Oxaspirodiindene compound, organic layer, application of oxaspirodiindene compound and organic layer, organic electroluminescent device and display or lighting device

Abstract

The invention discloses an oxa-spirobiindene compound, an organic layer, application of the oxa-spirobiindene compound and the organic layer, an organic electroluminescent device and a display or lighting device. The structural formula of the oxa-spirobiindene compound is shown in the formula I, r is selected from the following substituted or unsubstituted groups: a straight chain or branched chain C1-C60 alkyl group, a C3-C60 cycloalkyl group, a C1-C60 hetero-alkyl group, a C1-C60 hetero-cycloalkyl group, a C6-C60 aryl group, and a C3-C60 hetero-aryl group; m represents the number of R and is an integer selected from 0-8; r1 to R4 are independently selected from hydrogen, deuterium, deuterated methyl, and the following substituted or unsubstituted groups: straight chain or branched chain C1-C60 alkyl groups, C3-C60 cycloalkyl groups, C1-C60 heteroalkyl groups, C1-C60 heterocycloalkyl groups, C6-C60 aryl groups, and C3-C60 heteroaryl groups. When the oxa-spirodiindene compound is applied to the organic electroluminescent device, the working voltage of the device can be reduced, the current efficiency of the device can be improved, the service life of the device can be prolonged, and meanwhile, the oxa-spirodiindene compound also has excellent color purity.

Description

Technical Field

[0001] The present application relates to the technical field of organic electroluminescent materials, and in particular to an oxaspirobiindene compound and an organic layer and applications thereof, an organic electroluminescent device, and a display or lighting device. Background Art

[0002] Organic Light-Emitting Diodes (OLEDs) have attracted significant attention due to their thin design, ability to produce high brightness at low operating voltages, and the ability to produce multi-color light by selecting the right luminescent materials. They are currently widely used in various main display screens, and their practical application has made significant progress. Despite rapid research progress in OLED devices, many challenges remain, such as improving the device's operating voltage, current efficiency, and lifespan. Summary of the Invention

[0003] The purpose of this application is to provide an oxaspirobiindene compound and an organic layer and their applications, an organic electroluminescent device, a display or lighting device, which can significantly improve the current efficiency, luminous efficiency and life of the organic electroluminescent device, reduce the operating voltage of the device, and also have excellent color purity.

[0004] To achieve the above objectives, the technical solution of the present application provides an oxaspirobiindene compound, the structural formula of which is shown in Formula I: In the formula I, R is selected from the following substituted or unsubstituted groups: linear or branched C1-C60 alkyl, C3-C60 cycloalkyl, C1-C60 heteroalkyl, C1-C60 heterocycloalkyl, C6-C60 aryl, C3-C60 heteroaryl; m represents the number of R, and is selected from an integer of 0-8; R1-R4 are independently selected from hydrogen, deuterium, deuterated methyl, substituted or unsubstituted groups: linear or branched C1-C60 alkyl, C3-C60 cycloalkyl, C1-C60 heteroalkyl, C1-C60 heterocycloalkyl, C6-C60 aryl, C3-C60 heteroaryl.

[0005] In some embodiments of the present application, R is L1-EA; the structural formula of the oxaspirobiindene compound is shown in Formula II: In Formula II, L1 is selected from a single bond, a substituted or unsubstituted C6-C60 arylene group, or a substituted or unsubstituted C3-C60 heteroarylene group; EA is an electron-withdrawing group; and n represents the number of L1-EA and is an integer of 1 to 4.

[0006] In some embodiments of the present application, the EA is Ar6 and Ar7 are independently selected from substituted or unsubstituted C6-C60 aryl groups, substituted or unsubstituted C3-C60 heteroaryl groups; and n is 1 or 2.

[0007] In some embodiments of the present application, Ar6 and Ar7 are independently selected from the following substituted or unsubstituted groups: phenyl, naphthyl, biphenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, fluorenyl, spirofluorenyl, triphenylene, phenanthrenyl; L1 is selected from the following single bond, substituted or unsubstituted groups: phenylene, naphthyl, biphenylene, dibenzofuranyl, dibenzothiophenyl, carbazolyl, fluorenyl, triphenylene.

[0008] In some embodiments of the present application, the oxaspirobiindene compound shown in Formula II is represented by Formulas 1 to 70, in which R1 to R4 are independently selected from hydrogen, methyl, deuterated methyl, and phenyl; Ar7 is selected from phenyl, naphthyl, biphenyl, diphenylfuranyl, and 9,9-dimethylfluorenyl.

[0009] In some embodiments of the present application, the oxaspirobiindene compound represented by Formula II is selected from the following group:

[0010]

[0011] In some embodiments of the present application, R is The structural formula of the oxaspirobiindene compound is shown in Formula III: In the formula III, L is selected from a single bond, a substituted or unsubstituted C6-C60 arylene group, or a substituted or unsubstituted C3-C60 heteroarylene group; Ar1 ​​and Ar2 are independently selected from a substituted or unsubstituted C6-C60 aryl group, or a substituted or unsubstituted C3-C60 heteroaryl group, or Ar1 and Ar2 are bonded to form a ring; n1 represents The number of is an integer from 1 to 4.

[0012] In some embodiments of the present application, the structural formula of the oxaspirobiindene compound is as shown in Formula IV or Formula V: Among them, Ar8~Ar 11 Independently selected from the following substituted or unsubstituted single groups or combinations of multiple groups:

[0013]

[0014] In some embodiments of the present application, the oxaspirobiindene compound represented by Formula IV is represented by Formula 71 to Formula 98; in Formula 71 to Formula 98, Ar9 is selected from R1 to R4 are independently selected from hydrogen, methyl, deuterated methyl, and phenyl.

[0015] In some embodiments of the present application, the oxaspirobiindene compound represented by Formula V is represented by Formula 99 to Formula 138, in which Ar 11 Selected from R1 to R4 are independently selected from hydrogen, methyl, deuterated methyl, and phenyl.

[0016] In some embodiments of the present application, the oxaspirobiindene compound represented by formula V is selected from the following group:

[0017]

[0018] In some embodiments of the present application, R is The structural formula of the oxaspirobiindene compound is shown in Formula VI: In Formula VI, L2 is selected from a single bond, a substituted or unsubstituted C6-C60 arylene group, or a substituted or unsubstituted C3-C60 heteroarylene group; Ar3 is selected from a substituted or unsubstituted C6-C60 aryl group, or a substituted or unsubstituted C3-C60 heteroaryl group.

[0019] In some embodiments of the present application, Ar3 is independently selected from the following substituted or unsubstituted single groups or combinations of multiple groups:

[0020] In some embodiments of the present application, the oxaspirobiindene compound represented by Formula VI is selected from the following group:

[0021]

[0022] The present application also provides an oxaspirobiindene compound, the structural formula of which is shown in Formula VII: In the formula VII, CyA, CyB, Ar4 and Ar5 are independently selected from substituted or unsubstituted C6~C60 aryl groups, substituted or unsubstituted C3~C60 heteroaryl groups; R5 is selected from the following substituted or unsubstituted groups: straight-chain or branched C1~C60 alkyl groups, C3~C60 cycloalkyl groups, C1~C60 heteroalkyl groups, C1~C60 heterocycloalkyl groups, C6~C60 aryl groups, C3~C60 heteroaryl groups; and at least one of the R5, the CyA, the CyB, the Ar4 and the Ar5 comprises formula A, or the benzene ring connected to the R5 forms a structure represented by the formula A together with the R5.

[0023] In some embodiments of the present application, the oxaspirobiindene compound represented by formula VII is selected from the following group:

[0024]

[0025] The present application also provides an organic layer comprising any of the aforementioned oxaspirobiindene compounds.

[0026] The present application also provides use of any of the aforementioned oxaspirobiindene compounds and / or the aforementioned organic layer in an organic electroluminescent device.

[0027] The present application also provides an organic electroluminescent device, comprising a first electrode, a second electrode and the aforementioned organic layer, wherein the organic layer is at least one of a hole injection layer, a hole transport layer, a light-emitting layer, an electron injection layer or an electron transport layer.

[0028] The present application also provides a display or lighting device, comprising the aforementioned organic electroluminescent device.

[0029] The oxaspirobiindene compound provided in the present application uses an oxaspirobiindene structure as a parent core structure, so that when used as an organic electroluminescent material, it can improve various properties of an organic electroluminescent device. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] The following figures describe in detail exemplary embodiments disclosed in this application. Identical reference numerals denote similar structures in several views of the drawings. Those skilled in the art will appreciate that these embodiments are non-limiting, exemplary embodiments, and that the drawings are for illustration and description purposes only and are not intended to limit the scope of this application. Other embodiments may also achieve the same inventive intent as described in this application. It should be understood that the drawings are not drawn to scale. Among them:

[0031] Figure 1 is a schematic structural diagram of the organic electroluminescent device of Example 41;

[0032] Figure 2 is a schematic structural diagram of the organic electroluminescent device of Example 51;

[0033] Figure 3 is a schematic structural diagram of the organic electroluminescent device of Example 61;

[0034] Figure 4 This is a schematic structural diagram of the organic electroluminescent device of Example 71. DETAILED DESCRIPTION

[0035] The following description provides specific application scenarios and requirements of the present application, with the purpose of enabling those skilled in the art to make and use the content of this application. Various local modifications to the disclosed embodiments will be apparent to those skilled in the art, and the general principles defined herein may be applied to other embodiments and applications without departing from the spirit and scope of this application. Therefore, this application is not limited to the embodiments shown, but is intended to be of the widest scope consistent with the claims.

