WO2019105327A1

WO2019105327A1 - Organic composite film and application thereof in organic electronic device

Info

Publication number: WO2019105327A1
Application number: PCT/CN2018/117518
Authority: WO
Inventors: 潘君友; 黄宏; 谭甲辉
Original assignee: 广州华睿光电材料有限公司
Priority date: 2017-11-28
Filing date: 2018-11-26
Publication date: 2019-06-06
Also published as: CN108003365A; CN108003365B

Abstract

Disclosed are an organic composite film and an application thereof in an organic electronic device. The organic composite film comprises a functional layer L1 and a functional layer L2 in sequence. The functional layer L1 comprises an organic material M1, and the functional layer L2 comprises an organic material M2. At least one of M1 and M2 is a polymer, M1 and M2 have II-type semiconductor heterojunction structures, and min(Δ(LUMO M1-HOMO M2), Δ(LUMO M2-HOMO M1))≤min(E T(M1), E T(M 2))+0.1eV. An exciplex is easily formed at the interface between the functional layer L1 and the functional layer L2, so that the organic composite film of the present invention has high stability and can improve the device performance.

Description

Organic composite film and its application in organic electronic devices

The present application claims priority to Chinese Patent Application No. 200911217334.4, entitled "Organic Composite Film and Its Application in Organic Electronic Devices", issued on November 28, 2017, the entire contents of which are incorporated by reference. In this application.

Technical field

The present invention relates to the field of organic semiconductor technology, and in particular to an organic composite film and its application in an organic electronic device. The invention further relates to an electronic device comprising an organic film according to the invention and to its use.

Background technique

Organic light-emitting diode (OLED) was first prepared in 1987 by Kodak Corporation Tang et al. (see Tang C W, Vanslyke S A. Organic electroluminescent diodes. Appl Phys Lett, 1987, 51: 913-915). Compared with inorganic light-emitting diodes, OLEDs have been rapidly developed in the past three decades due to their versatility in synthesis, relatively low manufacturing cost, and excellent optical and electrical properties.

In general, OLED devices can be divided into single-layer, double-layer, and multilayer devices. The single-layer device has simple preparation process and low cost, but the luminous efficiency is not high, and the double-layer and multi-layer devices have high efficiency, but the preparation process is complicated, the luminescent color is unstable, and the production cost is high. In order to make the structure of the OLED device simple and improve the performance, Chen Dongcheng et al. (see Adv. Mater. 2016, 28, 239-244) of South China University of Technology proposed a planar pn heterojunction type organic light emitting diode, which is only composed of holes and The electron transporting materials are laminated in this order without a separate luminescent layer in between. In order to improve the performance of OLED devices, Kim proposed the concept of exciplex, which can use two different organic compounds to form an intermediate state, namely excimer complex, to improve device efficiency and lifetime (see Kim) Et al., Adv. Mater., Vol 26, 5864, (2014)).

However, the organic materials disclosed in these articles or disclosed in the patent capable of forming exciplex and p-n junction structures are small molecular materials and are only suitable for the preparation of vapor-deposited OLEDs. It is easy to prepare multi-layer, complex and high-efficiency OLED devices by vacuum evaporation method, but the production cost is expensive, time-consuming, and material utilization is not high; especially for RGBside-by-side technology, due to the use of precision metal masks (FMM), it is difficult to achieve the production of large-size displays. In contrast, solution-processed OLEDs are capable of producing large-area, flexible devices through inexpensive printing methods such as inkjet printing, and have broad application prospects and commercial value.

Therefore, a simple structure of OLED devices and material combinations suitable for the printing process is yet to be developed.

Summary of the invention

In view of the above deficiencies of the prior art, a main aspect of the present invention provides an organic composite film and its application in an organic electronic device, which provides an organic composite film for solving the complicated structure and energy of the existing OLED device. The vapor-deposited material forming the exciplex is not suitable for the printing process and improves the device performance. Another aspect of the present invention provides an organic electronic device comprising the organic composite film, and uses thereof.

The technical solution provided in one aspect of the invention is as follows:

An organic composite film comprising a functional layer L1 and a functional layer L2 in sequence, wherein the functional layer L1 comprises an organic material M1, and the functional layer L2 comprises an organic material M2, wherein 1) at least one of M1 and M2 is a polymer; 2) The M1 and M2 have a type II semiconductor heterojunction structure, and min(LUMO(M1)-HOMO(M2), LUMO(M2)-HOMO(M1))≤min(ET(M1), ET(M2) +0.1eV, where HOMO(M1), LUMO(M1), and ET(M1) represent the highest occupied orbital, lowest unoccupied orbital, and triplet energy levels of M1, HOMO(M2), LUMO(M2), and ET, respectively. (M2) indicates the energy level of the highest occupied orbit, the lowest unoccupied orbit, and the triplet state of M2, respectively.

In some particularly preferred embodiments, the functional layer L1 or L2 of the organic composite film further includes a luminescent material selected from the group consisting of a singlet illuminant (fluorescent illuminant) and a triplet illuminant (phosphorescent) Luminescent body) or TADF illuminant.

Another aspect of the present invention provides the use of the above organic composite film in an organic electronic device.

Yet another aspect of the present invention provides an organic electronic device comprising an organic composite film as described above.

In some particularly preferred embodiments, the organic electronic device is an electroluminescent device comprising at least an anode, an organic composite film as described above, and a cathode.

Advantageous Effects: In the above organic composite film, a type II semiconductor heterojunction structure can be formed between the organic material M1 of the functional layer L1 and the organic material M2 of the functional layer L2, and the interface between the functional layer L1 and the functional layer L2 is easily formed. Exciplex has better stability and can improve device performance. The above organic composite film can be applied to an organic electronic device, has a simple structure, and can be prepared by a printing process, thereby facilitating reduction of manufacturing cost.

DRAWINGS

1 is a diagram of a semiconductor heterojunction structure showing the relative position of energy levels according to the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) when two organic semiconductor materials A and B are in contact Two possible types, wherein the type II semiconductor heterojunction structure is an energy level structure in the composite film according to the present invention.

Detailed ways

In order to facilitate the understanding of the present invention, the present invention will be described more fully hereinafter. Preferred embodiments of the invention are given in the drawings. However, the invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that the understanding of the present disclosure will be more fully understood.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning meaning meaning The terminology used in the description of the present invention is for the purpose of describing particular embodiments and is not intended to limit the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.

The present invention provides an organic composite film and its use in an organic electronic device. The present invention will be further described in detail below in order to make the objects, technical solutions and effects of the present invention more clear and clear. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

In the present invention, the singlet and singlet states have the same meaning and are interchangeable.

In the present invention, the triplet and triplet states have the same meaning and are interchangeable.

In the present invention, the complex excited state, exciplex and Exciplex have the same meaning and are interchangeable.

The term "small molecule" as defined herein refers to a molecule that is not a polymer, oligomer, dendrimer or blend. In particular, there are no repeating structures in small molecules. The molecular weight of the small molecule is ≤3000 g/mol, preferably ≤2000 g/mol, most preferably ≤1500 g/mol.

The polymer, ie, Polymer, includes homopolymers, copolymers, and block copolymers. Also in the present invention, the polymer also includes a dendrimer. For the synthesis and application of the tree, see [Dendrimers and Dendrons, Wiley-VCH Verlag GmbH & Co. KGaA, 2002, Ed. George R. Newkome, Charles. N. Moorefield, Fritz Vogtle.].

A conjugated polymer is a polymer whose main chain is mainly composed of sp2 hybrid orbitals of C atoms. Typical examples are: polyacetylene and poly(phenylene vinylene). The C atom in its main chain can also be substituted by other non-C atoms, and when the sp2 hybrid on the main chain is interrupted by some natural defects, it is still considered to be a conjugated polymer. Further, in the present invention, the conjugated polymer also includes an aryl amine, an aryl phosphine and other heteroarmotics, and an organometallic complex in the main chain. Polymers such as complexes).

The non-conjugated side chain polymers of the present invention contain side chains and the polymer backbone is non-conjugated.

The present invention relates to an organic composite film comprising, in order, a functional layer L1 and a functional layer L2, wherein the functional layer L1 comprises an organic material M1, and the functional layer L2 comprises an organic material M2, wherein:

1) at least one of M1 and M2 is a polymer; 2) M1 and M2 have a semiconductor heterojunction structure of type II, and min(LUMO(M1)-HOMO(M2), LUMO(M2)-HOMO(M1) ≤min(E _T (M1), E _T (M2))+0.1eV, where HOMO(M1), LUMO(M1) and E _T (M1) respectively represent the highest occupied orbit, the lowest unoccupied orbit and the third line of M1 The energy levels of the states, HOMO (M2), LUMO (M2), and E _T (M2), respectively, represent the highest occupied orbital, minimum unoccupied orbital, and triplet energy levels of M2.

Wherein, the heterojunction refers to the interface region formed by the contact of two different semiconductors, and the heterojunction can be divided according to the alignment of the two material conduction bands (LUMO) and the valence band (HOMO) in the heterojunction. Type I heterojunctions and type II heterojunctions, the basic properties of type II heterojunctions are the separation of electron and hole spaces near the interface and localization in self-consistent quantum wells. Due to the overlap of the wave functions near the interface, the optical matrix elements are reduced, so that the radiation lifetime is lengthened and the exciton binding energy is reduced.

In a preferred embodiment, the organic composite film satisfies the following formula: min(LUMO(M1)-HOMO(M2), LUMO(M2)-HOMO(M1))≤min(E _T (M1), E _T (M2)) +0.05 eV;

In a more preferred embodiment, the organic composite film satisfies the following formula: min(LUMO(M1)-HOMO(M2), LUMO(M2)-HOMO(M1))≤min(E _T (M1), E _T (M2));

In a highly preferred embodiment, the organic composite film satisfies the following formula: min(LUMO(M1)-HOMO(M2), LUMO(M2)-HOMO(M1))≤min(E _T (M1), E _T (M2)) - 0.1 eV;

In a most preferred embodiment, the organic composite film satisfies the following formula: min(LUMO(M1)-HOMO(M2), LUMO(M2)-HOMO(M1))≤min(E _T (M1), E _T (M2)) - 0.15 eV;

In the embodiment of the present invention, the energy level structure of the organic material, the triplet energy levels E _T , HOMO, and LUMO play a key role. The following is an introduction to the determination of these energy levels.

The HOMO and LUMO levels can be measured by photoelectric effect, such as XPS (X-ray photoelectron spectroscopy) and UPS (UV photoelectron spectroscopy) or by cyclic voltammetry (hereinafter referred to as CV). Recently, quantum chemical methods, such as density functional theory (hereinafter referred to as DFT), have also become effective methods for calculating molecular orbital energy levels.

The triplet energy level E _{T of} organic materials can be measured by low temperature time-resolved luminescence spectroscopy, or by quantum simulation calculations (eg by Time-dependent DFT), as by commercial software Gaussian 03W (Gaussian Inc.), specific simulation methods. See WO2011141110 or the following examples.

