Patent Grant
11515363
This application claims priority to Korean Patent Application No. 10-2020-0120523, filed on Sep. 18, 2020, in the Korean Intellectual Property Office, and all the benefits accruing therefrom under 35 U.S.C. § 119, the disclosure of which is incorporated by reference herein in its entirety.
The present disclosure relates to a display apparatus.
A display apparatus is used to visually communicate data and information. A display apparatus may be used as a display unit for a small product such as a mobile phone or for commercial equipment, or as a display unit for a large product such as a television. A display apparatus includes a plurality of pixels that emit light by receiving an electrical signal resulting in an image. Each pixel includes a light-emitting element. For example, in the case of an organic light-emitting display apparatus, the light-emitting element is an organic light-emitting diode (OLED). In general, an organic light-emitting display apparatus includes a thin film transistor and an organic light-emitting diode positioned on a substrate whereby the organic light-emitting diode emits light.
In an OLED type display apparatus including a plurality of quantum dot color conversion elements and color filters, a blue-OLED structure, a white-OLED structure, or a green-OLED structure may be used as an incident light source.
Provided are display apparatuses having high performance.
Provided are display apparatuses in which incident green light and incident blue light are used as a light source that is provided with an organic light emitting diode (OLED), and a plurality of quantum dot color conversion elements and a plurality of color filter elements are used.
Provided are display apparatuses having high luminous efficiency and high color reproducibility by using incident green light from an OLED unit.
Additional aspects will be set forth in part in the description which follows and, in part, will be apparent from the description, or may be learned by practice of the presented embodiments of the disclosure.
According to an aspect of an embodiment, a display apparatus includes:
an organic light emitting diode (OLED) structure including at least one blue light-emitting unit configured to emit blue incident light and at least one green light-emitting unit configured to emit green incident light are stacked to provide incident light in which the blue incident light and the green incident light are mixed; a first pixel, a second pixel, and a third pixel disposed on the OLED structure and respectively configured to emit a first color light, a second color light, and a third color light;
at least two color conversion layers each separately disposed on at least two of the first, the second, or the third pixels, and including quantum dots for converting the mixed incident light from the OLED structure into light of a predetermined color; and
first, second, and third color filters disposed on the first, the second, and the third pixels, respectively, to absorb or block light of a predetermined wavelength band, wherein a conversion value (R) of an area of a spectrum in a wavelength region of 380 nanometers to 780 nanometers of the green incident light with respect to a difference between a maximum transmittance wavelength of the second color filter and the medial wavelength of the green incident light (Δλ) is 3.6 or greater and 13 or less,
wherein, the area of the spectrum is determined according to Equation 1 below,
in Equation 1, f(x) is a spectrum of the green incident light in which the maximum value of the light intensity is normalized to 1, and the medial wavelength is a wavelength dividing the area of the spectrum of the green incident light into two equal halves, and the conversion value is determined according to Equation 3.
R=Area/Δλ Equation 3
The OLED structure may have a tandem structure.
The OLED structure may include a first blue light-emitting unit, a green light-emitting unit, and a second blue light-emitting unit sequentially stacked, and the green light-emitting unit may be disposed between the first and second blue light-emitting units.
The display apparatus may further include a first charge generation layer disposed between the first blue light-emitting unit and the green light-emitting unit, and a second charge generation layer disposed between the green light-emitting unit and the second blue light-emitting unit.
The green light-emitting unit may include an organic material-based green light-emitting layer, and the green light-emitting layer may include a thermally activated delayed fluorescence (TADF) dopant.
The green light-emitting unit may include an organic material-based green light emitting layer, the green light-emitting layer may include a phosphorescent dopant, and the phosphorescent dopant may satisfy T1(dopant)≤S1(dopant)≤T1(dopant)+0.5 eV, where T1 (dopant) is a triplet energy level in eV and S1 (dopant) is a singlet energy level in eV of the phosphorescent dopant.
The phosphorescent dopant may be an organometallic compound including iridium Ir.
The phosphorescent dopant may be an organometallic compound including platinum Pt, osmium Os, titanium Ti, zirconium Zr, hafnium Hf, europium Eu, terbium Tb, thulium Tm, rhodium Rh, ruthenium Ru, rhenium Re, beryllium Be, magnesium Mg, aluminum Al, calcium Ca, manganese Mn, cobalt Co, copper Cu, zinc Zn, gallium Ga, germanium Ge, rhodium Rh, palladium Pd, silver Ag, or gold Au.
The phosphorescent dopant may be an organometallic compound having a square-planar coordination structure.
The phosphorescent dopant may include a metal M and an organic ligand, and the metal M and the organic ligand may form one, two or three cyclometallated rings in the organometallic compound.
The phosphorescent dopant may include a metal M and a four-coordinate organic ligand capable of forming 3 or 4 cyclometallated rings, the metal M may include platinum Pt, osmium Os, titanium Ti, zirconium Zr, hafnium Hf, europium Eu, terbium Tb, thulium Tm, rhodium Rh, ruthenium Ru, rhenium Re, beryllium Be, magnesium Mg, aluminum Al, calcium Ca, manganese Mn, cobalt Co, copper Cu, zinc Zn, gallium Ga, germanium Ge, rhodium Rh, palladium Pd, silver Ag, or gold Au, and the four-coordinate organic ligand may include a benzimidazole group or a pyridine group.
The first color filter may be a blue cut filter, and the second color filter may be a blue and green cut filter.
The first color filter may be an absorption-type green color filter, and the second color filter may be an absorption-type red color filter.
The third color filter may be a green cut filter or an absorption-type blue color filter.
The display apparatus may further include a fourth pixel, and the fourth pixel is configured to emit a color different from that of the first, the second, and the third pixels.
The fourth pixel may be a blank region.
