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CN114315868A - Lewis base anion-doped organic semiconductor electron acceptor molecule and method and device - Google Patents

Lewis base anion-doped organic semiconductor electron acceptor molecule and method and device Download PDF

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CN114315868A
CN114315868A CN202111658000.7A CN202111658000A CN114315868A CN 114315868 A CN114315868 A CN 114315868A CN 202111658000 A CN202111658000 A CN 202111658000A CN 114315868 A CN114315868 A CN 114315868A
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electron acceptor
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acceptor molecule
lewis base
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李昌治
蒋丹妮
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Zhejiang University ZJU
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Abstract

The invention discloses a Lewis base anion doped organic semiconductor electron acceptor molecule and a method and a device thereof, wherein the preparation method comprises the steps of adding an ion dopant containing Lewis base anions into the organic semiconductor electron acceptor molecule, and uniformly mixing the Lewis base anions and the organic semiconductor electron acceptor molecule by utilizing a chlorinated organic solvent to obtain a stable solution; and then removing the solvent of the stable solution to obtain the solid ion-doped organic semiconductor electron acceptor molecule. The doping method provided by the invention is mild and controllable, can be processed by solution, improves the charge transport capacity of the doped organic semiconductor acceptor molecule, and obviously improves the device performance when being applied to an organic photoelectric device.

Description

路易斯碱负离子掺杂有机半导体电子受体分子及方法和器件Lewis base anion doped organic semiconductor electron acceptor molecule and method and device

技术领域technical field

本发明属于化学掺杂领域,尤其涉及一种路易斯碱负离子掺杂有机半导体电子受体分子及方法和器件。The invention belongs to the field of chemical doping, in particular to a Lewis alkali anion-doped organic semiconductor electron acceptor molecule, a method and a device.

背景技术Background technique

掺杂作为改善半导体载流子浓度和电荷输运能力的有效方法,应用于光电器件时仍表现出局限性,如可溶液加工性、可控性以及激子和载流子过程的平衡性。因此,如果要将掺杂用于有机太阳电池,尤其是有机半导体电子受体分子,需要选取合适的n型掺杂方法来解决上述问题。As an effective method to improve the carrier concentration and charge transport capability of semiconductors, doping still exhibits limitations when applied to optoelectronic devices, such as solution processability, controllability, and balance of exciton and carrier processes. Therefore, if doping is to be used in organic solar cells, especially organic semiconductor electron acceptor molecules, it is necessary to select a suitable n-type doping method to solve the above problems.

尽管已有可溶液加工的n型掺杂剂存在不足,但强还原性掺杂剂(如BV和 DQ)和前体掺杂剂(如N-DMBI)已经在有机太阳电池中有所应用。前者在水氧环境中不稳定;后者具有较大的离子化电势(IP),需要热激活生成中间产物来实现掺杂。因此电子转移过程都需要在苛刻条件下完成。而基于离子(如F-、 OH-、AcO-、Cl-、Br-和I-)的n型掺杂剂可以在更温和条件下完成掺杂,通过溶剂分子屏蔽离子-π作用来稳定溶液态,仅在固态向有机半导体(如富勒烯及其衍生物)发生电子转移。但要将该方法应用于高性能器件,仍需要进一步探究其掺杂原理。Despite the deficiencies of existing solution-processable n-type dopants, strongly reducing dopants such as BV and DQ and precursor dopants such as N-DMBI have been used in organic solar cells. The former is unstable in a water-oxygen environment; the latter has a large ionization potential (IP) and requires thermal activation to generate intermediate products to achieve doping. Therefore, the electron transfer process needs to be completed under harsh conditions. While n-type dopants based on ions (such as F - , OH - , AcO - , Cl - , Br - and I - ) can be doped under milder conditions, stabilizing the solution by shielding the ion-π interaction by solvent molecules state, and electron transfer to organic semiconductors (such as fullerenes and their derivatives) occurs only in the solid state. However, in order to apply this method to high-performance devices, it is still necessary to further explore its doping mechanism.

现有技术中,可以在相对苛刻条件下利用特定掺杂方法提高有机光电器件的性能。但是,为简化制备过程,如何提供一种溶液稳定、固态掺杂有机半导体电子受体分子的方法,如何通过该掺杂方法实现器件性能的进一步提升,是本发明聚焦解决的问题。In the prior art, specific doping methods can be used to improve the performance of organic optoelectronic devices under relatively harsh conditions. However, in order to simplify the preparation process, how to provide a solution-stable, solid-state method for doping organic semiconductor electron acceptor molecules, and how to further improve device performance through the doping method are the problems that the present invention focuses on.

发明内容SUMMARY OF THE INVENTION

本发明的目的是克服现有技术的不足,并提供一种路易斯碱负离子掺杂有机半导体电子受体分子及方法和器件。本发明的制备方法不仅具备温和、可控、可溶液加工的优势,而且能够有效调控有机半导体电子受体分子的电荷输运能力,从而实现有机场效应晶体管和有机太阳电池的性能提升。The purpose of the present invention is to overcome the deficiencies of the prior art, and to provide a Lewis alkali anion-doped organic semiconductor electron acceptor molecule, a method and a device. The preparation method of the invention not only has the advantages of mildness, controllability and solution processing, but also can effectively regulate the charge transport ability of the organic semiconductor electron acceptor molecule, thereby realizing the performance improvement of the organic field effect transistor and the organic solar cell.

