A deuterated fluorene-based blue light polymer material and a preparation method of a film containing a planarized conformation

Abstract

The application provides a deuterated fluorene-based blue light polymer material and a preparation method of a planar conformation film. In order to solve the problems of insufficient stability of a PODPF material, the deuterated raw material is synthesized by using silver carbonate as a catalyst and heavy water as a deuterium source to directly perform H / D exchange on 2,7-dibromo-9-fluorenone deoxy, so that the problem of multiple deuterated synthesis steps is solved, and a novel main chain fully deuterated poly-4-alkoxy-9,9-diphenylfluorene polymer light-emitting material (d 15 -PODPF) is prepared, the material can be used for preparing the planar conformation film, the problems of high planar conformation content and strong inter-chain aggregation caused by annealing of the PODPF are solved, and the problems of reduced blue light color purity and fluorescence quantum efficiency are solved. The application further provides the deuterated fluorene-based blue light polymer material, the planar conformation film and application of the planar conformation film in an organic thin film optoelectronic device.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of optoelectronic polymer materials, and particularly relates to a deuterated fluorene-based blue light polymer material and a preparation method of a planar conformation film. BACKGROUND

[0002] In recent years, blue light emission stability has been one of the hotspots in the research of organic thin film optoelectronic devices. In order to solve this problem, researchers have proposed various solutions, among which the strategy of introducing deuterium element has gradually attracted attention. Deuterium (D) is a stable isotope of hydrogen (H) and has been widely studied due to its application in drug chemistry. In late 2021, LG Display Company used deuterated blue light materials to improve panel brightness, and by means of "heavy atom effect", the spin-orbit coupling of the light-emitting molecules was enhanced, significantly improving the quantum efficiency. At the same time, the shorter bond length and larger bond energy of C-D bond reduce the energy of the light-emitting material, thereby improving the stability and service life of the device.

[0003] Among the numerous light-emitting materials, polyfluorene polymers have become the most promising blue light polymers due to their excellent deep blue light emission, high fluorescence efficiency, and easy modification. The main chain of polyfluorene is composed of a conjugated backbone of carbon and hydrogen, which exhibits a wide bandgap structure, not only effectively emitting deep blue light, but also having certain mechanical flexibility, becoming a promising blue light semiconductor material. Previous studies have shown that inducing the polyfluorene main chain to form a planar conformation can significantly improve the performance and spectral stability of electroluminescent devices.

[0004] Despite some progress in improving the light-emitting efficiency and color purity of polyfluorene materials, there are still some technical problems. For example, the stability of the PODPF material itself is insufficient, and the purity of the device's light-emitting color needs to be improved. The existence of these problems limits its performance in practical applications, so further research is needed to optimize the synthesis and performance of polyfluorene polymer materials, thereby improving the overall performance of organic thin film optoelectronic devices. SUMMARY

[0005] The present application aims to at least solve one of the above-mentioned technical problems in the prior art. To this end, the present application provides a preparation method of a deuterated fluorene-based blue light polymer material, which solves the problems of high planar conformation content generated by PODPF annealing and strong inter-chain aggregation, which reduces the blue light color purity and fluorescence quantum efficiency.

[0006] The present application also provides a deuterated fluorene-based blue light polymer material.

[0007] The present application also provides a planar conformation film.

[0008] The present application also provides a preparation method of a planar conformation film.

[0009] The application further provides application of the planar conformation film in an organic thin film photoelectric device.

[0010] The first aspect of the application provides a preparation method of a deuterated fluorene-based blue light high polymer material, comprising the following steps:

[0011] S1: using 2,7-dibromo-9-fluorenone as a raw material, silver carbonate and cyclohexyl diphenyl phosphine as catalysts, and heavy water as a deuterium source, deuterated 2,7-dibromo-9-fluorenone is prepared;

[0012] S2: deuterated 2,7-dibromo lactone is prepared from the deuterated 2,7-dibromo-9-fluorenone through a Bayer-Villiger rearrangement reaction;

[0013] S3: deuterated 2,7-dibromo diol is prepared from the deuterated 2,7-dibromo lactone through a Grignard reaction;

[0014] S4: an alkyl substitution reaction of an alcohol hydroxyl group at the 4th position is performed on the deuterated 2,7-dibromo diol and 1-bromooctane to obtain an oil-like transparent solid product;

[0015] S5: the oil-like transparent solid product is used as a raw material to prepare a deuterated PODPF monomer;

[0016] S6: the deuterated PODPF monomer is made into a solution, and after a polymerization reaction, the deuterated fluorene-based blue light high polymer material is obtained through activation and reflux.

[0017] According to one technical solution in the preparation method of the deuterated fluorene-based blue light high polymer material, at least the following

[0018] Beneficial effects:

[0019] In view of the problems of insufficient stability of the PODPF material itself and the urgent need to improve the purity of the light-emitting color of the device, the application first uses silver carbonate as a catalyst and heavy water as a deuterium source to synthesize deuterated raw materials through one-step deoxygenation and direct H / D exchange of 2,7-dibromo-9-fluorenone, which solves the problem of multiple steps in deuterium synthesis, and a new type of main chain perdeuterated poly-4-alkoxy-9,9-diphenyl fluorene high polymer light-emitting material (d-PODPF) is prepared. 15 The material can be used to prepare a planar conformation film, and the problems of high planar conformation content generated by annealing of the PODPF and strong inter-chain aggregation reducing the blue light color purity and fluorescence quantum efficiency are solved.

[0020] The deuterated fluorene-based blue light high polymer material is a main chain perdeuterated conjugated structure.

[0021] According to some embodiments of the application, in step S1:

[0022] The CAS number of cyclohexyldiphenylphosphine is 6372-42-5.

[0023] Deuterated 2,7-dibromo-9-fluorenone was prepared in a high-boron glass sealed tube equipped with a magnetic stirring rod.

[0024] The preparation process can be repeated for several times, such as 3 times, and the deuterium enrichment rate is about 93%.

[0025] The raw material in the deuterium enrichment reaction can be 1 mmol, and the reaction is repeated three times.

[0026] The preparation method in step S1 adopts Yamamoto reaction.

[0027] When the polymer is purified, the solvent used is acetone.

[0028] According to some embodiments of the present application, in step S2, during the process of the Bayer-Villiger rearrangement reaction, trifluoroacetic acid and sodium carbonate are added.

[0029] According to some embodiments of the present application, in step S2, the Bayer-Villiger rearrangement reaction is carried out at room temperature.

[0030] According to some embodiments of the present application, in step S2, the time of the Bayer-Villiger rearrangement reaction is 60-80h.

[0031] According to some embodiments of the present application, in step S2, the time of the Bayer-Villiger rearrangement reaction is 70-80h.

[0032] According to some embodiments of the present application, in step S2, the time of the Bayer-Villiger rearrangement reaction is 72h.

[0033] According to some embodiments of the present application, in step S3, the solvent of the Grignard reaction includes toluene.

[0034] According to some embodiments of the present application, in step S3, the Grignard reaction is carried out under a protective atmosphere.

[0035] According to some embodiments of the present application, in step S3, the protective atmosphere includes nitrogen.

[0036] According to some embodiments of the present application, in step S3, the temperature of the reaction is 80-90℃.

[0037] According to some embodiments of the present application, in step S3, the temperature of the reaction is 85℃.

[0038] According to some embodiments of the present application, in step S3, the time of the reaction is 20h-30h.

[0039] According to some embodiments of the present application, the reaction time in step S3 is 24 hours.

[0040] According to some embodiments of the present application, the amount of Grignard reagent added in the reaction in step S3 is 4-6 equivalents of the deuterated 2,7-dibromolactone.

[0041] According to some embodiments of the present application, the alkyl substitution reaction in step S4 is carried out under alkaline conditions.

[0042] According to some embodiments of the present application, the solvent for the alkyl substitution reaction in step S4 is acetone.

[0043] According to some embodiments of the present application, the amount of 1-bromooctane added in step S4 is 1-2 equivalents of the deuterated 2,7-dibromolactone.

[0044] According to some embodiments of the present application, the amount of 1-bromooctane added in step S4 is 1.5 equivalents of the deuterated 2,7-dibromolactone.

[0045] In the present application, the addition of 1-bromooctane corresponds to a straight chain structure. If it is a branched chain, it cannot be controlled to form a planar conformation. The branched chain structure can only be controlled to form a spherulitic structure (tertiary structure). The present application controls the planar conformation, i.e., the secondary structure.

[0046] According to some embodiments of the present application, the alkyl substitution reaction in step S4 is carried out at room temperature.

[0047] According to some embodiments of the present application, the time for the alkyl substitution reaction in step S4 is 20-30 hours.

[0048] According to some embodiments of the present application, the time for the alkyl substitution reaction in step S4 is 24 hours.

[0049] According to some embodiments of the present application, the deuterated PODPF monomer is prepared by a Friedel-Crafts reaction in step S5.

[0050] According to some embodiments of the present application, the deuterated PODPF monomer is prepared by a Friedel-Crafts reaction in step S5, and the specific process can be that the product from the previous step is dissolved in anhydrous dichloromethane, and reacted for 2 hours under catalytic conditions of boron trifluoride-ethyl ether to obtain the product.

[0051] According to some embodiments of the present application, the specific process in step S6 can be:

[0052] Take equal amounts of bipyridine and nickel catalyst Ni(COD)2 in a Schlenk flask filled with N2, then activate in a DMF solution at 75℃ for 20min, then add a monomer solution dissolved in toluene, reflux at 85℃ for 3 days, then cap with 0.1mL dry deuterated bromobenzene, remove residual nickel catalyst with silicon-based metal scavenger during post-processing, purify the organic phase with Al2O3 column chromatography using DCM as the mobile phase, then concentrate the reaction solution, precipitate with anhydrous methanol, and finally wash with acetone by Soxhlet extraction for 3 days to obtain the polymer, then vacuum dry to obtain d 15 -PODPF yellow solid, i.e. deuterated poly-4-alkoxy-9,9-diphenylfluorene polymer light-emitting material (M n = 31747, n = 69).

