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• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C17/00—Preparation of halogenated hydrocarbons
  • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
  • C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
  • C07C17/266—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions of hydrocarbons and halogenated hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C23/00—Compounds containing at least one halogen atom bound to a ring other than a six-membered aromatic ring
  • C07C23/18—Polycyclic halogenated hydrocarbons
  • C07C23/20—Polycyclic halogenated hydrocarbons with condensed rings none of which is aromatic
  • C07C23/46—Polycyclic halogenated hydrocarbons with condensed rings none of which is aromatic with more than three condensed rings
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
  • H10K30/60—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation in which radiation controls flow of current through the devices, e.g. photoresistors
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
  • H10K30/80—Constructional details
  • H10K30/84—Layers having high charge carrier mobility
  • H10K30/85—Layers having high electron mobility, e.g. electron-transporting layers or hole-blocking layers
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K39/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic radiation-sensitive element covered by group H10K30/00
  • H10K39/30—Devices controlled by radiation
  • H10K39/32—Organic image sensors
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E10/00—Energy generation through renewable energy sources
  • Y02E10/50—Photovoltaic [PV] energy
  • Y02E10/549—Organic PV cells

Definitions

• the present invention relates to fullerene derivatives, thin films, photoelectric conversion elements, solid-state imaging devices, and methods for producing fullerene derivatives.
• Photoelectric conversion elements are elements that convert light into an electrical signal using the photoelectric effect, and include photodiodes and phototransistors, etc., and can be applied to electronic devices such as solid-state imaging devices.
• various fullerene derivatives have also been developed in which substituents are bonded to fullerenes that give them good light absorption or electrical properties.
• Patent Documents 1 to 3 disclose fullerene derivatives that exhibit sublimation properties, such as fullerene derivatives with multiple branched alkyl chains and fullerene derivatives with perfluoroalkyl groups.
• Non-Patent Document 1 describes fullerene derivatives having multiple difluoromethano structures and fullerene derivatives having multiple trifluoromethyl groups (C 60 (CF 3 ) 2 , etc.).
• fullerene derivatives can reduce aggregation during deposition, improving film formation characteristics, and can effectively reduce changes in the absorption wavelength range that occur due to aggregation.
• fullerene derivatives have the problem that they decompose when heated for deposition. Furthermore, even fullerene derivatives that are sublimable have problems such as the sublimation temperature being too high or being difficult to synthesize.
• the fullerene derivatives given in the synthesis examples of Patent Document 1 have a relatively high sublimation temperature of 400°C or higher, which is close to the decomposition temperature of the fullerene derivatives, making it difficult to stably deposit them.
• the fullerene derivative described in Patent Document 2 has a relatively low sublimation temperature of 400°C or less, but because it has a structurally unstable three-membered ring structure, when heated for a long period of time for deposition, the compound decomposes and the amount of compound available for deposition decreases.
• the fullerene derivative with a difluoromethano structure described in Non-Patent Document 1 has a high sublimation temperature and is not practical.
• the fullerene derivative with a trifluoromethyl group described in Non-Patent Document 1 has a low sublimation temperature of less than 400°C, but is not suitable for mass production because a special reaction device is required for synthesis.
• the present invention has been made in consideration of the above circumstances, and an object of the present invention is to provide a fullerene derivative that can be produced without the need for special synthesis equipment and that can be vapor-deposited at a low temperature with suppressed thermal decomposition. Another object of the present invention is to provide a thin film, a photoelectric conversion element, and a solid-state imaging device that include the fullerene derivative. Still another object of the present invention is to provide a method for producing the fullerene derivative.
• the present invention provides the following means to solve the above problems.
• [4] The fullerene derivative according to any one of the above items [1] to [3], wherein the fullerene skeleton is C 60 , C 70 , C 74 , C 76 , or C 78.
• [5] A thin film comprising the fullerene derivative according to any one of the preceding items [1] to [4].
• [6] The thin film according to the above [5], wherein the thin film is a vapor-deposited film.
• a first electrode and a second electrode facing each other; an organic layer disposed between the first electrode and the second electrode; having The organic layer of the photoelectric conversion element includes the fullerene derivative according to any one of items [1] to [4] above.
• the method for producing a fullerene derivative comprises reacting a radical obtained by eliminating X from a compound represented by the following formula with a fullerene.
• the fullerene derivative according to the present invention can be synthesized without requiring a special reaction apparatus, and can be sublimated at a low temperature at which thermal decomposition is suppressed, and can be formed into a film by a deposition method. Furthermore, the thin film, photoelectric conversion element, and solid-state imaging device according to the present invention can contain the above-mentioned fullerene derivative. Furthermore, the manufacturing method of the fullerene derivative according to the present invention can manufacture the above-mentioned fullerene derivative.