本发明所采用的具体技术方案如下:The concrete technical scheme adopted in the present invention is as follows:

第一方面,本发明提供了一种路易斯碱负离子掺杂有机半导体电子受体分子的制备方法,具体如下:将含有路易斯碱负离子的离子掺杂剂加入有机半导体电子受体分子中,利用氯代有机溶剂使两者均匀混合,得到稳定溶液;随后将稳定溶液的溶剂去除,得到固态的路易斯碱负离子掺杂有机半导体电子受体分子。In a first aspect, the present invention provides a method for preparing a Lewis base anion-doped organic semiconductor electron acceptor molecule, which is specifically as follows: adding an ion dopant containing a Lewis base anion to the organic semiconductor electron acceptor molecule, using chlorinated The organic solvent makes the two evenly mixed to obtain a stable solution; then the solvent of the stable solution is removed to obtain solid Lewis base anion-doped organic semiconductor electron acceptor molecules.

作为优选,氯代有机溶剂采用氯仿或氯苯。Preferably, chloroform or chlorobenzene is used as the chlorinated organic solvent.

作为优选,所述离子掺杂剂为四丁基铵盐(TBAX)、四丁基磷盐(TBPX) 或三苯基甲基磷盐(MTPPX)中的任意一种,结构式分别如下:Preferably, the ionic dopant is any one of tetrabutylammonium salt (TBAX), tetrabutylphosphonium salt (TBPX) or triphenylmethylphosphorus salt (MTPPX), and the structural formulas are as follows:

Figure BDA0003448902640000021
Figure BDA0003448902640000021

式中,X为F、OH、AcO(即CH3COO,乙酸根离子)、Cl、Br和I中的任意一种。In the formula, X is any one of F, OH, AcO (ie CH 3 COO, acetate ion), Cl, Br and I.

作为优选,所述有机半导体电子受体分子为Y6、BTP-4Cl、Y6-1O、IT-4F、 PTIC或PTB-4Cl中任意一种,结构式分别如下:Preferably, the organic semiconductor electron acceptor molecule is any one of Y6, BTP-4Cl, Y6-1O, IT-4F, PTIC or PTB-4Cl, and the structural formula is as follows:

Figure BDA0003448902640000022
Figure BDA0003448902640000022

式中,R1为2-乙基己基,R2为十一烷基,R3为2-丁基辛基,R4为4-己基苯基,R5为己基,R6为-己基癸基。In the formula, R 1 is 2-ethylhexyl, R 2 is undecyl, R 3 is 2-butyl octyl, R 4 is 4-hexyl phenyl, R 5 is hexyl, and R 6 is -hexyl decyl base.

作为优选,所述路易斯碱负离子掺杂有机半导体电子受体分子中离子掺杂剂和有机半导体电子受体分子的摩尔比为0.025-100mol%。Preferably, the molar ratio of the ion dopant to the organic semiconductor electron acceptor molecule in the Lewis base anion-doped organic semiconductor electron acceptor molecule is 0.025-100 mol%.

第二方面,本发明提供了一种根据第一方面任一所述制备方法得到的路易斯碱负离子掺杂有机半导体电子受体分子。In a second aspect, the present invention provides a Lewis base anion-doped organic semiconductor electron acceptor molecule obtained according to any one of the preparation methods in the first aspect.

第三方面,本发明提供了一种作为有机场效应晶体管的器件,该器件为底栅顶接触结构,从下至上依次为栅电极、介电层、半导体薄膜和源漏电极;所述半导体薄膜由第二方面所述的离子掺杂有机半导体电子受体分子制备所得。In a third aspect, the present invention provides a device as an organic field effect transistor, the device has a bottom-gate top-contact structure, and from bottom to top are a gate electrode, a dielectric layer, a semiconductor thin film and a source-drain electrode; the semiconductor thin film It is prepared from the ion-doped organic semiconductor electron acceptor molecule described in the second aspect.

作为优选,所述半导体薄膜厚度为10-100nm,路易斯碱负离子掺杂有机半导体电子受体分子中离子掺杂剂和有机半导体电子受体分子的摩尔比为5-30 mol%。Preferably, the thickness of the semiconductor thin film is 10-100 nm, and the molar ratio of the ion dopant to the organic semiconductor electron acceptor molecule in the Lewis base anion-doped organic semiconductor electron acceptor molecule is 5-30 mol%.

作为优选,栅电极材料为n型重掺杂硅(n++Si),厚度为200-300μm;介电层材料为苯丙环丁烯(BCB)修饰的二氧化硅(SiO2),厚度为300-350nm;源漏电极材料为金(Au),厚度为50-100nm。Preferably, the gate electrode material is n-type heavily doped silicon (n ++ Si) with a thickness of 200-300 μm; the dielectric layer material is phenylcyclobutene (BCB) modified silicon dioxide (SiO 2 ) with a thickness of 200-300 μm It is 300-350nm; the source and drain electrode material is gold (Au), and the thickness is 50-100nm.

