Simultaneous studies of pressure effect on charge transport and photophysical properties in organic semiconductors:A theoretical investigation

High-mobility and strong luminescent materials are essential as an important component of organic photodiodes,having received extensive attention in the field of organic optoelectronics.Beyond the conventional chemical synthesis of new molecules,pressure technology,as a flexible and efficient method,can tune the electronic and optical properties reversibly.However,the mechanism in organic materials has not been systematically revealed.Here,we theoretically predicted the pressure-depended luminescence and charge transport properties of high-performance organic optoelectronic semiconductors,2,6-diphenylanthracene(DPA),by first-principle and multi-scale theoretical calculation methods.The dispersion-corrected density functional theory(DFT-D)and hybrid quantum mechanics/molecular mechanics(QM/MM)method were used to get the electronic structures and vibration properties under pressure.Furthermore,the charge transport and luminescence properties were calculated with the quantum tunneling method and thermal vibration correlation function.We found that the pressure could significantly improve the charge transport performance of the DPA single crystal.When the applied pressure increased to 1.86 GPa,the hole mobility could be doubled.At the same time,due to the weak exciton coupling effect and the rigid flat structure,there is neither fluorescence quenching nor obvious emission enhancement phenomenon.The DPA single crystal possesses a slightly higher fluorescence quantum yield~0.47 under pressure.Our work systematically explored the pressure-dependence photoelectric properties and explained the inside mechanism.Also,we proposed that the exte rnal pressure would be an effective way to improve the photoelectric perfo rmance of organic semiconductors.

Charge transport in organic semiconductors: From incoherent to coherent

Quantum decoherence in organic charge transport is a complicated but crucial topic. In this paper, several theoretical approaches corresponding to it, from incoherent to coherent, are comprehensively reviewed. We mainly focus on the physical insight provided by each theory and extent of its validity. The aim of this review is to clarify some contentious issues and elaborate on the promising perspectives provided by different approaches. The device model approaches based on both continuous and discretized treatments of the transporting layer will be first discussed. The prominent focus of this review will be devoted to the dynamic disorder model and its variants considering that it is the most promising approach to tackle charge transport problems in organic materials. We will also address other theories such as the variational method.

Highly efficient solution-processed organic photovoltaics enabled by improving packing behavior of organic semiconductors

Solution processability is a unique property of organic semiconductors. The compact and regular π-π stacking between molecules is paramount in the performance of organic optoelectronic devices. However, it is still a challenge to improve their stacking quality without sacrificing the solution-processability from the aspect of materials design. Here, delicately engineered additives are presented to promote the formation of ordered aggregation of conjugated molecules by regulating their nucleation and growth dynamics. Intriguingly, the long-chain BTP-eC9-4F molecules can realize ordered aggregation comparable to short-chain ones without sacrificing processability. The domain size of BTP-eC9-4F aggregation is enlarged from 24.2 to 32.2 nm in blend films.Thereby exciton diffusion and charge transport become faster, contributing to the suppression of recombination losses. As a result, a power conversion efficiency of 19.2% is achieved in D18:BTP-eC9-4F based organic photovoltaics. Our findings demonstrate a facile strategy to improve the packing quality of solution-processed organic semiconductors for high-efficiency photovoltaics and beyond photovoltaics.

Experimental and theoretical study of the charge transport property of 4,4′-N,N′-dicarbazole-biphenyl

The hole and electron mobilities of the amorphous films of the organic semiconductor 4,4′-N,N′-dicarbazole-biphenyl (CBP) at different electric fields were measured through the time of flight (TOF) method. Based on its crystalline structure, the hole and electron mobilities of CBP were calculated. A detailed comparison between experimental and theoretical results is necessary for further understanding its charge transport properties. In order to do this, charge mobilities at zero electric field, μ(0), were deduced from experimental data as a link between experimental and theoretical data. It was found that the electron transport of CBP is less affected by traps compared with its hole transport. This unusual phenomenon can be understood through the distributions of frontier molecular orbitals. We showed that designing materials with frontier molecular orbitals localized at the center of the molecule has the potency to reduce the influence of traps on charge transport and provide new insights into designing high mobility charge transport materials.