[0036] The following are examples of substituents that may appear in this application, but the substituents are not limited thereto:

[0037] Substituted or unsubstituted: refers to being substituted with one or more substituents selected from the group consisting of deuterium, a halogen group, a nitrile group, a nitro group, a hydroxyl group, a carbonyl group, an ester group, an imide group, an amino group, a phosphine oxide group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, a silyl group, a boron group, a linear or branched or cyclic alkyl group, an alkenyl group, an aryl group, an aralkyl group, an aralkenyl group, an alkylaryl group, an alkylamino group, an aralkylamino group, a heteroarylamino group, an arylamino group, an arylphosphino group, a heterocyclic group, or being unsubstituted; or being substituted with a substituent that connects two or more of the substituents listed above, or being unsubstituted. For example, a “substituent that connects two or more substituents” may include a biphenyl group, i.e., a biphenyl group may be an aryl group, or a substituent that connects two phenyl groups. The linear, branched or cyclic alkyl group is preferably a C1 to C30 alkyl group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, methyl-substituted isobutyl, methyl-substituted tert-butyl, etc.

[0038] Aryl: There are no particular limitations and the aryl group may be a monocyclic aryl group or a polycyclic aryl group. In some embodiments, monocyclic aryl groups include, but are not limited to, phenyl, biphenyl, terphenyl, quaterphenyl, pentphenyl, and the like. Polycyclic aryl groups include, but are not limited to, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, perylenyl, and fluorenyl. The fluorenyl group may be substituted, such as 9,9'-dimethylfluorenyl and fluorenyl. Furthermore, two of the substituents may combine to form a spirocyclic structure, such as 9,9'-spirobifluorenyl.

[0039] The above description of the aryl group applies to the arylene group, except that the arylene group is divalent.

[0040] The above description of the aryl group can be applied to the aryl group in the aryloxy group, arylthio group, arylsulfonyl group, arylphosphino group, arylalkyl group, arylalkylamino group, arylalkenyl group, alkylaryl group, arylamino group and arylheteroarylamino group.

[0041] Heterocyclic group: contains one or more of B, N, O, P, S, Si and Se as heteroatoms. Heterocyclic groups include, but are not limited to, pyridyl, pyrrolyl, pyrimidinyl, pyridazinyl, furyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazolyl, oxadiazolyl, thiadiazolyl, dithiazolyl, tetrazolyl, pyranyl, thiopyranyl, pyrazinyl, azinyl, thiazinyl, dioxinyl, triazinyl, tetrazinyl, quinolyl, isoquinolyl, quinolyl, quinazolinyl, quinoxalinyl, naphthyridinyl, acridinyl, xanthanenyl, phenanthridinyl, naphthyridinyl, triazaindenyl, indolyl, dihydroindolinyl, indolizinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, Pyrazinopyrazinyl, benzothiazolyl, benzoxazolyl, benzimidazolyl, benzothiophenyl, dibenzothiophenyl, dibenzofuranyl, carbazolyl, benzocarbazolyl, dibenzocarbazolyl, indolocarbazolyl, indenocarbazolyl, phenazinyl, imidazopyridinyl, phenazinyl, phenanthridinyl, phenanthrolinyl, phenothiazinyl, imidazopyridinyl, imidazophenanthridinyl, benzimidazoquinazolinyl, benzimidazophenanthridinyl, spiro[fluorene-9,9'-xanthene], benzobinaphthyl, dinaphthofuranyl, naphthylbenzofuranyl, dinaphthothienyl, naphthylbenzothienyl, triphenylphosphine oxide, triphenylborane, etc.

[0042] The above description of heterocyclyl groups applies to heteroaryl groups, except that the heteroaryl group is aromatic.

[0043] The above description of the heterocyclic group can be applied to the heteroaryl group in the heteroaryl group, the heteroarylamine group and the arylheteroarylamine group.

[0044] The above description of the heterocyclyl group applies to the heteroarylene group, except that the heteroarylene group is divalent.

[0045] Alkyl group: may be linear, branched or cyclic, and the number of carbon atoms is not particularly limited. In some embodiments, alkyl groups include, but are not limited to, methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 4-methylhexyl, 5-methylhexyl, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, and the like.

[0046] The above description of the alkyl group can be applied to the alkyl group in the alkylthio group, alkylsulfonyl group, aralkyl group, aralkylamino group, alkylaryl group and alkylamino group.

[0047] On the one hand, the present application provides an oxaspirobiindene compound having the structural formula shown in Formula I:

[0048] In Formula I, R may substitute the benzene ring of the parent core and is selected from the following substituted or unsubstituted groups: linear or branched C1-C60 alkyl, C3-C60 cycloalkyl, C1-C60 heteroalkyl, C1-C60 heterocycloalkyl, C6-C60 aryl, C3-C60 heteroaryl. m represents the number of R and is selected from an integer from 0 to 8. R may substitute at any substitutable position in Formula I. In some embodiments, R mono- or poly-substituted one of the benzene rings of the parent core. In other embodiments, R mono- or poly-substituted each of the two benzene rings of the parent core.

[0049] R1 to R4 are independently selected from hydrogen, deuterium, deuterated methyl, substituted or unsubstituted following groups: linear or branched C1 to C60 alkyl, C3 to C60 cycloalkyl, C1 to C60 heteroalkyl, C1 to C60 heterocycloalkyl, C6 to C60 aryl, C3 to C60 heteroaryl.

[0050] Electron-withdrawing groups such as nitrogen heterocycles, cyano groups, and various large planar groups are typically introduced into the structure of electron transport materials. However, the introduction of these electron-withdrawing groups makes the synthesis of electron transport materials more difficult. Furthermore, the increased planarity of the molecules can lead to poor solubility of the materials. Therefore, the present application makes R in Formula I L1-EA, yielding the oxaspirobiindene compound of Formula II:

[0051] In Formula II, L1 is selected from a single bond, a substituted or unsubstituted C6-C60 arylene group, or a substituted or unsubstituted C3-C60 heteroarylene group. EA is an electron-withdrawing group. n represents the number of L1-EA groups and is an integer from 1 to 4. The oxaspirobiindene compound represented by Formula II can address the aforementioned issues with current electron transport materials and, when used to prepare organic electroluminescent devices, can improve the device's performance.

[0052] In some embodiments, EA is wherein Ar6 and Ar7 are independently selected from substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, and n is 1 or 2.

[0053] In some embodiments, Ar6 and Ar7 are independently selected from the following groups: substituted or unsubstituted: phenyl, naphthyl, biphenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, fluorenyl, spirofluorenyl, triphenylene, phenanthrenyl. L1 is selected from the following groups: single bond, substituted or unsubstituted: phenylene, naphthylene, biphenylene, dibenzofuranyl, dibenzothiophenylene, carbazolyl, fluorenyl, triphenylene.

[0054] In some specific embodiments, the oxaspirobiindene compound of Formula II is represented by any of the following structural formulas:

[0055]

[0056]

[0057]

[0058] In Formulae 1 to 70, R1 to R4 are independently selected from hydrogen, methyl, deuterated methyl, and phenyl; Ar7 is selected from phenyl, naphthyl, biphenyl, diphenylfuranyl, and 9,9-dimethylfluorenyl.

[0059] In some more specific embodiments, the oxaspirobiindene compound represented by Formula II is selected from the following group:

[0060]

[0061] Hole transport materials are generally modified based on triarylamine or carbazole, but the efficiency and service life still need to be improved. In order to solve this problem, the present application makes R The structural formula of the oxaspirobiindene compound is shown in Formula III: In formula III, L is selected from a single bond, a substituted or unsubstituted C6-C60 arylene group, or a substituted or unsubstituted C3-C60 heteroarylene group. Ar1 and Ar2 are independently selected from a substituted or unsubstituted C6-C60 aryl group, or a substituted or unsubstituted C3-C60 heteroaryl group, or Ar1 and Ar2 are bonded to form a ring. n1 represents The number of is an integer from 1 to 4.

[0062] In some embodiments, the structural formula of the oxaspirobiindene compound is as shown in Formula IV or Formula V: In formula IV and formula V, Ar8 to Ar 11 Independently selected from the following substituted or unsubstituted single groups or combinations of multiple groups:

[0063]

[0064] In some specific embodiments, the oxaspirobiindene compound of Formula IV is represented by any of the following structural formulas:

[0065] In formula 71 to formula 98, Ar9 is selected from R1 to R4 are independently selected from hydrogen, methyl, deuterated methyl, and phenyl.

[0066] In some specific embodiments, the oxaspirobiindene compound of Formula V is represented by any of the following structural formulas:

[0067]

[0068]

[0069] In formulas 99 to 138, Ar 11 Selected from R1 to R4 are independently selected from hydrogen, methyl, deuterated methyl, and phenyl.

