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WO2021201621A1 - Diode électroluminescente organique comprenant une structure en nano-ilôt et son procédé de fabrication - Google Patents

Diode électroluminescente organique comprenant une structure en nano-ilôt et son procédé de fabrication Download PDF

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Publication number
WO2021201621A1
WO2021201621A1 PCT/KR2021/004043 KR2021004043W WO2021201621A1 WO 2021201621 A1 WO2021201621 A1 WO 2021201621A1 KR 2021004043 W KR2021004043 W KR 2021004043W WO 2021201621 A1 WO2021201621 A1 WO 2021201621A1
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Prior art keywords
light emitting
nano
layer
organic light
emitting device
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PCT/KR2021/004043
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English (en)
Korean (ko)
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서민철
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경희대학교산학협력단
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Priority claimed from KR1020210042075A external-priority patent/KR102477831B1/ko
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Publication of WO2021201621A1 publication Critical patent/WO2021201621A1/fr

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    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
    • H10K77/10—Substrates, e.g. flexible substrates

Definitions

  • the present invention relates to an organic light emitting device and a method for manufacturing the same, and more particularly, to a technical idea of improving light emitting characteristics of an organic light emitting device using a nano-island structure.
  • Equation 1 in order to increase the external quantum efficiency coming out, the internal quantum efficiency must be high. In order to increase the internal quantum efficiency, the amount of exciton generation must be large, and for this purpose, an ideal charge balance must be obtained. In addition, if the charge balance is ideally matched, deterioration at the interface can be suppressed, which helps to improve the lifespan. For this reason, it is very important to balance the charge of the OLED and optimize the device.
  • a recombination zone in which carriers injected from the electrode form excitons and recombine should be formed in the central portion of the emission layer (EML).
  • EML emission layer
  • the recombination zone is affected by electron and hole injection characteristics.
  • An object of the present invention is to provide an organic light emitting device capable of effectively controlling the dependence of the viewing angle of the organic light emitting device by forming a nano-island structure on a substrate, and a method for manufacturing the same.
  • the present invention provides an organic light emitting device capable of improving angular chromaticity change through realization of a low pixel blurring effect due to a nano-island structure formed on a substrate, and a method for manufacturing the same. would like to provide
  • Another object of the present invention is to provide an organic light emitting device capable of easily forming a nano-island structure on a large-area display device using thermal evaporation, and a method for manufacturing the same.
  • Another object of the present invention is to provide an organic light emitting device capable of improving each chromaticity change and luminous efficiency through enhancement of microcavity characteristics based on optimization of the thickness of the hole transport layer and the anode electrode, and a method for manufacturing the same.
  • An organic light emitting device includes a substrate provided with a plurality of nano-island structures and a light emitting structure formed on the substrate, wherein the nano-island structures are dewetting (dewetting) of an inorganic material layer deposited on the substrate. It is formed through a dewetting) process, and a diameter and a height may be determined by at least one of a thickness of the deposited inorganic material layer, a temperature condition and a humidity condition during the dewetting process.
  • the nano-island structure may be formed through a dewetting process of an inorganic material layer deposited to a thickness of 50 nm to 10 nm on a substrate.
  • the deposited inorganic layer is cesium chloride (CsCl), cesium fluoride (CsF), cesium iodide (CsI), cesium bromide (CsBr), calcium chloride (CaCl 2 ) and lanthanum chloride (LaCl 3 ) of It may include at least one.
  • the nano-island structure may be formed by performing a dewetting process on the deposited inorganic material layer in an environment of a temperature of 30° C. and a relative humidity of 60%.
  • the substrate may further include a passivation layer that blocks exposure of the nano-island structure to air.
  • the light emitting structure may include an anode electrode, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode electrode sequentially formed on a substrate.
  • the light emitting structure may further include a metal thin film layer formed between the substrate and the anode electrode.
  • the hole transport layer may include a first hole transport layer formed on an adjacent surface of the anode electrode, a hole generating layer formed on the first hole transport layer, and a second hole transport layer formed on the hole generating layer.
  • a method of manufacturing an organic light emitting device includes forming a plurality of nano-island structures on a substrate and forming a light emitting structure on a substrate, wherein the nano-island structures are formed
  • the step is to form a nano-island structure through a dewetting process of the inorganic layer deposited on the substrate, but the nano-island structure is formed by at least one of the thickness of the deposited inorganic layer, temperature conditions and humidity conditions in the dewetting process.
  • the diameter and height of the island structure can be determined.
  • the step of forming the nano-island structure is cesium chloride (CsCl), cesium fluoride (CsF), cesium iodide (CsI), cesium bromide (CsBr), calcium chloride (CaCl 2 ) and lanthanum chloride ( LaCl 3 )
  • a nano-island structure may be formed by depositing an inorganic material layer including at least one of 50 nm to 10 nm on a substrate and performing a dewetting process of the deposited inorganic material layer.
  • the forming of the nano-island structure may include performing a dewetting process on the deposited inorganic material layer in an environment of a temperature of 30° C. and a relative humidity of 60% to form the nano-island structure.