第四方面,本发明提供了一种作为有机太阳电池的器件,该器件为多层层状结构,从下至上依次为基底、阳极、阳极修饰层、有机活性层、阴极修饰层和阴极;所述有机活性层由电子给体分子和如第二方面所述的路易斯碱负离子掺杂有机半导体电子受体分子依次旋涂所得。In a fourth aspect, the present invention provides a device as an organic solar cell, the device has a multi-layered structure, and from bottom to top, it is a substrate, an anode, an anode modification layer, an organic active layer, a cathode modification layer and a cathode; The organic active layer is obtained by successive spin coating of electron donor molecules and Lewis base anion-doped organic semiconductor electron acceptor molecules as described in the second aspect.

作为优选,所述有机活性层的厚度为50-300nm,其中,电子给体分子的厚度为30-150nm;路易斯碱负离子掺杂有机半导体电子受体分子中离子掺杂剂和有机半导体电子受体分子的摩尔比为0.025-5mol%。Preferably, the thickness of the organic active layer is 50-300 nm, wherein, the thickness of the electron donor molecule is 30-150 nm; Lewis base anion doped organic semiconductor electron acceptor molecule ion dopant and organic semiconductor electron acceptor The molar ratio of the molecules is 0.025-5 mol%.

作为优选,有机活性层的制备方法具体如下:As preferably, the preparation method of the organic active layer is as follows:

将6-12mg/mL的电子给体分子溶液旋涂在阳极修饰层上,制备得到厚度为 30-150nm的电子给体层;随后将7-18mg/mL的路易斯碱负离子掺杂有机半导体电子受体分子溶液旋涂在电子给体层上,最终制备得到厚度为50-300nm的有机活性层。The electron donor molecule solution of 6-12mg/mL was spin-coated on the anode modification layer to prepare an electron-donor layer with a thickness of 30-150nm; then 7-18mg/mL of Lewis base anion was doped with organic semiconductor electron acceptor. The bulk molecule solution is spin-coated on the electron donor layer, and finally an organic active layer with a thickness of 50-300 nm is prepared.

作为优选,电子给体分子为PM6,其结构式如下:Preferably, the electron donor molecule is PM6, and its structural formula is as follows:

Figure BDA0003448902640000041
Figure BDA0003448902640000041

作为优选,所述基底材料为玻璃;阳极材料为氧化铟锡(ITO),厚度为 100-200nm;阳极修饰层材料为聚(3,4-乙烯二氧噻吩)-聚(苯乙烯磺酸),即 PEDOT:PSS(型号为Baytron PAI 4083,PEDOT和PSS的质量比为1:6),厚度为20-40nm;阴极修饰层材料为聚(9,9-双(3'-(N,N-二甲基)-N-乙基铵-丙基-2,7- 芴)-alt-2,7-(9,9-二辛基芴))二溴化物,即PFN-Br,厚度为5-10nm;阴极材料为银 (Ag),厚度为80-120nm。Preferably, the base material is glass; the anode material is indium tin oxide (ITO) with a thickness of 100-200 nm; the anode modification layer material is poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid) , namely PEDOT:PSS (model is Baytron PAI 4083, the mass ratio of PEDOT and PSS is 1:6), the thickness is 20-40nm; the cathode modification layer material is poly(9,9-bis(3'-(N,N) -Dimethyl)-N-ethylammonium-propyl-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene))dibromide, i.e. PFN-Br, with a thickness of 5-10nm; the cathode material is silver (Ag), and the thickness is 80-120nm.

本发明相对于现有技术而言,具有以下有益效果:Compared with the prior art, the present invention has the following beneficial effects:

本发明通过溶剂分子屏蔽离子-π作用,抑制掺杂剂和有机半导体电子受体分子间的电子转移,形成稳定溶液;去溶剂化后,压缩两者空间距离,激活离子 -π作用,向有机半导体电子受体分子发生电子转移,成为了温和、可控和可溶液加工的掺杂方法。本发明制备得到的路易斯碱负离子掺杂有机半导体电子受体分子的电荷输运能力提高,在有机光电器件的应用中显著提高了器件性能。The invention shields the ion-π effect by solvent molecules, inhibits the electron transfer between the dopant and the organic semiconductor electron acceptor molecule, and forms a stable solution; Electron transfer from semiconductor electron acceptor molecules is a mild, controllable, and solution-processable doping method. The charge transport ability of the Lewis base anion-doped organic semiconductor electron acceptor molecule prepared by the invention is improved, and the device performance is significantly improved in the application of organic optoelectronic devices.