[0053] Among them, equal amounts of bipyridine and nickel catalyst Ni(COD)2 are used as catalysts.

[0054] According to some embodiments of the present application, in step S6, the reaction time is 1.5-4h.

[0055] According to some embodiments of the present application, in step S6, the activation is carried out in a DMF solution.

[0056] According to some embodiments of the present application, in step S6, the monomer solution dissolved in toluene is added during reflux.

[0057] According to some embodiments of the present application, in step S6, after reflux, the cap is capped with dry deuterated bromobenzene.

[0058] The second aspect of the present application provides a deuterated fluorene-based blue light polymer material prepared by the preparation method of the first aspect of the present application.

[0059] One of the technical solutions of the technical scheme of the deuterated fluorene-based blue light polymer material of the present application has at least the following

[0060] Advantages:

[0061] Better stability: the C-D bond of deuterated material has higher stability than the C-H bond, reducing the degradation risk of light-emitting material during operation, thereby prolonging the service life of optoelectronic devices.

[0062] Higher light-emitting efficiency: through the "heavy atom effect" to enhance the spin-orbit coupling, which helps to improve the quantum efficiency of light-emitting molecules, thereby improving the overall light output of the device.

[0063] Better spectral purity: deuterium treatment can reduce the non-radiative inactivation path in light-emitting materials, improve the color purity of blue light emission, and ensure that the device can emit more accurate blue light.

[0064] More simplified synthesis process: using heavy water as a deuterium source, the deuterated raw material is synthesized by one-step method, which simplifies the synthesis steps, reduces production cost and time, and improves synthesis efficiency.

[0065] Can promote the formation of coplanar conformation: the prepared deuterated PODPF material can effectively promote the formation of coplanar conformation, enhance the electroluminescent performance of the material, and reduce the spectral drift caused by interchain aggregation.

[0066] Can enhance mechanical flexibility: the conjugated backbone structure of polyfluorene material endows it with good mechanical flexibility, so that the prepared thin film has better adaptability and durability in practical application.

[0067] The third aspect of the present application provides a planar conformation thin film, and the preparation raw material comprises the deuterated fluorene-based blue light polymer material of the second aspect of the present application.

[0068] One of the technical solutions of the present application related to planar conformation thin film has at least the following beneficial effects:

[0069] The planar conformation thin film containing deuterated fluorene-based blue light polymer material has a plurality of beneficial effects, mainly including:

[0070] Planar conformation helps to improve the electroluminescent efficiency of the material, reduce interchain aggregation and non-radiative energy loss, thereby improving the luminous intensity and quantum efficiency.

[0071] The thin film shows better spectral stability under light and heat environment, ensuring the consistency of spectral characteristics during long-term use.

[0072] The use of deuterated material reduces the generation of impurities during light emission, improves the color purity of blue light emission, and meets the requirements of high-quality displays and lighting equipment.

[0073] Due to the conjugated structure of polyfluorene, the thin film has certain mechanical flexibility and is suitable for various flexible electronic devices.

[0074] Planar conformation can be realized at a lower annealing temperature, reducing the thermal influence on the substrate and being suitable for processing of heat-sensitive materials.

[0075] The thin film material of the present application can be prepared by a simple solution method, and the process is relatively simple and suitable for large-scale production.

[0076] Due to its excellent optoelectronic properties, this thin film material can be widely used in organic light-emitting diodes (OLED), solar cells and other optoelectronic devices.

[0077] The fourth aspect of the present application provides a method for preparing the planarized conformation thin film of the third aspect of the present application, comprising the steps of coating a solution containing the deuterated fluorene-based blue light polymer material on the surface of a substrate and then annealing.

[0078] The present application relates to a technical solution in the preparation method of planarized conformation thin film, which has at least the following beneficial effects:

[0079] By directly coating the deuterated fluorene-based blue light polymer material solution on the surface of the substrate, the complex processing steps are reduced, and the production efficiency is improved.

[0080] The coating process can form a uniform thin film, improve the performance consistency of optoelectronic devices, and ensure that the luminescent properties are uniformly distributed throughout the thin film.

[0081] The annealing process can promote the rearrangement of molecular chains, making them more tend to planarized conformation, thereby improving the electroluminescent performance and stability.

[0082] Annealing helps to remove solvent residues, improve the overall density of the thin film, and enhance the spectral stability under working conditions.

[0083] According to some embodiments of the present application, the preparation method of the planarized conformation thin film can be:

[0084] Different amounts of polymer powder are weighed and placed in a 1.5 mL clean sample bottle, 1 mL of solvent is added, and the mixture is stirred at 60℃ for 30 min. After the polymer powder is completely dissolved, polymer chloroform solutions with different concentrations are obtained.

[0085] A quartz piece with a side length of 1.5 cm is used as the substrate. The quartz substrate is cleaned with solvents such as acetone and dichloromethane. 45 microliters of polymer chloroform solution are obtained, and a uniform coating is formed on the quartz substrate using a spin coater or a doctor blade coater. The resulting thin film is used to prepare planarized conformation.

[0086] The above thin film is placed on a heating stage, and a series of planarized conformation thin films with different contents are obtained by adjusting the annealing temperature (higher than 200℃).

[0087] In the preparation method of the planarized conformation thin film, the heat annealing temperature is 180℃-340℃.

[0088] In the preparation method of the planarized conformation thin film, the heat annealing temperature is 200℃-280℃.

[0089] The fifth aspect of the present application provides the application of the planarized conformation thin film of the fourth aspect of the present application in organic thin film optoelectronic devices.

[0090] The planarized conformation thin film prepared from deuterated fluorene-based blue light polymer material applied to organic thin film optoelectronic devices can bring the following beneficial effects:

[0091] Enhanced luminous efficiency: due to the planarized conformation reducing inter-chain aggregation and non-radiative energy loss, it can significantly improve the luminous intensity and quantum efficiency in organic light-emitting diodes (OLED), thereby improving the overall optoelectronic performance.

[0092] Enhanced spectral stability: the thin film shows good spectral stability under light and heat environment, which helps to maintain the consistency of spectral characteristics during long-term use of the device, ensuring the display quality and service life.

[0093] Improved color purity: the introduction of deuterated material reduces the generation of impurities in the light-emitting process, improving the color purity of blue light emission, meeting the requirements of high-quality displays and lighting devices, and ensuring accurate color reproduction.

[0094] Mechanical flexibility: the conjugated structure of polyfluorene makes the thin film have certain mechanical flexibility, which is suitable for various flexible electronic devices, expanding the application range.

[0095] Low-temperature processing adaptability: the planarized conformation can be achieved at a lower annealing temperature, reducing the thermal impact on the substrate, suitable for processing of heat-sensitive materials, and expanding the types of compatible substrates.

[0096] Simplified preparation process: the thin film is prepared by a simple solution method, the process is relatively simple, easy to mass production, and reduces production cost and time.

[0097] Wide application potential: due to its excellent optoelectronic properties, the thin film material can be widely used in OLED, solar cells and other optoelectronic devices, promoting the progress of related technologies and market applications.

[0098] According to some embodiments of the present application, the organic thin film optoelectronic device includes an organic light-emitting diode, an organic field-effect transistor, an organic thin film laser, and an organic spin valve. BRIEF DESCRIPTION OF DRAWINGS

[0099] Figure 1 is the UV-Vis absorption spectrum and fluorescence emission spectrum of the original thin film and the thin film after heat treatment of the fluorene-based polymer obtained in Example 1 and Comparative Example 1 of the present application.

[0100] Figure 2 is the UV-Vis absorption spectrum and fluorescence emission spectrum of the original thin film and the thin film after heat treatment of the fluorene-based polymer obtained in Example 2 and Comparative Example 2 of the present application.

[0101] Figure 3 is the UV-Vis absorption spectrum and fluorescence emission spectrum of the original thin film and the thin film after heat treatment of the fluorene-based polymer obtained in Example 3 and Comparative Example 3 of the present application.

[0102] Figure 4 is the lifetime diagram of the fluorenyl high molecular raw film and the film after heat treatment obtained by the embodiment 123 and the comparative example 123 of the present application.

[0103] Figure 5 is the device structure diagram of the fluorenyl high molecular film with planarization conformation obtained by the embodiment 1 and the comparative example 1 of the present application.

[0104] Figure 6 is the device performance diagram of the fluorenyl high molecular film with planarization conformation obtained by the embodiment 1 and the comparative example 1 of the present application.

[0105] Figure 7 is the nuclear magnetic hydrogen spectrum of the polymer synthesized in the embodiment 1 of the present application.

[0106] Figure 8 is the GPC test of the polymer synthesized in the embodiment 1 of the present application. DETAILED DESCRIPTION

[0107] The following are specific embodiments of the present application, and the technical solutions of the present application are further described in combination with the embodiments, but the present application is not limited to these embodiments.

[0108] In the first aspect, some embodiments of the present application provide a preparation method of deuterated fluorenyl blue light high molecular material, comprising the following steps:

[0109] S1: taking 2,7-dibromo-9-fluorenone as raw material, silver carbonate and cyclohexyl diphenyl phosphine as catalyst, and heavy water as deuterium source, to prepare deuterated 2,7-dibromo-9-fluorenone;

[0110] S2: preparing deuterated 2,7-dibromo lactone from deuterated 2,7-dibromo-9-fluorenone by Bayer-Vilsmeyer rearrangement reaction;

[0111] S3: preparing deuterated 2,7-dibromo diol from deuterated 2,7-dibromo lactone by Grignard reaction;

[0112] S4: preparing oil transparent solid product by alkyl substitution reaction of alcohol hydroxyl group at position 4 from deuterated 2,7-dibromo diol and 1-bromooctane;

[0113] S5: taking the oil transparent solid product as raw material, to prepare deuterated PODPF monomer;

[0114] S6: preparing solution from the deuterated PODPF monomer, after polymerization reaction, activation and reflux, to obtain the deuterated fluorenyl blue light high molecular material.