The above and other aspects, features, and advantages of certain embodiments of the disclosure will be more apparent from the following description taken in conjunction with the accompanying drawings, in which:
The display apparatuses according to embodiments will be described in detail with reference to the accompanying drawings. In the drawings, widths and thicknesses of layers and regions may be exaggerated for clarity and convenience of explanation of the specification. Like reference numerals refer to like elements throughout the specification.
The advantages, features, and methods of achieving the advantages may be clear when referring to the embodiments described below together with the drawings. However, the disclosure may have different forms and should not be construed as being limited to the descriptions set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
It will be understood that when an element is referred to as being “on” another element, it can be directly on the other element or intervening elements may be present therebetween. In contrast, when an element is referred to as being “directly on” another element, there are no intervening elements present. Hereafter, the disclosure will be described more fully with reference to the accompanying drawings, in which embodiments of the disclosure are shown. In describing the disclosure with reference to drawings, like reference numerals are used for elements that are substantially identical or correspond to each other, and the descriptions thereof will not be repeated.
In the following descriptions, it will be understood that, although the terms “first”, “second”, etc., may be used to describe various elements, components, regions, layers, and/or sections, these elements, components, regions, layers, and/or sections, should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer, or section from another element, component, region, layer, or section. Thus, “a first element,” “component,” “region,” “layer,” or “section” discussed below could be termed a second element, component, region, layer, or section without departing from the teachings herein.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. As used herein, the singular forms “a,” “an,” and “the” are intended to include the plural forms, including “at least one,” unless the content clearly indicates otherwise. “At least one” is not to be construed as limiting “a” or “an.” “Or” means “and/or.” As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items. It will be further understood that the terms “comprises,” “comprising,” “includes,” and/or “including,” when used in this specification, specify the presence of stated features, regions, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, regions, integers, steps, operations, elements, components, and/or groups thereof.
Furthermore, relative terms, such as “lower” or “bottom” and “upper” or “top,” may be used herein to describe one element's relationship to another element as illustrated in the Figures. It will be understood that relative terms are intended to encompass different orientations of the device in addition to the orientation depicted in the Figures. For example, if the device in one of the figures is turned over, elements described as being on the “lower” side of other elements would then be oriented on “upper” sides of the other elements. The exemplary term “lower,” can therefore, encompasses both an orientation of “lower” and “upper,” depending on the particular orientation of the figure.
“About” or “approximately” as used herein is inclusive of the stated value and means within an acceptable range of deviation for the particular value as determined by one of ordinary skill in the art, considering the measurement in question and the error associated with measurement of the particular quantity (i.e., the limitations of the measurement system). For example, “about” can mean within one or more standard deviations, or within 10% of the stated value.
Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the present disclosure, and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
Exemplary embodiments are described herein with reference to cross section illustrations that are schematic illustrations of idealized embodiments. As such, variations from the shapes of the illustrations as a result, for example, of manufacturing techniques and/or tolerances, are to be expected. Thus, embodiments described herein should not be construed as limited to the particular shapes of regions as illustrated herein but are to include deviations in shapes that result, for example, from manufacturing. For example, a region illustrated or described as flat may, typically, have rough and/or nonlinear features. Moreover, sharp angles that are illustrated may be rounded. Thus, the regions illustrated in the figures are schematic in nature and their shapes are not intended to illustrate the precise shape of a region and are not intended to limit the scope of the present claims.
The term “substituted” refers to the replacement of a hydrogen in a compound, for example, a hydrogen on a ring carbon or an amine hydrogen, with deuterium, —F, —Cl, —Br, —I, —SF5, a hydroxyl group, a cyano group, a nitro group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or salt thereof, a sulfonic acid group or salt thereof, a phosphoric acid group or salt thereof, a substituted or unsubstituted C1-C60 alkyl group, a substituted or unsubstituted C2-C60 alkenyl group, a substituted or unsubstituted C2-C60 alkynyl group, a substituted or unsubstituted C1-C60 alkoxy group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C1-C10 heterocycloalkyl group, a substituted or unsubstituted C3-C10 cycloalkenyl group, a substituted or unsubstituted C1-C10 hetero-cycloalkenyl group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C6-C60 aryloxy group, a substituted or unsubstituted C6-C60 arylthio group, a substituted or unsubstituted C1-C60 heteroaryl group, a substituted or unsubstituted monovalent non-aromatic condensed polycyclic group, or a substituted or unsubstituted monovalent non-aromatic heterocondensed polycyclic group.
When a certain embodiment may be implemented differently, a specific process order may be performed differently from the described order. For example, two consecutively described processes may be performed substantially at the same time or performed in an order opposite to the described order.
In the following embodiments, when a film, a region, a constituent element, etc. are connected, it may include a case when a film, a region, a constituent element is directly connected or/and a case when the film, the region, and the components are indirectly connected by intervening another film, a region, a constituent element therebetween. For example, in the specification, when a film, a region, a constituent element, etc. are electrically connected, it may represent when a film, region, constituent element, etc. are directly electrically connected, and/or another film, region, component, etc. are indirectly electrically connected by intervening another film, region, constituent element, etc. there between.
The x-axis, y-axis, and z-axis are not limited to three axes on a Cartesian coordinate system, and may be interpreted in a broad sense including the Cartesian coordinate system. For example, the x-axis, y-axis, and z-axis may be orthogonal to each other, but may refer to different directions that are not orthogonal to each other.
Referring to
In
Referring to
A second substrate 300 may be provided on the first substrate 100. The second substrate 300 may face the first substrate 100 and constituent elements formed on the first substrate 100 are disposed between the first substrate 100 and the second substrate 300. As depicted in
The display area DA may be covered by a thin film encapsulation layer 400 to protect the display components from outside air or moisture, etc. Because an OLED is vulnerable to external factors, such as moisture and oxygen, the reliability of the display apparatus 1 may be improved by sealing the pixels P1, P2, and P3 as well as other OLED components with the thin film encapsulation layer 400. In this way, when the thin film encapsulation layer 400 is provided as described above, the thickness of the display apparatus 1 may be reduced and, at the same time, the flexibility may be improved.
