CN105226193B - Electroluminescent device containing fused ring compound and metal organic complex - Google Patents

Abstract

The invention relates to a novel electroluminescent device containing a host material and a metal organic complex, wherein the quantum number of ground state spin of the host material is 1, and delta (S1-T1) is not less than 0.75eV, and the quantum number of ground state spin of the metal complex is 2. In particular organic light emitting diodes, light emitting cells, thereby adding an option to the technology for use in display devices, lighting and other applications. The invention also relates to a method for the production of such an electroluminescent device, in particular a solution-based production method.

Description

Electroluminescent device containing fused ring compound and metal organic complex

Belongs to the technical field of:

the invention relates to an electroluminescent device, in particular an organic light-emitting diode, comprising a fused-ring compound and a metal-organic complex, to a device structure thereof, to a method for the production thereof and to the use thereof in lighting and display technology and in other applications.

Background art:

organic light emitting devices, particularly Organic Light Emitting Diodes (OLEDs) (see TANG et al appl. phys. lett.1987,51, p913), are currently the most promising next generation display and lighting technologies due to their autonomous light emission, high brightness, rich color tunability through chemical synthesis, flexibility, etc. In particular, they may be formed into films from a solution by Printing methods such as ink jet Printing (InkJet Printing), Screen Printing (Screen Printing) and the like, so that the manufacturing cost can be greatly reduced, and thus they are particularly attractive for large Screen displays and illuminators.

The performance of small molecule based OLEDs has advanced significantly and has reached the stage of commercialization. However, the performance, especially the efficiency and lifetime of the whole OLED are still required to be improved. Currently, high-efficiency OLEDs are generally realized by phosphorescent materials, but are limited to green and red phosphorescent OLEDs, and stable and high-efficiency blue phosphorescent OLEDs are not realized. This is because, in addition to the lack of a stable blue phosphorescent light emitting material, the host material corresponding to the stable blue phosphorescent light emitting material must have a large triplet energy level, otherwise, triplet excitons on the blue phosphorescent light emitting material are transferred to the host to generate a quenching effect; while the Hole Transport Layer (HTL), the Electron Transport Layer (ETL), or the exciton blocking layer (ExBL) adjacent to the light-emitting layer must also have a triplet energy level greater than that of the blue phosphorescent emitter. This presents significant challenges to the material design and synthesis of these functional layers. Host materials for blue-emitting fluorescent OLEDs typically contain condensed ring compounds, typically anthracene-based compounds, which have very good stability but low triplet energy levels and quench the emission of phosphorescent emitters when used in the light-emitting layer of a phosphorescent OLED or in the ETL or HTL adjacent to the light-emitting layer. It is therefore always desirable to have new material combinations or techniques available that can remedy the drawbacks of the prior art.

Disclosure of Invention

The invention provides a novel electroluminescent device, comprising 1) a luminescent layer, which at least comprises a host material, wherein the spin quantum number of the ground state of the host material is 1, and delta (S1-T1) is more than or equal to 0.75eV, and a metal complex, wherein the spin quantum number of the ground state of the metal complex is 2; 2) an anode electrode disposed on one side of the functional layer; 3) and a cathode electrode disposed on the other side of the functional layer. The electroluminescent device can be selected from organic light emitting diodes, quantum dot light emitting diodes, light emitting batteries and the like. The electroluminescent device according to the invention extends the technical options available for display devices, lighting and other applications. It is a second object of the invention to provide a method for the preparation of such an electroluminescent device, in particular a solution-based preparation method.

Brief Description of Drawings

Fig. 1 is a light emitting device structure according to the present invention. In the figure, 101, a substrate, 102, an anode, 103, an EML, 104 and a cathode.

Fig. 2 is a schematic diagram of a preferred light-emitting device according to the present invention. In the figure 201, substrate, 202, anode, 203, EML, 204, cathode, 205, HIL or HTL or EBL or ExBL.

Fig. 3 is a structural view of another preferred light emitting device according to the present invention. In the figure 301, substrate, 302, anode, 303, EML, 304, cathode, 305, EIL or ETL or HBL or ExBL.

Fig. 4 is a view showing a structure of a preferred light emitting device according to the present invention. In the figure 401 substrate, 402 anode, 403, EML, 404, cathode, 405, EIL or ETL or HBL or ExBL, 406, HIL or HTL or EBL or ExBL.

Wherein HIL denotes a hole injection layer, HTL denotes a hole transport layer, HBL denotes a hole blocking layer, EIL denotes an electron injection layer, ETL denotes an electron transport layer, EBL denotes an electron blocking layer, EML denotes an emission layer, and ExBL denotes an exciton blocking layer.

Detailed description of the invention

It should be recognized that the specific implementations described and illustrated below are examples of the invention and are not meant to otherwise limit the scope of the invention in any way. Indeed, for the sake of brevity, conventional electronic devices, fabrication methods, semiconductor devices, and nanocrystal, Nanowire (NW), nanorod, nanotube, and nanoribbon technologies, related organic materials, and other functions of the systems may not be described in detail herein.

The present invention provides a novel electroluminescent device comprising

1) A light-emitting layer containing at least a host material whose spin quantum number in the ground state is 1 and Δ (S1-T1) is 0.75eV or more, and a metal complex whose spin quantum number in the ground state is 2;

2) an anode electrode disposed on one side of the functional layer;

3) and a cathode electrode disposed on the other side of the functional layer.

Where S1 is the singlet energy level and T1 is the triplet energy level.

In a general embodiment, a light emitting device according to the present invention has a structural diagram shown in fig. 1, and includes a substrate (101), an anode (102), a light emitting layer (103), and a cathode (104). The substrate (101) may also be located on one side of the cathode (104). In a device, the functional layer is only the light emitting layer.

Preferably, the light-emitting device according to the present invention further comprises other functional layers.

In a preferred embodiment, a light emitting device according to the present invention has a structural diagram shown in fig. 2, and includes a substrate (201), an anode (202), a light emitting layer (203), a cathode (204), and an HIL or HTL or EBL or ExBL (205) between the light emitting layer and the anode. The substrate (201) may be positioned on one side of the cathode (204).

In another preferred embodiment, a light emitting device according to the present invention has a structure as shown in fig. 3, and comprises a substrate (301), an anode (302), a light emitting layer (303), a cathode (304), and an EIL or ETL or HBL or ExBL (305) between the light emitting layer and the cathode. The substrate (301) may also be located on one side of the cathode (304).

In another particularly preferred embodiment, a light emitting device according to the present invention has the structural diagram shown in fig. 4, and comprises a substrate (401), an anode (402), a light emitting layer (403), a cathode (404), an EIL or ETL or HBL (405) between the light emitting layer and the cathode, and an HIL or HTL or EBL or ExBL (406) between the light emitting layer and the anode. The substrate (401) may also be located on one side of the cathode (404).