Tailoring crystal polymorphs of organic semiconductors towards high-performance field-effect transistors

As a quite ubiquitous phenomenon,crystal polymorph is one of the key issues in the field of organic semiconductors.This review gives a brief summary to the advances on polymorph control of thin film and single crystal of representative organic semiconductors towards high-performance field-effect transistors.Particularly,the relationship between crystal polymporh and charge transport behaviour has been discussed to shed light on the rational preparation of outstanding organic semiconducting materials with desired crystal polymorph.

Hexyl substitution of pentathienoacene toward a significant improvement in charge transport

A novel semiconductor, dihexyl-substituted pentathienoacene(C6-PTA) is designed and synthesized in five steps with the total yield up to 25.2%. The introduction of hexyl chains endow the thin film semiconductor with about threefold increase in carrier mobility and one to three orders of magnitude improvement in current on/off ratio. Furthermore, single crystal FETs based on C6-PTA exhibited mobility up to 0.64 cm^2 V^(-1) s^(-1), which is over 50 times higher than the thin film counterpart. The results indicate clearly that C6-PTA is a promising organic semiconductor with high stability.

衬底对PTCDA薄膜结构与电荷输运特性的影响

在不同导电衬底(Au,Al和ITO)上制备了PTCDA薄膜,用XRD和AFM技术研究了PTCDA薄膜的结构和表面形貌。结果表明,薄膜中的大部分PTCDA分子平面与衬底不平行,这表明薄膜垂直方向的电流传导将以电子传输为主;在ITO和Au衬底上生长的PTCDA薄膜晶粒排列规则,在薄膜垂直方向呈现出较好的电子传输性能;而在Al衬底上生长的PTCDA薄膜晶粒排列无序,电子传输性能差。通过制备单层结构有机薄膜器件,研究了PTCDA薄膜垂直方向的电子迁移率。综合应用金属-有机界面的热电子发射理论和有机层体内空间电荷限制传导理论,并考虑电场强度对迁移率变化的影响,对ITO/PTCDA/Al器件的电流密度-电压曲线进行拟合,得到ITO衬底上生长的PTCDA薄膜在垂直方向随电场强度变化的电子迁移率数值。

Cocrystal engineering:towards high-performance near-infrared organic phototransistors based on donor-acceptor charge transfer cocrystals

Near-infrared organic phototransistors have wide application prospects in many fields.The active materials with the high mobility and near-infrared response are critical to building high-performance near-infrared organic phototransistors,which are scarce at present.Herein,a new charge transfer cocrystal using 5,7-dihydroindolo[2,3-b]carbazole(5,7-ICZ)as the donor and 2,2’-(benzo[1,2-b:4,5-b’]dithiophene-4,8-diylidene)dimalononitrile(DTTCNQ)as the acceptor is properly designed and prepared in a stoichiometric ratio(D:A=1:1),which not only displays a high electron mobility of 0.15 cm^(2)V^(-1)s^(-1) and very low dark current,but also can serve as the active layer materials in the region of near-infrared detection due to the narrowed band gap and good charge transport properties.A high photosensitivity of 1.8×10^(4),the ultrahigh photoresponsivity of 2,923 A W-1and the high detectivity of 4.26×10^(11)Jones of the organic near-infrared phototransistors are obtained.

量子化学研究不同取代基对六苯并蔻电荷传输性能的影响

应用密度泛函理论在B3LYP/6-311+G(d)、M06-2X/6-311+G(d)、CAM-B3LYP/6-311+G(d)理论水平,分别计算12个不同取代基取代的六苯并蔻分子的电荷传输速率.研究结果显示,采用长程较正泛函CAMB3LYP更适合目标体系的电荷传输性能研究.在六苯并蔻环上,引入6个—CH_(3)与—CN取代基,得到的六苯并蔻衍生物分子与母体六苯并蔻相比,空穴迁移率相对较大,分别为2.51、0.92 cm^(2)·V^(−1)·s^(−1),可设计为性能优良的p型有机半导体分子;引入6个—SH、—CH_(2)SCH_(3)及—COOCH_(3)取代基,得到的3个分子与母体六苯并蔻相比,对分子的电荷传输速率改善较小;引入—SCH_(3)、—OCH_(3)、—OH、—NHCH_(3)、—N(CH_(3))2等5个取代基,所得到的5个分子电子迁移速率为空穴迁移速率的1.7~18倍,有望设计成性能优良的n型有机半导体材料.

