CN110845497A - A kind of self-compensating radical ion salt and preparation method thereof, and optoelectronic device - Google Patents
A kind of self-compensating radical ion salt and preparation method thereof, and optoelectronic deviceDownload PDFInfo
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Abstract
Translated fromChinese
Description
Translated fromChinese技术领域technical field
本发明涉及有机光电器件的阴极修饰层材料领域，尤其涉及一种自补偿自由基离子盐及其制备方法、光电器件。The invention relates to the field of cathode modification layer materials of organic optoelectronic devices, in particular to a self-compensating free radical ion salt, a preparation method thereof, and an optoelectronic device.
背景技术Background technique
在常规的光电器件中，由金属制成的阴极和与之相接触的有机功能层(电子传输层、有机发光层或太阳能活性层)之间形成较大的电子注入/提取势垒，影响了电荷载流子在电极与有机功能层之间的注入与提取，从而降低了有机光电功能转换器件的综合效率。In conventional optoelectronic devices, a large electron injection/extraction barrier is formed between the cathode made of metal and the organic functional layer (electron transport layer, organic light-emitting layer or solar active layer) in contact with it, which affects the The injection and extraction of charge carriers between the electrode and the organic functional layer reduces the overall efficiency of the organic photoelectric functional conversion device.
为降低界面接触势垒以实现“准欧姆式”接触，目前一般会在阴极金属和有机功能层之间插入合适的阴极界面层，通常采用单一的界面诱导方式或界面化学掺杂的手段。其中，由于采用单一界面偶极诱导方法以降低阴极的功函能力有限，且制备阴极界面层的材料中通常需要引入大极性的基团(如酯基、胺基、羧基等)，这势必会造成电子传输性能的降低，额外增加的阴极界面层也增加了生产成本；而界面化学掺杂中，单纯的化学掺杂往往出现难以制备以及稳定性极差，掺杂工艺可控性差，以及易出现去掺杂和掺杂剂扩散的问题。In order to reduce the interface contact barrier to achieve "quasi-ohmic" contact, a suitable cathode interface layer is generally inserted between the cathode metal and the organic functional layer, usually using a single interface induction method or interface chemical doping. Among them, the use of a single interface dipole induction method to reduce the work function of the cathode is limited, and the preparation of the cathode interface layer usually requires the introduction of large polar groups (such as ester groups, amine groups, carboxyl groups, etc.), which is bound to be It will reduce the electron transport performance, and the additional cathode interface layer also increases the production cost; and in the chemical doping of the interface, the simple chemical doping is often difficult to prepare and has extremely poor stability, poor controllability of the doping process, and De-doping and dopant diffusion problems are prone to occur.
自掺杂阴极界面层(SDCIL)与上述两种方法相比，具有更明显的优势：一方面，SDCIL具有良好的稳定性，且成本单一，容易形成均一、稳定的薄膜；其二，自掺杂所带来的较高浓度的自由载流子浓度兼具界面修饰和导电性，可以实现电子注入/提取与传输功能的一体化，从而简化器件结构，因此SDCIL成为近年来光电器件材料的研究热点。但SDCIL也存在着难以克服的技术难题：自掺杂所诱导产生的自由基浓度有限，导致自掺杂阴极界面层的界面修饰能力有限；自掺杂所形成的掺杂剂阳离子和半导体阴离子自由基通过库仑力束缚共存的形式存在，这一形态不稳定，可能会出现去掺杂的现象，导致修饰效果不佳。Compared with the above two methods, self-doping cathode interface layer (SDCIL) has more obvious advantages: on the one hand, SDCIL has good stability, and the cost is single, and it is easy to form a uniform and stable film; on the other hand, self-doping The higher concentration of free carriers brought by impurities has both interface modification and conductivity, which can realize the integration of electron injection/extraction and transport functions, thereby simplifying the device structure. Therefore, SDCIL has become a research material for optoelectronic devices in recent years. hot spot. However, SDCIL also has technical difficulties that are difficult to overcome: the limited concentration of free radicals induced by self-doping leads to limited interface modification ability of the self-doping cathode interface layer; the dopant cations and semiconductor anions formed by self-doping are free The radicals exist in the form of coexistence bound by Coulomb force, which is unstable and may de-doping, resulting in poor modification effect.
因此，现有技术还有待于改进和发展。Therefore, the existing technology still needs to be improved and developed.
发明内容SUMMARY OF THE INVENTION
鉴于上述现有技术的不足，本发明的目的在于提供一种自补偿自由基离子盐及其制备方法、光电器件，旨在解决现有自掺杂阴极界面层材料掺杂的自由基浓度有限且稳定性低，而导致其界面修饰能力不佳问题。In view of the above-mentioned deficiencies in the prior art, the purpose of the present invention is to provide a self-compensating free radical ion salt, a preparation method thereof, and a photoelectric device, aiming to solve the problem that the free radical concentration doped by the existing self-doping cathode interface layer material is limited and The stability is low, which leads to the problem of poor interface modification ability.
本发明为解决上述技术问题所采用的技术方案如下：The technical scheme adopted by the present invention for solving the above-mentioned technical problems is as follows:
一种自补偿自由基离子盐的制备方法，其中，包括步骤：A preparation method of a self-compensating radical ion salt, wherein, comprising the steps:
将含N共轭杂环与卤代烃混合，反应得到自由基离子盐前体；The N-containing conjugated heterocycle is mixed with halogenated hydrocarbon, and the reaction is carried out to obtain a radical ion salt precursor;
向所述自由基离子盐前体中加入反离子盐并混合，反应得到所述自补偿自由基离子盐。A counter ion salt is added to the radical ion salt precursor and mixed to obtain the self-compensating radical ion salt.
所述自补偿自由基离子盐的制备方法，其中，所述将含N共轭杂环与卤代烃混合，反应得到自由基离子盐前体的步骤包括：The preparation method of the self-compensating radical ion salt, wherein the step of mixing the N-containing conjugated heterocycle with the halogenated hydrocarbon and reacting to obtain the radical ion salt precursor comprises:
利用液氮将含N共轭杂环与卤代烃形成的混合物冻成固体，抽真空后充入干燥的惰性气体，得到反应物体系；Utilize liquid nitrogen to freeze the mixture that N-conjugated heterocycle and halohydrocarbon form into solid, fill in dry inert gas after vacuuming, obtain reactant system;
将所述反应物体系密封并置于反应器中，在80-170℃的条件下搅拌反应，制得所述自由基离子盐前体。The reactant system is sealed and placed in a reactor, and the reaction is stirred at 80-170° C. to prepare the radical ion salt precursor.
所述自补偿自由基离子盐的制备方法，其中，所述向所述自由基离子盐前体中加入反离子盐并混合，反应得到所述自补偿自由基离子盐的步骤包括：The preparation method of the self-compensating radical ion salt, wherein the step of adding a counter ion salt to the radical ion salt precursor and mixing, and reacting to obtain the self-compensating radical ion salt comprises:
将反离子盐加入所述自由基离子盐前体中，通过内部离子交换得到自补偿自由基离子盐混合物；adding a counter ion salt to the radical ion salt precursor to obtain a self-compensating radical ion salt mixture through internal ion exchange;
通过良溶剂与不良溶剂的相互溶解-析出过程对所述自补偿自由基离子盐混合物进行纯化，得到所述自补偿自由基离子盐。The self-compensating radical ion salt mixture is purified through the mutual dissolution-precipitation process of the good solvent and the poor solvent to obtain the self-compensating radical ion salt.
所述自补偿自由基离子盐的制备方法，其中，所述含N共轭杂环选自含N五元杂环、含N六元杂环、含N多元稠环、由相同或不同含N五元杂环桥连组成的共轭杂环、由相同或不同含N六元杂环桥连组成的共轭杂环、由相同或不同含N多元稠环桥连组成的共轭杂环，和由含N五元杂环、含N六元杂环和含N多元稠环中的至少两种桥连组成的共轭杂环中的一种或多种。The preparation method of the self-compensating radical ion salt, wherein, the N-containing conjugated heterocycle is selected from the group consisting of N-containing five-membered heterocycles, N-containing six-membered heterocycles, N-containing multi-membered fused rings, identical or different N-containing heterocycles Conjugated heterocycles composed of five-membered heterocyclic bridges, conjugated heterocycles composed of the same or different N-containing six-membered heterocyclic bridges, conjugated heterocycles composed of the same or different N-containing multi-membered fused ring bridges, and one or more of the conjugated heterocycles consisting of at least two bridges among N-containing five-membered heterocycles, N-containing six-membered heterocycles and N-containing multi-membered fused rings.
