CN112928221B - Crystalline organic electroluminescent diode with light-emitting layer containing nano aggregate and application thereof - Google Patents
Crystalline organic electroluminescent diode with light-emitting layer containing nano aggregate and application thereof Download PDFInfo
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- 239000004065 semiconductor Substances 0.000 claims abstract description 36
- 230000001939 inductive effect Effects 0.000 claims abstract description 17
- 230000006698 induction Effects 0.000 claims abstract description 16
- 239000013078 crystal Substances 0.000 claims abstract description 13
- 238000005286 illumination Methods 0.000 claims abstract description 4
- 239000010410 layer Substances 0.000 claims description 106
- 239000002346 layers by function Substances 0.000 claims description 48
- 239000000463 material Substances 0.000 claims description 31
- 239000010408 film Substances 0.000 claims description 22
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 17
- -1 10- (4- (1-phenyl-1H-phenanthro [9,10-d ] imidazol-2-yl) phenyl) anthracene-9-benzonitrile Chemical compound 0.000 claims description 10
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 9
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 9
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 5
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004305 biphenyl Substances 0.000 claims description 4
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 claims description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 4
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 4
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 4
- 239000010409 thin film Substances 0.000 claims description 4
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- 239000007773 negative electrode material Substances 0.000 claims description 3
- 239000007774 positive electrode material Substances 0.000 claims description 3
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- UQPGQTCUTFQPPW-UHFFFAOYSA-N 2-(4,6-dihydropyren-1-yl)-3-phenylphenanthro[9,10-d]imidazole Chemical compound C1(=CC=C2CC=C3CC=CC4=CC=C1C2=C34)C1=NC2=C(N1C1=CC=CC=C1)C1=CC=CC=C1C=1C=CC=CC=12 UQPGQTCUTFQPPW-UHFFFAOYSA-N 0.000 claims description 2
- RBDBSEGUHLEKHX-UHFFFAOYSA-N 4-[10-(4-carbazol-9-ylphenyl)anthracen-9-yl]benzonitrile Chemical compound C1=CC(C#N)=CC=C1C(C1=CC=CC=C11)=C(C=CC=C2)C2=C1C1=CC=C(N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 RBDBSEGUHLEKHX-UHFFFAOYSA-N 0.000 claims description 2
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- AVGCJXFOQHSMMS-UHFFFAOYSA-N C1(=CC=CC=C1)N1C2=CC=CC=C2C=2C=C(C=CC1=2)C1=C2C=CC=CC2=C(C2=CC=CC=C12)C1=CC=C(C#N)C=C1 Chemical compound C1(=CC=CC=C1)N1C2=CC=CC=C2C=2C=C(C=CC1=2)C1=C2C=CC=CC2=C(C2=CC=CC=C12)C1=CC=C(C#N)C=C1 AVGCJXFOQHSMMS-UHFFFAOYSA-N 0.000 claims description 2
- YUTCDFYEYANZAV-UHFFFAOYSA-N FC1=CC(F)=CC(N2C(C=CC3=C4C(N5C(C=CC=C6)=C6C6=CC=CC=C56)=CC5=C3C=CC=C5)=C4N=C2)=C1 Chemical compound FC1=CC(F)=CC(N2C(C=CC3=C4C(N5C(C=CC=C6)=C6C6=CC=CC=C56)=CC5=C3C=CC=C5)=C4N=C2)=C1 YUTCDFYEYANZAV-UHFFFAOYSA-N 0.000 claims description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 2
- 229940112669 cuprous oxide Drugs 0.000 claims description 2
- 125000005504 styryl group Chemical group 0.000 claims description 2
- 229930192474 thiophene Natural products 0.000 claims description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims 1
- 238000000151 deposition Methods 0.000 description 30
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- WBSMVAWETYTHTA-UHFFFAOYSA-N 2,5-bis(4-phenylphenyl)thiophene Chemical compound C=1C=C(C=2C=CC(=CC=2)C=2C=CC=CC=2)SC=1C(C=C1)=CC=C1C1=CC=CC=C1 WBSMVAWETYTHTA-UHFFFAOYSA-N 0.000 description 13
- 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 8
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 5
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- 238000004528 spin coating Methods 0.000 description 4
- CYPVTICNYNXTQP-UHFFFAOYSA-N 10-[4-[4-(9,9-dimethylacridin-10-yl)phenyl]sulfonylphenyl]-9,9-dimethylacridine Chemical compound C12=CC=CC=C2C(C)(C)C2=CC=CC=C2N1C1=CC=C(S(=O)(=O)C=2C=CC(=CC=2)N2C3=CC=CC=C3C(C)(C)C3=CC=CC=C32)C=C1 CYPVTICNYNXTQP-UHFFFAOYSA-N 0.000 description 3
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- IVXBGKPGZOETEW-UHFFFAOYSA-N 10-[4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl]-9,9-dimethylacridine Chemical compound CC1(C)C2=C(C=CC=C2)N(C2=CC=C(C=C2)C2=NC(=NC(=N2)C2=CC=CC=C2)C2=CC=CC=C2)C2=C1C=CC=C2 IVXBGKPGZOETEW-UHFFFAOYSA-N 0.000 description 2
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 description 2
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- 238000002425 crystallisation Methods 0.000 description 2
