CN114591257B - Spiro compound, electron transport material and light-emitting device - Google Patents

Spiro compound, electron transport material and light-emitting device Download PDF

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CN114591257B
CN114591257B CN202210323740.3A CN202210323740A CN114591257B CN 114591257 B CN114591257 B CN 114591257B CN 202210323740 A CN202210323740 A CN 202210323740A CN 114591257 B CN114591257 B CN 114591257B
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electron transport
compound
light
layer
transport material
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CN114591257A (en
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高荣荣
黎俊聪
张东旭
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BOE Technology Group Co Ltd
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Abstract

The embodiment of the application provides a spiro compound, an electron transport material and a light-emitting device, wherein the structural general formula of the spiro compound is shown as the following general formula (I), and R1-R8 in the general formula (I) respectively and independently comprise a substituted or unsubstituted group; ar1 and Ar2 contain at least one electron withdrawing group and cannot be hydrogen at the same time; the a and B rings each independently comprise a substituted or unsubstituted monocyclic or polycyclic aromatic ring, or comprise a substituted or unsubstituted phenyl, naphthyl, phenanthrene, fluoranthene, fluorene, thiophene, or furanyl group; n is 0 or 1; when N is 1, X is one of a direct bond, O, S, C and N, wherein when X is a direct bond, both the a ring and the B ring cannot be unsubstituted phenyl groups, and the spiro compound has an orthogonal spatial stereo configuration, which can reduce intermolecular van der waals force, facilitate the prevention of crystallization of an electron transport material, and has a rigid structure, which can improve the light emitting efficiency of a light emitting device.

Description

Spiro compound, electron transport material and light-emitting device
Technical Field
The application relates to the technical field of luminescent materials, in particular to a spiro compound, an electron transport material and a luminescent device.
Background
With the progress of information industry, organic light-emitting diodes (OLEDs) in light-emitting devices have advantages of full solid state, self-luminescence, high brightness, high resolution, wide viewing angle, fast response speed, thin thickness, small volume, light weight, capability of using flexible substrates, low voltage direct current driving, low power consumption, wide operating temperature range, and the like, and can be applied to lighting systems, communication systems, vehicle-mounted displays, portable electronic devices, high-definition displays, military fields, and the like.
However, the electron transport material in the current light emitting device is easy to crystallize and has insufficient rigidity, which reduces the display performance and luminous efficiency of the light emitting device.
Disclosure of Invention
Aiming at the defects of the prior art, the application provides a spiro compound, an electron transport material and a light-emitting device, which are used for solving the technical problems that the electron transport material in the prior light-emitting device is easy to crystallize and insufficient in rigidity, and the display performance and the light-emitting efficiency of the light-emitting device are reduced.
In a first aspect, an embodiment of the present application provides a spiro compound, where the structural general formula of the spiro compound is shown in the following general formula (i):
In the general formula (I), R1 to R8 each independently comprise a substituted or unsubstituted design group; ar1 and Ar2 contain at least one electron withdrawing group and cannot be hydrogen at the same time; the a and B rings each independently comprise a substituted or unsubstituted monocyclic or polycyclic aromatic ring, or comprise a substituted or unsubstituted phenyl, naphthyl, phenanthrene, fluoranthene, fluorene, thiophene, or furanyl group; n is 0 or 1; in the case where N is 1, X is one of a direct bond, O, S, C, and N, where when X is a direct bond, both the A and B rings cannot be unsubstituted phenyl groups.
Alternatively, when n in the general formula (I) is 0, the structural general formula is shown as the following general formula (II):
Alternatively, when X in the general formula (I) is a direct bond, the structural formula is shown as the following general formula (III):
Alternatively, when N in the general formula (I) is 1, X is one of O, S, C and N, the structural general formula is shown in the following general formula (IV):
optionally, the spiro compound includes at least one of:
the electron withdrawing group is independently one of pyridyl, pyrimidyl, triazinyl, phosphinoxyl, nitrile, nitro, oxazolyl, quinoxalinyl, thiazolyl, quinolinyl, imidazole, phenylpyrimidine, oxaborole, sulfonyl and derivatives thereof;
Each of Ar1 and Ar2 is independently one of: hydrogen, deuterium, nitrile, nitro, hydroxyl, carbonyl, ester, imide, amide, alkyl, cycloalkyl, alkoxy, aryloxy, alkylthio, arylthio, alkylsulfonyl, arylsulfonyl, alkenyl, silyl, boron, amine, arylphosphino, phosphine oxide, aryl, heteroaryl, or adjacent groups are bonded to each other to form a ring.