所述自补偿自由基离子盐的制备方法，其中，所述含N五元杂环为
和/或，所述含N六元杂环为
和/或，所述含N多元稠环为
所述自补偿自由基离子盐的制备方法，其中，所述卤代烃为脂肪族卤代烃和芳香族卤代烃中的一种或两种。In the preparation method of the self-compensating radical ion salt, the halogenated hydrocarbon is one or both of aliphatic halogenated hydrocarbon and aromatic halogenated hydrocarbon.
所述自补偿自由基离子盐的制备方法，其中，所述反离子盐为无机离子盐、有机离子盐和有机离子液体中的一种或多种。The preparation method of the self-compensating radical ion salt, wherein the counter ion salt is one or more of inorganic ion salt, organic ion salt and organic ionic liquid.
一种自补偿自由基离子盐，其中，采用本发明所述制备方法制备而成。A self-compensating free radical ion salt, which is prepared by the preparation method of the present invention.
一种光电器件，其中，所述光电器件包括阴极以及设置在所述阴极表面的阴极界面修饰层，所述阴极界面修饰层材料为本发明所述制备方法制得的自补偿自由基离子盐或本发明所述的自补偿自由基离子盐。An optoelectronic device, wherein the optoelectronic device comprises a cathode and a cathode interface modification layer disposed on the surface of the cathode, and the cathode interface modification layer material is a self-compensating radical ion salt prepared by the preparation method of the present invention or The self-compensating free radical ion salt of the present invention.
所述的光电器件，其中，所述光电器件包括机发光二极管、有机太阳能电池、钙钛矿电池和钙钛矿发光二极管中的一种或多种。The optoelectronic device, wherein the optoelectronic device comprises one or more of organic light-emitting diodes, organic solar cells, perovskite cells and perovskite light-emitting diodes.
有益效果：本发明通过将N杂共轭杂环与卤代烃发生季铵反应生成季铵盐的过程中，采用热激发的方法同步诱导部分季铵盐阳离子发生异构化，异构化的季铵盐阳离子与体系中的卤离子发生阴离子-π相互作用诱导电荷转移从而形成自由基，且季铵盐阳离子的热激异构化可以有效促进体系中的电荷转移，促进了自由基的形成，从而有效提高自由基的浓度；将反离子盐加入到所述自由基离子盐混合物中，所述反离子盐作为抗衡阴离子可以与自由基发生内部阴离子交换，可以稳定体系中所产生的自由基，而且所引入新的阴离子可以中和阳离子自由基多余的电荷，以实现电荷的自补偿，避免去掺杂的问题，进一步提高自补偿自由基离子盐中自由基的浓度和稳定性。通过本发明提供的制备方法得到的自补偿自由基离子盐可以应用于有机光电功能器件的自掺杂阴极界面层中，用于对阴极金属电极的修饰，其修饰效果好，有效降低阴极金属电极的功函数，实现器件综合效率的优化。Beneficial effect: In the process of generating quaternary ammonium salt by quaternary ammonium reaction between N heteroconjugated heterocyclic ring and halogenated hydrocarbon, the method of thermal excitation is used to simultaneously induce isomerization of part of quaternary ammonium salt cations, and the isomerized The anion-π interaction between the quaternary ammonium salt cation and the halide ion in the system induces charge transfer to form free radicals, and the thermal shock isomerization of the quaternary ammonium salt cation can effectively promote the charge transfer in the system and promote the formation of free radicals , thereby effectively increasing the concentration of free radicals; adding a counter ion salt to the mixture of free radical ion salts, the counter ion salt can be used as a counter anion to undergo internal anion exchange with free radicals, which can stabilize the free radicals generated in the system. , and the introduced new anion can neutralize the excess charge of the cationic radical to realize the self-compensation of the charge, avoid the problem of de-doping, and further improve the concentration and stability of the free radical in the self-compensating radical ion salt. The self-compensating free radical ion salt obtained by the preparation method provided by the present invention can be applied to the self-doping cathode interface layer of the organic photoelectric functional device for the modification of the cathode metal electrode, the modification effect is good, and the cathode metal electrode is effectively reduced. The work function to achieve the optimization of the overall efficiency of the device.
附图说明Description of drawings
图1是本发明实施例提供的一种自补偿自由基离子盐的制备方法流程图。FIG. 1 is a flow chart of a method for preparing a self-compensating radical ion salt provided in an embodiment of the present invention.
图2为本发明实施例1提供的TPyPy-TFSI自由基离子盐的合成路线图。Fig. 2 is the synthetic route diagram of TPyPy-TFSI radical ion salt provided in Example 1 of the present invention.
图3为本发明实施例2提供的BCP-SBS自由基离子盐的合成路线图。Fig. 3 is the synthetic route diagram of BCP-SBS radical ion salt provided in Example 2 of the present invention.
图4为本发明实施例3提供的TPyZ-TfO自由基离子盐的合成路线图。FIG. 4 is a synthetic route diagram of the TPyZ-TfO radical ion salt provided in Example 3 of the present invention.
图5为本发明实施例4提供的BOZ-TfO自由基离子盐的合成路线图。Fig. 5 is the synthetic route diagram of BOZ-TfO radical ion salt provided in Example 4 of the present invention.
图6为本发明实施例5提供的SPhen-TFSI自由基离子盐的合成路线图。Fig. 6 is the synthetic route diagram of SPhen-TFSI radical ion salt provided in Example 5 of the present invention.
图7为本发明实施例6提供的HATCN-OSB自由基离子盐的合成路线图。Fig. 7 is the synthetic route diagram of HATCN-OSB radical ion salt provided in Example 6 of the present invention.
图8为本发明实施例7提供的自补偿自由基离子盐TPyPy-TFSI、BCP-SBS和TPyZ-TfO的电子顺磁共振(EPR)谱图。8 is the electron paramagnetic resonance (EPR) spectrum of the self-compensating radical ion salts TPyPy-TFSI, BCP-SBS and TPyZ-TfO provided in Example 7 of the present invention.
图9为本发明实施例8提供的有机太阳能电池器件的结构图。FIG. 9 is a structural diagram of an organic solar cell device provided in Embodiment 8 of the present invention.
图10为本发明实施例8提供的有机太阳能电池器件的电流密度-电压(J-V)曲线图。FIG. 10 is a current density-voltage (J-V) curve diagram of the organic solar cell device provided in Example 8 of the present invention.
具体实施方式Detailed ways
为使本发明的目的、技术方案及优点更加清楚、明确，以下参照附图并举实施例对本发明进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。In order to make the objectives, technical solutions and advantages of the present invention clearer and clearer, the present invention will be further described in detail below with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are only used to explain the present invention, but not to limit the present invention.
请参阅图1，图1为本发明提供的一种自补偿自由基离子盐的制备方法较佳实施例的流程图，如图所示，其包括以下步骤：Please refer to FIG. 1. FIG. 1 is a flowchart of a preferred embodiment of a method for preparing a self-compensating radical ion salt provided by the present invention. As shown in the figure, it includes the following steps:
S10、将含N共轭杂环与卤代烃混合，反应得到自由基离子盐前体；S10, mixing the N-containing conjugated heterocycle with the halogenated hydrocarbon, and reacting to obtain a radical ion salt precursor;
S20/向所述自由基离子盐前体中加入反离子盐并混合，反应得到所述自补偿自由基离子盐。S20/Adding a counter ion salt to the radical ion salt precursor and mixing, and reacting to obtain the self-compensating radical ion salt.