[0115] It can be understood that, in order to solve the problems of insufficient stability of the PODPF material itself and the purity of the light color of the device to be improved, the present application first uses silver carbonate as a catalyst and heavy water as a deuterium source to synthesize a deuterated raw material by directly deoxygenating 2,7-dibromo-9-fluorenone through H / D exchange in one step, which solves the problem of multiple steps in deuterated synthesis, and a new type of main chain perdeuterated poly-4-alkoxy-9,9-diphenylfluorene polymer light-emitting material (d 15 PODPF) can be used to prepare a planar conformation thin film, which solves the problems of high planar conformation content generated by annealing of the PODPF and strong inter-chain aggregation, which reduces the blue light color purity and the fluorescence quantum efficiency.

[0116] The deuterated fluorenyl blue light polymer material is a main chain perdeuterated conjugated structure.

[0117] According to some embodiments of the present application, in step S1:

[0118] The CAS number of cyclohexyldiphenyl phosphine is 6372-42-5.

[0119] The deuterated 2,7-dibromo-9-fluorenone is prepared in a high-boron glass envelope equipped with a magnetic stirring rod.

[0120] The preparation process can be repeated for multiple times, such as 3 times, and the deuterium enrichment rate is about 93%.

[0121] The raw material in the deuterium enrichment reaction can be 1 mmol, and the reaction is repeated three times.

[0122] The preparation method in step S1 adopts Yamamoto reaction.

[0123] When the polymer is purified, acetone is used as the solvent.

[0124] In combination with the first aspect, in some embodiments of the present application, in step S2, during the Bayer-Villiger rearrangement reaction, trifluoroacetic acid and sodium percarbonate are added.

[0125] In combination with the first aspect, in some embodiments of the present application, in step S2, the Bayer-Villiger rearrangement reaction is carried out at room temperature.

[0126] In combination with the first aspect, in some embodiments of the present application, in step S2, the time of the Bayer-Villiger rearrangement reaction is 60-80 h.

[0127] In combination with the first aspect, in some embodiments of the present application, in step S2, the time of the Bayer-Villiger rearrangement reaction is 70-80 h.

[0128] In combination with the first aspect, in some embodiments of the present application, in step S2, the time of the Bayer-Villiger rearrangement reaction is 72 h.

[0129] In some embodiments of the first aspect, the solvent for the formylation reaction in step S3 comprises toluene.

[0130] In some embodiments of the first aspect, the formylation reaction in step S3 is performed under a protective atmosphere.

[0131] In some embodiments of the first aspect, the protective atmosphere in step S3 comprises nitrogen.

[0132] In some embodiments of the first aspect, the temperature for the reaction in step S3 is 80-90℃.

[0133] In some embodiments of the first aspect, the temperature for the reaction in step S3 is 85℃.

[0134] In some embodiments of the first aspect, the time for the reaction in step S3 is 20-30h.

[0135] In some embodiments of the first aspect, the time for the reaction in step S3 is 24h.

[0136] In some embodiments of the first aspect, the amount of formylation reagent added in the formylation reaction in step S3 is 4-6 equivalents of the deuterated 2,7-dibromolactone.

[0137] In some embodiments of the first aspect, the alkyl substitution reaction in step S4 is performed under basic conditions.

[0138] In some embodiments of the first aspect, the solvent for the alkyl substitution reaction in step S4 is acetone.

[0139] In some embodiments of the first aspect, the amount of 1-bromooctane added in step S4 is 1-2 equivalents of the deuterated 2,7-dibromolactone.

[0140] In some embodiments of the first aspect, the amount of 1-bromooctane added in step S4 is 1.5 equivalents of the deuterated 2,7-dibromolactone.

[0141] In the present application, the addition of 1-bromooctane corresponds to a straight chain structure. If it is a branched chain, it cannot be controlled to form a planar conformation. The branched chain structure can only be controlled to form a spherulitic structure (tertiary structure). The present application controls the planar conformation, i.e., the secondary structure.

[0142] In some embodiments of the first aspect, the alkyl substitution reaction in step S4 is performed at room temperature.

[0143] In some embodiments of the first aspect, the time for the alkyl substitution reaction in step S4 is 20-30 hours.

[0144] In some embodiments of the first aspect, the time for the alkyl substitution reaction in step S4 is 24 hours.

[0145] In some embodiments of the first aspect, the deuterated PODPF monomer is prepared by a Friedel-Crafts reaction in step S5.

[0146] In some embodiments of the first aspect, the deuterated PODPF monomer is prepared by a Friedel-Crafts reaction in step S5, and the specific process can be that the product of the previous step is dissolved in anhydrous dichloromethane, and reacted for 2 hours under the catalysis of boron trifluoride-ethyl ether to obtain the product.

[0147] In some embodiments of the first aspect, the specific process in step S6 can be:

[0148] An equal amount of bipyridine and nickel catalyst Ni(COD)2 is placed in a Schlenk flask filled with N2, and then activated in a DMF solution at 75°C for 20 min. Then, a monomer solution dissolved in toluene is added, and the solution is refluxed at 85°C for 3 days. Then, 0.1 mL of dry deuterated bromobenzene is used for capping, and residual nickel catalyst is removed by a silicon-based metal scavenger. The organic phase is purified by column chromatography using DCM as the mobile phase and Al2O3 as the column material. Then, the reaction solution is concentrated, precipitated in anhydrous methanol, and washed by Soxhlet extraction with acetone for 3 days to obtain the polymer. Then, the polymer is dried under vacuum to obtain d 15 PODPF yellow solid, i.e., poly-4-alkoxy-9,9-diphenylfluorene macromolecular light-emitting material (M n = 31747, n = 69).

[0149] In the formula, an equal amount of bipyridine and nickel catalyst Ni(COD)2 is used as a catalyst to promote the reaction to proceed in the positive direction, and avoid the rapid quenching of the catalyst, which leads to the premature termination of the reaction.

[0150] In some embodiments of the first aspect, the time for the reaction in step S6 is 1.5-4 hours.

[0151] In some embodiments of the first aspect, the activation in step S6 is performed in a DMF solution.

[0152] In some embodiments of the first aspect, the monomer solution dissolved in toluene is added during the reflux process in step S6.

[0153] With reference to the first aspect, in some embodiments of the present application, in step S6, the polymerization is terminated by using dry deuterated bromobenzene after refluxing.

[0154] The specific preparation method of the deuterated fluorene-based polymer is as follows: the fluorenone raw material required for the reaction is subjected to one-step deuterated substitution, then a straight-chain fluorene-based monomer with a side chain of 8 carbons is synthesized for polymerization, the mass ratio of bipyridine and Ni(COD)2 is 1:1, after activation in a DMF solution at 75 DEG C for 20 min, a monomer solution dissolved in toluene is added. After refluxing at 85 DEG C in the dark for 3 days, 0.1 mL of dry deuterated bromobenzene is injected to terminate the reaction (12 hours), and the target polymer is obtained after purification treatment.

[0155] The purification is performed by using a Soxhlet extraction method with acetone as the solvent. The oligomers are quickly eluted and purified by taking advantage of the different solubilities of the oligomers and the polymer in acetone.

[0156] The preparation route of the poly-4-alkoxy-9,9-diphenylfluorene high polymer light-emitting material is as follows:

[0157]

[0158] In the molecular formula, x and y represent the number of monomer units in two different bonding modes, and the unit number is a positive integer; n is the number of structural monomers, which is a positive integer; the number of structural monomers ranges from 25 to 80, and the molecular weight of the polymer ranges from 20,000 to 50,000.

[0159] The poly-4-alkoxy-9,9-diphenylfluorene high polymer light-emitting material is a conjugated fluorene-based polymer material, and the main chain structure is a perdeuterated structure. The perdeuterated structure can significantly reduce the molecular chain vibration frequency of the material, improve the light-emitting stability and light-emitting efficiency of the material, and facilitate the regulation of the planar conformation. The material is synthesized by using a one-step reaction, the catalyst is silver carbonate, the deuterium source is heavy water, the polymerization reaction is Yamamoto reaction, the catalyst is an equal amount of bipyridine and Ni(COD)2, the capping agent is deuterated bromobenzene, and the reaction is performed in the dark and in an oxygen-free atmosphere.

[0160] In the second aspect, in some embodiments of the present application, a deuterated fluorene-based blue light high polymer material is provided, which is prepared by the preparation method of the first aspect of the present application.

[0161] The deuterated fluorene-based blue light high polymer material has at least the following beneficial effects:

[0162] Better stability: the C-D bond of the deuterated material has higher stability than the C-H bond, which reduces the degradation risk of the photosensitive material during operation, thereby prolonging the service life of the optoelectronic device.

[0163] Higher luminous efficiency: Enhanced spin-orbit coupling through "heavy atom effect" helps to improve the quantum efficiency of light-emitting molecules, thus increasing the overall light output of the device.

[0164] Better spectral purity: Deuterium treatment can reduce non-radiative inactivation pathways in light-emitting materials, improving the color purity of blue light emission, ensuring that the device can emit more accurate blue light.

[0165] Simplified synthesis process: Using heavy water as a deuterium source, deuterated raw materials are synthesized by one-step method, simplifying the synthesis steps, reducing production cost and time, and improving synthesis efficiency.

[0166] Promote coplanar conformation: The prepared deuterated PODPF material can effectively promote the formation of coplanar conformation, enhance the electroluminescent performance of the material, and reduce the spectral shift caused by interchain aggregation.

[0167] Enhance mechanical flexibility: The conjugated backbone structure of polyfluorene material gives it good mechanical flexibility, making the prepared thin film have better adaptability and durability in practical application.

[0168] In the third aspect, some embodiments of the present application provide a planar conformation thin film, and the preparation raw material includes the deuterated fluorene-based blue light polymer material of the second aspect of the present application.

[0169] It can be understood that the planar conformation thin film containing the deuterated fluorene-based blue light polymer material has many beneficial effects, mainly including:

[0170] Planar conformation helps to improve the electroluminescent efficiency of the material, reduces interchain aggregation and non-radiative energy loss, thereby improving the luminous intensity and quantum efficiency.

[0171] The thin film shows better spectral stability under light and heat environment, ensuring the consistency of spectral characteristics during long-term use.