It should be noted that the absolute values of HOMO, LUMO, E _T depend on the measurement method or calculation method used. Even for the same method, different evaluation methods, such as starting point and peak point on the CV curve, can give different HOMO/ LUMO value. Therefore, reasonable and meaningful comparisons should be made using the same measurement method and the same evaluation method. In the description of the embodiments of the present invention, the values of HOMO, LUMO, and E _T are simulations based on Time-dependent DFT, but do not affect the application of other measurement or calculation methods.

In the invention, (HOMO-1) is defined as the second highest occupied orbital level, (HOMO-2) is defined as the third highest occupied orbital level, and so on. (LUMO+1) is defined as the second lowest unoccupied orbital level, (LUMO+2) is defined as the third lowest occupied orbital level, and so on.

One of the advantages of the present invention is that in the organic composite film of the present invention, a type II semiconductor heterojunction structure can be formed between the organic material M1 of the functional layer L1 and the organic material M2 of the functional layer L2, and the functional layer L1 and the functional layer The exciplex is easily formed at the interface of L2, which has better stability and can improve device performance.

Another point of the present invention is that the organic composite film according to the present invention can be produced by a printing process, which is advantageous in reducing the manufacturing cost.

The energy gap of the exciplex is defined by min((LUMO(H1)-HOMO(H2), LUMO(H2)-HOMO(H1)). In some embodiments, min((LUMO(H1)-HOMO) (H2), LUMO(H2)-HOMO(H1) corresponds to an emission wavelength of from 300 nm to 1200 nm, preferably from 350 nm to 800 nm, more preferably from 380 nm to 750 nm, and most preferably from 380 nm to 680 nm.

In a preferred embodiment, according to the organic composite film of the present invention, the M1 has a hole transporting property.

In a preferred embodiment, according to the organic composite film of the invention, the M1 (HOMO-(HOMO-1)) ≥ 0.2 eV, preferably ≥ 0.25 eV, more preferably ≥ 0.3 eV, still more preferably ≥ 0.35 eV Very preferably ≥ 0.4 eV, most preferably ≥ 0.45 eV.

In a particularly preferred embodiment, according to the organic composite film of the invention, (HOMO-(HOMO-1)) ≥ 0.2 eV, preferably M1 (HOMO-(HOMO-1)) of each of M1 and M2 ) ≥ 0.25 eV, more preferably ≥ 0.3 eV, still more preferably ≥ 0.35 eV, very preferably ≥ 0.4 eV, most preferably ≥ 0.45 eV.

In another preferred embodiment, according to the organic composite film of the present invention, the M2 has electron transport properties.

In a preferred embodiment, according to the organic composite film of the present invention, ((LUMO+1)-LUMO) of the M2 is ≥0.15 eV, preferably ≥0.20 eV, more preferably ≥0.25 eV, still more preferably ≥0.30 eV Very preferably ≥ 0.35 eV, most preferably ≥ 0.40 eV.

In another particularly preferred embodiment, according to the organic composite film of the present invention, ((LUMO+1)-LUMO) of each of M1 and M2 is ≥0.15 eV, preferably M2((LUMO+1)- LUMO) ≥ 0.20 eV, more preferably ≥ 0.25 eV, still more preferably ≥ 0.30 eV, very preferably ≥ 0.35 eV, most preferably ≥ 0.40 eV.

In a more preferred embodiment, according to the organic composite film of the present invention, the M1 has a hole transporting property, and the M2 has an electron transporting property.

In some particularly preferred embodiments, in the organic composite film according to the invention, in the M1 and M2, M1 (HOMO-(HOMO-1)) ≥ 0.2 eV, preferably ≥ 0.25 eV, more preferably ≥ 0.3 eV, More preferably ≥0.35 eV, very preferably ≥0.4 eV, most preferably ≥0.45 eV; ((LUMO+1)-LUMO) of M2 ≥0.15 eV, preferably ≥0.20 eV, more preferably ≥0.25 eV, still more preferably ≥0.30 eV, very preferably ≥ 0.35 eV, most preferably ≥ 0.40 eV.

In a preferred embodiment, the organic composite film according to the present invention, wherein M1 is selected from the group consisting of an amine, a triarylamine, a phthalocyanine, a thiophene, a pyrrole, a carbazole, an indolocarbazole, a carbazole, and the like Small molecules and polymers of conformational and derivative groups.

In a more preferred embodiment, the organic composite film according to the present invention, wherein M1 is selected from small molecules and polymers comprising the following formula and isomers and derivative groups thereof:

Each of Ar ¹ to Ar ⁹ may be independently selected from the group consisting of: cyclic aromatic hydrocarbon compounds such as benzene, biphenyl, triphenyl, benzo, naphthalene, anthracene, phenalrene, phenanthrene, anthracene, pyrene, fluorene, fluorene, fluorene; Aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, furan, thiophene, benzofuran, benzothiophene, oxazole, pyrazole, imidazole, triazole, isoxazole, thiazole, oxadiazole, Oxtriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxazine, dioxazin, hydrazine, benzimidazole, oxazole, pyridazine, Benzooxazole, benzoxazole, benzothiazole, quinoline, isoquinoline, o-diaza(hetero)naphthalene, quinazoline, quinoxaline, naphthalene, anthracene, pteridine, xanthene, acridine , phenazine, phenothiazine, phenoxazine, dibenzoselenophene, benzoselenophene, benzofuranpyridine, carbazole, pyridinium, pyrrole dipyridine, furobipyridine, benzothiophenepyridine, Thiophenepyridine, benzoselenopyridine and selenophene dipyridine; a group comprising a 2 to 10 ring structure, which may be the same or different types of cyclic aromatic hydrocarbon groups or aromatic heterocyclic groups, and This is linked directly or through at least one of the following groups, 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, Ar ¹ to Ar ⁹ may be further substituted, and the substituent may be optionally an anthracene, an alkyl group, an alkoxy group, an amino group, an alkene group, an alkyne group, an aralkyl group, a heteroalkyl group, an aryl group and a heteroaryl group.

In certain preferred embodiments, the organic composite film according to the present invention, wherein M1 is selected from the group consisting of small molecules and polymers comprising the following formulas and isomers and derivative groups thereof:

among them,

L ¹ represents a single bond, an aromatic group having 6 to 30 carbon atoms or an aromatic hetero group having 3 to 30 carbon atoms, and the linking position of L ¹ may be any carbon atom on the benzene ring;

L ² , L ³ , L ⁴ and L ⁵ represent an aromatic group having 6 to 30 carbon atoms or an aromatic hetero group having 3 to 30 carbon atoms;

Ar ¹⁰ and Ar ¹¹ represent an aromatic group having 6 to 30 carbon atoms or an aromatic hetero group having 3 to 30 carbon atoms;

A ¹ and A ² independently represent N(R), C(R) ₂ , Si(R) ₂ , O, C=N(R), C=C(R) ₂ , P(R), P(= O) R, S, S=O or SO ₂ ;

A ³ and A ⁴ each independently represent a single bond, N(R), C(R) ₂ , Si(R) ₂ , O, C=N(R), C=C(R) ₂ , P(R), P(=O)R, S, S=O or SO ₂ , but not the same as a single bond;

Y ¹ to Y ⁸ independently represent N(R), C(R) ₂ , Si(R) ₂ , O, C=N(R), C=C(R) ₂ , P(R), P(= O) R, S, S=O or SO ₂ ;

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R each independently represent H, D, F, CN, alkenyl, alkynyl, nitrile, amine, nitro, acyl, alkoxy a carbonyl group, a sulfone group, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms or an aromatic heterocyclic ring having 3 to 60 carbon atoms. a group wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ may be bonded to any carbon atom on the fused ring.

m represents an integer of 1 to 6.

In a preferred embodiment, the organic composite film according to the present invention, wherein M2 is selected from the group consisting of pyridine, pyrimidine, pyrazine, phenazine, hydrazine, hydrazine, imidazole, oxadiazole, triazine, triazole, phenazine And small molecules and polymers of their isomers and derivative groups.

In another aspect, M2 can be selected from the group consisting of F, cyano, or any of the following formulas:

Wherein m1 is 1, 2 or 3; X ¹ -X ^{8 is} selected from CR or N, and at least one is N;

M ¹ , M ² , and M ³ independently represent N(R), C(R) ₂ , Si(R) ₂ , O, C=N(R), C=C(R) ₂ , P(R), P(=O)R, S, S=O, SO ₂ or none; in a preferred embodiment, the above M ¹ , M ² , M ^{3 are} preferably N(R), C(R) ₂ , Si (R) ₂ , O, S or none.

The meanings of R, R ¹ , R ² and R ³ are as described above.

In certain embodiments, according to the organic composite film of the present invention, both M1 and M2 are polymers;

In certain embodiments, according to the organic composite film of the present invention, both M1 and M2 are small molecules;

In a preferred embodiment, according to the organic composite film of the present invention, at least one of M1 and M2 is a polymer containing a crosslinkable group.

In a more preferred embodiment, according to the organic composite film of the present invention, the crosslinkable group described in M1 and M2 is selected from the group consisting of linear or cyclic alkenyl groups, linear dienyl groups, and alkynyl groups. , alkenyloxy, dienyloxy, acrylate, propylene oxide, butylene oxide, silane, cyclobutane.

In a most preferred embodiment, wherein the crosslinkable group is selected from the group consisting of:

The dotted line represents the position at which the crosslinking monomer is bonded to a functional group on other monomers or monomers in the polymer, and t and t1 represent an integer greater than or equal to zero.

Ar ¹² comprises an aromatic ring system or a heteroaromatic ring system having 5 to 40 ring atoms;

R ⁷ to R ^{9 are} independently selected from the group consisting of H, D, F, CN, alkyl chain, fluoroalkyl chain, aromatic ring, aromatic heterocyclic ring, amino group, silicon group, formamyl group, alkoxy group Base, aryloxy, fluoroalkoxy, siloxane, siloxy group, halogenated alkyl chain, deuterated partially fluorinated alkyl chain, deuterated aromatic ring, deuterated aromatic heterocyclic ring, fluorene Amino, deuterated silyl, deuterated mercapto, deuterated alkoxy, deuterated aryloxy, deuterated fluoroalkoxy, deuterated siloxane, deuterated siloxy, crosslinkable Group. And the adjacent R ⁷ , R ⁸ , R ⁹ may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other or a ring bonded to the group;

In a preferred embodiment, according to the organic composite film of the present invention, M1 or M2 is a conjugated polymer.

In a more preferred embodiment, the conjugated polymer of the present invention is selected from the group consisting of:

Where B, D can independently select the same or different structural units when appearing multiple times

B π-conjugated structural unit having a larger energy gap, also called a Backbone Unit, which is selected from a monocyclic or polycyclic aryl or heteroaryl group, and the preferred unit form is benzene, diphenylene. (Biphenylene), naphthalene, anthracene, phenanthrene, dihydrophenanthrene, 9,10-dihydrophenanthrene, anthracene, anthracene, stilbene, p-phenylacetylene, ruthenium, fluorene, dibenzo-indole , anthracene and its derivatives.

