Patent Application
20250154407
The present disclosure relates to the field of organic optoelectronic material preparation technologies, and in particular, to an organic electroluminescent device, a display apparatus and a composition.
With the development of multimedia technology and the improvement of informationization requirements, the requirements for performances of panel displays are increasing. An OLED, also referred to as an organic electroluminescent device, relates to a technology in which an organic material emits light under an action of an electric field by means of carrier injection and combination, and the OLED can convert electrical energy into light energy by means of an organic light-emitting material.
At present, most of light-emitting layers of OLED devices use a host-guest light-emitting system, i.e., doping a host material with a guest material. With regard to the development of organic materials with light-emitting properties of, for example, blue light which is one of the three primary colors of light and the development of organic materials with the ability to transport charges (which gives the organic materials the potential to become semiconductors and superconductors) such as holes and electrons, both polymer compounds and low molecular compounds have been actively studied so far. However, even using a plurality of materials in combination, the display technology still suffers from high driving voltage and short display life, which seriously affects the further practicality of the technology. Therefore, it is necessary to develop organic light-emitting devices with low driving voltage, high brightness and long service life through continuous efforts, and finding suitable photoelectric functional materials for OLEDs to use in OLED devices so as to solve the above-described problems is a long-term need in this field.
In order to solve the above-described technical problem, the present disclosure provides an organic electroluminescent device, a display apparatus and a composition.
The present disclosure provides a substrate, a first electrode, an organic light-emitting functional layer and a second electrode. The first electrode is located on the substrate. The organic light-emitting functional layer is located on the first electrode. The second electrode is located the organic light-emitting functional layer. The organic light-emitting functional layer includes a light-emitting layer. The light-emitting layer includes a boron-nitrogen compound. The boron-nitrogen compound has a structure as shown in a following formula (III):
Here, R12-R15 are each independently selected from hydrogen, deuterium, halogen, a C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C6-C30 aryl group, a C5-C30 heteroaryl group, a C3-C30 silyl group, a C6-C30 aryl silyl group and a C5-C30 fused ring group, and a combination thereof, the combination including a combination in a form of a fused ring, a heteroatom therein being O.
In some embodiments, R12 is selected from a methyl group, a tert-butyl group, a tert-butylphenyl group, an aryl cyclohexyl group and a phenyl group, and a combination thereof.
In some embodiments, R13 is a tert-butylphenyl group or a diphenylfuranyl group.
In some embodiments, R14 is selected from deuterium, fluorine (F), a methyl group, a tert-butyl group, a phenyl group, a triaryl silane group and a tert-butyldiphenylsilyl group, and a combination thereof.
In some embodiments, R15 is selected from a methyl group, a tert-butyl group, a phenyl group, a tert-butylphenyl group and a benzocyclohexyl group, and a combination thereof.
In some embodiments, the boron-nitrogen compound is any one selected from following chemical structures:
Here, D represents deuterium.
In some embodiments, the light-emitting layer further includes an organic compound. The organic compound has a structure as shown in a following formula (I):
In formula (I), R1-R8 are each independently selected from hydrogen and deuterium; R9 and R10 are each independently selected from hydrogen, deuterium, a C6-C30 aryl group, a C5-C30 heteroaryl group, a C6-C30 fused aromatic ring and a C3-C30 fused heterocyclic group, and a combination thereof, a heteroatom therein being O.
At least one of the substituents R9-R10 is selected from a structure as shown in a following formula (II):
In formula (II), R11 is selected from hydrogen, a C6-C30 aryl group, a C5-C30 heteroaryl group and a C5-C30 fused ring group, and a combination thereof, the combination including a combination in a form of a fused ring, a heteroatom therein being O; represents nonexistence or benzobfuran; and * represents a linkage position.
In some embodiments, in formula (I), R9 or R10 is selected from deuterium, a phenyl group, a naphthyl group, a phenanthryl group and a biphenyl group, and a combination thereof.
In some embodiments, in formula (II), R11 is selected from hydrogen, a phenyl group, a furanyl group and a benzofuranyl group, and a combination thereof, the combination including a combination in a form of a fused ring.
In some embodiments, the organic compound is any one selected from the following chemical structures:
Here, D represents deuterium.
The organic electroluminescent device in the present disclosure may be used in an OLED lighting or display apparatus. Specially, the organic electroluminescent devices in the present disclosure may be used in the commercial field, e.g., in display screens of products and equipment such as point of sale (POS) machines, automated teller machines (ATMs), copying machines, automatic vending machines, game machines, gas stations, card punching machines, access control systems and electronic scales; in the communication field, e.g., in display screens of products such as mobile phones, various types of visual intercom systems (video telephones), mobile network terminals and electronic books (e-books); in the computer field, e.g., in display screens of home computers and/or commercial computers (such as personal computers (PCs) or workstations), personal digital assistants (PDAs) and laptop computers; in display screens of consumer electronic products such as decorative articles (flexible screens) and lamps, various types of audio equipment, moving picture experts group audio layer-3 (MP3) players, calculators, digital cameras, head-mounted displays, digital video cameras, portable digital video disks (DVDs), portable televisions (TVs), electronic timepieces, handheld game consoles and various household appliances (OLED TVs); in the transportation field, e.g., in display screens of a global position system (GPS), in-vehicle acoustic systems, vehicle-installed telephones and aircraft instruments and equipment, and other various indicative iconic display screens.
For example, the organic electroluminescent device provided in the present disclosure is used in smart phones, tablet computers, smart wearable devices, TVs, virtual reality (VR) devices, micro-display fields, automobile center control screens and automobile rear lamps.
The present disclosure further provides a display or lighting apparatus. The display or lighting apparatus includes the organic electroluminescent device as described in any one of the embodiments above.
