Deuterated chiral luminescent material and application thereof

Abstract

The invention relates to the technical field of display, in particular to a deuterated chiral luminescent material and application thereof. According to the deuterated chiral luminescent material provided by the invention, the deuterated chiral luminescent material comprises an organic chiral luminescent compound subjected to at least partial deuteration, and the organic chiral luminescent compound is subjected to at least partial deuteration, so that circularly polarized light emission of the material can be enhanced; the luminous efficiency and the electroluminescent asymmetry factor of the circularly polarized organic electroluminescent device can be improved when the circularly polarized organic electroluminescent device is used in the device, so that the circularly polarized organic electroluminescent device can be better applied to the technical field of organic electroluminescence including 3D display equipment or virtual reality equipment.

Description

Technical Field

[0001] The present invention relates to the field of display technology, and in particular to a deuterated chiral luminescent material and application thereof. Background Art

[0002] Since the organic light-emitting diode (OLED) was proposed in the 1980s, it has been successfully commercialized through the continuous iteration of light-emitting materials and the continuous optimization of device structure. It has been widely recognized by the market for its excellent efficiency, lightness, thinness, wide viewing angle and other advantages, especially in the field of small size and low brightness display, such as smart watches, mobile phones and computer monitors. However, in high-brightness application fields, such as general lighting, outdoor display, transparent display and VR equipment, OLED technology is rarely used. This is mainly because in practical applications, OLED needs to introduce quarter-wave plates and polarizers to enhance the display effect, but at the same time it will cause the light output efficiency to be halved and the display brightness to be greatly reduced. When using a chiral light-emitting layer, the circularly polarized light emitted by the functional layer can effectively pass through the polarizer and quarter-wave plate, which is conducive to expanding the application of OLED in high-brightness fields.

[0003] At present, the research on circularly polarized OLEDs is mainly focused on the development of chiral luminescent molecules. In particular, the design strategies for chiral (Thermally activated delayed fluorescence, TADF) luminescent molecules mainly include the intrinsic chirality strategy and the chiral perturbation strategy. On the one hand, based on the intrinsic chirality strategy, although the relevant chiral TADF luminescent molecules can obtain a larger asymmetry factor, their molecular structure is composed of the hindered rotation of the luminescent group in three-dimensional space, which often increases the probability of material decomposition and device aging, and the luminescence efficiency is low due to the small electron-hole overlap during the radiation transition. On the other hand, based on the chiral perturbation strategy, although a higher luminescence efficiency can be guaranteed, the luminescence asymmetry factor of the relevant chiral luminophores is often small due to the long relative distance between the chiral unit and the luminescent group.

[0004] In summary, there is an urgent need in the prior art for materials that can simultaneously achieve high efficiency and a large asymmetry factor in circularly polarized organic electroluminescent devices. Summary of the invention

[0005] The purpose of the present invention is to overcome the lack of materials in the related art that simultaneously achieve high efficiency and large asymmetry factor of circularly polarized organic electroluminescent devices, resulting in low light extraction efficiency and low display brightness of organic electroluminescent devices containing the organic electroluminescent materials, and further provide a deuterated chiral luminescent material and its application.

[0006] The scheme adopted by the present invention is as follows:

[0007] The present invention provides a deuterated chiral luminescent material, which comprises an organic chiral luminescent compound which has been at least partially deuterated.

[0008] Preferably, the at least partially deuterated organic chiral luminescent compound is a circularly polarized thermally activated delayed fluorescent material, and its singlet energy level S 1 With triplet energy level T 1 The energy level difference ΔE ST Less than or equal to 300meV;

[0009] The photoluminescence asymmetry factor is 10 -4 ~10 -2 between;

[0010] Preferably, the energy level difference ΔE ST Less than or equal to 200meV, photoluminescence asymmetry factor greater than or equal to 10 -3 .

[0011] Preferably, the at least partially deuterated organic chiral luminescent compound has the following structure before being deuterated:

[0012]

[0013] Among them, R 1 -R 12 Each independently selected from cyano, or substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C6-C20 aryl; n 1 -n 12 are the numbers of the corresponding groups, and their corresponding values ​​are integers between 0 and the maximum number of the corresponding groups;

[0014] Me is selected from Au or Cu;

[0015] Wherein, the substituents in the substituted C1-C30 alkyl group and the substituted C6-C20 aryl group are selected from deuterium and cyano.

[0016] It can be understood that the organic chiral luminescent compound that has been at least partially deuterated, for example,

[0017]

[0018] n2 represents, R 2 The maximum value of n2 is R 2 The number of substitutable positions on the ring is 2;

[0019] The organic chiral luminescent compound which has been at least partially deuterated and has the structure of Formula 3 before being deuterated is substituted by replacing hydrogen on ring a, ring b, ring c, and ring d with deuterium to obtain a partially deuterated compound having the structure of Formula 3:

[0020]

[0021] For the compounds having the structures of Formulae 1 to 7, the hydrogen therein is replaced by deuterium, that is, the compounds are at least partially deuterated.

[0022] In the present invention:

[0023] alkyl

[0024] In the present application, the term "alkyl" refers to a saturated hydrocarbon group, whether used as part of other terms or alone, which can be straight or branched. The term "C1-C30 alkyl" is derived from a monovalent substituent of a straight or branched saturated hydrocarbon having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms, of course, examples thereof include but are not limited to methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl and hexyl.