Examples of further possible configurations of light emitting devices according to the present invention are, but not limited to, anode/HIL/HTL/EML/cathode, anode/HIL/HTL/EML/ETL/cathode, anode/HIL/HTL/EBL/EML/ETL/EIL/cathode, anode/HIL/HTL/EBL/EML/ETL/cathode, anode/HIL/HTL/EBL/EML 1/EML 2/ETL/EIL/cathode, anode/EML/ETL/EIL/cathode, anode/HIL/HTL/EBL/EML/HBL/EIL/cathode, and the like.

In the above-described devices, the thickness of the HIL or HTL or EBL or EML or ETL or EIL or ExBL may range from 5 to 1000nm, preferably 10 to 800nm, more preferably 10 to 500nm, most preferably 10 to 100 nm.

An electroluminescent device is a device that emits light under the influence of an electric field. In certain embodiments, the electroluminescent devices of the present invention emit light at wavelengths ranging from UV to near infrared, preferably from 350nm to 850nm, more preferably from 380nm to 800nm, and most preferably from 380nm to 680 nm.

In a preferred embodiment, the electroluminescent device of the invention is an organic light emitting diode OLED.

In general, in the light emitting layer (EML), a host material is a predominant component. The proportion of luminophor in the luminescent layer is 1-25 wt.%, preferably 2-20 wt.%, more preferably 3-15 wt.%, most preferably 5-10 wt.%.

In one embodiment, the light-emitting layer further comprises another host material. When the host of the light-emitting layer comprises two host materials, the weight ratio of the two host materials is from 1:5 to 5:1, preferably from 1:4 to 4:1, more preferably from 1:3 to 3:1, and most preferably from 1:2 to 2: 1. Which may be an inorganic material plus another inorganic material or an inorganic material plus another organic material. A preferred combination is one where the host material is a p-type semiconductor and the other is an n-type semiconductor. In the present invention, the p-type semiconductor material, the hole transport material and the HTM have the same meaning and they may be interchanged. The n-type semiconductor material electron transport material and ETM have the same meaning and they can be interchanged.

In some embodiments, an electroluminescent device according to the present invention comprises a light-emitting layer comprising an ionic compound. Such a light emitting device is also called a light emitting battery. Light emitting cells are well known to those skilled in the art and may be found in Pei & Heeger, Science (1995),269, pp1086-1088. the ionic compound may be a host material, a luminescent material or another compound that acts as a source of ions. In a preferred embodiment, the light emitting cell further comprises an ion transport material. Various ionic compounds and ion transport materials suitable for use in light emitting cells are described in detail in WO2012013270a1, WO2012126566a1 and WO2012152366a1, the entire contents of this 3 patent document being hereby incorporated by reference.

In the embodiment of the present invention, regarding the energy level structure of the organic material, HOMO, LUMO, triplet level (T1), and singlet level (S1), and somo (singly agglomerated mo), LUMO of the metal-organic complex whose ground state spin quantum number is 2 play a key role. The determination of these energy levels is described below. The HOMO, LUMO, SOMO energy levels can be measured by the photoelectric effect, for example XPS (X-ray photoelectron spectroscopy) and UPS (ultraviolet photoelectron spectroscopy) or by cyclic voltammetry (hereinafter referred to as CV). Recently, quantum chemical methods, such as the density functional theory (hereinafter abbreviated as DFT), have become effective methods for calculating the molecular orbital level.

The triplet energy level T1 of the organic material can be measured by low temperature Time resolved luminescence spectroscopy, or obtained by quantum simulation calculations (e.g. by Time-dependent DFT), such as by commercial software Gaussian 03W (Gaussian Inc.), and specific simulation methods can be found in WO 2011141110. The singlet energy level S1 of the organic material can be determined by absorption spectroscopy, or emission spectroscopy, or can be obtained by a calculation of the Time-dependent DFT.

It should be noted that the absolute values of HOMO, LUMO, SOMO, T1 and S1 depend on the measurement method or calculation method used, and even for the same method, different evaluation methods, such as starting point and peak point on the CV curve, can give different HOMO/LUMO values. Thus, a reasonably meaningful comparison should be made with the same measurement method and the same evaluation method. In the description of the embodiments of the present invention, the values of HOMO, LUMO, SOMO, T1, and S1 are based on the simulation of Time-dependent DFT, but do not affect the application of other measurement or calculation methods.

Suitable organometallic complexes have the formula M (L)_nWhere M is a transition metal or copper group element, L, which may be the same or different at each occurrence, is an organic ligand which is bonded or coordinately bound to the metal atom M via one or more positions, and n is an integer greater than 1, preferably 1,2,3,4, 5 or 6. Optionally, the metal complexes are coupled to a polymer through one or more sites, preferably through organic ligands.

In a preferred embodiment, the metal atom M is chosen from transition metals or lanthanides or actinides, preferably Ir, Pt, Pd, Au, Rh, Ru, Os, Sm, Eu, Gd, Tb, Dy, Re, Cu or Ag, particularly preferably Os, Ir, Ru, Rh, Re, Pd, Pt.

In another very preferred embodiment, the metal element is selected from the group of elements of the copper group, i.e. Au, Ag, Cu.

Preferably, the organometallic complex comprises a chelating ligand, i.e. a ligand which coordinates to the metal via at least two binding sites, particularly preferably the triplet emitter comprises two or three identical or different bidentate or polydentate ligands. The chelating ligands are advantageous for increasing the stability of the metal complexes.

Examples of organic ligands may be selected from phenylpyridine (phenyl quinoline) derivatives, 7,8-benzoquinoline (7,8-benzoquinoline) derivatives, 2(2-thienyl) pyridine (2(2-thienyl) pyridine) derivatives, 2(1-naphthyl) pyridine (2(1-naphthyl) pyridine) derivatives, or 2-phenylquinoline (2-phenylquinoline) derivatives. All of these organic ligands may be substituted, for example, with fluorine-containing or trifluoromethyl groups. The ancillary ligand may preferably be selected from acetone acetate (acetylacetate) or picric acid.

In a more preferred embodiment, the metal element is Au. A preferred gold-containing organometallic complex has the following formulae (I) and (II)

Wherein A is a derivative of a cyclic structure of a pyridine group, B and C are cyclic structures of phenyl derivatives, X is N, Y, Z is C or N, R1, R2 is a strong sigma donor group attached to the gold atom, or is an optionally substituted carbon donor ligand, R1 and R2 may be combined optionally to form a bidentate ligand.

In a preferred embodiment, R1, R2 is a group comprising an alkynyl group.

Examples of suitable ground state spin quantum number 2 organometallic complexes are

Generally, host materials suitable for use in the present invention have a spin quantum number of 1 in the ground state, and Δ (S1-T1) is 0.75eV or more, preferably Δ (S1-T1) is 0.85eV or more, more preferably Δ (S1-T1) is 0.95eV or more, and most preferably Δ (S1-T1) is 1.0eV or more.

Suitable host materials may be arbitrarily selected from organic compounds having a large conjugated system. In certain embodiments, there are at least more than two conjugated systems of benzene rings.