附图说明Description of drawings

图1是实施例1中的TBABr与BTP-4Cl混合氯仿溶液和未掺杂的BTP-4Cl 氯仿溶液的UV-vis-NIR吸光光谱测试图;Fig. 1 is the UV-vis-NIR absorption spectrum test diagram of TBABr and BTP-4Cl mixed chloroform solution and undoped BTP-4Cl chloroform solution in Example 1;

图2是实施例1中的被TBABr掺杂的BTP-4Cl固态粉末和TBABr与BTP-4Cl 混合氯仿溶液以及未掺杂的BTP-4Cl氯仿溶液的EPR测试图;Fig. 2 is the EPR test chart of the BTP-4Cl solid powder doped with TBABr and the mixed chloroform solution of TBABr and BTP-4Cl and the undoped BTP-4Cl chloroform solution in Example 1;

图3是实施例3和实施例5-7的有机场效应晶体管的器件结构图;Fig. 3 is the device structure diagram of the organic field effect transistor of embodiment 3 and embodiment 5-7;

图4是实施例3和实施例5-7中的有机场效应晶体管的转移特性曲线图;4 is a graph of transfer characteristics of organic field effect transistors in Example 3 and Examples 5-7;

图5是实施例3和实施例5-7中的有机场效应晶体管的电导率测试结果图;Fig. 5 is the conductivity test result graph of the organic field effect transistor in embodiment 3 and embodiment 5-7;

图6是实施例4和实施例8-10的有机太阳电池的器件结构图;6 is a device structure diagram of the organic solar cells of Example 4 and Examples 8-10;

图7是实施例4和实施例8-10中有机太阳电池的PCE测试结果图;7 is a graph of PCE test results of organic solar cells in Example 4 and Examples 8-10;

图8是单载流子器件的电子迁移率测试结果图。FIG. 8 is a graph of electron mobility test results of a single-carrier device.

具体实施方式Detailed ways

下面结合附图和具体实施方式对本发明做进一步阐述和说明。本发明中各个实施方式的技术特征在没有相互冲突的前提下,均可进行相应组合。The present invention will be further elaborated and described below with reference to the accompanying drawings and specific embodiments. The technical features of the various embodiments of the present invention can be combined correspondingly on the premise that there is no conflict with each other.

在本发明的各实施例中,PTIC、BTP-4Cl的分子结构如前述发明内容部分所示,可以采用现有材料,亦可以分别参考文献Yu et al.,Nat.Commun.2019,10, 2152和Cui etal.,Natl.Sci.Rev.2020,7,1239-1246制备;TBABr分子结构如前述发明内容部分所示,该材料购自上海旭硕生物科技有限公司;PM6分子结构如前述发明内容部分所示,该材料购自朔纶有机光电科技(北京)有限公司。In each embodiment of the present invention, the molecular structures of PTIC and BTP-4Cl are as shown in the foregoing section of the content of the invention, existing materials can be used, and references can also be made to Yu et al., Nat. Commun. 2019, 10, 2152 respectively. and Cui et al., Natl.Sci.Rev. 2020, 7, 1239-1246; TBABr molecular structure is shown in the foregoing content of the invention, and the material was purchased from Shanghai Xushuo Biotechnology Co., Ltd.; PM6 molecular structure is shown in the foregoing content of the invention Partly shown, the material was purchased from Shuolun Organic Photoelectric Technology (Beijing) Co., Ltd.

实施例1Example 1

本实施例提供了一种路易斯碱负离子掺杂有机半导体电子受体分子的制备方法,具体步骤如下:The present embodiment provides a method for preparing a Lewis base anion-doped organic semiconductor electron acceptor molecule, and the specific steps are as follows:

将TBABr(100mol%)与BTP-4Cl(5mg/mL)混合溶于氯仿溶液中,得到稳定溶液。之后在常温真空条件下去除氯仿溶剂,得到被TBABr掺杂的BTP-4Cl 粉末。TBABr (100 mol%) was mixed with BTP-4Cl (5 mg/mL) and dissolved in chloroform solution to obtain a stable solution. Then, the chloroform solvent was removed under vacuum conditions at room temperature to obtain BTP-4Cl powder doped with TBABr.

对实施例1中的TBABr与BTP-4Cl混合氯仿溶液以及纯BTP-4Cl氯仿溶液进行紫外-可见-近红外(UV-vis-NIR)吸光光谱测试。测试方法为:将测试样品装入密封的玻璃比色皿中,以避免暴露于环境空气中,在HITACHI U-4100分光仪上收集吸收光谱。The mixed chloroform solution of TBABr and BTP-4Cl in Example 1 and the pure BTP-4Cl chloroform solution were subjected to ultraviolet-visible-near-infrared (UV-vis-NIR) absorption spectrum test. The test method is: load the test sample into a sealed glass cuvette to avoid exposure to ambient air, and collect the absorption spectrum on a HITACHI U-4100 spectrometer.

测试结果如图1所示,从图中可以看出,本发明提供的掺杂方法在溶液态下不会改变有机半导体电子受体分子的吸光度,也不会产生新的自由基负离子的吸收峰,说明通过溶剂分子屏蔽离子-π作用,抑制掺杂剂和有机半导体电子受体分子间的电子转移,形成稳定溶液。The test results are shown in Figure 1. It can be seen from the figure that the doping method provided by the present invention will not change the absorbance of organic semiconductor electron acceptor molecules in solution state, nor will it generate new absorption peaks of radical anions , indicating that the ion-π interaction is shielded by solvent molecules, and the electron transfer between dopants and organic semiconductor electron acceptor molecules is inhibited, and a stable solution is formed.