[0172] The use of deuterated materials reduces the generation of impurities during light emission, improves the color purity of blue light emission, and meets the requirements of high-quality displays and lighting equipment.

[0173] Due to the conjugated structure of polyfluorene, the thin film has certain mechanical flexibility and is suitable for various flexible electronic devices.

[0174] Planar conformation can be achieved at a lower annealing temperature, reducing the thermal impact on the substrate and being suitable for processing of heat-sensitive materials.

[0175] The thin film material of the present application can be prepared by a simple solution method, and the process is relatively simple, which is convenient for large-scale production.

[0176] Due to its excellent photoelectric properties, the thin film material can be widely used in organic light emitting diodes (OLED), solar cells and other optoelectronic devices.

[0177] The planarized conformation thin film has an absorption shoulder peak at about 436-440 nm and fluorescence characteristic peaks at 448 nm and 478 nm.

[0178] In the fourth aspect, some embodiments of the present application provide a method for preparing the planarized conformation thin film of the third aspect of the present application, comprising the step of coating a solution containing the deuterated fluorene-based blue light polymer material on the surface of a substrate and then annealing.

[0179] By directly coating the deuterated fluorene-based blue light polymer material solution on the surface of the substrate, the complex processing steps are reduced, and the production efficiency is improved.

[0180] The coating process can form a uniform thin film, improve the performance consistency of optoelectronic devices, and ensure that the light-emitting characteristics are uniformly distributed throughout the thin film.

[0181] The annealing process can promote the rearrangement of molecular chains, making them more tend to planarized conformation, thereby improving the electroluminescent performance and stability.

[0182] Annealing helps to remove solvent residues, improve the overall density of the thin film, and enhance its spectral stability under working conditions.

[0183] According to some embodiments of the present application, the method for preparing the planarized conformation thin film can be:

[0184] Different amounts of polymer powder are weighed and placed in a 1.5 mL clean sample bottle, 1 mL of solvent is added, and the mixture is stirred at 60°C for 30 min. After the polymer powder is completely dissolved, polymer chloroform solutions of different concentrations are obtained.

[0185] A quartz piece with a side length of 1.5 cm is used as the substrate. The quartz substrate is cleaned with solvents such as acetone and dichloromethane. 45 microliters of polymer chloroform solution is obtained, which is uniformly coated on the quartz substrate using a spin coater (or a doctor blade coater), to obtain a thin film for preparing planarized conformation.

[0186] The above thin film is placed on a heating stage, and by adjusting the annealing temperature (higher than 200°C), a series of planarized conformation thin films with different contents can be obtained.

[0187] In the method for preparing the planarized conformation thin film, the heat annealing temperature is 180-340°C.

[0188] In the method for preparing the planarized conformation thin film, the heat annealing temperature is 200-280°C.

[0189] The thin film in S3 is regulated to have different contents of planarization conformations by using a thermal annealing method.

[0190] Properly increasing the temperature is beneficial to the material approaching its glass transition temperature, improving the activity of the molecular chain of the thin film, and more beneficial to the formation of planarization conformations.

[0191] The specific method is as follows: the thin film in S3 is placed on a heating table at 200 DEG C, in a nitrogen atmosphere (or an air atmosphere), heated for about 5 minutes, and cooled to room temperature to obtain a fluorene-based polymer thin film with a trace amount of planarization conformations.

[0192] In the preparation method of the planarization conformation thin film, chloroform is selected as the solvent, and the solution concentration is 6-10 mg / mL. The fluorene-based polymer material has high solubility in chloroform, and different concentrations are beneficial to the preparation of thin films with different thicknesses.

[0193] The thin film is prepared by using a spin coating and a blade coating process. Compared with the pouring film forming method, the spin coating and the blade coating thin film are more flat.

[0194] The spin coating rotation speed of the thin film is 1000 rmp, and the acceleration is 800 rmp / s. The blade coating speed is 5 mm / s, and the duration is 10 s.

[0195] The preparation method is as follows: a 1.5 cm*1.5 cm quartz sheet is used as a substrate, 45 microliters of the above-mentioned solution is taken, the rotation speed of the coating machine is adjusted to 1000 rmp, the acceleration is 800 rmp / s, and the duration is 60 s to obtain a deuterated fluorene-based polymer thin film. A 1 cm*1 cm quartz sheet is used as a substrate, 20 microliters of the above-mentioned solution is taken, the blade speed is adjusted to 5 mm / s, and the duration is 10 s to obtain a fluorene-based polymer thin film.

[0196] The polymer thin film with different thicknesses and flat surfaces can be obtained.

[0197] The preparation method of the present application utilizes the stability of C-D bonds and the large size of deuterium atoms to improve the planarization of the main chain, realizes the rapid batch preparation of the fluorene-based thin film with planarization conformations, improves the ability of the fluorene-based thin film to form planarization conformations, improves the blue light emission efficiency and stability, and solves the problem of reduced light emission efficiency of the planarization conformation thin film formed in ordinary fluorene-based polymer materials.

[0198] In a fifth aspect, in some embodiments of the present application, the planarization conformation thin film of the fourth aspect of the present application is applied to an organic thin film optoelectronic device.

[0199] The planarization conformation thin film prepared from the deuterated fluorene-based blue light polymer material is applied to an organic thin film optoelectronic device, which can bring the following beneficial effects:

[0200] Enhanced light-emitting efficiency: Due to the planarized conformation reducing inter-chain aggregation and non-radiative energy loss, the light-emitting intensity and quantum efficiency in organic light-emitting diodes (OLEDs) can be significantly improved, thus enhancing the overall optoelectronic performance.

[0201] Enhanced spectral stability: The thin film exhibits good spectral stability under light and heat environments, helping to maintain the consistency of spectral characteristics during long-term use of the device, ensuring display quality and service life.

[0202] Improved color purity: The introduction of deuterated materials reduces the generation of impurities during the light-emitting process, improving the color purity of blue light emission, meeting the requirements of high-quality displays and lighting devices, and ensuring accurate color reproduction.

[0203] Mechanical flexibility: The conjugated structure of polyfluorene makes the thin film mechanically flexible, suitable for various flexible electronic devices, expanding the application range.

[0204] Low-temperature processing adaptability: The planarized conformation can be achieved at a lower annealing temperature, reducing the thermal impact on the substrate, suitable for processing of heat-sensitive materials, and expanding the types of compatible substrates.

[0205] Simplified preparation process: The thin film is prepared using a simple solution method, with a relatively simple process, easy to mass-produce, reducing production costs and time.

[0206] Wide application potential: Due to its excellent optoelectronic properties, this thin film material can be widely used in OLEDs, solar cells, and other optoelectronic devices, promoting the progress of related technologies and market applications.

[0207] According to some embodiments of the present application, the organic thin film optoelectronic device includes an organic light-emitting diode, an organic field-effect transistor, an organic thin film laser, and an organic spin valve.

[0208] An organic light-emitting diode (OLED) is an electronic device that utilizes organic materials to emit light. Its working principle is to make the organic layer emit light through current flow. The main advantages include:

[0209] High color quality: Rich color performance and high contrast can be achieved.

[0210] Light and flexible: Ultra-thin and flexible display screens can be manufactured, suitable for various electronic devices.

[0211] Wide viewing angle: Color and brightness remain stable even at a very large viewing angle.

[0212] Low energy consumption: Compared with traditional liquid crystal displays, OLEDs perform better in energy efficiency.

[0213] An organic field-effect transistor (OFET) is a type of field-effect transistor based on organic materials, primarily used for switching and signal amplification. Its advantages include:

[0214] Plasticity: It can be made into flexible electronic devices, suitable for wearable devices and foldable screens.

[0215] Low cost: The production process is simple and suitable for large-scale manufacturing.

[0216] High mobility: In some organic materials, the mobility of electrons and holes can reach high levels, supporting high-performance devices.

[0217] Organic thin-film lasers are lasers based on organic materials, utilizing organic semiconductors to emit light under stimulated emission. Their characteristics include:

[0218] Low threshold excitation: Organic lasers typically have a lower threshold excitation energy compared to inorganic lasers.

[0219] Diverse colors: By selecting different organic materials, laser output in a variety of colors can be achieved.

[0220] Flexible and lightweight: suitable for a variety of applications, including portable and wearable devices.

[0221] An organic spin valve is a device that combines spintronics and organic materials to achieve information processing by manipulating electron spin. Its characteristics include:

[0222] Low power consumption: The spin transport property can significantly reduce power consumption, making it suitable for high-efficiency electronic devices.

[0223] Flexible applications: Due to the flexibility of organic materials, they can be integrated into devices of various shapes.

[0224] Novel features: Combining the properties of spin and charge allows for the development of novel storage and logic devices.

[0225] These devices have broad application prospects in modern electronic technology, especially in fields such as flexible electronics, wearable technology, and high-performance displays.

[0226] The following will describe the concept and technical effects of the present invention clearly and completely with reference to embodiments, so as to fully understand the purpose, features and effects of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are all within the scope of protection of the present invention.

[0227] In the description of the application, the description of the terms "one embodiment", "some embodiments", "exemplary embodiment", "example", "specific example", or "some examples" means that the specific feature, structure, material, or characteristic being described is included in at least one embodiment or example of the application. The illustrative descriptions of the above terms in this specification are not necessarily referring to the same embodiment or example. Moreover, the specific features, structures, materials, or characteristics can be combined in any suitable manner in one or more embodiments or examples.

[0228] Unless otherwise specified, "room temperature" in the present application means 25°C ± 5°C.

[0229] Unless otherwise specified, "about" in the present application means that the allowable error is within ± 2%.

[0230] Unless otherwise specified, the specific conditions in the examples are carried out according to the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used are not specified by the manufacturer, and are all conventional products that can be purchased on the market.