通过本实施例提供的方法可简单、快捷地制备出自补偿自由基离子盐，所制备得到的自补偿自由基离子盐含有高浓度及高稳定性的自由基，实现上述效果的原理具体如下：The method provided by this embodiment can simply and quickly prepare a self-compensating free radical ion salt, and the prepared self-compensating free radical ion salt contains free radicals with high concentration and high stability, and the principle for realizing the above effect is as follows:
本实施例通过将N杂共轭杂环与卤代烃发生季铵混合，在反应生成季铵盐的同时，采用热激发的方法诱导部分季铵盐阳离子发生异构化，异构化后的季铵盐阳离子与体系中的卤离子发生阴离子-π相互作用诱导电荷转移，形成自由基，得到自由基离子盐前体。本实施例中，由于热激异构化后的季铵盐阳离子的LUMO能级(最低未占分子轨道)能分裂出比原来LUMO更低的SUMO能级，SUMO轨道为空轨道，可以接纳任何自旋方向的电子，这有效促进了体系中的阴离子(电子给体)到SUMO能级(电子受体)的电荷转移，促进阴离子-π的相互作用，从而诱导产生更多的自由基，有效提高自由基的浓度。In this example, by mixing N heteroconjugated heterocycles with halogenated hydrocarbons to generate quaternary ammonium salts, while generating quaternary ammonium salts, thermal excitation is used to induce isomerization of some quaternary ammonium salt cations. The anion-π interaction between the quaternary ammonium salt cation and the halide ion in the system induces charge transfer to form free radicals to obtain radical ion salt precursors. In this embodiment, since the LUMO energy level (the lowest unoccupied molecular orbital) of the quaternary ammonium salt cation after thermal shock isomerization can split into a SUMO energy level lower than the original LUMO, the SUMO orbital is an empty orbital, which can accept any Electrons in the spin direction, which effectively promote the charge transfer from the anion (electron donor) to the SUMO energy level (electron acceptor) in the system, and promote the anion-π interaction, thereby inducing more free radicals, effectively Increase the concentration of free radicals.
本实施例中，将反离子盐加入所述自由基离子盐前体中，所述反离子盐作为抗衡阴离子与所述自由基离子盐前体中的自由基发生电荷转移，实现体系内部的阴离子交换，可以通过调控新引入的抗衡阴离子的能级和离子半径等参数来调节阴离子-π的作用，实现调控体系中自由基的稳定性，而且通过引入新的阴离子可以中和阳离子自由基多余的电荷，此过程为电荷的自补偿。通过自补偿方式，使体系中阳离子自由基多余的电荷被中和，避免与半导体的阴离子产生静电作用，从而避免出现去掺杂问题，进一步提高自由基的浓度和稳定性。In this embodiment, a counter ion salt is added to the radical ion salt precursor, and the counter ion salt acts as a counter anion to perform charge transfer with the free radicals in the radical ion salt precursor, so as to realize the internal anion of the system. Exchange, the effect of anion-π can be adjusted by adjusting parameters such as the energy level and ionic radius of the newly introduced counter anion, and the stability of free radicals in the system can be adjusted, and the excess of cation free radicals can be neutralized by introducing new anions. charge, this process is self-compensation of charge. Through the self-compensation method, the excess charge of the cationic radical in the system is neutralized to avoid electrostatic interaction with the anion of the semiconductor, thereby avoiding the problem of de-doping, and further improving the concentration and stability of the free radical.
在一些实施方式中，所述含N共轭杂环为含有C＝N双键的π平面共轭杂环，但不限于此。In some embodiments, the N-containing conjugated heterocycle is a π-plane conjugated heterocycle containing a C=N double bond, but not limited thereto.
在一些实施方式中，所述含N共轭杂环选自含N五元杂环、含N六元杂环、含N多元稠环、由相同或不同含N五元杂环桥连组成的共轭杂环、由相同或不同含N六元杂环桥连组成的共轭杂环、由相同或不同含N多元稠环桥连组成的共轭杂环，和由含N五元杂环、含N六元杂环和含N多元稠环中的至少两种桥连组成的共轭杂环中的一种或多种，但不限于此。In some embodiments, the N-containing conjugated heterocycle is selected from the group consisting of N-containing five-membered heterocycles, N-containing six-membered heterocycles, N-containing multi-membered fused rings, and bridged by the same or different N-containing five-membered heterocycles. Conjugated heterocycles, conjugated heterocycles composed of the same or different N-containing six-membered heterocycle bridges, conjugated heterocycles composed of the same or different N-containing multi-membered fused ring bridges, and N-containing five-membered heterocycles , N-containing six-membered heterocycle, and N-containing multiple-membered fused ring consisting of at least two bridged conjugated heterocycles, but not limited thereto.
在一些实施方式中，所述含N五元杂环为
在一些实施方式中，所述卤代烃为脂肪族卤代烃和芳香族卤代烃中的一种或两种，但不限于此。In some embodiments, the halogenated hydrocarbon is one or both of aliphatic halogenated hydrocarbons and aromatic halogenated hydrocarbons, but not limited thereto.
在一些实施方式中，所述步骤S10包括：利用液氮将含N共轭杂环与卤代烃混合物冻成固体，抽真空后充入干燥的惰性气体，得到反应物体系；将所述反应物体系密封并置于反应器中，在80-170℃的条件下搅拌反应，制得所述自由基离子盐前体。In some embodiments, the step S10 includes: using liquid nitrogen to freeze the mixture of N-containing conjugated heterocycles and halogenated hydrocarbons into a solid, vacuuming and then filling with dry inert gas to obtain a reactant system; The material system is sealed and placed in a reactor, and the reaction is stirred under the condition of 80-170° C. to prepare the radical ion salt precursor.
本实施例中，选择合适的含N共轭杂环和相应的卤代烃置于希兰克管中，加入适量的高沸点惰性非质子溶剂或者以卤代烃反应物本身作为溶剂。利用液氮将混合体系凝固成固体，用油泵抽真空后复充入干燥的氩气，重复此操作多次(如三次)，密封希兰克管并用锡箔纸将整个体系包裹。将混合体系置于适当温度的反应器中，避光搅拌数小时(如12小时)，反应结束冷却至室温，将装置转移到手套箱内处理。将混合物逐滴加入到搅拌的乙醚溶液中析出，过滤得到不同颜色的固体粉末，先后分别用超干石油醚、超干四氢呋喃溶液清洗得到自由基离子盐前体。In this example, a suitable N-containing conjugated heterocycle and corresponding halogenated hydrocarbon are selected and placed in a Schlenk tube, and an appropriate amount of high-boiling inert aprotic solvent is added or the halogenated hydrocarbon reactant itself is used as the solvent. Use liquid nitrogen to solidify the mixed system into a solid, vacuum with an oil pump and then refill with dry argon. Repeat this operation several times (for example, three times), seal the Hirank tube and wrap the entire system with tin foil. The mixed system is placed in a reactor at an appropriate temperature, stirred in the dark for several hours (eg 12 hours), cooled to room temperature after the reaction is completed, and the device is transferred to a glove box for processing. The mixture was added dropwise to the stirred ether solution for precipitation, filtered to obtain solid powders of different colors, which were washed successively with ultra-dry petroleum ether and ultra-dry tetrahydrofuran solution to obtain the radical ion salt precursor.
本实施例中，采用热激化的方式诱导体系中部分季铵盐阳离子发生异构化形成单重态或三重态自由基结构。具体的，反应所得到的自由基结构由所采用的含N共轭杂环的结构决定。In this embodiment, thermal excitation is used to induce isomerization of some quaternary ammonium salt cations in the system to form singlet or triplet free radical structures. Specifically, the free radical structure obtained by the reaction is determined by the structure of the N-containing conjugated heterocycle employed.
在一些实施例中，可以预先通过密度泛函理论(DFT)计算目标季铵盐阳离子的LUMO能级、热激异构化能、以及异构化后的SUMO能级对季铵盐阳离子进行筛选，再选择合适的含N共轭杂环和卤代烃。本发明通过采用DFT计算重要参数，可预见性地筛选合适的季铵盐阳离子，实现反应产物的可调控性，提高制备的成功率。In some embodiments, the quaternary ammonium salt cations can be screened in advance by calculating the LUMO energy level, heat shock isomerization energy, and isomerized SUMO energy level of the target quaternary ammonium salt cation through density functional theory (DFT) , and then select appropriate N-containing conjugated heterocycles and halogenated hydrocarbons. By adopting DFT to calculate important parameters, the present invention can predictably screen suitable quaternary ammonium salt cations, realize the controllability of reaction products, and improve the success rate of preparation.
在一些实施方式中，步骤S10中，所述含N共轭杂环与卤代烃的反应温度为80-170℃。具体的，在此步骤中，季铵化反应和热激发生成自由基的反应是同步进行的，其反应温度可以按具体反应物的反应活化能而定。In some embodiments, in step S10, the reaction temperature of the N-containing conjugated heterocycle and halogenated hydrocarbon is 80-170°C. Specifically, in this step, the quaternization reaction and the reaction of generating free radicals by thermal excitation are carried out simultaneously, and the reaction temperature can be determined according to the reaction activation energy of the specific reactants.