[0070] In some more specific embodiments, the oxaspirobiindene compound represented by Formula V is selected from the following group:

[0071]

[0072] The host material and doping material as the light-emitting layer material should have high stability and the ability to balance electrons and holes to make the device have better performance, but the current host material still needs to be improved. In view of this, the present application makes R Obtain the oxaspirobiindene compound shown in formula VI: In Formula VI, L2 is selected from a single bond, a substituted or unsubstituted C6-C60 arylene group, or a substituted or unsubstituted C3-C60 heteroarylene group. Ar3 is selected from a substituted or unsubstituted C6-C60 aryl group, or a substituted or unsubstituted C3-C60 heteroaryl group.

[0073] In some embodiments, Ar3 is independently selected from the following substituted or unsubstituted single groups or combinations of multiple groups:

[0074]

[0075] In some specific embodiments, the oxaspirobiindene compound represented by Formula VI is selected from the following group:

[0076]

[0077] In order to improve the doping material, the present application provides an oxaspirobiindene compound as shown in Formula VII: In Formula VII, CyA, CyB, Ar4, and Ar5 are independently selected from substituted or unsubstituted C6-C60 aryl groups and substituted or unsubstituted C3-C60 heteroaryl groups. R5 is selected from the following substituted or unsubstituted groups: linear or branched C1-C60 alkyl groups, C3-C60 cycloalkyl groups, C1-C60 heteroalkyl groups, C1-C60 heterocycloalkyl groups, C6-C60 aryl groups, and C3-C60 heteroaryl groups. Furthermore, at least one of R5, CyA, CyB, Ar4, and Ar5 comprises Formula A, or the benzene ring connected to R5 forms a ring with R5 to form the structure shown in Formula A.

[0078] In some specific embodiments, the oxaspirobiindene compound represented by Formula VII is selected from the following group:

[0079]

[0080] Another aspect of the present application provides an organic layer, which includes any one of the aforementioned oxaspirobiindene compounds. Any one of the aforementioned oxaspirobiindene compounds and the organic layer can be used in an organic electroluminescent device.

[0081] The present application also provides an organic electroluminescent device comprising a first electrode, a second electrode, and the aforementioned organic layer. As an example, the first electrode is an anode, the second electrode is a cathode, and the cathode can be one or more layers. The organic layer is located between the first and second electrodes. The organic layer can be a single layer or a multilayer tandem structure comprising two or more organic layers. The organic layer can be at least one of a hole injection layer, a hole transport layer, a light-emitting layer, an electron injection layer, or an electron transport layer.

[0082] In some specific embodiments, the structure of the organic electroluminescent device can be selected from one of the following:

[0083] (1) An organic electroluminescent device includes an anode, a hole injection layer, a first hole transport layer, a light-emitting layer, a first electron transport layer, and a cathode stacked in sequence, i.e., anode / hole injection layer / first hole transport layer / light-emitting layer / first electron transport layer / cathode. The device structure will be expressed in this simplified manner below.

[0084] (2) Anode / hole injection layer / second hole transport layer / first hole transport layer / light-emitting layer / first electron transport layer / cathode.

[0085] (3) Anode / hole injection layer / second hole transport layer / first hole transport layer / light-emitting layer / first electron transport layer / second electron transport layer / cathode.

[0086] (4) Anode / hole injection layer / second hole transport layer / first hole transport layer / light-emitting layer / first electron transport layer / second electron transport layer / electron injection layer / cathode.

[0087] (5) Anode / hole injection layer / second hole transport layer / first hole transport layer / light-emitting layer / first electron transport layer / second electron transport layer / multilayer cathode.

[0088] (6) Anode / hole injection layer / first hole transport layer / first light-emitting layer / carrier generation layer / first hole transport layer / second light-emitting layer / first electron transport layer / cathode.

[0089] (7) Anode / hole injection layer / first hole transport layer / first light-emitting layer / carrier generation layer / first hole transport layer / second light-emitting layer / first electron transport layer / second electron transport layer / cathode.

[0090] (8) Anode / hole injection layer / second hole transport layer / first hole transport layer / first light-emitting layer / carrier generation layer / first hole transport layer / second light-emitting layer / first electron transport layer / cathode.

[0091] (9) Anode / hole injection layer / second hole transport layer / first hole transport layer / first light-emitting layer / carrier generation layer / first hole transport layer / second light-emitting layer / first electron transport layer / second electron transport layer / cathode.

[0092] (10) Anode / hole injection layer / hole transport layer / electron blocking layer / light-emitting layer / electron transport layer / electron injection layer / cathode.

[0093] (11) Anode / hole injection layer / first hole transport layer / second hole transport layer / light-emitting layer / hole blocking layer / electron transport layer / cathode.

[0094] (12) Anode / hole injection layer / hole transport layer / electron blocking layer / light-emitting layer / electron transport layer / cathode.

[0095] (13) Anode / hole injection layer / hole transport layer / electron blocking layer / light-emitting layer / hole blocking layer / electron transport layer / cathode.

[0096] The light emission direction of the organic electroluminescent device can be emitted from the anode side or the cathode side. In some specific embodiments, if the light emission direction is the cathode side, it is necessary to add a cover layer on the cathode side. The specific structure is as follows:

[0097] 1) Anode / hole injection layer / first hole transport layer / light-emitting layer / first electron transport layer / cathode / covering layer.

[0098] 2) Anode / hole injection layer / second hole transport layer / first hole transport layer / light-emitting layer / first electron transport layer / cathode / covering layer.

[0099] 3) Anode / hole injection layer / second hole transport layer / first hole transport layer / light-emitting layer / first electron transport layer / second electron transport layer / cathode / covering layer.

[0100] 4) Anode / hole injection layer / second hole transport layer / first hole transport layer / light-emitting layer / first electron transport layer / second electron transport layer / electron injection layer / cathode / covering layer.

[0101] 5) Anode / hole injection layer / second hole transport layer / first hole transport layer / light-emitting layer / first electron transport layer / second electron transport layer / multilayer cathode / covering layer.

[0102] 6) Anode / hole injection layer / first hole transport layer / first light-emitting layer / carrier generation layer / first hole transport layer / second light-emitting layer / first electron transport layer / cathode / covering layer.

[0103] 7) Anode / hole injection layer / first hole transport layer / first light-emitting layer / carrier generation layer / first hole transport layer / second light-emitting layer / first electron transport layer / second electron transport layer / cathode / covering layer.

[0104] 8) Anode / hole injection layer / second hole transport layer / first hole transport layer / first light-emitting layer / carrier generation layer / first hole transport layer / second light-emitting layer / first electron transport layer / cathode / covering layer.

[0105] 9) Anode / hole injection layer / second hole transport layer / first hole transport layer / first light-emitting layer / carrier generation layer / first hole transport layer / second light-emitting layer / first electron transport layer / second electron transport layer / cathode / covering layer.

[0106] 10) Anode / hole injection layer / hole transport layer / electron blocking layer / light-emitting layer / electron transport layer / electron injection layer / cathode / covering layer.

[0107] 11) Anode / hole injection layer / first hole transport layer / second hole transport layer / light-emitting layer / hole blocking layer / electron transport layer / cathode / covering layer.

[0108] 12) Anode / hole injection layer / hole transport layer / electron blocking layer / light-emitting layer / electron transport layer / cathode / covering layer.

[0109] 13) Anode / hole injection layer / hole transport layer / electron blocking layer / light-emitting layer / hole blocking layer / electron transport layer / cathode / covering layer.

[0110] Some specific functional layers in the organic electroluminescent device are described below.

[0111] Substrate:

[0112] The substrate is typically located below the anode and can be made of plastic or glass, and can be rigid or flexible. The substrate has a driver unit that drives the corresponding pixel to emit light.

[0113] anode:

[0114] Organic EL (Organic Electro-Luminescence) components typically require the anode to have good conductivity, a flat surface, and be resistant to cracks. They also have certain requirements for the work function, primarily to ensure that it matches the hole injection layer and maximizes the hole injection effect.

[0115] When top emission is used (light emitting from the cathode side), the anode uses a metal compound with a work function of 4.2eV or more, such as indium tin oxide alloy, tin oxide, indium zinc oxide, gold, silver, platinum, copper, carbon nanotubes, carbon nanowires, graphene, etc. The thickness is 10nm to 200nm, preferably 10nm to 50nm. A reflective electrode is set below the anode (near the substrate end). The reflective electrode is generally made of metal or metal alloy, such as silver metal, copper metal, aluminum metal, gold metal, or alloys of these metals with other metals. The reflective electrode has a high reflectivity, which is required to be above 90%. The thickness is usually used in the range of 100nm to 500nm, preferably in the range of 80nm to 150nm.

[0116] When using a bottom emission method (light emitting from the cathode substrate side), the anode is made of a metal compound with a work function of 4.2 eV or higher, such as indium tin oxide alloy, tin oxide, indium zinc oxide, gold, silver, platinum, copper, carbon nanotubes, carbon nanowires, graphene, etc. The thickness is 10 nm to 1 μm, preferably 50 nm to 200 nm.

[0117] The anode can be produced by forming an electrode material into a thin film by a method such as vapor deposition, sputtering, or coating.