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- 238000010586 diagram Methods 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ULGYAEQHFNJYML-UHFFFAOYSA-N [AlH3].[Ca] Chemical compound [AlH3].[Ca] ULGYAEQHFNJYML-UHFFFAOYSA-N 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
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- 238000009792 diffusion process Methods 0.000 description 1
- IIDFEIDMIKSJSV-UHFFFAOYSA-N dipropoxyphosphinothioyloxy-dipropoxy-sulfanylidene-$l^{5}-phosphane Chemical compound CCCOP(=S)(OCCC)OP(=S)(OCCC)OCCC IIDFEIDMIKSJSV-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 238000002524 electron diffraction data Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 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
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
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Classifications
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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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
- H01S5/00—Semiconductor lasers
- H01S5/30—Structure or shape of the active region; Materials used for the active region
- H01S5/36—Structure or shape of the active region; Materials used for the active region comprising organic materials
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/865—Intermediate layers comprising a mixture of materials of the adjoining active 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
- H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/10—OLED displays
- H10K59/12—Active-matrix OLED [AMOLED] displays
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- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electromagnetism (AREA)
- Engineering & Computer Science (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention provides a crystalline organic electroluminescent diode with a luminescent layer containing nano aggregates and application thereof, belonging to the technical field of light emitting diodes. The crystalline organic electroluminescent diode comprises a first electrode, an induction layer, a luminescent layer and a second electrode which are arranged in sequence from bottom to top, wherein the induction layer is a crystalline organic semiconductor; the light-emitting layer comprises a nano aggregate and a crystalline organic semiconductor film, wherein the nano aggregate is positioned on the surface of the crystalline organic semiconductor film in the light-emitting layer or is partially or completely positioned inside the crystalline organic semiconductor film; an epitaxial relationship and/or an alignment relationship exists between the crystal lattice of the crystalline organic semiconductor in the light-emitting layer and the crystal lattice of the crystalline organic semiconductor in the inducing layer. The light-emitting diode has good electrical performance, stable performance and difficult attenuation, and can be widely used in the fields of display, illumination and laser.
Description
Technical Field
The invention belongs to the technical field of light-emitting diodes, and particularly relates to a crystalline organic electroluminescent diode with a light-emitting layer containing nano aggregates and application thereof.
Background
In recent years, organic Light Emitting Diodes (OLEDs) have been widely used in high-end display, lighting, and other fields because of their excellent light emission properties. OLED devices based on amorphous thin films present a number of challenges for their stability. Wherein, the amorphous material is crystallized due to heat generated by long-time use of the device, thereby reducing the lifetime of the OLED device. The method of using crystalline film in Chinese patent ZL 201810218296.2 effectively solves the problem of crystallization of materials under the thermal effect, and prolongs the service life of OLED devices. However, crystalline OLEDs also suffer from problems during manufacture and use. For example, crystallization can alter the location of material energy levels such that some of the otherwise efficient Thermally Activated Delayed Fluorescence (TADF) systems have reduced OLED device performance, even lost TADF performance. On the other hand, for triplet-triplet annihilation (TTA) delayed fluorescence, controlling the distribution of luminescent molecules in the luminescent layer is an important means to determine its performance. The dispersion degree of luminescent molecules is large, the distance between luminescent molecules is too large, and TTA delayed fluorescence effect cannot be realized; too high a molecular aggregation level will reduce the concentration of triplet excitons and reduce the luminous efficiency. In the prior art, no crystalline/amorphous OLED device has a good solution for controlling the uniformity of aggregation size of TTA type delayed fluorescence molecules in a light emitting layer.