The present disclosure further provides a composition. The composition contains a boron-nitrogen compound and an organic compound. The boron-nitrogen compound has a structure as shown in a following formula (III):
In formula (III), R12-R15 are each independently selected from hydrogen, deuterium, halogen, a C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C6-C30 aryl group, a C5-C30 heteroaryl group, a C3-C30 silyl group, a C6-C30 aryl silyl group and a C5-C30 fused ring group, and a combination thereof, the combination including a combination in a form of a fused ring, a heteroatom therein being O.
The organic compound has a structure as shown in a following formula (I):
Here, R1-R8 are each independently selected from hydrogen and deuterium; R9 and R10 are each independently selected from hydrogen, deuterium, a C6-C30 aryl group, a C5-C30 heteroaryl group, a C6-C30 fused aromatic ring and a C3-C30 fused heterocyclic group, and a combination thereof, a heteroatom therein being 0; and at least one of R9-R10 is selected from a structure as shown in a following formula (II):
Here, R11 is selected from hydrogen, a C6-C30 aryl group, a C5-C30 heteroaryl group and a C5-C30 fused ring group, and a combination thereof, the combination comprising a combination in a form of a fused ring, a heteroatom therein being O; represents nonexistence or benzobfuran; and * represents a linkage position.
In some embodiments, R12 is selected from a methyl group, a tert-butyl group, a tert-butylphenyl group, an aryl cyclohexyl group and a phenyl group, and a combination thereof.
In some embodiments, R13 is a tert-butylphenyl group or a diphenylfuranyl group.
In some embodiments, R14 is selected from deuterium, fluorine (F), a methyl group, a tert-butyl group, a phenyl group, a triaryl silane group and a tert-butyldiphenylsilyl group, and a combination thereof.
In some embodiments, R15 is selected from a methyl group, a tert-butyl group, a phenyl group, a tert-butylphenyl group and a benzocyclohexyl group, and a combination thereof.
In some embodiments, the boron-nitrogen compound is any one selected from following chemical structures:
Here D represents deuterium.
In some embodiments, R9 or R10 is selected from deuterium, a phenyl group, a naphthyl group, a phenanthryl group and a biphenyl group, and a combination thereof.
In some embodiments, R11 is selected from hydrogen, a phenyl group, a furanyl group and a benzofuranyl group, and a combination thereof, the combination comprising a combination in a form of a fused ring.
In some embodiments, a structural formula of the organic compound is any one selected from following structural formulas:
Here, D represents deuterium.
The present disclosure further provides a preparation. The preparation includes the composition as described in any one of the embodiments above and at least one solvent. The are no special limits to the solvent. The solvent may be a solvent that is well known to a person skilled in the art. For example, the solvent may be an unsaturated hydrocarbon solvent such as toluene, xylene, mesitylene, tetraline, decahydronaphthalene, bicyclohexane, n-butylbenzene, sec-butylbenzene or tert-butylbenzene; or may be a halogenated saturated hydrocarbon solvent such as carbon tetrachloride, chloroform, dichloromethane, dichlorethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane or bromocyclohexane; or may be an halogenated unsaturated hydrocarbon solvent such as chlorobenzene, dichlorobenzene or trichlorobenzene; or may be an ether solvent such as tetrahydrofuran or tetrahydropyra; or may be an ester-based solvent such as alkyl benzoate.
The light-emitting layer of the organic electroluminescent device in the embodiments of the present disclosure includes the boron-nitrogen compound. A boron-nitrogen parent nucleus of the boron-nitrogen compound defines that arylamine groups and a thiophene segment are paired with and connected to characteristic groups that are located on an edge of the boron-nitrogen compound. In this way, the boron-nitrogen compound may have good matching with an anthracene-based host material, which is conducive to the transmission of electrons and holes. Therefore, the organic electroluminescent device provided in the embodiments of the present disclosure may reduce the starting voltage, improve the light-emitting efficiency and prolong the service life to a certain extent.
Technical solutions of the present disclosure will be described clearly and completely by using embodiments below. However, the described embodiments are merely some but not all embodiments of the present disclosure. On the basis of the embodiments of the present disclosure, all other embodiments obtained by a person of ordinary skill in the art without making creative labour shall be included in the protection scope of the present disclosure.
An aryl group in the present disclosure refers to a generic term for monovalent groups remaining after removal of a hydrogen atom from a carbon atom of an aromatic nucleus of an aromatic molecule, and may be a monocyclic aryl group or a fused ring aryl group; and examples thereof may include a phenyl group, a biphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, etc., but are not limited thereto.
A heteroaryl group in the present disclosure refers to a generic term for groups obtained by replacing one or more carbon atoms of an aromatic nucleus of an aryl group by heteroatoms. A heteroatom includes but is not limited to an oxygen atom, a sulphur atom or a nitrogen atom. The heteroaryl group may be a monocyclic heteroaryl group or a fused ring heteroaryl group; and examples thereof may include a pyridyl group, a pyrrolyl group, a thienyl group, a furanyl group, an indolyl group, a quinolyl group, an isoquinolyl group, a benzothienyl group, a benzofuranyl group, a dibenzofuranyl group, a dibenzothienyl group, a carbazolyl group, etc., but not limited thereto.
Throughout the description, unless explicitly described to the contrary, the expression “including/comprising” any component are construed as implying the inclusion of other element(s), but not the exclusion of any other element. In addition, it will be understood that, throughout the description, when an element such as a layer, a film, a region or a substrate is described as being “on” or “above” another element, the element may be “directly on” the another element, or there may be intermediate element(s) between the element and the another element. Furthermore, the term “on” or “above” means being located on a side of a target portion, but does not necessarily mean being located above the target portion in a direction of gravity.