[0118] Hole injection layer:

[0119] The thickness of the hole injection layer is generally 3nm to 20nm. The hole injection layer uses a mixture of P-type material and hole transport material. The purpose of using P-type material is to accept holes from the anode and transfer them to the hole transport material. The weight proportion of P-type material in the hole injection layer is generally 0.5% to 10%. When the weight proportion is 0.5% to 3%, the absolute value of the difference between the lowest unoccupied molecular orbital (LUMO) energy level of the P-type material and the highest occupied molecular orbital (HOMO) energy level of the HTL material shall not exceed 0.3eV. When the weight proportion is 3% to 5%, the absolute value of the difference between the lowest unoccupied molecular orbital (LUMO) energy level of the P-type material and the highest occupied molecular orbital (HOMO) energy level of the HTL material shall not exceed 0.5eV. When the weight proportion is 5% to 10%, the absolute value of the difference between the lowest unoccupied molecular orbital (LUMO) energy level of the P-type material and the highest occupied molecular orbital (HOMO) energy level of the HTL material shall not exceed 1eV.

[0120] The P-type material can be a metal oxide, such as molybdenum oxide, vanadium oxide, tungsten oxide, etc.; it can also be an organic material, such as 4,4',4"-((1E,1'E,1"E)-cyclopropane-1,2,3-trimethylenetris(cyanoformylidene))tris(2,3,5,6-tetrafluorobenzyl) (PD1, CAS No.: 1224447-88-4), tetracyanoquinodimethane (TCNQ), 2,3,5,6-tetrafluoro-tetracyano-1,4-benzoquinodimethane (F4-TCNQ), 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HAT-CN), and is not limited thereto. The hole transport material used in combination with the P-type material can be selected from the material of the second hole transport layer and can be the same as or different from the material of the second hole transport layer.

[0121] Second hole transport layer:

[0122] The second hole transport layer is typically 40nm to 150nm thick and typically uses compounds containing aromatic amines, either monoamines or polyamines. The hole transport material must have high hole mobility, reduce driving voltage, and a glass transition temperature exceeding 100°C to avoid crystallization at high temperatures.

[0123] First hole transport layer:

[0124] The thickness of the first hole transport layer is generally 3nm to 220nm. When there is no second hole transport layer, the thickness of the first hole transport layer is generally 40nm to 150nm; when there is a second hole transport layer, the thickness of the first hole transport layer is generally 3nm to 120nm. Generally, red light, green light, blue light, yellow light, etc. need to be adjusted in thickness according to the "microcavity effect", and the thickness selection is also different. Taking the top-emitting light-emitting device as an example, the formula for the microcavity is as follows:

[0125] where n i and d i Respectively represent the refractive index coefficient and thickness of the i-th layer, m is an integer, which is the modulus of the microcavity, and is commonly taken as 1 or 2; θ1 and θ2 represent the phase shift generated by light at the anode interface and cathode interface, respectively.

[0126] Red light, green light, blue light or other colors of light have different wavelengths, so each color has its optimal thickness. Taking the modulus of 2 as an example, when red light is present, when there is no second hole transport layer, the thickness of the first hole transport layer is generally 160nm~220nm; when there is a second hole transport layer, the thickness of the first hole transport layer is generally 8nm~120nm. When green light is present, when there is no second hole transport layer, the thickness of the first hole transport layer is generally 100nm~180nm; when there is a second hole transport layer, the thickness of the first hole transport layer is generally 30nm~70nm. When blue light is present, when there is no second hole transport layer, the thickness of the first hole transport layer is generally 80nm~130nm; when there is a second hole transport layer, the thickness of the first hole transport layer is generally 3nm~30nm. When other colors are selected, there will be different optimal "microcavity adjustment thicknesses".

[0127] Electron blocking layer:

[0128] The electron blocking layer can have both hole transport and electron blocking functions. At the same time, the higher triplet excitation energy level of the electron blocking layer can lock excitons generated in the light-emitting layer in the light-emitting layer, thereby improving the luminous efficiency of the device.

[0129] Luminous layer:

[0130] The materials of the light-emitting layer generally include a host material and a guest dopant material. The content of the host material is greater than that of the guest dopant material. Optionally, the mass percentage of the guest dopant material in the light-emitting layer is 1% to 20%.

[0131] The guest dopant material used as the luminescent material may include a phosphorescent or fluorescent material or a thermally activated delayed fluorescent material. Red, green, and blue light can be selected from the above three types of guest dopant materials. For example, the guest dopant material for the luminescent layer corresponding to the red luminescent unit and the luminescent layer corresponding to the green luminescent unit is a phosphorescent material, while the guest dopant material for the luminescent layer corresponding to the blue luminescent unit is a fluorescent material.

[0132] Or for example, the guest doping material of the light-emitting layer corresponding to the light-emitting unit with red light emission color and the light-emitting layer corresponding to the light-emitting unit with green light emission color is a phosphorescent material, and the guest doping material of the light-emitting layer corresponding to the light-emitting unit with blue light emission color is a phosphorescent material.

[0133] Or for example, the guest doping material of the light-emitting layer corresponding to the light-emitting unit with red light-emitting color and the light-emitting layer corresponding to the light-emitting unit with green light-emitting color is a thermally activated delayed fluorescent material, and the guest doping material of the light-emitting layer corresponding to the light-emitting unit with blue light-emitting color is a fluorescent material.

[0134] Or for example, the guest doping material of the light-emitting layer corresponding to the light-emitting unit with red light-emitting color and the light-emitting layer corresponding to the light-emitting unit with green light-emitting color is a thermally activated delayed fluorescent material, and the guest doping material of the light-emitting layer corresponding to the light-emitting unit with blue light-emitting color is a phosphorescent material.

[0135] In order to reduce the power consumption of the organic light-emitting display panel in the organic electroluminescent device, the guest doping material can be selected to have excellent luminescence performance. Taking the top-emitting device as an example, the red light-emitting unit can be selected to have a luminous brightness of 1000 cd / m 2 The current efficiency is greater than 30cd / A, and the luminous unit with green luminous color has a luminous brightness of 6000cd / m 2 The current efficiency is greater than 100cd / A, and the light-emitting unit with a fluorescent blue light color has a light brightness of 1000cd / m 2 The current efficiency is greater than 5cd / A as the standard, and the appropriate guest doping material is selected. The luminous color of the luminescent unit is phosphorescent blue and the luminous brightness is 1000cd / m 2 The current efficiency is greater than 10cd / A. When the current efficiency is higher, the power consumption can be reduced.

[0136] As the light-emitting host material, one light-emitting host material or two light-emitting host materials can be selected.

[0137] Hole blocking layer:

[0138] To enhance the balance between hole and electron concentrations, a hole-blocking layer is inserted to balance carrier concentrations and prevent exciton quenching. Typically, the hole-blocking layer is located between the light-emitting layer and the electron-transporting layer. The hole-blocking layer material must meet requirements such as high stability, good film-forming properties, and a high maximum molecular orbital.

[0139] First electron transport layer:

[0140] The thickness of the first electron transport layer can generally be 3nm to 40nm, 3nm to 10nm, 10nm to 20nm, 20nm to 30nm, 30nm to 40nm, or 20nm to 40nm. When there is no second electron transport layer, the thickness of the first electron transport layer is generally 20nm to 50nm. When a second electron transport layer is present, the thickness of the first electron transport layer is generally 40nm to 20nm. The first electron transport layer is in direct contact with the light-emitting layer. Therefore, similar to the first hole transport layer, it will also undergo electronic changes during the electron transport process, resulting in increased molecular vibration and molecular deformation. The excitons of the light-emitting layer will also interact with the polarons of the electron transport material. This interaction can easily generate active free radicals that destroy the electron transport material. The electron transport material can be a single compound or mixed with other metals or metal compounds. It can include a mixture of an organic electron transport material and a metal compound, or a mixture of an organic electron transport material and a metal.

[0141] When the organic electron transport material is mixed with a metal compound material, for example, with an alkali metal compound, an alkaline earth metal compound, or a rare earth metal compound, more specifically, with a lithium metal compound, a calcium metal compound, a magnesium metal compound, a samarium metal compound, or a ytterbium metal compound, and more specifically, with lithium 8-hydroxyquinoline, lithium fluoride, magnesium fluoride, ytterbium fluoride, or calcium fluoride. When mixed with the metal compound, the weight proportion of the organic electron transport material can be 20% to 80%, 20% to 40%, 40% to 60%, or 60% to 80%.

[0142] When the organic electron transport material is mixed with a metal, for example, with an alkali metal, an alkaline earth metal, or a rare earth metal, more specifically, with lithium metal, magnesium metal, calcium metal, ytterbium metal, samarium metal, etc., when mixed with a metal, the mass proportion of the organic electron transport material can be 80% to 99%, 80% to 89%, 89% to 99%, 80% to 85%, 85% to 90%, 90% to 95%, or 95% to 99%, etc.

[0143] Second electron transport layer:

[0144] The thickness of the second electron transport layer is generally 10 nm to 40 nm. The material of the second electron transport layer may include a mixture of an organic electron transport material and a metal compound, or a mixture of an organic electron transport material and a metal.

[0145] When the organic electron transport material is mixed with a metal compound material, for example, with an alkali metal compound, an alkaline earth metal compound, or a rare earth metal compound, more specifically, with a lithium metal compound, a calcium metal compound, a magnesium metal compound, a samarium metal compound, or a ytterbium metal compound, and more specifically, with lithium 8-hydroxyquinoline, lithium fluoride, magnesium fluoride, ytterbium fluoride, or calcium fluoride. When mixed with the metal compound, the weight proportion of the organic electron transport material can be 20% to 80%, 20% to 40%, 40% to 60%, or 60% to 80%.