Disclosure of Invention
In order to solve the problems of the prior crystalline OLED device, the invention provides a crystalline organic electroluminescent diode with a luminescent layer containing nano aggregates and application thereof.
The technical scheme adopted by the invention is as follows:
a crystalline organic electroluminescent diode containing nano-aggregates comprises a first electrode, an induction layer, a light-emitting layer and a second electrode which are arranged in sequence from bottom to top,
the induction layer is a crystalline organic semiconductor;
the light-emitting layer comprises a nano aggregate and a crystalline organic semiconductor film, wherein the nano aggregate is positioned on the surface of the crystalline organic semiconductor film in the light-emitting layer or is partially or completely positioned inside the crystalline organic semiconductor film;
an epitaxial relationship and/or an alignment relationship exists between the crystal lattice of the crystalline organic semiconductor in the light-emitting layer and the crystal lattice of the crystalline organic semiconductor in the inducing layer.
Preferably, the dimension of the nano-aggregate in at least one dimension in the three-dimensional direction is not more than 20 nm;
preferably, the light emitting diode further includes one or more of a first functional layer disposed between the first electrode and the inducing layer, a second functional layer disposed between the inducing layer and the light emitting layer, and a third functional layer disposed between the light emitting layer and the second electrode.
Preferably, the thicknesses of the first functional layer, the second functional layer and the third functional layer are all 1-100 nanometers.
Preferably, one of the first electrode and the second electrode is used as a positive electrode, the other is used as a negative electrode, the absolute value of the work function of the positive electrode material is not less than 4.5 ev, and the absolute value of the work function of the negative electrode material is not more than 4.5 ev.
Preferably, when the first electrode is used as the positive electrode, the first functional layer material is poly (3, 4-vinyldioxythiophene): poly (styrene sulfonate) (hereinafter abbreviated as PEDOT: PSS), molybdenum oxide (MoO) x ) One or more of cuprous oxide and cuprous iodide; when the first electrode is used as a negative electrode, the first functional layer material is one or more of titanium oxide, lithium fluoride (LiF), lithium carbonate and cesium carbonate.
Preferably, the material of the induction layer is 2, 5-bis (4-biphenyl) thiophene (BP 1T), 5 '-bis (4-biphenyl) -2,2' -bithiophene (BP 2T) or hexabiphenyl (P-6P), and the thickness is 2-20 nanometers.
Preferably, the crystalline organic semiconductor thin film in the light emitting layer is one or both of 2- (4- (9H-carbazol-9-yl) -1- (3, 5-difluorophenyl) -1H-phenanthroimidazole (2 FPPICz) and 1, 4-bis (1-phenyl-1H-phenanthro [9,10-d ] imidazol-2-yl) benzene (p-DPPI).
Preferably, the material of the nano aggregate in the light emitting layer is 10- (4- (1-phenyl-1H-phenanthro [9,10-d ] imidazol-2-yl) phenyl) anthracene-9-benzonitrile (PIANCN), 2- (4, 6-dihydropyren-1-yl) -1-phenyl-1H-phenanthro [9,10-d ] imidazole (PIMPy), 4- (10- (4- (9H-carbazol-9-yl) phenyl) anthracene-9-yl) benzonitrile (pCzAnBzt), 4- (10- (9-phenyl-9H-carbazol-3-yl) anthracene-9-yl) benzonitrile (3 CzAmBzt), (E) -N, N-diphenyl-4- (4- (pyridin-1-yl) styryl) aniline (DPASP), 1' - (2, 5-dimethyl-1, 4-phenylene) bipyrene (DMPPP), 2- (4- (10- (3- (9H-carbazol-9-yl) phenyl) anthracene-9-yl) phenyl) -1-imidazol-9-yl) benzonitrile (pCzAnBzt), 4- (10- (9-H-phenyl) anthracene-9-yl) benzonitrile (E) -N, N-diphenyl-4- (4-diphenyl) aniline (DMPPP), 2- (2, 5-dimethyl-1, 4-phenylene) diphenyl) bis [ 1-4-p-phenylene ] 4-p-yl ] diphenyl sulfone (DPP At least one of 10- (4, 6-diphenyl-1, 3, 5-triazol-2-yl) phenyl) -9, 9-dimethyl-9, 10-dihydroacridine (DMAC-TRZ).