As shown in
The first scan driving circuit 120 may provide a scan signal to each of the pixels P1, P2, and P3 through a scan line SL. The first scan driving circuit 120 may provide an emission control signal to each pixel through an emission control line EL. The second scan driving circuit 130 may be disposed in parallel with the first scan driving circuit 120 with the display area DA therebetween.
A control signal generated by a controller may be transmitted to the first and second scan driving circuits 120 and 130 respectively through a printed circuit board. The controller may provide first and second power voltages ELVDD and ELVSS to the first and second power supply wirings 160 and 170, respectively. The first power voltage ELVDD may be provided to each of the pixels P1, P2, and P3 through a driving voltage line PL connected to the first power supply line 160, and the second power voltage ELVSS may be provided to counter electrodes of each of the pixels P1, P2, and P3 connected to the second power supply line 170.
The data driving circuit is electrically connected to a data line DL. A data signal of the data driving circuit may be provided to each of the pixels P1, P2, and P3 through the data line DL.
Referring to
The OLED structure 10 may be disposed under the first pixel P1, the second pixel P2, and the third pixel P3. The OLED structure 10 may be referred to as a light source OLED. The OLED structure 10 may include a stacked structure of at least one blue light-emitting unit and at least one green light-emitting unit.
The color conversion unit 20 may include the color filters 20R, 20G, and 20B and the color conversion layers 21R and 21G. Incident light emitted from the OLED structure 10 may be emitted as the first color light Lr, the second color light Lg, and the third color light Lb, respectively, after passing through the color filters 20R, 20G, and 20B, respectively, and the color conversion layers 21R and 21G.
The color filters 20R, 20G, and 20B and the color conversion layers 21R and 21G may be located directly on the second substrate 300. The term “directly located on the second substrate 300” denotes that the color conversion unit 20 is formed by directly forming the color filters 20R, 20G, 20B on the second substrate 300. Afterwards, the OLED structure 10 and the color conversion unit 20 may be bonded together in a state that the color filters 20R, 20G, and 20B, respectively, and the color conversion layers 21R and 21G, face the first pixel P1, the second pixel P2, and the third pixel P3.
Referring to
For example, as depicted in
As shown in
Referring to
Referring to
Light scattered by the scattering particles SP may be converted into second color light by the quantum dots QD included in the second color conversion layer 21G. For example, the quantum dots QD included in the second color conversion layer 21G are excited by the incident light I, and thus, may emit second intermediate light Lg′ having a wavelength greater than that of blue light in a relatively distributive manner.
As an example, the wavelength of light generated from the quantum dot (QD) may be determined by a size, material, or structure of particles (quantum dots). Specifically, when light having a wavelength greater than an energy band interval is incident on the quantum dots QD, the quantum dots QD are excited by absorbing the energy of the incident light and then emit light of a specific wavelength. In this case, as the size of the quantum dots (QD) decreases, light of a relatively short wavelength, for example, blue light or green light may be generated, and as the size of the quantum dots QD increases, light of a relatively long wavelength, for example, red light may be generated. Accordingly, light of various colors may be implemented according to the size of the quantum dots QD. Quantum dots QD that may emit green light may be referred to as green quantum dot particles, and quantum dots QD that may emit red light may be referred to as red quantum dot particles. For example, the green quantum dots QD may be particles having a width (diameter) in a range of about 2 nm to about 3 nm, and the red light quantum dots QD may be particles having a width (diameter) in a range of about 5 nm to about 6 nm. An emission wavelength may be controlled not only by the size (diameter) of the quantum dots (QD), but also by the constituent materials and structures.
The second intermediate light Lg′ converted by the second color conversion layer 21G may enter the second color filter 20G. The second color filter 20G according to an embodiment may block a wavelength of a blue region remaining in the second intermediate light Lg′ that has passed through the second color conversion layer 21G. Accordingly, the second color light Lg that has passed through the second color filter 20G may include only light of a predetermined wavelength band, that is, green light.
The second color filter 20G according to an embodiment may be a blue-cut filter. Accordingly, color control/filtering characteristics may be improved by the second color filter 20G. The second color filter 20G according to an embodiment may be, for example, a distributed Bragg reflector (DBR) structure. A DBR structure that transmits or reflects only a desired wavelength band may be formed by repeatedly stacking two material layers (dielectrics) having different refractive indices but controlling the thickness and the number of layers of the material layers. For example, the reflectance or transmittance of a desired wavelength band may be increased by repeatedly stacking a SiO2 layer and a TiO2 layer under a λ/4 condition (where A is the wavelength of light) and controlling the thickness and number of layers. The DBR structure is well known, and thus, the detailed descriptions thereof will be omitted. However, the present disclosure is not limited thereto, and the second color filter 20G may have a structure other than a DBR structure, for example, a high-contrast grating (HCG) structure.
Referring to
The first blue light-emitting unit 11 may include a first blue light-emitting layer EML1 including an organic material-based blue light-emitting material, and may further include a first hole transport layer HTL1 and a first electron transport layer ETL1. The first hole transport layer HTL1 may be disposed between the first blue light-emitting layer EML1 and the first electrode 14, and the first electron transport layer ETL1 may be disposed between the first blue light-emitting layer EML1 and the first charge generation layer 16.
The green light-emitting unit 12 may include a green light-emitting layer EML2 including an organic material-based green light-emitting material, and may further include a second hole transport layer HTL2 and a second electron transport layer ETL2.
The second blue light-emitting unit 13 may include a second blue light-emitting layer EML3 including an organic material-based blue light emitting material, and may further include a third hole transport layer HTL3 and a third electron transport layer ETL3. Although not shown, each of the first blue light-emitting unit 11, the green light-emitting unit 12, and the second blue light-emitting unit 13 may further include at least one of a hole injection layer and an electron injection layer. The first and second charge generation layers 16 and 17 may include a metal or a metallic material, and may increase the luminous efficiency of the OLED structure 10.