Optionally, the design groups of R1 to R8 are each independently one of the following: hydrogen, deuterium, cyano, halogen, nitro, hydroxy, carbonyl, ester, imide, amide, alkyl, cycloalkyl, alkoxy, aryloxy, alkylthio, arylthio, alkylsulfonyl, arylsulfonyl, alkenyl, silyl, boron, amino, phosphine oxide, aryl, heteroaryl, pyridyl, pyrimidinyl, triazinyl, phosphino, nitrile, nitro, oxazolyl, quinoxalinyl, thiazolyl, quinolinyl, imidazole, phenylpyrimidine, boron heterocyclyl, sulfone, and derivatives thereof.
Optionally, each of the a-ring and the B-ring is independently one of the following structural formulas:
in a second aspect, embodiments of the present application provide an electron transport material comprising the spiro compound described above.
In a third aspect, an embodiment of the present application provides a light emitting device, including a first electrode, a light emitting functional layer, and a second electrode that are sequentially stacked, where the light emitting functional layer includes an electron transport layer, and the electron transport layer includes the above-described electron transport material.
Optionally, the light-emitting functional layer further includes a hole blocking layer disposed on a side of the electron transport layer near the first electrode, and the hole blocking layer includes the electron transport material described above.
The technical scheme provided by the embodiment of the application has the beneficial technical effects that:
The application provides a spiro compound, which has an orthogonal space three-dimensional configuration, can reduce the Van der Waals force between molecules, is beneficial to preventing the crystallization of an electron transport material containing the spiro compound, and can further improve the display performance of a light-emitting device containing the electron transport material; the spiro compound has a rigid structure, so that an electron transport material containing the spiro compound has higher glass transition temperature, which is beneficial to improving the stability of the electron transport material, thereby improving the luminous efficiency of the luminous device and prolonging the service life of the luminous device; the electron withdrawing group is introduced into the spiro compound, so that effective separation of HOMO and LUMO can be realized, matching of adjacent functional layers can be adjusted, carrier transmission is smoother, and driving voltage of the light-emitting device is reduced.
Additional aspects and advantages of the application will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the application.
Drawings
The foregoing and/or additional aspects and advantages of the application will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings, in which:
Fig. 1 is a schematic diagram of a cross-sectional film structure of a light emitting device according to an embodiment of the present application.
Reference numerals illustrate:
1-a first electrode;
2-a light-emitting functional layer; 21-a hole injection layer; a 22-hole transport layer; 23-an electron blocking layer; 24-a light emitting layer; 25-hole blocking layer; 26-an electron transport layer; 27-electron injection layer.
3-A substrate;
4-a second electrode;
100-light emitting device.
Detailed Description
Embodiments of the present application are described below with reference to the drawings in the present application. It should be understood that the embodiments described below with reference to the drawings are exemplary descriptions for explaining the technical solutions of the embodiments of the present application, and the technical solutions of the embodiments of the present application are not limited.
As used herein, the singular forms "a", "an", "the" and "the" are intended to include the plural forms as well, unless expressly stated otherwise, as understood by those skilled in the art. It should be further understood that the terms "comprises" and/or "comprising," when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of other features, information, data, steps, operations, elements, components, and/or groups thereof, all of which may be included in the present application. The term "and/or" as used herein refers to at least one of the items defined by the term, e.g., "a and/or B" may be implemented as "a", or as "B", or as "a and B".
In the description of the present specification, the terms "one embodiment," "some embodiments," "example embodiments," "examples," "particular examples," or "some examples," etc., are intended to indicate that a particular feature, structure, material, or characteristic associated with the embodiment or example is included in at least one embodiment or example of the present disclosure. The schematic representations of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics may be combined in any suitable manner in any one or more embodiments or examples.
For the purpose of making the objects, technical solutions and advantages of the present application more apparent, the embodiments of the present application will be described in further detail with reference to the accompanying drawings.
The development idea of the application comprises the following steps: in general, hole mobility is higher than electron mobility in a light emitting device, and an electron transport material plays an important role in order to achieve charge balance transport and efficient recombination of carriers, preventing accumulation of a single carrier. At present, electron transport materials are easy to crystallize and have insufficient rigidity, so that the display performance and luminous efficiency of the light-emitting device are reduced.