The invention also provides application of the crystalline organic electroluminescent diode containing the nano aggregate in the fields of display, illumination and laser.
Among the first/second/third functional layers, the light-emitting layer and the induction layer, the term layer refers to a structure capable of realizing one or more functions in the OLED device, and the geometric structure of the structure can be a continuous or discontinuous film or a plurality of layers of continuous or discontinuous films which are overlapped in sequence; wherein, the chemical composition of each layer of film is the same, which can be a single material or a mixture of two or more materials;
for example, the inducing layer mainly has the function of inducing the organic semiconductor material growing on the inducing layer to grow into a large-size continuous crystalline film, and can also have the functions of charge transmission, contact improvement and the like; the light-emitting layer mainly functions to form a light-emitting center and can also transmit carriers and the like; the first/second/third functional layer may improve carrier injection, transport carriers, block exciton diffusion, and limit transport of different types of carriers.
The term "alignment relationship" means that a fixed angle exists between the crystal axis of the crystalline organic semiconductor in the light-emitting layer and the crystal axis of the crystalline organic semiconductor in the inducing layer, and the number thereof may be one or a limited number, and typically no more than 5.
The term "substrate" refers to a substrate, which is a rigid material such as glass, ceramic, or a flexible material such as plastic, metal foil, etc., and is used to prepare an OLED device electrode and different material layers sequentially on the surface of an object, which is required to be provided during the preparation process of the OLED device.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a crystalline organic electroluminescent diode with a luminescent layer containing nano aggregates and application thereof, compared with an amorphous organic semiconductor, the crystalline organic semiconductor has higher high mobility, so that under the same voltage, a crystalline OLED device can transmit larger current and emit more photons. The nano aggregate exists in the crystalline OLED device in an amorphous state, the original energy level position of the material is not changed, and the performance of the TADF type luminescent material is fully exerted. The crystalline organic electroluminescent diode with the luminescent layer containing the nano aggregate can effectively control TTA-type delayed fluorescent molecules to form nano aggregates with different scales in the crystalline luminescent layer, so that the concentration of the generated triplet state molecules is maximized, and the performance of an OLED device is effectively improved. Meanwhile, for the TTA guest material, the prepared nano aggregate can avoid the disadvantages of self hole and extremely unbalanced electron transmission, thereby improving the luminous efficiency of the OLED device. Meanwhile, for the crystalline state nano aggregate, a proper crystal direction is selected, so that the optical coupling-out efficiency of the OLED device is improved.
Drawings
Fig. 1 is a schematic structural diagram of a crystalline organic electroluminescent diode with a light-emitting layer containing nano-aggregates according to the present invention.
FIG. 2 is a graph of 2FPPICz growth X-ray diffraction on BP 1T.
FIG. 3 is a plot of 2FPPICz electron diffraction patterns for growth of selected regions on BP 1T.
FIG. 4 is an atomic force microscope image of PIANCN growth at BP1T/2 FPPICz.
Fig. 5 output photon number-voltage and current-voltage curves for the OLED device and the comparative device in example 2.
Fig. 6 output photon number-voltage and current-voltage curves for the OLED device and the comparative device in example 3.
Fig. 7 output photon number-voltage and current-voltage curves for the OLED device and the comparative device in example 4.
In the figure, 1, a first electrode, 2, a first functional layer, 3, an induction layer, 4, a second functional layer, 5, a light-emitting layer, 6, a third functional layer, 7, and a second electrode.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the detailed description, but it is to be understood that these descriptions are merely intended to further illustrate the features and advantages of the invention and are not limiting of the patent claims of the invention.
As shown in fig. 1, a crystalline organic electroluminescent diode with a light emitting layer containing nano-aggregates according to the present invention has a basic structure including a first electrode 1, an inducing layer 3, a light emitting layer 5 and a second electrode 7 which are closely arranged in order from bottom to top, wherein the inducing layer 3 is a crystalline organic semiconductor;
the light-emitting layer 5 comprises a nano aggregate and a crystalline organic semiconductor film, wherein the nano aggregate is positioned on the surface of the crystalline organic semiconductor film in the light-emitting layer or is partially or completely positioned inside the crystalline organic semiconductor film;
the dimension of the nano aggregate in at least one dimension in the three-dimensional direction is not more than 20 nanometers;
there is an epitaxial relationship and/or an alignment relationship between the crystal lattice of the crystalline organic semiconductor in the light-emitting layer 5 and the crystal lattice of the crystalline organic semiconductor in the inducing layer 3.
