US20200227671A1 - Organic light-emitting diode - Google Patents
Organic light-emitting diode Download PDFInfo
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- US20200227671A1 US20200227671A1 US16/353,578 US201916353578A US2020227671A1 US 20200227671 A1 US20200227671 A1 US 20200227671A1 US 201916353578 A US201916353578 A US 201916353578A US 2020227671 A1 US2020227671 A1 US 2020227671A1
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- 230000005283 ground state Effects 0.000 claims abstract description 15
- 230000000903 blocking effect Effects 0.000 claims description 18
- 230000005525 hole transport Effects 0.000 claims description 10
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 claims description 10
- LVTJYYZZSDQQPE-UHFFFAOYSA-N 1-(2,5-dimethyl-4-pyren-1-ylphenyl)pyrene Chemical compound C1=C2C(C=3C=C(C(=CC=3C)C=3C4=CC=C5C=CC=C6C=CC(C4=C65)=CC=3)C)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 LVTJYYZZSDQQPE-UHFFFAOYSA-N 0.000 claims description 4
- 239000005725 8-Hydroxyquinoline Substances 0.000 claims description 4
- 150000001454 anthracenes Chemical class 0.000 claims description 4
- 229960003540 oxyquinoline Drugs 0.000 claims description 4
- HDMYKJVSQIHZLM-UHFFFAOYSA-N 1-[3,5-di(pyren-1-yl)phenyl]pyrene Chemical compound C1=CC(C=2C=C(C=C(C=2)C=2C3=CC=C4C=CC=C5C=CC(C3=C54)=CC=2)C=2C3=CC=C4C=CC=C5C=CC(C3=C54)=CC=2)=C2C=CC3=CC=CC4=CC=C1C2=C43 HDMYKJVSQIHZLM-UHFFFAOYSA-N 0.000 claims description 3
- 150000004696 coordination complex Chemical class 0.000 claims description 3
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 3
- OBAJPWYDYFEBTF-UHFFFAOYSA-N 2-tert-butyl-9,10-dinaphthalen-2-ylanthracene Chemical compound C1=CC=CC2=CC(C3=C4C=CC=CC4=C(C=4C=C5C=CC=CC5=CC=4)C4=CC=C(C=C43)C(C)(C)C)=CC=C21 OBAJPWYDYFEBTF-UHFFFAOYSA-N 0.000 claims description 2
- VIZUPBYFLORCRA-UHFFFAOYSA-N 9,10-dinaphthalen-2-ylanthracene Chemical compound C12=CC=CC=C2C(C2=CC3=CC=CC=C3C=C2)=C(C=CC=C2)C2=C1C1=CC=C(C=CC=C2)C2=C1 VIZUPBYFLORCRA-UHFFFAOYSA-N 0.000 claims description 2
- SXGIRTCIFPJUEQ-UHFFFAOYSA-N 9-anthracen-9-ylanthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C(C=3C4=CC=CC=C4C=C4C=CC=CC4=3)=C21 SXGIRTCIFPJUEQ-UHFFFAOYSA-N 0.000 claims description 2
- MWPLVEDNUUSJAV-LSMJWXKXSA-N anthracene Chemical compound [13CH]1=[13CH][13CH]=[13CH][13C]2=CC3=CC=CC=C3C=[13C]21 MWPLVEDNUUSJAV-LSMJWXKXSA-N 0.000 claims description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Natural products C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 2
- GQVWHWAWLPCBHB-UHFFFAOYSA-L beryllium;benzo[h]quinolin-10-olate Chemical compound [Be+2].C1=CC=NC2=C3C([O-])=CC=CC3=CC=C21.C1=CC=NC2=C3C([O-])=CC=CC3=CC=C21 GQVWHWAWLPCBHB-UHFFFAOYSA-L 0.000 claims description 2
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 claims description 2
- 150000003220 pyrenes Chemical class 0.000 claims description 2
- 239000000463 material Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 16
- 238000010586 diagram Methods 0.000 description 12
- QBFQLEVWHCQDIR-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)-2-pyrrolidin-1-ylpropan-1-one Chemical compound CC1=C(C=CC(=C1)C)C(C(C)N1CCCC1)=O QBFQLEVWHCQDIR-UHFFFAOYSA-N 0.000 description 10
- 230000007246 mechanism Effects 0.000 description 9
- 238000005401 electroluminescence Methods 0.000 description 6
- 230000001052 transient effect Effects 0.000 description 6
- 238000005286 illumination Methods 0.000 description 4
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- 230000002708 enhancing effect Effects 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
- 230000001960 triggered effect Effects 0.000 description 2
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical compound C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- -1 tris(8-hydroxyquinoline)-aluminium Chemical compound 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
- H10K50/121—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants for assisting energy transfer, e.g. sensitization
-
- H01L51/5221—
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09G—ARRANGEMENTS OR CIRCUITS FOR CONTROL OF INDICATING DEVICES USING STATIC MEANS TO PRESENT VARIABLE INFORMATION
- G09G3/00—Control arrangements or circuits, of interest only in connection with visual indicators other than cathode-ray tubes
- G09G3/20—Control arrangements or circuits, of interest only in connection with visual indicators other than cathode-ray tubes for presentation of an assembly of a number of characters, e.g. a page, by composing the assembly by combination of individual elements arranged in a matrix no fixed position being assigned to or needed to be assigned to the individual characters or partial characters
- G09G3/2003—Display of colours
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/805—Electrodes
- H10K50/81—Anodes
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/805—Electrodes
- H10K50/82—Cathodes
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2101/00—Properties of the organic materials covered by group H10K85/00
- H10K2101/40—Interrelation of parameters between multiple constituent active layers or sublayers, e.g. HOMO values in adjacent layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
Definitions
- the present invention relates to a light-emitting diode, and specifically to an organic light-emitting diode.
- a conventional organic light-emitting diode is formed of several stacked nano-size layers including an anode, a hole transport layer (HTL), a luminescent layer, an electron transport layer (ETL) and a cathode in spatial order.
- HTL hole transport layer
- ETL electron transport layer
- a current of holes flows from the anode to the highest occupied molecular orbitals (HOMO) of the HTL, thus generating positive polarons
- HOMO highest occupied molecular orbitals
- LUMO unoccupied molecular orbitals
- the positive polarons and the negative polarons recombine in the luminescent layer, thereby generating singlet excitons and triplet excitons. Thereafter, the singlet excitons return to the ground state, upon which light is emitted.
