阅读说明：本技术 一种以咔唑为核心的芳胺类衍生物及其应用 (Arylamine derivative taking carbazole as core and application thereof ) 是由 陆颖 张兆超 李崇 崔明 于 2020-04-28 设计创作，主要内容包括：本发明涉及一种以咔唑为核心的芳胺类衍生物及其应用,属于半导体技术领域,本发明提供化合物的结构如通式(I)所示；本发明还公开了上述化合物的应用。本发明提供的化合物具有较强的电子阻挡的作用,提升激子在发光层中的复合效率；作为OLED发光器件的发光功能层材料使用时,搭配本发明范围内的支链可有效提高激子利用率和辐射效率。(The invention relates to an arylamine derivative taking carbazole as a core and application thereof, belonging to the technical field of semiconductors, wherein the structure of the compound provided by the invention is shown as a general formula (I); the invention also discloses application of the compound. The compound provided by the invention has a strong electron blocking effect, and the recombination efficiency of excitons in the light-emitting layer is improved; when the organic light emitting diode is used as a light emitting functional layer material of an OLED light emitting device, the exciton utilization rate and the radiation efficiency can be effectively improved by matching the branched chain in the range of the invention.)

1. An arylamine derivative taking carbazole as a core is characterized in that the structure of the derivative is shown as a general formula (I):

in the general formula (I), R is₁、R₂Each independently represents substituted or unsubstituted C_6-30Aryl, substituted or unsubstituted 5 to 30 membered heteroaryl, and R₁、R₂Are connected with the main structure by single substitution or by forming a fused ring respectively;

wherein m, n is 0, 1, 2 or 3;

the R is₃、R₄Each independently represents a hydrogen atom, a deuterium atom, a methyl group, a tert-butyl group, an adamantyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted dibenzofuranyl group, and R₃、R₄Are connected with the main structure by single substitution or by forming a fused ring respectively;

the R is₅Represented by a hydrogen atom, a deuterium atom, a methyl group, a tert-butyl group, an adamantyl group, a phenyl group, a naphthyl group or a dibenzofuranyl group,

the R is₆-R₉Each independently represents a hydrogen atom, a deuterium atom, a phenyl group, a biphenylyl group, a naphthyl group, a dibenzofuranyl group or a carbazolyl group, and R₆-R₉At least one is not represented as a hydrogen atom or a deuterium atom;

the "substitution" means that at least one hydrogen atom is replaced by the following substituent: deuterium atom, tritium atom, methyl group, t-butyl group, adamantyl group, phenyl group, naphthyl group, biphenylyl group, or dibenzofuranyl group.

2. The aromatic amine derivative of claim 1, wherein R is₁、R₂Each independently represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenylyl group, a substituted or unsubstituted terphenylyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted anthryl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted benzophenanthryl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted benzofuranyl groupOne of furyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted carbazolyl, and R₁、R₂To the main structure by monosubstitution or by formation of a fused ring, respectively.

3. The aromatic amine derivative according to claim 1, wherein the general formula (I) is represented by general formula (I-1) to general formula (I-3):

4. the aromatic amine derivative of claim 1, wherein R is₇Represented by phenyl, naphthyl, biphenylyl or dibenzofuranyl, R₆、R₈、R₉Represented as hydrogen atoms.

5. The aromatic amine derivative of claim 1, wherein R is₈Represented by phenyl, naphthyl, biphenylyl or dibenzofuranyl, R₆、R₇、R₉Represented as hydrogen atoms.

6. The aromatic amine derivative of claim 1, wherein R is₇Represented by phenyl, naphthyl, biphenylyl or dibenzofuranyl, R₆、R₈、R₉Is represented by a hydrogen atom, said R₃、R₄One representing a hydrogen atom and the other representing a phenyl or benzofuranyl group.