  • forming the nano-island structure may further include forming a passivation layer that blocks exposure of the nano-island structure to the air.
  • the light emitting structure may include an anode electrode, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode electrode sequentially formed on a substrate.
  • the light emitting structure may further include a metal thin film layer formed between the substrate and the anode electrode.
  • the hole transport layer may include a first hole transport layer formed on an adjacent surface of the anode electrode, a hole generating layer formed on the first hole transport layer, and a second hole transport layer formed on the hole generating layer.
  • the present invention can effectively control the viewing angle dependence of the organic light emitting device by forming a nano-island structure on a substrate.
  • the present invention can improve angular chromaticity change through the implementation of a low pixel blurring effect due to the nano-island structure formed on the substrate.
  • a nano-island structure can be easily formed even on a large-area display device by using thermal evaporation.
  • the present invention can improve each chromaticity change and luminous efficiency through enhancement of microcavity characteristics based on optimization of the thickness of the hole transport layer and the anode electrode.
  • FIG. 1 is a view for explaining an organic light emitting device according to an embodiment.
  • FIG. 2 is a diagram for describing a substrate of an organic light emitting device according to an exemplary embodiment in more detail.
  • FIG. 3 is a view for explaining a light emitting structure according to an embodiment in more detail.
  • 4A to 4C are diagrams for explaining an FS-SEM image of a nano-island structure according to an embodiment.
  • 5A to 5D are diagrams for explaining optical characteristics of a nano-island structure according to an embodiment.
  • 6A to 6B are diagrams for explaining luminous efficiency characteristics and chromaticity change characteristics according to a change in thickness of a hole transport layer and a metal thin film layer of an organic light emitting diode according to an exemplary embodiment.
  • FIGS. 7A to 7D are diagrams for explaining optical characteristics of an organic light emitting device having a light emitting structure according to an exemplary embodiment.
  • FIGS. 8A to 8F are diagrams for explaining each chromaticity change characteristic of an organic light emitting device having a light emitting structure according to an exemplary embodiment.
  • 9A to 9B are views for explaining each chromaticity trajectory of an organic light emitting device having a light emitting structure according to an exemplary embodiment.
  • FIGS. 10A to 10D are diagrams for explaining optical characteristics of an organic light emitting device including a light emitting structure and a nano-island structure according to an exemplary embodiment.
  • 11A to 11D are diagrams for explaining each chromaticity change characteristic of an organic light emitting device including a light emitting structure and a nano-island structure according to an exemplary embodiment.
  • 12A to 12B are diagrams for explaining pixel blur characteristics of an organic light emitting diode according to an exemplary embodiment.
  • FIG. 13 is a view for explaining a method of manufacturing an organic light emitting device according to an exemplary embodiment.
  • 14A to 14C are diagrams for explaining in more detail a method of forming a plurality of nano-island structures in a method of manufacturing an organic light emitting device according to an exemplary embodiment.
  • first or second may be used to describe various elements, but the elements should not be limited by the terms. The terms are used only for the purpose of distinguishing one element from another, for example, without departing from the scope of rights according to the inventive concept, a first element may be termed a second element, and similar The second component may also be referred to as the first component.
  • FIG. 1 is a view for explaining an organic light emitting device according to an embodiment.
  • the organic light emitting device 100 forms a nano-island structure on a substrate to effectively control the viewing angle dependence of the organic light emitting device.
  • the organic light emitting device 100 may improve angular chromaticity change by implementing a low pixel blurring effect due to the nano-island structure formed on the substrate.
  • the organic light emitting device 100 can easily form a nano-island structure even in a large-area display device by using thermal evaporation.
  • the organic light emitting device 100 may improve each chromaticity change and luminous efficiency through enhancement of microcavity characteristics based on optimization of the thickness of the hole transport layer and the anode electrode.
  • the organic light emitting device 100 may be a front light emitting device or a bottom light emitting device.
  • the organic light emitting device 100 according to an exemplary embodiment will be described through an example of the bottom light emitting device.
  • the organic light emitting device 100 may include a substrate 110 provided with a plurality of nano-island structures (NI) and a light emitting structure 120 formed on the substrate 110 . .
  • NI nano-island structures
  • a plurality of nano-island structures NI may be formed on a substrate 110 in the form of a nano-island array (NIA). have.
  • the nano-island structure (NI) is formed through a dewetting process of an inorganic material layer deposited on the substrate 110, the thickness of the deposited inorganic material layer, temperature conditions in the dewetting process, and A diameter and a height may be determined by at least one of the humidity conditions.
  • the nano-island structure NI may be formed through a dewetting process of an inorganic material layer deposited to a thickness of 50 nm to 10 nm on a substrate.
  • the deposited inorganic layer is at least one of cesium chloride (CsCl), cesium fluoride (CsF), cesium iodide (CsI), cesium bromide (CsBr), calcium chloride (CaCl 2 ), and lanthanum chloride (LaCl 3 ) may include.
  • the deposited inorganic material layer may be a cesium chloride layer.
  • the nano-island structure (NI) may be formed by performing a dewetting process on the deposited inorganic material layer in an environment of a temperature of 30° C. and a relative humidity of 60%.