Hereinafter, a blue light-emitting material included in the first blue light-emitting unit 11 and the second blue light-emitting unit 13 and a green light-emitting material included in the green light-emitting unit 12 of the display apparatus 1 according to the embodiment will be described.
The green light-emitting material or blue light-emitting material may include a phosphorescent dopant. The phosphorescent dopant may be selected from, for example, compounds PD1 to PD25, but is not limited thereto.
As described above, the phosphorescent dopant may include an organometallic compound including iridium Ir, an organometallic compound including platinum Pt, or an organometallic compound including osmium Os. Besides above, various materials may be applied as phosphorescent dopants.
A light-emitting layer of the green light-emitting unit (green organic light-emitting device) 12 may include an electron transport host, a hole transport host, and a dopant. The dopant may be an organometallic compound, and the dopant may or may not include iridium Ir. That is, the dopant may be an iridium-including or iridium-free organometallic compound. The dopant in the light-emitting layer of the green light-emitting unit (green organic light-emitting device) 12 may include a phosphorescent compound. The organic green light-emitting device may be explicitly distinguished from an organic light-emitting device that emits fluorescence by a fluorescence mechanism.
According to an embodiment, the dopant in the light-emitting layer may satisfy T1 (dopant)≤S1(dopant)≤T1(dopant)+0.5 eV, for example, T1(dopant)≤S1(dopant)≤T1(dopant)+0.36 eV, but is not limited thereto. Here, T1 (dopant) is a triplet energy level with a value in eV of a dopant in the light-emitting layer, and S1 (dopant) is a singlet energy level with a value in eV of a dopant included in the light-emitting layer. Since the S1 (dopant) satisfies the range described above, the dopant in the light-emitting layer may have a high radiative decay rate even though spin-orbit coupling (SOC) with the singlet energy level close to the triplet energy level is weak.
For example, the dopant may be an organometallic compound including iridium (Ir), or an organometallic compound including platinum Pt, osmium Os, titanium Ti, zirconium Zr, hafnium Hf, europium Eu, terbium Tb, thulium Tm, rhodium Rh, ruthenium Ru, rhenium Re, beryllium Be, magnesium Mg, aluminum Al, calcium Ca, manganese Mn, cobalt Co, copper Cu, zinc Zn, gallium Ga, germanium Ge, rhodium Rh, palladium Pd, silver Ag, or gold Au. For example, the dopant may be an organometallic compound including platinum Pt or palladium Pd, but is not limited thereto.
According to another embodiment, the dopant in the light-emitting layer may be an organometallic compound having a square-planar coordination structure.
Also, according to another embodiment, the dopant in the light-emitting layer may satisfy T1 (dopant)≤Egap (dopant)≤T1 (dopant)+0.5, but is not limited thereto. Here, T1 (dopant) is a triplet energy level in eV of a dopant in the light-emitting layer, and Egap (dopant) is an energy difference between HOMO (dopant) and LUMO (dopant) of a dopant included in the light-emitting layer. The HOMO (dopant) is a highest occupied molecular orbital (HOMO) energy level eV of the dopant included in the light-emitting layer, and the LUMO (dopant) is a lowest unoccupied molecular orbital (LUMO) energy level eV of the dopant included in the light-emitting layer. The HOMO (dopant) and LUMO (dopant) are negative values measured by using differential pulse voltammetry using ferrocene as a reference material, and the T1 (dopant) is calculated from a peak wavelength of a phosphorescence spectrum of the dopant measured by using a luminescence measuring device. The dopant in the light-emitting layer may satisfy −2.8 eV≤LUMO (dopant)≤−2.3 eV, −2.8 eV≤LUMO (dopant)≤−2.4 eV, −2.7 eV≤LUMO (dopant)≤−2.5 eV, or −2.7 eV≤LUMO (dopant)≤−2.61 eV.
According to another embodiment, the dopant in the light-emitting layer may satisfy −6.0 eV≤HOMO (dopant)≤−4.5 eV, −5.7 eV≤HOMO (dopant)≤−5.1 eV, −5.6 eV≤HOMO (dopant)≤−5.2 eV, or −5.6 eV≤HOMO (dopant)≤−5.25 eV.
According to another embodiment, the dopant may include a metal M and an organic ligand, and the metal M and the organic ligand may form 1, 2 or 3 cyclometallated rings. The metal M is iridium Ir, platinum Pt, osmium Os, titanium Ti, zirconium Zr, hafnium Hf, europium Eu, terbium Tb, thulium Tm, Rhodium Rh, ruthenium Ru, rhenium Re, beryllium Be, magnesium Mg, aluminum Al, calcium Ca, manganese Mn, cobalt Co, copper Cu, zinc Zn, gallium Ga, germanium Ge, rhodium Rh, palladium Pd, silver Ag, or gold Au.
According to another embodiment, the dopant may include a metal M and a four-coordinate organic ligand capable of forming 3 or 4 (e.g., 3) cyclometallated rings. With regards to the description of the metal M, refer to the descriptions made in this specification. The four-coordinate organic ligand may structurally include, for example, a benzimidazole group and/or a pyridine group, but is not limited thereto.
According to another embodiment, the dopant may include a metal M and at least one ligand from among ligands represented by Formulas 1-1 to 1-4 below.
For example, when the metal M is iridium Ir, the metal M may be combined with a ligand of Formula 1-1, and when the metal M is platinum Pt, the metal M may be combined with the ligands represented by Formulas 1-2 to 1-4. When the metal M is osmium Os, titanium Ti, zirconium Zr, hafnium Hf, europium Eu, terbium Tb, thulium Tm, rhodium Rh, ruthenium Ru, rhenium Re, beryllium Be, magnesium Mg, aluminum Al, calcium Ca, manganese Mn, cobalt Co, copper Cu, zinc Zn, gallium Ga, germanium Ge, rhodium Rh, palladium Pd, silver Ag, or gold Au, the metal M may be combined with any one of the ligands represented by Formulas 1-1 to 1-4.