• the fullerene derivative according to this embodiment is a fullerene derivative having a partial structure represented by the following general formula (1).
• C * are adjacent carbon atoms forming a fullerene skeleton, and Rf represents a perfluoroalkylene group having 3 to 5 carbon atoms.
• fullerene derivative refers to a compound having a structure in which a specific group is added to a fullerene skeleton
• fulllerene skeleton refers to a carbon skeleton that constitutes a closed shell structure derived from fullerene
• the fullerene derivative according to this embodiment has a ring structure with 5 to 7 carbon atoms formed by adjacent carbon atoms on the fullerene skeleton and a perfluoroalkylene group. This structure allows the sublimation temperature to be low, making it suitable for use in film formation by vapor deposition, etc.
• Rf is a perfluoroalkylene group.
• the carbon number of Rf is 3 to 5, and from the viewpoint of stability, 4 is preferable. If the carbon number is less than 3 or more than 5, the structure of the resulting compound becomes unstable, it becomes prone to thermal decomposition, and synthesis becomes difficult.
• the fullerene skeleton in the fullerene derivative according to this embodiment can be selected from one or more having a carbon number of 60 to 200, and specific examples include C 60 , C 70 , C 76 , C 78 , C 82 , C 84 , C 90 , C 94 , C 96 , C 120 , and C 200. If a specific fullerene skeleton is desired from the viewpoint of the characteristics of the photoelectric conversion element described later, it may be selected.
• At least one selected from C 60 , C 70 , C 74 , C 76 and C 78 is more preferable, C 60 or C 70 is more preferable, and C 60 is particularly preferable.
• the fullerene derivative according to this embodiment has the above-mentioned structure, and thus the sublimation temperature can be lowered while maintaining stability. Therefore, decomposition of the fullerene derivative is suppressed, and deposition by sublimation becomes possible. From the viewpoint of lowering the sublimation temperature, it is more preferable that there are multiple partial structures represented by the general formula (1) for one fullerene skeleton, and from the viewpoint of avoiding the complication of synthesis or purification, it is preferable that there is only one partial structure.
• deposition is usually possible if the temperature at which a 10% weight loss occurs based on the initial weight ratio is 400° C. or less, and deposition is more reliable if the temperature at which a 50% weight loss occurs based on the initial weight ratio is 400° C. or less.
• Method of producing fullerene derivative The method for producing the fullerene derivative according to this embodiment can be performed without using a special reaction apparatus, and examples thereof include the following method.
• each X independently represents a bromine atom or an iodine atom, and Rf is the same as in formula (1).
• the fullerene used in the reaction preferably has a carbon number of 60 to 200, and specific examples include C60, C70, C76, C78, C82, C84, C90, C94, C96, C120, C200, etc., and among them, at least one selected from C60 , C70 , C74 , C76 , and C78 is preferable , C60 or C70 is more preferable, and C60 is particularly preferable.
• the fullerene used as the raw material has a smaller carbon number, and it is easier to obtain a fullerene with a higher purity, and in particular, C60 is easier to obtain a fullerene with a higher purity than other fullerenes.
• a solvent may also be used in the reaction.
• the solvent is not particularly limited, but a liquid that dissolves fullerene and the compound of formula (2) is preferred.
• solvents include benzene, toluene, xylene, trimethylbenzene, chlorobenzene, and 1,2-dichlorobenzene. Among these, 1,2-dichlorobenzene is preferred because of its high solubility in fullerene and the compound of formula (2).
• the reaction proceeds by the elimination of a bromine atom or iodine atom represented by X from the compound represented by formula (2) to generate a radical, which then reacts with the fullerene.
• Methods such as heating, light irradiation, and addition of a radical initiator can be used to generate the radical.
• the heating temperature is preferably high from the viewpoint of shortening the reaction time, and is preferably low from the viewpoint of increasing the reaction selectivity and improving the yield of the target product. From both of these viewpoints, the heating temperature may be selected according to the purpose, but it is usually preferable to select a temperature between 100°C and 250°C, and more preferably between 150°C and 200°C. When radicals are generated by heating, copper powder may be added to promote the reaction.
• the reaction time may be selected according to the purpose, but it is usually preferable to select a time between 1 minute and 120 hours, more preferably between 10 minutes and 48 hours, and even more preferably between 30 minutes and 24 hours.
• the pressure during the reaction is not particularly limited, but the reaction can be carried out under pressure, for example, when it is desired to carry out the reaction at a temperature near or above the boiling point of the solvent.
• pressurizing it is preferable to select, for example, a pressure between normal pressure and a gauge pressure of 1 MPa, and it is even more preferable to select a pressure between normal pressure and a gauge pressure of 0.2 MPa. Within this range, there is no need to use a large-scale pressurized reaction device.
• the thin film according to the present embodiment includes the fullerene derivative.