本实施例中，季铵化和自由基生成反应中，所述卤代烃的加入量可以视具体实际情况而定，所述卤代烃的加入量为过量，以促进反应过程中的高转换率，确保季铵化成盐和自由基的高产率。In this embodiment, in the reaction of quaternization and free radical generation, the amount of halogenated hydrocarbons added can be determined according to the actual situation, and the amount of halogenated hydrocarbons added is excessive to promote high conversion during the reaction process. rate, ensuring high yields of quaternized salts and free radicals.
本实施例中，通过N杂共轭杂环与卤代烃发生季铵化反应，生成季铵盐，同时在热激发的作用下，体系中的季铵盐阳离子发生异构化，异构化后的季铵盐阳离子与体系中的阴离子(卤离子)在阴离子-π作用下，发生电荷转移，进而得到自由基。In this embodiment, the quaternary ammonium salt is generated through the quaternization reaction between the N heteroconjugated heterocycle and the halogenated hydrocarbon, and at the same time, under the action of thermal excitation, the quaternary ammonium salt cation in the system undergoes isomerization, and the isomerization occurs. The latter quaternary ammonium salt cation and the anion (halide ion) in the system undergo charge transfer under the action of anion-π, thereby obtaining free radicals.
本实施例中，采用热激发的方法，诱导季铵盐阳离子发生异构化，其LUMO能级能够裂分出新的能级：SUMO和SUMO+1能级，其中SUMO能级低于原来的LUMO能级，即体系中的卤离子(电子给体)可以更容易与异构化的季铵盐阳离子(电子受体)发生电荷转移，从而因电荷转移所生成的自由基浓度更高。In this example, the method of thermal excitation is used to induce isomerization of the quaternary ammonium salt cation, and its LUMO energy level can be split into new energy levels: SUMO and SUMO+1 energy levels, where the SUMO energy level is lower than the original energy level The LUMO level, that is, the halide ion (electron donor) in the system can more easily transfer charge with the isomerized quaternary ammonium salt cation (electron acceptor), so that the concentration of free radicals generated by the charge transfer is higher.
由于分裂出来的SUMO能级更低，后续所添加的抗衡阴离子不需要有很高的HOMO(最高占据态轨道)能级，也可以发生内部离子交换生成自由基，且热激发异构化所形成的SUMO轨道为空轨道，可以接纳任何自旋方向的电子，有效的避免了泡利不相容规则，使后续对反离子盐的选择不受限制，确保了自由基的稳定形成。Since the split SUMO energy level is lower, the counter anion added subsequently does not need to have a high HOMO (highest occupied state orbital) energy level, and internal ion exchange can also occur to generate free radicals, and the formation of thermally excited isomerization The SUMO orbital is an empty orbital, which can accept electrons in any spin direction, effectively avoiding the Pauli exclusion rule, so that the subsequent selection of counter ion salts is not restricted, and the stable formation of free radicals is ensured.
在一些实施方式中，所述反离子盐为无机离子盐、有机离子盐和有机离子液体中的一种或多种，但不限于此。In some embodiments, the counter ion salt is one or more of inorganic ionic salts, organic ionic salts and organic ionic liquids, but is not limited thereto.
本实施例中，所述反离子盐作为抗衡阴离子加入到自由基离子盐混合物，新引入的抗衡阴离子可以调节体系中阴离子-π的相互作用，从而稳定体系中所产生的自由基，而且引入的阴离子可以中和阳离子自由基的多余电荷，实现电荷的自补偿，以获得稳定的自补偿自由基离子盐。In this embodiment, the counter ion salt is added to the radical ion salt mixture as a counter anion, and the newly introduced counter anion can adjust the anion-π interaction in the system, thereby stabilizing the free radicals generated in the system, and the introduced counter anion can Anions can neutralize the excess charges of cationic radicals and realize self-compensation of charges to obtain stable self-compensating radical ion salts.
当自由基离子盐作为掺杂剂时，本发明通过自补偿的方式，可以避免阳离子自由基上的电荷与半导体阴离子自由基产生静电作用，从而避免去掺杂的问题。When the radical ion salt is used as the dopant, the present invention can avoid the electrostatic interaction between the charge on the cation radical and the semiconductor anion radical by means of self-compensation, thereby avoiding the problem of de-doping.
同时，由于抗衡阴离子的选择种类不受限制，可以通过选择适合参数(能级和离子半径等)的反离子盐对阴离子-π进行调节，进而能够优化所制备得到自补偿自由基离子盐材料的溶解性、成膜性、不可扩散性、界面诱导偶极矩等性能指标。At the same time, since the selection of counter anions is not limited, the anion-π can be adjusted by selecting a counter ion salt suitable for parameters (energy level, ionic radius, etc.) Solubility, film formation, non-diffusion, interface induced dipole moment and other performance indicators.
在一些实施方式中，所述步骤S20包括，将反离子盐加入所述自由基离子盐前体中，通过内部离子交换得到自补偿自由基离子盐混合物；通过良溶剂与不良溶剂的相互溶解-析出过程对所述自补偿自由基离子盐混合物进行纯化，得到所述自补偿自由基离子盐。In some embodiments, the step S20 includes: adding a counter ion salt to the radical ion salt precursor, and obtaining a self-compensating radical ion salt mixture through internal ion exchange; mutual dissolution of a good solvent and a poor solvent- The precipitation process purifies the self-compensating radical ion salt mixture to obtain the self-compensating radical ion salt.
本实施例中，首先将所述自由基离子盐前体溶解于有机溶剂中，加入过量的反离子盐，所述有机溶剂为甲醇、乙腈和DMF中的一种或多种，但不限于此。将反离子盐加入所述自由基离子盐前体的步骤中，通过内部离子交换得到自补偿自由基离子盐混合物，通过良溶剂与不良溶剂的相互溶解-析出对所述初产物进行纯化，得到自补偿自由基离子盐。In this embodiment, the radical ion salt precursor is first dissolved in an organic solvent, and an excess of counter ion salt is added, and the organic solvent is one or more of methanol, acetonitrile and DMF, but not limited to this . In the step of adding a counter ion salt to the radical ion salt precursor, a self-compensating radical ion salt mixture is obtained through internal ion exchange, and the initial product is purified by mutual dissolution-precipitation of a good solvent and a poor solvent to obtain Self-compensating free radical ion salt.
本实施例中，所述良溶剂是指可以溶解所生成的自由基离子盐的溶剂，所述不良溶剂是指不能溶解所生成的自由基离子盐的溶剂。良溶剂和不良溶剂主要以其对自由基离子盐的溶解度而定。一些实施方式中，所述良溶剂可以是甲醇、水、DMF和乙腈，但不限于此。所述不良溶剂可以是乙醚、THF和PE，但不限于此。In this embodiment, the good solvent refers to a solvent that can dissolve the generated radical ion salt, and the poor solvent refers to a solvent that cannot dissolve the generated radical ion salt. Good solvents and poor solvents are mainly determined by their solubility in radical ion salts. In some embodiments, the good solvent may be methanol, water, DMF and acetonitrile, but not limited thereto. The poor solvent may be diethyl ether, THF and PE, but is not limited thereto.
本实施例中，通过良溶剂与不良溶剂的溶解-析出，可以去除反应中过量的反应物，得到纯化后的自补偿自由基离子盐。In this embodiment, through the dissolution-precipitation of the good solvent and the poor solvent, excess reactants in the reaction can be removed to obtain a purified self-compensating radical ion salt.
本发明提供的自补偿自由基离子盐的制备方法，季铵化成盐和热激化形成自由基是采用“一锅法”进行的，加入反离子盐进行内部阴离子交换过程也容易操作，本发明提供的制备方法工艺简单，操作方便。In the preparation method of the self-compensating free radical ion salt provided by the present invention, the quaternary ammonium salt formation and the thermal excitation to form free radicals are carried out by a "one-pot method", and the internal anion exchange process by adding counter ion salt is also easy to operate. The present invention provides The preparation method has simple process and convenient operation.