[0025] Aryl

[0026] In the present application, the term "aryl" includes monocyclic, polycyclic or condensed-ring aromatic groups, the rings may be interrupted by short non-aromatic units, and may contain spiro structures. Aryl groups include but are not limited to phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthracenyl, fluorenyl, spirobifluorenyl, etc., and arylene groups include but are not limited to phenylene, biphenylene, terphenylene, naphthylene, phenanthrylene, anthracenyl, fluorenyl, spirobifluorenyl, etc., wherein arylene groups refer to divalent or polyvalent groups formed by further losing one or more hydrogen atoms of aryl.

[0027] Preferably, R 1 -R 12 Each independently selected from cyano, or substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C6-C15 aryl;

[0028] Wherein, the substituents in the substituted C1-C10 alkyl and substituted C6-C15 aryl are selected from deuterium and cyano;

[0029] Preferably, R 1 -R 12 Each independently selected from cyano, substituted or unsubstituted A group, A group includes: phenyl, naphthyl, methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl or hexyl;

[0030] wherein the substituent of the substituted A group is selected from deuterium and cyano;

[0031] Preferably, the at least partially deuterated organic chiral luminescent compound contains at least 3 deuteriums.

[0032] Preferably, the deuterated chiral luminescent material comprises at least two organic chiral luminescent compounds which are at least partially deuterated, wherein one is a guest material and the other is a host material.

[0033] Preferably, the mass ratio of the guest material to the host material is (0.1-20):(80:99.9);

[0034] Preferably, the at least partially deuterated organic chiral light-emitting compound has the following structure:

[0035]

[0036]

[0037] Among them, R p / S p -I-PC1, R p / S p -I-PC2, R p / S p -I-PC3 and R p / S p -I-PC4 has a planar chiral structure, which constructs chirality through two asymmetric non-coplanar rings; R / SI-CC1, R / SI-CC2, R / SI-CC3, R / SI-CC4, R / SI-CC5, R / SI-CC6, R / SI-CC7, R / SI-CC8, R / SI-Au1, R / SI-Au2, R / SI-Cu1 and R / SI-Cu2 have point chiral structures, which construct chirality through the presence of chiral stereocenters; R / SI-AC1, R / SI-AC2, R / SI-AC3, R / SI-AC4, R / SI -AC5, R / SI-AC6, R / SI-AC7, and R / SI-AC8 have axial chiral structures, which construct chirality through the existence of chiral axes; P / MI-HC1, P / MI-HC2, P / MI-HC3, P / MI-HC4, P / MI-HC5, P / MI-HC6, and P / MI-HC7 have spiral chiral structures, which construct chirality through the spiral of the condensed ring structure; P / MI-TC1 and P / MI-TC2 have topological chiral structures, which cannot be converted into their mirror structures through continuous deformation in three-dimensional space to construct chirality due to the special connection method of chemical bonds.

[0038] The non-deuterated compounds corresponding to the above-mentioned specific deuterated compounds are all existing materials or can be prepared by simply replacing the raw materials on the basis of existing materials.

[0039] The preparation of a specific deuterated compound can be obtained by replacing the corresponding fragment with the corresponding deuterated fragment.

[0040] Specifically, in the present invention, the synthesis of part of the first material is carried out by PtO 2 The catalytic HD isotope exchange reaction synthesizes the core deuterated fragment (such as deuterated carbazole and deuterated benzene ring), which is then synthesized with another deuterated fragment or a non-deuterated fragment through CN coupling or CC coupling reaction.

[0041] The synthesis of deuterated carbazole is as follows:

[0042] Synthesis route:

[0043]

[0044] Specific synthesis steps: Take a Teflon reaction cup, add platinum dioxide (0.34g, 1.5mmol), carbazole (5.0g, 29.9mmol), and then add 100mL of heavy water as the reaction solvent. Put the Teflon reaction cup into the high-pressure reactor and lock it, replace the vacuum / hydrogen five times, and heat to 250℃ for 10h. After returning to room temperature, the reaction system is extracted three times with dichloromethane, and then anhydrous Na 2 SO 4 The product was dried and spin-dried, and deuterated carbazole (4.9 g, 93.5%, 99% D) was obtained by silica gel column chromatography.

[0045] The synthesis of deuterated tert-butylcarbazole is as follows:

[0046] Synthesis route:

[0047]

[0048] Specific synthesis steps: Take a Teflon reaction cup, add platinum dioxide (0.34g, 1.5mmol), carbazole (8.3g, 29.9mmol), and then add 100mL of heavy water as the reaction solvent. Put the Teflon reaction cup into the high-pressure reactor and lock it, replace the vacuum / hydrogen five times, and heat to 250℃ for 10h. After returning to room temperature, the reaction system is extracted three times with dichloromethane, and then anhydrous Na 2 SO 4 The residue was dried and spin-dried, and then chromatographed on a silica gel column to obtain deuterated tert-butylcarbazole (8.5 g, 93.5%, 99% D).

