Novel compound and organic electronic device comprising same

Abstract

One embodiment of the present invention provides a novel compound centered on a carbazole derivative and an organic electronic device comprising the same. According to an embodiment of the present invention, a compound comprising various substituents and containing deuterium is provided, which has the feature of increasing the stability of the organic electronic device and optimizing its characteristics.

Description

Technology Field

[0001] The present invention relates to a novel compound centered on a carbazole derivative and an organic electronic device containing the same. Background Technology

[0002] Organic solar cells are devices that utilize conjugated organic compounds to absorb light in the visible spectrum from the sun and convert it into electricity. Compared to conventional inorganic semiconductor devices, they are attracting attention as next-generation solar cells because their film deposition conditions are less stringent, the materials are inexpensive, and they can be applied to flexible transparent substrates such as plastic.

[0003] The characteristics of organic solar cells depend not only on the aforementioned conjugated organic compounds but also on other materials such as host / matrix materials, electron transport materials, and hole transport materials, and improvements in these materials can lead to significant improvements in organic solar cells. Prior art literature

[0004] Republic of Korea Published Patent Application 2019-0112026 The problem to be solved

[0005] The present invention provides a compound capable of improving charge transfer ability by introducing various substituents to control the work function and optimize interfacial properties, as a method to solve the problems of the aforementioned prior art.

[0006] The technical problems that the present invention aims to solve are not limited to those mentioned above, and other unmentioned technical problems will be clearly understood by those skilled in the art to which the present invention belongs from the description below. means of solving the problem

[0007] To achieve the above technical problem, one embodiment of the present invention provides a novel compound.

[0008] A compound according to one embodiment of the present invention is characterized by being represented by the following chemical formula 1.

[0009] [Chemical Formula 1]

[0010]

[0011] (In the above chemical formula 1,

[0012] R is a chain-type or branched alkyl having 1 to 30 carbon atoms, and

[0013] X1 to X8 are each independently hydrogen, deuterium, halogen, or alkoxy groups, and the alkoxy group may be one in which at least one hydrogen is substituted with deuterium.

[0014] At least one of X1 to X8 comprises a deuterium or an alkoxy group in which at least one hydrogen is substituted with deuterium.

[0015] In an embodiment of the present invention, the above chemical formula 1 may be a compound characterized by being selected from any one of the following compound group 1.

[0016] [Compound Group 1]

[0017]

[0018] To achieve the above technical problem, another embodiment of the present invention provides an organic electronic device comprising a compound according to an embodiment of the present invention. Effects of the invention

[0019] According to an embodiment of the present invention, the compound has high efficiency and high stability and is characterized by being usable as a charge transport material in various organic electronic devices, such as organic solar cells (OSCs) or perovskite solar cells (PSCs).

[0020] The effects of the present invention are not limited to the effects described above, and should be understood to include all effects that can be inferred from the configuration of the invention described in the detailed description of the invention or the claims. Specific details for implementing the invention

[0021] The present invention will be described below with reference to the attached drawings. However, the present invention may be implemented in various different forms and is therefore not limited to the embodiments described herein. Furthermore, in order to clearly explain the present invention in the drawings, parts unrelated to the explanation have been omitted, and similar parts throughout the specification have been given similar reference numerals.

[0022] Throughout the specification, when it is stated that a part is "connected (connected, in contact, combined)" with another part, this includes not only cases where they are "directly connected," but also cases where they are "indirectly connected" with other members interposed between them. Furthermore, when it is stated that a part "includes" a certain component, this means that, unless specifically stated otherwise, it does not exclude other components but rather allows for the inclusion of additional components.

[0023] The terms used herein are merely for describing specific embodiments and are not intended to limit the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this specification, terms such as “comprising” or “having” are intended to indicate the presence of the features, numbers, steps, actions, components, parts, or combinations thereof described in the specification, and should be understood as not precluding the existence or addition of one or more other features, numbers, steps, actions, components, parts, or combinations thereof.