D: a π-conjugated structural unit having a small energy gap, also called a functional unit, may be selected from a structure including a hole transporting material (HTM) and an electron transporting material (ETM) according to different functional requirements. unit.

x, y is the mol% of the repeating unit, wherein x>0, y>0, and x+y=1;

In another preferred embodiment, the conjugated polymer of the present invention is selected from the group consisting of:

Wherein B and D are the same as Formula I;

The group having a light-emitting function of G may be selected from structural units including the singlet light-emitting body (fluorescent light-emitting body) and the triplet light-emitting body (phosphorescent light-emitting body) described above.

x, y, z is the mol% of the repeating unit, x>0, y>0, z>0, and x+y+z=1;

In a preferred embodiment, M1 is a homopolymer, and preferred homopolymers are selected from the group consisting of polythiophenes, polypyrroles, polyanilines, polybiphenyl triarylamines, polyvinylcarbazoles, and derivatives thereof.

In a more preferred embodiment, M1 is a conjugated copolymer represented by the formula (I) or formula (II), wherein D is selected from structural units comprising a hole transporting material (HTM). It is preferably selected from the group consisting of an amine, a triarylamine, a phthalocyanine, a thiophene, a pyrrole, a carbazole, an indolocarbazole, a carbazole, and isomers and derivative groups thereof.

In a preferred embodiment, the polymer of formula (I) or (II) comprises a crosslinkable group. Preferably, repeating structural unit B or D comprises a substituent comprising a crosslinkable group as described above.

In another preferred embodiment, in the polymer of the formula (II), the repeating structural unit G contains a substituent comprising a crosslinkable group as described above.

In a more preferred embodiment, M1 is selected from, but not limited to, the following structure:

among them

R ₁ to R ₁₀ are each independently hydrogen, or a linear alkyl group, an alkoxy group or a thioalkoxy group having 1 to 20 C atoms, or a branch or ring having 3 to 20 C atoms. An alkyl, alkoxy or thioalkoxy group or a silyl group, or a substituted keto group having 1 to 20 C atoms, or an alkane having 2 to 20 C atoms An oxycarbonyl group, or an aryloxycarbonyl group having 7 to 20 C atoms, a cyano group (-CN), a carbamoyl group (-C(=O)NH ₂ ), a haloformyl group a group (-C(=O)-X wherein X represents a halogen atom), a formyl group (-C(=O)-H), an isocyano group, an isocyanate group, a thiocyanate group or Isothiocyanate group, hydroxyl group, nitro group, CF3 group, Cl, Br, F, crosslinkable group or substituted or unsubstituted aromatic group having 5 to 40 ring atoms or a heteroaromatic ring system, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems, wherein one or more groups R may be bonded to each other and/or to said group The R-bonded ring forms a monocyclic or polycyclic aliphatic or aromatic ring system;

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

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

x, y has the same meaning as above, usually y ≥ 0.10, preferably ≥ 0.15, more preferably ≥ 0.20, most preferably x = y = 0.5.

In a particularly preferred embodiment, at least one of R ₁ to R ₁₀ comprises a crosslinkable group as described above.

In another preferred embodiment, M2 is a conjugated copolymer represented by the formula (I) or the formula (II), and M2 is a homopolymer, and a preferred homopolymer is selected from the group consisting of polyphenanthrene and polyphenanthroline. , 茚茚芴, 螺芴芴, poly 芴 and its derivatives.

In another more preferred embodiment, M2 is a conjugated copolymer represented by the general formula (I) or the general formula (II), wherein D is selected from structural units containing an electron transporting material (ETM). It is preferably selected from the group consisting of pyridine, pyrimidine, pyrazine, phenazine, anthracene, anthracene, imidazole, oxadiazole, triazine, triazole, phenazine, and isomers and derivative groups thereof.

In certain preferred embodiments, M2 is selected from, but not limited to, the following structure:

Wherein R ₁₁ to R ₁₇ are the same as R ₁ to R ₁₀ , and r and s are as defined above.

x, y, z have the same meaning as above, and x + y + z = 1; preferably y ≥ 0.10, more preferably ≥ 0.15, still more preferably ≥ 0.20, most preferably x = y = z.

In a particularly preferred embodiment, at least one of R ₁₁ to R ₁₇ comprises a crosslinkable group as described above.

In another preferred embodiment, according to the organic composite film of the present invention, M1 or M2 is a non-conjugated polymer.

In another more preferred embodiment, the organic composite film according to the present invention, wherein M1 is a non-conjugated side chain polymer, comprises a repeating unit as shown in Chemical Formula 1, and min(LUMO(H1)-HOMO(M2) ), LUMO(M2)-HOMO(H1)) ≤ min(E _T (H1), E _T (M2)) + 0.1 eV. Among them, HOMO(H1), LUMO(H1) and E _T (H1) respectively represent the highest occupied orbital, lowest unoccupied orbital and triplet energy levels of H1.

Chemical formula 1

Where: q represents the number of repeating units, and q is a natural number greater than or equal to 1. H1 is an organic material having hole transport properties. Preference is given to organic compounds selected from the group consisting of amines, triarylamines, phthalocyanines, thiophenes, pyrroles, oxazoles, indolocarbazoles, oxazoles and the isomers and derivatives thereof.

In a preferred embodiment, the organic composite film satisfies the following formula: min(LUMO(H1)-HOMO(M2), LUMO(M2)-HOMO(H1))≤min(E _T (H1), E _T (M2)) +0.05 eV;

In a more preferred embodiment, the organic composite film satisfies the following formula: min(LUMO(H1)-HOMO(M2), LUMO(M2)-HOMO(H1))≤min(E _T (H1), E _T (M2));

In a highly preferred embodiment, the organic composite film satisfies the following formula: min(LUMO(H1)-HOMO(M2), LUMO(M2)-HOMO(H1)) ≤min(E _T (H1), E _T (M2)) - 0.1 eV;

In a most preferred embodiment, the organic composite film satisfies the following formula: min(LUMO(H1)-HOMO(M2), LUMO(M2)-HOMO(H1))≤min(E _T (H1), E _T (M2)) - 0.15 eV;

In a preferred embodiment, the polymer of Chemical Formula 1 contains a crosslinkable group. Preferably, H1 comprises a substituent comprising a crosslinkable group as described above.

In another more preferred embodiment, the organic composite film according to the present invention, wherein M2 is a non-conjugated side chain polymer comprising a repeating unit as shown in Chemical Formula 2, and min(LUMO(M1)-HOMO(H2) ), LUMO(H2)-HOMO(M2)) ≤ min(E _T (M1), E _T (H2)) + 0.1 eV. Among them, HOMO(H2), LUMO(H2) and ET(H2) represent the highest occupied orbital, lowest unoccupied orbital and triplet energy levels of H2, respectively.

Chemical formula 2

Where: p represents the number of repeating units, and p is a natural number greater than or equal to 1. H2 is an organic material having electron transport properties, preferably selected from the group consisting of pyridine, pyrimidine, pyrazine, phenazine, anthraquinone, anthracene, imidazole, oxadiazole, triazine, triazole, phenazine, and isomers and derivatives thereof. An organic compound of a group.

In a preferred embodiment, the organic composite film satisfies the following formula: min(LUMO(M1)-HOMO(H2), LUMO(H2)-HOMO(M1))≤min(E _T (M1), E _T (H2)) + 0.05 eV;

In a more preferred embodiment, the organic composite film satisfies the following formula: min(LUMO(M1)-HOMO(H2), LUMO(H2)-HOMO(M1))≤min(E _T (M1), E _T (H2));

In a highly preferred embodiment, the organic composite film satisfies the following formula: min(LUMO(M1)-HOMO(H2), LUMO(H2)-HOMO(M1))≤min(E _T (M1), E _T (H2)) - 0.1 eV;

In a most preferred embodiment, the organic composite film satisfies the following formula: min(LUMO(M1)-HOMO(H2), LUMO(H2)-HOMO(M1))≤min(E _T (M1), E _T (H2)) - 0.15 eV;

In a preferred embodiment, the polymer of Chemical Formula 2 contains a crosslinkable group. Preferably, H2 comprises a substituent comprising a crosslinkable group as described above.

According to the organic composite film of the present invention, preferred non-limiting examples of M1 are as follows:

According to the organic composite film of the present invention, preferred non-limiting examples of M2 are as follows:

The synthesis method of the polymer represented by the general formula (I), the general formula (II), the chemical formula 1 and the chemical formula 2 is selected from the group consisting of SUZUKI-, YAMAMOTO-, STILLE-, NIGESHI-, KUMADA-, HECK-, SONOGASHIRA-, HIYAMA- , FUKUYAMA-, HARTWIG-BUCHWALD- and ULLMAN.

In a preferred embodiment, the above polymer has a glass transition temperature (Tg) ≥ 100 ° C, preferably ≥ 120 ° C, more preferably ≥ 140 ° C, still more preferably ≥ 160 ° C, most preferably ≥ 180 ° C.

In a preferred embodiment, the molecular weight distribution (PDI) of the above polymer preferably ranges from 1 to 5; more preferably from 1 to 4; more preferably from 1 to 3, still more preferably from 1 to 2, most preferably It is 1 to 1.5.

In a preferred embodiment, the weight average molecular weight (Mw) of the above polymer is preferably in the range of 10,000 to 1,000,000; more preferably 50,000 to 500,000; more preferably 100,000 to 400,000, still more preferably It is 150,000 to 300,000, and most preferably 200,000 to 250,000.

In a more preferred embodiment, according to the organic composite film of the present invention, the functional layer L1 or L2 further includes a luminescent material selected from the group consisting of singlet illuminants (fluorescent illuminants), triplet states. Luminescent (phosphorescent) or TADF illuminant.

In some embodiments, according to the organic composite film of the present invention, the functional layer L1 or L2 further comprises a fluorescent illuminant, wherein the fluorescent illuminant occupies ≤10% by weight of the functional layer L1 or L2, preferably ≤ 9 wt%, more preferably ≤ 8 wt%, particularly preferably ≤ 7 wt%, most preferably ≤ 5 wt%.

In a particularly preferred embodiment, according to the organic composite film of the present invention, the functional layer L1 or L2 further comprises a phosphorescent emitter, wherein the phosphorescent emitter accounts for ≤25 wt% of the functional layer L1 or L2. Preferably, ≤ 20 wt%, more preferably ≤ 15 wt%.

In another more preferred embodiment, according to the organic composite film of the present invention, the functional layer L1 or L2 further comprises a TADF material, wherein the TADF material accounts for ≤15% by weight of the functional layer L1 or L2, It is preferably ≤ 10% by weight, more preferably ≤ 8% by weight.

In certain embodiments, the functional layer L1 has a thickness of 5 nm to 1000 nm, preferably 5 nm to 500 nm, more preferably 5 nm to 500 nm, still more preferably 10 nm to 200 nm, and most preferably 20 nm to 100 nm.

In other embodiments, the functional layer L2 has a thickness of 5 nm to 1000 nm, preferably 5 nm to 500 nm, more preferably 5 nm to 500 nm, still more preferably 10 nm to 200 nm, and most preferably 20 nm to 100 nm.

In other embodiments, the total thickness of the functional layers L1 and L2 is from 10 nm to 1000 nm, preferably from 20 nm to 500 nm, more preferably from 50 nm to 300 nm, still more preferably from 50 nm to 200 nm, and most preferably from 50 nm to 150 nm.