- One of the objectives of the present invention is to provide an organic light-emitting diode which emits light utilizing the triplet energy thereof, thereby extending the lifetime of the organic light-emitting diode.
- One embodiment of the present embodiment provides an organic light emitting diode including an anode, a cathode and a luminescent layered structure.
- the luminescent layered structure is disposed between the anode and the cathode.
- the luminescent layered structure has a luminescent layer and a sensitizer layer.
- the luminescent layer has a luminescent-layer ground state, a luminescent-layer singlet state and a luminescent-layer triplet state, in which two times of the luminescent-layer triplet state is higher than the luminescent-layer singlet state.
- the sensitizer layer has a sensitizer-layer triplet state, which is between the luminescent-layer singlet state and the luminescent-layer triplet state.
- the molecules of the sensitizer layer at the sensitizer layer triplet layer transfers energy to the molecules of the luminescent layer at the luminescent-layer triplet state and triggers triplet-triplet annihilation upconversion in the luminescent layer such that the luminescent layer emits light of a first color.
- FIG. 1 is a schematic view illustrating an organic light-emitting diode according to a first embodiment of the present invention.
- FIG. 2 illustrates a variant embodiment of the organic light-emitting diode according to the first embodiment of the present invention.
- FIG. 3 illustrates another variant embodiment of the organic light-emitting diode according to the first embodiment of the present invention.
- FIG. 4 is an energy level diagram of the luminescent layered structure of a first experimental example according to the first embodiment of the present invention.
- FIG. 5 is a diagram illustrating the transient electroluminescence of the first experimental example according to the first embodiment of the present invention.
- FIG. 6 illustrates the transient electroluminescence of the luminescent layer of the first experimental example according to the first embodiment of the present invention.
- FIG. 7 is a diagram illustrating the external quantum efficiency of the first experimental example according to the first embodiment and those of comparative examples.
- FIG. 8 illustrates an energy level diagram of the luminescent layered structure of a second experimental example according to the first embodiment of the present invention.
- FIG. 9 illustrates the transient electroluminescence of the luminescent layer of the second experimental example according to the first embodiment of the present invention.
- FIG. 10 is a diagram illustrating the external quantum efficiency of the second experimental example according to the first embodiment and those of the comparative examples.
- FIG. 11A is a schematic view of the organic light-emitting diode according to the second embodiment of the present invention.
- FIG. 11B illustrates an energy level diagram of the luminescent layered structure according to the second embodiment of the present invention.
- FIG. 12 is a diagram illustrating the external quantum efficiency of a first experimental example, a second experimental example and a third experimental example according to the second embodiment of the present invention.
- the organic light-emitting diode Z according to the first embodiment of the present invention is described between with reference to FIG. 1 to FIG. 7 .
- the organic light-emitting diode Z provided by the first embodiment of the present invention includes an anode 1 , a cathode 2 , a luminescent layered structure 3 , a hole transport layer 4 and an electron transport layer 5 .
- the hole transport layer 4 is disposed between the anode 1 and the luminescent layered structure 3
- the electron transport layer 5 is disposed between the cathode 2 and the luminescent layered structure 3 .
- the luminescent layered structure 3 has a luminescent layer 31 and a sensitizer layer 32 .
- the luminescent layer 31 includes a luminescent-layer ground state, a luminescent-layer singlet state and a luminescent-layer triplet state.
- the luminescent layer 31 is a TTA material layer, that is to say, two times of the luminescent-layer triplet state is higher than the luminescent-layer singlet state.
- the luminescent layer 31 is preferably made of an anthracene derivative, a pyrene derivative or a perylene derivative; however, the present invention is not limited thereto.
- the anthracene derivative may be but not limited to 9,10-Di(2-naphthyl)anthracene (ADN), 2-methyl-9,10-D(2-naphthyl)anthracene, 2-tert-butyl-9,10-Di(2-naphthyl)anthracene, or 9,9′-dianthracene.
- ADN 9,10-Di(2-naphthyl)anthracene
- 2-methyl-9,10-D(2-naphthyl)anthracene 2-methyl-9,10-D(2-naphthyl)anthracene
- 2-tert-butyl-9,10-Di(2-naphthyl)anthracene 2-tert-butyl-9,10-Di(2-naphthyl)anthracene
- 9,9′-dianthracene 9,9′-dianthracene.
- the sensitizer layer 32 is disposed between the luminescent layer 31 and the hole transport layer 4 .
- the present invention is not limited thereto.
- the position of the luminescent layer 31 and that of the sensitizer layer 32 are interchangeable. That is to say, in other embodiments, the sensitizer layer 32 can be disposed between the luminescent layer 31 and the electron transport layer 5 .
- the sensitizer layer 32 has a sensitizer-layer triplet state, which is between the luminescent-layer singlet state and the luminescent-layer triplet state.
- the material of the sensitizer layer 32 is preferably a (8-hydroxyquinoline) metal complex or a 10-hydroxybenzo [h] quinoline-metal complex.
- the (8-hydroxyquinoline) metal complex may include but not limited to tris(8-hydroxyquinoline)-aluminium (Alq 3 ) and tris-(8-hydroxyquinoline)gallium (Gaq 3 )
- examples of 10-hydroxybenzo [h] quinoline-metal complex may include but not limited to bis(10-hydroxybenzo[h]quinolinato)beryllium.
- the sensitizer layer 32 can transport electron holes and acts as a hole transport layer disposed between the luminescent layer 31 and the anode 1 , as shown in FIG. 2 .
- the sensitizer layer 32 can transport electrons and serve as an electron transport layer disposed between the luminescent layer 31 and the cathode 2 , as shown in FIG. 3 .
- the sensitizer layer 32 can be added to the luminescent layer 31 as a dopant. It should be noted that the present invention is not limited to any of the above examples.
- FIG. 4 shows an energy level diagram of the luminescent layered structure 3 of the first experimental example.
- the luminescent-layer singlet state S 1 the sensitizer-layer triplet state T 1 and the sensitizer-layer ground state G 1 of sensitizer layer 32 and the luminescent-layer singlet state S 2 , the luminescent-layer triplet state T 2 , and the luminescent-layer ground state G 2 of the luminescent layer 31 are shown.
- FIG. 4 shows an energy level diagram of the luminescent layered structure 3 of the first experimental example.