[0146] When the organic electron transport material is mixed with a metal, for example, with an alkali metal, an alkaline earth metal, or a rare earth metal, more specifically, with lithium metal, magnesium metal, calcium metal, ytterbium metal, samarium metal, etc., when mixed with a metal, the mass proportion of the organic electron transport material can be 80% to 99%, 80% to 89%, 89% to 99%, 80% to 85%, 85% to 90%, 90% to 95%, or 95% to 99%, etc.

[0147] Charge generation layer:

[0148] When using a single-layer light-emitting device, holes and electrons are injected from the anode and cathode, respectively, eliminating the need for a charge generation layer. When using a dual-layer or multi-layer light-emitting device, a charge generation layer is required between the light-emitting layers to achieve charge generation, injection, and transport. The charge generation layer is located between the two light-emitting layers and is typically composed of a P / N-type dual-layer material. The P-type material is selected from the hole-injection materials mentioned above, and the N-type material is a mixture of an organic electron transport material doped with a metal. The organic electron transport layer material is selected from the second electron transport layer mentioned above, and the metal is selected from alkali metals, alkaline earth metals, and rare earth metals, with lithium, magnesium, calcium, ytterbium, and samarium being more specific examples. When the organic electron transport material is mixed with the metal, the weight proportion of the organic electron transport material can range from 80% to 99%, 80% to 89%, 89% to 99%, 80% to 85%, 85% to 90%, 90% to 95%, or 95% to 99%, etc.

[0149] cathode:

[0150] The cathode requires a material with good electrical conductivity and surface flatness. To improve electron injection, materials with a low work function are generally selected. The cathode material can be a single-layer cathode, or a double-layer or multi-layer cathode, typically made of a metal or metal alloy. For a single-layer cathode, silver, copper, aluminum, gold, or alloys of these metals with other metals, such as rare earth metals, alkali metals, and alkaline earth metals, can be used. Examples include magnesium-indium alloys, magnesium-aluminum alloys, aluminum-potassium alloys, aluminum-scandium-potassium alloys, magnesium-silver alloys, silver-ytterbium alloys, and silver-samarium alloys. If a double-layer cathode is used, the cathode layer closer to the light-emitting layer can be made of alkali metals, alkaline earth metals, or rare earth metals, such as lithium, calcium, magnesium, and ytterbium, to enhance electron injection. The cathode layer farther from the light-emitting layer, primarily to enhance conductivity, can typically be made of silver, copper, aluminum, or gold, or alloys of these metals with other metals, such as rare earth metals, alkali metals, and alkaline earth metals. Examples include magnesium-indium alloys, magnesium-aluminum alloys, aluminum-potassium alloys, aluminum-scandium-potassium alloys, magnesium-silver alloys, silver-ytterbium alloys, and silver-samarium alloys. The cathode can also be formed as a thin film by methods such as evaporation and sputtering.

[0151] When light comes out from the anode side, the cathode is required to be opaque, and a cathode thicker than 100nm can be evaporated. When light comes out from the cathode side, the cathode is required to be transparent, with a transmittance greater than 40% and a thickness of 10nm to 20nm.

[0152] Covering:

[0153] The refractive index n and absorption coefficient of the single-layer cover layer need to meet the following conditions:

[0154] The refractive index between the wavelengths of 450 and 650 nm is n(450-650 nm)>1.8, and the extinction coefficient between the wavelengths of 450 and 650 nm is below 0.1; the extinction coefficient at 380 nm is greater than 0.2; the difference between the refractive index of 450 nm and the refractive index of 530 nm is n(450 nm)-n(530 nm)<0.5, more preferably n(450 nm)-n(530 nm)<0.3; the difference between the refractive index of 510 nm and the refractive index of 620 nm is n(510 nm)-n(620 nm)<0.4, more preferably the difference between the refractive index of 510 nm and the refractive index of 620 nm is n(510 nm)-n(620 nm)<0.2.

[0155] Materials that can meet the requirements of the cover layer for the refractive index n can further achieve high luminous efficiency of the device, while at the same time achieving more balanced light extraction efficiency and viewing angles for red, green, and blue light.

[0156] In some specific embodiments, the thickness of the covering layer is 50nm to 90nm, for example, 50nm, 55nm, 57nm, 59nm, 62nm, 64nm, 67nm, 68nm, 70nm, 75nm, 77nm, 79nm, 80nm, 82nm, 85nm, 88nm, 90nm, etc.

[0157] After the covering layer is formed on the side of the semi-transparent cathode of the OLED display panel away from the substrate, the light transmittance of the stacked layer formed by the covering layer and the semi-transparent cathode between 450nm and 650nm can be ≥65%, for example, 68%, 69%, 73%, 77%, 79%, 83%, 88%, 93%, etc.

[0158] When two covering layers are used, the refractive index n and absorption coefficient need to meet the following conditions:

[0159] The covering layer close to the cathode side (the first covering layer) has a refractive index n450~650nm<1.8 between 450 and 650nm, and an extinction coefficient between 450 and 650nm below 0.1; the maximum coefficient at any wavelength between 250nm and 350nm is greater than 0.3, and optimally greater than 0.6.

[0160] The covering layer away from the cathode side (the second covering layer) has a refractive index n450~650nm>1.8 between wavelengths of 450~650nm, and an extinction coefficient between wavelengths of 450~650nm is below 0.1; the extinction coefficient at 380nm is greater than 0.1, and more preferably greater than 0.2.

[0161] The difference between the refractive index at 450 nm and the refractive index at 530 nm, n(450 nm)-n(530 nm), is less than 0.5, and more preferably, the difference between the refractive index at 450 nm and the refractive index at 530 nm, n(450 nm)-n(530 nm), is less than 0.3;

[0162] The difference between the refractive index at 510 nm and the refractive index at 620 nm is n(510 nm)-n(620 nm)<0.4, and more preferably, the difference between the refractive index at 450 nm and the refractive index at 530 nm is n(450 nm)-n(530 nm)<0.2.

[0163] The total thickness of the double-layer covering layer is 50nm to 90nm, for example: 50nm, 55nm, 57nm, 59nm, 62nm, 64nm, 67nm, 68nm, 70nm, 75nm, 77nm, 79nm, 80nm, 82nm, 85nm, 88nm, 90nm, etc.

[0164] The thickness of the covering layer close to the cathode side (first covering layer) is 5nm to 40nm, for example: 5nm, 7nm, 10nm, 12nm, 15nm, 18nm, 20nm, 22nm, 25nm, 27nm, 30nm, 32nm, 34nm, 36nm, 38nm, 40nm, etc.

[0165] The thickness of the covering layer away from the cathode side (the second covering layer) is 35nm to 85nm, for example: 35nm, 40nm, 43nm, 45nm, 48nm, 50nm, 55nm, 57nm, 59nm, 62nm, 64nm, 67nm, 68nm, 70nm, 75nm, 77nm, 79nm, 80nm, 82nm, 85nm, etc.

[0166] On the other hand, the present application further provides a display or lighting device, comprising the above-mentioned organic electroluminescent device.

[0167] The oxaspirobiindene compounds of the present application can be synthesized using known methods. For example, cross-coupling reactions using transition metals such as nickel and palladium, or CC and CN coupling reactions using transition metals such as magnesium and zinc, can also be used. Preferably, the Suzuki-Buchwald reaction is employed, which offers mild reaction conditions and excellent selectivity for various functional groups.

[0168] In some embodiments, the reactants are heated in an organic solvent in the presence of a cross-coupling catalyst (catalytic amount) in an inert atmosphere, and the reaction is stirred under reflux. After the desired reaction time, the reaction system is obtained, cooled, and water is added. The precipitated solid is washed and then vacuum-dried to obtain a crude product. The obtained crude product is refined (including but not limited to silica gel column chromatography) to obtain the oxaspirobiindene compound product.

[0169] The technical solutions of the present application will be described clearly and completely below in conjunction with the specific examples of the present application. Unless otherwise specified, the reagents and raw materials used can be purchased through commercial channels. The experimental methods for which specific conditions are not specified in the following specific examples are generally determined in accordance with national standards. If there are no corresponding national standards, then the methods are based on general international standards, conventional methods and conditions, or according to the conditions recommended by the manufacturer, or selected according to the product specifications. Unless otherwise specified, all parts are parts by weight and all percentages are percentages by weight. The following examples only illustrate some of the oxaspirobiindene compounds and their preparation methods of the present application and should not be regarded as limitations on the oxaspirobiindene compounds and their preparation methods of the present application.

[0170] The starting materials and solvents used in the following examples were purchased from Shanghai Titan Technology Co., Ltd. Commonly used OLED intermediates and other products were purchased from domestic OLED intermediate manufacturers. Various palladium catalysts and ligands were purchased from Shaanxi Ruike New Materials Co., Ltd. HPLC data were measured using a Waters Corporation UPLC ultra-high performance liquid chromatograph. LC-MS (liquid chromatography-mass spectrometry) was performed on a Waters Corporation UPLC+SQD2 instrument.