In a preferred embodiment, a suitable host material is a group comprising the following formula (III):

wherein

A,B¹,B²In a plurality of occurrences independently of one another, from a divalent radical, preferably-CR¹R²-,-NR¹-,-PR¹-,-O-,-S-,-SO-,-SO₂-,-CO-,-CS-,-CSe-,-P(＝O)R¹-,-P(＝S)R¹-，-SiR¹R²-,-CR¹R²-CR³R⁴-,-CR¹R²-SiR³R⁴-，-CR¹R²-NR³-，-CR¹R²-O-，-CR¹R²-N R³-，-CR¹R²-C(＝O)-，-CR¹R²-S-，-SiR¹R²-NR³-，-SiR¹R²-O-，-SiR¹R²-N R³-，-SiR¹R²-C(＝O)-，-SiR¹R²-S-，-CR¹＝CR¹-，-CR¹＝N-，-CR¹＝CR¹-，-C≡C-，

R¹,R²,R³,R⁴Are identical or different radicals, independently of one another, and are selected from the group consisting of H, halogen, -CN, -NC, -NCO, -NCS, -OCN, -SCN, -C (═ O) NR⁰R⁰⁰,-C(＝O)R⁰,-NH₂,-NR⁰R⁰⁰,-SH,-SR⁰,-SO₃H,-SO₂R⁰,-OH,-NO₂,-CF₃,-SF₅Optionally substituted silyl groups, or hydrocarbon groups or carbonyl groups containing 1 to 40 carbon atoms; said silyl, hydrocarbyl or carbonyl group may be optionally substituted, optionally including one or more heteroatoms,

R⁰,R⁰⁰are independently of one another hydrogen or optionally substituted hydrocarbon radicals or carbonyl radicals,optionally containing one or more heteroatom groups,

each n is independently 0 or 1, and h is 0 or 1 in the same subunit as each of the counterparts,

m is an integer of 1 or more.

Preferred examples according to formula (III) are, but not limited to, the following

In a preferred embodiment, suitable host materials are organic compounds comprising a fused-ring aromatic or fused-ring heteroaromatic system with two or more 5-or 6-membered rings.

Examples of preferred fused ring systems, but are not limited to, are as follows

The invention also relates to a mixture, which at least comprises a host material and a metal complex, wherein the spin quantum number of the ground state of the host material is 1, and delta (S1-T1) is more than or equal to 0.75eV, and the spin quantum number of the ground state of the metal complex is 2.

The invention also relates to a composition comprising at least one of the aforementioned mixtures, at least one organic solvent. Examples of organic solvents include, but are not limited to, methanol, ethanol, 2-methoxyethanol, dichloromethane, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1, 4-dioxane, acetone, methyl ethyl ketone, 1, 2-dichloroethane, 3-phenoxytoluene, 1,1, 1-trichloroethane, 1,1,2, 2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydronaphthalene, decalin, indene, and/or mixtures thereof.

In a preferred embodiment, the composition according to the invention is a solution. In another embodiment, the composition according to the invention is a suspension.

The composition of the present invention can comprise 0.01 to 20 wt%, preferably 0.1 to 15 wt%, more preferably 0.2 to 10 wt%, most preferably 0.25 to 5 wt% of the functional material. The percentage data relate to 100% of solvent or solvent mixture.

The invention also relates to the use of said composition as a coating or printing ink for the production of organic electronic devices, particularly preferred is a production process by printing or coating.

Suitable printing or coating techniques include, but are not limited to, ink jet printing, letterpress printing, screen printing, dip coating, spin coating, doctor blade coating, roll printing, twist roll printing, lithographic printing, flexographic printing, rotary printing, spray coating, brush or pad printing, slot die coating, and the like. Gravure printing, screen printing and ink jet printing are preferred. Gravure printing, ink jet printing, will be used in the examples of the present invention. The solution or suspension may additionally include one or more components such as surface active compounds, lubricants, wetting agents, dispersants, hydrophobing agents, binders, and the like, for adjusting viscosity, film forming properties, enhancing adhesion, and the like. For details on the printing technology and its requirements concerning the solutions, such as solvents and concentrations, viscosities, etc., reference is made to the Handbook of Print Media, technology and Production Methods, published by Helmut Kipphan, ISBN 3-540-67326-1.

The invention further relates to an electronic component comprising one or more organic functional films, at least one of which comprises a mixture according to the invention. Suitable electronic devices include, but are not limited to, Organic light Emitting diodes, Organic light Emitting cells, Organic photovoltaic cells, Organic field effect transistors, Organic light Emitting field effect transistors, Organic sensors, and Organic Plasmon Emitting diodes (Organic plasma Emitting diodes). Preferred organic electronic devices are organic light emitting diodes, organic light emitting cells.

In a further aspect of the invention, an electroluminescent device is provided which is large-area and which comprises, in particular, the steps of a process for preparation from solution, in particular printing, that is to say that at least one layer of the electroluminescent device is prepared from solution, in particular by printing. Since in mass production, even if only one layer is prepared by the printing method, the production cost can be greatly reduced. In a preferred embodiment of the invention, the light-emitting layer is prepared from solution, in particular by a printing process. Some descriptions (but not limitations) will be given below of a method for preparing a functional film, particularly a light-emitting layer, from a solution.

For ease of preparation from solution or printing, the individual components of the light-emitting layer, such as the matrix and/or the organic radical compound and the luminophore, must be formulated in a certain form in a certain solvent. The formulation may be a solution or a suspension.

In a preferred embodiment, the components of the light-emitting layer may be present in an organic solvent in the form of a solution or a homogeneous suspension. In certain embodiments, the matrix material comprises inorganic semiconductor nanocrystals. In a sense, such solutions or homogeneous suspensions are also referred to as ultra-fine colloidal dispersions (dispersions). The nanocrystal matrix can be prepared by various methods, such as the methods of preparation of semiconductor nanocrystals described above. In certain instances, nanocrystals are commercially available as matrices, such as those of Evonik Degussa

TiO₂And P25. In another embodiment, the material comprises an organic material that is soluble in an organic solvent.

Therefore, a first preferred method for fabricating a functional film, particularly a light-emitting layer, of the device of the present invention comprises the steps of:

1) preparing various components in an organic solvent to form a solution or a uniform suspension;

2) uniformly coating the solution or suspension on a substrate by printing or other coating methods;

3) baking at the temperature T1 to remove residual organic solvent and form a film; the process can be carried out in air, or in an inert gas, or in a moderate vacuum

Steps 2) -3) can be carried out in air, or in an inert gas such as a glove box. If desired, step 3) can be carried out under moderate vacuum. Suitably, T1 ≦ 300 ℃, preferably 250 ≦ 250 ℃, more preferably 220 ≦ 220 °, and most preferably 200 ℃. This is because the lower the temperature, the lower the cost in mass production. In particular, when the substrate is plastic, T1< ═ 250 ℃ is preferred.