  • the nano-island structure NI is formed by depositing a cesium chloride layer with a thickness of 50 nm to 100 nm on the substrate 110, and depositing a cesium chloride layer at a temperature of 30° C. and a relative humidity of 60%. It may be formed to a diameter of 600 nm or less and a height of 200 nm to 250 nm by performing a dewetting process for the .
  • the substrate 110 may further include a passivation layer 130 that blocks exposure of the nano-island structure NI to the air.
  • the light emitting structure 120 is an anode electrode (anode) sequentially formed on the substrate 110, a hole transport layer (hole transport layer, HTL), a light emitting layer (emission layer, EML), an electron transport layer (electron transport layer, ETL) and a cathode electrode (cathode).
  • anode electrode anode electrode sequentially formed on the substrate 110, a hole transport layer (hole transport layer, HTL), a light emitting layer (emission layer, EML), an electron transport layer (electron transport layer, ETL) and a cathode electrode (cathode).
  • the light emitting structure 120 includes an anode electrode, a hole transport layer, an electron transport layer (ETL), a light emitting layer, an electron transport layer, an electron injection layer that are sequentially formed on the substrate 110 . and a cathode electrode.
  • ETL electron transport layer
  • the light emitting structure 120 may further include a metal thin film layer formed between the substrate and the anode electrode, and a capping layer formed between the substrate and the metal thin film layer.
  • the metal thin film layer may be a silver (Ag) thin film layer.
  • the hole transport layer may include a first hole transport layer formed on an adjacent surface of the anode electrode, a hole generating layer formed on the first hole transport layer, and a second hole transport layer formed on the hole generating layer.
  • FIG. 2 is a diagram for describing a substrate of an organic light emitting device according to an exemplary embodiment in more detail.
  • a substrate 200 may include a glass substrate 210 , a plurality of nano-island structures (NI) formed on the glass substrate, and a passivation layer 220 .
  • NI nano-island structures
  • a cesium chloride layer may be formed on the glass substrate 210 through a vacuum deposition method, and the cesium chloride layer deposited on the glass substrate 210 is in an environment of a temperature of 30° C. and a relative humidity of 60% for 3 minutes. When exposed to , it can be transformed into a plurality of randomly distributed nano-island structures (NI) by absorbing water vapor through a dewetting process.
  • NI nano-island structures
  • the plurality of nano-island structures NI may be formed in at least one of a hemispherical shape, an elliptical shape, and an irregular shape.
  • the passivation layer 220 may prevent the plurality of nano-island structures (NI) randomly distributed on the glass substrate 210 from being dissolved or volatilized in the air.
  • the passivation layer 220 may include SPC-370 (FOSPIA Co., Ltd.).
  • FIG. 3 is a view for explaining a light emitting structure according to an embodiment in more detail.
  • the light emitting structure 300 includes a capping layer 310, a metal thin film layer 320, an anode electrode 330, a hole transport layer 340, and an electron blocking layer that are sequentially stacked. 350 ), an emission layer 360 , an electron transport layer 370 , an electron injection layer 380 , and a cathode electrode 390 .
  • the hole transport layer 340 is formed on the first hole transport layer 341 formed on the adjacent surface of the anode electrode 330 , the hole generating layer 342 and the hole generating layer 342 formed on the first hole transport layer 341 .
  • a second hole transport layer 343 formed therein may be included.
  • a thin metal thin film layer 320 may be deposited under the anode electrode 330 to increase the reflectivity of the anode electrode 330 to implement a strong micro-cavity effect. , may further include a capping layer formed before deposition of the metal thin film layer 320 in order to increase the luminous efficiency.
  • a hole generating layer 342 is provided in the hole transport layer 340 in order to strengthen the micro-cavity effect and improve hole transport efficiency through optimizing the thickness of the hole transport layer 340 .
  • the capping layer 310 may have a thickness of 55 nm and include indium tin oxide (ITO).
  • ITO indium tin oxide
  • the metal thin film layer 320 may have a thickness of 16 nm to 24 nm, and may include silver (Ag).
  • the anode electrode 330 is formed to a thickness of 10 nm and may include ITO.
  • the first hole transport layer 341 is formed to a thickness of 75 nm to 85 nm
  • the second hole transport layer 343 is formed to a thickness of 85 nm
  • the first hole transport layer 341 and the second hole transport layer 343 are NPB. (N, N'-bis (naphthalen-1-yl) -N, N'-bis (phenyl) benzidine).
  • the hole generating layer 342 may have a thickness of 7 nm and include HAT-CN (1,4,5,8,9,11-hexaazatriphenylene hexacarbonitrile).
  • the electron blocking layer 350 is formed to a thickness of 18 nm and may include Tris (4-carbazol-9-ylphenyl) amine (TCTA).
  • TCTA Tris (4-carbazol-9-ylphenyl) amine
  • the light emitting layer 360 is formed to a thickness of 20 nm, Bepp2 (beryllium bis(2-(20-hydroxyphenyl) pyridine)) and Ir(ppy) 2 (acac) (bis(2-phenylpyridine) acetylacetonato) corresponding to blue phosphorescence iridium(III)), wherein Bepp2 and Ir(ppy) 2 (acac) may be used as host and dopant materials, respectively.