In Formulas 1-1 to 1-4,
A1 to A4 may be each independently a substituted or unsubstituted C5-C30 carbocyclic group, a substituted or unsubstituted C1-C30 heterocyclic group, or a non-cyclic group,
Y11 to Y14 may be each independently a chemical bond, O, S, N(R91), B(R91), P(R91) or C(R91)(R92),
T1 to T4 may be each independently a single bond, a double bond, *—N(R93)—*′, *—B(R93)—*′, *—P(R93)—*′, *—C(R93)(R94)—*′, *—Si(R93)(R94)—*′, *—Ge(R93)(R94)—*′, *—S—*′, *—Se—*′, *—O—*′, *—C(═O)—*′, *—S(═O)—*′, *—S(═O)2—*′, *—C(R93)=*′, *=C(R93)—*′, *—C(R93)═C(R94)—*′, *—C(═S)—*′, or *—C≡C—*′,
The substituent of the substituted C5-C30 carbocyclic group, the substituent of the substituted C1-C30 heterocyclic group, and R91 to R94 may be each independently hydrogen, deuterium, —F, —Cl, —Br, —I, —SF5, a hydroxyl group, a cyano group, a nitro group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or salt thereof, a sulfonic acid group or salt thereof, a phosphoric acid group or salt thereof, a substituted or unsubstituted C1-C60 alkyl group, a substituted or unsubstituted C2-C60 alkenyl group, a substituted or unsubstituted C2-C60 alkynyl group, a substituted or unsubstituted C1-C60 alkoxy group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C1-C10 heterocycloalkyl group, a substituted or unsubstituted C3-C10 cycloalkenyl group, a substituted or unsubstituted C1-C10 hetero-cycloalkenyl group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C6-C60 aryloxy group, a substituted or unsubstituted C6-C60 arylthio group, a substituted or unsubstituted C1-C60 heteroaryl group, a substituted or unsubstituted monovalent non-aromatic condensed polycyclic group, a substituted or unsubstituted monovalent non-aromatic heterocondensed polycyclic group, —N(Q1)(Q2), —Si(Q3)(Q4)(Q5), —B(Q6)(Q7), or —P(═O)(Q8)(Q9), wherein Q1 to Q9 are each independently —CH3, —CD3, —CD2H, —CDH2, —CH2CH3, —CH2CD3, —CH2CD2H, —CH2CDH2, —CHDCH3, —CHDCD2H, —CHDCDH2, —CHDCD3, —CD2CD3, —CD2CD2H, or —CD2CDH2; an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a sec-pentyl group, a tert-pentyl group, a phenyl group, or a naphthyl group, and
*1, *2, *3 and *4 are bonding sites of the dopant with the metal M, respectively.
For example, the dopant may include a ligand represented by Formula 1-3, and any two of A1 to A4 in Formula 1-3 respectively may be a substituted or unsubstituted benzimidazole group and a substituted or unsubstituted pyridine group, but is not limited thereto.
According to another embodiment, the dopant may be an organometallic compound represented by Formula 1A.
In Formula 1A,
M represents beryllium Be, magnesium Mg, aluminum Al, calcium Ca, titanium Ti, manganese Mn, cobalt Co, copper Cu, zinc Zn, gallium Ga, germanium Ge, zirconium Zr, ruthenium Ru, rhodium Rh, palladium Pd, silver Ag, rhenium Re, platinum Pt or gold Au,
X1 represents O or S, and a bond between X1, and M is a covalent bond,
X2 to X4 are each independently C or N,
at least one of a bond between X2 and M, a bond between X3 and M, and a bond between X4 and M is a covalent bond, and the other two bonds are coordination bonds,
Y1 and Y3 to Y5 are each independently C or N,
a bond between X2 and Y3, a bond between X2 and Y4, a bond between Y4 and Y5, a bond between Y5 and X51, and a bond between X51 and Y3 are chemical bonds,
CY1 to CY5 are each independently a C5-C30 carbocyclic group or a C1-C30 heterocyclic group, and CY4 is not benzimidazole, and the cyclometallated ring formed by CY5, CY2, CY3 and M is a 6-membered ring,
X51 is O, S, N-[(L7)b7-(R7)c7], C(R7)(R8), Si(R7)(R8), Ge(R7)(R8), C(═O), N, C(R7), Si(R7), or Ge(R7),
R7 and R8 may form a substituted or unsubstituted C5-C30 carbocyclic group or a substituted or unsubstituted C1-C30 heterocyclic group by optionally bonding to each other through a first linking group,
L1 to L4 and L7 may be each independently a substituted or unsubstituted C5-C30 carbocyclic group or a substituted or unsubstituted C1-C30 heterocyclic group,
b1 to b4 and b7 may be each independently an integer of 0 to 5,
R1 to R4, R7 and R8 may be each independently hydrogen, deuterium, —F, —Cl, —Br, —I, —SF5, a hydroxyl group, a cyano group, a nitro group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a substituted or unsubstituted C1-C60 alkyl group, a substituted or unsubstituted C2-C60 alkenyl group, a substituted or unsubstituted C2-C60 alkynyl group, a substituted or unsubstituted C1-C60 alkoxy group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C1-C10 heterocycloalkyl group, a substituted or unsubstituted C3-C10 cycloalkenyl group, a substituted or unsubstituted C1-C10 heterocycloalkenyl group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C6-C60 aryloxy group, a substituted or unsubstituted C6-C60 arylthio group, a substituted or unsubstituted C1-C60 heteroaryl group, a substituted or unsubstituted monovalent non-aromatic condensed polycyclic group, a substituted or unsubstituted monovalent non-aromatic condensed heteropolycyclic group, —N(Q1)(Q2), —Si(Q3)(Q4)(Q5), —B(Q6)(Q7), and —P(═O)(Q8)(Q9), wherein Q1 to Q9 is defined above;
c1 to c4 may be each independently selected from an integer of 1 to 5,
a1 to a4 are each independently 0, 1, 2, 3, 4 or 5,
two of a plurality of R1 adjacent to each other may form a substituted or unsubstituted C5-C30 carbocyclic group or a substituted or unsubstituted C1-C30 heterocyclic group by optionally bonding to each other,
two of a plurality of R2 adjacent to each other may form a substituted or unsubstituted C5-C30 carbocyclic group or a substituted or unsubstituted C1-C30 heterocyclic group by optionally bonding to each other,
two of a plurality of R3 adjacent to each other may form a substituted or unsubstituted C5-C30 carbocyclic group or a substituted or unsubstituted C1-C30 heterocyclic group by optionally bonding to each other,
two of a plurality of R4 adjacent to each other may form a substituted or unsubstituted C5-C30 carbocyclic group or a substituted or unsubstituted C1-C30 heterocyclic group by optionally bonding to each other, and
two of R1 to R4 adjacent to each other may form a substituted or unsubstituted C5-C30 carbocyclic group or a substituted or unsubstituted C1-C30 heterocyclic group by optionally bonding to each other.