[0231] Example 1

[0232] First, a deuterated fluorene-based blue light polymer material is prepared, and then a planarized conformation film is prepared, as follows:

[0233] S1, deuterated 2,7-dibromo-9-fluorenone (1) is prepared in a high boron glass sealed tube equipped with a magnetic stirring rod:

[0234] 1 mmol of 2,7-dibromo-9-fluorenone, 0.2 mmol of silver carbonate, 0.5 mmol of cyclohexyldiphenyl phosphine, 1 mmol of potassium carbonate, 20 mmol of heavy water, and 0.2 mL of toluene are placed in the sealed tube, the reaction temperature is adjusted to 120°C, and the reaction is stopped after stirring for 24 hours. The sealed tube is removed and allowed to cool to room temperature, then saturated ammonium chloride solution is added to the high boron glass sealed tube to quench the reaction, and liquid-liquid extraction is performed to obtain the organic extract, which is dried with anhydrous magnesium sulfate and concentrated in a rotary evaporator to obtain the crude product.

[0235] Subsequently, purification is carried out by silica gel column chromatography with petroleum ether: dichloromethane (2:1) as the eluent to obtain a yellow powder. The above procedure is repeated 3 times, and the deuterium substitution rate is about 93%. Note: Do not open a large amount, the best reaction amount is 1 mmol (338 mg of fluorenone), and the amount of toluene should not be too much, about 0.2 mL is appropriate, otherwise it will affect the deuterium substitution rate (fluorenone is difficult to dissolve, but it can be dissolved after heating and stirring, but it cannot be completely dissolved).

[0236] To a reaction flask was added 2.8 g of deuterated 2,7-dibromo-9-fluorenone (8.28 mmol) (1) and 30 mL of dichloromethane was added to dissolve the compound in an ice water bath. 25 mL of trifluoroacetic acid was added and 1.0 g of sodium percarbonate was added every 15 minutes for a total of 5 times. The ice water bath was removed and the reaction was stirred at room temperature for 72 hours. The reaction was then quenched with saturated aqueous sodium bicarbonate solution and the residual trifluoroacetic acid was removed. The aqueous phase was extracted with dichloromethane to obtain the organic extract which was dried over anhydrous magnesium sulfate and concentrated by evaporation in a rotary evaporator to obtain the crude product.

[0237] The crude product was purified by silica gel column chromatography using petroleum ether: dichloromethane (4: 1) as the eluent to obtain deuterated 2,7-dibromolactone as a white powder (2).

[0238] Next, 12 mL of deuterated bromobenzene, 72.4 mmol of magnesium turnings (1.8 g), and an iodine pellet were added to a reaction flask and purged with N2 three times. Tetrahydrofuran was added to the flask under an ice water bath until the magnesium turnings were completely reacted to obtain a gray Grignard reagent (3).

[0239] To a three-necked flask was added 12 mmol of deuterated 2,7-dibromolactone (4.2 g) (2) and purged with N2 three times. The flask was sealed and 60 mL of anhydrous toluene and the Grignard reagent were added. The reaction was refluxed at 85°C for 8 hours and then cooled to room temperature. The reaction was quenched with saturated aqueous ammonium chloride solution and the aqueous phase was extracted with dichloromethane to obtain the organic extract which was dried over anhydrous magnesium sulfate and concentrated by evaporation in a rotary evaporator to obtain the crude product. The crude product was purified by silica gel column chromatography using petroleum ether: dichloromethane (2: 1) and then petroleum ether: ethyl acetate (6: 1) as the eluent to obtain deuterated 2,7-dibromodiol as a white solid (4).

[0240] Next, 4 mmol of (4), 7.2 mmol of anhydrous potassium carbonate, and 7.8 mmol of n-bromooctane were added to a pear-shaped flask and dissolved in 30 mL of acetone. The reaction was carried out at room temperature for 12 hours.

[0241] The crude product was extracted, washed, dried, and concentrated to obtain a transparent oily solid (5) which was dissolved in anhydrous dichloromethane. Then, about 0.2 mL of boron trifluoride etherate was added and the reaction was stirred at room temperature for 24 hours. The reaction was quenched with 5 mL of water. The crude product was extracted, washed, dried, and concentrated. The product was purified by silica gel column chromatography using petroleum ether: dichloromethane (3: 1) as the eluent to obtain deuterated PODPF monomer as a white solid (6).

[0242] A target polymer d was prepared in a 10 mL Schlenk flask equipped with a magnetic stir bar 15-PODPF(7): 0.5 g of bipyridine and Ni(COD)2 were taken in a Schlenk tube, washed with N2 for three times, after activation in DMF solution at 75 °C for 20 min, monomer solution dissolved in dry and oxygen-free toluene was injected, the reaction temperature was adjusted to 85 °C, after dark reflux reaction for 3 days, 0.1 mL of dry deuterated bromobenzene was injected to terminate the reaction for 12 h, after the reaction was completed, the residual reactants were removed by suction filtration with a Buchner funnel, the filtrate of the target polymer was obtained, the residual nickel catalyst was removed with a silicon-based scavenger, the organic phase was purified with an Al2O3 column chromatography with dichloromethane as the mobile phase, then the reaction liquid was concentrated, anhydrous methanol was added to precipitate a yellowish silk-like solid, after Soxhlet extraction with acetone for 3 days, vacuum drying was performed to obtain d 15 -PODPF yellow solid (M n = 31747, n = 69).

[0243] S2, 10 mg of polymer was weighed and placed in a 1.5 mL clean sample bottle, 1 mL of chloroform solvent was added, and stirred at 60 °C for 30 min, until the polymer was completely dissolved, obtaining a polymer chloroform solution with a concentration of 10 mg / mL.

[0244] S3, a quartz sheet with a side length of 1.5 cm was used as the substrate, the quartz substrate was first cleaned with solvents such as acetone and dichloromethane, the spin coater speed was adjusted to 1000 rpm, the acceleration was 800 rpm / s, 45 microliters of polymer chloroform solution was taken, and the uniform coating spin coater was used to uniformly coat it on the quartz substrate, obtaining a thin film with a thickness of 55 nanometers.

[0245] S4, the above original thin film was placed on a heating stage, the annealing temperature was adjusted to 200 °C, and heated for 10 min, obtaining a thin film with a planar conformation content of about 6%.

[0246] Example 2

[0247] First, a deuterated fluorene-based blue light polymer material was prepared, and then a planar conformation thin film was prepared, as follows:

[0248] S1. Preparation of deuterated 2,7-dibromo-9-fluorenone (1) in a high boron glass vial equipped with a magnetic stir bar: 1 mmol of 2,7-dibromo-9-fluorenone, 0.2 mmol of silver carbonate, 0.5 mmol of cyclohexyldiphenylphosphonium, 1 mmol of potassium carbonate, 20 mmol of heavy water and 0.2 mL of toluene were placed in the vial and the reaction temperature was adjusted to 120 °C. The reaction was stopped after 24 hours of stirring and the vial was removed to allow the temperature to drop to room temperature. Subsequently, a saturated solution of ammonium chloride was added to the high boron glass vial to quench the reaction and the liquid-liquid extraction was performed. The organic extract was dried over anhydrous magnesium sulfate and concentrated in a rotary evaporator to obtain the crude product. Subsequently, the yellow powder was purified by column chromatography on silica gel using petroleum ether: dichloromethane (2: 1) as eluent. The procedure was repeated three times with a deuterium incorporation of about 93%. Notes: Do not open the vial too much, the optimal reaction amount is 1 mmol (338 mg of fluorenone) and the amount of toluene should not be too high, about 0.2 mL is appropriate, otherwise the deuterium incorporation of the material will be affected (the fluorenone does not dissolve well, after heating and stirring it dissolves but not completely).

[0249] To a reaction flask was added 2.8 g of deuterated 2,7-dibromo-9-fluorenone (8.28 mmol) (1) and 30 mL of dichloromethane was injected to dissolve the compound in an ice water bath. 25 mL of trifluoroacetic acid was injected and 1.0 g of sodium percarbonate was added every 15 minutes for a total of 5 times. After the ice water bath was removed, the reaction was stirred at room temperature for 72 hours. The reaction was then quenched with saturated aqueous sodium bicarbonate solution to remove the residual trifluoroacetic acid. The aqueous phase was extracted with dichloromethane to obtain the organic extract which was dried over anhydrous magnesium sulfate and concentrated by evaporation in a rotary evaporator to obtain the crude product. The crude product was purified by silica gel column chromatography using petroleum ether: dichloromethane (4: 1) as the eluent to obtain deuterated 2,7-dibromolactone as a white powder (2). Next, 12 mL of deuterated bromobenzene, 72.4 mmol of magnesium turnings (1.8 g), and a pellet of iodine were added to a reaction flask and purged with N2three times. Tetrahydrofuran was injected into the flask under an ice water bath until the magnesium turnings were completely reacted to obtain a gray Grignard reagent (3). 12 mmol of deuterated 2,7-dibromolactone (4.2 g) (2) was placed in a three-necked flask, sealed and purged with N2three times. 60 mL of anhydrous toluene and the Grignard reagent were injected and the reaction was refluxed at 85°C for 8 hours. The reaction was then cooled to room temperature and quenched with saturated aqueous ammonium chloride solution. The aqueous phase was extracted with dichloromethane to obtain the organic extract which was dried over anhydrous magnesium sulfate and concentrated by evaporation in a rotary evaporator to obtain the crude product. The crude product was first purified by silica gel column chromatography using petroleum ether: dichloromethane (2: 1) and then petroleum ether: ethyl acetate (6: 1) as the eluent to obtain deuterated 2,7-dibromodiol as a white solid (4). Next, 4 mmol (4), 7.2 mmol of anhydrous potassium carbonate, and 7.8 mmol of n-bromooctane were placed in a pear-shaped flask and dissolved in 30 mL of acetone. The reaction was carried out at room temperature for 12 hours. The crude product was obtained by extraction, washing, and drying. The crude product was purified by silica gel column chromatography using petroleum ether: dichloromethane = 8: 1 as the eluent to obtain a transparent oily solid (5). The solid was dissolved in anhydrous dichloromethane and then 0.2 mL of boron trifluoride etherate was injected. The reaction was stirred at room temperature for 24 hours and then quenched with 5 mL of water. The crude product was obtained by extraction, washing, and drying. The crude product was purified by silica gel column chromatography using petroleum ether: dichloromethane (3: 1) as the eluent to obtain deuterated PODPF monomer as a white solid (6).