[0024] As used herein, the term “alkyl” means a saturated straight-chain or branched non-cyclic hydrocarbon having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms (where the number of carbon atoms is not particularly limited). Representative saturated straight-chain alkyls include -methyl, -ethyl, -n-propyl, -n-butyl, -n-pentyl, -n-hexyl, -n-heptyl, -n-octyl, -n-nonyl, and -n-decyl, while saturated branched alkyls include -isopropyl, -sec-butyl, -isobutyl, -tert-butyl, isopentyl, 2-methylhexyl, 3-methylbutyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylhexyl, 3-methylhexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 2,3-dimethylbutyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, It includes 2,3-dimethylhexyl, 2,4-dimethylhexyl, 2,5-dimethylhexyl, 2,2-dimethylpentyl, 2,2-dimethylhexyl, 3,3-dimethylpentyl, 3,3-dimethylhexyl, 4,4-dimethylhexyl, 2-ethylpentyl, 3-ethylpentyl, 2-diethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 2-methyl-2-ethylpentyl, 2-methyl-3-ethylpentyl, 2-methyl-4-ethylpentyl, 2-methyl-2-ethylhexyl, 2-methyl-3-ethylhexyl, 2-methyl-4-ethylhexyl, 2,2-diethylpentyl, 3,3-diethylhexyl, 2,2-diethylhexyl, and 3,3-diethylhexyl.

[0025] In this specification, "C 1-5 When written as ", this means that the number of carbon atoms is 1 to 5. For example, C 1-5 Alkyl means an alkyl having 1 to 5 carbon atoms.

[0026] The terms “halogen” and “halo” as used in this specification mean fluorine, chlorine, bromine, or iodine.

[0027] As used in this specification, the term “alkoxy” means -O-(alkyl), including -OCH3, -OCH2CH3, -O(CH2)2CH3, -O(CH2)3CH3, -O(CH2)4CH3, -O(CH2)5CH3, and similar ones, wherein alkyl is as defined above.

[0028] As used herein, the term "aryl" means a carbon-ring aromatic group containing 5 to 10 ring atoms. Representative examples include, but are not limited to, phenyl, tolyl, xylyl, naphthyl, tetrahydronaphthyl, anthracenyl, fluorenyl, indenyl, azulenyl, etc. The carbon-ring aromatic group may be optionally substituted.

[0029] As used herein, the term "cycloalkyl" means a monocyclic or polycyclic saturated ring having carbon and hydrogen atoms and not having carbon-carbon multiple bonds. Examples of cycloalkyl groups include, but are not limited to, (C3-C10)cycloalkyls (e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl). Cycloalkyl groups may be optionally substituted. In one embodiment, the cycloalkyl group is a monocyclic or bicyclic ring.

[0030] As used herein, the term “heterocycloalkyl” refers to a stable 3- to 18-membered saturated or partially unsaturated radical composed of 2 to 12, preferably 2 to 10, carbon atoms and 1 to 6 heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur, e.g., 1 to 5 heteroatoms, 1 to 4 heteroatoms, 1 to 3 heteroatoms, or 1 to 2 heteroatoms. Exemplary heterocycloalkyls include, without limitation, stable 3-15 member saturated or partially unsaturated radicals, stable 3-12 member saturated or partially unsaturated radicals, stable 3-9 member saturated or partially unsaturated radicals, stable 8 member saturated or partially unsaturated radicals, stable 7 member saturated or partially unsaturated radicals, stable 6 member saturated or partially unsaturated radicals, or stable 5 member saturated or partially unsaturated radicals.

[0031] As used herein, the term “heteroaryl” is an aromatic heterocycle ring of 5 to 10 members comprising at least one carbon atom selected from the group consisting of nitrogen, oxygen and sulfur, and having at least one heteroatom selected from the group consisting of mono- and bicyclic ring systems. Representative heteroaryls are triazoleyl, tetrazolyl, oxadiazoleyl, pyridyl, furyl, benzofuranyl, thiophenyl, benzothiophenyl, quinolinyl, pyrrolyl, indoleyl, oxazolyl, benzoxazolyl, imidazoleyl, benzimidazoleyl, thiazolyl, benzothiazoleyl, isoxazolyl, pyrazolyl, isothiazoleyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, cinnolinyl, phthalazinyl, quinazolinyl, pyrimidyl, oxetanil, azefinil, piperazinyl, morpholinyl, dioxanil, tiethanil, and oxazolyl. The heteroaryl group can be monocyclic or bicyclic. Heteroaryl may be used interchangeably with the terms heteroaryl ring, heteroaryl group, or heteroaromatic, all of which may include an arbitrarily substituted ring.

[0032] The term "D" as used in this specification means deuterium.

[0033] Meanwhile, in this specification " " refers to the connected location.

[0034] Embodiments of the present invention will be described in detail below with reference to the attached drawings.

[0036] A compound according to one embodiment of the present invention is described.