In Formulas 1-1 to 1-4 and 1A, C5-C30 carbocyclic group, C1-C30 heterocyclic group, and CY1 to CY4 may be each independently selected from a) a 6-membered ring, b) a condensed ring in which two or more 6-membered rings are condensed with each other, or c) one or more 6-membered rings and one 5-membered ring condensed with each other, the 6-membered ring is selected from a cyclohexane group, a cyclohexene group, an adamantane group, a norbornane group, a norbornene group, a benzene group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, and a triazine group, and the 5-membered ring is selected from a cyclopentane group, a cyclopentene group, a cyclopentadiene group, a furan group, a thiophene group, a silol group, a pyrrole group, a pyrazole group, an imidazole group, a triazole group, an oxazole group, a isoxazole group, a thiazole group, an isothiazole group, an oxadiazole group, and a thiadiazole group.
In Formulas 1-1 to 1-4, non-cyclic groups may include *—C(═O)—*′, *—O—C(═O)—*′, *—S—C(═O)—*′, *—O—C(═S)—*′, *—S—C(═S)—*′, etc., but is not limited thereto.
In Formulas 1-1 to 1-4 and 1A, a substituent of a substituted C5-C30 carbocyclic group, a substituent of a substituted C1-C30 heterocyclic group, and R91 to R94, R1 to R4, R7, and R8 may be each independently hydrogen, deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or salt thereof, a sulfonic acid group or salt thereof, a phosphoric acid group or a salt thereof, —SF5, C1-C20 alkyl group, or a C1-C20 alkoxy group;
a C1-C20 alkyl group and a C1-C20 alkoxy group substituted with at least one of deuterium, —F, —Cl, —Br, —I, —CD3, —CD2H, —CDH2, —CF3, —CF2H, —CFH2, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or salt thereof, a sulfonic acid group or salt thereof, a phosphoric acid group or salt thereof, a C1-C10 alkyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantanyl group, norbornanyl, norbornenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, phenyl, naphthyl, pyridinyl, or pyrimidinyl group;
a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantanyl group, a norbornanyl group, a norbornenyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, a phenyl group, a naphthyl group, a fluorenyl group, a phenanthrenyl group, an anthracenyl group, a fluoranthenyl group, a triphenylenyl group, a pyrenyl group, a chrysenyl group, a pyrroleyl group, a thiophenyl group, a furanyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, an isothiazolyl group, an oxazolyl group, an isoxazolyl group, a pyridinyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, an isoindoleyl group, an indoleyl group, an indazolyl group, a furanyl group, a quinolinyl group, an isoquinolinyl group, a benzoquinolinyl group, a quinoxalinyl group, a quinazolinyl group, a cinnolinyl group, a carbazolyl group, a phenanthrolyl group, a benzoimidazolyl group, a benzofuranyl group, a benzothiophenyl group, an isobenzothiazolyl group, a benzoxazolyl group, an isobenzooxazolyl group, a triazolyl group, a tetrazolyl group, an oxadiazolyl group, a triazinyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a dibenzosilolyl group, a benzocarbazolyl group, a dibenzocarbazolyl group, an Imidazopyridinyl group, or imidazopyrimidinyl group;
a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantanyl group, a norbornanyl group, a norbornenyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, a phenyl group, a naphthyl group, a fluorenyl group, a phenanthrenyl group, an anthracenyl group, a fluoranthenyl group, a triphenylenyl group, a pyrenyl group, a chrysenyl group, pyrroleyl group, a thiophenyl group, a furanyl group, an imidazolyl group, a pyrazolyl group, thiazolyl group, an isothiazolyl group, an oxazolyl group, an isoxazolyl group, a pyridinyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, an isoindole group, an indolyl group, an indazolyl group, a furanyl group, a quinolinyl group, an isoquinolinyl group, a benzoquinolinyl group, a quinoxalinyl group, a quinazolinyl group, a cinnolinyl group, a carbazolyl group, a phenanthrolinyl group, a benzoimidazolyl group, a benzofuranyl group, a benzothiophenyl group, a isobenzothiazolyl group, a benzoxazolyl group, an isobenzooxazolyl group, a triazolyl group, a tetrazolyl group, an oxadiazolyl group, a triazinyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a dibenzosilolyl group, a benzocarbazolyl group, a dibenzocarbazolyl group, an imidazopyridinyl group, and imidazopyrimidinyl group substituted with at least one selected from deuterium, —F, —Cl, —Br, —I, —CD3, —CD2H, —CDH2, —CF3, —CF2H, —CFH2, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a C1-C20 alkyl group, a C1-C20 alkoxy group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantanyl group, a norbornanyl group, a norbornenyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, a phenyl group, a naphthyl group, a fluorenyl group, a phenanthrenyl group, an anthracenyl group, a fluoranthenyl