One object of the present disclosure is to provide an organic electroluminescent device.
In some embodiments, the organic electroluminescent device includes: a substrate, a first electrode on the substrate, an organic light-emitting functional layer on the first electrode, and a second electrode on the organic light-emitting functional layer. The organic light-emitting functional layer includes a light-emitting layer. The light-emitting layer includes an organic compound having an anthracene ring structure.
In an embodiment of the present disclosure, the light-emitting layer of the organic electroluminescent device (e.g., an organic light-emitting diode (OLED)) includes one or more of compounds as shown in the above general formula (I) as a light-emitting host material (hereinafter referred to as “host material”); and further includes one or more of compounds as shown in the above general formula (III) as a light-emitting dopant material (hereinafter referred to as “dopant material”).
In an embodiment of the present disclosure, an OLED is provided. The OLED includes a substrate, an anode, a cathode and an organic light-emitting functional layer. The organic light-emitting functional layer may include a light-emitting layer, a hole transport layer, a hole injection layer, an electron transport layer and an electron injection layer; or the organic light-emitting functional layer may include only the light-emitting layer and one or more of the other layers. The light-emitting layer includes one or more of the compounds as shown in the above general formula (I). In some examples, the light-emitting layer further includes one or more of the compounds as shown in the above general formula (III). Optionally, a cover layer, a protective layer and/or an encapsulation layer are further provided on the organic light-emitting functional layer.
In some embodiments, the light-emitting layer does not necessarily include an organic compound having an anthracene ring structure.
For example, the organic electroluminescent device includes a substrate, a first electrode, an organic light-emitting functional layer and a second electrode. The first electrode is located on the substrate, the organic light-emitting functional layer is located on the first electrode, and the second electrode is located on the organic light-emitting functional layer. The organic light-emitting functional layer includes a light-emitting layer. The light-emitting layer includes a boron-nitrogen compound. The boron-nitrogen compound has a structure as shown in the above general formula (III).
In some examples, the light-emitting layer of the organic electroluminescent device (e.g., an OLED) includes one or more of compounds as shown in the above general formula (III) as a dopant material. A host material of the light-emitting layer may be determined according to needs.
In an embodiment of the present disclosure, an OLED is provided. The OLED includes a substrate, an anode, a cathode and an organic light-emitting functional layer. The organic light-emitting functional layer may include a light-emitting layer, a hole transport layer, a hole injection layer, an electron transport layer and an electron injection layer; or the organic light-emitting functional layer may include only the light-emitting layer and one or more of the other layers. The light-emitting layer includes one or more of the compounds as shown in the above general formula (III). In some examples, a cover layer, a protective layer and/or an encapsulation layer are further provided on the organic light-emitting functional layer.
The substrate in the present disclosure may be any substrate selected from substrates applied in typical organic light-emitting apparatuses. The substrate may be a glass substrate or a transparent plastic substrate, or may be a substrate of an opaque material such as silicon or stainless steel, or may be a flexible polyimide (PI) film. Different substrates are different in mechanical strength, thermal stability, transparency, surface smoothness and waterproofness; and depending on natures of the different substrates, the different substrates are used in different directions.
Materials of the hole injection layer, the hole transport layer and the electron injection layer may be any materials selected from known relevant materials used in OLED apparatuses.
As guest materials capable of generating blue fluorescence, green fluorescence and blue-green fluorescence, the materials not only need to have extremely high fluorescence quantum light-emitting efficiency, but also needs to have appropriate energy levels so as to effectively absorb excitation energy of host materials to emit light.
The specific explanation of the present disclosure is given in conjunction with specific embodiments below. Unless otherwise specified, all raw materials and solvents in synthetic embodiments may be purchased commercially, and the solvents are directly used without further processing.
1) In a three-necked reaction flask, compound 1-031-1 (15 mmol) and compound 1-031-2 (15 mmol) are dissolved in 150 mL of 1,4-dioxane, and K2CO3 (20 mmol) which has been dissolved in 100 mL of H2O is added; then, Pd(P(t-Bu)3)2 (0.15 mmol) is added therein, and stirring is performed for 5 hours under a reflux condition in an argon atmosphere; after the reaction ends, a reaction solution in the three-necked reaction flask is cooled to room temperature; then the reaction solution is transferred to a separatory funnel, and extraction is performed with water and toluene to obtained an extract; the extract is dried by using MgSO4; filtering and concentration are performed to obtained a sample; and finally chromatography purification is performed on the sample by using silica gel column to obtain an intermediate product 1-031-3.
2) In a double-necked reaction flask, the intermediate product 1-031-3 (10 mmol), N-bromosuccinimide (NBS) (12 mmol) and 100 mL of dimethylformamide (DMF) are added, and stirring is performed in an argon atmosphere at room temperature for 10 hours; after the reaction ends, a reaction solution in the double-necked reaction flask is transferred to a separatory funnel, and extraction is performed with water and ethyl acetate to obtain an extract; the extract is dried by using MgSO4; filtering and concentration are performed to obtained a sample; and finally chromatography purification is performed on the sample by using silica gel column to obtain an intermediate product 1-031-4.
3) In a three-necked reaction flask, the intermediate product 1-031-4 (6 mmol), compound 1-031-5 (6 mmol) are dissolved in 150 mL of 1,4-dioxane, and K2CO3 (20 mmol) which has been dissolved in 100 mL of H2O is added; then, Pd(P(t-Bu)3)2 (0.06 mmol) is added therein, and stirring is performed for 5 hours under a reflux condition in an argon atmosphere; after the reaction ends, a reaction solution in the three-necked reaction flask is cooled to room temperature; then the reaction solution is transferred to a separatory funnel, and extraction is performed with water and toluene to obtained an extract; the extract is dried by using MgSO4; filtering and concentration are performed to obtained a sample; and finally chromatography purification is performed on the sample by using silica gel column to obtain a target product 1-031. A structure of the target product 1-031 is tested. Through liquid chromatography-mass spectrometry (LC-MS) analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 596.21, and a tested value being 596.49.