- the triplet state T 1 of the sensitizer layer 32 is between the luminescent-layer singlet state S 2 and the luminescent-layer triplet state T 2 .
- the material of the luminescent layer 31 of the first experimental example is ADN
- that of the sensitizer layer 32 is Alq 3 , in which the energy level of the luminescent layered structure 3 is shown in Table 1 below.
- the sensitizer layer 32 is disposed next to the luminescent layer 31 such that triplet-triplet energy transfer mechanism (TTET) between the sensitizer layer 32 and the luminescent layer 31 can occur, i.e. the molecules of the sensitizer layer 32 at the sensitizer-layer triplet state T 1 transfer energy to the molecules of the luminescent layer 31 at the luminescent-layer triplet state T 2 in a manner such that triplet-triplet annihilation upconversion mechanism (TTAUC) is triggered in the luminescent layer 31 thereafter.
- TTET triplet-triplet energy transfer mechanism
- the aforementioned TTAUC mechanism occurs among excited triplet state molecules, wherein one excited triplet state molecule transfers energy to another excited triplet state molecule and returns to the ground state, and the excited triplet state molecule that receives the energy is raised to the singlet state.
- molecules of the luminescent layer 31 that arc raised to the singlet state return to the luminescent-layer ground state G 2 , thereby emitting light of a first color L 1 .
- molecules of the sensitizer layer 32 at the sensitizer-layer singlet state S 1 emit light of a second color L 2 when returning to the sensitizer-layer ground state G 1 .
- white light can be generated by mixing the first color light L 1 , the second color light L 2 , and light of a third color.
- Alq 3 as the sensitizer layer 32 and ADN as the luminescent layer 31
- a white light can be obtained by mixing the blue light emitted by ADN, the green light emitted by Alq 3 and the red light.
- the present invention is not limited thereto.
- the material of the luminescent layer 31 and that of the sensitizer layer 32 are selected based on a predetermined color of light emitted by the organic light-emitting diode Z, thereby generating light of the predetermined color by mixing the first color light L 1 and the second color light L 2 .
- FIG. 5 shows a diagram illustrating the electroluminescent property of the first experimental example according to the present embodiment
- FIG. 6 shows a diagram illustrating the transient electroluminescence of the luminescent layer of the first experimental example according to the present embodiment
- ITO indium tin oxide
- LiF/Al is used as the cathode 2
- the thickness of the hole transport layer 4 is 50 nm, and the material thereof is N,N′-di(1-naphthyl)-N,N′-diphenyl benzidine (NPB).
- the thickness of the electron transport layer 5 is 65 nm, and the material thereof is 4,7-diphenyl-1,10-phenanthroline (Bphen).
- the thickness of the sensitizer layer 32 is 5 nm, and the material thereof is Alq 3 .
- the thickness of the luminescent layer 31 is 10 nm, and the material thereof is ADN.
- the transient electroluminescence of the organic light-emitting diode Z is measured by first applying an electro-pulse to the organic light-emitting diode Z, and the light emitted by the organic light-emitting diode Z in response to the electro-pulse is gauged and converted into electric output with a photomultiplier.
- the curves shown in FIG. 5 respectively represent the electric signals outputted by the organic light-emitting diode Z in response to an input voltage of 5 V, 4.6 V, 4.2 V, 3.8 V and 3.4 V. As shown in FIG.
- the speed at which the organic light-emitting diode Z of the first experimental example emits light is of microsecond-scale.
- the speed at which singlet excitons emit light is of nanosecond-scale, and that of triplet excitons is of microsecond-scale since triplet excitons decay slower owing to the spin conservation. That is to say, FIG. 5 shows that in the first experimental example the triplet excitons contribute to a larger percentage of total emission than organic light-emitting diodes in the prior art.
- the curves shown in FIG. 6 respectively represent the electric signals outputted by the luminescent layer 31 corresponding to an input electro-pulse of 5 V, 4.6 V, 4.2 V, 3.8 V and 3.4 V. It can be seen from FIG. 6 that in the first experimental example of the present embodiment, the first color light L 1 emitted by the luminescent layer 31 (ADN) is mainly from the triplet excitons thereof.
- FIG. 7 illustrates the external quantum efficiency of the first experimental example (shown with the curve marked as Alq 3 /ADN) according to the present embodiment and those of a first comparative example (shown with the curve marked as ADN) and a second comparative example (shown with the curve marked as Alq 3 ).
- the difference between the first experimental example and the first and second comparative examples lies in that the first experimental example has a sensitizer layer and a luminescent layer, whereas the first comparative example has only ADN as the luminescent layer and does not have a sensitizer layer; the second comparative example has only Alq 3 as the luminescent layer and does not have a sensitizer layer.
- the first experimental example has a sensitizer layer and a luminescent layer
- the first comparative example has only ADN as the luminescent layer and does not have a sensitizer layer
- the second comparative example has only Alq 3 as the luminescent layer and does not have a sensitizer layer.
- the first experimental example exhibits higher external quantum efficiency than the first comparative example and the second comparative example do within most part of the operational current density.
- 75% of recombined positive polarons and negative polarons transform into triplet excitons, which means the waste in energy in the prior art.
- the sensitizer layer 32 in the organic light-emitting diode Z by adding the sensitizer layer 32 in the organic light-emitting diode Z and adjusting the thicknesses of the hole transport layer 4 and the electron transport layer 5 , the negative polarons and the positive polarons recombine in the sensitizer layer 32 instead of the luminescent layer 31 so that singlet excitons and triplet excitons can be generated in the sensitizer layer 32 , which triggers triplet-triplet energy transfer mechanism (TTET) between the luminescent layer 31 and the sensitizer layer 32 and then triplet-triplet annihilation upconversion mechanism (TTAUC) in the luminescent layer 31 thereafter.
- TTET triplet-triplet energy transfer mechanism
- TTAUC triplet-triplet annihilation upconversion mechanism
- the second experimental example of the organic light-emitting diode Z of the present embodiment is described below with reference to FIG. 8 to FIG. 10 .
- the second experimental example has a structure that is similar to that of the first experimental example with the main difference being that the material of the sensitizer layer 32 of the second experimental example is 1-(2,5-dimethyl-4-(1-pyrenyl)phenyl)pyrene (DMPPP).