The thickness of the first electrode 1 and the second electrode 7 is preferably 20-1000 nm. One of the first electrode 1 and the second electrode 7 serves as a positive electrode of the OLED device, the other serves as a negative electrode, and the absolute value of the work function of the positive electrode material is not less than 4.5 electron volts, preferably Indium Tin Oxide (ITO), p-doped zinc oxide, gold or p-doped silicon; the absolute value of the work function of the negative electrode material is not more than 4.5 electron volts, preferably aluminum, calcium, magnesium-silver complex, calcium-aluminum complex or n-doped zinc oxide.
The material of the induction layer 3 is preferably BP1T, BP T or P-6P, and the thickness is preferably 2-20 nanometers.
The crystalline organic semiconductor film in the light emitting layer 5 is preferably one or both of 2FPPICz and p-DPPI.
The material of the nano aggregate in the light-emitting layer 5 is preferably at least one of PIAnCN, PIMPy, pCzAnBzt, 3CzAmBzt, DPASP, DMPPP, PAC, DMAC-DPS and DMAC-TRZ. The thickness of the light emitting layer is preferably 1 to 50 nm.
The diode further comprises one or more of a first functional layer 2, a second functional layer 4 and a third functional layer 6, wherein the first functional layer 2 is arranged between the first electrode 1 and the inducing layer 3, the second functional layer 4 is arranged between the inducing layer 3 and the light-emitting layer 5, and the third functional layer 6 is arranged between the light-emitting layer 5 and the second electrode 7.
The thickness of each of the first, second and third functional layers 2, 4 and 6 is preferably 1 to 100 nm. The material of the first functional layer 2 may Be one or more of PSS, molybdenum oxide, cuprous iodide, titanium oxide, lithium fluoride, lithium carbonate and cesium carbonate, and the material of the second functional layer 4 and the third functional layer 6 may Be one or more of metal phthalocyanine, NPB, NPD, TAPC, molybdenum oxide doped TAPC, be (PP) 2, lithium carbonate doped Be (PP) 2, alq3 and lithium fluoride. The choice of the specific materials of the first functional layer 2, the second functional layer 4 and the third functional layer 6, which are associated with the positive or negative electrode of the first electrode 1, can be determined according to techniques known to those skilled in the art. The material of the first functional layer 2 is preferably one or more of PEDOT: PSS, molybdenum oxide, cuprous iodide, when the first electrode 1 is used as the positive electrode, and one or more of titanium oxide, lithium fluoride, lithium carbonate, cesium carbonate, when the first electrode 1 is used as the negative electrode.
The invention also provides application of the crystalline organic electroluminescent diode in the fields of display, illumination and laser.
The invention is further illustrated below with reference to examples. In the examples, all sources of materials are shown in table 1 below,
TABLE 1
Example 1
Preparation of a crystalline organic semiconductor film containing nano-aggregates:
step (a)1. Vacuum evaporation method is adopted, and the vacuum degree is 8 multiplied by 10 -4 Pascal, substrate temperature 150 ℃, sequentially depositing 6 nm BP1T and 5 nm 2FPPICz on a smooth glass surface at a deposition rate of 1 nm/min;
step two, depositing PIAnCN, wherein the deposition rate is 1 nanometer/min, and the deposition time is 1 min;
step three, alternately depositing 5 nm 2FPPICz and 1 nm PIAnCN for 3 periods according to the processes of the step one and the step two;
and step four, depositing 2FPPICz of 10 nanometers, and completely wrapping the PIANCN nanometer aggregate in the 2FPPICz crystalline film.
FIG. 2 is an X-ray diffraction pattern corresponding to BP1T/2FPPICz prepared in step one, wherein a 006 crystal plane diffraction peak of BP1T can be observed, illustrating the ordered arrangement of molecules in the BP1T film, with the pi-pi arrangement direction parallel to the substrate; the 002 and 004 crystal plane diffraction peaks of 2FPPICz were observed to indicate ordered arrangement of molecules in the 2FPPICz film, with the pi-pi alignment direction parallel to the substrate.
Fig. 3 is a selective electron diffraction diagram corresponding to BP1T/2FPPICz prepared in step one, wherein the a-axis of BP1T coincides with the a-axis of 2FPPICz, indicating that there is an epitaxial relationship between the two.