group, a triphenylenyl group, a pyrenyl group, a chrysenyl group, a pyrroleyl group, a thiophenyl group, a furanyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, an isothiazolyl group, an oxazolyl group, an isoxazolyl group, a pyridinyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, an isoindole group, an indolyl group, an indazolyl group, a furanyl group, a quinolinyl group, an isoquinolinyl group, a benzoquinolinyl group, a quinoxalinyl group, a quinazolinyl group, a cinnolinyl group, a carbazolyl group, a phenanthrolinyl group, a benzoimidazolyl group, a benzofuranyl group, a benzothiophenyl group, an isobenzothiazolyl group, a benzoxazolyl group, an isobenzooxazolyl group, a triazolyl group, a tetrazolyl group, an oxadiazolyl group, a triazinyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a dibenzosilolyl group, a benzocarbazolyl group, a dibenzocarbazolyl group, an imidazopyridinyl group, an imidazopyrimidinyl group, or —Si(Q33)(Q34)(Q35); and
—N(Q1)(Q2), —Si(Q3)(Q4)(Q5), —B(Q6)(Q7), or —P(═O)(Q3)(Q9);
Q1 to Q9 and Q33 to Q35 may be each independently —CH3, —CD3, —CD2H, —CDH2, —CH2CH3, —CH2CD3, —CH2CD2H, —CH2CDH2, —CHDCH3, —CHDCD2H, —CHDCDH2, —CHDCD3, —CD2CD3, —CD2CD2H, or —CD2CDH2; an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a sec-pentyl group, a tert-pentyl group, a phenyl group, or a naphthyl group; or
an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a sec-pentyl group, a tert-pentyl group, a phenyl group, and a naphthyl group substituted with at least one selected from deuterium, C1-C10 alkyl group, or a phenyl group, but is not limited thereto.
According to another embodiment, the dopant is an organometallic compound represented by Formula 1A, and in Formula 1A,
X2 and X3 are each independently C or N,
X4 is N,
i) M is Pt, ii) X1 is O, iii) X2 and X4 are N, X3 is C, bonds between X2 and M and between X4 and M are coordination bonds, and a bond between X3 and M is a covalent bond, iv) Y1 to Y5 are C, v) bonds between Y5 and X51 and between Y3 and X5, are a single bond, vi) CY1, CY2, and CY3 are benzene groups, and CY4 is a pyridine group, vii) X51 is O, S or N-[(L7)b7-(R7)c7], viii) b7 is 0, c7 is 1, when R7 is a substituted or unsubstituted C1-C60 alkyl group, a1 to a4 are each independently, 1, 2, 3, 4 or 5, and at least one of R1 to R4 may be each independently selected from among: a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C1-C10 heterocycloalkyl group, a substituted or unsubstituted C3-C10 cycloalkenyl group, a substituted or unsubstituted C1-C10 hetero-cycloalkenyl group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C1-C60 heteroaryl group, a substituted or unsubstituted monovalent non-aromatic condensed polycyclic group, or a substituted or unsubstituted monovalent non-aromatic heterocondensed polycyclic group.
According to another embodiment, the dopant may be represented by the following Formula 1A-1.
In Formula 1A-1, M, X1 to X3, and X5, are the same as described for Formula 1A,
X11 is N or C-[(L11)b11-(R11)c11], X12 is N or C-[(L12)b12-(R12)c12], X13 is N or C-[(L13) b13-(R13)c13], and X14 is N or C-[(L14)b14-(R14)c14],
L11 to L14, b11 to b14, R11 to R14, and c11 to c14, refer to the descriptions of L1, b1, R1, and c1 in the present specification, respectively,
X21 is N or C-[(L21)b21-(R21)c21], X22 is N or C-[(L22)b22-(R22)c22], and X23 is N or C-[(L23)b23-(R23)c23]
L21 to L23, b21 to b23, R21 to R23, and c21 to c23, refer to the descriptions of L2, b2, R2, and c2 in the present specification, respectively,
X31 is N or C-[(L31)b31-(R31)c31], X32 is N or C-[(L32)b32-(R32)c32] and, X33 is N or C-[(L33)b33-(R33)c33],
L31 to L33, b31 to b33, R31 to R33, and c31 to c33, refer to the description of L3, b3, R3 and c3 in the present specification, respectively,
X41 is N or C-[(L41)b41-(R41)c41], X42 is N or C-[(L42)b42-(R42)c42], X43 is N or C-[(L43) b43-(R43)c43], and X44 is N or C-[(L44)b44-(R44)c44],
L41 to L44, b41 to b44, R41 to R44, and c41 to c44, refer to the descriptions of L4, b4, R4 and c4 in the present specification, respectively,
two of R11 to R14 may form a substituted or unsubstituted C5-C30 carbocyclic group or a substituted or unsubstituted C1-C30 heterocyclic group by optionally bonding to each other,
two of R21 to R23 may form a substituted or unsubstituted C5-C30 carbocyclic group or a substituted or unsubstituted C1-C30 heterocyclic group by optionally bonding to each other,
two of R31 to R33 may form a substituted or unsubstituted C5-C30 carbocyclic group or a substituted or unsubstituted C1-C30 heterocyclic group by optionally bonding to each other, and
two of R41 to R44 may form a substituted or unsubstituted C5-C30 carbocyclic group or a substituted or unsubstituted C1-C30 heterocyclic group by optionally bonding to each other.
For example, the dopant may be one of the following compounds 1-1 to 1-88, 2-1 to 2-47, and 3-1 to 3-582, but is not limited thereto.