之后对实施例1中的被TBABr掺杂的BTP-4Cl固态粉末以及TBABr与 BTP-4Cl混合氯仿溶液进行电子顺磁共振(EPR)测试。测试方法为:将测试样品装入密封的EPR测试管,以避免暴露于环境空气中,在Bruker A300 X-band EPR波谱仪上收集EPR波谱。Afterwards, electron paramagnetic resonance (EPR) tests were performed on the BTP-4Cl solid powder doped with TBABr in Example 1 and the mixed chloroform solution of TBABr and BTP-4Cl. The test method was as follows: The test samples were loaded into sealed EPR test tubes to avoid exposure to ambient air, and EPR spectra were collected on a Bruker A300 X-band EPR spectrometer.

测试结果如图2所示,从图中可以看出,本发明提供的掺杂方法在固态时会产生新的自由基负离子的顺磁信号,说明去溶剂化后,压缩空间距离,激活离子 -π作用,发生掺杂剂向有机半导体电子受体分子的电子转移。The test results are shown in Figure 2. It can be seen from the figure that the doping method provided by the present invention will generate a new paramagnetic signal of radical anion in the solid state. π action, electron transfer from dopants to organic semiconductor electron acceptor molecules occurs.

由此可见,本发明提供的掺杂方法相比现有技术,可以在温和条件下实现可控掺杂。It can be seen that, compared with the prior art, the doping method provided by the present invention can realize controllable doping under mild conditions.

实施例2Example 2

本实施例提供了一种路易斯碱负离子掺杂有机半导体电子受体分子的方法,具体步骤如下:This embodiment provides a method for doping organic semiconductor electron acceptor molecules with Lewis base anions, and the specific steps are as follows:

将TBABr(100mol%)与BTP-4Cl(15mg/mL)混合溶于氯仿溶液,得到混合溶液;之后对混合溶液进行旋涂,在旋涂过程中溶剂蒸发,完成去溶剂化过程,最终得到被TBABr掺杂的BTP-4Cl薄膜。TBABr (100 mol%) and BTP-4Cl (15 mg/mL) were mixed and dissolved in chloroform solution to obtain a mixed solution; then the mixed solution was spin-coated, and the solvent evaporated during the spin-coating process to complete the desolvation process. TBABr-doped BTP-4Cl films.

实施例3Example 3

本实施例提供了一种作为有机场效应晶体管的器件,其结构从下至上依次为: n++Si/SiO2(300nm)/BCB(10nm)/半导体薄膜(30nm)/Au(50nm)。其中,半导体薄膜为被TBABr掺杂的有机半导体电子受体分子PTIC。This embodiment provides a device as an organic field effect transistor, and its structure from bottom to top is: n ++ Si/SiO 2 (300nm)/BCB (10nm)/semiconductor thin film (30nm)/Au (50nm). The semiconductor thin film is an organic semiconductor electron acceptor molecule PTIC doped with TBABr.

上述有机场效应晶体管的制备方法为:The preparation method of above-mentioned organic field effect transistor is:

将BCB(30mg/mL)均三甲苯溶液旋涂在SiO2/n++Si基底上,然后在热台上交联;将TBABr(20mol%)与PTIC(10mg/mL)混合氯仿溶液旋涂在BCB层上,转速为2000rpm,得到指定厚度的半导体层;最后,在高真空1×10-7Pa条件下,蒸镀指定厚度的Au电极作为源漏电极,得到作为有机场效应晶体管的器件。通过覆盖特定图案的掩膜版,可以得到所需尺寸的沟道,其长宽比可以为1:20。BCB (30 mg/mL) solution in mesitylene was spin-coated on SiO 2 /n ++ Si substrate and then cross-linked on a hot stage; TBABr (20 mol%) mixed with PTIC (10 mg/mL) was spin-coated in chloroform solution On the BCB layer, the rotation speed is 2000rpm to obtain a semiconductor layer with a specified thickness; finally, under the condition of high vacuum 1×10 -7 Pa, Au electrodes with a specified thickness are evaporated as source and drain electrodes to obtain a device as an organic field effect transistor. . By covering a mask with a specific pattern, a channel of the desired size can be obtained, and its aspect ratio can be 1:20.

实施例4Example 4

本实施例提供了一种作为有机太阳电池的器件,其结构从下至上依次为:玻璃基底/ITO/PEDOT:PSS(20nm)/有机活性层(100nm)/PFN-Br(10nm)/Ag (100nm)其中,有机活性层为由给体分子PM6和被TBABr掺杂的有机半导体电子受体分子BTP-4Cl形成的共混薄膜。This embodiment provides a device as an organic solar cell, and its structure from bottom to top is: glass substrate/ITO/PEDOT:PSS(20nm)/organic active layer(100nm)/PFN-Br(10nm)/Ag ( 100 nm) wherein, the organic active layer is a blend film formed by the donor molecule PM6 and the organic semiconductor electron acceptor molecule BTP-4Cl doped with TBABr.