The following describes the technical scheme of the present application and how the technical scheme of the present application solves the above technical problems in detail with specific embodiments. It should be noted that the following embodiments may be referred to, or combined with each other, and the description will not be repeated for the same terms, similar features, similar implementation steps, and the like in different embodiments.
The embodiment of the application provides a spiro compound, which has a structural formula shown in a general formula (I):
In the general formula (I), R1 to R8 each independently include a substituted or unsubstituted design group; ar1 and Ar2 contain at least one electron withdrawing group and cannot be hydrogen at the same time; the a and B rings each independently comprise a substituted or unsubstituted monocyclic or polycyclic aromatic ring, or comprise a substituted or unsubstituted phenyl, naphthyl, phenanthrene, fluoranthene, fluorene, thiophene, or furanyl group; n is 0 or 1; in the case where N is 1, X is one of a direct bond, O, S, C, and N, where when X is a direct bond, both the A and B rings cannot be unsubstituted phenyl groups.
The ring a and the ring B each independently include a substituted or unsubstituted monocyclic or polycyclic aromatic ring, meaning that the ring a and the ring B each independently include a substituted monocyclic aromatic ring, an unsubstituted monocyclic aromatic ring, a substituted polycyclic aromatic ring, or an unsubstituted polycyclic aromatic ring; polycyclic means at least two rings.
In this embodiment, the spiro compound has an orthogonal spatial three-dimensional configuration, which can reduce the van der waals force between molecules, and is favorable for preventing the crystallization of the electron transport material containing the spiro compound, so as to improve the display performance of the light emitting device; the spiro compound has a higher triplet state energy level, and the electron transport material containing the spiro compound has a higher triplet state energy level, so that excitons generated in the light-emitting layer can be prevented from diffusing to the electron transport layer, and the light-emitting efficiency of the light-emitting device is improved.
And, utilizing SP3 hybridization of central C atom in the spiro compound, can break the conjugation of the molecule, make HOMO (highest occupied molecular orbital, highest occupied orbit of electron in the molecule) and LUMO (lowest unoccupied molecular orbital, lowest unoccupied orbit of electron in the molecule) energy level separate upper and lower two parts, help the regulation and control of the energy level of electron transport material and help prevent the triplet level from decreasing; the spiro compound has a rigid structure, so that an electron transport material containing the spiro compound has higher glass transition temperature, the stability of the electron transport material is improved, and the luminous efficiency and the service life of a luminous device are further improved; meanwhile, the spiro compound adopts an asymmetric spiro structure, so that the symmetry of molecules can be reduced, and the film forming property of the molecules can be improved.
Alternatively, the electron withdrawing group is independently a pyridyl, pyrimidinyl, triazinyl, phosphinoxy, nitrile, nitro, oxazolyl, quinoxalinyl, thiazolyl, quinolinyl, imidazole, phenylpyrimidine, oxaborole, sulfone group, and derivatives thereof, wherein the derivatives refer to one of pyridyl, pyrimidinyl, triazinyl, phosphinoxy, nitrile, nitro, oxazolyl, quinoxalinyl, thiazolyl, quinolinyl, imidazole, phenylpyrimidine, oxaborole, and sulfone group.
In this embodiment, an electron-withdrawing group is introduced into the spiro compound, and the electron-withdrawing group is connected with the electron group, so that effective separation of HOMO and LUMO can be achieved, and adjustment of energy level of the light-emitting layer to match with an adjacent functional layer is facilitated, so that carrier transmission is smoother.
Alternatively, the introduction of specific electron withdrawing groups, such as phosphino, cyano, imidazolyl, into the spiro compound may improve the injectability of the electron transport material, thereby reducing the driving voltage of the light emitting device.
Alternatively, ar1 and Ar2 are each independently one of the following: hydrogen, deuterium, nitrile, nitro, hydroxyl, carbonyl, ester, imide, amide, alkyl, cycloalkyl, alkoxy, aryloxy, alkylthio, arylthio, alkylsulfonyl, arylsulfonyl, alkenyl, silyl, boron, amine, arylphosphino, phosphine oxide, aryl, heteroaryl, or adjacent groups are bonded to each other to form a ring, wherein adjacent groups refer to any two adjacent groups in the structure of the compound.