[0250] The target polymer d was prepared in a 10 mL Schlenk flask equipped with a magnetic stir bar 15-PODPF(7): 0.5 g of bipyridine and Ni(COD)2 were taken in a Schlenk tube, washed with N2 for three times, after activation in DMF solution at 75℃ for 20 min, monomer solution dissolved in dry and oxygen-free toluene was injected, the reaction temperature was adjusted to 85℃, after refluxing in dark for 3 days, 0.1 mL of dry deuterated bromobenzene was injected to terminate the reaction for 12 hours, after the reaction was completed, the residual reactants were removed by suction filtration with a Buchner funnel, the filtrate of the target polymer was obtained, the residual nickel catalyst was removed with a silicon-based scavenger, the organic phase was purified with an Al2O3 column chromatography with dichloromethane as the mobile phase, then the reaction liquid was concentrated, anhydrous methanol was added to precipitate a yellowish silk-like solid, after Soxhlet extraction with acetone for 3 days, vacuum drying was performed to obtain d 15 -PODPF yellow solid (M n = 31747, n = 69).

[0251] S2, 10 mg of polymer was weighed and placed in a 1.5 mL clean sample bottle, 1 mL of chloroform solvent was added, and stirred at 60℃ for 30 min, until the polymer was completely dissolved, obtaining a polymer chloroform solution with a concentration of 6 mg / mL.

[0252] S3, a quartz sheet with a side length of 1.5 cm was used as the substrate, the quartz substrate was first cleaned with solvents such as acetone and dichloromethane, the spin coater speed was adjusted to 1000 rpm and the acceleration was 800 rpm / s, 45 microliters of polymer chloroform solution was taken and uniformly coated on the quartz substrate using the spin coater, obtaining a thin film with a thickness of 45 nanometers.

[0253] S4, the above original thin film was placed on a heating stage, the annealing temperature was adjusted to 220℃, and heated for 10 min to obtain a thin film with a planar conformation content of about 24%.

[0254] Example 3

[0255] First, a deuterated fluorene-based blue light polymer material was prepared, and then a planar conformation thin film was prepared, as follows:

[0256] S1. Preparation of deuterated 2,7-dibromo-9-fluorenone (1) in a high boron glass vial equipped with a magnetic stir bar: 1 mmol of 2,7-dibromo-9-fluorenone, 0.2 mmol of silver carbonate, 0.5 mmol of cyclohexyldiphenylphosphonium, 1 mmol of potassium carbonate, 20 mmol of heavy water and 0.2 mL of toluene were placed in the vial and the reaction temperature was adjusted to 120 °C. The reaction was stopped after 24 hours of stirring. The vial was removed and allowed to cool to room temperature. Subsequently, saturated ammonium chloride solution was added to the high boron glass vial to quench the reaction and the mixture was partitioned. The organic extract was dried over anhydrous magnesium sulfate and concentrated on a rotary evaporator to give the crude product. Subsequently, the crude product was purified by silica gel column chromatography using petroleum ether: dichloromethane (2: 1) as the eluent to give a yellow powder. The above procedure was repeated three times with a deuterium incorporation of approximately 93%. Notes: Do not open the vial too much. The optimal reaction size is 1 mmol (338 mg of fluorenone). Do not add too much toluene. Approximately 0.2 mL is appropriate. Otherwise, the deuterium incorporation of the material will be affected (fluorenone is difficult to dissolve. After heating and stirring, it will dissolve, but it cannot be completely dissolved).

[0257] To a reaction flask was added 2.8 g of deuterated 2,7-dibromo-9-fluorenone (8.28 mmol) (1) and 30 mL of dichloromethane was injected to dissolve the compound in an ice water bath. 25 mL of trifluoroacetic acid was injected and 1.0 g of sodium percarbonate was added every 15 minutes for a total of 5 times. After the ice water bath was removed, the reaction was stirred at room temperature for 72 hours. The reaction was then quenched with saturated aqueous sodium bicarbonate solution to remove the residual trifluoroacetic acid. The aqueous phase was extracted with dichloromethane to obtain the organic extract which was dried over anhydrous magnesium sulfate and concentrated by evaporation in a rotary evaporator to obtain the crude product. The crude product was purified by silica gel column chromatography using petroleum ether: dichloromethane (4: 1) as the eluent to obtain deuterated 2,7-dibromolactone as a white powder (2). Next, 12 mL of deuterated bromobenzene, 72.4 mmol of magnesium turnings (1.8 g), and a pellet of iodine were added to a reaction flask and purged with N2three times. Tetrahydrofuran was injected into the flask under an ice water bath until the magnesium turnings were completely reacted to obtain a gray Grignard reagent (3). 12 mmol of deuterated 2,7-dibromolactone (4.2 g) (2) was placed in a three-necked flask, sealed and purged with N2three times. 60 mL of anhydrous toluene and the Grignard reagent were injected and the reaction was refluxed at 85°C for 8 hours. The reaction was then cooled to room temperature and quenched with saturated aqueous ammonium chloride solution. The aqueous phase was extracted with dichloromethane to obtain the organic extract which was dried over anhydrous magnesium sulfate and concentrated by evaporation in a rotary evaporator to obtain the crude product. The crude product was first purified by silica gel column chromatography using petroleum ether: dichloromethane (2: 1) and then petroleum ether: ethyl acetate (6: 1) as the eluent to obtain deuterated 2,7-dibromodiol as a white solid (4). Next, 4 mmol (4), 7.2 mmol of anhydrous potassium carbonate, and 7.8 mmol of n-bromooctane were placed in a pear-shaped flask and dissolved in 30 mL of acetone. The reaction was carried out at room temperature for 12 hours. The crude product was obtained by extraction, washing, and drying. The crude product was purified by silica gel column chromatography using petroleum ether: dichloromethane = 8: 1 as the eluent to obtain a transparent oily solid (5). The solid was dissolved in anhydrous dichloromethane and then 0.2 mL of boron trifluoride etherate was injected. The reaction was stirred at room temperature for 24 hours and then quenched with 5 mL of water. The crude product was obtained by extraction, washing, and drying. The crude product was purified by silica gel column chromatography using petroleum ether: dichloromethane (3: 1) as the eluent to obtain deuterated PODPF monomer as a white solid (6).

[0258] The target polymer d was prepared in a 10 mL Schlenk flask equipped with a magnetic stir bar 15PODPF(7): 0.5 g of bipyridine and Ni(COD)2 were taken in a Schlenk tube, washed with N2 for three times, after activation in DMF solution at 75℃ for 20 min, monomer solution dissolved in dry and oxygen-free toluene was injected, the reaction temperature was adjusted to 85℃, after refluxing in dark for 3 days, 0.1 mL of dry deuterated bromobenzene was injected to terminate the reaction for 12 hours, after the reaction was completed, the residual reactants were removed by suction filtration with a Buchner funnel, the filtrate of the target polymer was obtained, the residual nickel catalyst was removed with a silicon-based scavenger, the organic phase was purified with an Al2O3 column chromatography with dichloromethane as the mobile phase, then the reaction liquid was concentrated, anhydrous methanol was added to precipitate a yellow silk-like solid, after Soxhlet extraction with acetone for 3 days, vacuum drying was performed to obtain d 15 PODPF yellow solid (M n = 31747, n = 69).

[0259] S2, 10 mg of polymer was weighed and placed in a 1.5 mL clean sample bottle, 1 mL of chloroform solvent was added, and stirring was performed at 60℃ for 30 min, and a polymer chloroform solution with a concentration of 6 mg / mL was obtained after the polymer was completely dissolved.

[0260] S3, a quartz sheet with a side length of 1.5 cm was used as a substrate, the quartz substrate was first cleaned with solvents such as acetone and dichloromethane, the spin coater speed was adjusted to 1000 rpm and the acceleration was 800 rpm / s, 45 microliters of polymer chloroform solution was taken and uniformly coated on the quartz substrate using a spin coater, and a thin film with a thickness of 45 nanometers was obtained.

[0261] S4, the above original thin film was placed on a heating stage, the annealing temperature was adjusted to 240℃, and heating was performed for 10 min to obtain a thin film with a planarization conformation content of about 32%.

[0262] Comparative Example 1

[0263] First, a fluorene-based polymer material PODPF with a conjugated mechanism was prepared, and then a thin film was prepared, as follows:

[0264] S1, a fluorene-based polymer material PODPF with a conjugated mechanism was prepared by Yamamoto polymerization,

[0265] The preparation method is as follows:

[0266] To a reaction flask was added 2.8 g of 2,7-dibromo-9-fluorenone (8.28 mmol) and 30 mL of dichloromethane was added to dissolve the compound in the solvent under ice water bath condition. 25 mL of trifluoroacetic acid was added and 1.0 g of sodium percarbonate was added every 15 minutes for a total of 5 times. After the ice water bath was removed, the reaction was stirred at room temperature for 72 hours. The reaction was then quenched with saturated aqueous sodium bicarbonate solution to remove the residual trifluoroacetic acid. The aqueous phase was extracted with dichloromethane to obtain the organic extract which was dried over anhydrous magnesium sulfate and concentrated by evaporation in a rotary evaporator to obtain the crude product. The crude product was purified by silica gel column chromatography using petroleum ether:dichloromethane (4:1) as the eluent to obtain 2,7-dibromo-lactone as a white powder. Next, 12 mL of bromobenzene, 72.4 mmol of magnesium turnings (1.8 g), and an iodine pellet were added to a reaction flask and eluted three times. Tetrahydrofuran was added under ice water bath until the magnesium turnings were completely reacted to obtain a gray Grignard reagent. 12 mmol of 2,7-dibromo-lactone (4.2 g) was placed in a three-necked flask, sealed and eluted three times. 60 mL of anhydrous toluene and the Grignard reagent were added and the reaction was refluxed at 85°C for 8 hours. The reaction was then cooled to room temperature and quenched with saturated aqueous ammonium chloride solution. The aqueous phase was extracted with dichloromethane to obtain the organic extract which was dried over anhydrous magnesium sulfate and concentrated by evaporation in a rotary evaporator to obtain the crude product. The crude product was purified by silica gel column chromatography using petroleum ether:dichloromethane (2:1) and then petroleum ether:ethyl acetate (6:1) as the eluent to obtain 2,7-dibromo-diol as a white solid. Next, 4 mmol of 2,7-dibromo-diol, 7.2 mmol of anhydrous potassium carbonate, and 7.8 mmol of n-bromooctane were placed in a pear-shaped flask and dissolved in 30 mL of acetone. The reaction was carried out at room temperature for 12 hours. The reaction was extracted, washed, dried, and concentrated to obtain the crude product. The crude product was purified by silica gel column chromatography using petroleum ether:dichloromethane (8:1) as the eluent to obtain a transparent oily solid. The oily solid was dissolved in anhydrous dichloromethane and then 0.2 mL of boron trifluoride etherate was added. The reaction was stirred at room temperature for 24 hours and then quenched with 5 mL of water. The reaction was extracted, washed, dried, and concentrated to obtain the crude product. The crude product was purified by silica gel column chromatography using petroleum ether:dichloromethane (3:1) as the eluent to obtain the PODPF monomer as a white solid.