在一些实施方式中，还提供一种自补偿自由基离子盐，采用上述的制备方法制备而成。In some embodiments, a self-compensating radical ion salt is also provided, which is prepared by the above-mentioned preparation method.
所述自补偿自由基离子盐含有高浓度的自由基，从而对半导体的重掺杂，提高电极的导电性，而且本发明提供的自由基骨架为季铵盐结构，极性大，不仅可以通过降低界面接触的“耗尽层”厚度来降低电子注入/提取的隧穿势垒，还可以通过形成界面诱导偶极来降低功函数。因此，所述自补偿自由基离子盐可以用于制备有机光电器件的阴极界面修饰层，其修饰效果好，可有效改善电荷载流子在电极与有机功能层之间的注入和提取问题，提高电子传输效率。The self-compensating free radical ion salt contains a high concentration of free radicals, so that the semiconductor is heavily doped and the conductivity of the electrode is improved, and the free radical skeleton provided by the present invention is a quaternary ammonium salt structure with high polarity, which can not only pass Reducing the "depletion layer" thickness of the interfacial contact reduces the tunneling barrier for electron injection/extraction, and also reduces the work function by forming an interface-induced dipole. Therefore, the self-compensating radical ion salt can be used to prepare the cathode interface modification layer of the organic optoelectronic device, and the modification effect is good, which can effectively improve the injection and extraction of charge carriers between the electrode and the organic functional layer, and improve the Electron transfer efficiency.
在一些实施方式中，还提供一种光电器件，所述光电器件包括阴极以及设置在所述阴极表面的阴极界面修饰层，所述阴极界面修饰层材料为本发明所述的自补偿自由基离子盐。In some embodiments, an optoelectronic device is also provided, the optoelectronic device includes a cathode and a cathode interface modification layer disposed on the surface of the cathode, and the cathode interface modification layer material is the self-compensating free radical ions of the present invention Salt.
在一些实施方式中，所述光电器件具体为有机光电器件，所述有机光电器件包括有机发光二极管、有机太阳能电池、钙钛矿电池、钙钛矿发光二极管等光电功能转换器件，但不限于此。In some embodiments, the optoelectronic device is specifically an organic optoelectronic device, and the organic optoelectronic device includes photoelectric functional conversion devices such as organic light emitting diodes, organic solar cells, perovskite cells, perovskite light emitting diodes, etc., but is not limited thereto .
下面通过具体实施例对本发明进行详细说明。The present invention will be described in detail below through specific embodiments.
实施例1TPyPy-TFSI自由基离子盐的制备Example 1 Preparation of TPyPy-TFSI radical ion salt
具体合成路线如图2所示。首先称取510mg TPyPy(1mmol)于25mL的希兰克管中，依次加入超干DMF 5mL，1.2g碘甲烷(8mmol，过量)，然后用液氮将体系冻成固体，油泵抽真空，然后充入干燥的氩气，重复抽通三次。将体系密封，然后置于150℃的反应器中，避光搅拌反应12小时，然后冷却至室温后转移至手套箱。将悬浊液逐滴加入到干燥的乙醚溶液中，搅拌分散，沉淀，然后过滤得到棕黄色固体粉末。用石油醚和四氢呋喃先后冲洗固体相，抽干备用。然后将该棕黄色固体粉末分散于适量的超干甲醇溶液中，加入过量的双三氟甲磺酰亚胺锂，室温搅拌3～5小时，然后将混合液于超干乙醚中析出，过滤，固体又溶于适量乙醇当中，然后于超干石油醚中析出，彻底抽干得到自补偿自由基离子盐TPyPy-TFSI(1.2g)，综合产率85％。The specific synthetic route is shown in Figure 2. First weigh 510mg TPyPy (1mmol) into a 25mL Schlenk tube, add 5mL of ultra-dry DMF, 1.2g methyl iodide (8mmol, excess) in turn, then freeze the system into a solid with liquid nitrogen, evacuated with an oil pump, and then filled with Into dry argon, repeat the pumping three times. The system was sealed, then placed in a reactor at 150°C, stirred for 12 hours in the dark, cooled to room temperature, and then transferred to a glove box. The suspension was added dropwise to the dry ether solution, stirred to disperse, precipitated, and then filtered to obtain a brownish-yellow solid powder. The solid phase was washed successively with petroleum ether and tetrahydrofuran, and drained for use. Then the brown-yellow solid powder was dispersed in an appropriate amount of ultra-dry methanol solution, an excess of lithium bis-trifluoromethanesulfonimide was added, and the mixture was stirred at room temperature for 3 to 5 hours, and then the mixed solution was precipitated in ultra-dry ether, filtered, and The solid was dissolved in an appropriate amount of ethanol, then precipitated in ultra-dry petroleum ether, and thoroughly drained to obtain a self-compensating radical ion salt TPyPy-TFSI (1.2 g) with a comprehensive yield of 85%.
TPyPy是一种常见的含N杂环类电子传输材料，但是界面修饰能力非常弱，通过本发明所提供的方法能够显著提升其界面修饰能力，进而获得兼具界面修饰和电子传输的多功能材料TPyPy-TFSI。TPyPy is a common N-containing heterocyclic electron transport material, but its interface modification ability is very weak. The method provided by the present invention can significantly improve its interface modification ability, thereby obtaining a multifunctional material with both interface modification and electron transport. TPyPy-TFSI.
由于自补偿式自由基离子盐TPyPy-TFSI内含大量顺磁性自由基，H NMR和C NMR数据未能获得。HRMS：calcd for C46H34F18N7O12S6190.0922[M-3TFSI]·3+；Found 190.0924.Due to the large amount of paramagnetic radicals contained in the self-compensating radical ion salt TPyPy-TFSI, H NMR and C NMR data could not be obtained. HRMS: calcd for C46 H34 F18 N7 O12 S6 190.0922[M-3TFSI]·3+ ; Found 190.0924.
实例二：BCP-SBS自由基离子盐的制备Example 2: Preparation of BCP-SBS Radical Ion Salt
具体合成路线如图3所示。首先，称取720mg BCP(2mm)于25mL超干希兰克管中，然后加入重蒸的1,2-二溴乙烷10mL，用液氮将该悬浊液体系降至凝固点以下，用油泵抽真空，复充入干燥的氩气，重复该操作三次，然后将体系密封避光后置于140℃的反应器中，在该温度下搅拌12小时后冷却至室温，转移至手套箱处理。将棕色的悬浊液逐滴加入到搅拌的超干乙醚溶液中，然后过滤得到棕褐色的固体粉末，依次用石油醚，四氢呋喃超干溶液洗涤，抽干转移至手套箱外备用。将该固体溶于适量的甲醇溶液中，加入过量的糖精钠，室温搅拌3～5小时，将混合溶液倒入100mL去离子水中，搅拌一会儿后过滤，抽干后用四氢呋喃溶液洗涤，彻底抽干得到棕黑色固体粉末BCP-SBS(1.05g)，两步综合产率92％。The specific synthetic route is shown in Figure 3. First, weigh 720 mg of BCP (2 mm) into a 25 mL ultra-dry Schlenk tube, then add 10 mL of redistilled 1,2-dibromoethane, drop the suspension system below the freezing point with liquid nitrogen, and use an oil pump Vacuum, refill with dry argon, repeat this operation three times, then seal the system to protect from light and place it in a reactor at 140°C, stir at this temperature for 12 hours, cool to room temperature, and transfer to a glove box for processing. The brown suspension was added dropwise to the stirred ultra-dry ether solution, and then filtered to obtain a tan solid powder, which was washed with petroleum ether and tetrahydrofuran ultra-dry solution in turn, drained and transferred to the glove box for later use. The solid was dissolved in an appropriate amount of methanol solution, excess sodium saccharin was added, stirred at room temperature for 3 to 5 hours, the mixed solution was poured into 100 mL of deionized water, stirred for a while, filtered, and washed with tetrahydrofuran solution after draining. The brown-black solid powder BCP-SBS (1.05 g) was obtained with a two-step combined yield of 92%.
BCP是一种常见的电子传输材料，其电子迁移率高达10-3cm-2V-1s-1量级，但是同样不具备界面修饰能力。通过本发明提供的方法，制备了具有良好界面修饰和电荷传输能力的自补偿式自由基离子盐BCP-SBS。BCP is a common electron transport material, and its electron mobility is as high as 10-3cm-2V-1s-1, but it also has no interface modification ability. By the method provided by the present invention, the self-compensating radical ion salt BCP-SBS with good interface modification and charge transport ability is prepared.