Alternatively, the design groups of R1-R8 are each independently one of the following: hydrogen, deuterium, cyano, halogen, nitro, hydroxy, carbonyl, ester, imide, amide, alkyl, cycloalkyl, alkoxy, aryloxy, alkylthio, arylthio, alkylsulfonyl, arylsulfonyl, alkenyl, silyl, boron, amino, phosphine oxide, aryl, heteroaryl, pyridyl, pyrimidinyl, triazinyl, phosphino, nitrile, nitro, oxazolyl, quinoxalinyl, thiazolyl, quinolinyl, imidazole, phenylpyrimidine, boron heterocyclyl, sulfone, and derivatives thereof.
Alternatively, each of the a and B rings is independently one of the following structural formulas:
The A, B ring is not limited to the above structure, and a specific suitable structure may be selected according to practical situations.
Alternatively, when n in the general formula (I) is 0, the structural general formula is shown as the following general formula (II):
in this embodiment, the compound having the general formula (ii) may include the following compounds 1 to 3:
the structure of the compound of the general formula (ii) is not limited to the above structure.
Alternatively, when X in the general formula (I) is a direct bond, the structural general formula is shown as the following general formula (III):
In this embodiment, the compound having the general formula (iii) may include the following compounds 4 to 60:
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The structure of the compound of the general formula (iii) is not limited to the above structure.
Alternatively, when N in the general formula (I) is 1, X is one of O, S, C and N, the structural general formula is shown as the following general formula (IV):
in this embodiment, the compounds having the general formula (iv) may include the following compounds 61 to 87:
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The structure of the compound of the general formula (iv) is not limited to the above structure.
Specific methods for preparing the spiro compounds of the present application will be described below by way of example only, but the methods of preparing the present application are not limited to these examples.
The various chemicals used in the application, such as 4-bromophenanthrene, tetrahydrofuran, butyllithium, acetic acid, sulfuric acid, dioxane, potassium acetate, aqueous solution of potassium carbonate, anhydrous magnesium sulfate and other basic chemical raw materials, can be purchased in the domestic chemical product market.
Synthesis example 1
Synthesis of compound E1:
Step 1: the synthetic intermediate 1 is specifically as follows:
In a three-necked flask, 70 millimoles (mmol) of compound 1a (4-bromophenanthrene) are dissolved in 200mL of Tetrahydrofuran (THF), and the temperature is reduced to-78 ℃; slowly dropwise adding 64mmol of butyl lithium (n-BuLi) at the temperature of not more than-75 ℃, and raising the temperature to room temperature after the dropwise adding of the butyl lithium to react for 1h; 200mL of THF solution containing 60mmol of compound 1b was added to the reaction flask, and the mixture was refluxed for 3 hours; after completion of the reaction, TLC (THIN LAYER Chromatography) was used for extraction with ethyl acetate; after completion of extraction, concentration was performed to obtain compound 1c.
The 50mmol of compound 1c is added into 200mL of acetic acid, stirred at 80 ℃ and dropped into sulfuric acid for 1 to 2 drops; after refluxing for 3 hours, the temperature is reduced to normal temperature, after the reaction is finished, dichloromethane is used for extraction, and the compound 1d is obtained after separation.
After the above 38mmo of compound 1d and 40.5mmo of compound 1e were completely dissolved in 170mL of Dioxane (Dioxane), 110.5mmo of potassium acetate was added thereto and stirred under heating, the temperature was lowered to room temperature, after the reaction was completed, the potassium carbonate solution was removed, and the potassium acetate was removed by filtration; solidifying the filtrate with ethanol and filtering; the white solids were washed with ethanol 2 times, respectively, to give intermediate 1 in 82% yield.
Step 2: the compound E1 is synthesized as follows:
after 15mmol of intermediate 1 and 13mmol of compound A1 were completely dissolved in 300ml of tetrahydrofuran in a 500ml round bottom flask under nitrogen atmosphere, 100ml of a 2M aqueous potassium carbonate solution was added; after adding 0.39mmol of tetrakis (triphenylphosphine) palladium (Pd (PPh 3) 4), the mixture was heated and stirred for 4 hours; cooling to room temperature, removing water layer, drying with anhydrous magnesium sulfate, and concentrating under reduced pressure; recrystallisation from 250ml of ethyl acetate gave compound E1 in 76% yield.