- DMPPP 1-(2,5-dimethyl-4-(1-pyrenyl)phenyl)pyrene
- FIG. 8 shows the energy level diagram of the luminescent layered structure 3 of the second experimental example.
- the sensitizer-layer triplet state T 3 of the sensitizer layer 32 (DMPPP) is higher than the luminescent-layer triplet state T 2 of the luminescent layer 31
- the sensitizer-layer singlet state S 3 of the sensitizer layer 32 is higher than the luminescent-layer singlet state S 2 of the luminescent layer 31 .
- the energy level of the luminescent layered structure 3 is shown in Table 2 below.
- FIG. 9 illustrates the transient electroluminescence of the luminescent layer of the first experimental example according to the present embodiment.
- the curves shown in FIG. 9 respectively represent the electric signals outputted by the luminescent layer 31 (ADN) in response to an input voltage of 5.5 V-6 V, 5.5 V, 5.0 V, 4.5 V, and 4.0 V.
- ADN luminescent layer 31
- FIG. 9 when each applied voltage is turned off at 0 second, the speed at which the organic light-emitting diode Z of the second experimental example emits light is of microsecond-scale, which indicates that a larger percentage of the total emission of the second experimental example is converted from the triplet energy as compared to a conventional organic light-emitting diode.
- FIG. 10 illustrates the external quantum efficiency of the second experimental example (shown with the curve marked as DMPPP/ADN) according to the present embodiment and those of a third comparative example (shown with the curve marked as ADN) and a fourth comparative example (shown with the curve marked as DMPPP).
- the difference between the second experimental example and the third and fourth comparative examples lies in that the second experimental example has a sensitizer layer 32 and a luminescent layer 31 , whereas the third comparative example has only ADN has only the luminescent layer and does not have a sensitizer layer; the fourth comparative example has only DMPPP as the luminescent layer and does not have a sensitizer layer either.
- the second experimental example which includes DMPPP as the sensitizer layer 32 and ADN as the luminescent layer 31 , exhibits higher external quantum efficiency than the third comparative example and the fourth comparative example.
- the relative difference between the sensitizer-layer singlet state and the luminescent-layer singlet state is not limited in the present invention.
- a person skilled in the art can select the material of the sensitizer layer and that of the luminescent layer according to actual needs. For instance, when in a condition that ADN which emits blue light has been determined to be the material of the luminescent layer 31 , the material of the sensitizer layer 32 can be decided based on the predetermined light color of the organic light-emitting diode Z.
- the predetermined light color is white
- a material that has a singlet state lower than the luminescent-layer singlet state S 2 can be selected as the material of the sensitizer layer 32 , as in the case of the first experimental example, so that the second color light L 2 is green.
- the organic light-emitting diode Z can emit white light.
- the predetermined light color of the organic light-emitting diode Z is blue
- a material that has a singlet state higher than the luminescent-layer singlet state S 2 can be chosen to be the material of the sensitizer layer 32 , as in the case of the second experimental example, so that the second color light L 2 and the first light color L 1 are both blue light.
- the first embodiment of the present invention uses mainly the triplet energy thereof to emit light utilizing the technical solution of the sensitizer layer 32 , which serves as the place the recombination between the positive polarons and the negative polarons takes place such that triplet-triplet annihilation upconversion mechanism can be triggered in the luminescent layer 31 by the triplet excitons in the sensitizer layer 32 generated from the recombination. Since the sensitizer layer 32 acts as the recombination zone in the present embodiment, high energy polarons are prevented from reacting with the excitons in the luminescent layer 31 . Therefore, the triplet energy in the sensitizer layer 32 can be utilized to emit light by being transferred to the luminescent layer 31 and converted through TTAUC mechanism, thereby enhancing the illumination efficiency of the organic light-emitting diode Z and extending the lifetime thereof.
- the main difference between the present embodiment and the first embodiment lies in that the organic light-emitting diode Z of the second embodiment further includes a blocking layer 33 between the luminescent layer 31 and the sensitizer layer 32 .
- the blocking layer 33 has a blocking-layer singlet state S 4 and a blocking-layer triplet state T 4 , in which the blocking-layer singlet state S 4 is higher than the luminescent-layer singlet state S 2 , and the blocking-layer triplet state T 4 is higher than the luminescent-layer triplet state T 2 .
- the triplet energy of the sensitizer layer 32 can be transferred to the triplet state of the luminescent layer 31 .
- the quenching effects between the sensitizer layer 32 and the luminescent layer 31 can be reduced. In this way, the illumination efficiency of the organic light-emitting diode Z can be further improved.
- the material of the blocking layer 33 can be 1-(2,5-dimethyl-4-(1-pyrenyl)phenyl)pyrene (DMPPP) or 1,3,5-Tri(1-pyrenyl)benzene (TPB3).
- DMPPP 1-(2,5-dimethyl-4-(1-pyrenyl)phenyl)pyrene
- TPB3 1,3,5-Tri(1-pyrenyl)benzene
- the present invention is not limited thereto.
- the blocking layer 33 of the present embodiment is DMPPP, whose energy level is shown in Table 3 below.
- FIG. 12 shows a diagram illustrating the external quantum efficiency of a first experimental example, a second experimental example and a third experimental example according to the second embodiment of the present invention.
- the first experimental example of the present embodiment uses ADN as the luminescent layer, Alq 3 as the sensitizer layer, and the first experimental example has no blocking layer.
- the second experimental example is shown with a curve marked as 5 nm in FIG. 12 .
- the difference between the first experimental example and the second experimental example is that the second experimental example has a blocking layer 33 with a thickness of 5 nm between the luminescent layer 31 and the sensitizer layer 32 .
- the material of the blocking layer 33 is DMPPP.
- the third experimental example is shown with a curve marked as 10 nm in FIG. 12 .
- the difference between the first experimental example and the third experimental example is that the third experimental example has a blocking layer 33 with a thickness of 10 nm between the luminescent layer 31 and the sensitizer layer 32 .
- the material of the blocking layer 33 of the third experimental example is DMPPP.
- the third experimental example exhibits higher external quantum efficiency than the second experimental example, which in turn offers higher external quantum efficiency than the first experimental example. Therefore, the present embodiment shows that adding a blocking layer 33 to the organic light-emitting diode Z (as in the second experimental example and third experimental example of the present embodiment compared to the first experimental example) can effectively enhance the efficiency of the organic light-emitting diode Z.