[0049] The synthesis of deuterated benzene ring is as follows:

[0050] Synthesis route:

[0051]

[0052] Specific synthesis steps: Take a Teflon reaction cup, add benzene (1.0 g, 12.81 mmol) and 10% Pd / 90% C (100 mg), then add 19 mL of heavy water (D 2 O) as the reaction solvent. Place the Teflon reaction cup into the high-pressure reactor and lock it, replace the vacuum / hydrogen five times, heat to 170°C, and react for 16 hours. After the reaction is completed, turn off the heater, wait for the temperature to return to room temperature, open the high-pressure reactor, take out the Teflon reaction cup, filter the catalyst by gravity, and extract it twice with ethyl acetate and water. Collect the organic layer and precipitate it with anhydrous MgSO 4 After removing water and concentrating under reduced pressure to remove the solvent, white solid deuterated benzene (862 mg, 10.25 mmol) was obtained with a yield of 80%.

[0053] The synthesis of deuterated iodobenzene is as follows:

[0054] Synthesis route:

[0055]

[0056] Specific synthesis steps: Take a round-bottom flask, add deuterated benzene (0.6 g, 7.14 mmol) and NIS (3.3 g, 14.87 mmol), dissolve in AcOH and add a few drops of H 2 SO 4 The mixture was heated to reflux under N2 for 8 h. After the reaction was confirmed by TLC, the reaction solvent was removed in vacuo, and the mixture was extracted twice with ethyl acetate and water. The organic layer was collected and concentrated with anhydrous MgSO 4 After removing water, the solvent was removed by vacuum concentration, and finally column chromatography was used to separate (SiO 2 , EA / hexane=1:5), then white solid deuterated iodobenzene (1.28 g, 6.14 mmol) was obtained with a yield of 86%.

[0057] The present invention also provides a deuterated chiral luminescent material composition, which comprises a first material and a second material; wherein the deuterated chiral luminescent material described in the above item; the second material comprises a non-deuterated non-chiral compound.

[0058] Preferably, when the first material is a host material, the second material is a guest material;

[0059] Preferably, the second material is selected from phosphorescent materials, or conventional fluorescent dyes, or multi-resonance thermally activated delayed fluorescent materials;

[0060] Preferably, the mass ratio of the first material to the second material is (50-99.9):(0.1-50);

[0061] Preferably, the mass ratio of the first material to the second material is (80-99.9):(0.1-20).

[0062] Preferably, when the first material is a guest material, the second material is a host material;

[0063] Preferably, the second material is selected from hole-type materials, electron-type materials, or bipolar materials, or bipolar materials formed by a combination of hole-type materials and electron-type materials;

[0064] Preferably, the mass ratio of the first material to the second material is (0.1-50):(50-99.9);

[0065] Preferably, the mass ratio of the first material to the second material is (0.1-20):(80-99.9).

[0066] Preferably, the second material has a structure as shown below:

[0067]

[0068]

[0069]

[0070] In the present invention, the second material is an existing material, and part of the second material is prepared or combined by referring to the methods in the following documents:

[0071] 1.Hu YX, et al. Efficient selenium-integrated TADF OLEDs with reducedroll-off. Nat. Photon. 16, 803-810 (2022).

[0072] 2.Sun J, et al. Exceptionally stable blue phosphorescent organic light-emitting diodes. Nat. Photon. 16, 212-218 (2022).

[0073] 3. Zhang Y, et al. Multi-Resonance Deep-Red Emitters with ShallowPotential-Energy Surfaces to Surpass Energy-Gap Law. Angew. Chem. Int. Ed. 60, 20498 (2021).

[0074] 4.Tuong Ly, et al. Near-infrared organic light-emitting diodes with very high external quantum efficiency and radiance. Nat. Photon. 11, 63-68 (2017)

[0075] 5.Zhang D,et al.Highly Efficient Full-Color Thermally ActivatedDelayed Fluorescent Organic Light-Emitting Diodes:Extremely Low EfficiencyRoll-Off Utilizing a Host with Small Singlet-Triplet Splitting.ACSAppl.Mater.Interfaces.9,4769-4777(2017)

[0076] The present invention also provides a circularly polarized organic electroluminescent device, wherein the circularly polarized organic electroluminescent device comprises the above-mentioned deuterated chiral luminescent material or the above-mentioned deuterated chiral luminescent material composition;

[0077] Preferably, the circularly polarized organic electroluminescent device comprises a light-emitting layer; the light-emitting layer comprises the above-mentioned deuterated chiral light-emitting material or the above-mentioned deuterated chiral light-emitting material composition;

[0078] Preferably, the light-emitting layer has a thickness of 5-100 nm;

[0079] Preferably, the light-emitting layer has a thickness of 20-50 nm.

[0080] Preferably, the circularly polarized organic electroluminescent device comprises a substrate, an anode, a cathode and organic functional layers in both stages.

[0081] Preferably, the organic functional layer comprises a hole injection layer (HIL), a hole transport layer (HTL), a chiral light emitting layer (chiral EML) and an electron transport layer (ETL);

[0082] Preferably, a hole blocking layer (HBL) is further included between the chiral light-emitting layer and the electron transport layer;

[0083] Preferably, an electron blocking layer (EBL) is further included between the hole transport layer and the chiral light-emitting layer;

[0084] The selection of materials for each functional layer is described below.

[0085] The substrate of the circularly polarized organic electroluminescent device can be selected from but not limited to glass, a flexible plastic substrate, etc. The embodiments in this patent all use glass as the substrate.