Synthesis example 2
Synthesis of compound E2:
step 1: the synthetic intermediate 2 is specifically as follows:
The synthesis procedure was the same as that of intermediate 1 except that compound 1b was changed to compound 2b, and the other reagents were unchanged, to give intermediate 2 in a yield of 72.3%.
Step 2: the compound E1 is synthesized as follows:
after 18.9mmol of intermediate 2 and 16.47mmol of compound B1 were completely dissolved in 150ml of tetrahydrofuran in a 500ml round bottom flask under nitrogen atmosphere, 100ml of a 2M aqueous potassium carbonate solution was added; 0.48mmol of tetrakis (triphenylphosphine) palladium was added and stirred with heating for 4 hours; the temperature was lowered to room temperature, the aqueous layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized from 250ml of ethyl acetate to give compound E2 in 75.8% yield.
Synthesis example 3
Synthesis of compound E3:
Step 1: the synthetic intermediate 3 is specifically as follows:
the synthesis procedure was the same as that of intermediate 1 except that compound 1b was changed to 3b, the other reagents were unchanged, to give intermediate 3 in 79.5% yield.
Step 2: the compound E3 is synthesized as follows:
After 18.9mmol of intermediate 3 and 16.47mmol of compound C1 were completely dissolved in 150ml of tetrahydrofuran in a 500ml round bottom flask under nitrogen atmosphere, 100ml of 2M aqueous potassium carbonate solution was added, and after 0.48mmol of tetrakis (triphenylphosphine) palladium was added, the mixture was heated and stirred for 4 hours; the temperature was lowered to room temperature, the aqueous layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized from 250ml of ethyl acetate to give compound E2 in 75.8% yield.
Synthesis example 4
Synthesis of compound E4:
step 1: the synthetic intermediate 4 is specifically as follows:
the synthesis procedure was the same as that of intermediate 1 except that compound 1b was changed to 4b, the other reagents were unchanged, to give intermediate 4 in 83.6% yield.
Step 2: the compound E4 is synthesized as follows:
After 16.7mmol of intermediate 4 and 13.26mmol of compound D1 were completely dissolved in 150ml of tetrahydrofuran in a 500ml round bottom flask under nitrogen atmosphere, 100ml of 2M aqueous potassium carbonate solution was added, and after 0.41mmol of tetrakis (triphenylphosphine) palladium was added, the mixture was heated and stirred for 4 hours; the temperature was lowered to room temperature, the aqueous layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized from 250ml of ethyl acetate to give compound E4 in a yield of 81.3%.
As shown in the following Table 1, the spatial configuration of the spiro compounds of the general formula (II), the general formula (III) and the general formula (IV) was simulated by using molecular simulation software, and the specific examples are as follows:
TABLE 1
As can be seen from Table 1, the spiro compound of the present application belongs to an orthogonal spatial three-dimensional configuration, and the electron transport material containing the spiro compound is utilized to make molecules have a better spatial three-dimensional structure, reduce the van der Waals force between molecules, effectively prevent crystallization of the electron transport material, and improve the luminescence performance of the light emitting device.
As shown in table 2 below, the distribution of electron clouds of spiro compounds of general formula (ii), general formula (iii) and general formula (iv) was simulated using molecular simulation software, specifically as follows:
TABLE 2
As can be seen from Table 2, SP3 hybridization of the central C atom in the spiro compound can break the conjugation of molecules, so that the HOMO and LUMO energy levels are distributed in an upper part and a lower part, the regulation and control of the energy level of an electron transport material and the prevention of the reduction of the triplet level are facilitated, the matching with an adjacent functional layer can be realized, and meanwhile, the spiro compound adopts an asymmetric spiro structure, the symmetry of the molecules can be reduced, and the film forming property of the molecules is facilitated to be improved.
As shown in the following Table 3, the glass transition temperatures (Tg) of the spiro compounds of the general formula (II), the general formula (III) and the general formula (IV) were measured by using a DSC differential scanning calorimeter in which the measuring instrument was nitrogen gas and the temperature rise rate was 10 ℃/min and the temperature range was 50 to 380 ℃, and the examples were as follows:
TABLE 3 Table 3
As can be seen from Table 3, the spiro compound of the application has a rigid three-dimensional structure, and the electron transport material containing the spiro compound has a higher glass transition temperature, which is beneficial to improving the thermodynamic stability of the electron transport material; when the vapor plating process is carried out, the electron transport material is not cracked and changed, has better molding property and prolongs the service life of the electron transport material. The use of electron transport materials with high glass transition temperatures in light emitting devices can significantly improve the performance of the device.