上述有机太阳电池的制备方法为:The preparation method of above-mentioned organic solar cell is:

将表面刻蚀有条状ITO的透明导电玻璃依次用洗涤剂、去离子水、丙酮、异丙醇超声清洗后,烘干备用;用氧等离子体处理15min后,在ITO上旋涂PEDOT:PSS层,转速为4500rpm,然后在170℃退火处理20min;将PM6(7.5mg/mL) 氯仿溶液旋涂在PEDOT:PSS层上,转速为2500rpm,然后将TBABr(0.25mol%) 与BTP-4Cl(8mg/mL,添加有0.25vol%DIO)混合氯仿溶液旋涂在PM6层上,转速为3000rpm,接着在100℃退火处理10min,得到指定厚度的有机活性层;将PFN-Br(0.5mg/mL)甲醇溶液旋涂在有机活性层上,转速为3800rpm;最后,在高真空1.5×10-4Pa条件下,蒸镀指定厚度的Ag电极,得到作为有机太阳电池的器件。The transparent conductive glass with strips of ITO etched on the surface was ultrasonically cleaned with detergent, deionized water, acetone, and isopropanol in sequence, and then dried for use; after being treated with oxygen plasma for 15 min, PEDOT:PSS was spin-coated on ITO. layer at 4500 rpm, and then annealed at 170 °C for 20 min; PM6 (7.5 mg/mL) chloroform solution was spin-coated on the PEDOT:PSS layer at 2500 rpm, and then TBABr (0.25 mol%) was mixed with BTP-4Cl ( 8mg/mL, added with 0.25vol% DIO) mixed with chloroform solution spin-coated on the PM6 layer at 3000rpm, followed by annealing at 100°C for 10min to obtain an organic active layer with a specified thickness; PFN-Br (0.5mg/mL) ) methanol solution was spin-coated on the organic active layer at 3800 rpm; finally, under the condition of high vacuum 1.5×10 -4 Pa, Ag electrodes with specified thickness were evaporated to obtain devices as organic solar cells.

实施例5Example 5

本实施例提供了一种作为有机场效应晶体管的器件,制备方法中除将 TBABr与PTIC混合氯仿溶液中TBABr的摩尔比分别替换成5mol%外,其余与实施例3一致。This embodiment provides a device used as an organic field effect transistor. The preparation method is the same as that of Embodiment 3, except that the molar ratio of TBABr in the mixed chloroform solution of TBABr and PTIC is replaced by 5 mol% respectively.

实施例6Example 6

本实施例提供了一种作为有机场效应晶体管的器件,制备方法中除将 TBABr与PTIC混合氯仿溶液中TBABr的摩尔比替换成10mol%外,其余与实施例3一致。This embodiment provides a device used as an organic field effect transistor. The preparation method is the same as that of Embodiment 3 except that the molar ratio of TBABr in the mixed chloroform solution of TBABr and PTIC is replaced by 10 mol%.

实施例7Example 7

本实施例提供了一种作为有机场效应晶体管的器件,制备方法中除将 TBABr与PTIC混合氯仿溶液中TBABr的摩尔比替换成30mol%外,其余与实施例3一致。This embodiment provides a device used as an organic field effect transistor. The preparation method is the same as that of Embodiment 3 except that the molar ratio of TBABr in the mixed chloroform solution of TBABr and PTIC is replaced by 30 mol%.

测试实施例3、实施例5-7,对比所得有机场效应晶体管的电学性能,并计算被掺杂的有机半导体电子受体分子的电导率,具体如下:Test Example 3, Examples 5-7, compare the electrical properties of the obtained organic field effect transistors, and calculate the conductivity of the doped organic semiconductor electron acceptor molecules, as follows:

测试方法为:将测试样品放置在填充氮气的手套箱中,使用Keithley 4200-SCS半导体参数分析仪进行电学性能测试,得到转移特性(ID-VG)曲线和输出特性(ID-VD)曲线,随后根据方程σ=(ID/VD)·(L/(W·h))来计算电导率,其中ID和VD分别是栅源电压VG为0V时的漏源电流和漏源电压,L是沟道长度, W是沟道宽度,h是半导体薄膜厚度。The test method is: place the test sample in a nitrogen-filled glove box, use Keithley 4200-SCS semiconductor parameter analyzer to test the electrical properties, and obtain the transfer characteristic (ID-V G ) curve and output characteristic (ID- V D ) ) curve, then the conductivity is calculated according to the equation σ=(ID /V D ) ·(L/(W·h)), where ID and V D are the drain-source current when the gate-source voltage V G is 0V, respectively and drain-source voltage, L is the channel length, W is the channel width, and h is the semiconductor film thickness.