[0037] The present invention relates to a compound capable of optimizing interfacial properties and improving the charge transfer capability of a device by introducing halogens, alkoxy, or various substituents at various positions of a carbazole derivative to control the work function of an electronic material and control surface energy.

[0038] In particular, by substituting deuterium, it can enhance the stability of organic electronic devices, making it applicable to next-generation energy harvesting devices.

[0039] Specifically, a compound according to one embodiment of the present invention is characterized by being represented by the following chemical formula 1.

[0040] [Chemical Formula 1]

[0041]

[0042] In the above chemical formula 1, R is an alkyl group and corresponds to a saturated straight-chain or branched non-cyclic hydrocarbon linker having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and preferably 1 to 5 carbon atoms.

[0043] In the above chemical formula 1, X1 to X8 may each independently be hydrogen, deuterium, a halogen, or an alkoxy group. The alkoxy group refers to -O-(alkyl), including, for example, -OCH3, -OCH2CH3, -O(CH2)2CH3, -O(CH2)3CH3, -O(CH2)4CH3, -O(CH2)5CH3, and similar ones. In this case, in the above chemical formula 1, all hydrogens of the alkoxy group may be partially or entirely substituted with deuterium.

[0044] In the above chemical formula 1, at least one of X1 to X8 comprises a deuterium or an alkoxy group in which at least one hydrogen is substituted with deuterium.

[0045] In a specific embodiment of the present invention, the formula 1 may be selected from the following compound group 1, but is not limited to the following examples.

[0046] [Compound Group 1]

[0047]

[0049] Referring to Chemical Formula 1, the compound of the present invention introduces substituents such as halogens and alkoxy groups at various positions of carbazole derivatives to control the work function and surface energy of electronic materials, thereby optimizing interfacial properties and improving the charge transfer capability of the device. In particular, the compound of the present invention has the characteristic of being applicable to next-generation energy harvesting devices, as it can bring about the effect of enhancing the stability of organic electronic devices by substituting deuterium.

[0050] In one embodiment of the present invention, an organic electronic device comprising a compound according to the above embodiment is provided. In this case, the organic electronic device may be an organic solar cell or a perovskite solar cell. However, it is not limited to the examples described above and may be used as a charge transport material for various organic electronic devices.

[0051] Specifically, when the organic electronic device is a solar cell such as an organic solar cell or a perovskite solar cell, the solar cell may include a first electrode; a second electrode; a photoactive layer formed between the first electrode and the second electrode; and an electron transport layer formed between the first electrode and the photoactive layer, and the electron transport layer may include a compound according to an embodiment of the present invention.

[0052] The present invention will be explained in more detail below through manufacturing examples, comparative examples, and experimental examples. However, the present invention is not limited to the following manufacturing examples and experimental examples.

[0054] [Example 1]: Synthesis of Example 1 Compound (5)

[0055] (Step 1: Synthesis of Compound (2))

[0056]

[0057] First, 3,6-dibromo-9H-carbazole-1,2,4,5,7,8-d6 (compound (2)) was synthesized.

[0058] 9H-Carbazole-1,2,3,4,5,6,7,8-d8 (5.0 g, 28.53 mmol) was dissolved in a 500 mL round-bottom flask containing DMF (300 mL). Then, NBS (11.2 g, 62.8 mmol) was added with a magnetic bar stirrer. The mixture was stirred at 0 °C for 1 hour and at room temperature for 1.5 hours.

[0059] The reaction mixture was poured into ice water, and the resulting solid was collected by filtration. The solid was dissolved in acetone (500 mL) and then dried with Na2SO4. After filtration, the solution was vacuum concentrated. The residue was purified by silica gel column chromatography (n-hexane / ethyl acetate, 2:1) to obtain the desired product as a white solid (6.1 g, 64% yield).

[0061] (Step 2: Synthesis of Compound (3))

[0062]

[0063] Next, 3,6-dimethoxy-9H-carbazole-1,2,4,5,7,8-d6 (compound (3)) was synthesized.

[0064] DMF (10 mL), CuI (2.3 g, 9.1 mmol), and compound (2) (1.0 g, 3.0 mmol) were added to a solution of metallic sodium (1.8 g, 75 mmol) dissolved in pure methanol (15 mL). The reaction mixture was refluxed under a nitrogen atmosphere for 3 hours.

[0065] After the reaction, ethyl acetate was added to the reaction mixture, and the insoluble material was filtered through Celite and washed with ethyl acetate. The filtrate was washed with brine, dried with Na2SO4, filtered, and concentrated. The residue was chromatographed using silica gel column chromatography with 10:1 n-hexane / ethyl acetate to obtain a white powder product (0.5 g, 69% yield).