[0171] Compound Preparation Examples

[0172] Example 1

[0173] Synthesis of compound 1

[0174]

[0175] Under an argon atmosphere, a reaction vessel was charged with 31.2 g (100 mmol) of organic compound 1-A, 26.8 g (100 mmol) of organic compound 1-B, 23.4 g (240 mmol) of sodium tert-butoxide, 575 mg (1 mmol%) of bisdibenzylideneacetone palladium, 348 mg (1.2 mmol%) of tri-tert-butylphosphine tetrafluoroborate, and 1000 mL of xylene. The mixture was heated and stirred at 140°C for 15 hours. The reaction mixture was cooled to room temperature, 1000 mL of water was added, and the mixture was filtered. The filter cake was washed with a large amount of water and dried under vacuum. The crude product was purified by silica gel column chromatography (eluent: ethyl acetate / hexane) to obtain 29.6 g of compound 1 with an HPLC purity of 99.9% and a yield of 65%. LC MS: M / Z 455.16 (M+).

[0176] Examples 2 to 10

[0177] The reaction raw materials and products of Examples 2 to 10 can be referred to as shown in Table 1, and the specific synthesis method can be referred to as Example 1.

[0178] Table 1 Reaction materials and products of Examples 2 to 10

[0179]

[0180]

[0181] Example 11

[0182] Synthesis of compound 11

[0183]

[0184] 1) Synthesis of Intermediate 11-1

[0185] Under an argon atmosphere, a reaction vessel was charged with 30.3 g (100 mmol) of organic compound 11-A, 16.9 g (100 mmol) of organic compound 11-B, 23.4 g (240 mmol) of sodium tert-butoxide, 575 mg (1 mmol%) of bis(dibenzylideneacetonepalladium), 348 mg (1.2 mmol%) of tri-tert-butylphosphine tetrafluoroborate, and 1000 mL of xylene. The mixture was heated and stirred at 140°C for 15 hours. The reaction mixture was cooled to room temperature, 1000 mL of water was added, and the mixture was filtered. The filter cake was washed with a large amount of water and dried under vacuum. The crude product was purified by silica gel column chromatography (eluent: ethyl acetate / hexane) to obtain 30.9 g of intermediate 11-1 with an HPLC purity of 99.5% and a yield of 79%. LC MS: M / Z 391.16 (M+).

[0186] 2) Synthesis of compound 11

[0187] The synthesis of intermediate 11-1 was the same as that of compound 11-1, except that the starting materials were replaced with intermediate 11-1 and compound 11-C. LC MS: M / Z 583.25 (M+). HPLC purity: 99.9%, yield: 63%.

[0188] Examples 12 to 20

[0189] The reaction raw materials and products of Examples 12 to 20 can be referred to as shown in Table 2, and the specific synthesis method can be referred to Example 11.

[0190] Table 2 Reaction materials and products of Examples 12 to 20

[0191]

[0192]

[0193] Example 21

[0194] Synthesis of compound 21

[0195]

[0196] 1) Synthesis of Intermediate 21-1

[0197] Under an argon atmosphere, a reaction vessel was charged with 33.6 g (100 mmol) of compound 21-A, 17.2 g (100 mmol) of compound B-1-B, 1.4 g (2 mmol) of Pd(PPh3)2Cl2, 200 mL (300 mmol) of 1.5 M sodium carbonate solution, and 1000 mL of ethylene glycol dimethyl ether (DME). The mixture was heated and stirred at 80°C for 5 hours. After cooling to room temperature, 800 mL of water was added, and a large amount of solid precipitated. The solid was filtered, and the filter cake was washed three times with water and dried under vacuum. The crude product was purified by silica gel column chromatography (eluent: ethyl acetate / hexane) to obtain 16.5 g of intermediate 21-1, with a yield of 43% and an HPLC purity of 99.4%. LC MS: M / Z 382.04 (M+).

[0198] 2) Synthesis of Compound 21

[0199] The synthesis of intermediate 21-1 was the same as that of compound 21-1, except that the starting materials were replaced with intermediate 21-1 and compound 21-C. LC MS: M / Z 594.33 (M+). HPLC purity: 99.9%, yield: 65%.

[0200] Examples 22 to 30

[0201] The reaction raw materials and products of Examples 22 to 30 can be referred to as shown in Table 3, and the specific synthesis method can be referred to Example 21.

[0202] Table 3 Reaction materials and products of Examples 22 to 30

[0203]

[0204] Example 31

[0205] Synthesis of compound 31

[0206]

[0207] Under an argon atmosphere, a reaction vessel was charged with 86.8 g (101 mmol) of compound 31-A, 35.9 g (100 mmol) of compound 31-B, 787 mg (1 mmol%) of XPhos Pd G3, 50 mL (300 mmol) of 1.5 M potassium phosphate, and 1000 mL of tetrahydrofuran (THF). The mixture was stirred under reflux for 12 hours. After cooling to room temperature, 800 mL of water was added. A large amount of solid precipitated and was filtered. The filter cake was washed three times with water and dried under vacuum. The crude product was purified by silica gel column chromatography (eluent: ethyl acetate / hexane) to obtain 72.2 g of compound 31, a yield of 63%, with an HPLC purity of 99.9%. LC MS: M / Z 1145.61 (M+).

[0208] Examples 32 to 40

[0209] The reaction raw materials and products of Examples 32 to 40 can be referred to as shown in Table 4, and the specific synthesis method can be referred to Example 31.

[0210] Table 4 Reaction materials and products of Examples 32 to 40

[0211]

[0212]

[0213] Device preparation example

[0214] The organic electroluminescent device is prepared using the compound of the present application as an electron transport material. In addition to the compound of the present application, other compounds involved are as follows:

[0215]

[0216] Example 41

[0217] refer to Figure 1 The method for preparing an organic electroluminescent device in this embodiment includes:

[0218] (1) A transparent anode ITO film layer (thickness 150 nm) was formed on a glass substrate 100 , and the glass substrate was ultrasonically cleaned with acetone, ethanol, and distilled water in sequence, and then treated with ozone plasma for 15 minutes to obtain a first electrode as the anode 110 .

[0219] (2) After the glass substrate 100 is mounted on the substrate holder of the vacuum vapor deposition equipment, the system pressure is controlled to 10 -6 On the surface of the anode 110 , HAT-CN with a thickness of 10 nm, TAPC with a thickness of 40 nm, and TCTA with a thickness of 10 nm are sequentially deposited to form a hole injection layer 120 , a hole transport layer 130 , and an electron blocking layer 140 , respectively.

[0220] (3) A light-emitting layer 150 with a thickness of 40 nm was evaporated on the electron blocking layer 140. The light-emitting layer 150 was composed of RH-1 and RD at a mass ratio of 94:6.

[0221] (4) Compound 1 prepared in Example 1 was evaporated on the light-emitting layer 150 to a thickness of 30 nm as the electron transport layer 160 .

[0222] (5) LiF was evaporated to a thickness of 1 nm on the electron transport layer 160 to form the electron injection layer 170 .

[0223] (6) Al with a thickness of 80 nm was evaporated on the electron injection layer 170 to form the cathode 180 , and the device was encapsulated using a glass encapsulation cap 190 .

[0224] Examples 42 to 50

[0225] An organic electroluminescent device was prepared by the same method as in Example 41, except that Compounds 2 to 10 prepared in Examples 2 to 10 were used instead of Compound 1 when forming the electron transport layer 160 .

[0226] Comparative Example 1

[0227] An organic electroluminescent device was prepared by the same method as in Example 41, except that compound ETL-1 was used instead of compound 1 when forming the electron transport layer 160.

[0228] The organic electroluminescent device prepared above was tested by a computer-controlled Keithley 2400 test system at a test current of 10 mA / cm 2 , the operating voltage and current efficiency are calculated.

[0229] The LT95 device lifetime under dark conditions was measured using a Flustar lifetime measurement system equipped with a power supply and a photodiode as a detection unit. The LT95 device lifetime is the time it takes for the luminance at initial brightness to decrease to 95% of its initial brightness. A longer time indicates a longer device lifetime.

[0230] Each group of devices of Examples and Comparative Examples were produced and tested in the same batch. The operating voltage, current efficiency, and LT95 life of the device of Comparative Example 1 were all recorded as 1. The ratios of the corresponding indicators of Examples 41 to 50 and Comparative Example 1 were calculated to obtain the relative operating voltage, relative current efficiency, and relative life as shown in Table 5.

[0231] Table 5 Test results of Examples 41 to 50 and Comparative Example 1

[0232] Device Electron transport layer materials Relative working voltage Relative current efficiency Relative lifespan Comparative Example 1 ETL-1 1 1 1 Example 41 Compound 1 0.956 1.187 1.356 Example 42 Compound 2 0.955 1.218 1.289 Example 43 Compound 3 0.946 1.201 1.432 Example 44 Compound 4 0.948 1.257 1.342 Example 45 Compound 5 0.967 1.289 1.280 Example 46 Compound 6 0.939 1.321 1.457 Example 47 Compound 7 0.948 1.267 1.310 Example 48 Compound 8 0.951 1.279 1.326 Example 49 Compound 9 0.969 1.335 1.475 Example 50 Compound 10 0.953 1.265 1.482

[0233] Compared with the organic electroluminescent device prepared in Comparative Example 1, the operating voltage of the organic electroluminescent device prepared using the compound of the present application as the electron transport material is reduced, and the current efficiency and device life are significantly improved.