In the devices described above, the substrate may be opaque or transparent. A transparent substrate may be used to fabricate a transparent light emitting device. See, for example, Bulovic et al Nature 1996,380, p29, and Gu et al, appl.Phys.Lett.1996,68, p 2606. The substrate may be rigid or elastic. The substrate may be plastic, metal, semiconductor wafer or glass. Preferably, the substrate has a smooth surface. A substrate free of surface defects is a particularly desirable choice. In a preferred embodiment, the substrate may be selected from a polymeric film or plastic having a glass transition temperature Tg of 150 deg.C or greater, preferably greater than 200 deg.C, more preferably greater than 250 deg.C, and most preferably greater than 300 deg.C. Examples of suitable substrates are poly (ethylene terephthalate) (PET) and polyethylene glycol (2, 6-naphthalene) (PEN).

The anode may comprise a metal or conductive metal oxide, or a conductive polymer. The anode can easily inject holes into the HIL or HTL or the light emitting layer. In one embodiment, the absolute value of the difference between the work function of the anode and the HOMO level or valence band level of the emitter in the light emitting layer or the p-type semiconductor material as HIL or HTL or EBL is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2 eV. Examples of anode materials include, but are not limited to, Al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, aluminum-doped zinc oxide (AZO), and the like. Other suitable anode materials are known and can be readily selected for use by one of ordinary skill in the art. The anode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.

In certain embodiments, the anode is pattern structured. Patterned ITO conductive substrates are commercially available and can be used to prepare devices according to the present invention.

The cathode may comprise a conductive metal or metal oxide. The cathode can easily inject electrons into the EIL or ETL or directly into the light emitting layer. In one embodiment, the absolute value of the difference between the work function of the cathode and the LUMO level or conduction band level of the emitter or n-type semiconductor material as EIL or ETL or HBL in the light-emitting layer is less than 0.5eV, preferably less than 0.3eV, and most preferably less than 0.2 eV. In principle, all materials which can be used as cathodes in OLEDs are possible as cathode materials for the device according to the invention. Examples of cathode materials include, but are not limited to, Al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloys, BaF₂Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, etc. The cathode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.

In a preferred embodiment, the anode or cathode may be prepared by printing. In one embodiment, the anode or cathode may be prepared by a sol-gel method using a metal salt or metal complex as a precursor. WO2008151094 discloses preparation and application of an ink containing a metal salt, and WO2010011974 discloses an ink containing an aluminum metal salt. The entire contents of the patent documents listed herewith are also incorporated herein by reference. In another embodiment, the anode or cathode may be fabricated by printing an ink containing metal nanoparticles. Some metallic Nano-inks are commercially available, such as Nano-silver paste from Xerox corporation and Advanced Nano Products co.

The present invention also relates to the use of light emitting devices according to the present invention in a variety of applications including, but not limited to, various display devices, backlights, illumination sources, and the like.

Some more detailed descriptions (but not limitations) of the organic functional materials are provided below. Various organic functional materials are described in detail in WO2010135519a1, US20090134784a1 and WO 2011110277a1, the entire contents of this 2 patent document being hereby incorporated by reference. The organic functional material can be small molecule and high polymer material.

1.HIM/HTM/EBM

Suitable organic HIM/HTM materials may be selected from compounds containing structural units selected from the group consisting of phthalocyanines, porphyrins, amines, aromatic amines, triphenylamines, thiophenes, benzothiophenes such as dithienothiophene and benzothiophenes, pyrroles, anilines, carbazoles, benzazoles, and derivatives thereof. Alternatively suitable HIMs also include fluorocarbon-containing polymers; a polymer containing conductive dopants; conductive polymers such as PEDOT/PSS; self-assembling monomers, such as compounds containing phosphonic acids and sliane derivatives; metal oxides such as MoOx; metal complexes, and crosslinking compounds, and the like.

Examples of cyclic aromatic amine derivative compounds that may be used as a HIM or HTM or EBM include, but are not limited to, the following general structures:

each Ar¹To Ar⁹Can be independently selected from cyclic aromatic hydrocarbon compounds, such as benzene, biphenyl, triphenyl, benzo, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene; aromatic heterocyclic compounds, such as dibenzothiophene, dibenzofuran, furan, thiophene, benzofuran, benzothiophene, carbazole, pyrazole, imidazole, triazole, isoxazole, thiazole, oxadiazole, oxadiazine, bisoxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathizine, oxadiazine, indoles, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, benzodiazepine, quinazoline, quinoxaline, naphthalene, phthalein, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, dibenzoenophene, benzoselenophenephene, benzofuropyradine, indolocarbazole, pyridoline, pyrolidodine, pyrolydidine, furydipyridine, pyrolydidine, pyrolydipyridine, pyrolydidine and pyrolydidine; groups containing 2 to 10 ring structures, which may be identical or differentA cyclic aromatic hydrocarbon group or an aromatic heterocyclic group of the type and bonded to each other directly or through at least one group such as an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit and an aliphatic ring group. Wherein each Ar may be further substituted, and the substituents may be selected from the group consisting of hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl.

In one aspect, Ar¹To Ar⁹May be independently selected from the group comprising:

n is an integer from 1 to 20; x¹To X⁸Is CH or N; ar (Ar)⁰Is aryl or heteroaryl.

Further examples of cyclic aromatic amine derivative compounds can be found in US3567450, US4720432, US5061569, US3615404, and US5061569.

Examples of metal complexes that may be used as HTMs or HIMs include, but are not limited to, the following general structures:

m is a metal having an atomic weight greater than 40;

(Y¹-Y²) Is a bidentate ligand, Y¹And Y²Independently selected from C, N, O, P, and S; l is an ancillary ligand; m is an integer having a value from 1 to the maximum coordination number of the metal; m + n is the maximum coordination number of the metal.

In one embodiment, (Y)¹-Y²) Is a 2-phenylpyridine derivative.

In another embodiment, (Y)¹-Y²) Is a carbene ligand.

In another embodiment, M is selected from Ir, Pt, Os, and Zn.

In another aspect, the HOMO of the metal complex is greater than-5.5 eV (relative to vacuum level).

Examples of suitable HIM/HTM compounds are listed in the following table:

2.EIM/ETM/HBM

examples of the EIM/ETM material are not particularly limited, and any metal complex or organic compound may be used as the EIM/ETM as long as they can transport electrons. Preferred organic EIM/ETM materials may be selected from tris (8-hydroxyquinoline) aluminum (AlQ)₃) Phenazine, phenanthroline, anthracene, phenanthrene, fluorene, bifluorene, spirobifluorene, paraphenyleneyne, triazine, triazole, imidazole, pyrene, perylene, trans-indenofluorene, cis-indeno, dibenzo-indenofluorene, indenonaphthalene, benzanthracene and derivatives thereof.

Hole Blocking Layers (HBLs) are commonly used to block holes from adjacent functional layers, particularly the light emitting layer. The presence of HBL generally results in an increase in luminous efficiency compared to a light emitting device without a blocking layer. The Hole Blocking Material (HBM) of the Hole Blocking Layer (HBL) needs to have a lower HOMO than the adjacent functional layer, such as the light emitting layer. In a preferred embodiment, the HBM has a larger excited state energy level, such as a singlet state or a triplet state, depending on the emitter, than the adjacent light-emitting layer. EIM/ETM materials that typically have deep HOMO levels can be used as HBMs.