[0267] The target polymer PODPF was prepared in a 10 mL Schlenk flask equipped with a magnetic stirring rod: 0.5 g of bipyridine and Ni(COD)2 were taken in a Schlenk tube, washed with N2 for three times, after activation in a DMF solution at 75℃ for 20 min, a monomer solution dissolved in dry and oxygen-free toluene was injected, the reaction temperature was adjusted to 85℃, and the reaction was carried out in the dark for 3 days, then 0.1 mL of dry bromobenzene was injected to terminate the reaction for 12 hours, after the reaction was completed, the residual reactants were removed by suction filtration with a Buchner funnel, the filtrate of the target polymer was obtained, the residual nickel catalyst was removed with a silicon-based scavenger, the organic phase was purified by column chromatography with dichloromethane as the mobile phase, then the reaction liquid was concentrated, anhydrous methanol was added to precipitate a yellow silk-like solid, after Soxhlet extraction with acetone for 3 days, the yellow solid PODPF was obtained by vacuum drying. n = 54812, n = 123).

[0268] The prepared fluorenyl polymer material with conjugated structure PODPF has the following structure:

[0269]

[0270] S2, 10 mg of polymer was weighed and placed in a 1.5 mL clean sample bottle, 1 mL of chloroform solvent was added, and it was stirred at 60℃ for 30 min, and the polymer was completely dissolved to obtain a polymer chloroform solution with a concentration of 10 mg / mL.

[0271] S3, a quartz sheet with a side length of 1.5 cm was used as the substrate, the quartz substrate was first cleaned with solvents such as acetone and dichloromethane, the spin coater speed was adjusted to 1000 rpm, the acceleration was 800 rpm / s, 45 microliters of polymer chloroform solution was taken, and the uniform coating spin coater was used to uniformly coat it on the quartz substrate to obtain a thin film with a thickness of 55 nanometers.

[0272] S4, the above-mentioned thin film was placed on the heating stage, the original thin film was placed on the heating stage, the annealing temperature was adjusted to 200℃, and it was heated for 10 minutes, and the planarization conformation was not formed.

[0273] The reason why Comparative Example 1 did not form a planarization conformation is that the temperature was not reached.

[0274] Comparative Example 2

[0275] First, the fluorenyl polymer material PODPF with conjugated structure was prepared, and then the thin film was prepared, as follows:

[0276] S1, the fluorenyl polymer material PODPF with conjugated structure was prepared by Yamamoto polymerization,

[0277] The preparation method is as follows:

[0278] To a reaction flask was added 2.8 g of 2,7-dibromo-9-fluorenone (8.28 mmol) and 30 mL of dichloromethane was added to dissolve the compound in the solvent under ice water bath condition. 25 mL of trifluoroacetic acid was added and 1.0 g of sodium percarbonate was added every 15 minutes for a total of 5 times. After the ice water bath was removed, the reaction was stirred at room temperature for 72 hours. The reaction was then quenched with saturated aqueous sodium bicarbonate solution to remove the residual trifluoroacetic acid. The aqueous phase was extracted with dichloromethane to obtain the organic extract which was dried over anhydrous magnesium sulfate and concentrated by evaporation in a rotary evaporator to obtain the crude product. The crude product was purified by silica gel column chromatography using petroleum ether:dichloromethane (4: 1) as the eluent to obtain 2,7-dibromo-lactone as a white powder. Next, 12 mL of bromobenzene, 72.4 mmol of magnesium turnings (1.8 g), and an iodine pellet were added to a reaction flask and eluted three times. Tetrahydrofuran was added under ice water bath until the magnesium turnings were completely reacted to obtain a gray Grignard reagent. 12 mmol of 2,7-dibromo-lactone (4.2 g) was placed in a three-necked flask, sealed and eluted three times. 60 mL of anhydrous toluene and the Grignard reagent were added and the reaction was refluxed at 85°C for 8 hours. The reaction was then cooled to room temperature and quenched with saturated aqueous ammonium chloride solution. The aqueous phase was extracted with dichloromethane to obtain the organic extract which was dried over anhydrous magnesium sulfate and concentrated by evaporation in a rotary evaporator to obtain the crude product. The crude product was purified by silica gel column chromatography using petroleum ether:dichloromethane (2: 1) and then petroleum ether: ethyl acetate (6: 1) as the eluent to obtain 2,7-dibromo-diol as a white solid. Next, 4 mmol of 2,7-dibromo-diol, 7.2 mmol of anhydrous potassium carbonate, and 7.8 mmol of n-bromooctane were placed in a pear-shaped flask and dissolved in 30 mL of acetone. The reaction was carried out at room temperature for 12 hours. The reaction was extracted, washed, dried, and concentrated to obtain the crude product. The crude product was purified by silica gel column chromatography using petroleum ether:dichloromethane (8: 1) as the eluent to obtain a transparent oily solid. The oily solid was dissolved in anhydrous dichloromethane and then 0.2 mL of boron trifluoride etherate was added. The reaction was stirred at room temperature for 24 hours and then quenched with 5 mL of water. The reaction was extracted, washed, dried, and concentrated to obtain the crude product. The crude product was purified by silica gel column chromatography using petroleum ether:dichloromethane (3: 1) as the eluent to obtain the PODPF monomer as a white solid.

[0279] The target polymer PODPF was prepared in a 10 mL Schlenk flask equipped with a magnetic stirring rod: 0.5 g of bipyridine and Ni(COD)2 were taken in a Schlenk tube, washed with N2 for three times, after activation in a DMF solution at 75 °C for 20 min, a monomer solution dissolved in dry and oxygen-free toluene was injected, the reaction temperature was adjusted to 85 °C, and the reaction was carried out in the dark for 3 days, then 0.1 mL of dry bromobenzene was injected to terminate the reaction for 12 h, after the reaction was completed, the residual reactants were removed by suction filtration with a Buchner funnel, the filtrate of the target polymer was obtained, the residual nickel catalyst was removed with a silicon-based scavenger, the organic phase was purified by column chromatography with dichloromethane as the mobile phase, then the reaction solution was concentrated, anhydrous methanol was added to precipitate a yellow silk-like solid, after Soxhlet extraction with acetone for 3 days, the yellow solid PODPF was obtained by vacuum drying (M n = 54812, n = 123).

[0280] The prepared fluorenyl polymer material with conjugated structure PODPF has the following structure:

[0281]

[0282] S2, 10 mg of the polymer was weighed and placed in a 1.5 mL clean sample bottle, 1 mL of chloroform solvent was added, and it was stirred at 60 °C for 30 min, and the polymer was completely dissolved to obtain a polymer chloroform solution with a concentration of 10 mg / mL.

[0283] S3, a quartz piece with a side length of 1.5 cm was used as the substrate, the quartz substrate was cleaned with acetone, dichloromethane and other solvents, the spin coater speed was adjusted to 1000 rpm, the acceleration was 800 rpm / s, 45 microliters of the polymer chloroform solution was taken, and the uniform coating spin coater was used to uniformly coat it on the quartz substrate to obtain a thin film with a thickness of 55 nanometers.

[0284] S4, the above original thin film was placed on a heating table, the annealing temperature was adjusted to 220 °C, and it was heated for 10 min to form a planar conformation of about 11% of the thin film.

[0285] Comparative Example 3

[0286] S1, a fluorenyl polymer material PODPF with conjugated structure was prepared by yamamoto polymerization,

[0287] The preparation method is as follows:

[0288] To a reaction flask was added 2.8 g of 2,7-dibromo-9-fluorenone (8.28 mmol) and 30 mL of dichloromethane was added to dissolve the compound in the solvent under ice water bath condition. 25 mL of trifluoroacetic acid was added and 1.0 g of sodium percarbonate was added every 15 minutes for a total of 5 times. After the ice water bath was removed, the reaction was stirred at room temperature for 72 hours. The reaction was then quenched with saturated aqueous sodium bicarbonate solution to remove the residual trifluoroacetic acid. The aqueous phase was extracted with dichloromethane to obtain the organic extract which was dried over anhydrous magnesium sulfate and concentrated by evaporation in a rotary evaporator to obtain the crude product. The crude product was purified by silica gel column chromatography using petroleum ether:dichloromethane (4:1) as the eluent to obtain 2,7-dibromo-lactone as a white powder. Next, 12 mL of bromobenzene, 72.4 mmol of magnesium turnings (1.8 g), and an iodine pellet were added to a reaction flask and eluted three times. Tetrahydrofuran was added under ice water bath until the magnesium turnings were completely reacted to obtain a gray Grignard reagent. 12 mmol of 2,7-dibromo-lactone (4.2 g) was placed in a three-necked flask, sealed and eluted three times. 60 mL of anhydrous toluene and the Grignard reagent were added and the reaction was refluxed at 85°C for 8 hours. The reaction was then cooled to room temperature and quenched with saturated aqueous ammonium chloride solution. The aqueous phase was extracted with dichloromethane to obtain the organic extract which was dried over anhydrous magnesium sulfate and concentrated by evaporation in a rotary evaporator to obtain the crude product. The crude product was purified by silica gel column chromatography using petroleum ether:dichloromethane (2:1) and then petroleum ether:ethyl acetate (6:1) as the eluent to obtain 2,7-dibromo-diol as a white solid. Next, 4 mmol of 2,7-dibromo-diol, 7.2 mmol of anhydrous potassium carbonate, and 7.8 mmol of n-bromooctane were placed in a pear-shaped flask and dissolved in 30 mL of acetone. The reaction was carried out at room temperature for 12 hours. The reaction was extracted, washed, dried, and concentrated to obtain the crude product. The crude product was purified by silica gel column chromatography using petroleum ether:dichloromethane (8:1) as the eluent to obtain a transparent oily solid. The oily solid was dissolved in anhydrous dichloromethane and then 0.2 mL of boron trifluoride etherate was added. The reaction was stirred at room temperature for 24 hours and then quenched with 5 mL of water. The reaction was extracted, washed, dried, and concentrated to obtain the crude product. The crude product was purified by silica gel column chromatography using petroleum ether:dichloromethane (3:1) as the eluent to obtain the PODPF monomer as a white solid.