[0234] The following organic electroluminescent devices are prepared using the compounds of the present application as hole transport materials. In addition to the compounds of the present application, other compounds involved are as follows:

[0235]

[0236] Example 51

[0237] refer to Figure 2 The method for preparing an organic electroluminescent device in this embodiment includes:

[0238] (1) A transparent anode ITO film layer (thickness 150 nm) is formed on a glass substrate 101 to obtain a first electrode as the anode 102 .

[0239] (2) A mixture of compound T-1 and compound T-2 was deposited on the surface of the anode 102 by vacuum evaporation as the hole injection layer 103 , with a mixing ratio of 3:97 (mass ratio) and a thickness of 10 nm.

[0240] (3) Compound T-2 was deposited on the hole injection layer 103 to a thickness of 100 nm to obtain the first hole transport layer 104 .

[0241] (4) Compound 11 prepared in Example 11 was evaporated onto the first hole transport layer 104 to a thickness of 10 nm to obtain a second hole transport layer 105 .

[0242] (5) On the second hole transport layer 105 , compound T-3 and compound T-4 were co-evaporated at a mass ratio of 95:5 to form an organic light-emitting layer 106 with a thickness of 40 nm.

[0243] (6) Compound T-5 was sequentially evaporated on the organic light-emitting layer 106 to form a hole blocking layer 107 (thickness 10 nm), and compound T-6 and LiQ with a mixing ratio of 4:6 (mass ratio) were formed into an electron transport layer 108 (thickness 30 nm).

[0244] (7) Magnesium (Mg) and silver (Ag) are mixed at a deposition rate of 1:9 and vacuum evaporated on the electron transport layer 108 to serve as the second electrode 109, thereby completing the manufacture of the organic electroluminescent device.

[0245] Examples 52 to 60

[0246] An organic electroluminescent device was prepared by the same method as in Example 51, except that compounds 12 to 20 prepared in Examples 12 to 20 were used instead of compound 11 when forming the second hole transport layer 105 .

[0247] Comparative Examples 2-3

[0248] An organic electroluminescent device was prepared by the same method as in Example 51, except that compound HT-1 and compound HT-2 were used instead of compound 11 when forming the second hole transport layer 105.

[0249] The organic electroluminescent devices prepared in Examples 51-60 and Comparative Examples 2-3 were tested using the same testing methods as described above to obtain the operating voltage, current efficiency, and LT95 values. The devices in each Example and Comparative Example were produced and tested in the same batch. The operating voltage, current efficiency, and lifetime of the device in Comparative Example 2 were all recorded as 1. The ratios of the corresponding indicators for Examples 51-60 and Comparative Example 3 to Comparative Example 2 were calculated, yielding the relative operating voltage, relative current efficiency, and relative lifetime shown in the following table.

[0250] Table 6 Test results of Examples 51 to 60 and Comparative Examples 2 to 3

[0251] Device Second hole transport layer material Relative working voltage Relative efficiency Relative lifespan Comparative Example 2 HT-1 1 1 1 Comparative Example 3 HT-2 1.091 1.056 1.447 Example 51 Compound 11 0.933 1.201 1.741 Example 52 Compound 12 0.945 1.190 1.654 Example 53 Compound 13 0.956 1.215 1.768 Example 54 Compound 14 0.948 1.256 1.697 Example 55 Compound 15 0.932 1.198 1.716 Example 56 Compound 16 0.955 1.187 1.669 Example 57 Compound 17 0.948 1.245 1.820 Example 58 Compound 18 0.950 1.251 1.775 Example 59 Compound 19 0.942 1.221 1.985 Example 60 Compound 20 0.940 1.249 1.663

[0252] Compared with the devices formed by using the compounds used in Comparative Examples 2 to 3 as hole transport materials, the devices prepared by using the compounds of the present application as hole transport materials have lower operating voltage, higher current efficiency and longer life.

[0253] The following organic electroluminescent devices are prepared using the compounds of the present application as blue light host materials. In addition to the compounds of the present application, other compounds involved are as follows:

[0254]

[0255] Example 61

[0256] refer to Figure 3 The method for preparing an organic electroluminescent device in this embodiment includes:

[0257] (1) A transparent anode ITO film layer (thickness 150 nm) is formed on a glass substrate 10 to obtain a first electrode as the anode 11 .

[0258] (2) Compound F4-TCNQ was evaporated on the surface of the anode 11 by vacuum evaporation to form a hole injection layer 12 with a thickness of 10 nm, and compound NPB was vacuum evaporated on the hole injection layer 12 to form a hole transport layer (HTL) 13 with a thickness of 110 nm.

[0259] (3) Compound EB-01 was evaporated to a thickness of 10 nm on the hole injection layer 13 to obtain the electron blocking layer 14 .

[0260] (4) Compound 21 prepared in Example 21 was used as the host material on the electron blocking layer 14 and doped with BD-1 at a film thickness ratio of 100:3 to form an emitting layer (EML) 15 with a thickness of 10 nm.

[0261] (5) ET-01 and LiQ were evaporated on the light-emitting layer 15 at a film thickness ratio of 1:1 to form an electron transport layer (ETL) 16 with a thickness of 30 nm, and Yb was evaporated on the electron transport layer 16 to form an electron injection layer (EIL) 17 with a thickness of 15 angstroms.

[0262] (6) Magnesium (Mg) and silver (Ag) were vacuum-deposited on the electron injection layer 17 at a film thickness ratio of 1:9 to form a cathode 18 with a thickness of 11 nm.

[0263] (7) CP-1 with a thickness of 65 nm was evaporated on the cathode 18 as an organic cover layer (CPL) 19 to complete the preparation of the organic electroluminescent device.

[0264] Examples 62 to 70

[0265] An organic electroluminescent device was prepared by the same method as in Example 61, except that Compounds 22 to 30 prepared in Examples 22 to 30 were used instead of Compound 21 when forming the light-emitting layer 15 .

[0266] Comparative Examples 4-5

[0267] An organic electroluminescent device was prepared by the same method as in Example 61, except that Compound BH-1 and Compound BH-2 were used instead of Compound 21 when forming the light-emitting layer 15.

[0268] The organic electroluminescent devices produced in Examples 61-70 and Comparative Examples 4-5 were tested using the same testing methods as described above to determine their operating voltage, current efficiency, and LT95. The devices in Examples 61-70 and Comparative Examples 4-5 were produced and tested in the same batch. The operating voltage, current efficiency, and lifetime of the device in Comparative Example 4 were all recorded as 1. The ratios of the corresponding indicators for Examples 61-70 and Comparative Example 5 were calculated to obtain the relative operating voltage, relative current efficiency, and relative lifetime shown in the table below.

[0269] Table 7 Test results of Examples 61 to 70 and Comparative Examples 4 to 5

[0270] Example Main material Relative working voltage Relative efficiency Relative lifespan CIE-x CIE-y Comparative Example 4 BH-1 1 1 1 0.14 0.05 Comparative Example 5 BH-2 1.089 0.978 1.050 0.14 0.05 Example 61 21 0.954 1.188 1.689 0.14 0.05 Example 62 22 0.940 1.204 1.359 0.14 0.05 Example 63 23 0.979 1.179 1.410 0.14 0.05 Example 64 24 0.954 1.189 1.298 0.14 0.05 Example 65 25 0.943 1.223 1.369 0.14 0.05 Example 66 26 0.946 1.195 1.410 0.14 0.05 Example 67 27 0.932 1.234 1.697 0.14 0.05 Example 68 28 0.931 1.219 1.389 0.14 0.05 Example 69 29 0.949 1.198 1.357 0.14 0.05 Example 70 30 0.951 1.235 1.298 0.14 0.05

[0271] Compared with the commercial products used in Comparative Examples 4 to 5, the devices formed using the compounds used in Examples 61 to 70 as the main material have lower operating voltage, higher current efficiency and longer device life, while also exhibiting color purity comparable to that of the commercial products.

[0272] The following organic electroluminescent devices are prepared using the compounds of the present application as blue light doping materials. In addition to the compounds of the present application, other compounds involved are as follows:

[0273]

[0274] Example 71

[0275] refer to Figure 4 The method for preparing an organic electroluminescent device in this embodiment includes:

[0276] (1) A 15Ω / cm 2 An ITO (anode 2) glass substrate 1 (Corning Incorporated) was cut into a size of 50 mm x 50 mm x 0.75 mm, and cleaned using acetone, isopropyl alcohol, and pure water, each subjected to ultrasonic treatment for 15 minutes, followed by ultraviolet irradiation and ozone exposure for 30 minutes. The resulting glass substrate 1 was then mounted on a vacuum deposition apparatus.

[0277] (2) HT-3 was vacuum deposited on the anode 2 to form a hole injection layer 3 having a thickness of 10 nm, and HT-47 was vacuum deposited on the hole injection layer 3 to form a hole transport layer 4 having a thickness of 120 nm.

[0278] (3) Compound BH-3 (host) and Compound 31 (dopant) prepared in Example 31 were vacuum deposited on the hole transport layer 4 at a weight ratio of 98:2 to form a light-emitting layer 5 with a thickness of 20 nm.