In another aspect, a compound useful as EIM/ETM/HBM is a molecule comprising at least one of the following groups:

R¹a group selected from the group consisting of hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl, when they are aryl or heteroaryl, with Ar in the above HTM¹And Ar²The meanings are the same;

Ar¹-Ar⁵with Ar as described in HTM¹The meanings are the same;

n is an integer from 0 to 20;

X¹-X⁸selected from CH or N.

On the other hand, examples of metal complexes that can be used as EIM/ETM include (but are not limited to) the following general structures:

(O-N) or (N-N) is a bidentate ligand wherein the metal is coordinated to O, N or N, N; l is an ancillary ligand; m is an integer having a value from 1 up to the maximum coordination number of the metal.

Examples of suitable ETM compounds are listed in the following table:

in another preferred embodiment, an organic alkali metal compound can be used as the EIM. In the context of the present invention, an organic alkali metal compound is understood to mean a compound in which at least one alkali metal, i.e. lithium, sodium, potassium, rubidium, cesium, and further comprises at least one organic ligand.

Suitable organic alkali metal compounds include those described in US 7767317B2, EP 1941562B1 and EP 1144543B 1.

Preferred organic alkali metal compounds are those of the following formula:

wherein R is¹As mentioned above, the arcs represent two or three atoms and bonds, in order to form, if appropriate, a 5-or six-membered ring with the metal M, where the atoms may also be formed by one or more R¹And M is alkali metal selected from lithium, sodium, potassium, rubidium and cesium.

The organic alkali metal compound may be in the form of a monomer, as described above, or in the form of an aggregate, for example, two alkali metal ions with two ligands, 4 alkali metal ions with 4 ligands, 6 alkali metal ions with 6 ligands or in other forms.

Preferred organic alkali metal compounds are those of the following formula:

wherein the symbols used have the same definitions as above, and further:

o, which may be the same or different at each occurrence, is 0,1,2,3 or 4;

p, which may be the same or different at each occurrence, is 0,1,2 or 3;

in a preferred embodiment, the alkali metal M is selected from lithium, sodium, potassium, more preferably lithium or sodium, most preferably lithium.

In a preferred embodiment, the organic alkali metal compound electron injection layer is composed of an organic alkali metal compound.

In another preferred embodiment, the organic alkali metal compound is doped into the other ETM to form an electron transport layer or an electron injection layer.

Examples of suitable organic alkali metal compounds are listed in the following table:

3. triplet Host material (Triplet Host):

examples of the triplet host material are not particularly limited, and any metal complex or organic compound may be used as the host as long as the triplet energy thereof is higher than that of a light emitter, particularly a triplet light emitter or a phosphorescent light emitter.

Examples of metal complexes that can be used as triplet hosts (Host) include, but are not limited to, the following general structures:

m is a metal; (Y)³-Y⁴) Is a bidentate ligand, Y³And Y⁴Independently selected from C, N, O, P, and S; l is an ancillary ligand; m is an integer having a value from 1 to the maximum coordination number of the metal; m + n is the maximum coordination number of the metal.

In a preferred embodiment, the metal complexes useful as triplet hosts are of the form:

(O-N) is a bidentate ligand in which the metal is coordinated to both the O and N atoms.

In one embodiment, M may be selected from Ir and Pt.

Examples of organic compounds which can act as triplet hosts are selected from compounds containing a cyclic aromatic group such as benzene, biphenyl, triphenyl, benzo, fluorene; testing; compounds containing aromatic heterocyclic groups, such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridilidone, pyrrolipiridine, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxadizole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazides, oxazines, oxazidines, indole, benzimidazole, indoxazole, indoxazine, bisbenzoxazoles, benzisoxazoles, benzothiazole, quinoline, isoquinoline, cinnolines, quinazoline, quinoxaline, naphthalene, phthalein, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazines, benzofuranazine, benzodiazepine, furyldipyridine, pyridodiazine, and benzodiazepine; groups having 2 to 10 ring structures, which may be the same or different types of cyclic aromatic hydrocarbon groups or aromatic heterocyclic groups, are bonded to each other directly or through at least one group selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit and an alicyclic group. Wherein each Ar may be further substituted, and the substituents may be selected from the group consisting of hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl.

In a preferred embodiment, the triplet matrix material may be selected from compounds comprising at least one of the following groups:

R¹-R⁷independently of one another, from the group consisting of hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl, where they are aryl or heteroaryl, with Ar as described above¹And Ar²The meanings are the same;

n is an integer from 0 to 20; x¹-X⁸Selected from CH or N; x⁹Is selected from CR¹R²Or NR¹.

Examples of suitable triplet matrix materials are listed in the following table:

4. singlet Host material (Singlet Host):

examples of the singlet state host material are not particularly limited, and any organic compound may be used as the host as long as the singlet state energy thereof is higher than that of the light emitter, particularly the singlet state light emitter or the fluorescent light emitter.

Examples of the organic compound used as the singlet state matrix material may be selected from the group consisting of cyclic aromatic hydrocarbon-containing compounds such as benzene, biphenyl, triphenyl, benzo, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene; aromatic heterocyclic compounds, such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridilidone, pyrrodistyrine, pyrazole, imidazole, triazole, isoxazole, thiazole, oxadiazole, oxadiazine, bisoxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathizine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthalene, phthalein, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furydipyridine, benzoquinonedine, thiendine, pyrolidine, and quinonediazide; groups having 2 to 10 ring structures, which may be the same or different types of cyclic aromatic hydrocarbon groups or aromatic heterocyclic groups, are bonded to each other directly or through at least one group selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit and an alicyclic group. .

In a preferred embodiment, the singlet matrix material may be selected from compounds comprising at least one of the following groups:

examples of suitable singlet matrix materials are listed in the following table:

5. singlet state luminophor (Singlet Emitter)

Singlet emitters tend to have longer conjugated pi-electron systems. To date, there have been many examples such as styrylamine and its derivatives disclosed in JP2913116B and WO2001021729a1, and indenofluorene and its derivatives disclosed in WO2008/006449 and WO 2007/140847.

In a preferred embodiment, the singlet emitters may be selected from the group consisting of monostyrenes, distyrenes, tristyrenes, tetrastyrenes, styrylphosphines, styrenates, and arylamines.

A monostyrene amine is a compound comprising an unsubstituted or substituted styryl group and at least one amine, preferably an aromatic amine. A distyrene amine refers to a compound comprising two unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine. A tristyrenylamine refers to a compound comprising three unsubstituted or substituted styrene groups and at least one amine, preferably an aromatic amine. A tetrastyrene amine refers to a compound comprising four unsubstituted or substituted styrene groups and at least one amine, preferably an aromatic amine. One preferred styrene is stilbene, which may be further substituted. The corresponding phosphines and ethers are defined analogously to the amines. Arylamine or aromatic amine refers to a compound comprising three unsubstituted or substituted aromatic rings or heterocyclic systems directly linked to nitrogen. At least one of these aromatic or heterocyclic ring systems is preferably a fused ring system and preferably has at least 14 aromatic ring atoms. Among them, preferred examples are aromatic anthracenamines, aromatic anthracenediamines, aromatic pyrenediamines, aromatic chrysenamines and aromatic chrysenediamines. An aromatic anthracylamine refers to a compound in which a diarylamino group (diarylamino) is attached directly to the anthracene, preferably at the 9 position. An aromatic anthracenediamine refers to a compound in which two diarylamino groups (diarylamino groups) are attached directly to the anthracene, preferably at the 9,10 positions. Aromatic pyrene amines, aromatic pyrene diamines, aromatic chrysene amines and aromatic chrysene diamines are similarly defined, wherein the diarylamine groups are preferably attached to the 1 or 1,6 position of pyrene.