Based on the same inventive concept, the embodiment of the present application provides an electron transport material including the spiro compound provided in the above embodiment.
In this embodiment, if the electron transport material includes the spiro compound, the beneficial effects of the electron transport material include the beneficial effects of the spiro compound, and are not described herein.
Based on the same inventive concept, an embodiment of the present application provides a light emitting device 100, as shown in fig. 1, including a first electrode 1, a light emitting functional layer 2, and a second electrode 4, which are sequentially stacked, the light emitting functional layer 2 including an electron transporting layer 26, the electron transporting layer 26 including the electron transporting material provided in the above embodiment.
In this embodiment, the first electrode 1 is an anode, and may be transparent oxide ITO, IZO, or may be a composite electrode formed of ITO/Ag/ITO, ag/IZO, CNT/ITO, CNT/IZO, GO/ITO, GO/IZO, or the like; the second electrode 4 is a cathode. The electron transport material in the light emitting device 100 is introduced into the spiro compound, so that the electron transport material has a higher triplet state energy level, and excitons generated in the light emitting layer 24 can be prevented from diffusing to the electron transport layer 26, thereby improving the light emitting efficiency of the light emitting device 100; the introduction of the electron transport material into the spiro compound can improve the injectability of the electron transport material, thereby reducing the driving voltage of the light emitting device 100; the electron transport material has a high glass transition temperature, which is beneficial to improving the stability of the electron transport material, thereby improving the luminous efficiency of the light emitting device 100 and prolonging the service life of the light emitting device 100.
Optionally, the light emitting functional layer 2 further includes a hole blocking layer 25 disposed on a side of the electron transport layer 26 adjacent to the first electrode 1, the hole blocking layer 25 including the electron transport material provided in the above embodiment.
Optionally, the light emitting device 100 further comprises a substrate 3 arranged on the side of the first electrode 1 remote from the second electrode 4, the substrate 3 may be a transparent rigid or flexible substrate 3 material, such as glass, polyimide, etc.
Optionally, the light-emitting functional layer 2 further includes a hole injection layer 21, a hole transport layer 22, an electron blocking layer 23, and a light-emitting layer 24, which are sequentially stacked and disposed on one side of the first electrode 1 near the hole blocking layer 25; the light-emitting functional layer 2 further includes an electron injection layer 27 provided on a side of the electron transport layer 26 remote from the hole blocking layer 25.
In this embodiment, the hole injection layer 21 may be an inorganic oxide, such as molybdenum oxide, titanium oxide, vanadium oxide, rhenium oxide, ruthenium oxide, chromium oxide, zirconium oxide, hafnium oxide, tantalum oxide, silver oxide, tungsten oxide, manganese oxide, or the like, or may be a dopant of a strong electron-withdrawing system, such as F4TCNQ, HATCN, or the like, or may be P-doped in a hole transport material, and the thickness of the hole injection layer 21 may be 5nm (nanometers) to 30nm (nanometers). The hole transport layer 22 is made of aromatic amine or carbazole material, such as NPB, TPD, BAFLP, DFLDPBi, and the thickness of the hole transport layer 22 may be 100nm to 2000nm. The electron blocking layer 23, i.e., the light emitting auxiliary layer, has hole transporting characteristics, and may be a red light emitting auxiliary layer, a green light emitting auxiliary layer, or a blue light emitting auxiliary layer, and the material of the light emitting auxiliary layer may be an arylamine or carbazole material, such as CBP, PCzPA, etc., and the thickness of the electron blocking layer 23 may be 5nm to 100nm.
The light emitting layer 24 may be a phosphorescent host and a red phosphorescent dopant, a phosphorescent host and a green phosphorescent dopant, or a fluorescent host and a fluorescent dopant, and the host material of the light emitting layer 24 may comprise one material or may comprise a mixture of two or more materials, wherein the host material of the blue light emitting layer 24 may be selected from anthracene derivatives ADN, MADN, etc., and the guest material may be pyrene derivatives, fluorene derivatives, perylene derivatives, styrylamine derivatives, metal complexes, etc., such as TBPe, BDAVBi, DPAVBi, FIrpic, etc.; the host material of the green light emitting layer 24 may be selected from coumarin dyes, quinacridone derivatives, polycyclic aromatic hydrocarbons, diamine anthracene derivatives, carbazole derivatives, such as DMQA, BA-NPB, alq3, etc., and the guest material may be a metal complex, such as Ir (ppy) 3, ir (ppy) 2 (acac), etc.; the red light-emitting host material may be selected from DCM materials such as DCM, DCJTB, DCJTI, etc., the guest material may be a metal complex such as Ir (piq) 2 (acac), ptOEP, ir (btp) 2 (acac), etc., and the thickness of the light-emitting layer 24 may be 20 nm-100 nm.