  • the electron transport layer 370 is formed to a thickness of 35 nm and may include 4,7-diphenyl-1,10-phenanthroline (BPhen).
  • BPhen 4,7-diphenyl-1,10-phenanthroline
  • the electron injection layer 380 may have a thickness of 1.5 nm and may include lithium fluoride (LiF).
  • the cathode electrode 390 is formed to a thickness of 100 nm and may include aluminum (Al).
  • FIGS. 4A to 4C are diagrams for explaining a field emission scanning electron microscope (FS-SEM) image of a nano-island structure according to an exemplary embodiment.
  • FS-SEM field emission scanning electron microscope
  • reference numeral 410 shows a front image of a nano-island structure formed by depositing a cesium chloride layer (CsCl) on a substrate
  • reference numeral 420 shows a side image of the nano-island structure
  • reference numeral 430 shows a side image of a substrate according to an embodiment consisting of an organic substrate, a nano-island structure, and a passivation layer.
  • the diameter and height of the nano-island structure may change according to the deposition thickness of the cesium chloride layer.
  • the cesium chloride layer deposited on the substrate may be deposited to a thickness of 50 nm or 100 nm.
  • a plurality of nano-island structures having a diameter of 400 nm and a height of 200 nm were exposed on a glass substrate by exposing a cesium chloride layer deposited to a thickness of 50 nm to an environment of 30° C. and 60% relative humidity for 10 minutes. can be randomly distributed.
  • a plurality of nano-island structures having a diameter of 600 nm or less and a height of 250 nm were exposed on a glass substrate by exposing a cesium chloride layer deposited to a thickness of 100 nm to an environment of 30° C. and 60% relative humidity for 10 minutes. can be randomly distributed.
  • a passivation layer may be formed on the glass substrate on which the plurality of nano-island structures are formed, and it can be seen that the shape of the plurality of nano-island structures is well maintained even after the passivation layer is formed.
  • the cesium chloride layer deposited on the glass substrate may be subjected to a dewetting process by absorbing water vapor in the air, and the cesium chloride-based nano-island structure formed through the dewetting process may be a passivation layer.
  • SPC-370 can be used as a passivation layer to increase the scattering effect.
  • 5A to 5D are diagrams for explaining optical characteristics of a nano-island structure according to an embodiment.
  • reference numeral 510 denotes a parallel transmittance characteristic according to a change in wavelength of a plurality of nano-island structures (NIAs)
  • reference numeral 520 denotes a plurality of nano-islands.
  • a diffuse transmittance characteristic according to a change in wavelength of the structure is shown
  • reference numeral 530 denotes a total transmittance characteristic according to a change in wavelength of a plurality of nano-island structures
  • reference numeral 540 denotes a plurality of nano-island structures.
  • 'NIAs (50 nm)' shown in reference numerals 510 to 540 shows the optical properties of a plurality of nano-island structures formed through a cesium chloride layer having a thickness of 50 nm
  • 'NIAs (100 nm)' is a chloride having a thickness of 100 nm
  • 'NIAs (50 nm)/passivation layer' is a plurality of nano-island structures formed through a cesium chloride layer with a thickness of 50 nm and coated with a passivation layer.
  • the optical properties are shown
  • 'NIAs (100 nm)/passivation layer' shows the optical properties of a plurality of nano-island structures formed through a 100 nm thick cesium chloride layer and coated with a passivation layer.
  • the non-diffuse transmittance and diffuse transmittance of 'NIAs (50 nm)' were 66% and 23%, respectively, at a wavelength of 550 nm
  • the non-diffuse transmittance and diffuse transmittance of 'NIAs (100 nm)' were at a wavelength of 550 nm. 45% and 40%, respectively.
  • the non-diffuse transmittance and diffuse transmittance of 'NIAs (50 nm)/passivation layer' were 89% and 4%, respectively, at 550 nm wavelength
  • the non-diffuse transmittance and diffuse transmittance of 'NIAs (100 nm)' were 84% at 550 nm wavelength, respectively. and 9%.
  • the passivation layer is formed in the plurality of nano-island structures, it can be confirmed that the non-diffuse transmittance characteristics and the diffuse transmittance characteristics are improved.
  • the total transmittance of the plurality of nano-island structures can be calculated through the calculation of the arithmetic sum of the parallel transmittance and the diffusion transmittance, and a plurality of nano-island structures without a passivation layer (that is, 'NIAs (50 nm) ' and 'NIAs(100nm)') are more than the total transmittance of a plurality of nanoisland structures (ie, 'NIAs(50nm)/passivation layer' and ''NIAs(100nm)/passivation layer') on which a passivation layer is formed. appeared relatively low.
  • the optical haze value of 'NIAs (50 nm)' is 26%
  • the optical haze value of 'NIAs (100 nm)' is 47%
  • the optical haze value of 'NIAs (50 nm)/passivation layer' is 4%
  • the optical haze value of 'NIAs (100nm)/passivation layer' was 10%.