7. The aromatic amine derivative according to claim 1, having the specific structure:

8. an organic electroluminescent device, comprising a cathode, an anode and functional layers, wherein the functional layers are positioned between the anode and the cathode, characterized in that at least one functional layer of the organic electroluminescent device contains the arylamine derivative taking carbazole as the core in any one of claims 1 to 7.

9. The organic electroluminescent device according to claim 8, wherein the functional layer comprises an electron blocking layer, and the electron blocking layer comprises the carbazole-based arylamine derivative according to any one of claims 1 to 7.

10. A lighting or display element comprising the organic electroluminescent device according to any one of claims 8 and 9.

Technical Field

The invention relates to the technical field of semiconductors, in particular to an arylamine derivative taking carbazole as a core and application thereof.

Background

The Organic Light Emission Diodes (OLED) device technology can be used for manufacturing novel display products and novel lighting products, is expected to replace the existing liquid crystal display and fluorescent lamp lighting, and has wide application prospect. The OLED light-emitting device is of a sandwich structure and comprises electrode material film layers and organic functional materials clamped between different electrode film layers, and the various different functional materials are mutually overlapped together according to the application to form the OLED light-emitting device. When voltage is applied to two end electrodes of the OLED light-emitting device as a current device, positive and negative charges in the organic layer functional material film layer are acted through an electric field, and the positive and negative charges are further compounded in the light-emitting layer, namely OLED electroluminescence is generated.

At present, the OLED display technology has been applied in the fields of smart phones, tablet computers, and the like, and will further expand to large-size application fields such as televisions, but compared with actual product application requirements, the light emitting efficiency, the service life, and other performances of the OLED device need to be further improved. The research on the improvement of the performance of the OLED light emitting device includes: the driving voltage of the device is reduced, the luminous efficiency of the device is improved, the service life of the device is prolonged, and the like. In order to realize the continuous improvement of the performance of the OLED device, not only the innovation of the structure and the manufacturing process of the OLED device but also the continuous research and innovation of the OLED photoelectric functional material are needed to create the functional material of the OLED with higher performance.

The photoelectric functional materials of the OLED applied to the OLED device can be divided into two broad categories from the application, i.e., charge injection transport materials and light emitting materials, and further, the charge injection transport materials can be further divided into electron injection transport materials, electron blocking materials, hole injection transport materials and hole blocking materials, and the light emitting materials can be further divided into main light emitting materials and doping materials.

In order to fabricate a high-performance OLED light-emitting device, various organic functional materials are required to have good photoelectric properties, for example, as a charge transport material, good carrier mobility, high glass transition temperature, etc. are required, and as a host material of a light-emitting layer, a material having good bipolar property, appropriate HOMO/LUMO energy level, etc. is required.

The OLED photoelectric functional material film layer for forming the OLED device at least comprises more than two layers of structures, and the OLED device structure applied in industry comprises a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and other various film layers, namely the photoelectric functional material applied to the OLED device at least comprises a hole injection material, a hole transport material, a light emitting material, an electron transport material and the like, and the material type and the matching form have the characteristics of richness and diversity. In addition, for the collocation of OLED devices with different structures, the used photoelectric functional materials have stronger selectivity, and the performance of the same materials in the devices with different structures can also be completely different.

Therefore, aiming at the industrial application requirements of the current OLED device, different functional film layers of the OLED device and the photoelectric characteristic requirements of the device, a more suitable OLED functional material or material combination with high performance needs to be selected to realize the comprehensive characteristics of high efficiency, long service life and low voltage of the device. In terms of the actual demand of the current OLED display illumination industry, the development of the current OLED material is far from enough, and lags behind the requirements of panel manufacturing enterprises, and the development of organic functional materials with higher performance is very important as a material enterprise.

Disclosure of Invention

In order to solve the problems in the prior art, the applicant of the present invention provides an arylamine derivative with carbazole as a core and an application thereof. The compound has higher glass transition temperature, higher molecular thermal stability and proper HOMO energy level, and can effectively improve the photoelectric property of an OLED device and the service life of the OLED device through device structure optimization.