由于自补偿式自由基离子盐BCP-SBS具有较强的顺磁性，未能获得H NMR和C NMR的数据。HRMS：calcd for C35H28N3O3S 388.1934[M-SBS]·+；Found 388.1934.Due to the strong paramagnetic properties of the self-compensating radical ion salt BCP-SBS, H NMR and C NMR data could not be obtained. HRMS: calcd for C35 H28 N3 O3 S 388.1934 [M-SBS]·+ ; Found 388.1934.
实施例3、TPyZ-TfO自由基离子盐的制备Example 3. Preparation of TPyZ-TfO radical ion salt
具体合成路线如图4所示。首先取TPyZ((含N杂环类电子传输材料前体)原料543mg(1mmol)于10mL的超干希兰克管中，然后加入溴化苄5mL(过量)，用油泵抽真空，然后再复充入干燥的氩气，重复该操作三次后，密封、避光置于160℃的油浴中，在该温度下搅拌12小时后冷却至50℃左右，然后转移至手套箱操作。将该悬浊液分散于大量的乙醚溶液中，搅拌后析出固体，过滤，滤渣先后用乙醚、石油醚、四氢呋喃溶液洗涤后抽干备用。将该棕黄色固体分散于适量的超干甲醇溶液中，然后再加入3mmol的三氟甲磺酸银，室温搅拌1～3小时后转移至手套箱外操作。将悬浊液离心，取上清液逐滴加入到乙醚溶液中，搅拌析出，过滤，滤渣先后用四氢呋喃、石油醚和乙醚洗涤，之后彻底抽干得到棕黄色TPyZ-TfO离子盐1.01g，两步综合产率80％。The specific synthetic route is shown in Figure 4. First, take 543 mg (1 mmol) of TPyZ ((N-containing heterocyclic electron transport material precursor) raw material into a 10 mL ultra-dry Schlenk tube, then add 5 mL of benzyl bromide (excess), use an oil pump to evacuate, and then repeat Fill with dry argon, repeat this operation for three times, seal and place it in an oil bath at 160°C in the dark, stir at this temperature for 12 hours, cool down to about 50°C, and then transfer to a glove box for operation. The turbid liquid is dispersed in a large amount of diethyl ether solution, and after stirring, separates out solid, filters, and the filter residue is washed successively with diethyl ether, petroleum ether, tetrahydrofuran solution and then drained for subsequent use.This brown-yellow solid is dispersed in an appropriate amount of ultra-dry methanol solution, and then again Add 3 mmol of silver trifluoromethanesulfonate, stir at room temperature for 1 to 3 hours and then transfer to the outside of the glove box for operation. Centrifuge the suspension, take the supernatant and add it dropwise to the ether solution, stir to separate out, filter, and use the filter residue successively After washing with tetrahydrofuran, petroleum ether and diethyl ether, and then thoroughly draining to obtain 1.01 g of brown-yellow TPyZ-TfO ion salt, the combined yield of the two steps is 80%.
TPyZ(如下图所示)为早期报道过的含N杂环电子传输材料。由于该化合物内含有顺磁性自由基，未能获得其H NMR和C NMR数据。HRMS：calcd for C56H42F6N9O6S2 408.1776[M-2TfO]·2+；Found 408.1773.TPyZ (shown below) is an early reported N-containing heterocyclic electron transport material. H NMR and C NMR data could not be obtained due to the presence of paramagnetic radicals in this compound. HRMS: calcd for C56 H42 F6 N9 O6 S2 408.1776[M-2TfO]2+ ; Found 408.1773.
实施例4、BOZ-TfO自由基离子盐的制备Example 4. Preparation of BOZ-TfO radical ion salt
具体合成路线如图5所示。首先取BOZ(含N杂环类电子传输材料前体)原料5mmol、硼酸酯单体(tert-butyldimethyl(2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenethoxy)silane)6mmol、Pd(PP3)4 200mg、2M碳酸钾水溶液20mL、甲苯60mL和乙醇10mL于250mL的双口瓶中，排气之后于90℃油浴中反应24h。冷却后，减压旋干溶剂，柱层析分离纯化得到淡黄色油状中间体，直接投入下一步。在20mL氯化亚砜中室温反应3～5h，减压除掉溶剂，甲醇溶解后乙醚中析出，然后用乙醇/正己烷纯化得黄色BOZ-Cl离子盐。将该黄色固体分散于适量的超干甲醇溶液中，然后再加入10mmol的三氟甲磺酸银，室温搅拌1～3小时后将悬浊液离心，取上清液逐滴加入到乙醚溶液中，搅拌析出，过滤，滤渣先后用四氢呋喃、石油醚和乙醚洗涤，之后彻底抽干得到棕黄色BOZ-TfO，两步综合产率53％。The specific synthetic route is shown in Figure 5. First, take 5 mmol of BOZ (N-containing heterocyclic electron transport material precursor) raw material, boronic ester monomer (tert-butyldimethyl(2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2 -yl)phenethoxy)silane) 6mmol, Pd(PP3)4 200mg, 2M potassium carbonate aqueous solution 20mL, toluene 60mL and ethanol 10mL in a 250mL double-necked flask, exhausted and reacted in an oil bath at 90°C for 24h. After cooling, the solvent was spin-dried under reduced pressure, separated and purified by column chromatography to obtain a light yellow oily intermediate, which was directly put into the next step. The reaction was carried out in 20 mL of thionyl chloride at room temperature for 3 to 5 h, and the solvent was removed under reduced pressure. After methanol was dissolved, it was precipitated in ether, and then purified with ethanol/n-hexane to obtain yellow BOZ-Cl ion salt. The yellow solid was dispersed in an appropriate amount of ultra-dry methanol solution, and then 10 mmol of silver trifluoromethanesulfonate was added. After stirring at room temperature for 1 to 3 hours, the suspension was centrifuged, and the supernatant was added dropwise to the ether solution. , stirred to separate out, filtered, and the filter residue was washed successively with tetrahydrofuran, petroleum ether and diethyl ether, and then thoroughly drained to obtain brown-yellow BOZ-TfO with a two-step comprehensive yield of 53%.
由于该化合物内含有顺磁性自由基，未能获得其H NMR和C NMR数据。HRMS：calcdfor C35H22F3N2O5S 490.1676[M-TfO]·+；Found 490.1668.H NMR and C NMR data could not be obtained due to the presence of paramagnetic radicals in this compound. HRMS: calcdfor C35 H22 F3 N2 O5 S 490.1676[M-TfO]·+ ; Found 490.1668.
实施例5、SPhen-TFSI自由基离子盐的制备Example 5. Preparation of SPhen-TFSI radical ion salt
具体合成路线如图6所示。首先取SPhen(含N稠环电子传输材料)原料1mmol于10mL的超干希兰克管中，然后加入1,2-二溴乙烷5mL(过量)，用油泵抽真空，然后再复充入干燥的氩气，重复该操作三次后，密封、避光置于140℃的油浴中，在该温度下搅拌12小时后冷却至50℃左右，然后转移至手套箱操作。将该悬浊液分散于大量的乙醚溶液中，搅拌后析出固体，过滤，滤渣先后用乙醚、石油醚、四氢呋喃溶液洗涤后抽干备用。将该棕褐色固体分散于适量的超干甲醇溶液中，然后再加入3mmol的TFSI-Li，室温搅拌1～3小时后转移至手套箱外操作。将悬浊液离心，取上清液逐滴加入到乙醚溶液中，搅拌析出，过滤，滤渣先后用四氢呋喃、石油醚和乙醚洗涤，之后彻底抽干得到棕褐色SPhen-TFSI离子盐目标化合物，两步综合产率70％。The specific synthetic route is shown in Figure 6. First, take 1 mmol of SPhen (N-containing fused ring electron transport material) raw material into a 10 mL ultra-dry Schlenk tube, then add 5 mL of 1,2-dibromoethane (excess), use an oil pump to evacuate, and then refill Dry argon, after repeating this operation three times, seal it, place it in an oil bath at 140 °C in the dark, stir at this temperature for 12 hours, cool it to about 50 °C, and then transfer it to a glove box for operation. The suspension was dispersed in a large amount of diethyl ether solution, a solid was precipitated after stirring, filtered, and the filter residue was washed successively with diethyl ether, petroleum ether and tetrahydrofuran solution and then drained for use. The brown solid was dispersed in an appropriate amount of ultra-dry methanol solution, then 3 mmol of TFSI-Li was added, stirred at room temperature for 1 to 3 hours, and then transferred to the outside of the glove box for operation. The suspension was centrifuged, the supernatant was added dropwise to the ether solution, stirred to separate out, filtered, the filter residue was washed with tetrahydrofuran, petroleum ether and ether successively, and then thoroughly drained to obtain the brown SPhen-TFSI ion salt target compound, two. The overall yield of the step was 70%.