Preferred non-limiting combinations of composite films according to the present invention are listed below:

Mode 1: L1 contains M1, M1 is a polymer having hole transporting property, L2 contains M2, and M2 is a small molecular material having electron transporting properties.

Mode 2: L1 contains M1, M1 is a small molecule material having hole transport properties, L2 contains M2, and M2 is a polymer having electron transport properties.

Mode 3: L1 contains M1, M1 is a crosslinkable polymer having hole transporting properties, L2 contains M2, and M2 is a small molecular material having electron transporting properties.

Mode 4: L1 contains M1, M1 is a small molecule material having hole transport properties, L2 contains M2, and M2 is a crosslinkable polymer having electron transport properties.

Mode 5: L1 contains M1, M1 is a polymer having hole transporting property, L2 contains M2 and an illuminant, M2 is a small molecular material having electron transporting property, and illuminant is selected from singlet illuminant, triplet luminescence Body or TADF.

Mode 6: L1 contains M1 and illuminant, M1 is a small molecule material with hole transporting properties, illuminant is selected from singlet illuminant, triplet illuminant or TADF illuminant, L2 contains M2, and M2 has electron transport Performance of the polymer.

Mode 7: L1 comprises M1, M1 is a crosslinkable polymer having hole transporting properties, L2 comprises M2 and an illuminant, M2 is a small molecular material having electron transporting properties, and the illuminant is selected from the group consisting of singlet illuminants, triple Light emitter or TADF emitter.

Mode 8: L1 contains M1 and an illuminant, M1 is a small molecule material having hole transporting properties, and the illuminant is selected from a singlet illuminant, a triplet illuminant or a TADF illuminant, L2 contains M2, and M2 has electron transport. Performance of crosslinkable polymers.

Mode 9: L1 contains M1, M1 is a crosslinkable polymer having hole transporting properties, L2 contains M2, and M2 is a polymer having electron transporting properties.

Mode 10: L1 contains M1, M1 is a polymer having hole transporting property, L2 contains M2, and M2 is a crosslinkable polymer having electron transporting properties.

Mode 11: L1 comprises M1, M1 is a crosslinkable polymer having hole transporting properties, L2 comprises M2 and an illuminant, M2 is a polymer having electron transporting properties, and the illuminant is selected from the group consisting of singlet illuminants, triplet states Luminescent or TADF illuminant.

Mode 12: L1 comprises M1 and an illuminant, M1 is a polymer having hole transporting properties, the illuminant is selected from a singlet illuminant, a triplet illuminant or a TADF illuminant, L2 comprises M2, and M2 has electron transport properties. Crosslinkable polymer.

Some more detailed and non-limiting descriptions of fluorescent or singlet emitters, phosphorescent or triplet emitters and TADF materials are provided below.

1. Singlet emitter (Singlet Emitter)

Singlet emitters tend to have longer conjugated pi-electron systems. To date, there have been many examples, such as the styrylamines and derivatives thereof disclosed in JP 2913116 B and WO 2001021729 A1, the indenoindenes and their derivatives disclosed in WO 2008/006449 and WO 2007/140847 and in US Pat. No. 7,233,019, KR2006-0006760 A disclosed triarylamine derivative of hydrazine.

In a preferred embodiment, the singlet emitter can be selected from the group consisting of monostyrylamine, dibasic styrylamine, ternary styrylamine, quaternary styrylamine, styrene phosphine, styrene ether, and arylamine.

Monostyrylamine refers to a compound comprising an unsubstituted or substituted styryl group and at least one amine, most preferably an aromatic amine. The distyrylamine refers to a compound comprising two unsubstituted or substituted styryl groups and at least one amine, most preferably an aromatic amine. Ternary styrylamine refers to a compound comprising three unsubstituted or substituted styryl groups and at least one amine, most preferably an aromatic amine. Tetrastyrylamine refers to a compound comprising four unsubstituted or substituted styryl groups and at least one amine, most preferably an aromatic amine. The preferred styrene is stilbene, which may be further substituted. The corresponding phosphines and ethers are defined similarly to amines. An arylamine or an aromatic amine refers to a compound comprising three unsubstituted or substituted aromatic ring or heterocyclic systems directly bonded to nitrogen. At least one of these aromatic or heterocyclic ring systems is preferably selected from the group consisting of fused ring systems, and most preferably has at least 14 aromatic ring atoms. Preferred non-limiting examples thereof are: aromatic decylamine, aromatic quinone diamine, aromatic decylamine, aromatic quinone diamine, aromatic thiamine and aromatic quinone diamine. Aromatic decylamine refers to a compound in which one of the diarylamine groups is attached directly to the oxime, most preferably at the position of 9. Aromatic quinone diamine refers to a compound in which two diaryl arylamine groups are attached directly to the oxime, most preferably at the 9,10 position. The definitions of aromatic decylamine, aromatic quinone diamine, aromatic thiamine and aromatic quinone diamine are similar, wherein the diaryl aryl group is most preferably bonded to the 1 or 1 and 6 positions of hydrazine.

Examples of singlet emitters based on vinylamines and arylamines are also preferred examples and can be found in the following patent documents: WO 2006/000388, WO 2006/058737, WO 2006/000389, WO 2007/065549, WO 2007 /115610, US Pat. No. 7,250,532, B2, DE 102005058557 A1, CN 1583691 A, JP 08053397 A, US Pat. No. 6,215,531, B1, US 2006/210830 A, EP 1 957 606 A1, and US 2008/0113101 A1, the entire contents of which are incorporated herein by reference. This article serves as a reference.

An example of a singlet emitter based on a stilbene extreme derivative is US 5121029.

Further preferred singlet emitters may be selected from the indolo-amines and indeno-quinone-diamines as disclosed in WO 2006/122630, such as the benzoindeno-amines and benzoses disclosed in WO 2008/006449 An indeno-diamine such as dibenzoindeno-amine and dibenzoindeno-diamine as disclosed in WO2007/140847.

Further preferred singlet emitters may be selected from the group consisting of ruthenium-based fused ring systems as disclosed in US2015333277A1, US2016099411A1, US2016204355A1.

More preferred singlet emitters may be selected from the group consisting of: a derivative of ruthenium, such as the structure disclosed in US Pat. No. 1, 1975, 509, A1; a triarylamine derivative of ruthenium, such as a triarylamine derivative of ruthenium containing a dibenzofuran unit disclosed in CN102232068B; Other triarylamine derivatives of hydrazine having a specific structure are disclosed in CN105085334A, CN105037173A. Other materials which can be used as singlet emitters are polycyclic aromatic hydrocarbon compounds, in particular derivatives of the following compounds: for example, 9,10-bis(2-naphthoquinone), naphthalene, tetraphenyl, xanthene, phenanthrene , 芘 (such as 2,5,8,11-tetra-t-butyl fluorene), anthracene, phenylene such as (4,4'-bis(9-ethyl-3-carbazolevinyl)-1 , 1 '-biphenyl), indenyl hydrazine, decacycloolefin, hexacene benzene, anthracene, spirobifluorene, aryl hydrazine (such as US20060222886), arylene vinyl (such as US5121029, US5130603), cyclopentane Alkene such as tetraphenylcyclopentadiene, rubrene, coumarin, rhodamine, quinacridone, pyran such as 4 (dicyanomethylidene)-6-(4-p-dimethylaminobenzene Vinyl-2-methyl)-4H-pyran (DCM), thiopyran, bis(pyridazinyl)imine boron compound (US 2007/0092753 A1), bis(pyridazinyl)methylene compound, carbostyryl Compounds, oxazinone, benzoxazole, benzothiazole, benzimidazole and pyrrolopyrroledione. Materials for some singlet illuminants can be found in the following patent documents: US 20070252517 A1, US 4769292, US 6020078, US 2007/0252517 A1, US 2007/0252517 A1. The entire contents of the above-listed patent documents are hereby incorporated by reference.

Non-limiting examples of some suitable singlet emitters are listed in the table below:

2. 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 formula M(L)n, wherein M is a metal atom and each time L can be the same or a different organic ligand, it Attached to the metal atom M by one or more position linkages or coordination, n is an integer greater than 1, preferably 1, 2, 3, 4, 5 or 6. Optionally, these metal complexes are attached to the polymer by one or more positions, most preferably by an organic ligand.

In a preferred embodiment, the metal atom M may be selected from transition metal elements or lanthanides or actinides, preferably selected from the group consisting of Ir, Pt, Pd, Au, Rh, Ru, Os, Sm, Eu, Gd, Tb. Dy, Re, Cu or Ag is particularly preferably selected from the group consisting of Os, Ir, Ru, Rh, Re, Pd, Au or Pt.

Preferably, the triplet emitter may comprise a chelating ligand, ie a ligand, coordinated to the metal by at least two bonding sites, with particular preference being given to the triplet emitter comprising two or three identical or different Double or multidentate ligand. Chelating ligands are beneficial for increasing the stability of metal complexes.

Non-limiting examples of organic ligands may be selected from the group consisting of phenylpyridine derivatives, 7,8-benzoquinoline derivatives, 2(2-thienyl)pyridine derivatives, 2(1-naphthyl)pyridine derivatives or 2 phenylquinoline derivatives. All of these organic ligands may be substituted, for example by fluorine or trifluoromethyl. The ancillary ligand may preferably be selected from the group consisting of acetone acetate or picric acid.

In a preferred embodiment, the metal complex that can be used as the triplet emitter can have the following form:

Wherein M is a metal selected from a transition metal element or a lanthanide or lanthanide element, particularly preferably selected from the group consisting of Ir, Pt, and Au;

Each occurrence of Ar ₁ may be the same or different cyclic group, which contains at least one donor atom, that is, an atom having a lone pair of electrons, such as nitrogen or phosphorus, through which a cyclic group is coordinated to the metal; Each occurrence of Ar ₂ may be the same or different cyclic group, which contains at least one C atom through which a cyclic group is bonded to the metal; Ar ₁ and Ar ₂ are linked by a covalent bond, respectively Carrying one or more substituent groups, which may also be linked together by a substituent group; each occurrence of L' may be the same or a different bidentate chelated auxiliary ligand, most preferably a monoanionic bidentate chelate The ligand; q1 may be 0, 1, 2 or 3, preferably 2 or 3; q2 may be 0, 1, 2 or 3, preferably 1 or 0.

Non-limiting examples of materials for some triplet emitters and their use can be found in the following patent documents and documents: WO 200070655, WO 200141512, WO 200202714, WO 200215645, EP 1191613, EP 1191612, EP 1191614, WO 2005033244, WO 2005019373, US 2005/0258742, WO 2009146770, WO 2010015307, WO 2010031485, WO 2010054731, WO 2010054728, WO 2010086089, WO 2010099852, WO 2010102709, US 20070087219 A1, US 20090061681 A1, US 20010053462 A1, Baldo, Thompson et al. 403, (2000), 750-753, US 20090061681 A1, US 20090061681 A1, Adachi et al. Appl. Phys. Lett. 78 (2001), 1622-1624, J. Kido et al. Appl. Phys. Lett. (1994), 2124, Kido et al. Chem. Lett. 657, 1990, US 2007/0252517 A1, Johnson et al., JACS 105, 1983, 1795, Wrighton, JACS 96, 1974, 998, Ma et al., Synth.Metals 94,1998,245, US 6824895, US 7029766, US 6835469, US 6830828, US 20010053462 A1, WO 2007095118 A1, US 2012004407A1, WO 2012007088A1, WO2 012007087A1, WO 2012007086A1, US 2008027220A1, WO 2011157339A1, CN 102282150A, WO 2009118087A1, WO 2013107487A1, WO 2013094620A1, WO 2013174471A1, WO 2014031977A1, WO 2014112450A1, WO 2014007565A1, WO 2014038456A1, WO 2014024131A1, WO 2014008982A1, WO2014023377A1. The entire contents of the aforementioned patent documents and documents are hereby incorporated herein by reference.