The first aspect of the invention provides an arylamine derivative taking carbazole as a core, and the structure of the derivative is shown as a general formula (I):

in the general formula (I), R is₁、R₂Each independently represents substituted or unsubstituted C_6-30Aryl, substituted or unsubstituted 5 to 30 membered heteroaryl, and R₁、R₂Are connected with the main structure by single substitution or by forming a fused ring respectively;

wherein m, n is 0, 1, 2 or 3;

the R is₃、R₄Each independently represents a hydrogen atom, a deuterium atom, a methyl group, a tert-butyl group, an adamantyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted dibenzofuranyl group, and R₃、R₄Are connected with the main structure by single substitution or by forming a fused ring respectively;

the R is₅Represented by a hydrogen atom, a deuterium atom, a methyl group, a tert-butyl group, an adamantyl group, a phenyl group, a naphthyl group or a dibenzofuranyl group,

the R is₆-R₉Each independently represents a hydrogen atom, a deuterium atom, a phenyl group, a biphenylyl group, a naphthyl group, a dibenzofuranyl group or a carbazolyl group, and R₆-R₉At least one is not represented as a hydrogen atom or a deuterium atom;

the "substitution" means that at least one hydrogen atom is replaced by the following substituent: deuterium atom, tritium atom, methyl group, t-butyl group, adamantyl group, phenyl group, naphthyl group, biphenylyl group, or dibenzofuranyl group.

In a preferred embodiment, the R group₁、R₂Each independently represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenylyl group, a substituted or unsubstituted terphenylyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted anthryl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted benzophenanthryl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted benzofuranyl groupOne of furyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted carbazolyl, and R₁、R₂To the main structure by monosubstitution or by formation of a fused ring, respectively.

In a preferred embodiment, the R group₇Represented by phenyl, naphthyl, biphenylyl or biphenylyl, R₆、R₈、R₉Represented as hydrogen atoms.

In a preferred embodiment, the R group₈Represented by phenyl, naphthyl, biphenylyl or biphenylyl, R₆、R₉、R₇Represented as hydrogen atoms.

In a preferred embodiment, the R group₇Represented by phenyl, naphthyl, biphenylyl or biphenylyl, R₆、R₈、R₉Is represented by a hydrogen atom, said R₃、R₄At least one represents a hydrogen atom and the other represents a phenyl group or a benzofuranyl group, and are linked in an acyclic manner.

In a preferred embodiment, the R group₈Represented by phenyl, naphthyl, biphenylyl or biphenylyl, R₆、R₇、R₉Is represented by a hydrogen atom, said R₃、R₄At least one represents a hydrogen atom and the other represents a phenyl group or a benzofuranyl group, and are linked in an acyclic manner.

In a preferred embodiment, the R group₇Represented by phenyl, naphthyl, biphenylyl or biphenylyl, R₆、R₈、R₉Is represented by a hydrogen atom, said R₃、R₄At least one represents a hydrogen atom and the other represents a phenyl group or a biphenylyl group, and are bonded in a substituted manner.

In a preferred embodiment, the R group₈Represented by phenyl, naphthyl, biphenylyl or biphenylyl, R₆、R₇、R₉Is represented by a hydrogen atom, said R₃、R₄At least one represents a hydrogen atom and the other represents a phenyl group or a biphenylyl group, and are bonded in a substituted manner.

In a preferred embodiment, the R group₇Represented by phenyl, naphthyl, biphenylyl or biphenylyl, R₆、R₈、R₉Is represented by a hydrogen atom, said R₁、R₂At least one is substituted or unsubstituted naphthyl, and is connected in a substituted manner.

In a preferred embodiment, the R group₈Represented by phenyl, naphthyl, biphenylyl or biphenylyl, R₆、R₉、R₇Is represented by a hydrogen atom, said R₁、R₂At least one is substituted or unsubstituted naphthyl, and is connected in a substituted manner.