[0086] The anode is preferably made of a material with high work function and transmittance, such as indium tin oxide (ITO), indium zinc oxide (IZO), etc. The embodiments of the present invention all use ITO as the anode material.

[0087] The cathode preferably has a material with a low work function, and is preferably an active metal with a low work function, such as aluminum (Al), calcium (Ca), silver (Ag), lithium (Li), magnesium (Mg) or any combination of alloys. In particular, a layer of insulating material, such as lithium fluoride (LiF), cesium fluoride (CsF), rubidium fluoride (RbF), etc., can be added between the electron transport layer and the cathode to form a double electrode with the metal, further improving the injection efficiency.

[0088] There is no clear limitation on the hole injection layer (HIL), hole transport layer (HTL), electron blocking layer (EBL), hole blocking layer (HBL), and electron transport layer (ETL). Existing material systems or newly developed materials can be used to improve the injection and transport performance of the device. Material combinations that can achieve carrier balance are particularly preferred.

[0089] The chiral EML can be a layer of multiple materials co-evaporated, or they can be evaporated separately to form a multi-layer composite light-emitting layer. However, regardless of whether it is a single layer or a multi-layer structure, the light-emitting layer region must contain at least the following functional materials: First, a chiral host material with thermally activated delayed fluorescence as the main carrier for carrier transfer and exciton recombination, which can be in the form of a single molecule or an exciton complex. Preferably, the photoinduced quantum efficiency does not decrease significantly with the increase of the doping concentration of the material in the film, and particularly preferably, a circularly polarized TADF material whose PLQY can exceed 80% in the pure film state; second, a phosphorescent material with fast intersystem crossing (ISC) as a non-chiral phosphorescent guest, preferably a material with heavy atoms (such as sulfur, selenium, noble metals, etc.), and particularly preferably a room temperature phosphorescent material containing noble metals such as iridium and platinum; third, a material with a high radiative transition rate (k r >10 7 s -1 ) as non-chiral fluorescent objects, such as traditional fluorescence, BODIPY and multiple resonance (MR) based fluorescence or thermally activated delayed fluorescence materials, including boron-containing or boron-free dyes. In a specific embodiment of the present invention, MR dyes represented by II-MR1 are selected for device preparation, which has verified the rationality of the deuterated chiral light-emitting layer composition emphasized in the invention for improving device efficiency and asymmetry factor.

[0090] Beneficial effects of the present invention:

[0091] The present invention provides a deuterated chiral luminescent material, which includes an organic chiral luminescent compound that has been at least partially deuterated; the organic chiral luminescent compound is at least partially deuterated, so that the circularly polarized light emission of the material can be enhanced, thereby improving the luminous efficiency and electroluminescent asymmetry factor of the circularly polarized organic electroluminescent device used in the device, and thus being better applied to the field of organic electroluminescent technology including 3D display devices or virtual reality devices. BRIEF DESCRIPTION OF THE DRAWINGS

[0092] In order to more clearly illustrate the specific implementation methods of the present invention or the technical solutions in the prior art, the drawings required for use in the specific implementation methods or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some implementation methods of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0093] Figure 1 A structural diagram of a circularly polarized organic light emitting diode in an embodiment of the device of the present invention;

[0094] Among them, 1-substrate, 2-anode; 3-hole injection layer; 4-hole transport layer; 5-electron blocking layer; 6-chiral light-emitting layer; 7-hole blocking layer; 8-electron transport layer; 9-electron injection layer; 10-cathode.

[0095] Figure 2 The graphs are graphs showing the change in quantum efficiency versus brightness of device Example 9 and device Comparative Example 6 of the present invention;

[0096] Figure 3 Circularly polarized electroluminescence spectra of device Example 9 and device Comparative Example 6 of the present invention;

[0097] Figure 4 This is a test graph of the electroluminescent asymmetry factor of device Example 9 and device Comparative Example 6 of the present invention. DETAILED DESCRIPTION

[0098] The following examples are provided for a better understanding of the present invention, but are not intended to limit the best mode of implementation, nor to limit the content and protection scope of the present invention. Any product identical or similar to the present invention obtained by anyone under the inspiration of the present invention or by combining the features of the present invention with other prior arts shall fall within the protection scope of the present invention.

[0099] If no specific experimental steps or conditions are specified in the examples, the conventional experimental steps or conditions described in the literature in the field can be used. If no manufacturer is specified for the reagents or instruments used, they are all conventional reagent products that can be obtained commercially.

[0100] Example 1

[0101] This embodiment provides a deuterated chiral luminescent material composition, which includes a deuterated chiral luminescent material having the following formula R p / S p -A first material having an I-PC1 structure (planar chirality, partial deuteration) and a second material having the following II-Ir1 structure (achiral, non-deuteration), the mass ratio of the first material to the second material being 90:10.

[0102]

[0103] Example 2

[0104] This embodiment provides a deuterated chiral luminescent material composition, which includes a deuterated chiral luminescent material having the following formula R p / S p -A first material with an I-PC2 structure (planar chirality, partial deuteration) and a second material with the following II-Ir1 structure (achiral, non-deuteration), the mass ratio of the first material to the second material is 90:10.