Some non-limiting examples of suitable triplet emitters are listed in the table below:

3. Thermally activated delayed fluorescent luminescent material (TADF)

Traditional organic fluorescent materials can only use 25% singlet excitons formed by electrical excitation, and the internal quantum efficiency of the device is low (up to 25%). Although the phosphorescent material enhances the inter-system traversal due to the strong spin-orbit coupling of the center of the heavy atom, it can effectively utilize the singlet excitons and triplet exciton luminescence formed by electrical excitation, so that the internal quantum efficiency of the device reaches 100%. However, the problems of expensive phosphorescent materials, poor material stability, and severe roll-off of device efficiency limit their application in OLEDs. The thermally activated delayed fluorescent luminescent material is a third generation organic luminescent material developed after organic fluorescent materials and organic phosphorescent materials. Such materials generally have a small singlet-triplet energy level difference (ΔE _st ), and triplet excitons can be converted into singlet exciton luminescence by inter-system crossing. This can make full use of the singlet excitons and triplet excitons formed under electrical excitation. The quantum efficiency in the device can reach 100%. At the same time, the material structure is controllable, the property is stable, the price is cheap, no precious metal is needed, and the application prospect in the OLED field is broad.

The TADF material needs to have a smaller singlet-triplet energy level difference generally ΔEst < 0.3 eV, preferably ΔEst < 0.2 eV, most preferably ΔEst < 0.1 eV. In a preferred embodiment, the TADF material has a relatively small ΔEst, and in another preferred embodiment, the TADF has a better fluorescence quantum efficiency. Non-limiting examples of TADF luminescent materials can be found in the following patent documents: CN103483332(A), TW201309696(A), TW201309778(A), TW201343874(A), TW201350558(A), US20120217869(A1), WO2013133359(A1) , WO2013154064 (A1), Adachi, et.al. Adv. Mater., 21, 2009, 4802, Adachi, et. al. Appl. Phys. Lett., 98, 2011, 083302, Adachi, et.al. Appl. Phys. Lett., 101, 2012, 093306, Adachi, et. al. Chem. Commun., 48, 2012, 11392, Adachi, et. al. Nature Photonics, 6, 2012, 253, Adachi, et. al. , 492, 2012, 234, Adachi, et. al. J. Am. Chem. Soc, 134, 2012, 14706, Adachi, et. al. Angew. Chem. Int. Ed, 51, 2012, 11311, Adachi, et .al.Chem.Commun.,48,2012,9580,Adachi,et.al.Chem.Commun.,48,2013,10385,Adachi,et.al.Adv.Mater.,25,2013,3319,Adachi, et.al.Adv.Mater., 25, 2013, 3707, Adachi, et. al. Chem. Mater., 25, 2013, 3038, Adachi, et. al. Chem. Mater., 25, 2013, 3766, Adachi , et.al.J.Mater.Chem. C.,1,2013,4599,Adachi,et.al.J.Phys.Chem.A.,117 , 2013, 5,607, the entire disclosure of which is incorporated herein by reference.

Some non-limiting examples of suitable TADF luminescent materials are listed in the table below:

Another aspect of the invention relates to providing a technical route for printing organic electronic devices, and in particular to a method of preparing the above organic composite film.

In the method of producing an organic composite film according to the present invention, at least one of L1 and L2 is formed by a printing or coating method.

In some embodiments, one of L1 and L2 is formed by printing or coating, and the other layer is formed by vacuum evaporation.

In certain preferred embodiments, one of L1 and L2 is formed by printing or coating, and the other layer is also formed by printing or printing.

In order to facilitate printing or printing, another aspect of the invention also provides a composition or printing ink comprising all of the components of the L1 or L2 layer of the invention, and at least one organic solvent.

In a preferred embodiment, the composition according to the invention comprises a crosslinkable polymer.

In another preferred embodiment, the composition according to the invention comprises a small molecule or polymer having hole or electron transport properties.

In a further preferred embodiment, the composition according to the invention comprises an illuminant selected from the group consisting of a singlet emitter, a triplet emitter or a TADF emitter.

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

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

The composition in the examples of the present invention may comprise from 0.01 to 20% by weight of the organic compound, preferably from 0.1 to 15% by weight, more preferably from 0.2 to 10% by weight, most preferably from 0.25 to 5% by weight of the organic compound.

In some preferred embodiments, the solvent according to the invention is selected from the group consisting of aromatic or heteroaromatic, ester, aromatic ketone or aromatic ether, aliphatic ketone or aliphatic ether, alicyclic or olefin a compound, or an inorganic ester compound such as a boronic acid ester or a phosphate ester, or a mixture of two or more solvents.

In a further preferred embodiment, the composition according to the invention comprises at least 50% by weight of an aromatic or heteroaromatic solvent; preferably at least 80% by weight of an aromatic or heteroaromatic solvent; particularly preferably at least 90% by weight of aromatic A family or heteroaromatic solvent.

Non-limiting examples based on aromatic or heteroaromatic solvents according to the invention are: 1-tetralone, 3-phenoxytoluene, acetophenone, 1-methoxynaphthalene, p-diisopropylbenzene , pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylcumene, dipentylbenzene, o-diethylbenzene, methylene Ethylbenzene, p-diethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, butylbenzene, dodecylbenzene, 1-methylnaphthalene, 1,2,4-trichlorobenzene, 1,3-dipropoxybenzene, 4,4-difluorodiphenylmethane, diphenyl ether, 1,2-dimethoxy-4 -(1-propenyl)benzene, diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether, N -methyldiphenylamine, 4-isopropylbiphenyl,

-dichlorodiphenylmethane, 4-(3-phenylpropyl)pyridine, benzyl benzoate, 1,1-bis(3,4-dimethylphenyl)ethane, 2-isopropylnaphthalene, Dibenzyl ether and the like.

In other embodiments, suitable and preferred solvents are aliphatic, cycloaliphatic or aromatic hydrocarbons, amines, thiols, amides, nitriles, esters, ethers, polyethers, alcohols, glycols or polyols.

In other embodiments, the alcohol represents a suitable class of solvent. Preferred alcohols include alkylcyclohexanols, especially methylated aliphatic alcohols, naphthols and the like.

The solvent may be a cycloalkane such as decalin.

The solvent may be used singly or as a mixture of two or more organic solvents.

In certain embodiments, the composition according to the present invention comprises an organic functional compound as described above and at least one organic solvent, and may further comprise another organic solvent, and examples of the other organic solvent include but not Limited to: methanol, ethanol, 2-methoxyethanol, dichloromethane, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, p-pair Toluene, 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, hydrazine and/or mixtures thereof.

In some preferred embodiments, the solvent particularly suitable for the present invention is a solvent having Hansen solubility parameters in the following ranges:

Δd (dispersion force) is in the range of 17.0 to 23.2 MPa 1/2, especially in the range of 18.5 to 21.0 MPa 1/2;

Δp (polar force) is in the range of 0.2 to 12.5 MPa 1/2, especially in the range of 2.0 to 6.0 MPa 1/2;

Δh (hydrogen bond force) is in the range of 0.9 to 14.2 MPa 1/2, particularly in the range of 2.0 to 6.0 MPa 1/2.

The composition according to the invention wherein the organic solvent is selected taking into account its boiling point parameters. In the present invention, the organic solvent has a boiling point of ≥ 150 ° C; preferably ≥ 180 ° C; more preferably ≥ 200 ° C; more preferably ≥ 250 ° C; most preferably ≥ 275 ° C or ≥ 300 ° C. The boiling points within these ranges are beneficial for preventing nozzle clogging of the inkjet printhead. The organic solvent can be evaporated from the solvent system to form a film comprising the functional material.

In some preferred embodiments, the composition according to the invention is characterized by:

1) its viscosity @25 ° C, in the range of 1 cPs to 100 cPs, and / or

2) Its surface tension @25 ° C, in the range of 19 dyne / cm to 50 dyne / cm.

The composition according to the invention wherein the organic solvent is selected taking into account its surface tension parameters. Suitable ink surface tension parameters are suitable for a particular substrate and a particular printing method. For example, for ink jet printing, in a preferred embodiment, the surface tension of the organic solvent at 25 ° C is in the range of about 19 dyne / cm to 50 dyne / cm; more preferably in the range of 22 dyne / cm to 35 dyne / cm; It is preferably in the range of 25 dyne/cm to 33 dyne/cm.

In a preferred embodiment, the surface tension of the ink according to the invention is in the range of from about 19 dyne/cm to 50 dyne/cm at 25 ° C; preferably in the range of from 22 dyne/cm to 35 dyne/cm; most preferably at 25 dyne/cm to 33dyne/cm range.

The composition according to the invention wherein the organic solvent is selected taking into account the viscosity parameters of its ink. The viscosity can be adjusted by different methods, such as by selection of a suitable organic solvent and concentration of functional materials in the ink. In a preferred embodiment, the viscosity of the organic solvent is less than 100 cps; more preferably less than 50 cps; most preferably from 1.5 to 20 cps. Viscosity herein refers to the viscosity at ambient temperature at the time of printing, generally 15-30 ° C, preferably 18-28 ° C, more preferably 20-25 ° C, and most preferably 23-25 ° C. Compositions so formulated will be particularly suitable for ink jet printing.

In a preferred embodiment, the viscosity of the composition according to the invention is in the range of from about 1 cps to 100 cps at 25 °C; more preferably in the range of from 1 cps to 50 cps; most preferably in the range of from 1.5 cps to 20 cps.

An ink obtained from an organic solvent satisfying the above boiling point, surface tension parameters, and viscosity parameters can form a functional material film having uniform thickness and composition properties.

Based on the above composition or printing ink, a preferred embodiment of the preparation method according to the present invention corresponds to the mode of the composite film described above as follows:

Mode 1:1) L1 is formed by printing or coating first, and dried; 2) L2 is deposited on L1 by vacuum evaporation to form L2.

Mode 2: 1) L2 is formed by printing or coating first, and dried; 2) L1 is deposited on L2 by vacuum evaporation.

Mode 3: 1) First, L1 is formed by printing or coating, cross-linking is assisted by UV or heat, and dried; 2) L2 is formed on L1 by printing or coating, and dried.

Mode 4: 1) L2 is first formed by printing or coating, cross-linked by UV or heat, and dried; 2) L1 is formed on L2 by printing or coating, and dried.

Mode 5: 1) L1 is first formed by printing or coating, and dried; 2) L2 is deposited on L1 by vacuum evaporation to form L2.

Mode 6: 1) L2 is formed by printing or coating first, and dried; 2) L1 is deposited on L2 by vacuum evaporation.