In a preferred embodiment, the R group₇Represented by phenyl, naphthyl, biphenylyl or biphenylyl, R₆、R₈、R₉Is represented by a hydrogen atom, said R₁、R₂At least one is represented by substituted or unsubstituted dibenzofuran and is attached in a substituted manner.

In a preferred embodiment, the R group₈Represented by phenyl, naphthyl, biphenylyl or biphenylyl, R₆、R₉、R₇Is represented by a hydrogen atom, said R₁、R₂At least one is represented by substituted or unsubstituted dibenzofuran and is attached in a substituted manner.

Alternative scheme, the said R₇Represented by phenyl, naphthyl, biphenylyl or biphenylyl, R₆、R₈、R₉Is represented by a hydrogen atom, said R₃、R₄At least one of which represents a hydrogen atom and the other represents a phenyl or benzofuranyl group, said R₁、R₂At least one is substituted or unsubstituted naphthyl, and is connected in a substituted manner.

In a preferred embodiment, the R group₈Represented by phenyl, naphthyl, biphenylyl or biphenylyl, R₆、R₇、R₉Is represented by a hydrogen atom, said R₃、R₄At least one of which represents a hydrogen atom and the other represents a phenyl or benzofuranyl group, said R₁、R₂At least one is substituted or unsubstituted naphthyl, and is connected in a substituted manner.

In a preferred embodiment, the R group₇Represented by phenyl, naphthyl, biphenylOr biphenylyl radical, R₆、R₈、R₉Is represented by a hydrogen atom, said R₁、R₂At least one of which is represented by phenyl or benzofuranyl and is linked in an acyclic manner.

In a preferred embodiment, the R group₈Represented by phenyl, naphthyl, biphenylyl or biphenylyl, R₆、R₉、R₇Is represented by a hydrogen atom, said R₁、R₂At least one is represented by phenyl or benzofuran, and is connected in a ring-by-ring manner.

In a preferred embodiment, the R group₇Represented by phenyl, naphthyl, biphenylyl or biphenylyl, R₆、R₈、R₉Is represented by a hydrogen atom, said R₃、R₄At least one of which represents a hydrogen atom and the other represents a phenyl or benzofuranyl group, said R₁、R₂At least one of which is represented by phenyl or benzofuranyl and is linked in an acyclic manner.

In a preferred embodiment, the R group₈Represented by phenyl, naphthyl, biphenylyl or biphenylyl, R₆、R₇、R₉Is represented by a hydrogen atom, said R₃、R₄At least one of which represents a hydrogen atom and the other represents a phenyl or benzofuranyl group, said R₁、R₂At least one of which is represented by phenyl or benzofuranyl and is linked in an acyclic manner.

In a preferred embodiment, the R group₇Represented by phenyl, naphthyl, biphenylyl or biphenylyl, R₆、R₈、R₉Expressed as a hydrogen atom, the m + n ═ 3.

In a preferred embodiment, the R group₈Represented by phenyl, naphthyl, biphenylyl or biphenylyl, R₆、R₉、R₇Expressed as a hydrogen atom, the m + n ═ 3.

Preferably, the general formula (I) can be represented by a structure represented by general formula (I-1) to general formula (I-3):

in a further preferred scheme, the specific structure of the arylamine derivative is as follows:

the second aspect of the invention is to provide the application of the aromatic amine derivative taking carbazole as the core in preparing organic electroluminescent devices.

In a third aspect of the present invention, there is provided an organic electroluminescent device characterized in that the organic electroluminescent device comprises at least one functional layer containing the aromatic amine derivative having carbazole as a core.

In a fourth aspect of the present invention, there is provided an organic electroluminescent device comprising an electron blocking layer, wherein the electron blocking layer contains the aromatic amine derivative having a carbazole as a core.