The thickness of the hole blocking layer 25 may be 5nm to 100nm, the thickness of the electron transport layer 26 may be 20nm to 100nm, and the hole blocking layer 25 and the electron transport layer 26 independently include aromatic heterocyclic compounds such as imidazole derivatives, for example, benzimidazole derivatives, imidazopyridine derivatives, imidazophenanthridine derivatives, and other imidazole derivatives, pyrimidine derivatives, triazine derivatives, and other oxazine derivatives, quinoline derivatives, isoquinoline derivatives, phenanthroline derivatives, and other compounds having a nitrogen-containing six-membered ring structure, and may include compounds having a phosphine oxide substituent on the heterocycle, for example: OXD-7, TAZ, p-EtTAZ), BPhen, BCP, the electron transport material of the present application, and the like. The thickness of the electron injection layer 27 may be 1nm to 10nm, and the material of the electron injection layer 27 includes alkali metal or metal, for example LiF, yb, mg, ca or a compound thereof, and the like.
Taking fig. 1 as an embodiment, the structure of the light emitting device 100 is as follows: substrate 3 (glass plate)/first electrode 1 (ITO)/hole injection layer 21 (10 nm)/hole transport layer 22 (100 nm)/electron blocking layer 23 (35 nm)/light emitting layer 24 (20 nm)/hole blocking layer 25 (5 nm)/electron transport layer 26 (30 nm)/electron injection layer 27 (1 nm)/second electrode 4 (100 nm).
The following specifically describes the manufacturing process of the light emitting device 100 in fig. 1:
The substrate 3 (glass plate) provided with the first electrode 1 (ITO) was sonicated in a cleaning agent, rinsed in deionized water, sonicated in an acetone-ethanol mixed solvent to remove oil, and baked in a clean environment to completely remove water.
The glass plate provided with the ITO is placed in a vacuum cavity, the vacuum is pumped to 1 multiplied by 10 -5～1×10-6, and a hole injection material is evaporated in vacuum on one side of the ITO far away from the glass plate, so that a hole injection layer 21 is formed.
A hole transport layer 22 is formed by vapor deposition of a hole transport material on the side of the hole injection layer 21 remote from the ITO.
An electron blocking material is vacuum-evaporated on the side of the hole transport layer 22 remote from the hole injection layer 21 to form an electron blocking layer 23.
The light-emitting layer 24 is formed by vacuum evaporation of a light-emitting material on the side of the electron blocking layer 23 far from the hole transport layer 22, the light-emitting material comprises a host material and a guest material, and the weight ratio of the host material to the guest material is 97 by using a multi-source co-evaporation method: 3.
A hole blocking material is vacuum vapor deposited on the side of the light emitting layer 24 remote from the electron blocking layer 23 to form a hole blocking layer 25.
An electron transport layer 26 is formed by vacuum evaporation of an electron transport material on the side of the hole blocking layer 25 remote from the light emitting layer 24.
An inorganic material (LiF) having a thickness of 1nm was vacuum-deposited as an electron injection material on the side of the electron transport layer 26 remote from the hole blocking layer 25 to form an electron injection layer 27.
An Al layer is plated as a cathode on the electron injection layer 27 away from the vapor electron transport layer 26.
As shown in table 4 below, the materials used for the hole injection layer 21, the hole transport layer 22, the electron blocking layer 23, the light emitting layer 24, the hole blocking layer 25, and the electron transport layer 26 were compounds.