With reference to the synthesis steps and reaction conditions of Embodiment 1, compound 1-003 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 496.18, and a tested value being 496.48.
With reference to the synthesis steps and reaction conditions of Embodiment 1, compound 1-004 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 546.20, and a tested value being 546.54.
With reference to the synthesis steps and reaction conditions of Embodiment 1, compound 1-005 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 470.17, and a tested value being 470.49.
With reference to the synthesis steps and reaction conditions of Embodiment 1, compound 1-019 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 520.18, and a tested value being 520.52.
With reference to the synthesis steps and reaction conditions of Embodiment 1, compound 1-022 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 596.21, and a tested value being 596.49.
With reference to the synthesis steps and reaction conditions of Embodiment 1, compound 1-025 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 646.23, and a tested value being 646.56.
With reference to the synthesis steps and reaction conditions of Embodiment 1, compound 1-032 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 570.20, and a tested value being 570.53.
With reference to the synthesis steps and reaction conditions of Embodiment 1, compound 1-036 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 546.20, and a tested value being 546.48.
With reference to the synthesis steps and reaction conditions of Embodiment 1, compound 1-037 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 596.21, and a tested value being 596.54.
With reference to the synthesis steps and reaction conditions of Embodiment 1, compound 1-050 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 546.20, and a tested value being 546.55.
With reference to the synthesis steps and reaction conditions of Embodiment 1, compound 1-051 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 622.23, and a tested value being 622.64.
With reference to the synthesis steps and reaction conditions of Embodiment 1, compound 1-053 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 572.21, and a tested value being 572.51.
With reference to the synthesis steps and reaction conditions of Embodiment 1, compound 1-054 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 596.21, and a tested value being 596.61.
With reference to the synthesis steps and reaction conditions of Embodiment 1, compound 1-058 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 520.18, and a tested value being 520.53.
With reference to the synthesis steps and reaction conditions of Embodiment 1, compound 1-061 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 560.18, and a tested value being 560.62.
With reference to the synthesis steps and reaction conditions of Embodiment 1, compound 1-062 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 510.16, and a tested value being 510.45.
With reference to the synthesis steps and reaction conditions of Embodiment 1, compound 1-064 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 686.22, and a tested value being 686.63.
With reference to the synthesis steps and reaction conditions of Embodiment 1, compound 1-065 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 636.21, and a tested value being 636.56.
With reference to the synthesis steps and reaction conditions of Embodiment 1, compound 1-068 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 610.19, and a tested value being 610.48.
With reference to the synthesis steps and reaction conditions of Embodiment 1, compound 1-103 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 586.19, and a tested value being 586.47.
1) In a three-necked reaction flask, compound 1-165-1 (15 mmol) and compound 1-165-2 (15 mmol) are dissolved in 150 mL of 1,4-dioxane, and K2CO3 (20 mmol) which has been dissolved in 100 mL of H2O is added; then, Pd(P(t-Bu)3)2 (0.15 mmol) is added therein, and stirring is performed for 5 hours under a reflux condition in an argon atmosphere; after the reaction ends, a reaction solution in the three-necked reaction flask is cooled to room temperature; then the reaction solution is transferred to a separatory funnel, and extraction is performed with water and toluene to obtained an extract; the extract is dried by using MgSO4; filtering and concentration are performed to obtained a sample; and finally chromatography purification is performed on the sample by using silica gel column to obtain an intermediate product 1-165-3.
2) In a double-necked reaction flask, the intermediate product 1-165-3 (10 mmol), N-bromosuccinimide (NBS) (12 mmol) and 100 mL of dimethylformamide (DMF) are added, and stirring is performed in an argon atmosphere at room temperature for 10 hours; after the reaction ends, a reaction solution in the double-necked reaction flask is transferred to a separatory funnel, and extraction is performed with water and ethyl acetate to obtain an extract; the extract is dried by using MgSO4; filtering and concentration are performed to obtained a sample; and finally chromatography purification is performed on the sample by using silica gel column to obtain an intermediate product 1-165-4.
3) In a three-necked reaction flask, the intermediate product 1-165-4 (6 mmol), compound 1-165-5 (6 mmol) are dissolved in 150 mL of 1,4-dioxane, and K2CO3 (20 mmol) which has been dissolved in 100 mL of H2O is added; then, Pd(P(t-Bu)3)2 (0.06 mmol) is added therein, and stirring is performed for 5 hours under a reflux condition in an argon atmosphere; after the reaction ends, a reaction solution in the three-necked reaction flask is cooled to room temperature; then, the reaction solution is transferred to a separatory funnel, and extraction is performed with water and toluene to obtained an extract; the extract is dried by using MgSO4; filtering and concentration are performed to obtained a sample; and finally chromatography purification is performed on the sample by using silica gel column to obtain a target product 1-165. A structure of the target product 1-165 is tested. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 518.21, and a tested value being 518.53.
With reference to the synthesis steps and reaction conditions of Embodiment 22, compound 1-108 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 618.24, and a tested value being 618.57.
With reference to the synthesis steps and reaction conditions of Embodiment 22, compound 1-110 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 594.24, and a tested value being 594.61.
With reference to the synthesis steps and reaction conditions of Embodiment 22, compound 1-111 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 644.26, and a tested value being 644.57.