[0066] 1H NMR (300 MHz, DMSO-d6) δ7.96 (s, 1H), 3.94 (s, 6H).

[0068] (Step 3: Synthesis of Compound (4))

[0069]

[0070] Next, diethyl (2-(3,6-dimethoxy-9H-carbazol-9-yl-1,2,4,5,7,8-d6)ethyl)phosphonate (compound (4)) was synthesized.

[0071] Compound (3) (2.0 g, 8.6 mmol) was added to dry DMSO (15 mL) and 60% NaH (0.4 g, 9.4 mmol) was added, and the mixture was stirred at room temperature for 0.5 hours under an N2 atmosphere.

[0072] Next, diethyl (2-bromoethyl)phosphonate (2.3 g, 9.4 mmol) was added, and the mixture was heated at 60 °C for 20 hours. The reaction mixture was poured into water (100 mL), acidified with 1 M hydrochloric acid, and then extracted with ethyl acetate (3 x 100 mL).

[0073] The combined organic extract was washed with brine, dried with magnesium sulfate, and the solvent was removed. The residue was dissolved in a minimal amount of ethyl acetate and eluted with petroleum ether:ethyl acetate (2:1) and separated by silica gel column chromatography. The solvent was removed under reduced pressure to obtain diethyl(2-(9H-carbazol-9-yl)ethyl)phosphonate as a pale yellow liquid (0.75 g, 47% yield).

[0074] 1 H NMR (CD2Cl2, 300 MHz): 4.61 (m, 2H), 4.15 (m, 4H), 3.94 (s, 6H), 2.30 (m, 2H), 1.36 (m, 6H).

[0076] (Step 4: Synthesis of Compound (5))

[0077]

[0078] Finally, (2-(3,6-dimethoxy-9H-carbazol-9-yl-1,2,4,5,7,8-d6)ethyl)phosphonic acid (compound (5)) was synthesized.

[0079] Compound (4) (1.0 g, 2.5 mmol) was added to dried CH2Cl2 (5 mL), and trimethylsilyl bromide (0.73 mL, 5.5 mmol) was added under an N2 atmosphere. The solution was stirred for 6 hours, then quenched with MeOH and vigorously stirred.

[0080] After stirring for another 2 hours, the solvent was removed under reduced pressure and water (5 mL) was added. Then, the mixture was concentrated under reduced pressure. This step was repeated four times to obtain the desired product as an off-white solid (0.8 g, 94%).

[0081] 1 H NMR (DMSO-d6, 300 MHz): 4.5 (m, 2H), 3.86 (m, 6H), 2.0 (m, 2H).

[0083] The foregoing description of the present invention is for illustrative purposes only, and those skilled in the art will understand that other specific forms can be easily modified without altering the technical spirit or essential features of the present invention. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive. For example, each component described as a single unit may be implemented in a distributed manner, and components described as distributed may likewise be implemented in a combined form.

[0084] The scope of the present invention is defined by the claims set forth below, and all modifications or variations derived from the meaning and scope of the claims and equivalent concepts thereof should be interpreted as being included within the scope of the present invention.

Claims

Claim 1 Compound characterized by being represented by the following chemical formula 1: [Chemical Formula 1] (In the above chemical formula 1, R is a chain-type or branched alkyl having 1 to 30 carbon atoms, and X1 to X8 are each independently hydrogen, deuterium, halogen, or alkoxy groups, wherein at least one hydrogen may be substituted with deuterium, and at least one of X1 to X8 comprises deuterium or an alkoxy group in which at least one hydrogen is substituted with deuterium.) Claim 2 A compound according to claim 1, characterized in that in the above chemical formula 1, X1, X2, X4, X5, X7, and X8 are each independently hydrogen or deuterium, and X3 and X6 are each independently hydrogen, deuterium, halogen, or alkoxy group. Claim 3 A compound according to claim 1, characterized in that the above chemical formula 1 is any one selected from the following compound group 1: [Compound group 1] Claim 4 An organic electronic device comprising a compound according to any one of claims 1 to 3. Claim 5 An organic electronic device according to claim 4, characterized in that the organic electronic device is a solar cell. Claim 6 An organic electronic device according to claim 5, wherein the solar cell comprises a first electrode; a second electrode; a photoactive layer and an electron transport layer formed between the first electrode and the second electrode, and the electron transport layer comprises the compound.

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