In a fifth aspect of the present invention, there is provided an organic electroluminescent device characterized in that the organic electroluminescent device comprises a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, and an electron transport region, the electron blocking layer is adjacent to the light-emitting layer, the hole injection layer comprises a P-doped material and an arylamine organic material, the hole transport layer comprises the same arylamine organic material as the hole injection layer, the electron blocking layer comprises the arylamine derivative having carbazole as a core, and the hole auxiliary layer comprises one or two materials.

A sixth aspect of the present invention provides a full-color display device including, in order from bottom to top, a substrate, a first electrode, an organic functional material layer, and a second electrode, the organic functional material layer including: a hole transport region over the first electrode; a light emitting layer on the hole transport region, the light emitting layer having a red light emitting layer, a green light emitting layer and a blue light emitting layer patterned in a red pixel region, a green pixel region and a blue pixel region, respectively; an electron transport region over the light emitting layer; the hole transport region sequentially comprises a hole injection layer, a hole transport layer and a hole transport auxiliary layer from bottom to top, the hole injection layer comprises a P-type doping material, the red pixel unit, the green pixel unit and the blue pixel unit share the hole injection layer and the hole transport layer and respectively comprise the hole transport auxiliary layer, and the hole transport region comprises the arylamine derivative taking carbazole as the core and shown in the general formula (1).

A seventh aspect of the present invention is to provide a lighting or display element having such features, including the organic electroluminescent device described above.

Compared with the prior art, the invention has the beneficial technical effects that:

in the case of a compound having high symmetry and high planarity and containing a plurality of aryl groups in a molecule, when an OLED device is manufactured, crystallization is likely to occur to block a crucible opening for vapor deposition, or crystallization is likely to occur to cause defects in a thin film, resulting in low device yield, a high sublimation temperature, problems such as vapor deposition decomposition and vapor deposition unevenness, and the like, resulting in a short device life. Compared with the comparative patents CN104628624A, CN102574790A and KR1020160091198A, the compound provided by the invention has relatively poor planarity and poor molecular symmetry, so that the compound provided by the invention is not easy to cause the problem of blocking, has higher glass transition temperature, lower sublimation temperature and more excellent film phase stability, and can effectively solve the problem of poor service life of devices;

the compound has a wider band gap, and can effectively prevent electrons from being transmitted to one side of a hole transmission; the organic electroluminescent device contains the carbazole group, the carbazole group can transmit electrons and holes, the problem of interface charge accumulation under high current density can be effectively solved, exciton quenching is prevented, and the service life of the device is prolonged;

the compound also has a high triplet state energy level, can effectively block exciton diffusion, and improves the exciton recombination efficiency of a light-emitting layer;

the compound structure of the invention effectively reduces the intermolecular interaction force due to poor molecular planarity, so that the molecules have lower evaporation temperature during evaporation and are molten materials, so that the compound of the invention has excellent industrial processing performance;

the compound has high electron tolerance due to the carbazole group, and the EB layer is close to the light-emitting layer, so the material has high electron tolerance, and the material degradation caused by electrons which are not consumed in the light-emitting layer can be inhibited, thereby the OLED device has long service life.

Drawings

FIG. 1 is a schematic structural diagram of an OLED device using the materials listed in the present invention;

wherein, 1 is a transparent substrate layer, 2 is an anode layer, 3 is a hole injection layer, 4 is a hole transport layer, 5 is an electron blocking layer, 6 is a light emitting layer, 7 is an electron transport or hole blocking layer, 8 is an electron injection layer, 9 is a cathode layer, and 10 is a CPL layer.