Examples, also preferred, of singlet emitters based on vinylamines and arylamines can be found in WO 2006/000388, WO 2006/058737, WO 2006/000389, WO 2007/065549, WO 2007/115610, US 7250532B 2, DE 102005058557A 1, CN 1583691A, JP 08053397A, US 6251531B1, US 2006/210830A, EP 1957606A 1 and US 2008/0113101A 1 and the entire contents of the patent documents listed above are hereby incorporated by reference.

An example of singlet emitters based on stilbene (distyrylbenzene) and derivatives thereof is US5121029.

Further preferred singlet emitters may be selected from indenofluorene-amines and indenofluorene-diamines, as disclosed in WO 2006/122630, benzindenofluorene-amines and benzindenofluorene-diamines, as disclosed in WO2008/006449, dibenzoindenofluorene-amines and dibenzoindenofluorene-diamines, as disclosed in WO 2007/140847.

Other materials which can be used as singlet emitters are polycyclic aromatic compounds, in particular derivatives of anthracene, such as 9, 10-bis (2-naphthoanthracene), naphthalene, tetraphene, xanthene, phenanthrene, pyrene, such as 2,5,8, 11-tetra-t-butyperfluorene, indenopyrene, phenylene, such as (4,4'- (bis (9-ethyl-3-carbazovinyl) -1, 1' -biphenol), periflanthene, decacyclobenzene, fluorene, spirobifluorene, arylpyrene (such as US 200602886), aryleneethylene (such as US5121029, US 3065103), cyclopentadiene, such as tetraphenylcyclopentadiene, rubrene, coumarin, rhodamine, quinacridone, pyrans, such as 4(dicyanoethylene) -6- (4-diazacyclo-2-methyl) -4H-pyrane), thiazylene, bis (DCM), DCM-1), bis (azinyl) methane compounds, carbostyryl compounds, oxazinones, benzoxazoles, benzothiazoles, benzimidazoles and diketopyrrolopyrroles. Some singlet emitter materials can be found in the patent documents US20070252517 a1, US 4769292, US 6020078, US 2007/0252517a1, US 2007/0252517a 1. The entire contents of the above listed patent documents are hereby incorporated by reference.

Some examples of suitable singlet emitters are listed in the following table:

6. triplet Emitter (Triplet Emitter)

Triplet emitters are also known as phosphorescent emitters. In a preferred embodiment, the triplet emitter is a metal complex of the general formula M (L) n, where M is a metal atom, L, which may be the same or different at each occurrence, is an organic ligand which is bonded or coordinately bound to the metal atom M via one or more positions, and n is an integer greater than 1, preferably 1,2,3,4, 5 or 6. Optionally, the metal complexes are coupled to a polymer through one or more sites, preferably through organic ligands.

In a preferred embodiment, the metal atom M is chosen from transition metals or lanthanides or actinides, preferably Ir, Pt, Pd, Au, Rh, Ru, Os, Sm, Eu, Gd, Tb, Dy, Re, Cu or Ag, particularly preferably Os, Ir, Ru, Rh, Re, Pd, Pt.

Preferably, the triplet emitter comprises a chelating ligand, i.e. a ligand, which coordinates to the metal via at least two binding sites, particularly preferably the triplet emitter comprises two or three identical or different bidentate or polydentate ligands. Chelating ligands are advantageous for increasing the stability of the metal complex.

Examples of organic ligands may be selected from phenylpyridine (phenyl quinoline) derivatives, 7,8-benzoquinoline (7,8-benzoquinoline) derivatives, 2(2-thienyl) pyridine (2(2-thienyl) pyridine) derivatives, 2(1-naphthyl) pyridine (2(1-naphthyl) pyridine) derivatives, or 2-phenylquinoline (2-phenylquinoline) derivatives. All of these organic ligands may be substituted, for example, with fluorine-containing or trifluoromethyl groups. The ancillary ligand may preferably be selected from acetone acetate (acetylacetate) or picric acid.

In a preferred embodiment, the metal complexes which can be used as triplet emitters are of the form:

wherein M is a metal selected from the group consisting of transition metals or lanthanides or actinides;

Ar¹each occurrence of which may be the same or different, is a cyclic group containing at least one donor atom, i.e., an atom having a lone pair of electrons, such as nitrogen or phosphorus, through which the cyclic group is coordinately bound to the metal; ar (Ar)²Each occurrence, which may be the same or different, is a cyclic group containing at least one C atom through which the cyclic group is attached to the metal; ar (Ar)¹And Ar²Linked together by a covalent bond, which may each carry one or more substituent groups, which may in turn be linked together by substituent groups; l, which may be the same or different at each occurrence, is an ancillary ligand, preferably a bidentate chelating ligand, most preferably a monoanionic bidentate chelating ligand; m is 1,2 or 3, preferably 2 or 3Particularly preferably 3; n is 0,1, or 2, preferably 0 or 1, particularly preferably 0;

examples of materials and their use for some triplet emitters can be found in WO200070655, WO 200141512, WO 200202714, WO 200215645, EP 1191613, EP 1191612, EP1191614, WO 2005033244, WO 2005019373, US 2005/0258742, WO 2009146770, WO2010015307, WO 2010031485, WO 2010054731, WO 2010054728, WO 2010086089, WO2010099852, WO 2010086089, US 2010086089A 2010086089, US 2010086089A 2010086089, Baldo, Thompon et al Nature, (750) 753, US 2010086089A 2010086089, US 20090061681A 2010086089, Adachi et al 65l Phys.Lett.78(2001),1622 1624, J.Kido et al.Appys.Lett.65 (WO 4, Kido et al 2010086089, US 2003672, US 2010086089A 2010086089, US 2010086089A 2010086089, US 2010086089A 3672,3672,3672, US 3672,3672, US 3672,3672,3672,3672,3672,3672,3672,3672, US 3672,3672,3672,3672,3672,3672,3672,3672,3672,3672,3672,3672,3672,3672,3672,3672, WO 2011157339A1, CN 102282150A, WO 2009118087A 1. The entire contents of the above listed patent documents and literature are hereby incorporated by reference.

7. High polymer

Polymers, i.e., polymers, including homopolymers (homo polymers), copolymers (co polymers), and mosaic copolymers (block co polymers). in addition, in the present invention, polymers also include Dendrimers (Dendrimers). for the synthesis and use of Dendrimers, see Dendrimers and Dendrons, Wiley-VCH Verlag GmbH & Co.KGaA,2002, Ed.George R.Newkome, Charles N.Moorefield, Fritz Vogtle.