• the thin film may be formed by any method, such as a wet film formation method such as spin coating or slit coating, or a dry film formation method such as vapor deposition, but is preferably a vapor deposition film formed by vapor deposition.
• the thin film may be composed of only the fullerene derivative according to this embodiment, or may be composed of a mixture with other compounds.
• the other compounds may be, for example, compounds that are generally used in the organic layers of photoelectric conversion elements, which will be described later.
• the thin film is likely to maintain the inherent properties of the fullerene derivative, which can improve the optical properties and further improve the properties of the photoelectric conversion element and solid-state imaging device described later, compared to a thin film of unsubstituted fullerene (e.g., C60 ) that is prone to aggregation during film formation.
• a thin film of unsubstituted fullerene e.g., C60
• the absorption in the visible light region of about 400 nm to 500 nm is particularly reduced.
• the absorption coefficient of the thin film at a wavelength of 450 nm is smaller than the absorption coefficient of the thin film containing unsubstituted fullerene at a wavelength of 450 nm, and for example, the absorption coefficient of the thin film at a wavelength of 450 nm is about 1/2 or less of the absorption coefficient of the thin film containing unsubstituted fullerene at a wavelength of 450 nm.
• Compound 1b was a mixture of isomers with different positions at which the substituents were added. These compounds were identified by analysis using 13 C-NMR and 19 F-NMR (Advance Neo 400, manufactured by Bruker Japan) and a liquid chromatograph mass spectrometer (Agilent 6120 single quadrupole LC/MS, manufactured by Agilent Technologies).
• Synthesis Example 3 Synthesis of Compound 3 Synthesis and analysis were performed in the same manner as in Synthesis Example 1 above, except that decafluoro-1,5-diiodopropane was used instead of octafluoro-1,4-diiodobutane, to obtain 9 mg of compound 3a and 3 mg of compound 3b as brown solids.
• the chemical formula of compound 3a is shown below as (C3a)
• the chemical formula of compound 3b is shown below as (C3b).
• Compound 3b was a mixture of isomers with different positions at which the substituents were added.
• Synthesis Example 4 Synthesis of Compound 4 Synthesis and analysis were performed in the same manner as in Synthesis Example 1, except that the same molar amount of C70 was used instead of C60 in Synthesis Example 1, to obtain 15 mg of compound 4 as a brown solid.
• the chemical formula of compound 4 is shown below as (C4).
• Synthesis Example 5 Synthesis of Compound 5 Synthesis and analysis were performed in the same manner as in Synthesis Example 2, except that the same molar amount of C70 was used instead of C60 in Synthesis Example 1, to obtain 16 mg of compound 5 as a brown solid.
• the chemical formula of compound 5 is shown below as (C5).
• Example 1 Thermogravimetric analysis was carried out in a vacuum to confirm whether deposition by sublimation of compound 1a was possible and the sublimation temperature.
• a sample (about 5 mg) was placed in a vacuum thermogravimetric analyzer (VPE-9000, manufactured by Advance Riko Co., Ltd.). In a vacuum of 1 Pa or less, the temperature was raised from room temperature to 1000°C at a rate of 10°C/min. The temperature at which the weight of the sample decreased by 10% relative to the initial weight of the sample was defined as Ts (°C) (-10%), and the temperature at which the weight of the sample decreased by 50% relative to the initial weight of the sample was defined as Ts (°C) (-50%). The results are shown in Table 1.
• Example 1 Comparative Examples 1 to 5
• Thermogravimetric analysis and thermal stability test were carried out in the same manner as in Example 1, except that the compounds shown in Table 1 were used instead of compound 1a.
• the measurement results are shown in Table 1.
• Example 7 Comparative Examples 6 to 7
• Thermogravimetric analysis and thermal stability test were carried out in the same manner as in Example 1, except that the compounds shown in Table 2 were used instead of compound 1a.
• the measurement results are shown in Table 2.
• Example 1 to 6 when Examples 1 to 6 are compared with Comparative Examples 2 to 5, it is found that the fullerene derivative according to this embodiment can be sublimated at a lower temperature or at the same temperature as fullerene derivatives that have been known to sublime.
• Ts (°C) (-10%) when Example 3 is compared with Comparative Example 4 as an example of the same temperature, Ts (°C) (-10%) was 350°C for both, and Ts (°C) (-50%) was 390°C for both, but the residual rate was higher for compound 2a of Example 3.
• Example 8 when Example 8 is compared with Comparative Example 7, it is found that the results were similar even though the fullerene skeleton was different. From these, it was confirmed that the fullerene derivative according to this embodiment has higher thermal stability.
• the fullerene derivative according to this embodiment can be preferably used in photoelectric elements, solid-state imaging devices, etc.

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• 2023
  • 2023-11-28 JP JP2024561500A patent/JPWO2024117115A1/ja active Pending
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