FIG. 4 is an atomic force microscope photograph of PIANCN grown in BP1T/2FPPIcz prepared in step two.
Example 2
The crystalline organic electroluminescent diode with the luminescent layer containing nano aggregate consists of a first electrode 1, an induction layer 3, a luminescent layer 5 and a second electrode 7 which are arranged in sequence from bottom to top; wherein, glass is taken as a substrate, ITO is taken as a first electrode 1, BP1T is adopted as an induction layer 3, and the thickness is 6 nanometers; in the light emitting layer 5, a crystalline organic semiconductor thin film material using 2FPPICz: the p-DPPI eutectic film has a molar ratio of 95:5 and a thickness of 40 nanometers, the nano particles use TADF luminescent molecules DMAC-DPS, the second electrode 7 adopts metal aluminum, and the thickness is 100 nanometers.
Preparation of the crystalline organic electroluminescent diode with the luminescent layer containing the nano-aggregates:
step one, vacuum vapor deposition is adoptedMethod, vacuum degree is 8×10 -4 Pascal, the temperature of the substrate is 150 ℃, and 6 nanometers of BP1T is sequentially deposited on the surface of the ITO conductive glass;
step two, vacuum codeposition is carried out on 40 nanometers 2FPPIcz, p-DPPI, the molar ratio of the two is 95:5, the deposition rate is 1 nanometer/min, and the deposition time is 40 min;
step three, the temperature of the substrate is reduced to room temperature, DMAC-DPS is deposited, the deposition rate is 1 nanometer/min, the deposition time is 1 min,
and fourthly, depositing 100 nanometers of metal aluminum by using a mask plate, wherein the deposition rate is 50 nanometers/min, and obtaining the crystalline organic electroluminescent diode with the luminescent layer containing the nano aggregate.
Fig. 5 is photon number-voltage and current-voltage curves of the OLED device prepared in example 1, while amorphous devices of the same structure are given as a comparison. Because of the crystalline structure, the resistance of the device is obviously reduced, so that the current flowing through the device is obviously increased under the same voltage. Meanwhile, due to the adoption of the nano aggregate structure, the output photon number of the crystalline device is obviously increased under the same voltage.
Example 3
The crystalline organic electroluminescent diode with a luminescent layer containing nano aggregates consists of a first electrode 1, a first functional layer 2, an induction layer 3, a second functional layer 4, a luminescent layer 5, a third functional layer 6 and a second electrode 7 which are arranged in sequence from bottom to top; wherein glass is used as a substrate, ITO is used as a first electrode 1; the first functional layer 2 consists of a PEDOT PSS layer and a molybdenum oxide layer which are sequentially arranged from bottom to top, wherein the thickness of the molybdenum oxide layer is 2 nanometers, and the PEDOT is 40 nanometers; the induction layer 3 adopts P-6P with the thickness of 2 nanometers; the second functional layer 4 is p-DPPI with the thickness of 15 nanometers, 2FPPIcz is adopted as a crystalline organic semiconductor film material in the light-emitting layer 5, DPASP is adopted as a material of a nano aggregate with the thickness of 40 nanometers; the third functional layer 6 adopts TPBi and LiF, and the thickness is 40 nanometers and 1 nanometer respectively; the second electrode 7 is made of metal aluminum and has a thickness of 100 nm.
The preparation of the crystalline organic electroluminescent diode with the luminescent layer containing the nano aggregate comprises the following steps:
step one, spin coating a layer of PEDOT on the surface of ITO conductive glass, wherein the spin coating speed is 3000 rpm, and the time is 30 seconds;
step two, adopting a vacuum evaporation method, wherein the vacuum degree is 8 multiplied by 10 -4 Pascal, substrate temperature is room temperature, 2 nm MoO is deposited on PEDOT: PSS surface x Deposition rate 1 nm/min;
step three, raising the temperature of the substrate to 180 ℃, and sequentially depositing 2 nm of P-6P and 15 nm of P-DPPI at a deposition rate of 1 nm/min;
step four, the temperature of the substrate is reduced to 150 ℃, and 2FPPICz is deposited in vacuum for 20 minutes, wherein the molar ratio of the two is 10:1, and the deposition rate is 1 nanometer/minute;
step five, the temperature of the substrate is reduced to room temperature, 40 nanometers of TPBi is deposited, and the deposition rate is 10 nanometers/min
Step six, depositing LiF of 1 nanometer, wherein the deposition rate is 0.5 nanometer/min;
and step seven, depositing 100 nanometer metal aluminum by using a mask plate, wherein the deposition rate is 50 nanometers per minute, and obtaining the crystalline organic electroluminescent diode with the luminescent layer containing the nanometer aggregate.