With reference to the synthesis steps and reaction conditions of Embodiment 22, compound 1-115 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 568.23, and a tested value being 568.58.
With reference to the synthesis steps and reaction conditions of Embodiment 22, compound 1-124 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 694.27, and a tested value being 694.64.
With reference to the synthesis steps and reaction conditions of Embodiment 22, compound 1-132 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 654.28, and a tested value being 654.65.
With reference to the synthesis steps and reaction conditions of Embodiment 22, compound 1-137 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 604.26, and a tested value being 604.66.
With reference to the synthesis steps and reaction conditions of Embodiment 22, compound 1-139 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 578.25, and a tested value being 578.58.
With reference to the synthesis steps and reaction conditions of Embodiment 22, compound 1-140 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 554.25, and a tested value being 554.62.
With reference to the synthesis steps and reaction conditions of Embodiment 22, compound 1-151 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 528.23, and a tested value being 528.63.
With reference to the synthesis steps and reaction conditions of Embodiment 22, compound 1-171 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 478.22, and a tested value being 478.52.
With reference to the synthesis steps and reaction conditions of Embodiment 22, compound 1-173 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 475.20, and a tested value being 475.48.
With reference to the synthesis steps and reaction conditions of Embodiment 22, compound 1-174 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 505.24, and a tested value being 505.58.
1) Compound 2-009-1 (1 mmol) and compound 2-009-2 (1 mmol) are dissolved in 50 mL of toluene; in a nitrogen atmosphere, sodium tert-butoxide (NaOBu-t) (2 mmol), palladium acetate (Pd(OAc)2) (0.05 mmol) and tri-tert-butylphosphine tetrafluoroborate (t-Bu3P HBF4) (0.5 mmol) are added; refluxing is perform for 72 hours, and then such a reaction system is cooled to room temperature; a solvent of the reaction system is removed through rotary evaporation; extraction is performed on the residue with 100 mL of dichloromethane, and this step is repeated three times to obtain an organic phase; the organic phase is washed with water, and then is dried with sodium sulfate; and a solvent is removed through reduced pressure distillation to obtain a crude product, and the crude product is separated and purified by means of silica gel chromatography column, where an eluent used therein is a mixture of dichloromethane and petroleum ether, and a volume ratio of dichloromethane to petroleum ether is 1:4. Thus, an intermediate product 2-009-3 is obtained.
2) The intermediate product 2-009-3 (1 mmol) and compound 2-009-4 (1 mmol) are dissolved in 50 mL of toluene; in a nitrogen atmosphere, sodium tert-butoxide (2 mmol), palladium acetate (0.05 mmol) and tri-tert-butylphosphine tetrafluoroborate (0.5 mmol) are added; refluxing is perform for 72 hours, and then such a reaction system is cooled to room temperature; a solvent of the reaction system is removed through rotary evaporation; extraction is performed on the residue with 100 mL of dichloromethane, and this step is repeated three times to obtain an organic phase; the organic phase is washed with water, and then is dried with sodium sulfate; and a solvent is removed through reduced pressure distillation to obtain a crude product, and the crude product is separated and purified by means of silica gel chromatography column, where an eluent used therein is a mixture of dichloromethane and petroleum ether, and a volume ratio of dichloromethane to petroleum ether is 1:4. Thus, an intermediate product 2-009-5 is obtained.
3) The intermediate product 2-009-5 (1 mmol) and compound 2-009-6 (1 mmol) are dissolved in 50 mL of toluene; in a nitrogen atmosphere, sodium tert-butoxide (2 mmol), palladium acetate (0.05 mmol) and tri-tert-butylphosphine tetrafluoroborate (0.5 mmol) are added; refluxing is perform for 72 hours, and then such a reaction system is cooled to room temperature; a solvent of the reaction system is removed through rotary evaporation; extraction is performed on the residue with 100 mL of dichloromethane, and this step is repeated three times to obtain an organic phase; the organic phase is washed with water, and then is dried with sodium sulfate; and a solvent is removed through reduced pressure distillation to obtain a crude product, and the crude product is separated and purified by means of silica gel chromatography column, where an eluent used therein is a mixture of dichloromethane and petroleum ether, and a volume ratio of dichloromethane to petroleum ether is 1:4. Thus, an intermediate product 2-009-7 is obtained.
4) The intermediate product 2-009-7 (1 mmol) and compound 2-009-8 (1 mmol) are dissolved in 50 mL of toluene. in a nitrogen atmosphere, sodium tert-butoxide (2 mmol), palladium acetate (0.05 mmol) and tri-tert-butylphosphine tetrafluoroborate (0.5 mmol) are added; refluxing is perform for 72 hours, and then such a reaction system is cooled to room temperature; a solvent of the reaction system is removed through rotary evaporation; extraction is performed on the residue with 100 mL of dichloromethane, and this step is repeated three times to obtain an organic phase; the organic phase is washed with water, and then is dried with sodium sulfate; a solvent is removed through reduced pressure distillation to obtain a crude product, and the crude product is separated and purified by means of silica gel chromatography column, where an eluent used therein is a mixture of dichloromethane and petroleum ether, and a volume ratio of dichloromethane to petroleum ether is 1:4. Thus, an intermediate product 2-009-9 is obtained.