由于该化合物内含有顺磁性自由基，未能获得其H NMR和C NMR数据。HRMS：calcdfor C18H10F6N7O4S3 318.0682[M-TFSI]·+；Found 318.0677.H NMR and C NMR data could not be obtained due to the presence of paramagnetic radicals in this compound. HRMS: calcd for C18 H10 F6 N7 O4 S3 318.0682 [M-TFSI]·+ ; Found 318.0677.
实施例6、HATCN-OSB自由基离子盐的制备Example 6. Preparation of HATCN-OSB radical ion salt
具体合成路线如图7所示。首先,取HATCN(常见的含N杂环电子受体)原料2mmol,于25mL的超干希兰克管中，然后加入1,2-二溴乙烷10mL(过量)，用油泵抽真空，然后再复充入干燥的氩气，重复该操作三次后，密封、避光置于160℃的油浴中，在该温度下搅拌12小时后冷却至50℃左右，然后转移至手套箱操作。将该悬浊液分散于大量的乙醚溶液中，搅拌后析出固体，过滤，滤渣先后用乙醚、石油醚、四氢呋喃溶液洗涤后抽干备用。将该棕黑色固体分散于适量的超干甲醇溶液中，然后再加入5mmol的KOSB盐(见下图)，室温搅拌1～3小时后转移至手套箱外操作。将悬浊液离心，取上清液逐滴加入到乙醚溶液中，搅拌析出，过滤，滤渣先后用四氢呋喃、石油醚和乙醚洗涤，之后彻底抽干得到棕黑色HATCN-OSB自由基离子盐，两步综合产率80％。The specific synthetic route is shown in Figure 7. First, take 2 mmol of HATCN (a common N-containing heterocyclic electron acceptor) raw material, put it in a 25 mL ultra-dry Schlenk tube, then add 10 mL of 1,2-dibromoethane (excess), use an oil pump to vacuum, then Then refill with dry argon, repeat this operation three times, seal it, place it in an oil bath at 160 °C in the dark, stir at this temperature for 12 hours, cool it to about 50 °C, and then transfer it to a glove box for operation. The suspension was dispersed in a large amount of diethyl ether solution, a solid was precipitated after stirring, filtered, and the filter residue was washed successively with diethyl ether, petroleum ether and tetrahydrofuran solution and then drained for use. The brown-black solid was dispersed in an appropriate amount of ultra-dry methanol solution, and then 5 mmol of KOSB salt (see the figure below) was added, stirred at room temperature for 1 to 3 hours, and then transferred to the glove box for operation. The suspension was centrifuged, the supernatant was added dropwise to the ether solution, stirred to separate out, filtered, and the filter residue was washed with tetrahydrofuran, petroleum ether and ether successively, and then thoroughly drained to obtain a brown-black HATCN-OSB radical ion salt. The overall yield of the step is 80%.
由于该化合物内含有顺磁性自由基，未能获得其H NMR和C NMR数据。HRMS：calcdfor C68H68N11O32S5 180.0661[M-5OSB]·5+；Found 180.0664.H NMR and C NMR data could not be obtained due to the presence of paramagnetic radicals in this compound. HRMS: calcdfor C68 H68 N11 O32 S5 180.0661[M-5OSB]5+ ; Found 180.0664.
实施例7、自补偿式自由基离子盐对高功函金属的界面修饰能力测试示例Example 7. Test example of the interface modification ability of self-compensating radical ion salts on high work function metals
根据有机光电功能器件中对阴极界面层的要求，以及为了印证此方法的实用性，选择了上述实施例1、2、3中制备得到的自补偿自由基离子盐(TPyPy-TFSI、BCP-SBS、TPyZ-TfO)，分别测试其对常用阴极金属电极Al和Ag的界面修饰能力。According to the requirements for the cathode interface layer in organic optoelectronic functional devices, and in order to prove the practicability of this method, the self-compensating radical ion salts (TPyPy-TFSI, BCP-SBS, TPyPy-TFSI, BCP-SBS) prepared in the above Examples 1, 2, and 3 were selected. , TPyZ-TfO), and tested their interfacial modification ability on common cathode metal electrodes Al and Ag, respectively.
样品制备方法：选择导电性好的n-型硅片若干，尺寸大小均为5×5mm，先后用丙酮、去离子水、异丙醇超声处理，然后光面用紫外-臭氧处理10分钟，然后在光面分别生长100nm左右的金属Al或者金属Ag电极。然后将这些离子盐的三氟乙醇溶液(1.0mg/mL)，按照3000转/分钟的速度旋涂于金属电极之上。为了排除溶剂的影响，空白组的金属电极表面旋涂纯三氟乙醇溶液。所有样品均置于氮气氛围的保护之中，待测试时快速取出测试。Sample preparation method: select a number of n-type silicon wafers with good conductivity, the size of which is 5 × 5 mm, and ultrasonically treat them with acetone, deionized water, and isopropanol successively, and then treat the smooth surface with UV-ozone for 10 minutes. Metal Al or metal Ag electrodes of about 100 nm are grown on the smooth surface, respectively. A solution of these ionic salts in trifluoroethanol (1.0 mg/mL) was then spin-coated on the metal electrode at a speed of 3000 rpm. In order to exclude the influence of solvent, pure trifluoroethanol solution was spin-coated on the metal electrode surface of blank group. All samples are placed under the protection of nitrogen atmosphere, and they are quickly taken out for testing when they are to be tested.
分别采用紫外光电子能谱(UPS)和开尔文探针(KP)测试被修饰的金属表面功函数(WF)。其中，KP结果是采用石墨烯样品(4.600eV)校准，UPS结果参照Au(5.1eV)标注费米能级零点。具体测试结果详见表1。The work function (WF) of the modified metal surface was measured by ultraviolet photoelectron spectroscopy (UPS) and Kelvin probe (KP), respectively. Among them, the KP result is calibrated with the graphene sample (4.600eV), and the UPS result refers to Au (5.1eV) to mark the Fermi level zero point. The specific test results are shown in Table 1.
相比于对照组，TPyPy-TFSI、BCP-SBS和TPyZ-TfO自由基离子盐均能够显著降低金属Ag和Al的功函数，表明这些自补偿自由基离子盐均可作为潜在的阴极界面层。Compared with the control group, TPyPy-TFSI, BCP-SBS, and TPyZ-TfO radical ion salts can significantly reduce the work function of metallic Ag and Al, indicating that these self-compensating radical ion salts can all serve as potential cathode interfacial layers.
表1、自补偿式自由基离子盐修饰的金属表面功函数。Table 1. Work functions of metal surfaces modified by self-compensating radical ion salts.
a)相对于Ag电极的功函降低数，b)相对于Al电极的功函降低数。a) Decreases in work function relative to Ag electrodes,b) Decreases in work function relative to Al electrodes.
如图8所示的是这三个化合物的电子顺磁共振(EPR)谱图，很明显，这三个化合物均显示很强的EPR信号表明其自由基含量均很高。值得说明的是，这些自由基离子盐均表现出非常好的空气稳定性和溶剂稳定性。将这些化合物暴露在空气中半年，或者溶于常规的良溶剂(甲醇、DMF等)中一周以上均未发现颜色的变化，其EPR信号也未见衰弱。Figure 8 shows the electron paramagnetic resonance (EPR) spectra of these three compounds. Obviously, these three compounds all show strong EPR signals, indicating that their radical content is high. It is worth noting that these radical ion salts all exhibit very good air stability and solvent stability. These compounds were exposed to air for half a year, or dissolved in conventional good solvents (methanol, DMF, etc.) for more than a week, and no color change was found, and their EPR signals were not weakened.