Fig. 6 is photon number-voltage and current-voltage curves of the OLED device prepared in example 3, while amorphous devices of the same structure are given as a comparison. Because of the crystalline structure, the resistance of the device is obviously reduced, so that the current flowing through the device is obviously increased under the same voltage. Meanwhile, due to the adoption of the nano aggregate structure, the output photon number of the crystalline device is obviously increased under the same voltage.
Table 2 shows the composition of light-emitting layer 5 in a series of crystalline organic electroluminescent diodes having a light-emitting layer comprising nano-aggregates prepared as in example 3.
TABLE 2
The results show that the organic electroluminescent diode prepared according to the composition of the light emitting layer 5 in table 2 has significantly reduced resistance due to the crystalline structure, and thus the current flowing through the device increases significantly at the same voltage. Meanwhile, due to the adoption of the nano aggregate structure, the output photon number of the crystalline device is obviously increased under the same voltage.
Example 4
The crystalline organic electroluminescent diode with a luminescent layer containing nano aggregates consists of a first electrode 1, a first functional layer 2, an induction layer 3, a luminescent layer 5, a third functional layer 6 and a second electrode 7 which are arranged in sequence from bottom to top; wherein glass is used as a substrate, and ITO is used as a first electrode 1; the first functional layer 2 is a PEDOT PSS layer with the thickness of 40 nanometers; the induction layer 3 adopts BP1T with the thickness of 6 nanometers; in the luminescent layer 5, 2FPPICz is adopted as a crystalline organic semiconductor film material, the thickness is 20 nanometers, a mixture of DPASP and DMPPP is adopted as a material of a nano aggregate, and the molar ratio of the DPASP to the DMPPP is 1:10; the third functional layer 6 adopts TPBi and LiF, and the thickness is 40 nanometers and 1 nanometer respectively; the second electrode 7 is made of metal aluminum and has a thickness of 100 nm.
The preparation of the crystalline organic electroluminescent diode with the luminescent layer containing the nano aggregate comprises the following steps:
step one, spin coating a layer of PEDOT on the surface of ITO conductive glass, wherein the spin coating speed is 3000 rpm, and the time is 30 seconds;
step two, adopting a vacuum evaporation method, wherein the vacuum degree is 8 multiplied by 10 -4 Pascal, substrate temperature 150 ℃, sequentially depositing 6 nm BP1T and 5 nm 2FPPICz at a rate of 1 nm/min;
step three, vacuum codeposition DPASP and DMPPP, wherein the molar ratio of the DPASP to the DMPPP is 1:10, the deposition rate is 1 nanometer/min, and the deposition time is 2 min;
step four, alternately depositing 2FPPICz and DPASP, wherein the conditions are the same as those of the step two and the step three, namely DMPPP three periods;
step five, the temperature of the substrate is reduced to room temperature, 40 nanometers of TPBi is deposited, and the deposition rate is 10 nanometers/min
Step six, depositing LiF of 1 nanometer, wherein the deposition rate is 0.5 nanometer/min;
step seven, 100 nanometer metal aluminum is deposited by using a mask plate, the deposition rate is 50 nanometers/min, and the crystalline organic electroluminescent diode with the luminescent layer containing nanometer aggregates is obtained
Fig. 7 is photon number-voltage and current-voltage curves of the OLED device prepared in example 4, while amorphous devices of the same structure are given as a comparison. Because of the crystalline structure, the resistance of the device is obviously reduced, so that the current flowing through the device is obviously increased under the same voltage. Meanwhile, due to the adoption of the nano aggregate structure, the output photon number of the crystalline device is obviously increased under the same voltage.
Claims (10)
1. A crystalline organic electroluminescent diode with a luminescent layer containing nano-aggregates comprises a first electrode (1), an induction layer (3), a luminescent layer (5) and a second electrode (7) which are arranged in sequence from bottom to top,
the induction layer (3) is a crystalline organic semiconductor,
the light-emitting layer (5) comprises a nano aggregate and a crystalline organic semiconductor film, wherein the nano aggregate is positioned on the surface of the crystalline organic semiconductor film in the light-emitting layer or is partially or completely positioned inside the crystalline organic semiconductor film;
an epitaxial relationship and/or an alignment relationship exists between the crystal lattice of the crystalline organic semiconductor in the light-emitting layer (5) and the crystal lattice of the crystalline organic semiconductor in the inducing layer (3).