[0279] (4) ETL-1 was vacuum deposited on the light-emitting layer 5 to form an electron transport layer 6 with a thickness of 40 nm, and KI and Yb were vacuum deposited on the electron transport layer 6 at a weight ratio of 8:2 to form an electron injection layer 7 with a thickness of 1 nm. Ag and Mg were vacuum deposited on the electron injection layer 7 at a weight ratio of 90:10 to form a cathode 8 with a thickness of 10 nm, thereby completing the preparation of the organic electroluminescent device.

[0280] Examples 72 to 80

[0281] An organic electroluminescent device was prepared by the same method as in Example 71, except that compounds 32 to 40 prepared in Examples 32 to 40 were used instead of compound 31 when forming the light-emitting layer 5.

[0282] Comparative Examples 6-7

[0283] An organic electroluminescent device was prepared by the same method as in Example 71, except that compound BD-2 and compound BD-3 were used instead of compound 31 when forming the light-emitting layer 5.

[0284] The organic electroluminescent devices produced in Examples 71-80 and Comparative Examples 6-7 were tested using the same testing methods as described above to determine their operating voltage, current efficiency, and LT95. The devices in Examples 71-80 and Comparative Examples 6-7 were produced and tested in the same batch. The operating voltage, current efficiency, and lifetime of the device in Comparative Example 6 were all recorded as 1. The ratios of the corresponding indicators for Examples 71-80 and Comparative Example 7 were calculated to obtain the relative operating voltage, relative current efficiency, and relative lifetime shown in the table below.

[0285] Table 8 Test results of Examples 71 to 80 and Comparative Examples 6 to 7

[0286] Example Doping materials Relative working voltage Relative current efficiency Relative lifespan Comparative Example 6 BD-2:BH-3=2:98 1 1 1 Comparative Example 7 BD-3:BH-3=2:98 0.964 1.246 1.307 Example 71 Compound 31: BH-3 = 2:98 0.947 1.415 1.564 Example 72 Compound 32: BH-3 = 2:98 0.921 1.467 1.673 Example 73 Compound 33: BH-3 = 2:98 0.927 1.485 1.715 Example 74 Compound 34: BH-3 = 2:98 0.936 1.432 1.631 Example 75 Compound 35: BH-3 = 2:98 0.946 1.469 1.589 Example 76 Compound 36: BH-3 = 2:98 0.922 1.563 1.767 Example 77 Compound 37: BH-3 = 2:98 0.947 1.497 1.732 Example 78 Compound 38: BH-3 = 2:98 0.939 1.443 1.798 Example 79 Compound 39: BH-3 = 2:98 0.932 1.401 1.779 Example 80 Compound 40: BH-3 = 2:98 0.945 1.467 1.790

[0287] According to Table 8, the devices prepared in Examples 71 to 80 have lower operating voltage, higher current efficiency and longer service life compared with the devices prepared in Comparative Examples 6 to 7.

[0288] The above description of the embodiments is intended to facilitate understanding and application of the present application by those skilled in the art. It will be apparent that those skilled in the art can readily make various modifications to these embodiments and apply the general principles described herein to other embodiments without expending any creative effort. Therefore, the present application is not limited to the embodiments described herein, and improvements and modifications made by those skilled in the art based on the disclosure of this application without departing from the scope and spirit of this application are within the scope of this application.

Claims

1. An oxaspirobiindene compound, characterized in that Its structural formula is shown in Formula I: In the formula I, R is selected from the following substituted or unsubstituted groups: linear or branched C1-C60 alkyl, C3-C60 cycloalkyl, C1-C60 heteroalkyl, C1-C60 heterocycloalkyl, C6-C60 aryl, C3-C60 heteroaryl; m represents the number of R, and is selected from an integer of 0 to 8; R1 to R4 are independently selected from hydrogen, deuterium, deuterated methyl, substituted or unsubstituted following groups: linear or branched C1 to C60 alkyl, C3 to C60 cycloalkyl, C1 to C60 heteroalkyl, C1 to C60 heterocycloalkyl, C6 to C60 aryl, C3 to C60 heteroaryl.

2. The oxaspirobiindene compound according to claim 1, wherein The R is L1-EA; the structural formula of the oxaspirobiindene compound is shown in Formula II: In Formula II, L1 is selected from a single bond, a substituted or unsubstituted C6-C60 arylene group, or a substituted or unsubstituted C3-C60 heteroarylene group; EA is an electron-withdrawing group; and n represents the number of L1-EA and is an integer of 1 to 4.

3. The oxaspirobiindene compound according to claim 2, wherein The EA is Ar6 and Ar7 are independently selected from substituted or unsubstituted C6-C60 aryl groups, substituted or unsubstituted C3-C60 heteroaryl groups; and n is 1 or 2.

4. The oxaspirobiindene compound according to claim 3, wherein Ar6 and Ar7 are independently selected from the following substituted or unsubstituted groups: phenyl, naphthyl, biphenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, fluorenyl, spirofluorenyl, triphenylene, phenanthryl; L1 is selected from the following single bond, substituted or unsubstituted groups: phenylene, naphthyl, biphenylene, dibenzofuranyl, dibenzothiophenyl, carbazolyl, fluorenyl, triphenylene.

5. The oxaspirobiindene compound according to claim 4, wherein The oxaspirobiindene compound shown in Formula II is represented by any of the following structural formulas: In Formulae 1 to 70, R1 to R4 are independently selected from hydrogen, methyl, deuterated methyl, and phenyl; Ar7 is selected from phenyl, naphthyl, biphenyl, diphenylfuranyl, and 9,9-dimethylfluorenyl.

6. The oxaspirobiindene compound according to claim 5, wherein The oxaspirobiindene compound represented by formula II is selected from the following group:

7. The oxaspirobiindene compound according to claim 1, wherein The R is The structural formula of the oxaspirobiindene compound is shown in Formula III: In the formula III, L is selected from a single bond, a substituted or unsubstituted C6-C60 arylene group, or a substituted or unsubstituted C3-C60 heteroarylene group; Ar1 and Ar2 are independently selected from substituted or unsubstituted C6-C60 aryl groups, substituted or unsubstituted C3-C60 heteroaryl groups, or Ar1 and Ar2 are bonded to form a ring; n1 represents The number of is an integer from 1 to 4.

8. The oxaspirobiindene compound according to claim 7, wherein The structural formula of the oxaspirobiindene compound is shown in Formula IV or Formula V: Among them, Ar8~Ar 11 Independently selected from the following substituted or unsubstituted single groups or combinations of multiple groups:

9. The oxaspirobiindene compound according to claim 8, characterized in that The oxaspirobiindene compound represented by formula IV is represented by any of the following structural formulas: In formula 71 to formula 98, Ar9 is selected from R1 to R4 are independently selected from hydrogen, methyl, deuterated methyl, and phenyl.

10. The oxaspirobiindene compound according to claim 9, characterized in that The oxaspirobiindene compound represented by formula V is represented by any of the following structural formulas: In formulas 99 to 138, Ar 11 Selected from R1 to R4 are independently selected from hydrogen, methyl, deuterated methyl, and phenyl.

11. The oxaspirobiindene compound according to claim 10, characterized in that The oxaspirobiindene compound represented by formula V is selected from the following group:

12. The oxaspirobiindene compound according to claim 1, characterized in that The R is The structural formula of the oxaspirobiindene compound is shown in Formula VI: In the formula VI, L2 is selected from a single bond, a substituted or unsubstituted C6-C60 arylene group, or a substituted or unsubstituted C3-C60 heteroarylene group; Ar3 is selected from a substituted or unsubstituted C6-C60 aryl group and a substituted or unsubstituted C3-C60 heteroaryl group.

13. The oxaspirobiindene compound according to claim 12, characterized in that The Ar3 is independently selected from the following substituted or unsubstituted single groups or combinations of multiple groups:

14. The oxaspirobiindene compound according to claim 13, characterized in that The oxaspirobiindene compound represented by formula VI is selected from the following group:

15. An oxaspirobiindene compound, characterized in that Its structural formula is shown in Formula VII: In the formula VII, CyA, CyB, Ar4 and Ar5 are independently selected from substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl; R5 is selected from the following substituted or unsubstituted groups: linear or branched C1-C60 alkyl, C3-C60 cycloalkyl, C1-C60 heteroalkyl, C1-C60 heterocycloalkyl, C6-C60 aryl, C3-C60 heteroaryl; At least one of R5, CyA, CyB, Ar4 and Ar5 comprises Formula A, or the benzene ring connected to R5 forms a structure represented by Formula A with R5.

16. The oxaspirobiindene compound according to claim 15, wherein the oxaspirobiindene compound represented by formula VII is selected from the group consisting of:

17. An organic layer, characterized in that The invention comprises the oxaspirobiindene compound according to any one of claims 1 to 16.

18. Use of the oxaspirobiindene compound according to any one of claims 1 to 16 and / or the organic layer according to claim 17 in an organic electroluminescent device.

19. An organic electroluminescent device, characterized in that: The device comprises a first electrode, a second electrode and the organic layer according to claim 17, wherein the organic layer is at least one of a hole injection layer, a hole transport layer, a light emitting layer, an electron injection layer or an electron transport layer.

20. A display or lighting device, characterized in that: The organic electroluminescent device according to claim 19 is included.

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