The Potential Game-Changer:A Concept-to-Proof Study on D:A Heterojunction-Free Organic Photovoltaics

Since 1986,the donor-acceptor (D:A) heterojunction has been regarded a necessity for high-efficiency organic photovoltaics (OPVs),due to its unique advantage in compensating the intrinsic limitations of organic semiconductors,such as high exciton binding energy and poor ambipolar charge mobility. While this adversely causes tremendous non-radiative charge recombination and instability issues,which currently become the most critical limits for commercialization of OPVs. Here,we present a concept-to-proof study on the potential of D:A heterojunction free OPV by taking advantage of recent progress of non-fullerene acceptors. First,we demonstrate that the “free carriers” can be spontaneously generated upon illumination in an NFA,i.e.,the 6TIC-4F single layer. Second,the 6TIC-4F layer also exhibits good ambipolar charge transporting property. These exceptional characteristics distinguish it from the traditional organic semiconductors,and relieve it from the reliance of D:A heterojunction to independently work as active layer. As a result,the subsequent OPV by simply sandwiching the 6TIC-4F layer between the cathode and anode yields a considerably high power conversion efficiency ~1%. Moreover,we find the D:A heterojunction free device exhibits two order of magnitude higher electroluminescence quantum efficiency and significantly reduced VOC loss by 0.16 eV compared to those of the D:A BHJ structure,validating its promise for higher efficiency in the future. Therefore,our work demonstrates the possibility of using D:A heterojunction-free device structure for high performance,that can potentially become the next game changer of OPV.

基于不同π核扩展方式萘四甲酰基二酰亚胺有机半导体电荷传输性质的理论研究

n型半导体材料在逻辑互补电路中必不可少,但由于多数n型有机半导体材料空气稳定性差、迁移率较低,其发展相对滞后.本文基于几种典型的不同π核扩展的萘四甲酰基二酰亚胺(NDI)有机半导体材料,利用第一性原理计算分析了其电荷传输性质,分别从单分子结构特征、分子间堆积方式以及分子间相互作用等方面阐明不同核心结构对载流子传输性质的影响.结果表明,所研究分子均具有良好的空气稳定性,并表现为电子传输性.其中,长轴π扩展的分子A2具有较高的电子亲和势,其空气稳定性最好.其次,沿长轴/短轴π扩展的NDI有机半导体的重组能均降低,但二者重组能降低的起因明显不同:相比于A1分子,沿短轴π扩展的A2分子在高频区的振动受到有效的抑制,从而重组能大幅下降;而沿长轴π扩展的A3与A4分子则在高低频区的振动均受到抑制,使重组能降低.另外,不同的分子堆积对传输影响较大,发现沿长轴π扩展的A3和A4具有较小的短轴滑移,表现为二维传输材料,二维平均电子迁移率分别约为0.06与0.15cm^(2)·V^(-1)·s^(-1);沿短轴π扩展的A2分子具有较大的短轴滑移,因此表现为一维传输材料,其一维电子迁移率高达0.96cm^(2)·V^(-1)·s^(-1).

Study of a ternary blend system for bulk heterojunction thin film solar cells

In this research, we report a bulk heterojunction（BHJ） solar cell consisting of a ternary blend system. Poly（3-hexylthiophene） P3 HT is used as a donor and [6,6]-phenyl C61-butyric acid methylester（PCBM） plays the role of acceptor whereas vanadyl 2,9,16,23-tetraphenoxy-29 H, 31H-phthalocyanine（VOPc Ph O） is selected as an ambipolar transport material. The materials are selected and assembled in such a fashion that the generated charge carriers could efficiently be transported rightwards within the blend. The organic BHJ solar cells consist of ITO/PEDOT：PSS/ternary BHJ blend/Al structure. The power conversion efficiencies of the ITO/ PEDOT：PSS/P3HT：PCBM/Al and ITO/PEDOT：PSS/P3HT：PCBM：VOPcPhO/Al solar cells are found to be 2.3% and 3.4%, respectively.

Electronic polarization in dipolar organic molecular semiconductors:The case study of 1,2,3,4-tetrafluoro-6,7-dimethylnaphthalene crystal

Electronic polarization has an important impact on the site energies of charge carriers that play a key role in determining the charge transport in organic semiconductors.Dipolar molecules have strong intermolecular interactions and widespread applications in organic optoelectronics.Howeve r,compared with nonpolar organic semiconductors,electronic polarization for dipolar systems has been rarely studied.Here,taking 1,2,3,4-tetrafluoro-6,7-dimethylnaphthalene as representative,we have calculated the electronic polarization energies of dipolar organic molecular crystals by means of a polarizable forcefield method.Surprisingly,our results point to that the polarization energies for this dipolar system are similar to those of nonpolar systems.In addition,theπ-πstack contributes only about 30%~40%to the total polarization energy,thus the polarization effects along the three dimensions should be treated equally even for the one-dimensional stacking crystals.