- the embodiments of the present invention achieves “the molecules of the sensitizer layer at the sensitizer-layer triplet layer transfers energy to the molecules of the luminescent layer at the luminescent-layer triplet state and triggers triplet-triplet annihilation upconversion in the luminescent layer such that the luminescent layer emits light of a first color” through the technical solutions that “two times of the luminescent-layer triplet state is higher than the luminescent-layer singlet state” and “the sensitizer-layer triplet state is between the luminescent-layer singlet state and the luminescent-layer triplet state”.
- the organic light-emitting diode Z of the present embodiments utilizes the sensitizer layer 32 to perform triplet-triplet energy transfer between the sensitizer layer 32 and the luminescent layer 31 , thereby triggering triplet-triplet annihilation upconversion mechanism in the luminescent layer 31 .
- triplet energy of the luminescent layer 31 and that of the sensitizer layer 32 can be converted into light emitted by the organic light-emitting diode Z, thereby effectively enhancing the illumination efficiency and the lifespan of the organic light-emitting diode Z.
- a blocking layer can be added to the organic light-emitting diode Z, in which the singlet state of the blocking layer is higher than the singlet state of the luminescent layer, and the triplet state of the blocking layer is higher than the triplet state of the luminescent layer. In this way, the illumination efficiency of the organic light-emitting diode can be further increased.
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Abstract
Description
- The present invention relates to a light-emitting diode, and specifically to an organic light-emitting diode.
- A conventional organic light-emitting diode (OLED) is formed of several stacked nano-size layers including an anode, a hole transport layer (HTL), a luminescent layer, an electron transport layer (ETL) and a cathode in spatial order. When a voltage is applied to an OLED, a current of holes flows from the anode to the highest occupied molecular orbitals (HOMO) of the HTL, thus generating positive polarons, and at the same time a current of electrons flows from the cathode to the lowest unoccupied molecular orbitals (LUMO) of the ETL, thus generating negative polarons. The positive polarons and the negative polarons recombine in the luminescent layer, thereby generating singlet excitons and triplet excitons. Thereafter, the singlet excitons return to the ground state, upon which light is emitted.
- In the evolution of OLEDs, extending the lifetime of blue OLEDs has been a key issue, the reason being that the energy of blue photons is relatively high, which results in the property of rapid degradation. To be specific, active exciton-polaron annihilation exists in blue OLEDs since excitons possess long lifespan and thus tend to react with excitons and form high energy polarons that break molecular bonds in the luminescent material and consequently reduce the lifetime of blue OLEDs.
- In addition, light is emitted when singlet excitons return to the ground state, while triplet excitons in fluorescent materials cannot return to the ground state with photon emission. That is to say, a considerable amount of energy is wasted taking into consideration of the fact that triplet excitons account for 75 percent of excited excitons as a result of the recombination between the positive polarons and the negative polarons.
- Therefore, in light of the above-mentioned drawbacks, OLEDs of the prior art still have room for improvement.
- One of the objectives of the present invention is to provide an organic light-emitting diode which emits light utilizing the triplet energy thereof, thereby extending the lifetime of the organic light-emitting diode.
- One embodiment of the present embodiment provides an organic light emitting diode including an anode, a cathode and a luminescent layered structure. The luminescent layered structure is disposed between the anode and the cathode. The luminescent layered structure has a luminescent layer and a sensitizer layer. The luminescent layer has a luminescent-layer ground state, a luminescent-layer singlet state and a luminescent-layer triplet state, in which two times of the luminescent-layer triplet state is higher than the luminescent-layer singlet state. The sensitizer layer has a sensitizer-layer triplet state, which is between the luminescent-layer singlet state and the luminescent-layer triplet state. The molecules of the sensitizer layer at the sensitizer layer triplet layer transfers energy to the molecules of the luminescent layer at the luminescent-layer triplet state and triggers triplet-triplet annihilation upconversion in the luminescent layer such that the luminescent layer emits light of a first color.
- To further understand the features and technical content of the present invention, please refer to the following detailed descriptions and drawings related to the present invention. However, the provided drawings are used only for providing reference and descriptions, and are not intended to limit the present invention.
-
FIG. 1 is a schematic view illustrating an organic light-emitting diode according to a first embodiment of the present invention. -
FIG. 2 illustrates a variant embodiment of the organic light-emitting diode according to the first embodiment of the present invention. -
FIG. 3 illustrates another variant embodiment of the organic light-emitting diode according to the first embodiment of the present invention. -
FIG. 4 is an energy level diagram of the luminescent layered structure of a first experimental example according to the first embodiment of the present invention. -
FIG. 5 is a diagram illustrating the transient electroluminescence of the first experimental example according to the first embodiment of the present invention. -
FIG. 6 illustrates the transient electroluminescence of the luminescent layer of the first experimental example according to the first embodiment of the present invention. -
FIG. 7 is a diagram illustrating the external quantum efficiency of the first experimental example according to the first embodiment and those of comparative examples. -
FIG. 8 illustrates an energy level diagram of the luminescent layered structure of a second experimental example according to the first embodiment of the present invention. -
FIG. 9 illustrates the transient electroluminescence of the luminescent layer of the second experimental example according to the first embodiment of the present invention. -
FIG. 10 is a diagram illustrating the external quantum efficiency of the second experimental example according to the first embodiment and those of the comparative examples. -
FIG. 11A is a schematic view of the organic light-emitting diode according to the second embodiment of the present invention. -
FIG. 11B illustrates an energy level diagram of the luminescent layered structure according to the second embodiment of the present invention. -
FIG. 12 is a diagram illustrating the external quantum efficiency of a first experimental example, a second experimental example and a third experimental example according to the second embodiment of the present invention. - Embodiments of the present invention are described below with reference to