实施例8、自补偿式自由基离子盐作为阴极界面层在有机光电功能器件中的应用示例Example 8. Application example of self-compensating radical ion salt as cathode interface layer in organic optoelectronic functional devices
为了表征这些自由基离子盐在光电功能器件中的应用，本实施例采用上述实施例1、2、3所制备得到的自补偿自由基离子盐作为OSC器件的阴极界面层。采用全溶液旋涂的加工方法制备了基于含自补偿式自由基离子盐为阴极界面修饰层(CILs)、PBDB-IT-M为有机活性层的有机太阳能电池器件，其具体结构为：ITO/PEDOT:PSS/PBDB-IT-M/CILs/Al，具体结构如图9所示。In order to characterize the application of these radical ion salts in optoelectronic functional devices, the self-compensating radical ion salts prepared in the above Examples 1, 2, and 3 are used as the cathode interface layer of the OSC device in this example. Organic solar cell devices based on self-compensating radical ion salts as cathode interface modification layers (CILs) and PBDB-IT-M as organic active layers were fabricated by all-solution spin coating. The specific structure is: ITO/ITO PEDOT:PSS/PBDB-IT-M/CILs/Al, the specific structure is shown in Figure 9.
其中所涉及的CIL包括TPyPy-TFSI、BCP-SBS和TPyZ-TfO，对照组为三氟乙醇空白溶液。这些器件的电流密度-电压(J-V)曲线展示如图10所示，对应器件的测试结果如表2所示。The CILs involved included TPyPy-TFSI, BCP-SBS and TPyZ-TfO, and the control group was a trifluoroethanol blank solution. The current density-voltage (J-V) curves of these devices are shown in FIG. 10 , and the test results of the corresponding devices are shown in Table 2.
表2自补偿自由基离子盐作为阴极界面层的OSC数据Table 2 OSC data of self-compensating radical ion salts as cathode interfacial layer
从上表可知，相比于对照组，自补偿式自由基离子盐的插入能够显著提升器件的开路电压(Voc)、短路电流(Jsc)以及填充因子(FF％)从而显著提升器件的综合效率。得益于自由基和界面诱导偶极的存在，这些自补偿式自由基离子盐的引入能够显著降低有机太阳能活性层和金属阴极之间的接触势垒，降低了整个器件的电阻，从而保证了器件的效率提升。这些以TPyPy-TFSI、BCP-SBS或TPyZ-TfO为CIL的器件均达到或接近文献所报道的基于PBDB-IT-M为有机太阳能活性层的最佳值之一，综合表明了本发明方案的实用性。It can be seen from the above table that compared with the control group, the insertion of self-compensating radical ion salts can significantly improve the open circuit voltage (Voc), short circuit current (Jsc) and fill factor (FF%) of the device, thereby significantly improving the overall efficiency of the device . Benefiting from the existence of radicals and interface-induced dipoles, the introduction of these self-compensating radical ion salts can significantly reduce the contact barrier between the organic solar active layer and the metal cathode, reducing the resistance of the entire device, thereby ensuring The efficiency of the device is improved. These devices using TPyPy-TFSI, BCP-SBS or TPyZ-TfO as CIL all reach or approach one of the best values reported in the literature based on PBDB-IT-M as the organic solar active layer, which comprehensively shows that the scheme of the present invention has practicality.
综上所述，本发明提供一种自补偿自由基离子盐及其制备方法、应用。本发明通过将N杂共轭杂环与卤代烃发生季铵反应生成季铵盐的同时，采用热激发的方法诱导部分季铵盐阳离子发生异构化，异构化的季铵盐阳离子与体系中的卤离子发生阴离子-π相互作用诱导电荷转移，形成自由基，得到自由基离子盐混合物。热激异构化的季铵盐阳离子的LUMO(最低未占分子轨道)能分裂出更低的空轨道(SUMO)，SUMO轨道可以接纳任何自旋方向的电子，有效促进了体系中的阴离子到异构化季铵盐阳离子的电荷转移，从而促进了自由基的形成，有效提高自由基的浓度。将反离子盐加入到所述自由基离子盐混合物中，所述反离子盐作为抗衡阴离子可以与自由基发生内部阴离子交换，一方面是新引入抗衡阴离子可以起调节体系中阴离子-π的相互作用，从而稳定体系中所产生的自由基，另一方面通过引入新的阴离子可以中和阳离子自由基多余的电荷，以实现电荷的自补偿，进一步提高了体系中自由基的浓度和稳定性。通过本发明提供的制备方法得到的自补偿自由基离子盐可以应用于有机光电功能器件的自掺杂阴极界面层中，可以有效降低阴极金属电极的功函数，实现器件综合效率的优化。To sum up, the present invention provides a self-compensating free radical ion salt and a preparation method and application thereof. In the present invention, the quaternary ammonium salt is generated by the quaternary ammonium reaction between the N heteroconjugated heterocycle and the halogenated hydrocarbon, and the isomerization of part of the quaternary ammonium salt cation is induced by the method of thermal excitation, and the isomerized quaternary ammonium salt cation and The halide ions in the system undergo anion-π interaction to induce charge transfer to form free radicals, resulting in radical ion salt mixtures. The LUMO (lowest unoccupied molecular orbital) of the heat-shock isomerized quaternary ammonium salt cation can split into a lower empty orbital (SUMO), and the SUMO orbital can accept electrons in any spin direction, effectively promoting the anion in the system to reach The charge transfer of isomerized quaternary ammonium salt cations promotes the formation of free radicals and effectively increases the concentration of free radicals. Adding a counter ion salt to the radical ion salt mixture, the counter ion salt as a counter anion can undergo internal anion exchange with free radicals, on the one hand, the newly introduced counter anion can play a role in regulating the anion-π interaction in the system , thereby stabilizing the free radicals generated in the system. On the other hand, by introducing new anions, the excess charges of the cationic radicals can be neutralized to achieve self-compensation of the charges, which further improves the concentration and stability of the free radicals in the system. The self-compensating radical ion salt obtained by the preparation method provided by the present invention can be applied to the self-doping cathode interface layer of the organic optoelectronic functional device, which can effectively reduce the work function of the cathode metal electrode and realize the optimization of the overall efficiency of the device.
应当理解的是，本发明的应用不限于上述的举例，对本领域普通技术人员来说，可以根据上述说明加以改进或变换，所有这些改进和变换都应属于本发明所附权利要求的保护范围。It should be understood that the application of the present invention is not limited to the above examples. For those of ordinary skill in the art, improvements or transformations can be made according to the above descriptions, and all these improvements and transformations should belong to the protection scope of the appended claims of the present invention.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106521543A (en)* | 2016-09-18 | 2017-03-22 | 燕山大学 | Reduced ionic salt of perylene bisimide and derivative of perylene bisimide and preparation method |
| CN107098919A (en)* | 2017-03-13 | 2017-08-29 | 华南理工大学 | The molten conjugation small molecule of A D A types water/alcohol and its application in organic electronic device |
- 2019
- 2019-10-10CNCN201910959658.8Apatent/CN110845497B/enactiveActive
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106521543A (en)* | 2016-09-18 | 2017-03-22 | 燕山大学 | Reduced ionic salt of perylene bisimide and derivative of perylene bisimide and preparation method |
| CN107098919A (en)* | 2017-03-13 | 2017-08-29 | 华南理工大学 | The molten conjugation small molecule of A D A types water/alcohol and its application in organic electronic device |
Non-Patent Citations (2)
| Title |
|---|
| XIAOJUN YIN等: "Multichannel Strategies to Produce Stabilized Azaphenalene Diradicals: A Predictable Model to Generate Self-Doped Cathode Interfacial Layers for Organic Photovoltaics", 《ADVANCED FUNCTIONAL MATERIALS》* |
| XIAOJUN YIN等: "Self-Doping Cathode Interfacial Material Simultaneously Enabling High Electron Mobility and Powerful Work Function Tunability for High-Efficiency All-Solution-Processed Polymer Light-Emitting Diodes", 《ADVANCED FUNCTIONAL MATERIALS》* |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113999208A (en)* | 2021-10-25 | 2022-02-01 | 华中师范大学 | An ionic thermally activated delayed fluorescent material and its application in solid-state light-emitting electrochemical cells |
| CN113999208B (en)* | 2021-10-25 | 2022-12-16 | 华中师范大学 | An Ionic Thermally Activated Delayed Fluorescent Material and Its Application in Solid-State Luminescent Electrochemical Cells |
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