  • the cesium chloride layer with a thickness of 100 nm The haze value of the nano-island structure formed through the nano-island structure was larger than that of the nano-island structure formed through the cesium chloride layer with a thickness of 50 nm.
  • 6A to 6B are diagrams for explaining luminous efficiency characteristics and chromaticity change characteristics according to a change in thickness of a hole transport layer and a metal thin film layer of an organic light emitting diode according to an exemplary embodiment.
  • reference numeral 610 denotes a contour diagram simulation result of luminous efficiency according to a change in thickness of the hole transport layer and the metal thin film layer
  • reference numeral 620 denotes each chromaticity according to the thickness change of the hole transport layer and the metal thin film layer.
  • the contour plot of the change shows the simulation result.
  • 'A' denotes a case where the thickness of the hole transport layer is 165 nm and the thickness of the metal thin film layer is 16 nm
  • 'B' denotes the case where the thickness of the hole transport layer is 165 nm and the thickness of the metal thin film layer is 24 nm
  • 'C' represents the case where the thickness of the hole transport layer is 175 nm and the thickness of the metal thin film layer is 16 nm
  • 'D' represents the case where the thickness of the hole transport layer is 175 nm and the thickness of the metal thin film layer is 24 nm.
  • the metal thin film layer may be a silver (Ag) thin film layer.
  • the luminous efficiency shows a slight increase of 2% or less, It was found that when the thickness of the hole transport layer was changed from 165 nm to 175 nm, the luminous efficiency increased by 1.3 times.
  • the organic light emitting device showed that the luminous efficiency under the condition of 'D' was improved by 1.4 times compared to the luminous efficiency under the condition of 'A'.
  • each chromaticity change was 0.036 or less under the condition of 'B', and each chromaticity change was 0.019 under the condition of 'D'.
  • the organic light emitting device is designed to optimize the thickness of the hole transport layer based on the optical simulation results of reference numerals 610 to 620 Therefore, high luminous efficiency and stable chromaticity change can be realized at the same time.
  • FIGS. 7A to 7D are diagrams for explaining optical characteristics of an organic light emitting device having a light emitting structure according to an exemplary embodiment.
  • reference numeral 710 shows current density-voltage-luminance (JVL) characteristics of organic light emitting devices (BEOLED A to BEOLED F) designed under different conditions
  • Reference numeral 720 denotes current efficacy-luminance characteristics of organic light emitting devices designed under different conditions
  • reference numeral 730 denotes power efficacy-luminance characteristics of organic light emitting devices designed under different conditions.
  • reference numeral 740 denotes normalized luminance-viewing angle characteristics of organic light emitting devices designed under different conditions.
  • the light emitting structures of the organic light emitting devices BEOLED A to BEOLED F designed under different conditions at reference numerals 710 to 740 may be designed under the conditions shown in Table 1 below.
  • the optical properties of the organic light emitting device described below with reference numerals 710 to 740 are obtained by changing the thickness of the metal thin film layer of the light emitting structure to 16 nm to 24 nm, and changing the thickness of the first hole transport layer to 75 nm to 85 nm. indicates characteristics.
  • BEOLED A, BEOLED B, and BEOLED C having a hole transport layer having a thickness of 75 nm require driving voltages of 4.20V, 4.23V, and 4.23V, respectively, to realize a luminance of 1000cd/m 2 .
  • BEOLED A, BEOLED B, and BEOLED C having a hole transport layer having a thickness of 75 nm had a luminance of 100.7 cd/A, 97.9 cd/A and 92.1 cd/A at a luminance of 1000 cd/m 2 , respectively.
  • Current efficiency was realized, and current efficiencies of 113.6 cd/A, 129.1 cd/A and 134.1 cd/A were realized for BEOLED D, BEOLED E, and BEOLED F with a hole transport layer of 85 nm thickness at a luminance of 1000 cd/m 2 , respectively. , it can be confirmed that this is quite consistent with the efficiency characteristics derived through optical simulation.
  • BEOLED A, BEOLED B, and BEOLED C having a hole transport layer with a thickness of 75 nm realized power efficiency of 61.3 lm/W, 52.5 lm/W, and 44.2 lm/W, respectively, at a luminance of 1000 cd/m 2 , and achieved a thickness of 85 nm. It can be seen that BEOLED D, BEOLED E, and BEOLED F having a hole transport layer realized power efficiency of 74.2 lm/W, 76.0 lm/W, and 72.6 lm/W, respectively, at a luminance of 1000 cd/m 2 .
  • BEOLED F current efficiency and power efficiency of BEOLED F were improved by 1.46 times and 1.64 times compared to BEOLED C
  • BEOLED E current efficiency and power efficiency of BEOLED E were improved by 1.32 times and 1.21 times compared to BEOLED B, and that of BEOLED D.
  • Current efficiency and power efficiency were improved by 1.16 times and 1.21 times compared to BEOLED A.
  • the discrepancy between the improvement of current efficiency and the improvement of power efficiency may be caused by the change in luminance of each organic light emitting device (BEOLED A to BEOLED F), and the power efficiency may be caused by the change in luminance of each organic light emitting device (BEOLED A to BEOLED F). It can be computed by integrating.