Tetramethylammonium Iodide Additive for Enhancing the Charge Carrier Mobilities of Diketopyrrolopyrrole-Based Conju-gated Polymer in Ambipolar Organic Field-Effect Transistors

Diketopyrrolopyrrole(DPP)is one of the most promising building blocks for constructing polymer semiconductors with high charge-carrier mobilities in organic field-effect transistors(OFETs).In this study,a novel DPP-based conjugated polymer,PDPPy-BDD,was designed and synthesized.The ambipolar field-effect transistor characteristics were realized with the average hole and electron mobilities of 3.5×10^(-3)and 3.07×10^(-2)cm^(2)V^(-1)s^(-1),respectively.Both the hole and electron mobilities could be successfully en-hanced by using a tetramethylammonium iodide(NMe4l)additive.Such an enhancement was attributed to the formation of stronger interchainπ-πstackings,the weakening of the face-on packing orientation in the thin film state,and the higher channel conductivi-ties in the OFETs.

“薄膜即是界面,界面即是薄膜”:二维有机半导体晶体的研究进展

自首次于聚乙炔发现导电现象以来,具有共轭结构的有机半导体材料赖其种类丰富多样、制备工艺简捷低耗、以及优异的机械柔性等特点,在“后硅时代”中有望以先进光电子设备展现其广阔前景,因而多年来备受学界和产业界的瞩目。如何进一步阐明有机半导体中结构和性能之间的关系,探索电荷载流子微观动力学行为,构筑高性能、新功能的有机光电子器件,是当下有机电子学领域的前沿核心问题,也是保证其持续发展的基石。近年来,二维有机半导体晶体材料在秉持高度有序的分子排列与极低的杂质缺陷浓度等优点的同时,更是以“薄膜即是界面、界面即是薄膜”为一帜,克服传统体材料在研究与应用中的瓶颈,为揭示材料构性关系及其中基本物理过程提供了良好的平台,也是实现多样化的新型有机光电子器件的理想材料,有望为微纳电子领域带来新一轮变革。本文从二维有机半导体晶体的制备工艺、电荷载流子微观动力学行为,再到新型器件的光电功能应用等方面,综述了最新研究进展,做出总结和展望,并提出目前面临的挑战及未来研究方向,旨在为进一步深入理论研究,结合有机材料与先进技术,推动有机电子学的发展提供有益帮助。

Remove the water-induced traps toward improved performance in organic solar cells

Clusters of water molecules have low ionization energies because of stabilization of charge from the dipole moment of surrounding molecules,and thus can form potential traps resulting in the undesirable photovoltaic performance in organic solar cells(OSCs).Herein,we demonstrated a solvent-water evaporation(SWE)strategy,which can effectively remove the water-induced traps that are omnipresent in photoactive layers,leading to a significant improvement in device performance.A higher power conversion efficiency of 17.10%and a better device photostability are achieved by using this SWE method,as compared with the untreated binary PM6:Y6 system(15.83%).We highlight the water-related traps as a limiting factor for carrier transport and extraction properties,and further reveal the good universality of the SWE strategy applied into OSCs.In addition,organic light-emitting diodes and organic field-effect transistors are investigated to demonstrate the applicability of this SWE approach.This strategy presents a major step forward for advancing the field of organic electronics.

有机半导体异质界面电荷传输解析模型研究

有机半导体多层薄膜器件的性质很大程度上由有机-有机界面的传输性质所决定,但是现有的关于有机-有机界面的分析模型很难适用于实际器件的模拟.以Miller-Abrahams跳跃传导理论为基础,充分考虑有机-有机界面和金属-有机界面性质的不同,建立了一个新的描述有机-有机异质界面电荷传输的解析模型.结果表明有机异质界面的载流子传输不仅取决于界面的肖特基势垒,而且还取决于界面附近两边的电场强度和载流子浓度.此模型可用于有机半导体多层薄膜器件的电流密度、电场分布和载流子浓度分布的自洽计算.