Conjugated polymers (conjugated polymers) are polymers whose main chain backbone is composed mainly of the sp2 hybrid orbital of the C atom, notable examples being polyacetylene and poly (phenylene vinylene); in addition, the conjugated polymer in the present invention also includes polymers containing arylamines (aryl amines), arylphosphines (aryl phosphines), and other heterocyclic aromatics (heterocyclic aromatics), organometallic complexes (organometalic complexes), etc. in the main chain, the present invention also includes polymers containing arylamines (aryl amines), arylphosphines (aryl phosphines), and other heterocyclic aromatics (organometalic complexes).

In a preferred embodiment, the polymer suitable for the present invention is a conjugated polymer. Generally, conjugated polymers have the general formula:

wherein B and A can independently select the same or different structural units when appearing for multiple times

B.pi-conjugated structural units with a larger energy gap, also known as Backbone units, selected from monocyclic or polycyclic aryl or heteroaryl groups, preferably in the form of benzene, Biphenylene (Biphenylene), naphthalene, anthracene, phenanthrene, dihydrophenanthrene, 9,10-dihydrophenanthrene, fluorene, bifluorene, spirobifluorene, p-phenylene vinylene, trans-indenofluorene, cis-indeno, dibenzo-indenofluorene, indenonaphthalene and derivatives thereof.

A, a pi-conjugated structural Unit with a smaller energy gap, also called a Functional Unit, can be selected from structural units comprising the hole injection or transmission material (HIM/HTM), the Hole Blocking Material (HBM), the electron injection or transmission material (EIM/ETM), the Electron Blocking Material (EBM), the organic matrix material (Host), the singlet state luminophor (fluorescent luminophor) and the singlet state luminophor (phosphorescent luminophor) according to different Functional requirements.

x, y: >0, and x + y ═ 1;

in a preferred embodiment, the polymeric HTM material is a homopolymer, preferably a homopolymer selected from the group consisting of polythiophenes, polypyrroles, polyanilines, polybiphenyls of triarylamines, polyvinylcarbazoles, and derivatives thereof.

In another preferred embodiment, the high polymer HTM material is a conjugated copolymer represented by formula 1, wherein

A, functional group with hole transport capability, which can be selected from structural units containing the hole injection or transport material (HIM/HTM) mentioned above; in a preferred embodiment, A is selected from the group consisting of amines, triarylamines of the biphenyl class, thiophenes, bithiophenes such as dithienothiophene and bithiophenes, pyrrole, aniline, carbazole, indolocarbazole, benzazepine, pentacene, phthalocyanines, porphyrins and derivatives thereof.

x, y: >0, and x + y ═ 1; generally, y is 0.10 or more, preferably 0.15 or more, more preferably 0.20 or more, and most preferably x is 0.5 or more, examples of suitable conjugated polymers which can be used as HTM are listed below:

wherein

Each R is independently of the others hydrogen, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 20C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20C atoms or a silyl group, or a substituted keto group having 1 to 20C atoms, an alkoxycarbonyl group having 2 to 20C atoms, an aryloxycarbonyl group having 7 to 20C atoms, a cyano group (-CN), a carbamoyl group (-C (═ O) NH₂) Haloformyl groups (-C (═ O) -X wherein X represents a halogen atom), formyl groups (-C (═ O) -H), isocyano groups, isocyanate groups, thiocyanate or isothiocyanate groups, hydroxyl groups, nitro groups, CF3 groups, Cl, Br, F, crosslinkable groups or substituted or unsubstituted aromatic or heteroaromatic ring systems having from 5 to 40 ring atoms, or aryloxy or heteroaryloxy groups having from 5 to 40 ring atoms, or combinations of these systems, wherein one or more radicals R may form a mono-or polycyclic aliphatic or aromatic ring system with one another and/or with the ring to which said radicals R are bonded;

r is 0,1,2,3 or 4;

s is 0,1,2,3,4o or 5;

x, y: >0, and x + y ═ 1; generally, y is not less than 0.10, preferably not less than 0.15, more preferably not less than 0.20, and most preferably x and y are not less than 0.5.

Another preferred class of organic ETM materials are polymers with electron transport capabilities, including conjugated polymers and non-conjugated polymers.

Preferred polymeric ETM materials are homopolymers, preferably selected from the group consisting of poly (phenanthrene), poly (phenanthroline), poly (indenofluorene), poly (spirobifluorene), poly (fluorene) and their derivatives.

The preferred polymeric ETM material is a conjugated copolymer represented by formula 1, wherein a can be independently selected in the same or different forms at multiple occurrences:

a is a functional group having an electron transporting ability, preferably selected from tris (8-hydroxyquinoline) aluminum (AlQ3), benzene, biphenylene, naphthalene, anthracene, phenanthrene, Dihydrophenanthrene, fluorene, bifluorene, spirobifluorene, paraphenylenevinylene, pyrene, perylene, 9,10-Dihydrophenanthrene, phenazine, phenanthroline, anti-indenofluorene, cis-indeno, dibenzo-indenofluorene, indenonaphthalene, benzanthracene and derivatives thereof

x, y ≧ 0, and x + y ═ 1. generally, y is not less than 0.10, preferably not less than 0.15, more preferably not less than 0.20, and most preferably, x ═ y ═ 0.5.

B is the same as that of formula 1.

A1 functional group with hole or electron transport capability, can be selected from structural units containing hole injection or transport materials (HIM/HTM) or electron injection or transport materials (EIM/ETM) as described above.

A2 radical with luminous function is selected from the structural units containing the above-mentioned singlet luminophores (fluorescent luminophores) and singlet luminophores (phosphorescent luminophores).

x, y, z: >0, and x + y + z ═ 1;

examples of luminescent polymers are disclosed in the following patent applications: WO2007043495, WO2006118345, WO2006114364, WO2006062226, WO2006052457, WO2005104264, WO2005056633, WO2005033174, WO 2004113413412, WO2004041901, WO2003099901, WO2003051092, WO2003020790, US2020040076853, US2020040002576, US2007208567, US2005962631, EP201345477, EP2001344788, DE102004020298, the entire contents of the above patent documents being hereby incorporated by reference.

In another embodiment, the polymers suitable for the present invention are nonconjugated polymers. This may be a polymer in which all functional groups are in the side chains and the main chain is non-conjugated. Some of such non-conjugated polymers used as phosphorescent hosts or phosphorescent light emitting materials are disclosed in patent applications such as US 7250226B 2, JP2007059939A, JP2007211243 a2 and JP2007197574a2, and some of such non-conjugated polymers used as fluorescent light emitting materials are disclosed in patent applications such as JP2005108556, JP2005285661 and JP 2003338375. Alternatively, the non-conjugated polymer may be a polymer in which conjugated functional units in the main chain are linked by non-conjugated linking units, examples of which are disclosed in DE102009023154.4 and DE 102009023156.0. The entire contents of the above patent documents are hereby incorporated by reference.