  • the increase rate of power efficiency can appear significantly larger than the increase rate of current efficiency when the luminance change is extended in the direction of Lambertian behavior.
  • BEOLED D, BEOLED E and BEOLED F having a hole transport layer of 85 nm thickness is closer to the Lambertian behavior than that of BEOLED A, BEOLED B and BEOLED C having a hole transport layer of 75 nm thickness.
  • FIGS. 8A to 8F are diagrams for explaining each chromaticity change characteristic of an organic light emitting device having a light emitting structure according to an exemplary embodiment.
  • reference numerals 810 to 860 denote wavelength-EL intensity (ie, angular EL) in each of BEOLED A to BEOLED F described with reference to FIGS. 7A to 7D .
  • Spectral change) characteristics, and the plots inserted at reference numerals 810 to 860 show angular chromaticity changes in each of BEOLED A to BEOLED F obtained through operation in the CIE1976 color space.
  • the chromaticity change of the organic light emitting diode having a hole transport layer having a thickness of 75 nm increases as the thickness of the metal thin film layer increases.
  • each chromaticity change and each EL peak wavelength (W p ) change for an angle ranging from 0° to 60° was 0.017 and 2 nm for BEOLED A, 0.028 and 3 nm for BEOLED B, and 0.037 and 5 nm for BEOLED C.
  • each EL peak wavelength (W p ) change according to an increase in the thickness of the metal thin film layer is larger than that of the organic light emitting device having a hole transport layer having a thickness of 75 nm
  • each chromaticity change was less than that of an organic light emitting diode having a hole transport layer having a thickness of 75 nm.
  • each chromaticity change and each EL peak wavelength (W p ) change for an angle ranging from 0 ° to 60 ° was 0.015 and 10 nm for BEOLED D, 0.017 and 13 nm for BEOLED E, and 0.019 and 16 nm for BEOLED F.
  • 9A to 9B are views for explaining each chromaticity trajectory of an organic light emitting device having a light emitting structure according to an exemplary embodiment.
  • reference numeral 910 denotes angular chromaticity loci of BEOLEDs A to BEOLED C having a hole transport layer having a thickness of 75 nm
  • reference numeral 920 denotes a BEOLED having a hole transport layer having a thickness of 85 nm.
  • Each chromaticity locus of D to BEOLED F is shown, and the locus of reference numerals 910 to 920 can be evaluated from the CIE 1976 color space (L', u', v').
  • each chromaticity locus is 0.023 for BEOLED D, 0.033 for BEOLED E, and 0.041 for 'BEOLED F', and the maximum chromaticity change angle of each of BEOLED D, BEOLED E and BEOLED F is appeared to be 40°.
  • the organic light emitting diode according to the exemplary embodiment may reduce each chromaticity change by adjusting the thickness of the device without reducing current efficiency.
  • FIGS. 10A to 10D are diagrams for explaining optical characteristics of an organic light emitting device including a light emitting structure and a nano-island structure according to an exemplary embodiment.
  • reference numeral 1010 denotes current density-voltage-luminance (JVL) characteristics of organic light emitting devices (BEOLED D′ to BEOLED F′) designed under different conditions.
  • Reference numeral 1020 denotes current efficacy-luminance characteristics of organic light emitting devices designed under different conditions
  • reference numeral 1030 denotes power efficiency-luminance characteristics of organic light emitting devices designed under different conditions.
  • -luminance luminance-viewing angle characteristics of organic light emitting devices designed under different conditions.
  • each of BEOLED D' to BEOLED F' denotes BEOLED D' to BEOLED F' having a passivation layer formed to a thickness of 8 ⁇ m and a plurality of nano-island structures having a height of 250 nm or less.
  • BEOLED D', BEOLED E' and BEOLED F' were found to require driving voltages of 4.24V, 4.21V, and 4.19V, respectively, to realize a luminance of 1000cd/m 2 , which is Compared with the driving voltages of BEOLED D, BEOLED E, and BEOLED F described through FIG. 7A, BEOLED D', BEOLED E', and BEOLED F' slightly increased the driving voltage as a plurality of nano-island structures were formed on the substrate. can confirm that
  • current efficiency and power efficiency are 107.7 cd/A and 73.0 lm/W for BEOLED D', 125.4 cd/A and 74.2 lm/W for BEOLED E', and 130.7 cd/A for BEOLED F'. and 71.5 lm/W.
  • the organic light emitting devices (BEOLED D' to BEOLED F') having the light emitting structure and the nano-island structure according to an embodiment are compared to the organic light emitting devices (BEOLED D to BEOLED F) not having the nano-island structure. It was found that the optical efficiency decreased slightly, but the decrease rate of the efficiency was not large.
  • 11A to 11D are diagrams for explaining each chromaticity change characteristic of an organic light emitting device including a light emitting structure and a nano-island structure according to an exemplary embodiment.
  • reference numerals 1110 to 1130 denote each wavelength-EL intensity (ie, each EL ( angular EL) spectral change) characteristics, and the plots inserted at 1110 to 1130 are angular chromaticity changes in each of BEOLED D' to BEOLED F' obtained through operation in the CIE1976 color space. ) is shown.