FIG. 1 toFIG. 12 . A person skilled in the art can understand the advantages and effects of the present invention from the description disclosed below. However, the content disclosed below is not intended to limit the protection scope of the present invention. The present invention can be implemented by a person skilled in the art based on different perspectives and applications without departing from the concept and spirit of the present invention. In addition, it should be stated in advance that the accompanying drawings of the present invention are merely used for illustration, and are not drawn according to actual dimensions for sake of clear illustration. Moreover, the same reference number corresponds to the same component. It should also be understood that expressions such as one component is “connected to” or “disposed on” another may mean that the former is either directly or indirectly connected to or disposed on the latter, wherein “connected” may refer to either physical or electrical connection. - The organic light-emitting diode Z according to the first embodiment of the present invention is described between with reference to
FIG. 1 toFIG. 7 . First of all, referring toFIG. 1 , the organic light-emitting diode Z provided by the first embodiment of the present invention includes ananode 1, acathode 2, a luminescentlayered structure 3, ahole transport layer 4 and anelectron transport layer 5. Thehole transport layer 4 is disposed between theanode 1 and the luminescentlayered structure 3, and theelectron transport layer 5 is disposed between thecathode 2 and the luminescent layeredstructure 3. - As shown in
FIG. 1 , the luminescentlayered structure 3 has aluminescent layer 31 and asensitizer layer 32. Theluminescent layer 31 includes a luminescent-layer ground state, a luminescent-layer singlet state and a luminescent-layer triplet state. Specifically, in the present embodiment, theluminescent layer 31 is a TTA material layer, that is to say, two times of the luminescent-layer triplet state is higher than the luminescent-layer singlet state. More specifically, theluminescent layer 31 is preferably made of an anthracene derivative, a pyrene derivative or a perylene derivative; however, the present invention is not limited thereto. The anthracene derivative may be but not limited to 9,10-Di(2-naphthyl)anthracene (ADN), 2-methyl-9,10-D(2-naphthyl)anthracene, 2-tert-butyl-9,10-Di(2-naphthyl)anthracene, or 9,9′-dianthracene. - In the embodiment shown in
FIG. 1 , thesensitizer layer 32 is disposed between theluminescent layer 31 and thehole transport layer 4. However, the present invention is not limited thereto. In other embodiments, the position of theluminescent layer 31 and that of thesensitizer layer 32 are interchangeable. That is to say, in other embodiments, thesensitizer layer 32 can be disposed between theluminescent layer 31 and theelectron transport layer 5. Thesensitizer layer 32 has a sensitizer-layer triplet state, which is between the luminescent-layer singlet state and the luminescent-layer triplet state. In the present embodiment, the material of thesensitizer layer 32 is preferably a (8-hydroxyquinoline) metal complex or a 10-hydroxybenzo [h] quinoline-metal complex. More specifically, examples of the (8-hydroxyquinoline) metal complex may include but not limited to tris(8-hydroxyquinoline)-aluminium (Alq3) and tris-(8-hydroxyquinoline)gallium (Gaq3), and examples of 10-hydroxybenzo [h] quinoline-metal complex may include but not limited to bis(10-hydroxybenzo[h]quinolinato)beryllium. - In a variant embodiment of the present embodiment, the
sensitizer layer 32 can transport electron holes and acts as a hole transport layer disposed between theluminescent layer 31 and theanode 1, as shown inFIG. 2 . In another variant embodiment, thesensitizer layer 32 can transport electrons and serve as an electron transport layer disposed between theluminescent layer 31 and thecathode 2, as shown inFIG. 3 . Furthermore, in other embodiments, thesensitizer layer 32 can be added to theluminescent layer 31 as a dopant. It should be noted that the present invention is not limited to any of the above examples. - The light emitting mechanism of the organic light-emitting diode of a first experimental example according to the present embodiment is described below with reference to
FIG. 4 , which shows an energy level diagram of the luminescentlayered structure 3 of the first experimental example. InFIG. 4 , the luminescent-layer singlet state S1, the sensitizer-layer triplet state T1 and the sensitizer-layer ground state G1 ofsensitizer layer 32 and the luminescent-layer singlet state S2, the luminescent-layer triplet state T2, and the luminescent-layer ground state G2 of theluminescent layer 31 are shown. As shown inFIG. 4 , the triplet state T1 of thesensitizer layer 32 is between the luminescent-layer singlet state S2 and the luminescent-layer triplet state T2. To be specific, the material of theluminescent layer 31 of the first experimental example is ADN, and that of thesensitizer layer 32 is Alq3, in which the energy level of the luminescentlayered structure 3 is shown in Table 1 below. -
TABLE 1 Sensitizer Luminescent layer 32 layer 32Singlet state (eV) 2.3 2.83 Triplet state (eV) 2.0 1.67 - In the present embodiment, through the technical solution that the
sensitizer layer 32 is disposed next to theluminescent layer 31 such that triplet-triplet energy transfer mechanism (TTET) between thesensitizer layer 32 and theluminescent layer 31 can occur, i.e. the molecules of thesensitizer layer 32 at the sensitizer-layer triplet state T1 transfer energy to the molecules of theluminescent layer 31 at the luminescent-layer triplet state T2 in a manner such that triplet-triplet annihilation upconversion mechanism (TTAUC) is triggered in theluminescent layer 31 thereafter. - Specifically, the aforementioned TTAUC mechanism occurs among excited triplet state molecules, wherein one excited triplet state molecule transfers energy to another excited triplet state molecule and returns to the ground state, and the excited triplet state molecule that receives the energy is raised to the singlet state. Next, molecules of the
luminescent layer 31 that arc raised to the singlet state return to the luminescent-layer ground state G2, thereby emitting light of a first color L1. - Referring to
FIG. 4 , in the present embodiment, molecules of thesensitizer layer 32 at the sensitizer-layer singlet state S1 emit light of a second color L2 when returning to the sensitizer-layer ground state G1. Furthermore, in the present embodiment, white light can be generated by mixing the first color light L1, the second color light L2, and light of a third color. For example, when using Alq3 as thesensitizer layer 32 and ADN as theluminescent layer 31, then with an added light-emitting material that emits red light, a white light can be obtained by mixing the blue light emitted by ADN, the green light emitted by Alq3 and the red light. However, the present invention is not limited thereto. For instance, in other embodiments, the material of theluminescent layer 31 and that of thesensitizer layer 32 are selected based on a predetermined color of light emitted by the organic light-emitting diode Z, thereby generating light of the predetermined color by mixing the first color light L1 and the second color light L2. - Please refer to