The present invention will be described in connection with preferred embodiments, but the present invention is not limited to the following embodiments, and it should be understood that the appended claims outline the scope of the present invention and those skilled in the art, guided by the inventive concept, will appreciate that certain changes may be made to the embodiments of the invention, which are intended to be covered by the spirit and scope of the appended claims.

Detailed Description

1. Material

The following materials will be used in specific embodiments.

The host 1 is a host material (ALD-E00, giline alder materials technologies, ltd.) and the emitter 1 is a green phosphorescent emitter (ALD-H004, giline alder materials technologies, ltd.). Luminophore 2 is a metal complex with a spin quantum number of 2, which is synthesized according to j.am.chem.soc.2010,132, 14273-14278. TFB (poly [ (9,9-dioctyl fluoro-2, 7-diyl) -co- (4,4' - (N- (4-sec-butyl)) diphenyl amine) ], h.w. sands Corp) is an organic hole transport material which can also be synthesized by methods well known in the literature, as disclosed in the patent application WO 99/54385. TPBi (1,3,5-Tris (1-phenyl-1H-benzimidazol-2-yl) bezene is used as an electron transport material and an exciton blocking material (ALD-C003, Jilin Orleder materials technologies, Ltd.).

2. Preparation of light emitting devices

The device structure is listed in table 1. The light emitting device was prepared as follows.

1. Substrate preparation the patterned ITO conductive glass substrate was first cleaned with various solvents (chloroform → acetone → isopropanol) and then subjected to uv ozone plasma treatment.

HIL PEDOT PSS (Clevios P VP AI4083) was spin-coated on an ITO conductive glass substrate in a clean room in air to obtain a thickness of 80 nm. Then baked in air at 120 ℃ for 10 minutes to remove moisture.

HTL TFB as a hole transport layer, TFB was first dissolved in toluene at a concentration of 0.5 wt%, this solution was spin-coated on a PEDOT: PSS film in a nitrogen glove box, and then annealed at 180 ℃ for 60 minutes. The thickness of the obtained TFB is 10-20nm.

EML in LED1-LED2, EML has a composition of 10 in Table 1^-7The film is formed by vacuum thermal evaporation in a vacuum atmosphere of Torr and by co-evaporation deposition by using a metal mask.

ETL or ExBL by applying a voltage at 10^-7In a vacuum atmosphere of Torr, by a method of vacuum thermal evaporation, and by using a metal mask for deposition.

6. Cathodes-all cathodes were at 10^-7And depositing the film by a vacuum thermal evaporation method in a vacuum atmosphere of Torr by using a metal mask.

7. Encapsulation all devices were glass-capped in a nitrogen glove box with an ultraviolet-curable resin.

TABLE 1

Device with a metal layer	EML	ETM(ExBL)	Cathode electrode
				LED1	Main body 1 (15%) luminous body 1(40nm)	TPBi(20nm)	LiF(1nm)/Al(100nm)
LED2	Main body 1 (15%) luminous body 2(40nm)	TPBi(20nm)	LiF(1nm)/Al(100nm)

3. Measurement and comparison of light emitters

The current-voltage (I-V) characteristics of the LEDs were recorded by computer controlled (Keithley 2400source measurement unit) and (Keithley 2000multimeter), while the brightness was measured by using a calibrated silicon photodiode (Newport 2112). The electroluminescence spectra were measured by a spectrometer (Ocean optics usb 2000). The performance of LED1-2 is summarized in table 2 below, where eqe (external quantum efficiency) represents the external quantum efficiency. Host 1 in LED1 has a very low T1, quenching all triplet excitons of emitter 1. Even if T1 of host 1 is low in LED2, emitter 2 has high luminous efficiency, which may be 2 to the ground state spin quantum number of emitter 2, so that its excited state cannot be quenched by host 1.

TABLE 2

Device with a metal layer	Lighting voltage (V)	Maximum EQE (%)
			LED1	>10	0.0％
LED2	3.10	8.4％

Claims (10)

1. An electroluminescent device comprising 1) a light-emitting layer containing at least a host material which is an organic small molecule material whose spin quantum number in the ground state is 1 and Δ (S1-T1) is 0.75eV, and a metal complex whose spin quantum number in the ground state is 2; 2) an anode electrode disposed on one side of the functional layer; 3) and a cathode electrode disposed on the other side of the functional layer.

2. The electroluminescent device of claim 1 wherein the metal complex comprises Au, Ag, Cu.

3. An electroluminescent device according to claim 1, wherein the host material is a group comprising the formula:

wherein

A,B¹,B²In a plurality of occurrences independently of one another, from a divalent radical, preferably-CR¹R²-,-NR¹-,-PR¹-,-O-,-S-,-SO-,-SO₂-,-CO-,-CS-,-CSe-,-P(＝O)R¹-,-P(＝S)R¹-，-SiR¹R²-,-CR¹R²-CR³R⁴-,-CR¹R²-SiR³R⁴-，-CR¹R²-O-，-CR¹R²-NR³-，-CR¹R²-C(＝O)-，-CR¹R²-S-，，-SiR¹R²-O-，-SiR¹R²-NR³-，-SiR¹R²-C(＝O)-，-SiR¹R²-S-，-CR¹＝CR¹-，-CR¹＝N-，-C≡C-，

R¹,R²,R³,R⁴Are identical or different radicals, independently of one another, and are selected from the group consisting of H, halogen, -CN, -NC, -NCO, -NCS, -OCN, -SCN, -C (═ O) NR⁰R⁰⁰,-C(＝O)R⁰,-NH₂,-NR⁰R⁰⁰,-SH,-SR⁰,-SO₃H,-SO₂R⁰,-OH,-NO₂,-CF₃,-SF₅Optionally substituted silyl, or hydrocarbyl or carbonyl containing 1 to 40 carbon atoms; said silyl, hydrocarbyl or carbonyl group may be optionally substituted, optionally including one or more heteroatoms,

R⁰,R⁰⁰are independently of one another hydrogen or optionally substituted hydrocarbon radicals or carbonyl radicals, radicals which may optionally contain one or more heteroatoms,

each n is independently 0 or 1, and h is 0 or 1 in the same subunit as each of the counterparts,

m is an integer of 1 or more.

4. An electroluminescent device as claimed in claim 1 in which the host material is an organic compound containing a fused ring aromatic or fused ring heteroaromatic system.

5. An electroluminescent device as claimed in claim 4 in which the host material is a fused ring system comprising

6. A mixture for an electronic device, comprising at least a host material whose spin quantum number in the ground state is 1 and Δ (S1-T1) ≥ 0.75eV, and a metal complex whose spin quantum number in the ground state is 2.

7. A composition for the preparation of electronic devices comprising at least one mixture according to claim 6 and at least one organic solvent.

8. Use of a mixture according to claim 6 in an organic electronic device.

9. An organic electronic device comprising at least one mixture according to claim 6.

10. The organic electronic device according to claim 9, selected from the group consisting of organic light Emitting diodes, organic light Emitting cells, organic photovoltaic cells, organic field effect transistors, organic light Emitting field effect transistors, organic sensors and organic plasmon Emitting diodes (organic plasma Emitting diodes).

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