5) The intermediate product 2-009-9 (1 mmol) is dissolved in 60 mL of anhydrous tert-butylbenzene (t-BuPh); such a reaction system is cooled to −78° C., and n-butyl lithium (BuLi) (1 mL, 2 mmol, 2 M in hexane) is slowly added; reaction is performed for 4 hours at −78° C., and then BBr3 (250.5 mg, 1 mmol) is slowly added; reaction is performed for 1 hour at −50° C., the reaction system is warmed up to room temperature; then, N,N-diisopropylethylamine (EtN(Pr-i)2) (387 mg, 3 mmol) is added, and the reaction system is heated to 120° C. for 12 hours; after the reaction is complete, the reaction system is cooled to room temperature, and 5 mL of aqueous sodium acetate solution (1 M) is added; a solvent is removed through rotary evaporation; extraction is performed on the residue with 100 mL of dichloromethane, and this step is repeated three times to obtain an organic phase; the organic phase is washed with water, and then is dried with sodium sulfate; and a solvent is removed through reduced pressure distillation to obtain a crude product, and the crude product is separated and purified by means of silica gel chromatography column, where an eluent used therein is a mixture of dichloromethane and petroleum ether, and a volume ratio of dichloromethane to petroleum ether is 1:8. Thus, a target product 2-009 is obtained. A structure of the target product 2-009 is tested. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 1107.53, and a tested value being 1107.97.
With reference to the synthesis steps and reaction conditions of Embodiment 36, compound 2-001 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 686.22, and a tested value being 686.63.
With reference to the synthesis steps and reaction conditions of Embodiment 36, compound 2-004 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 686.22, and a tested value being 686.63.
With reference to the synthesis steps and reaction conditions of Embodiment 36, compound 2-005 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 686.22, and a tested value being 686.63.
With reference to the synthesis steps and reaction conditions of Embodiment 36, compound 2-008 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 686.22, and a tested value being 686.63.
With reference to the synthesis steps and reaction conditions of Embodiment 36, compound 2-012 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 1125.52, and a tested value being 1125.86.
With reference to the synthesis steps and reaction conditions of Embodiment 36, compound 2-013 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 1058.52, and a tested value being 1058.86.
With reference to the synthesis steps and reaction conditions of Embodiment 36, compound 2-016 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 1024.57, and a tested value being 1024.93.
With reference to the synthesis steps and reaction conditions of Embodiment 36, compound 2-017 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 1024.57, and a tested value being 1024.93.
With reference to the synthesis steps and reaction conditions of Embodiment 36, compound 2-020 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 1201.59, and a tested value being 1201.87.
With reference to the synthesis steps and reaction conditions of Embodiment 36, compound 2-021 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 1201.59, and a tested value being 1201.87.
With reference to the synthesis steps and reaction conditions of Embodiment 36, compound 2-025 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 1201.59, and a tested value being 1201.87.
With reference to the synthesis steps and reaction conditions of Embodiment 36, compound 2-029 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 1201.59, and a tested value being 1201.87.
1) Compound 2-036-1 (1 mmol) and compound 2-036-2 (1 mmol) are dissolved in 50 mL of toluene; in a nitrogen atmosphere, sodium tert-butoxide (2 mmol), palladium acetate (0.05 mmol) and tri-tert-butylphosphine tetrafluoroborate (0.5 mmol) are added; refluxing is perform for 72 hours, and then such a reaction system is cooled to room temperature; a solvent of the rection system is removed through rotary evaporation; extraction is performed on the residue with 100 mL of dichloromethane, and this step is repeated three times to obtain an organic phase; the organic phase is washed with water, and then is dried with sodium sulfate; and a solvent is removed through reduced pressure distillation to obtain a crude product, and the crude product is separated and purified by means of silica gel chromatography column, where an eluent used therein is a mixture of dichloromethane and petroleum ether, and a volume ratio of dichloromethane to petroleum ether is 1:4. Thus, an intermediate product 2-036-3 is obtained.
2) The intermediate product 2-036-3 (1 mmol) and compound 2-036-4 (1 mmol) are dissolved in 50 mL of toluene; in a nitrogen atmosphere, sodium tert-butoxide (2 mmol), palladium acetate (0.05 mmol) and tri-tert-butylphosphine tetrafluoroborate (0.5 mmol) are added; refluxing is perform for 72 hours, and then such a reaction system is cooled to room temperature; a solvent of the reaction system is removed through rotary evaporation; extraction is performed on the residue with 100 mL of dichloromethane, and this step is repeated three times to obtain an organic phase; the organic phase is washed with water, and then is dried with sodium sulfate; and a solvent is removed through reduced pressure distillation to obtain a crude product, and the crude product is separated and purified by means of silica gel chromatography column, where an eluent used therein is a mixture of dichloromethane and petroleum ether, and a volume ratio of dichloromethane to petroleum ether is 1:4. Thus, an intermediate product 2-036-5 is obtained.
3) The intermediate product 2-036-5 (1 mmol) and compound 2-036-6 (1 mmol) are dissolved in 50 mL of toluene; in a nitrogen atmosphere, sodium tert-butoxide (2 mmol), palladium acetate (0.05 mmol) and tri-tert-butylphosphine tetrafluoroborate (0.5 mmol) are added; refluxing is perform for 72 hours, and then such a reaction system is cooled to room temperature; a solvent of the reaction system is removed through rotary evaporation; extraction is performed on the residue with 100 mL of dichloromethane, and this step is repeated three times to obtain an organic phase; the organic phase is washed with water, and then is dried with sodium sulfate; and a solvent is removed through reduced pressure distillation to obtain a crude product, and the crude product is separated and purified by means of silica gel chromatography column, where an eluent used therein is a mixture of dichloromethane and petroleum ether, and a volume ratio of dichloromethane to petroleum ether is 1:4. Thus, an intermediate product 2-036-7 is obtained.