Detailed Description

Example 1: synthesis of intermediate B1:

adding 0.01mol of raw material 1-1, 0.012mol of raw material 2-1, 150ml of toluene into a 250ml three-neck flask under the protection of nitrogen, stirring and mixing, and then adding 5X 10^-5molPd₂(dba)₃，5×10^-5molP(t-Bu)₃Heating 0.03mol of sodium tert-butoxide to 105 ℃, carrying out reflux reaction for 24 hours, and sampling a sample point plate to complete the reaction; naturally cooling to room temperature, filtering, carrying out rotary evaporation on the filtrate until no fraction is obtained, and passing through a neutral silica gel column to obtain a target product intermediate B1; HPLC purity 98.55%, yield 79.36%; elemental analysis Structure (molecular formula C)₂₄H₁₉N): theoretical value C, 89.68; h, 5.96; n, 4.36; test values are: c, 89.65; h, 5.97; and N, 4.38. ESI-MS (M/z) (M +): theoretical value is 321.15, found 321.21.

The intermediates B required in the examples are synthesized as shown in table 1:

TABLE 1

Example 2: synthesis of intermediate C1:

adding 0.01mol of 3-1 of raw material, 0.012mol of 4-1 of raw material and 150ml of toluene into a 250ml three-neck flask under the protection of nitrogen, stirring and mixing, and then adding 5 multiplied by 10^-5molPd₂(dba)₃，5×10^-5molP(t-Bu)₃Heating 0.03mol of sodium tert-butoxide to 105 ℃, carrying out reflux reaction for 24 hours, and sampling a sample point plate to complete the reaction; naturally cooling to room temperature, filtering, carrying out rotary evaporation on the filtrate until no fraction is obtained, and passing through a neutral silica gel column to obtain a target product intermediate C-1; HPLC purity 99.09%, yield 80.2%; elemental analysis Structure (molecular formula C)₃₀H₂₀BrN): theoretical value C, 75.95; h, 4.25; br, 16.84; n, 2.95; test values are: c, 75.91; h, 4.28; br, 16.83; and N, 2.97. ESI-MS (M/z) (M +): theoretical value is 473.08, found 473.35.

The intermediates C required in the examples are synthesized as shown in table 2:

TABLE 2

Example 3: synthesis of compound 14:

introducing nitrogen into a 250ml three-mouth bottleAdding 0.01mol of intermediate B1, 0.012mol of intermediate C1 and 150ml of toluene, stirring and mixing, and then adding 5X 10^-5molPd₂(dba)₃，5×10^-5molP(t-Bu)₃Heating 0.03mol of sodium tert-butoxide to 105 ℃, carrying out reflux reaction for 24 hours, and sampling a sample point plate to complete the reaction; naturally cooling to room temperature, filtering, rotatably evaporating the filtrate until no fraction is obtained, and passing through a neutral silica gel column to obtain the target product with the HPLC purity of 99.34% and the yield of 75.6%. Elemental analysis Structure (molecular formula C)₅₄H₃₈N₂): theoretical value C, 90.72; h, 5.36; n, 3.92; test value C, 90.71; h, 5.35; and N, 3.94. ESI-MS (M/z) (M +): calculated 714.30, found 714.39.¹HNMR(500MHz,Chloroform-d)δ8.16–8.09(m,2H),7.78(t,J＝1.5Hz,1H),7.65–7.50(m,11H),7.52–7.24(m,21H),7.19–7.12(m,3H).

The preparation of examples 4-22 was similar to that of example 3, and the specific structures of intermediate B, intermediate C and the product used in this example, as well as the structural characterization of the final product, are shown in tables 3a and 3B.

TABLE 3a

TABLE 3b

The compound of the invention is used in a light-emitting device and can be used as an electron blocking layer material. The compounds prepared in the above examples of the present invention were tested for thermal performance, T1 energy level, HOMO energy level and hole mobility, respectively, and the test results are shown in table 4:

TABLE 4

Note: the triplet energy level T1 was measured by Fluorolog-3 series fluorescence spectrometer from Horiba under the conditions of 2 x 10^-5A toluene solution of mol/L; the glass transition temperature Tg is determined by differential scanning calorimetry (DSC, DSC204F1 DSC, Germany Chi corporation), the heating rate is 10 ℃/min; the thermogravimetric temperature Td is a temperature at which 1% of the weight loss is observed in a nitrogen atmosphere, and is measured on a TGA-50H thermogravimetric analyzer of Shimadzu corporation, Japan, and the nitrogen flow rate is 20 mL/min; the highest occupied molecular orbital HOMO energy level is tested by an ionization energy testing system (IPS-3), and the test is a nitrogen environment; eg is tested by a double-beam ultraviolet-visible spectrophotometer (model: TU-1901); and (3) testing hole mobility, namely preparing the material into a single-charge device and measuring by using an SCLC (liquid crystal display cell) method.