FIG. 5 andFIG. 6 , whereinFIG. 5 shows a diagram illustrating the electroluminescent property of the first experimental example according to the present embodiment, andFIG. 6 shows a diagram illustrating the transient electroluminescence of the luminescent layer of the first experimental example according to the present embodiment. Specifically, in the first experimental example, indium tin oxide (ITO) is used as theanode 1, and LiF/Al is used as thecathode 2. The thickness of thehole transport layer 4 is 50 nm, and the material thereof is N,N′-di(1-naphthyl)-N,N′-diphenyl benzidine (NPB). The thickness of theelectron transport layer 5 is 65 nm, and the material thereof is 4,7-diphenyl-1,10-phenanthroline (Bphen). The thickness of thesensitizer layer 32 is 5 nm, and the material thereof is Alq3. The thickness of theluminescent layer 31 is 10 nm, and the material thereof is ADN. It should be noted that the above description regarding the materials used and the specifications thereof are the exemplary embodiment of the present invention; the present invention is not limited thereto. - In the experimental example shown in
FIG. 5 andFIG. 6 , the transient electroluminescence of the organic light-emitting diode Z is measured by first applying an electro-pulse to the organic light-emitting diode Z, and the light emitted by the organic light-emitting diode Z in response to the electro-pulse is gauged and converted into electric output with a photomultiplier. The curves shown inFIG. 5 respectively represent the electric signals outputted by the organic light-emitting diode Z in response to an input voltage of 5 V, 4.6 V, 4.2 V, 3.8 V and 3.4 V. As shown inFIG. 5 , when each applied voltage is turned off at 0 second, the speed at which the organic light-emitting diode Z of the first experimental example emits light is of microsecond-scale. In general, the speed at which singlet excitons emit light is of nanosecond-scale, and that of triplet excitons is of microsecond-scale since triplet excitons decay slower owing to the spin conservation. That is to say,FIG. 5 shows that in the first experimental example the triplet excitons contribute to a larger percentage of total emission than organic light-emitting diodes in the prior art. The curves shown inFIG. 6 respectively represent the electric signals outputted by theluminescent layer 31 corresponding to an input electro-pulse of 5 V, 4.6 V, 4.2 V, 3.8 V and 3.4 V. It can be seen fromFIG. 6 that in the first experimental example of the present embodiment, the first color light L1 emitted by the luminescent layer 31 (ADN) is mainly from the triplet excitons thereof. -
FIG. 7 illustrates the external quantum efficiency of the first experimental example (shown with the curve marked as Alq3/ADN) according to the present embodiment and those of a first comparative example (shown with the curve marked as ADN) and a second comparative example (shown with the curve marked as Alq3). The difference between the first experimental example and the first and second comparative examples lies in that the first experimental example has a sensitizer layer and a luminescent layer, whereas the first comparative example has only ADN as the luminescent layer and does not have a sensitizer layer; the second comparative example has only Alq3 as the luminescent layer and does not have a sensitizer layer. As shown inFIG. 7 , the first experimental example exhibits higher external quantum efficiency than the first comparative example and the second comparative example do within most part of the operational current density. As stated in the background of the invention, 75% of recombined positive polarons and negative polarons transform into triplet excitons, which means the waste in energy in the prior art. In the present embodiment, by adding thesensitizer layer 32 in the organic light-emitting diode Z and adjusting the thicknesses of thehole transport layer 4 and theelectron transport layer 5, the negative polarons and the positive polarons recombine in thesensitizer layer 32 instead of theluminescent layer 31 so that singlet excitons and triplet excitons can be generated in thesensitizer layer 32, which triggers triplet-triplet energy transfer mechanism (TTET) between theluminescent layer 31 and thesensitizer layer 32 and then triplet-triplet annihilation upconversion mechanism (TTAUC) in theluminescent layer 31 thereafter. In this way, most of the triplet energy in thesensitizer layer 32 and the triplet energy in theluminescent layer 31 are converted to light emitted by the organic light-emitting diode Z, thereby increasing the external quantum efficiency of the organic light-emitting diode Z. - The second experimental example of the organic light-emitting diode Z of the present embodiment is described below with reference to
FIG. 8 toFIG. 10 . The second experimental example has a structure that is similar to that of the first experimental example with the main difference being that the material of thesensitizer layer 32 of the second experimental example is 1-(2,5-dimethyl-4-(1-pyrenyl)phenyl)pyrene (DMPPP).FIG. 8 shows the energy level diagram of the luminescentlayered structure 3 of the second experimental example. As shown in the figure, the sensitizer-layer triplet state T3 of the sensitizer layer 32 (DMPPP) is higher than the luminescent-layer triplet state T2 of theluminescent layer 31, and the sensitizer-layer singlet state S3 of thesensitizer layer 32 is higher than the luminescent-layer singlet state S2 of theluminescent layer 31. More specifically, the energy level of the luminescentlayered structure 3 is shown in Table 2 below. -
TABLE 2 Sensitizer Luminescent layer 32 layer 31Singlet state (eV) 3.15 2.83 Triplet state (eV) 2.01 1.67 - Please refer to
FIG. 9 .FIG. 9 illustrates the transient electroluminescence of the luminescent layer of the first experimental example according to the present embodiment. The curves shown inFIG. 9 respectively represent the electric signals outputted by the luminescent layer 31 (ADN) in response to an input voltage of 5.5 V-6 V, 5.5 V, 5.0 V, 4.5 V, and 4.0 V. As shown inFIG. 9 , when each applied voltage is turned off at 0 second, the speed at which the organic light-emitting diode Z of the second experimental example emits light is of microsecond-scale, which indicates that a larger percentage of the total emission of the second experimental example is converted from the triplet energy as compared to a conventional organic light-emitting diode. -
FIG. 10 illustrates the external quantum efficiency of the second experimental example (shown with the curve marked as DMPPP/ADN) according to the present embodiment and those of a third comparative example (shown with the curve marked as ADN) and a fourth comparative example (shown with the curve marked as DMPPP). The difference between the second experimental example and the third and fourth comparative examples lies in that the second experimental example has asensitizer layer 32 and aluminescent layer 31, whereas the third comparative example has only ADN has only the luminescent layer and does not have a sensitizer layer; the fourth comparative example has only DMPPP as the luminescent layer and does not have a sensitizer layer either. As shown inFIG. 10 , the second experimental example, which includes DMPPP as thesensitizer layer 32 and ADN as theluminescent layer 31, exhibits higher external quantum efficiency than the third comparative example and the fourth comparative example. - It should be noted that the relative difference between the sensitizer-layer singlet state and the luminescent-layer singlet state is not limited in the present invention. A person skilled in the art can select the material of the sensitizer layer and that of the luminescent layer according to actual needs. For instance, when in a condition that ADN which emits blue light has been determined to be the material of the