Mode 7: 1) L1 is formed by printing or coating first, cross-linking is assisted by UV or heat, and dried; 2) L2 is formed on L1 by printing or coating, and dried.

Mode 8: 1) L2 is formed by printing or coating first, cross-linking is assisted by UV or heat, and dried; 2) L1 is formed on L2 by printing or coating, and dried.

Mode 9: 1) L1 is formed by printing or coating first, cross-linking is assisted by UV or heat, and dried; 2) L2 is formed on L1 by printing or coating, and dried.

Mode 10: 1) L2 is first formed by printing or coating, cross-linked by UV or heat, and dried; 2) L1 is formed on L2 by printing or coating, and dried.

Mode 11:1) L1 is formed by printing or coating first, cross-linking is assisted by UV or heat, and dried; 2) L2 is formed on L1 by printing or coating, and dried.

Mode 12: 1) L2 is first formed by printing or coating, cross-linked by UV or heat, and dried; 2) L1 is formed on L2 by printing or coating, and dried.

Suitable printing or coating techniques in the present invention include, but are not limited to, ink jet printing, letterpress printing, screen printing, dip coating, spin coating, knife coating, roll printing, reverse roll printing, lithography, Flexographic printing, rotary printing, spraying, brushing or pad printing, slit-type extrusion coating, etc. Preferred are gravure, screen printing and inkjet printing. Gravure printing, ink jet printing will be applied in embodiments of the invention. The solution or suspension may additionally comprise one or more components such as surface active compounds, lubricants, wetting agents, dispersing agents, hydrophobic agents, binders and the like for adjusting viscosity, film forming properties, adhesion, and the like. For information on printing techniques and their requirements for solutions, such as solvents and concentrations, viscosity, etc., please refer to Helmut Kipphan's "Printing Media Handbook: Techniques and Production Methods" (Handbook of Print Media: Technologies and Production Methods). ), ISBN 3-540-67326-1.

According to the above production method, the total thickness of the organic composite film is from 5 nm to 1000 nm.

The present invention also provides an application of the organic composite film as described above, that is, the organic composite film is applied to an organic electronic device, and the organic electronic device may be selected from, but not limited to, an organic light emitting diode (OLED), an organic photovoltaic device. Battery (OPV), organic light-emitting battery (OLEEC), organic field effect transistor (OFET), organic light-emitting field effect transistor, organic laser, organic spintronic device, organic sensor and organic plasmon emitting diode (Organic Plasmon Emitting Diode) ), etc., especially OLED. In the embodiment of the present invention, the organic composite film is preferably applied to an organic electroluminescence device such as an OLED, an OLEEC, or an organic light-emitting field effect transistor.

Yet another aspect of the invention further relates to an organic electronic device comprising at least one organic composite film as described above. Generally, the organic electronic device comprises at least one anode, one cathode and a functional layer between the cathode and the anode, wherein the functional layer contains at least one organic composite film as described above. The organic electronic device may be selected from, but not limited to, an organic light emitting diode (OLED), an organic photovoltaic cell (OPV), an organic light emitting cell (OLEEC), an organic field effect transistor (OFET), an organic light emitting field effect transistor, an organic laser, Organic spintronic devices, organic sensors, and organic plasmon emitting diodes (Organic Plasmon Emitting Diode), especially OLEDs. In an embodiment of the invention, the organic composite film is preferably applied to an organic electroluminescent device such as an OLED, an OLEEC, or an organic light-emitting field effect transistor.

In a particularly preferred embodiment, the organic electronic device is an organic electroluminescent device, most preferably an OLED. The organic electronic device comprises at least an anode, an organic composite film according to any one of the above, and a cathode.

In some particularly preferred embodiments, the functional layer L1 or L2 of the organic composite film of the organic electroluminescent device further comprises a luminescent material selected from the group consisting of singlet illuminants (fluorescent illuminants) ), a triplet emitter (phosphorescent emitter) or a TADF material.

The above-mentioned light emitting device, particularly an OLED, comprises a substrate, an anode, at least one functional layer, and a cathode.

The substrate can be opaque or transparent. Transparent substrates can be used to make transparent light-emitting components. See, for example, Bulovic et al. Nature 1996, 380, p29 and Gu et al, Appl. Phys. Lett. 1996, 68, p2606. The substrate can be rigid or elastic. The substrate can be made of plastic, metal, semiconductor wafer or glass. Most preferably, the substrate has a smooth surface. Substrates without surface defects are a particularly desirable choice. In a preferred embodiment, the substrate is flexible and may be selected from polymeric films or plastics having a glass transition temperature Tg of 150 ° C or higher, preferably more than 200 ° C, more preferably more than 250 ° C, and most preferably more than 300 ° C. Non-limiting examples of suitable flexible substrates are poly(ethylene terephthalate) (PET) and polyethylene glycol (2,6-naphthalene) (PEN).

The anode can include a conductive metal or metal oxide, or a conductive polymer. The anode can easily inject holes into a hole injection layer (HIL), a hole transport layer (HTL), or a light-emitting layer. In one embodiment, the work function of the anode and the absolute value of the difference between the HOMO level or the valence band level of the luminescent material in the luminescent layer as the p-type semiconductor material of the HIL, HTL or electron blocking layer (EBL) is less than 0.5 eV. Preferably, it is less than 0.3 eV, and most preferably less than 0.2 eV. Examples of the anode material 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 can be deposited using any suitable technique, such as a suitable physical vapor deposition process, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like. In certain embodiments, the anode is patterned. Patterned ITO conductive substrates are commercially available and can be used to prepare devices in accordance with the present invention.

The cathode can include a conductive metal or metal oxide. The cathode can easily inject electrons into the EIL or ETL or directly into the luminescent layer. In one embodiment, the work function of the cathode and the LUMO level or conduction band of the n-type semiconductor material of the illuminant in the luminescent layer as an electron injection layer (EIL), an electron transport layer (ETL) or a hole blocking layer (HBL) The absolute value of the difference in energy levels is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV. In principle, all materials which can be used as cathodes for OLEDs are possible as cathode materials for the devices of the invention. Examples of the cathode material include, but are not limited to, Al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF2/Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, and the like. The cathode material can be deposited using any suitable technique, such as a suitable physical vapor deposition process, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.

The electroluminescent device, in particular the OLED, may also comprise other functional layers, such as a hole injection layer (HIL), an electron blocking layer (EBL), an electron injection layer (EIL), a hole blocking layer (HBL). Materials suitable for use in these functional layers are described in detail above and in WO2010135519A1, US20090134784A1, and WO2011110277A1, the entire disclosure of each of which is incorporated herein by reference.

The light-emitting device according to the invention has an emission wavelength of between 300 and 1000 nm, preferably between 350 and 900 nm, more preferably between 400 and 800 nm.

Another aspect of the invention also relates to the use of an electroluminescent device according to the invention in various electronic devices, including but not limited to display devices, illumination devices, light sources, sensors, and the like.

The present invention will be described with reference to the preferred embodiments thereof, but the present invention is not limited to the embodiments described below. It is to be understood that the scope of the invention is intended to be It is to be understood that the modifications of the various embodiments of the invention are intended to be

Example

1. Synthesis of compounds

Synthetic route of Example 1

Synthesis of Compound 1-3:

The specific synthetic route is as shown above, wherein the intermediate 1 and the intermediate 2 are commercially available directly, and in a 250 ml flask, 1.0 mmol of the intermediate 1, 1.1 mmol of the intermediate 2, 0.05 mmol of the catalyst Pd are sequentially added ( OAc) ₂ and 2.0 mmol of dry K ₂ CO ₃ powder, and finally dissolved in 100 ml of toluene to dissolve the above solid, and 0.10 mmol of tri-tert-butylphosphine (t-Bu) ₃ P was injected into the reaction solution under nitrogen protection. The temperature was raised to 120 ° C and refluxed overnight. The reaction is stopped by TLC, and the reaction is stopped by cooling. When the reaction solution is cooled to room temperature, the reaction is quenched by adding water, the reaction solution is added with dichloromethane, the organic phase is combined, and the organic solvent is evaporated to obtain a crude product. The compound was purified to give a compound 1-3, and the reaction yield was 80.5%. MS (ASAP) = 639.2

Synthetic route of Example 2

Synthesis of compound 1-5:

The synthetic route is as shown above, and the synthesis procedure is similar to that of the compound 1-3, wherein the intermediate 3 is reacted instead of the intermediate 1. Finally product compound 1-5 is obtained. The reaction yield was 75.4% and MS (ASAP) = 563.2.

Synthetic route of Example 3

Synthesis of Compound 1-13:

The synthetic route was as shown above, and the synthesis procedure was as follows: 3.63 g, 10 mmol (9-([1,1'-diphenyl]-3-yl)-9H-carbazole-3-yl was added to a 250 ml three-necked flask. Boric acid (intermediate 4), 3.98 g, 10 mmol of 9-([1,1'-diphenyl]-4-yl)-3-bromo-9H-indazole (intermediate 5), 6.9 g, 50 mmol of potassium carbonate 0.58 g, 0.5 mmol of Pd(PPh ₃ ) ₄ , 100 ml of toluene, 25 ml of water and 25 ml of ethanol were reacted in a N ₂ atmosphere at 110 ° C, and the progress of the reaction was followed by TLC until the reaction was completed and then cooled to room temperature. The reaction solution was poured into water, washed with K ₂ CO ₃ and then filtered to give a solid product which was washed with dichloromethane. The crude product was recrystallized from dichloromethane and methanol to give the product 6-(9-([1,1'-diphenyl]-3-yl)-9H-carbazole-3-yl)-9- ([1, 1'-Diphenyl]-4-yl)-9H-pyridine [2,3-b]indole 5.4 g, reaction yield: 84.8%, MS (ASAP) = 636.6.

Synthetic route of Example 4

Synthesis of compound 2-9:

The synthetic route was as shown above, and the synthesis procedure was as follows: 10 mmol of Intermediate 6, 10 mmol of Intermediate 7, 6.9 g, 50 mmol of potassium carbonate, 0.58 g, 0.5 mmol of Pd(PPh ₃ ) ₄ , 100 ml of toluene and 25 ml were added to a 250 ml three-necked flask. Ethanol was reacted at 110 ° C in a N ₂ atmosphere for about 5 hours, and the reaction was completed and lowered to room temperature. The reaction solution was poured into water, washed to remove K ₂ CO ₃ , and then suction filtered to obtain a solid product which was removed by a flash column and then extracted with dichloromethane and toluene, respectively. Finally, the product was dissolved in chloroform and precipitated in a methanol solution to obtain 2.0 g of a polymer, and the reaction yield was 45.4%.

Synthetic route of Example 5

Synthesis of Compound 3-2:

The synthesis route is as shown above, and the polymerization step is similar to the chemical 2-9. When x:y = 1:1, the specific polymerization route is as follows: 10 mmol of the intermediate 8 and 10 mmol of the intermediate 9, 6.9 are added to a 250 ml three-necked flask. g, 50 mmol of potassium carbonate, 0.58 g, 0.5 mmol of Pd(PPh ₃ ) ₄ , 100 ml of toluene and 25 ml of ethanol were reacted in a N ₂ atmosphere at 110 ° C for about 5 hours until the reaction was completed and lowered to room temperature. The reaction solution was poured into water, washed to remove K ₂ CO ₃ , and then suction filtered to obtain a solid product which was removed by a flash column and then extracted with dichloromethane and toluene, respectively. Finally, the product was dissolved in chloroform and precipitated in a methanol solution to obtain 1.8 g of a polymer, and the reaction yield was 55.1%.