TABLE 4 Table 4
The driving voltage and luminous efficiency of the following five light emitting devices were measured at a fixed current density, and the life span of the light emitting device was tested at a current density of 15mA/cm 2, and the electron transport material in the light emitting device of example 1 included compound E1; the electron transport layer material in the light-emitting device of embodiment 2 includes a compound E2; the electron transporting material in the light-emitting device of embodiment 3 includes a compound E3; the electron transporting material in the light-emitting device of embodiment 4 includes a compound E4; the electron transporting material in the light-emitting device of embodiment 5 includes a compound 83; the electron transport material in the light emitting device of example 6 includes a comparative compound, and the test results are shown in table 5.
TABLE 5
As can be seen from table 5, the driving voltages of examples 1 to 5 are lower than those of example 6, because the compounds E1, E2, E3, E4 and 83 contained in the electron transport layer are hybridized with SP3 of the central C atom thereof, which breaks the conjugation of the molecules, facilitates the separation of HOMO from LUMO, facilitates the adjustment of energy levels, facilitates the matching of adjacent functional layers, and further the light emitting device has a lower driving voltage.
It is also known from table 5 that the light-emitting efficiency and the service life of examples 1 to 5 are higher than those of example 6, because the compounds E1, E2, E3, E4 and 83 contained in the electron transport layer have orthogonal spatial stereo configurations, which can reduce the intermolecular van der waals force, facilitate the prevention of crystallization containing the electron transport material, and thus can improve the display performance of the light-emitting device, and the compounds E1, E2, E3, E4 and 83 have rigid structures, so that the electron transport material has a higher glass transition temperature, which can facilitate the improvement of the stability of the electron transport material, and thus the light-emitting efficiency and the service life of the light-emitting device.
By applying the embodiment of the application, at least the following beneficial effects can be realized:
1. The spiro compound provided by the embodiment of the application has an orthogonal space three-dimensional configuration, can reduce the van der Waals force among molecules, is beneficial to preventing the crystallization of an electron transport material containing the spiro compound, and can further improve the display performance of a light-emitting device.
2. The spiro compound provided by the embodiment of the application has higher triplet energy level, and the electron transport material containing the spiro compound has higher triplet energy level, so that excitons generated in the light-emitting layer can be prevented from diffusing to the electron transport layer, and the light-emitting efficiency of the light-emitting device is improved.
3. The SP3 hybridization of the central C atom in the spiro compound provided by the embodiment of the application can break the conjugation of molecules, so that the HOMO and LUMO energy levels are distributed in an upper part and a lower part, which is beneficial to the regulation and control of the energy level of an electron transport material and the prevention of the reduction of the triplet state level.
4. The spiro compound provided by the embodiment of the application has a rigid structure, so that an electron transport material containing the spiro compound has a higher glass transition temperature, the stability of the electron transport material is improved, and meanwhile, the spiro compound adopts an asymmetric spiro structure, so that the symmetry of molecules can be reduced, and the film forming property of the molecules is improved.
Those of skill in the art will appreciate that the various operations, methods, steps in the flow, acts, schemes, and alternatives discussed in the present application may be alternated, altered, combined, or eliminated. Further, other steps, means, or steps in a process having various operations, methods, or procedures discussed herein may be alternated, altered, rearranged, disassembled, combined, or eliminated. Further, steps, measures, schemes in the prior art with various operations, methods, flows disclosed in the present application may also be alternated, altered, rearranged, decomposed, combined, or deleted.
The terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present application, unless otherwise indicated, the meaning of "a plurality" is two or more.
In the description of the present specification, a particular feature, structure, material, or characteristic may be combined in any suitable manner in one or more embodiments or examples.
The foregoing is only a part of the embodiments of the present application, and it should be noted that, for those skilled in the art, other similar implementation means based on the technical idea of the present application may be adopted without departing from the technical idea of the solution of the present application, which is also within the protection scope of the embodiments of the present application.

Claims (4)

1. A spiro compound, wherein the spiro compound has the structural formula shown below:
the spiro compound includes at least one of compounds 1 to 88:
Compound 1 to compound 3:
Compound 4 to compound 60:
Compound 61 to compound 88:
2. an electron transport material, comprising: the spiro compound as defined in claim 1.
3. A light-emitting device comprising a first electrode, a light-emitting functional layer, and a second electrode which are sequentially stacked, wherein the light-emitting functional layer comprises an electron-transporting layer comprising the electron-transporting material according to claim 2.
4. A light-emitting device according to claim 3, wherein the light-emitting functional layer further comprises a hole blocking layer provided on a side of the electron transport layer close to the first electrode, the hole blocking layer comprising the electron transport material according to claim 2.
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