luminescent layer 31, the material of thesensitizer layer 32 can be decided based on the predetermined light color of the organic light-emitting diode Z. Specifically, when in one embodiment the predetermined light color is white, a material that has a singlet state lower than the luminescent-layer singlet state S2 can be selected as the material of thesensitizer layer 32, as in the case of the first experimental example, so that the second color light L2 is green. In this way, with a doped red light-emitting material the organic light-emitting diode Z can emit white light. When in another embodiment the predetermined light color of the organic light-emitting diode Z is blue, then a material that has a singlet state higher than the luminescent-layer singlet state S2 can be chosen to be the material of thesensitizer layer 32, as in the case of the second experimental example, so that the second color light L2 and the first light color L1 are both blue light. - In summary, the first embodiment of the present invention uses mainly the triplet energy thereof to emit light utilizing the technical solution of the
sensitizer layer 32, which serves as the place the recombination between the positive polarons and the negative polarons takes place such that triplet-triplet annihilation upconversion mechanism can be triggered in theluminescent layer 31 by the triplet excitons in thesensitizer layer 32 generated from the recombination. Since thesensitizer layer 32 acts as the recombination zone in the present embodiment, high energy polarons are prevented from reacting with the excitons in theluminescent layer 31. Therefore, the triplet energy in thesensitizer layer 32 can be utilized to emit light by being transferred to theluminescent layer 31 and converted through TTAUC mechanism, thereby enhancing the illumination efficiency of the organic light-emitting diode Z and extending the lifetime thereof. - Referring to
FIG. 11A , the main difference between the present embodiment and the first embodiment lies in that the organic light-emitting diode Z of the second embodiment further includes ablocking layer 33 between theluminescent layer 31 and thesensitizer layer 32. With reference toFIG. 11B , theblocking layer 33 has a blocking-layer singlet state S4 and a blocking-layer triplet state T4, in which the blocking-layer singlet state S4 is higher than the luminescent-layer singlet state S2, and the blocking-layer triplet state T4 is higher than the luminescent-layer triplet state T2. - With the
blocking layer 33, the triplet energy of thesensitizer layer 32 can be transferred to the triplet state of theluminescent layer 31. At the same time, the quenching effects between thesensitizer layer 32 and theluminescent layer 31 can be reduced. In this way, the illumination efficiency of the organic light-emitting diode Z can be further improved. - Furthermore, the material of the
blocking layer 33 can be 1-(2,5-dimethyl-4-(1-pyrenyl)phenyl)pyrene (DMPPP) or 1,3,5-Tri(1-pyrenyl)benzene (TPB3). However, the present invention is not limited thereto. Specifically, theblocking layer 33 of the present embodiment is DMPPP, whose energy level is shown in Table 3 below. -
TABLE 3 Sensitizer Blocking Luminescent layer 32 layer 33layer 31Singlet state (eV) 2.8 3.15 2.83 Triplet state (eV) 2.0 2.05 1.67 - Please refer to
FIG. 12 , which shows a diagram illustrating the external quantum efficiency of a first experimental example, a second experimental example and a third experimental example according to the second embodiment of the present invention. The first experimental example of the present embodiment uses ADN as the luminescent layer, Alq3 as the sensitizer layer, and the first experimental example has no blocking layer. The second experimental example is shown with a curve marked as 5 nm inFIG. 12 . The difference between the first experimental example and the second experimental example is that the second experimental example has ablocking layer 33 with a thickness of 5 nm between theluminescent layer 31 and thesensitizer layer 32. The material of theblocking layer 33 is DMPPP. The third experimental example is shown with a curve marked as 10 nm inFIG. 12 . The difference between the first experimental example and the third experimental example is that the third experimental example has ablocking layer 33 with a thickness of 10 nm between theluminescent layer 31 and thesensitizer layer 32. The material of theblocking layer 33 of the third experimental example is DMPPP. As shown inFIG. 12 , the third experimental example exhibits higher external quantum efficiency than the second experimental example, which in turn offers higher external quantum efficiency than the first experimental example. Therefore, the present embodiment shows that adding ablocking layer 33 to the organic light-emitting diode Z (as in the second experimental example and third experimental example of the present embodiment compared to the first experimental example) can effectively enhance the efficiency of the organic light-emitting diode Z. - In summary, the embodiments of the present invention achieves “the molecules of the sensitizer layer at the sensitizer-layer triplet layer transfers energy to the molecules of the luminescent layer at the luminescent-layer triplet state and triggers triplet-triplet annihilation upconversion in the luminescent layer such that the luminescent layer emits light of a first color” through the technical solutions that “two times of the luminescent-layer triplet state is higher than the luminescent-layer singlet state” and “the sensitizer-layer triplet state is between the luminescent-layer singlet state and the luminescent-layer triplet state”.
- Through the aforementioned technical solutions, the organic light-emitting diode Z of the present embodiments utilizes the
sensitizer layer 32 to perform triplet-triplet energy transfer between thesensitizer layer 32 and theluminescent layer 31, thereby triggering triplet-triplet annihilation upconversion mechanism in theluminescent layer 31. In this way, triplet energy of theluminescent layer 31 and that of thesensitizer layer 32 can be converted into light emitted by the organic light-emitting diode Z, thereby effectively enhancing the illumination efficiency and the lifespan of the organic light-emitting diode Z. - In addition, in some embodiments, a blocking layer can be added to the organic light-emitting diode Z, in which the singlet state of the blocking layer is higher than the singlet state of the luminescent layer, and the triplet state of the blocking layer is higher than the triplet state of the luminescent layer. In this way, the illumination efficiency of the organic light-emitting diode can be further increased.
- The present invention has been described with reference to the above embodiments, but the above embodiments are merely examples for implementing the present invention. It should be noted that the disclosed embodiments are not intended to limit the scope of the present invention. On the contrary, any modification and equivalent configuration within the spirit and scope of the appended claims shall fall within the scope of the present invention.
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| TWI560171B (en) * | 2015-10-16 | 2016-12-01 | Tetrahedron Technology Corp | Organic electroluminescent devices and material thereof |
| TWI611612B (en) * | 2016-11-30 | 2018-01-11 | 財團法人工業技術研究院 | Organic light-emitting diode and white organic light-emitting diode |
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| TWI708827B (en) | 2020-11-01 |
| TW202026395A (en) | 2020-07-16 |
| US10700303B1 (en) | 2020-06-30 |
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