[0105]

[0106] Example 3

[0107] This embodiment provides a deuterated chiral luminescent material composition, which includes a deuterated chiral luminescent material having the following formula R p / S p -A first material with an I-PC3 structure (planar chirality, partial deuteration) and a second material with the following II-Ir1 structure (achiral, non-deuteration), the mass ratio of the first material to the second material is 90:10.

[0108]

[0109] Example 4

[0110] This embodiment provides a deuterated chiral luminescent material composition, which includes a first material (point chirality, partial deuteration) having the following R / SI-CC1 structure and a second material (non-chiral, non-deuteration) having the following II-Pt1 structure, and the mass ratio of the first material to the second material is 90:10.

[0111]

[0112] Example 5

[0113] This embodiment provides a deuterated chiral luminescent material composition, which includes a first material (point chirality, partial deuteration) having the following structure R / SI-CC3 and a second material (non-chiral, non-deuteration) having the following structure II-Pt1, and the mass ratio of the first material to the second material is 90:10.

[0114]

[0115] Example 6

[0116] This embodiment provides a deuterated chiral luminescent material composition, which includes a first material (point chirality, all deuterated) having the following structure R / SI-CC8 and a second material (non-chiral, non-deuterated) having the following structure II-Pt1, and the mass ratio of the first material to the second material is 90:10.

[0117]

[0118] Example 7

[0119] This embodiment provides a deuterated chiral luminescent material composition, which includes a first material (axial chirality, partial deuteration) having the following R / SI-AC1 structure and a second material (non-chiral, non-deuteration) having the following II-F11 structure, and the mass ratio of the first material to the second material is 99:1.

[0120]

[0121] Example 8

[0122] This embodiment provides a deuterated chiral luminescent material composition, which includes a first material (axial chirality, partial deuteration) having the following R / SI-AC3 structure and a second material (non-chiral, non-deuteration) having the following II-F11 structure, and the mass ratio of the first material to the second material is 99:1.

[0123]

[0124] Example 9

[0125] This embodiment provides a deuterated chiral luminescent material composition, which includes a first material (axial chirality, partial deuteration) having the following structure R / SI-AC6 and a second material (non-chiral, non-deuteration) having the following structure II-MR3, and the mass ratio of the first material to the second material is 99:1.

[0126]

[0127] Example 10

[0128] This embodiment provides a deuterated chiral luminescent material composition, which includes a first material (axial chirality, fully deuterated) having the following structure R / SI-AC8 and a second material (non-chiral, non-deuterated) having the following structure II-F11, and the mass ratio of the first material to the second material is 99:1.

[0129]

[0130] Embodiment 11

[0131] This embodiment provides a deuterated chiral luminescent material composition, which includes a first material (spiro chirality, all deuterated) having the following structure P / MI-HCl and a second material (non-chiral, non-deuterated) having the following structure II-MR1, and the mass ratio of the first material to the second material is 99:1.

[0132]

[0133] Example 12

[0134] This embodiment provides a deuterated chiral luminescent material composition, which includes a first material (spiro chirality, partially deuterated) having the following structure P / MI-HC2 and a second material (non-chiral, non-deuterated) having the following structure II-MR1, and the mass ratio of the first material to the second material is 99:1.

[0135]

[0136] Embodiment 13

[0137] This embodiment provides a deuterated chiral luminescent material composition, which includes a first material (spiro chirality, all deuterated) having the following structure P / MI-HC4 and a second material (non-chiral, non-deuterated) having the following structure II-MR1, and the mass ratio of the first material to the second material is 99:1.

[0138]

[0139] Embodiment 14

[0140] This embodiment provides a deuterated chiral luminescent material composition, which includes a first material (axial chirality, partial deuteration) having the following R / SI-Aul structure and a second material (non-chiral, non-deuteration) having the following II-MR2 structure, and the mass ratio of the first material to the second material is 99:1.

[0141]

[0142] Embodiment 15

[0143] This embodiment provides a deuterated chiral luminescent material composition, which includes a first material (axial chirality, partial deuteration) having a structure of the following formula R / SI-Cu1 and a second material (non-chiral, non-deuteration) having a structure of the following formula II-MR4, and the mass ratio of the first material to the second material is 99:1.

[0144]

[0145] Example 16

[0146] This embodiment provides a deuterated chiral luminescent material composition, which includes a first material (topological chirality, partial deuteration) having a structure of the following formula P / MI-TC1 and a second material (non-chiral, non-deuteration) having a structure of the following formula II-MR5, and the mass ratio of the first material to the second material is 99:1.

[0147]

[0148] Embodiment 17

[0149] This embodiment provides a deuterated chiral luminescent material composition, which includes a first material (topological chirality, partial deuteration) having the following P / MI-TC2 structure and a second material (non-chiral, non-deuteration) having the following II-MR5 structure, and the mass ratio of the first material to the second material is 99:1.

[0150]

[0151] Embodiment 18

[0152] This embodiment provides a deuterated chiral luminescent material composition, which includes a first material (spiro chirality, partially deuterated) having a structure of the following formula P / MI-HC5 and a second material (non-chiral, non-deuterated) having a structure of the following formula II-H1, and the mass ratio of the first material to the second material is 1:99.