The data in the table show that the organic compound has a proper HOMO energy level and can be applied to an electron blocking layer, and the organic compound has high hole mobility and high thermal stability, so that the efficiency and the service life of the OLED device containing the organic compound are improved.

The application effect of the synthesized OLED material of the present invention in the device is detailed by device examples 1-27, device comparative example 2 and device comparative example 1. Compared with the device comparative example 1, the device manufacturing processes of the device examples 1 to 27 and the device comparative example 2 are completely the same, the same substrate material and the same electrode material are adopted, the film thickness of the electrode material is also kept consistent, and the difference is that the material of the electron barrier layer in the device is replaced.

Device comparative example 1

The preparation process comprises the following steps:

as shown in fig. 1, the anode layer 2(ITO (15nm)/Ag (150nm)/ITO (15nm)) is washed, that is, washed with alkali, washed with pure water, dried, and then washed with ultraviolet rays and ozone to remove organic residues on the surface of the anode layer 1. HT-1 and P-1 having a film thickness of 10nm were deposited on the anode layer 2 after the above washing as the hole injection layer 3 by a vacuum deposition apparatus, and the mass ratio of HT-1 to P-1 was 97: 3. HT-1 was then evaporated to a thickness of 120nm as the hole transport layer 4. EB-1 was then evaporated to a thickness of 10nm as an electron blocking layer 5. After the evaporation of the electron blocking material is finished, the light emitting layer 6 of the OLED light emitting device is manufactured, and the structure of the OLED light emitting device comprises that BH-1 used by the OLED light emitting layer 6 is used as a main material, BD-1 is used as a doping material, the doping proportion of the doping material is 3% by weight, and the thickness of the light emitting layer is 20 nm. After the light-emitting layer 6, ET-1 and Liq are continuously evaporated, wherein the mass ratio of ET-1 to Liq is 1: 1. The vacuum evaporation film thickness of the material was 30nm, and this layer was a hole-blocking/electron-transporting layer 7. On the hole-blocking/electron-transporting layer 7, a LiF layer having a film thickness of 1nm was formed by a vacuum evaporation apparatus, and this layer was an electron-injecting layer 8. On the electron injection layer 8, a vacuum deposition apparatus was used to produce a 16 nm-thick Mg: the Ag electrode layer has a Mg/Ag mass ratio of 1:9, and is used as the cathode layer 9. On the cathode layer 9, 70nm of CP-1 was vacuum-deposited as a CPL layer 10.

The molecular structural formula of the related material is shown as follows:

after the OLED light emitting device was completed as described above, the anode and cathode were connected by a known driving circuit, and the current efficiency, the light emission spectrum, and the lifetime of the device were measured. Specific structures of device examples 1 to 27 and device comparative example 2 prepared in the same manner are shown in table 5; the results of the current efficiency, voltage and lifetime tests of the resulting devices are shown in table 6.

TABLE 5

TABLE 6

Note: voltage, current efficiency and color coordinates were measured using an IVL (Current-Voltage-Brightness) test System (Fushda scientific instruments, Suzhou) at a current density of 10mA/cm²(ii) a The life test system is an EAS-62C type OLED device life tester of Japan System research company; LT95 refers to the time it takes for the device luminance to decay to 95% at a particular luminance (blue: 1000 nits).

It can be seen from the device data results that the organic light emitting device of the present invention achieves a greater improvement in both efficiency and lifetime compared to the device comparative example over the OLED device of known materials.