Synthetic route of Example 6

Synthesis of Compound 3-4:

The synthesis route is as shown above, and the polymerization step is similar to the chemical 2-9. The specific polymerization route is as follows: 10 mmol of the intermediate 10, 10 mmol of the intermediate 11, 6.9 g, 50 mmol of potassium carbonate, 0.58 g, 0.5 mmol of Pd are added to a 250 ml three-necked flask. (PPh ₃ ) ₄ , 100 ml of toluene and 25 ml of ethanol were reacted in a N ₂ atmosphere at 110 ° C for about 5 hours, and the reaction was completed and lowered to room temperature. The reaction solution was poured into water, washed to remove K ₂ CO ₃ , and then suction filtered to obtain a solid product which was removed by a flash column and then extracted with dichloromethane and toluene, respectively. Finally, the product was dissolved in chloroform and precipitated in a methanol solution to obtain a polymer of 1.9 g, and the reaction yield was 45.1%.

Synthetic route of Example 7

Synthesis of Compound 4-1:

The synthetic route is as shown above, and the polymerization procedure is as follows: 1.0 mmol of intermediate 12, 0.1 mmol of free radical initiator AIBN and 20 ml of dry toluene are added to a 50 ml three-necked flask, and reacted at 60 ° C in a N ₂ atmosphere. After about 5 hours, the reaction was quenched with water and lowered to room temperature. The reaction solution was poured into water, washed to remove K ₂ CO ₃ , and then suction filtered to obtain a solid product which was removed by a flash column and then extracted with dichloromethane and toluene, respectively. Finally, the product was dissolved in chloroform and precipitated in a methanol solution to obtain 0.4 g of a polymer, and the reaction yield was 60.5%.

Synthetic route of Example 8

Synthesis of compound 6-4:

The synthetic route was as shown above, and the synthesis procedure was as follows: 10 mmol of intermediate 13, 10 mmol of intermediate 14, 6.9 g, 50 mmol of potassium carbonate, 0.58 g, 0.5 mmol of Pd(PPh ₃ ) ₄ , 100 ml of toluene, 25 ml were added to a 250 ml three-necked flask. Water and 25 ml of ethanol were reacted in a N ₂ atmosphere at 110 ° C, and the progress of the reaction was followed by TLC, and the reaction was allowed to proceed to room temperature. The reaction solution was poured into water, washed with K ₂ CO ₃ and then filtered to give a solid product which was washed with dichloromethane. The crude product was recrystallized from methylene chloride and methanol to give the product (yield: 5.5 g, yield: 88.3%), MS (ASAP) = 623.6.

Synthetic route of Example 9

Synthesis of compound 6-18:

The synthetic route is as shown above, and the synthesis procedure is similar to that of compound 6-1. The specific synthetic procedure is as follows: 10 mmol of intermediate 15, 10 mmol of intermediate 16, 6.9 g, 50 mmol of potassium carbonate, 0.58 g, 0.5 mmol of Pd are added to a 250 ml three-necked flask. (PPh ₃ ) ₄ , 100 ml of toluene, 25 ml of water and 25 ml of ethanol were reacted at 110 ° C in a N ₂ atmosphere, and the progress of the reaction was followed by TLC until the reaction was completed and the temperature was lowered to room temperature. The reaction solution was poured into water, washed with K ₂ CO ₃ and then filtered to give a solid product which was washed with dichloromethane. The crude product was recrystallized from methylene chloride and methanol to afford 5.8 g,yiel.

Synthetic route of Example 10

Synthesis of compound 9-7:

The synthetic route is as shown above, and the polymerization route is similar to that of the compound 4-1. The specific polymerization route is as follows: 1.0 mmol of the intermediate 17, 0.1 mmol of the radical initiator AIBN and 20 ml of dry toluene are added to a 50 ml three-necked flask in a N ₂ atmosphere. The reaction was carried out at 60 ° C for about 5 hours, and the reaction was quenched with water and lowered to room temperature. The reaction solution was poured into water, washed to remove K ₂ CO ₃ , and then suction filtered to obtain a solid product which was removed by a flash column and then extracted with dichloromethane and toluene, respectively. Finally, the product was dissolved in chloroform and precipitated in a methanol solution to obtain 0.2 g of a polymer, and the reaction yield was 35.0%.

Synthetic route of Example 11

Synthesis of compound 9-16:

The synthetic route is as shown above, and the polymerization route is similar to that of the compound 4-1. The specific polymerization route is as follows: 1.0 mmol of the intermediate 17, 0.1 mmol of the radical initiator AIBN and 20 ml of dry toluene are added to a 50 ml three-necked flask in a N ₂ atmosphere. The reaction was carried out at 60 ° C for about 5 hours, and the reaction was quenched with water and lowered to room temperature. The reaction solution was poured into water, washed to remove K ₂ CO ₃ , and then suction filtered to obtain a solid product which was removed by a flash column and then extracted with dichloromethane and toluene, respectively. Finally, the product was dissolved in chloroform and precipitated in a methanol solution to obtain a polymer of 0.35 g, and the reaction yield was 57.7%.

Synthetic route of Example 12

Synthesis of compound 10-9:

Synthetic route As shown above, the polymerization route of the intermediate 20 was similar to that of the compound 4-1, and the specific polymerization route was as follows: 1.0 mmol of the intermediate 17, 0.1 mmol of the radical initiator AIBN and 20 ml of dry toluene were added to a 50 ml three-necked flask at N. _{2 In the} atmosphere, the reaction was carried out at 60 ° C, the reaction was carried out for about 5 hours, and the reaction was quenched with water and lowered to room temperature. The reaction solution was poured into water, washed to remove K ₂ CO ₃ , and then suction filtered to obtain a solid product which was removed by a flash column and then extracted with dichloromethane and toluene, respectively. Finally, the product was dissolved in chloroform and precipitated in a methanol solution to obtain 0.5 g of a polymer, and the reaction yield was 75.0%.

In a 50 ml single-mouth flask, 0.5 g of Intermediate 20 and 1.0 mmol of NaH powder were successively added, and dissolved in 20 ml of DMF solution, and stirred under a nitrogen atmosphere at room temperature for 0.5 hour, and 1.0 mmol of methylphosphine ylide solution was slowly added. Stirring was continued for 4 hours at room temperature, the reaction was quenched with water, extracted with chloroform, the organic phase was combined, and the organic solvent was evaporated to dryness. The obtained crude product was removed by a flash chromatography column to obtain a white solid product. Extraction with methyl chloride, toluene and ethanol. Finally, the product 10-9 was dissolved in chloroform and precipitated in a methanol solution to obtain a polymer of 0.3 g, and the reaction yield was about 60.0%.

2. The energy level structure of the compound

The organic small molecule energy structure can be obtained by quantum calculation, for example, by TD-DFT (time-dependent density functional theory) by Gaussian03W (Gaussian Inc.), and the specific simulation method can be found in WO2011141110. First, the semi-empirical method "Ground State/Semi-empirical/Default Spin/AM1" (Charge 0/Spin Singlet) is used to optimize the molecular geometry, and then the energy structure of the organic molecule is determined by TD-DFT (time-dependent density functional theory) method. Calculated "TD-SCF/DFT/Default Spin/B3PW91" and the base group "6-31G(d)" (Charge 0/Spin Singlet).

For conjugated polymers, the energy structure of the polymer can be obtained by calculating the trimer. Compound 3-2, trimer M1-M2-M1 and/or M2-M1-M2, as polymerized by the monomers M1 and M2 shown below, was used to calculate the energy level in which the polymerizable group was shifted. Go, the long alkyl chain is replaced with a methyl group.

Trimer M1-M2-M1:

Trimer M2-M1-M2:

For the side chain non-conjugated polymer as shown in Chemical Formulas 1 and 2, the energy structure of the polymer can be obtained by calculating a functional group such as H1 or H2 on the side chain, wherein the linkage of H1 or H2 with the main chain is Substituted.

The HOMO and LUMO energy levels calculated above are calculated according to the following calibration formula, and S1 and T1 are used directly.

HOMO(eV)=((HOMO(G)×27.212)-0.9899)/1.1206

LUMO(eV)=((LUMO(G)×27.212)-2.0041)/1.385

Among them, HOMO(G) and LUMO(G) are direct calculation results of Gaussian 09W, and the unit is eV. The results are shown in Table 1, where ΔHOMO=HOMO-(HOMO-1):

Table 1

3. An organic composite film functional layer composition mode

An organic composite film functional layer composition method is shown in Table 2.

Table 2

Among them, compounds A, B, and C are as follows:

4. Preparation and measurement of OLED devices

The preparation process of the OLED device using the organic composite film as shown in Table 2 will be described in detail below by way of a specific embodiment. The structure of the OLED device is: ITO/HIL/organic composite film/cathode, and the preparation steps are as follows:

a, ITO (indium tin oxide) conductive glass substrate cleaning: using a variety of solvents (such as one or several of chloroform, acetone or isopropanol) cleaning, and then UV ozone treatment;

B, HIL (hole injection layer, 60nm): 60nm is of PEDOT (polyethylene dioxythiophene, Clevios ^TM AI4083) in a clean room as HIL spin coated from, and heat-treated at 180 [deg.] C for 10 minutes plate ;

c, the production method of organic composite film:

Composite film 1:1) The L2 material was dissolved in toluene at a solution concentration of 5 mg/ml, spin-coated in a clean room, and treated on a hot plate at 180 ° C for 10 minutes with a thickness of 65 nm; 2) passing the L1 material A vacuum deposition (1 × 10 ^-6 mbar) was deposited on L2 to a thickness of 20 nm.

Composite film 2-3: 1) The L1 material was dissolved in toluene at a solution concentration of 5 mg/ml, spin-coated in a clean room, and treated on a hot plate at 180 ° C for 10 minutes, thickness 20 nm; 2) L2 The material was deposited on L1 by vacuum evaporation (1 x 10 ^-6 mbar) with a thickness of 80 nm.

Composite film 4-5: 1) The L1 material is dissolved in toluene, the solution concentration is 5 mg/ml, and it is spin-coated in a clean room, and heated to 100 ° C on a hot plate for 0-40 min to cause cross-linking reaction. 2 nm thick; 2) The L2 material was dissolved in toluene at a solution concentration of 5 mg/ml, formed on L1 by spin coating, and treated on a hot plate at 180 ° C for 10 minutes to a thickness of 80 nm.