[0153]

[0154] Embodiment 19

[0155] This embodiment provides a deuterated chiral luminescent material composition, which includes a first material (spiro chirality, all deuterated) having the following structure P / MI-HC7 and a second material (non-chiral, non-deuterated) having the following structure II-H1, and the mass ratio of the first material to the second material is 1:99.

[0156]

[0157] Embodiment 20

[0158] This embodiment provides a deuterated chiral luminescent material, wherein there is and only includes a material having the following formula Rp / Sp - Materials with I-PC1 structure (planar chirality, partial deuteration).

[0159]

[0160] Comparative Example 1

[0161] This comparative example provides a luminescent material composition, which includes a second material (non-chiral, non-deuterated) having the following structures of formula II-H1 and II-Irl, with a mass ratio of 90:10.

[0162]

[0163] Comparative Example 2

[0164] This comparative example provides a luminescent material composition, wherein there is and only includes a material having the following structure I-PC1-H (planar chirality).

[0165]

[0166] Comparative Example 3

[0167] This comparative example provides a luminescent material composition, including a material having a structure of formula I-PC1-H (planar chirality) and a second material (non-chiral, non-deuterated) having a structure of formula II-Ir1, wherein the mass ratio of the material having a structure of formula I-PC1-H (planar chirality) to the second material is 90:10.

[0168]

[0169] Comparative Example 4

[0170] This comparative example provides a luminescent material composition, which includes a material having a structure of the following formula I-CC1-H (point chirality) and a second material having a structure of the following formula II-Pt1 (non-chiral, non-deuterated), and the mass ratio of the material having a structure of the following formula I-CC1-H and the second material is 90:10.

[0171]

[0172] Comparative Example 5

[0173] This comparative example provides a luminescent material composition, which includes a material having a structure of the following formula I-AC1-H (axial chirality) and a second material having a structure of the following formula II-F11 (non-chiral, non-deuterated), and the mass ratio of the material having a structure of the following formula I-AC1-H and the second material is 99:1.

[0174]

[0175] Comparative Example 6

[0176] This comparative example provides a luminescent material composition, which includes a material having a structure of the following formula I-AC6-H (axial chirality) and a second material having a structure of the following formula II-MR3 (non-chiral, non-deuterated), and the mass ratio of the material having a structure of the following formula I-AC5-H and the second material is 99:1.

[0177]

[0178] Comparative Example 7

[0179] This comparative example provides a luminescent material composition, which includes a material having a structure of the following formula I-HC1-H (spiro chirality) and a second material having a structure of the following formula II-MR1 (non-chiral, non-deuterated), and the mass ratio of the material having a structure of the following formula I-HC1-H to the second material is 99:1.

[0180]

[0181] Comparative Example 8

[0182] This comparative example provides a luminescent material, which includes a material having a structure of the following formula I-Au1-H (axial chirality) and a second material having a structure of the following formula II-MR2 (non-chiral, non-deuterated), and the mass ratio of the material having a structure of the following formula I-Au1-H and the second material is 99:1.

[0183]

[0184] Comparative Example 9

[0185] This comparative example provides a luminescent material composition, which includes a material having a structure of the following formula I-Cu1-H (axial chirality) and a second material having a structure of the following formula II-MR4 (non-chiral, non-deuterated), and the mass ratio of the material having a structure of the following formula I-Cu1-H and the second material is 99:1.

[0186]

[0187] Comparative Example 10

[0188] This comparative example provides a luminescent material composition, which includes a material having a structure of the following formula I-TC1-H (spiro chirality) and a second material having a structure of the following formula II-MR5 (non-chiral, non-deuterated), and the mass ratio of the material having a structure of the following formula I-TC1-H and the second material is 99:1.

[0189]

[0190] Comparative Example 11

[0191] This comparative example provides a luminescent material composition, which includes a material having a structure of the following formula I-HC5-H (spiro chirality) and a second material having a structure of the following formula II-H1 (non-chiral, non-deuterated), and the mass ratio of the material having a structure of the following formula I-HC5-H to the second material is 1:99.

[0192]

[0193] Material performance test:

[0194] The singlet energy level S of the chiral material in the device embodiment and the device comparison example is tested. 1 With triplet energy level T 1 The energy level difference ΔE ST and the photoluminescence asymmetry factor, ΔE ST The test material was fixed at a concentration of 1.0×10 -5 mol / L) toluene solution to obtain S 1 , the test material is a fixed concentration (1.0×10 -5 mol / L) toluene solution to obtain T 1 , S 1 and T 1 The difference is ΔE ST ;

[0195] The photoluminescence asymmetry factor was measured by JASCO CPL-300 spectrophotometer and further calculated. The sample was fixed concentration (1.0×10 -5 mol / L) toluene solution, the test temperature was room temperature; the test results are shown in Table 1.

[0196] Device Embodiment

[0197] Device Example 1

[0198] This embodiment provides a circularly polarized organic electroluminescent device, such as Figure 1 As shown, it includes a substrate 1, an anode 2, a hole injection layer 3, a hole transport layer 4, an electron blocking layer 5, a chiral light-emitting layer 6, a hole blocking layer 7, an electron transport layer 8, an electron injection layer 9, and a cathode 10 which are stacked in sequence.