图3为上述实施例所得有机场效应晶体管的器件结构图。测试结果如图4、 5所示。从转移特性曲线中可以看出,基于本发明提供的掺杂方法制得的有机场效应晶体管在更低工作电压下就开始工作,且开态电流显著增大,说明该方法可以有效提升器件电学性能。从电导率结果中可以看出,本发明提供的掺杂方法能够显著提高薄膜电导率,说明该方法不仅具备温和、可控、可溶液加工优势,而且具有良好的掺杂效果,可以有效调控有机半导体电子受体分子的电荷输运能力。FIG. 3 is a device structure diagram of the organic field effect transistor obtained in the above embodiment. The test results are shown in Figures 4 and 5. It can be seen from the transfer characteristic curve that the organic field effect transistor prepared based on the doping method provided by the present invention starts to work at a lower operating voltage, and the on-state current increases significantly, indicating that the method can effectively improve the electrical properties of the device performance. It can be seen from the conductivity results that the doping method provided by the present invention can significantly improve the conductivity of the thin film, indicating that the method not only has the advantages of mildness, controllability and solution processing, but also has a good doping effect and can effectively control the organic The charge transport capacity of semiconductor electron acceptor molecules.

实施例8Example 8

本实施例提供了一种作为有机太阳电池的器件,制备方法中除将TBABr与 BTP-4Cl混合氯仿溶液中TBABr的摩尔比替换成0.025mol%外,其余与实施例4 一致。This example provides a device as an organic solar cell. The preparation method is the same as Example 4 except that the molar ratio of TBABr in the mixed chloroform solution of TBABr and BTP-4Cl is replaced by 0.025 mol%.

实施例9Example 9

本实施例提供了一种作为有机太阳电池的器件,制备方法中除将TBABr与 BTP-4Cl混合氯仿溶液中TBABr的摩尔比替换成0.05mol%外,其余与实施例4 一致。This example provides a device as an organic solar cell. The preparation method is the same as Example 4 except that the molar ratio of TBABr in the mixed chloroform solution of TBABr and BTP-4Cl is replaced by 0.05 mol%.

实施例10Example 10

本实施例提供了一种作为有机太阳电池的器件,制备方法中除将TBABr与 BTP-4Cl混合氯仿溶液中TBABr的摩尔比分别替换成1mol%外,其余与实施例 4一致。This example provides a device as an organic solar cell. The preparation method is the same as Example 4, except that the molar ratio of TBABr in the mixed chloroform solution of TBABr and BTP-4Cl is replaced by 1 mol% respectively.

测试实施例4、实施例8-10,对比所得有机太阳电池的光电转换效率(PCE),具体如下:Test Example 4, Examples 8-10, and compare the photoelectric conversion efficiency (PCE) of the obtained organic solar cells, as follows:

测试方法为:将测试样品放置在填充氮气的手套箱中,使用太阳光模拟器 AM1.5在100mW/cm2的光照强度下测试得到相应的电流-电压(J-V)曲线。The test method is as follows: the test sample is placed in a nitrogen-filled glove box, and the corresponding current-voltage (JV) curve is obtained by using a solar simulator AM1.5 under the illumination intensity of 100 mW/cm 2 .

图6为上述实施例所得有机太阳电池的器件结构图。测试结果如图7所示。从PCE结果中可以看出,基于本发明提供的掺杂方法制得的有机太阳电池,通过调节掺杂浓度,PCE最高可由16.61%提升至17.63%,说明该方法可以有效提升器件光伏性能。FIG. 6 is a device structure diagram of the organic solar cell obtained in the above embodiment. The test results are shown in Figure 7. It can be seen from the PCE results that for the organic solar cells prepared based on the doping method provided by the present invention, the PCE can be increased from 16.61% to 17.63% by adjusting the doping concentration, indicating that the method can effectively improve the photovoltaic performance of the device.

为进一步测试电子传输过程对器件光伏性能的影响,以实施例2中的掺杂方法为基础,对比实施例4、实施例8-10中对应BTP-4Cl薄膜的电子迁移率,具体如下:In order to further test the influence of the electron transport process on the photovoltaic performance of the device, based on the doping method in Example 2, the electron mobility of the corresponding BTP-4Cl films in Example 4 and Examples 8-10 were compared, as follows:

测试方法为:测试样品为单载流子器件,其结构从下至上依次为:玻璃基底 /ITO/ZnO(30nm)/半导体薄膜(60nm)/PFN-Br(10nm)/Ag(100nm)。半导体层的制备方法中除将TBABr与BTP-4Cl混合氯仿溶液中TBABr的摩尔比分别替换成0.025mol%、0.05mol%、0.25mol%、1mol%外,其余与实施例2一致。使用空间电荷限制电流(SCLC)测试得到相应的电流-电压(J-V)曲线,随后根据方程J=(9/8)×εr×ε0×μ×(V2/L3)来计算电子迁移率,其中εr≈3是平均介电常数,ε0是真空介电系数,μ是迁移率,L是膜厚。The test method is as follows: the test sample is a single-carrier device, and its structure from bottom to top is: glass substrate/ITO/ZnO(30nm)/semiconductor film(60nm)/PFN-Br(10nm)/Ag(100nm). The preparation method of the semiconductor layer is the same as Example 2 except that the molar ratio of TBABr in the mixed chloroform solution of TBABr and BTP-4Cl is replaced by 0.025mol%, 0.05mol%, 0.25mol% and 1mol% respectively. The corresponding current-voltage (JV) curves were obtained using the space charge limited current (SCLC) test, and the electron migration was then calculated according to the equation J = (9/8)× εr ×ε0×μ×(V 2 /L 3 ) rate, where ε r ≈ 3 is the average permittivity, ε 0 is the vacuum permittivity, μ is the mobility, and L is the film thickness.

