 3 was 3 wt%. A thin film was formed on an ITO substrate using dispersion liquid 3. The baking treatment temperature after spin coating was 100°C. The obtained thin film is referred to as "thin film 3.”
  • a dispersion containing nanoparticles 12 (hereinafter referred to as "dispersion 12") was prepared by diluting nanoparticles 12 with an ethanol solvent. The concentration of nanoparticles 12 was 3 wt%. A thin film was formed on an ITO substrate using dispersion liquid 12. The baking treatment temperature after spin coating was 100°C. The obtained thin film is referred to as "thin film 12.”
  • the dispersion liquid was prepared as follows.
  • Nanoparticles 13 were added to 1-propanol solvent at room temperature and mixed thoroughly. The concentration of nanoparticles 13 was 3 wt%. As a result, a dispersion liquid (hereinafter referred to as "dispersion liquid 13”) was prepared.
  • Dispersion 1 was applied to each of the two types of substrates by a spin coating method to form a coating film. Thereafter, the coating film was baked at 100°C to form a thin film (hereinafter referred to as "thin film 13"). The thickness of the thin film 13 was targeted to be 130 nm.
  • a silica glass substrate and an ITO substrate were used as the substrates.
  • the thin film 13 on the silica glass substrate was used for flatness evaluation shown below, and the thin film 13 on the ITO substrate was used for work function evaluation.
  • an ultraviolet-visible spectrophotometer manufactured by JASCO Corporation, product number: V-750 was used, and the value was determined from the obtained light transmission spectrum.
  • Ionization potential and work function Ionization potential and work function
  • UV photoelectron spectroscopy was used to measure the work function.
  • the excitation light used for ultraviolet photoelectron spectroscopy was HeI (21.2 eV).
  • nanoparticles 1 to 3 were 3.7 eV, 3.2 eV, and 3.6 eV, respectively.
  • the work functions of nanoparticles 12 and 13 were found to be 4.0 eV and 3.3 eV, respectively.
  • the electron affinities of nanoparticles 1 to 3 were determined by subtracting the above band gap value from the above ionization potential value. As a result, it was found that the electron affinities of nanoparticles 1 to 3 were 3.6 eV, 2.7 eV, and 3.2 eV, respectively.
  • the surface roughness (RMS) of thin film 1 and thin film 13 was measured using AFM (Dimension Icon, manufactured by Bruker).
  • the surface roughness RMS of thin film 1 was 1.4 nm, and a flat surface was obtained.
  • the surface roughness RMS of thin film 13 was 8 nm, indicating that a flat surface was not obtained.

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Abstract

La présente invention concerne des nanoparticules qui sont conçues à partir d'un oxyde métallique. Pour ce qui concerne le spectre des nanoparticules, tel que mesuré par spectrométrie infrarouge, si I1 est l'intensité maximale attribuée à une liaison Zn-O-Zn dans la plage de 400 cm-1 à 600 cm-1, I2 est l'intensité maximale attribuée à une liaison Zn-O-Si dans la plage de 870 cm-1 à 970 cm-1 et I3 est l'intensité maximale attribuée à une liaison Si-O-Si dans la plage de 1 050 cm-1 à 1 150 cm-1, le rapport entre intensités maximales I2/(I1 + I2 + I3) est de 0,28 ou plus. Le rapport en atomes Zn/(Zn + Si) dans les nanoparticules est compris dans la plage de 0,3 à 0,95 ; et le diamètre de Scherrer des nanoparticules est compris dans la plage de 1 nm à 10 nm.
PCT/JP2023/018779 2022-06-02 2023-05-19 Nanoparticules, liquide de dispersion, encre, couche mince, diode électroluminescente organique, affichage à boîtes quantiques et procédé de production de nanoparticules WO2023234074A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009008393A1 (fr) * 2007-07-06 2009-01-15 M.Technique Co., Ltd. Procédé de fabrication de nanoparticules par procédé de rotation à film ultra-mince forcé
US20140255293A1 (en) * 2013-03-11 2014-09-11 Oregon State University Controlled synthesis of nanoparticles using ultrasound in continuous flow
WO2016043231A1 (fr) * 2014-09-18 2016-03-24 国立大学法人東京工業大学 Élément électroluminescent, dispositif d'affichage et dispositif d'éclairage
WO2016043084A1 (fr) * 2014-09-18 2016-03-24 旭硝子株式会社 Élément électroluminescent et élément de production d'électricité
JP2017222574A (ja) * 2016-06-02 2017-12-21 エム・テクニック株式会社 色特性を制御された酸化物粒子、並びにその酸化物粒子を含む塗布用又はフィルム状組成物
JP2019505403A (ja) * 2015-12-31 2019-02-28 ダウ グローバル テクノロジーズ エルエルシー ナノ構造材料の連続フロー合成

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009008393A1 (fr) * 2007-07-06 2009-01-15 M.Technique Co., Ltd. Procédé de fabrication de nanoparticules par procédé de rotation à film ultra-mince forcé
US20140255293A1 (en) * 2013-03-11 2014-09-11 Oregon State University Controlled synthesis of nanoparticles using ultrasound in continuous flow
WO2016043231A1 (fr) * 2014-09-18 2016-03-24 国立大学法人東京工業大学 Élément électroluminescent, dispositif d'affichage et dispositif d'éclairage
WO2016043084A1 (fr) * 2014-09-18 2016-03-24 旭硝子株式会社 Élément électroluminescent et élément de production d'électricité
JP2019505403A (ja) * 2015-12-31 2019-02-28 ダウ グローバル テクノロジーズ エルエルシー ナノ構造材料の連続フロー合成
JP2017222574A (ja) * 2016-06-02 2017-12-21 エム・テクニック株式会社 色特性を制御された酸化物粒子、並びにその酸化物粒子を含む塗布用又はフィルム状組成物

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