4) The intermediate product 2-036-7 (1 mmol) and compound 2-036-8 (1 mmol) are dissolved in 50 mL of toluene. in a nitrogen atmosphere, sodium tert-butoxide (2 mmol), palladium acetate (0.05 mmol) and tri-tert-butylphosphine tetrafluoroborate (0.5 mmol) are added; refluxing is perform for 72 hours, and then such a reaction system is cooled to room temperature; a solvent of the reaction system is removed through rotary evaporation; extraction is performed on the residue with 100 mL of dichloromethane, and this step is repeated three times to obtain an organic phase; the organic phase is washed with water, and then is dried with sodium sulfate; and a solvent is removed through reduced pressure distillation to obtain a crude product, and the crude product is separated and purified by means of silica gel chromatography column, where an eluent used therein is a mixture of dichloromethane and petroleum ether, and a volume ratio of dichloromethane to petroleum ether is 1:4. Thus, an intermediate product 2-036-9 is obtained.
5) The intermediate product 2-036-9 (1 mmol) is dissolved in 60 mL of anhydrous tert-butylbenzene; such a reaction system is cooled to −78° C., and n-butyl lithium (BuLi) (1 mL, 2 mmol, 2 M in hexane) is slowly added; reaction is performed for 4 hours at −78° C., and then BBr3 (250.5 mg, 1 mmol) is slowly added; reaction is performed for 1 hour at −50° C., the reaction system is warmed up to room temperature; then N,N-diisopropylethylamine (EtN(Pr-i)2) (387 mg, 3 mmol) is added, and then the reaction system is heated to 120° C. for 12 hours; after the reaction is complete, the reaction system is cooled to room temperature, and 5 mL of aqueous sodium acetate solution (1 M) is added; a solvent is removed through rotary evaporation; extraction is performed on the residue with 100 mL of dichloromethane, and this step is repeated three times to obtain an organic phase; the organic phase is washed with water, and then is dried with sodium sulfate; and a solvent is removed through reduced pressure distillation to obtain a crude product, and the crude product is separated and purified by means of silica gel chromatography column, where an eluent used therein is a mixture of dichloromethane and petroleum ether, and a volume ratio of dichloromethane to petroleum ether is 1:8. Thus, a target product 2-036 is obtained. A structure of the target product 2-036 is tested. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 1078.62, and a tested value being 1078.98.
With reference to the synthesis steps and reaction conditions of Embodiment 49, compound 2-033 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 1112.56, and a tested value being 1112.92.
With reference to the synthesis steps and reaction conditions of Embodiment 49, compound 2-038 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 1121.55, and a tested value being 1121.89.
With reference to the synthesis steps and reaction conditions of Embodiment 49, compound 2-040 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 1235.54, and a tested value being 1235.87.
With reference to the synthesis steps and reaction conditions of Embodiment 49, compound 2-042 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 1166.61, and a tested value being 1166.97.
With reference to the synthesis steps and reaction conditions of Embodiment 49, compound 2-044 is synthesized. Through LC-MS analysis, a following result of LC-MS (m/z) (M+) is obtained: a theoretical value being 1215.57, and a tested value being 1215.93.
Application examples, in which several of the organic compounds described in the present disclosure are applied in OLED devices, are listed below, so as to further illustrate the beneficial effects of the compounds in the present disclosure. Materials used in the examples are purchased commercially or synthesized in-house.
As a reference fabrication method for device embodiments of, in the present disclosure, 50-500 nm of indium tin oxide/Ag/indium tin oxide (ITO/Ag/ITO) is evaporated on an alkali-free glass substrate to serve as an anode; a hole injection layer (5-20 nm), a hole transport layer (50-120 nm), a light-emitting auxiliary layer (5-120 nm), a light-emitting layer (20-50 nm), an electron transport layer (20-80 nm) and an electron injection layer (1-10 nm) are evaporated on the anode; Mg and Ag (a weight ratio of 10:1, 10-50 nm) are co-evaporated to form a semi-transparent cathode; then, a cover layer compound is evaporated; and finally, such a light-emitting device is encapsulated in a nitrogen atmosphere by using an epoxy resin adhesive.
A specific material and a film thickness of the electron injection layer may be determined according to needs. For example, the electron injection layer is made of lithium fluoride (LiF) or ytterbium (Yb), and the film thickness of the electron injection layer is 1 nm.
According to actual needs, the weight ratio of Mg and Ag in the semi-transparent cathode may be set to other values, e.g., 1:9. A film thickness of the semi-transparent cathode may be determined according to needs. For example, the weight ratio of Mg and Ag in the semi-transparent cathode is 10:1, and the film thickness of the semi-transparent cathode is 15 nm. For example, the weight ratio of Mg and Ag in the semi-transparent cathode is 1:9, and the film thickness of the semi-transparent cathode is 14 nm.
A specific material and a film thickness of the hole transport layer may be determined according to needs. For example, the hole transport layer is made of N,N′-diphenyl-N,N′-bis(1-naphthyl)-(1,1′-biphenyl)-4,4′-diamine (NPB), and the film thickness of the hole transport layer is 30 nm. For example, the hole transport layer is made of compound HT (as shown below), and the film thickness of the hole transport layer is 120 nm.