测试结果如图8所示,从迁移率结果可以看出,基于本发明提供的掺杂方法制得的单载流子器件,通过调节掺杂浓度,电子迁移率最高可由6.35×10-4cm2 V-1s-1提升至9.44×10-4cm2V-1s-1,说明该方法可以提升有机半导体电子受体分子的电荷输运能力。The test results are shown in Figure 8. It can be seen from the mobility results that the single-carrier device prepared based on the doping method provided by the present invention can achieve a maximum electron mobility of 6.35×10 -4 cm by adjusting the doping concentration. 2 V -1 s -1 is increased to 9.44×10 -4 cm 2 V -1 s -1 , indicating that this method can improve the charge transport ability of organic semiconductor electron acceptor molecules.

由此可见,电子迁移率的变化趋势和PCE变化趋势基本一致,说明基于该掺杂方法制得的有机太阳电池,有利于提高受体的电子传输,最终实现器件性能进一步提升。It can be seen that the change trend of electron mobility is basically the same as that of PCE, indicating that the organic solar cell prepared based on this doping method is beneficial to improve the electron transport of the acceptor, and finally achieve further improvement of device performance.

以上所述的实施例只是本发明的一种较佳的方案,然其并非用以限制本发明。有关技术领域的普通技术人员,在不脱离本发明的精神和范围的情况下,还可以做出各种变化和变型。因此凡采取等同替换或等效变换的方式所获得的技术方案,均落在本发明的保护范围内。The above-mentioned embodiment is only a preferred solution of the present invention, but it is not intended to limit the present invention. Various changes and modifications can also be made by those of ordinary skill in the relevant technical field without departing from the spirit and scope of the present invention. Therefore, all technical solutions obtained by means of equivalent replacement or equivalent transformation fall within the protection scope of the present invention.

Claims (10)

1. A preparation method of Lewis base negative ion doped organic semiconductor electron acceptor molecule is characterized in that an ion dopant containing Lewis base negative ion is added into the organic semiconductor electron acceptor molecule, and the Lewis base negative ion and the ion dopant are uniformly mixed by using a chlorinated organic solvent to obtain a stable solution; and then removing the solvent of the stable solution to obtain the solid Lewis base negative ion doped organic semiconductor electron acceptor molecule.
2. The method of claim 1, wherein the ionic dopant is any one of TBAX, TBPX or MTPPX, and the structural formula is as follows:
Figure FDA0003448902630000011
in the formula, X is any one of F, OH, AcO, Cl, Br and I.
3. The method according to claim 1, wherein the organic semiconductor electron acceptor molecule is any one of Y6, BTP-4Cl, Y6-1O, IT-4F, PTIC or PTB-4Cl, and the structural formulas are respectively as follows:
Figure FDA0003448902630000012
in the formula, R1Is 2-ethylhexyl, R2Is undecyl, R3Is 2-butyloctyl, R4Is 4-hexylphenyl, R5Is hexyl, R6Is hexyldecyl.
4. The process according to claim 1, wherein the Lewis base anion dopes the organic semiconductor electron acceptor molecule in a molar ratio of the ion dopant to the organic semiconductor electron acceptor molecule of from 0.025 to 100 mol%.
5. A Lewis base anion doped organic semiconductor electron acceptor molecule obtained by the preparation process according to any one of claims 1 to 4.
6. A device used as an organic field effect transistor is characterized in that the device is of a bottom gate top contact structure and sequentially comprises a gate electrode, a dielectric layer, a semiconductor film and a source drain electrode from bottom to top; the semiconductor thin film is prepared by doping the Lewis base negative ion with the organic semiconductor electron acceptor molecule according to claim 5.
7. A device as an organic field effect transistor according to claim 6, wherein the semiconductor thin film has a thickness of 10 to 100nm, and the molar ratio of the ion dopant to the organic semiconductor electron acceptor molecule in the Lewis base anion-doped organic semiconductor electron acceptor molecule is 5 to 30 mol%; preferably, the gate electrode material is n-type heavily doped silicon, the dielectric layer material is benzocyclobutene modified silicon dioxide, and the source and drain electrode material is gold.
8. The device as the organic solar cell is characterized in that the device is of a multilayer layered structure and sequentially comprises a substrate, an anode modification layer, an organic active layer, a cathode modification layer and a cathode from bottom to top; the organic active layer is a blended film obtained by spin-coating an electron donor molecule and the Lewis base anion doped organic semiconductor electron acceptor molecule according to claim 5 in sequence.
9. The device as claimed in claim 8, wherein the organic active layer has a thickness of 50-300 nm; the mol ratio of the ion dopant and the organic semiconductor electron acceptor molecule in the Lewis base negative ion doped organic semiconductor electron acceptor molecule is 0.025-5 mol%; the electron donor molecule is PM6, and has the following structural formula:
Figure FDA0003448902630000021
10. the device as claimed in claim 8, wherein the substrate is glass, the anode is indium tin oxide, the anode modification layer is PEDOT: PSS, the cathode modification layer is PFN-Br, and the cathode is silver.
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