[0199] The preparation of the circularly polarized organic electroluminescent device comprises the following steps:

[0200] 1) Substrate cleaning:

[0201] The glass substrate coated with transparent ITO was cleaned with surfactant and deionized water and dried before use, and activated in ultraviolet and ozone environment for 10 minutes before use:

[0202] 2) Preparation of organic layer:

[0203] Transfer the ITO transparent substrate to the evaporation equipment and evacuate the vacuum to less than 10 -4 Pa, after the vacuum degree is maintained for 20 minutes, The hole injection layer is evaporated onto the ITO surface at an evaporation rate of ;

[0204] On the hole injection layer Evaporating the hole transport layer at a speed of

[0205] On the hole transport layer The electron blocking layer is evaporated at a rate of

[0206] On the electron blocking layer The chiral light-emitting layer is evaporated at a speed of

[0207] On the chiral light-emitting layer The hole blocking layer is evaporated at a rate of

[0208] On the hole blocking layer The electron transport layer is evaporated at a rate of

[0209] On the electron transport layer The electron injection layer is evaporated at a rate of

[0210] On the electron injection layer The cathode is evaporated at a rate of .

[0211] in:

[0212] The anode is indium tin oxide (ITO, thickness 200 nm);

[0213] The material of the hole injection layer is HATCN (thickness 5 nm);

[0214] The material of the hole transport layer is TAPC (thickness 30 nm);

[0215] The electron blocking layer material is TCTA (thickness 15nm)

[0216] The thickness of the chiral light-emitting layer material is 55 nm, and the materials are shown in Table 1

[0217] The hole blocking layer material is POT2T (thickness 20nm)

[0218] The electron transport layer material is ANT-BIZ (thickness 30nm)

[0219] The electron injection layer material is Liq (thickness 2nm)

[0220] The cathode material is aluminum (Al, thickness 100 nm).

[0221] The structures of device embodiments 2-18 and device comparative examples 1-9 are similar to those of device embodiment 1, except that the chiral light-emitting layer materials are different, as shown in Table 1:

[0222] Table 1

[0223]

[0224]

[0225]

[0226] The embodiments refer to device embodiments, and the comparative examples refer to device comparative examples; wherein the compounds having structures of II-H1, I-CC1-H, I-AC1-H, I-HCl-H, I-PC1-H, I-PC1-H, I-AC6-H, I-Aul-H, I-Cul-H, I-TC1-H, and I-HC5-H are all existing compounds in the prior art, or compounds that can be prepared by conventional methods;

[0227] The materials used to prepare the above device examples or device comparative examples are shown in Table 2 below:

[0228] Table 2

[0229]

[0230] Device Test Case

[0231] The circularly polarized organic electroluminescent devices of device examples 1 to 20 and the organic electroluminescent devices obtained from device comparative examples 1 to 11 in the device examples were tested.

[0232] The relationship between quantum efficiency and brightness, maximum external quantum efficiency EQE max The circularly polarized electroluminescence spectrum and electroluminescence asymmetry factor gEL were obtained by a JASCO CPL-300 instrument. The test results are shown in Table 3 and Figure 2-4 , Figure 2 The quantum efficiency of the device embodiment and the device comparison example varies with brightness. Figure 3 Circularly polarized electroluminescence spectra of device examples and device comparison examples, Figure 4 Electroluminescence asymmetry factor test graph of the device example and the device comparative example.

[0233] Table 3

[0234] project <![CDATA[EQE max (%)]]> <![CDATA[g EL (×10 -3 ) <!-- 26 -->]]> Example 1 26.1 1.1 Example 2 24.4 1.0 Example 3 28.5 2.2 Example 4 23.8 2.0 Example 5 24.6 2.3 Example 6 29.6 3.3 Example 7 23.2 2.6 Example 8 29.3 2.8 Example 9 37.7 4.6 Example 10 40.3 5.2 Embodiment 11 24.6 2.2 Example 12 18.5 1.5 Embodiment 13 26.6 2.0 Embodiment 14 25.8 1.2 Embodiment 15 22.3 1.0 Example 16 22.6 9.2 Embodiment 17 25.4 10.0 Embodiment 18 40.9 5.8 Embodiment 19 42.5 7.6 Embodiment 20 25.6 1.3 Comparative Example 1 26.3 0.0 Comparative Example 2 17.0 0.6 Comparative Example 3 20.4 0.8 Comparative Example 4 19.8 1.3 Comparative Example 5 19.1 1.2 Comparative Example 6 26.3 1.9 Comparative Example 7 13.6 1.1 Comparative Example 8 15.4 0.6 Comparative Example 9 13.2 0.5 Comparative Example 10 12.8 7.6 Comparative Example 11 35.5 4.9

[0235] As can be seen from Table 3, the device embodiments provided by the present invention have significantly improved device efficiency and electroluminescent asymmetry factor compared with the corresponding device comparison examples; and with the increase in the number of deuterated generations of the chiral material, the device efficiency and the electroluminescent asymmetry factor are significantly improved, achieving a breakthrough in the coexistence of high device efficiency and large electroluminescent asymmetry factor.

[0236] The quantum efficiency of device example 9 and device comparative example 6 varies with brightness as shown in FIG. Figure 2 As shown, the circularly polarized electroluminescence of device example 9 and device comparative example 6 is as follows Figure 3 As shown, the electroluminescent asymmetric factors of device example 9 and device comparative example 6 are as follows Figure 4 shown.