2. A crystalline organic electroluminescent diode comprising nano-aggregates in the light-emitting layer according to claim 1, wherein the dimension of the nano-aggregates in the light-emitting layer (5) in at least one dimension in the three-dimensional direction is not more than 20 nm.
3. A crystalline organic electroluminescent diode comprising nano-aggregates in a light-emitting layer according to claim 1, characterized in that the light-emitting diode further comprises one or more of a first functional layer (2), a second functional layer (4) and a third functional layer (6), the first functional layer (2) being arranged between the first electrode (1) and the inducing layer (3), the second functional layer (4) being arranged between the inducing layer (3) and the light-emitting layer (5), the third functional layer (6) being arranged between the light-emitting layer (5) and the second electrode (7).
4. A crystalline organic electroluminescent diode comprising nano-aggregates in a light-emitting layer according to claim 3, characterized in that the thickness of the first functional layer (2), the second functional layer (4) and the third functional layer (6) is 1-100 nm.
5. A crystalline organic electroluminescent diode comprising nano-aggregates in a light-emitting layer according to claim 1, characterized in that one of the first electrode (1) and the second electrode (7) is used as a positive electrode and the other as a negative electrode, the absolute value of the work function of the positive electrode material is not less than 4.5 ev, and the absolute value of the work function of the negative electrode material is not more than 4.5 ev.
6. The crystalline organic electroluminescent diode with a light-emitting layer comprising nano-aggregates according to claim 5, wherein when the first electrode (1) is used as a positive electrode, the first functional layer (2) is made of poly (3, 4-vinyldioxythiophene): one or more of poly (styrenesulfonate), molybdenum oxide, cuprous oxide, and cuprous iodide; when the first electrode (1) is used as a negative electrode, the material of the first functional layer (2) is one or more of titanium oxide, lithium fluoride, lithium carbonate and cesium carbonate.
7. The crystalline organic electroluminescent diode having a light-emitting layer containing nano-aggregates according to claim 1, wherein the material of the inducing layer (3) is 2, 5-bis (4-biphenyl) thiophene, 5 '-bis (4-biphenyl) -2,2' -bithiophene or hexabiphenyl, and the thickness is 2-20 nm.
8. The crystalline organic electroluminescent diode having a light-emitting layer containing nano-aggregates according to claim 1, wherein the crystalline organic semiconductor thin film in the light-emitting layer (5) is one or both of 2- (4- (9H-carbazol-9-yl) -1- (3, 5-difluorophenyl) -1H-phenanthroimidazole and 1, 4-bis (1-phenyl-1H-phenanthro [9,10-d ] imidazol-2-yl) benzene.
9. The crystalline organic electroluminescent diode with a nano-aggregate-containing light-emitting layer according to claim 1, wherein the nano-aggregate material in the light-emitting layer (5) is 10- (4- (1-phenyl-1H-phenanthro [9,10-d ] imidazol-2-yl) phenyl) anthracene-9-benzonitrile, 2- (4, 6-dihydropyren-1-yl) -1-phenyl-1H-phenanthro [9,10-d ] imidazole, 4- (10- (4- (9H-carbazol-9-yl) phenyl) anthracene-9-yl) benzonitrile, 4- (10- (9-phenyl-9H-carbazol-3-yl) anthracene-9-yl) benzonitrile, (E) -N, N-diphenyl-4- (4- (pyridin-1-yl) styryl) aniline, 1' - (2, 5-dimethyl-1, 4-phenylene) bipyrene, 2- (10- (3- (9H-carbazol-9-yl) phenyl) anthracene-9-yl) phenyl) -1-phenanthro-phenyl-9-yl ] anthracene-9-yl, 4- (10- (9H-phenyl) butan-9-yl) benzonitrile, 4- (E) -N, N-diphenyl-4- (4-diphenyl) diphenyl-4-diphenyl) phenanthro [ 9-4-diphenyl ] disulfide At least one of 10- (4, 6-diphenyl-1, 3, 5-triazol-2-yl) phenyl) -9, 9-dimethyl-9, 10-dihydroacridine.
10. Use of the crystalline organic electroluminescent diode containing nano-aggregates according to claim 1 in the fields of display, illumination and laser.
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