A light emitting-layer of the green light-emitting unit (green organic light emitting device) 12 includes a phosphorescent light-emitting material has been described, but the present embodiment is not limited thereto. The light-emitting layer of the green light-emitting unit (green organic light-emitting device) 12 may include a thermally activated delayed fluorescence (TADF) dopant. The TADF dopant may also be referred to as a thermally assisted delayed fluorescence dopant. In this case, it is possible to emit highly efficient delayed fluorescence.
The light-emitting layer of the green light-emitting unit (green organic light emitting device) 12 may include the phosphorescent light emitting material described above, but the present embodiment is not limited thereto. The light-emitting layer may include a phosphorescent material other than the phosphorescent light-emitting material described above. Also, the light-emitting layer of the green light-emitting unit 12 may include a fluorescent light-emitting material. Any green fluorescent material used in the OLED related art may be applied as the green light-emitting layer material of the present embodiment. A fluorescent light-emitting material for emitting green light are well known to a person of ordinary skill, and thus, detailed descriptions of such materials are omitted.
In the present embodiment, the light-emitting layer of the blue light-emitting units 11 and 13 may include a fluorescent light-emitting material and/or a phosphorescent light-emitting material that emits blue light. Any blue fluorescent/phosphorescent materials used in the OLED related art may be applied as the blue light-emitting layer material of the present embodiment. A fluorescent light-emitting material for emitting blue light are well known to a person of ordinary skill, and thus, detailed descriptions of such materials are omitted.
As described above, the OLED structure 10 according to an embodiment may include the first blue light-emitting unit 11, the second blue light-emitting unit 13, and the green light-emitting unit 12. Since the green light-emitting units 12 as well as the blue light-emitting units 11 and 13 are included in the OLED structure 10, it is possible to achieve higher current efficiency than when an OLED designed to emit white light is used. However, because an emission spectrum of the green incident light Ig generated from the green light-emitting unit 12 is typically broader than an emission spectrum of the quantum dots QD included in the second color conversion layer 21G, it is necessary to improve the characteristics of incident green light Ig in order to improve color purity and efficiency.
Referring to
According to an embodiment, when the transmittance of the second color filter 20G, that is, the green color filter with respect to the green incident light Ig generated from the green light-emitting unit 12 is high, the current efficiency for the second color light Lg may be improved.
Also, in order to improve color purity of the second color light Lg, it is necessary to improve a match rate to the UHD (4K) color standard (hereinafter, referred to as BT2020) established by the ITU. As shown in
In addition, as the transmittance of the first color filter 20R and the third color filter 20B with respect to the green incident light Ig generated from the green light-emitting unit 12 is lower, the color purity of the first color light Lr and the third color light Lb may be improved. Accordingly, the current efficiency and color purity improvement may be determined according to the spectral shape of the green incident light Ig generated from the green light-emitting unit 12.
The spectrum of green incident light Ig shown in
According to an embodiment, the spectral shape of the green incident light Ig may be controlled so that the area of the spectrum is 64 or less in a wavelength region of 380 nm to 780 nm.
In the present specification, the medial wavelength λc is defined as a wavelength that divides the area of the spectrum of the incident green light Ig into two equal halves. According to an embodiment, the area of the spectrum of the green incident light Ig may be determined by Equation 1, and it may be seen that an area of the first area A1 disposed on the left side and an area of the second area A2 disposed on the right side are the same based on the medial wavelength λc.
Referring to
Referring to
R=Area/Δλ Equation 3
Also, in the CIE1931 chromaticity diagram shown in
As indicated in the above Tables and
As an example, in region I where the conversion value R is less than 3.6, the transmittance (blue transmittance) of the blue incident light Ib with respect to the second color filter 20G may be less than 3%, but the color coordinate Green CIEx of the green area exceeds 0.200, thus, the color reproducibility may be reduced. Also, in region III where the conversion value R exceeds 13, the color coordinate Green CIEx of the green region may be less than 0.180, but the transmittance (blue transmittance) of the incident blue light Ib with respect to the second color filter 20G exceeds 5%, thus, the color purity may be reduced.
On the other hand, in region II where the conversion value R is 3.6 or more and 13 or less, it may be confirmed that the color coordinate Green CIEx of the green area is 0.200 or less and the transmittance (blue transmittance) of the incident blue light Ib with respect to the second color filter 20G is 5% or less. Accordingly, when the conversion value R is 3.6 or more and 13 or less, the color purity of the first to third color lights Lr, Lg, and Lb may be improved, thereby improving the match rate of BT2020 in the CIE1931 chromaticity diagram. Also, the current efficiency of the second color light Lg, that is, green light, may be improved.
Referring to
Referring to
Referring to
In a display apparatus in which green light is applied to a light source OLED, a display apparatus having high efficiency as well as high color reproducibility may be implemented.
A display apparatus having high performance may be implemented by applying green light and blue light to the light source OLED and using a plurality of quantum dot color conversion elements and a plurality of color filter elements.
It should be understood that embodiments described herein should be considered in a descriptive sense only and not for purposes of limitation. Descriptions of features or aspects within each embodiment should typically be considered as available for other similar features or aspects in other embodiments. While one or more embodiments have been described with reference to the figures, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope as defined by the following claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2020-0120523 | Sep 2020 | KR | national |
| Number | Name | Date | Kind |
|---|---|---|---|
| 10520765 | Chung | Dec 2019 | B2 |
| 10944068 | Cho et al. | Mar 2021 | B2 |
| 20170194535 | Park et al. | Jul 2017 | A1 |
| 20200251040 | Lee et al. | Aug 2020 | A1 |
| Number | Date | Country |
|---|---|---|
| 1020150047401 | May 2015 | KR |
| 1020170034055 | Mar 2017 | KR |
| 1020190000759 | Jan 2019 | KR |
| 1020190136737 | Dec 2019 | KR |
| Entry |
|---|
| English Abstract of KR 1020190136737. |
| Number | Date | Country | |
|---|---|---|---|
| 20220093689 A1 | Mar 2022 | US |