[0289] The target polymer PODPF was prepared in a 10 mL Schlenk flask equipped with a magnetic stirring rod: 0.5 g of bipyridine and Ni(COD)2 were taken in a Schlenk tube, washed with N2 for three times, after activation in a DMF solution at 75℃ for 20 min, a monomer solution dissolved in dry and oxygen-free toluene was injected, the reaction temperature was adjusted to 85℃, and the reaction was carried out in dark for 3 days, then 0.1 mL of dry bromobenzene was injected to terminate the reaction for 12 hours, after the reaction was completed, the residual reactants were removed by suction filtration with a Buchner funnel, the filtrate of the target polymer was obtained, the residual nickel catalyst was removed with a silicon-based scavenger, the organic phase was purified with an Al2O3 column chromatography with dichloromethane as the mobile phase, then the reaction liquid was concentrated, anhydrous methanol was added to precipitate a yellow silk-like solid, after Soxhlet extraction with acetone for 3 days, the yellow solid of PODPF was obtained by vacuum drying (M n = 54812, n = 123).

[0290] The prepared fluorenyl polymer material with a conjugated mechanism has the following structure:

[0291]

[0292] S2, 10 mg of the polymer was weighed and placed in a 1.5 mL clean sample bottle, 1 mL of chloroform solvent was added, and the mixture was stirred at 60℃ for 30 min, and the polymer was completely dissolved to obtain a polymer chloroform solution with a concentration of 10 mg / mL.

[0293] S3, a quartz piece with a side length of 1.5 cm was used as a substrate, the quartz substrate was cleaned with acetone, dichloromethane and other solvents, the spin coating instrument was adjusted to a rotation speed of 1000 rpm and an acceleration of 800 rpm / s, 45 microliters of the polymer chloroform solution was taken and uniformly coated on the quartz substrate by using the spin coating instrument to obtain a thin film with a thickness of 55 nanometers.

[0294] S4, the above original thin film was placed on a heating table, the annealing temperature was adjusted to 240℃, and the heating was carried out for 10 min to form a thin film with a planar conformation of about 18%.

[0295] It should be noted that although Comparative Examples 2 and 3 also form a thin film with a planar conformation, the difference from the examples is that the main chain deuteration increases the size of the molecular chain aggregate, and the aggregate is more closely packed, which is beneficial to the formation of the planar conformation, so the temperature for forming the planar conformation is reduced.

[0296] Test analysis

[0297] Figure 1 are the ultraviolet-visible absorption spectra and fluorescence emission spectra of the original thin film and the heat-treated fluorenyl polymer obtained in Example 1 and Comparative Example 1 of the present application, from which it can be seen that the original thin film has a planar conformation, and the heat-treated thin film has a planar conformation. Figure 1It can be seen that the absorption and emission spectra of the PODPF film can be obtained, the UV spectrum of the film annealed at 200°C does not change significantly, and the peak intensity of the PL spectrum at 460 nm (0-1 peak) slightly increases, indicating that the annealing temperature is not sufficient to induce the conformational transition of the PODPF molecular chain. The same annealing method is used on d 15 -PODPF film, and the comparison of the luminescence spectra can be obtained, when the annealing temperature is 200°C, d 15 -PODPF has a weak absorption peak at 438 nm, indicating that the transition from random conformation to planar conformation is induced at this temperature, and it is also confirmed that the main chain deuteration can improve the ability of PODPF to form planar conformation.

[0298] Figure 2 are the UV-visible absorption spectra and fluorescence emission spectra of the fluorenyl polymer raw film and the heat-treated film obtained in Example 2 and Comparative Example 2 of the present application, from Figure 2 It can be seen that when the heat annealing temperature increases to 220°C, the PODPF film and d 15 -PODPF film all form planar conformation, and compared with the PODPF film, the conformation content of the deuterated film is higher than that of the non-deuterated film.

[0299] Figure 3 are the UV-visible absorption spectra and fluorescence emission spectra of the fluorenyl polymer raw film and the heat-treated film obtained in Example 3 and Comparative Example 3 of the present application, from Figure 3 It can be seen that when the heat annealing temperature increases to 240°C, the PODPF film and d 15 -PODPF film all form planar conformation, and compared with the PODPF film, the conformation content of the deuterated film is higher than that of the non-deuterated film.

[0300] Figure 4 are the lifetime diagrams of the fluorenyl polymer raw film and the heat-treated film obtained in Example 123 and Comparative Example 123 of the present application, from Figure 4 It can be seen that d 15 -PODPF film has a higher overall lifetime than the PODPF film, and the trend of the lifetime of the two films with temperature is opposite.

[0301] Figure 5 is the device structure diagram of the fluorenyl polymer film with planar conformation obtained in Example 1 and Comparative Example 1 of the present application, and the device structure is ITO / PEDOT:PSS / EML / TPBi / LiF / Al.

[0302] Figure 6 is the device performance diagram of the fluorenyl polymer film with planar conformation obtained in Example 1 and Comparative Example 1 of the present application, from Figure 6It can be seen that, compared with the device based on the PODPF of Comparative Example 1 as the light-emitting layer, the device based on the deuterated thin film emits deep blue light, and presents more stable color purity as the device operates, still emitting deep blue light after 2 hours of operation.

[0303] Figure 7 is the nuclear magnetic hydrogen spectrum of the polymer synthesized in Example 1 of the present application, from Figure 7 It can be seen that the characteristic peak of hydrogen on the benzene ring in the high field position of the nuclear magnetic is almost non-existent, proving that d 15 - The PODPF material is successfully prepared.

[0304] Figure 8 is the GPC test of the polymer synthesized in Example 1 of the present application, from Figure 8 It can be seen that the polymer PDI curve is in the form of a sharp peak, indicating that the molecular weight of the polymer is relatively uniform.

[0305] The above has made a detailed description of the present application in combination with the examples, but the present application is not limited to the above examples, and various changes can be made within the knowledge range possessed by those skilled in the art without departing from the purpose of the present application.

Claims

1. A method for preparing deuterated fluorene-based blue light polymer material, characterized in that, The method comprises the following steps: S1: using 2,7-dibromo-9-fluorenone as raw material, silver carbonate and cyclohexyl diphenyl phosphine as catalyst, and heavy water as deuterium source to prepare deuterated 2,7-dibromo-9-fluorenone; S2: preparing deuterated 2,7-dibromo lactone by Bayer-Villiger rearrangement reaction from the deuterated 2,7-dibromo-9-fluorenone; S3: preparing deuterated 2,7-dibromo diol by Grignard reaction from the deuterated 2,7-dibromo lactone; S4: preparing oil transparent solid product by alkyl substitution reaction of alcohol hydroxyl group at position 4 from the deuterated 2,7-dibromo diol and 1-bromooctane; S5: using the oil transparent solid product as raw material to prepare deuterated PODPF monomer; S6: preparing solution of the deuterated PODPF monomer, and obtaining the deuterated fluorenyl blue light polymer material by activation and reflux after polymerization.

2. The production method according to claim 1, characterized by, In step S2, trifluoroacetic acid and sodium carbonate are added in the process of the Bayer-Villiger rearrangement reaction; and / or, in step S2, the Bayer-Villiger rearrangement reaction is carried out at room temperature; and / or, in step S2, the time of the Bayer-Villiger rearrangement reaction is 60-80 h.

3. The preparation method according to claim 1, characterized in that, In step S3, the solvent of the Grignard reaction includes toluene; and / or, in step S3, the Grignard reaction is carried out in a protective atmosphere; and / or, in step S3, the reaction temperature is 80-90℃; and / or, in step S3, the reaction time is 20-30 h; and / or, in step S3, the amount of Grignard reagent added in the Grignard reaction is 4-6 times of the equivalent of the deuterated 2,7-dibromo lactone.

4. The production method according to claim 1, characterized by, In step S4, the amount of 1-bromooctane added is 1-2 times of the equivalent of the deuterated 2,7-dibromo diol; and / or, in step S4, the alkyl substitution reaction is carried out at room temperature; and / or, in step S4, the time of the alkyl substitution reaction is 20-30 h.

5. The method of claim 1, wherein, In step S5, the deuterated PODPF monomer is prepared by a Friedel-Crafts reaction.

6. The method of claim 1, wherein, In step S6, the time of the polymerization reaction is 1.5-4 h; and / or, in step S6, the activation is carried out in a DMF solution; and / or, in step S6, the monomer solution dissolved in toluene is added in the reflux process; and / or, in step S6, the reflux is terminated by end-capping with dry deuterated bromobenzene.

7. A deuterated fluorene-based blue light high molecular material, characterized in that, The method is prepared by any one of claims 1-6.

8. A planarized conformational film characterized by, The raw material comprises the deuterated fluorenyl blue light polymer material of claim 7.

9. A method of preparing the planarized conformational film according to claim 8, characterized by, The method comprises the following steps: coating a solution containing the deuterated fluorenyl blue light polymer material on the surface of a substrate, and then annealing.

10. Use of the planarized conformational film of claim 8 in an organic thin film photovoltaic device.

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