[0237] from Figure 2 It can be seen that the device external quantum efficiency of the device embodiment 9 based on the deuterated chiral luminescent material composition is 1.4 times that of the device comparative example 6 based on the non-deuterated (i.e. hydrogenated) chiral luminescent material composition, and the device external quantum efficiency is as high as 37.7%. Figure 3 and Figure 4 It can be seen that the device electroluminescence asymmetry factor of the device embodiment 9 based on the deuterated chiral luminescent material composition is 2.4 times that of the device comparative example 6 based on the non-deuterated (i.e., hydrogenated) chiral luminescent material composition, and the device electroluminescence asymmetry factor is as high as 4.6×10 -3 , the circularly polarized electroluminescence emission is significantly enhanced.

[0238] In addition, it can be seen from device embodiments 1-3 that with the increase of the number of deuterated generations, both the external quantum efficiency and the electroluminescence asymmetry factor of the device based on the deuterated chiral luminescent material composition are significantly improved. In device embodiment 3 based on the full deuterated chiral luminescent material composition, the maximum device external quantum efficiency can reach 28.5%, and the circularly polarized electroluminescence asymmetry factor can reach 2.2×10 -3 This is also confirmed by device examples 4-20.

[0239] Obviously, the above embodiments are merely examples for the purpose of clear explanation, and are not intended to limit the implementation methods. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived therefrom are still within the scope of protection of the invention.

Claims

1. A deuterated chiral luminescent material, characterized in that: The deuterated chiral luminescent material includes an organic chiral luminescent compound that has been at least partially deuterated.

2. The deuterated chiral luminescent material according to claim 1, characterized in that: The organic chiral luminescent compound which has been at least partially deuterated is a circularly polarized thermally activated delayed fluorescent material, and the energy level difference ΔE between the singlet energy level S1 and the triplet energy level T1 is ST Less than or equal to 300meV; The photoluminescence asymmetry factor is 10 -4 ~10 -2 between; Preferably, the energy level difference ΔE ST Less than or equal to 200meV, photoluminescence asymmetry factor greater than or equal to 10 -3 .

3. The deuterated chiral luminescent material according to claim 1 or 2, characterized in that: The at least partially deuterated organic chiral luminescent compound has the following structure before being deuterated: Among them, R1-R 12 Each independently selected from cyano, or substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C6-C20 aryl; n1-n 12 are the numbers of the corresponding groups, and their corresponding values ​​are integers between 0 and the maximum number of the corresponding groups; Me is selected from Au or Cu; Wherein, the substituents in the substituted C1-C30 alkyl group and the substituted C6-C20 aryl group are selected from deuterium and cyano.

4. The deuterated chiral luminescent material according to any one of claims 1 to 3, characterized in that: R1-R 12 Each independently selected from cyano, or substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C6-C15 aryl; Wherein, the substituents in the substituted C1-C10 alkyl and substituted C6-C15 aryl are selected from deuterium and cyano; Preferably, R1-R 12 Each independently selected from cyano, substituted or unsubstituted A group, A group includes: phenyl, naphthyl, methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl or hexyl; wherein the substituent of the substituted A group is selected from deuterium and cyano; Preferably, the at least partially deuterated organic chiral luminescent compound contains at least 3 deuteriums.

5. The deuterated chiral luminescent material according to any one of claims 1 to 4, characterized in that: The at least partially deuterated organic chiral light-emitting compound has the following structure:

6. A deuterated chiral luminescent material composition, characterized in that: The deuterated chiral luminescent material composition comprises a first material and a second material; wherein the first material comprises the deuterated chiral luminescent material according to any one of claims 1 to 5; and the second material comprises a non-deuterated achiral compound.

7. The deuterated chiral luminescent material composition according to claim 6, characterized in that: When the first material is a host material and the second material is a guest material, the mass ratio of the first material to the second material is (50-99.9):(0.1-50); Preferably, the second material is selected from phosphorescent materials, or conventional fluorescent dyes, or multi-resonance thermally activated delayed fluorescent materials; Further preferably, the mass ratio of the first material to the second material is (80-99.9):(0.1-20).

8. The deuterated chiral luminescent material composition according to claim 6, characterized in that: When the first material is a guest material, the second material is a host material, and the mass ratio of the first material to the second material is (0.1-50):(50-99.9); Preferably, the second material is selected from hole-type materials, electron-type materials, or bipolar materials, or bipolar materials formed by a combination of hole-type materials and electron-type materials; Further preferably, the mass ratio of the first material to the second material is (0.1-20):(80-99.9).

9. The deuterated chiral luminescent material composition according to any one of claims 6 to 8, characterized in that: The second material has the following structure:

10. A circularly polarized organic electroluminescent device, characterized in that: A circularly polarized organic electroluminescent device comprising the deuterated chiral luminescent material according to any one of claims 1 to 5 or the deuterated chiral luminescent material composition according to any one of claims 6 to 9; Preferably, the circularly polarized organic electroluminescent device comprises a light-emitting layer; the light-emitting layer comprises the deuterated chiral light-emitting material according to any one of claims 1 to 5 or the deuterated chiral light-emitting material composition according to any one of claims 6 to 9; Preferably, the thickness of the light-emitting layer is 5-100 nm; Preferably, the light-emitting layer has a thickness of 20-50 nm.

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