  • reference numeral 1140 denotes angular chromaticity loci of BEOLED D' to BEOLED F'.
  • each chromaticity change and each EL peak wavelength (W p ) change for an angle ranging from 0 ° to 60 ° is 0.013 and 9 nm for BEOLED D', 0.014 and 12 nm for BEOLED E', and 0.014 and 12 nm for BEOLED F. ' appeared as 0.016 and 13 nm.
  • the organic light emitting devices (BEOLED D' to BEOLED F') having the nano-island structure according to the exemplary embodiment do not include the nano-island structure according to the exemplary embodiment as described with reference to FIGS. 10A to 10D.
  • the optical efficiency is slightly decreased, but it can be seen that each chromaticity change is significantly improved (suppressed).
  • each chromaticity locus was 0.013 for BEOLED D', 0.014 for BEOLED E, and 0.016 for 'BEOLED F'.
  • 12A to 12B are diagrams for explaining pixel blur characteristics of an organic light emitting diode according to an exemplary embodiment.
  • reference numeral 1210 denotes a result of brightness information conversion of pixel images corresponding to the organic light emitting devices BEOLED D, BEOLED D′, and BEOLED D′′, and reference numeral 1210 denotes a result of brightness information conversion.
  • 1220 shows pixel blur distance profiles derived from edges of each organic light emitting device.
  • BEOLED D'' denotes an organic light emitting device to which a plurality of microlens arrays (MLAs) having a diameter of 80 ⁇ m are applied.
  • MLAs microlens arrays
  • pixel blur distances of BEOLED D, BEOLED D', and BEOLED D'', each having a pixel area of 4 mm 2 were found to be 160 ⁇ m, 191 ⁇ m, and 594 ⁇ m, respectively. This indicates that the nano-island structure according to the exemplary embodiment is much more effective in suppressing the blur of the pixel due to the low haze characteristics and the nano-sized scattering pattern compared to the conventional microlens.
  • FIG. 13 is a view for explaining a method of manufacturing an organic light emitting device according to an exemplary embodiment.
  • FIG. 13 is a view for explaining a method of manufacturing an organic light emitting device according to an exemplary embodiment described with reference to FIGS. 1 to 12B .
  • FIG. 13 illustrates a view for explaining a method of manufacturing an organic light emitting device according to an exemplary embodiment described with reference to FIGS. 1 to 12B .
  • the contents described with reference to FIGS. 1 to 12B are omitted.
  • a plurality of nano-island structures may be formed on a substrate.
  • a nano-island structure is formed through a dewetting process of an inorganic material layer deposited on a substrate, but the thickness of the deposited inorganic material layer and the dewetting process
  • the diameter and height of the nano-island structure may be determined by at least one of a temperature condition and a humidity condition.
  • the method of manufacturing an organic light emitting device is cesium chloride (CsCl), cesium fluoride (CsF), cesium iodide (CsI), cesium bromide (CsBr), calcium chloride (CaCl) 2 ) and an inorganic material layer including at least one of lanthanum chloride (LaCl 3 ) is deposited on a substrate to a thickness of 50 nm to 10 nm, and a dewetting process of the deposited inorganic material layer is performed to form a nano-island structure.
  • the inorganic layer may be a cesium chloride layer.
  • step 1310 in the method of manufacturing an organic light emitting device according to an embodiment, a dewetting process is performed on the inorganic material layer deposited at a temperature of 30° C. and a relative humidity of 60% to form a nano-island structure. have.
  • the method of manufacturing an organic light emitting device may form a passivation layer that blocks exposure of the nano-island structure to air.
  • a light emitting structure may be formed on a substrate.
  • the light emitting structure may include an anode electrode, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode electrode sequentially formed on a substrate.
  • the light emitting structure may further include a metal thin film layer formed between the substrate and the anode electrode, and a capping layer formed between the substrate and the metal thin film layer.
  • the metal thin film layer may be a silver (Ag) thin film layer.
  • the hole transport layer may include a first hole transport layer formed on an adjacent surface of the anode electrode, a hole generating layer formed on the first hole transport layer, and a second hole transport layer formed on the hole generating layer.
  • the method of manufacturing an organic light emitting device includes a capping layer, a metal thin film layer, an anode electrode, a first hole transport layer, a hole generating layer, a second hole transport layer, an electron blocking layer, a light emitting layer, an electron on a substrate.
  • a transport layer, an electron injection layer, and a cathode electrode may be sequentially formed.
  • the method of manufacturing an organic light emitting device deposits an organic layer at a deposition rate of 1 ⁇ /s or less under a vacuum condition of 5 x 10 -5 Pa, and , the electron injection layer and the cathode electrode can be deposited at deposition rates of 0.15 ⁇ /s and 2.5 ⁇ /s, respectively.
  • 14A to 14C are diagrams for explaining in more detail a method of forming a plurality of nano-island structures in a method of manufacturing an organic light emitting device according to an exemplary embodiment.
  • FIGS. 14A to 14C may be performed in operation 1310 of FIG. 13 .
  • an inorganic material layer 1412 may be deposited on a glass substrate 1411 .