In a specific embodiment, a fabrication method for an OLED device provided in the present disclosure is as follows: an alkali-free glass substrate is first washed with isopropanol by using an ultrasonic cleaning instrument for 15 minutes, and then ultraviolet (UV) ozone washing treatment is performed in air for 30 minutes; on the treated substrate, 100 nm of ITO/Ag/ITO is evaporated by using a vacuum evaporation method to form an anode; on the anode, a hole injection layer (made of compound HT and compound PD, a ratio of a film thickness of compound HT to a film thickness of compound PD being 2:100, 10 nm), a hole transport layer (made of N,N′-diphenyl-N,N′-bis(1-naphthyl)-(1,1′-biphenyl)-4,4′-diamine (NPB), 30 nm), a light-emitting auxiliary layer (made of compound BP, 5 nm), a blue light-emitting layer (respectively using compound 1-031 and compound 2-009 as a host material and a dopant material, a weight ratio of host material to the dopant material (i.e., a weight ratio of compound 1-031 to compound 2-009) being 97:3, 30 nm), an electron transport layer (made of compound ET and compound Liq, a weight ratio of compound ET to compound Liq being 1:1, 30 nm), an electron injection layer (made of LiF, 1 nm) are sequentially evaporated in a stacked manner; Mg and Ag (with a weight ratio of 10:1, 15 nm) are co-evaporated to form a semi-transparent cathode; then, compound CPL (65 nm) is evaporated to form a cover layer; and finally, such a light-emitting device is encapsulated in a nitrogen atmosphere by using an epoxy resin adhesive. This embodiment is recorded as Application Example 1. Molecular structure formulas of the relevant materials are as follows:
OLED devices in Application Examples 2 to 35 and Comparison Example 1 are each fabricated with reference to the method provided in Application Example 1, the only difference lies in that, respective compounds as listed in Table 1 replace compound 1-003 in Application Example 1 to serve as host materials in Application Examples 2 to 35 and Comparison Example 1. A structure of compound BH-002 in Comparison Example 1 is as follows:
Currents of each OLED device at different voltages are tested by means of Keithley 2365A digital nanovoltmeter, and then current densities of the OLED device at the different voltages are obtained by dividing the currents by a light-emitting area of the OLED device; brightnesses and radiation energy flux densities of the OLED device at the different voltages are tested by means of Konicaminolta CS-2000 spectroradiometer; according to the current densities and the brightnesses of the OLED device at the different voltages, an operation voltage Volt and a current efficiency (cd/A) at the same current density (10 mA/cm2) are obtained; BI=E/CIEy, where BI refers to a blue index of blue light, which is also a parameter for measuring the light-emitting efficiency of the blue light, E refers to a current efficiency, and CIEy refers to a color point of a vertical coordinate obtained by substituting a full band spectrum of the device into the software CIE1930 for integration. Test data are shown in Table 1.
It can be seen from Table 1 that, compared with the light-emitting device in Comparison Example 1, the light-emitting devices in Application Examples 1 to 35 have lower operation voltages, higher BI light-emitting efficiencies and longer service lives. The performance improvements of the light-emitting devices in the application examples are based on that the organic compound materials in the disclosure have better charge transport capabilities.
In order to further verify the excellent performances of the organic compounds provided in the present disclosure, with reference to the method provided in Application Example 1 above, light-emitting devices in Application Examples 36 to 58 and Comparison Examples 2 to 5 are fabricated. The only difference lies in that, respective compounds as listed in Table 2 replace compound 1-031 and 2-009 in Application Example 1 to serve as host materials and dopant materials in Application Examples 36 to 58 and Comparison Examples 2 to 5. Structures of the new materials involved in the comparison examples in Table 2 are as follows:
It can be seen from Table 2 that, compared with the light-emitting devices in Comparison Examples 2 to 5, the light-emitting devices in Application Examples 36 to 58 have superior operation voltages, higher BI light-emitting efficiencies and longer service lives. It is clear that, the host materials and the dopant materials in the present disclosure have a better compatibility, which enables blue light-emitting layers to achieve a better balance between electron transport and hole transport and a better exciton conversion yield, significantly reduces the power consumption of a white light device and improves the service life of a panel. The light-emitting efficiency of the device can be improved significantly.
In order to clearly illustrate the beneficial effects of the introduction of the boron-nitrogen compound in the organic electroluminescent device, the following Application Examples 59 to 76 are provided for specific explanation. Materials used in the examples are purchased commercially or synthesized in-house.
Light-emitting devices in Application Examples 59 to 76 are fabricated with reference to the method provided in Application Example 1 above. The only difference lies in that, respective compounds as listed in Table 3 replace compound 1-031 and 2-009 in Application Example 1 to serve as host materials and dopant materials in Application Examples 59 to 76.
It can be seen from Table 3 that, compared with the light-emitting devices in Comparison Examples 4 and 5, the light-emitting devices in Application Examples 59 to 76 may reduce the device starting voltage, improve the light-emitting efficiency and prolong the service life to a certain extent. This is because, for each of the boron-nitrogen compounds 2-001 to 2-044 as a blue dopant (BD) material in the present disclosure, a boron-nitrogen parent nucleus thereof defines that arylamine groups and a thiophene segment are paired with and connected to restricted groups (also referred to as “characteristic groups”, such as R13 and R15 in the formula (III)) that are located on an edge of the boron-nitrogen compound. In this way, the boron-nitrogen compounds in the present disclosure may have good matching with an anthracene-based host material (e.g., the compound BH002), which is conducive to the transmission of electrons and holes.
These specific embodiments are only explanations of the present disclosure, but not limitations of the present disclosure. Those skilled in the art may make modifications, without creative contribution, to these embodiments according to needs after reading this description, but those modifications shall be included in the scope, which are protected by the patent law, of the claims of the present disclosure.
| Number | Date | Country | Kind |
|---|---|---|---|
| 202311482550.7 | Nov 2023 | CN | national |
This application is a Continuation-in-Part application of the U.S. patent application Ser. No. 18/943,851, filed on Nov. 11, 2024, which claims priority to Chinese Patent Application No. 202311482550.7, filed with the Chinese Patent Office on 9 Nov. 2023, which is incorporated herein by reference in its entirety.
| Number | Date | Country | |
|---|---|---|---|
| Parent | 18943851 | Nov 2024 | US |
| Child | 19021042 | US |