Composite film 6: 1) Dissolve L1 material in toluene, solution concentration 5mg/ml, spin coating in a clean room, heat on a hot plate to 100 ° C for 0-40min, causing cross-linking reaction, thickness 20nm; 2) The L2 material is dissolved in toluene, the concentration of the solution is 5 mg/ml, formed on L1 by spin coating, heated to 100 ° C on a hot plate for 0-40 min, causing cross-linking reaction, thickness 80nm;

Composite film 7-8: 1) The L1 material was dissolved in toluene at a solution concentration of 5 mg/ml, spin-coated in a clean room, and treated on a hot plate at 180 ° C for 10 minutes, thickness 20 nm; 2) L2 The material was deposited on L1 by vacuum evaporation (1 x 10 ^-6 mbar) with a thickness of 65 nm.

Composite film 9-10: 1) The L1 material was dissolved in toluene at a solution concentration of 5 mg/ml, spin-coated in a clean room, and treated on a hot plate at 180 ° C for 10 minutes, thickness 20 nm; 2) L2 The material is dissolved in toluene, the solution concentration is 5 mg/ml, formed on L1 by spin coating, and treated on a hot plate at 180 ° C for 10 minutes, thickness 65 nm;

Composite film 11:1) The L2 material was dissolved in toluene at a solution concentration of 5 mg/ml, spin-coated in a clean room, and treated on a hot plate at 180 ° C for 10 minutes, thickness 65 nm; 2) passing the L1 material A vacuum deposition (1 × 10 ^-6 mbar) was deposited on L2 to a thickness of 20 nm.

Composite film 12: 1) Dissolve L1 material in toluene, solution concentration 5mg/ml, spin coating in a clean room, and treat on a hot plate at 180 ° C for 10 minutes, thickness 20nm; 2) dissolve L2 material Toluene, solution concentration 5mg / ml, formed on L1 by spin coating, and treated on a hot plate at 180 ° C for 10 minutes, thickness 80nm;

Composite film 13: 1) The L1 material was dissolved in toluene at a solution concentration of 5 mg/ml, spin-coated in a clean room, and treated on a hot plate at 180 ° C for 10 minutes to a thickness of 20 nm; 2) the L2 material was passed A vacuum deposition (1 × 10 ^-6 mbar) was deposited on L1 to a thickness of 65 nm.

Composite film 14: 1) The L2 material was dissolved in toluene at a solution concentration of 5 mg/ml, spin-coated in a clean room, and treated on a hot plate at 180 ° C for 10 minutes, thickness 80 nm; 2) passing the L1 material A vacuum deposition (1 × 10 ^-6 mbar) was deposited on L2 to a thickness of 20 nm.

Composite film 15: 1) The L1 material was dissolved in toluene at a solution concentration of 5 mg/ml, spin-coated in a clean room, and treated on a hot plate at 180 ° C for 10 minutes to a thickness of 20 nm; 2) the L2 material was passed A vacuum deposition (1 × 10 ^-6 mbar) was deposited on L1 to a thickness of 65 nm.

Composite film 16:1) Dissolve L1 material in toluene, solution concentration 5mg/ml, spin coating in a clean room, and treat on a hot plate at 180 °C for 10 minutes, thickness 20nm; 2) dissolve L2 material Toluene, solution concentration 5mg / ml, formed on L1 by spin coating, and treated on a hot plate at 180 ° C for 10 minutes, thickness 65nm;

d, cathode: Ba / Al (2nm / 100nm) in a high vacuum (1 × 10 ^-6 mbar) in the thermal evaporation;

e. Package: The device is packaged in a UV glove box with a UV curable resin.

The current and voltage (IVL) characteristics of each OLED device are characterized by characterization equipment while recording important parameters such as efficiency, lifetime and drive voltage. The performance of OLED devices is summarized in Table 3.

table 3

The technical features of the above-described embodiments may be arbitrarily combined. For the sake of brevity of description, all possible combinations of the technical features in the above embodiments are not described. However, as long as there is no contradiction in the combination of these technical features. It should be considered as the scope of this manual.

The above-described embodiments are merely illustrative of several embodiments of the present invention, and the description thereof is more specific and detailed, but is not to be construed as limiting the scope of the invention. It should be noted that a number of variations and modifications may be made by those skilled in the art without departing from the spirit and scope of the invention. Therefore, the scope of the invention should be determined by the appended claims.

Claims

An organic composite film comprising, in order, a functional layer L1 and a functional layer L2, wherein the functional layer L1 comprises an organic material M1, and the functional layer L2 comprises an organic material M2, wherein:

1) at least one of M1 and M2 is a polymer; 2) M1 and M2 have a semiconductor heterojunction structure of type II, and min(Δ(LUMO M1 -HOMO M2 ), Δ(LUMO M2 -HOMO M1 )) ≤ Min(E T (M1), E T (M2))+0.1eV, where HOMO(M1), LUMO(M1) and E T (M1) respectively represent the highest occupied orbit, the lowest unoccupied orbit and the triplet of M1 The energy levels, HOMO (M2), LUMO (M2), and E T (M2) represent the highest occupied orbital, minimum unoccupied orbital, and triplet energy levels of M2, respectively.
The organic composite film according to claim 1, wherein said M1 has a hole transporting property, and said M2 has an electron transporting property.
The organic composite film according to claim 1 or 2, wherein the HOMO-(HOMO-1) of the M1 is ≥0.3 eV, or ((LUMO+1)-LUMO) of the M2 is ≥0.15 eV.
The organic composite film according to claim 1 or 2, wherein the M1 is selected from the group consisting of an amine, a triarylamine, a phthalocyanine, a thiophene, a pyrrole, a carbazole, an indolocarbazole, a carbazole or Small molecules or polymers of isomers and derivative groups thereof.
The organic composite film according to claim 4, wherein said M1 is selected from small molecules or polymers containing a group of the following formula or an isomer thereof and a derivative group:

among them,

L 1 represents a single bond, an aromatic group having 6 to 30 carbon atoms or an aromatic hetero group having 3 to 30 carbon atoms, and the linking position of L 1 may be any carbon atom on the benzene ring;

L 2 , L 3 , L 4 and L 5 represent an aromatic group having 6 to 30 carbon atoms or an aromatic hetero group having 3 to 30 carbon atoms;

Ar 10 and Ar 11 represent an aromatic group having 6 to 30 carbon atoms or an aromatic hetero group having 3 to 30 carbon atoms;

A 1 and A 2 independently represent N(R), C(R) 2 , Si(R) 2 , O, C=N(R), C=C(R) 2 , P(R), P(= O) R, S, S=O or SO 2 ;

A 3 and A 4 each independently represent a single bond, N(R), C(R) 2 , Si(R) 2 , O, C=N(R), C=C(R) 2 , P(R), P(=O)R, S, S=O or SO 2 , but not both single bonds;

Y 1 to Y 8 independently represent N(R), C(R) 2 , Si(R) 2 , O, C=N(R), C=C(R) 2 , P(R), P(= O) R, S, S=O or SO 2 ;

R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R each independently represent H, D, F, CN, alkenyl, alkynyl, nitrile, amine, nitro, acyl, alkoxy a carbonyl group, a sulfone group, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms or an aromatic heterocyclic ring having 3 to 60 carbon atoms. a group, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 may be bonded to any carbon atom on the fused ring;

m represents an integer of 1 to 6.
The organic composite film according to claim 4, wherein the M1 is selected from the following structures:

among them

R 1 to R 10 are each independently hydrogen, or a linear alkyl group, an alkoxy group or a thioalkoxy group having 1 to 20 C atoms, or a branch or ring having 3 to 20 C atoms. An alkyl, alkoxy or thioalkoxy group or a silyl group, or a substituted keto group having 1 to 20 C atoms, an alkoxy group having 2 to 20 C atoms a carbonyl group, an aryloxycarbonyl group having 7 to 20 C atoms, a cyano group (-CN), a carbamoyl group (-C(=O)NH 2 ), a haloformyl group (-C(=O)-X wherein X represents a halogen atom), formyl group (-C(=O)-H), isocyanato group, isocyanate group, thiocyanate group or isosulfur Cyanate group, hydroxyl group, nitro group, CF 3 group, Cl, Br, F, crosslinkable group or substituted or unsubstituted aromatic or heterocyclic group having 5 to 40 ring atoms An aromatic ring system, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems, wherein one or more groups R may be bonded to each other and/or to said group R The bonded ring forms a monocyclic or polycyclic aliphatic or aromatic ring system;

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

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

x, y is the mol% of the repeating unit, x>0, y>0, and x+y=1.
The organic composite film according to claim 1 or 2, wherein the M2 is selected from the group consisting of pyridine, pyrimidine, pyrazine, phenazine, hydrazine, hydrazine, imidazole, oxadiazole, triazine, triazole, A small molecule or polymer of phenazine or its isomers and derivative groups.
The organic composite film according to claim 7, wherein the M2 is selected from the group consisting of F, a cyano group or a skeleton having any one of the following formulae:

Wherein m1 is 1, 2 or 3; X 1 -X 8 is selected from CR or N, and at least one is N;

M 1 , M 2 , and M 3 independently represent N(R), C(R) 2 , Si(R) 2 , O, C=N(R), C=C(R) 2 , P(R), P(=O)R, S, S=O, SO 2 or none;

R, R 1 , R 2 and R 3 each independently represent H, D, F, CN, alkenyl, alkynyl, nitrile, amine, nitro, acyl, alkoxy, carbonyl, sulfone, carbon atom An alkyl group of 1 to 30, a cycloalkyl group having 3 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms or an aromatic heterocyclic group having 3 to 60 carbon atoms, wherein R 1 and R 2 The connection position of R 3 may be on any carbon atom on the fused ring.
The organic composite film according to claim 1 or 2, wherein at least one of M1 and M2 is a polymer containing a crosslinkable group.
The organic composite film according to claim 9, wherein the crosslinkable group described in M1 and M2 is selected from the group consisting of linear or cyclic alkenyl groups, linear dienyl groups, alkynyl groups, alkenyloxy groups, and Alkenyloxy, acrylate, propylene oxide, butylene oxide, silane, cyclobutane.
The organic composite film according to claim 1 or 2, wherein M1 or M2 is a conjugated polymer.
The organic composite film according to claim 1 or 2, wherein M1 or M2 is a non-conjugated side chain polymer.
The organic composite film according to claim 12, wherein M1 is a non-conjugated side chain polymer comprising a repeating unit as shown in Chemical Formula 1, and min (Δ(LUMO H1 - HOMO M2 ), Δ (LUMO M2 - HOMO H1 )) ≤ min(E T (H 1 ), E T (M2)) ± 0.1eV, where HOMO(H1), LUMO(H1) and E T (H1) respectively represent the highest occupied orbit of H1 and the lowest unoccupied The energy level of the orbit and the triplet;

Wherein H1 is an organic group having a hole transporting property, and q is a natural number greater than or equal to 1.
The organic composite film according to claim 1 or 2, wherein the functional layer L1 or the functional layer L2 further comprises a luminescent material selected from the group consisting of a singlet illuminant, a triplet illuminant or TADF illuminator.
An organic electronic device comprising the organic composite film according to any one of claims 1-14.
The organic electronic device according to claim 15, wherein the organic electronic device is an electroluminescent device, and the electroluminescent device comprises an anode, the organic composite film according to any one of claims 1 to 14. And cathode.
The organic electronic device according to claim 15, wherein the organic composite film further comprises a luminescent material selected from the group consisting of a singlet illuminant, a triplet illuminant or a TADF illuminant.