  • the inorganic material layer 1412 may be a cesium chloride layer.
  • step 1410 in the method of manufacturing an organic light emitting device according to an embodiment, the glass substrate 1411 is continuously washed with acetone, isopropyl alcohol, and deionized water (DI) before the cesium chloride layer is deposited. After that, a pretreatment process of exposure to UV (ultraviolet rays) and ozone can be performed.
  • DI deionized water
  • a pretreated glass substrate 1411 is inserted into a vacuum chamber, and then, an inorganic material powder is placed on the glass substrate 1411 using thermal evaporation.
  • an inorganic material powder may be deposited at a deposition rate of 1 ⁇ /s or less to form the inorganic material layer 1412 .
  • a plurality of nano-island structures NI may be formed on the glass substrate 1411 through a dewetting process of the deposited inorganic layer 1412 .
  • the inorganic material layer 1412 deposited in an environment of a temperature of 30° C. and a relative humidity of 60% may be exposed to the air, and in this process, air
  • the inorganic material layer 1412 exposed therein absorbs water vapor through a dewetting process, and may be changed into a plurality of nano-island structures (NI), in which case the plurality of nano-island structures (NI) is a glass substrate 1411 . may be randomly distributed over the phase.
  • step 1430 the method of manufacturing an organic light emitting device according to an embodiment is performed by coating a passivation layer 1431 on a glass substrate 1411 on which a plurality of nano-island structures (NI) are formed using a spin coating method.
  • a phenomenon in which the plurality of nano-island structures NI are exposed to the air and are dissolved or volatilized may be prevented.
  • step 1430 in the method of manufacturing an organic light emitting device according to an embodiment, after coating the passivation layer 1431 , the coated passivation layer 1431 may be cured by UV treatment.
  • the present invention it is possible to effectively control the dependence of the viewing angle of the organic light emitting device by forming the nano-island structure on the substrate.
  • the present invention can improve angular chromaticity change through the implementation of a low pixel blurring effect due to the nano-island structure formed on the substrate.
  • a nano-island structure can be easily formed even on a large-area display device by using thermal evaporation.
  • the present invention can improve each chromaticity change and luminous efficiency by strengthening the microcavity characteristics based on the thickness optimization of the hole transport layer and the anode electrode.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

La présente invention concerne une diode électroluminescente organique comprenant des structures en nano-ilôt et son procédé de fabrication. Une diode électroluminescente organique selon un mode de réalisation comprend : un substrat comportant une pluralité de structures de nano-îlot ; et une structure électroluminescente formée sur le substrat, les structures de nano-îlot étant formées par un processus de démouillage d'une couche inorganique déposée sur le substrat, et le diamètre et la hauteur de celui-ci peuvent être déterminés par au moins l'une de l'épaisseur de la couche inorganique déposée, et des conditions de température et d'humidité dans le processus de démouillage.
PCT/KR2021/004043 2020-04-01 2021-04-01 Diode électroluminescente organique comprenant une structure en nano-ilôt et son procédé de fabrication WO2021201621A1 (fr)

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KR20200039749 2020-04-01
KR10-2020-0039749 2020-04-01
KR10-2021-0042075 2021-03-31
KR1020210042075A KR102477831B1 (ko) 2020-04-01 2021-03-31 나노-섬 구조체를 포함하는 유기 발광소자 및 그 제조방법

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KR20050015902A (ko) * 2003-08-14 2005-02-21 엘지전자 주식회사 유기 ｅｌ 소자 및 그 제조방법
KR20120059483A (ko) * 2009-06-15 2012-06-08 애스트론 피암 세이프티 기판 평탄화층을 가지는 유기 발광 다이오드 및 이를 만드는 방법
KR20120105951A (ko) * 2011-03-17 2012-09-26 한국과학기술원 강유전체 폴리머 나노도트 소자 및 그 제조를 위한 디웨팅 프로세스
KR20140109122A (ko) * 2013-03-05 2014-09-15 코닝정밀소재 주식회사 광추출 효율이 향상된 유기발광소자용 기판, 그 제조방법 및 이를 포함하는 유기발광소자
US20160158798A1 (en) * 2011-11-30 2016-06-09 Corning Incorporated Metal dewetting methods and articles produced thereby

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20050015902A (ko) * 2003-08-14 2005-02-21 엘지전자 주식회사 유기 ｅｌ 소자 및 그 제조방법
KR20120059483A (ko) * 2009-06-15 2012-06-08 애스트론 피암 세이프티 기판 평탄화층을 가지는 유기 발광 다이오드 및 이를 만드는 방법
KR20120105951A (ko) * 2011-03-17 2012-09-26 한국과학기술원 강유전체 폴리머 나노도트 소자 및 그 제조를 위한 디웨팅 프로세스
US20160158798A1 (en) * 2011-11-30 2016-06-09 Corning Incorporated Metal dewetting methods and articles produced thereby
KR20140109122A (ko) * 2013-03-05 2014-09-15 코닝정밀소재 주식회사 광추출 효율이 향상된 유기발광소자용 기판, 그 제조방법 및 이를 포함하는 유기발광소자

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