Influence of Intermolecular Vibrations on the Electronic Coupling in Organic Semiconductors: The Case of Anthracene and Perfluoropentacene

We have performed classical molecular dynamics simulations and quantum‐chemical calculations on molecular crystals of anthracene and perfluoropentacene. Our goal is to characterize the amplitudes of the room‐temperature molecular displacements and the corresponding thermal fluctuations in electronic transfer integrals, which constitute a key parameter for charge transport in organic semiconductors. Our calculations show that the thermal fluctuations lead to Gaussian‐like distributions of the transfer integrals centered around the values obtained for the equilibrium crystal geometry. The calculated distributions have been plugged into Monte‐Carlo simulations of hopping transport, which show that lattice vibrations impact charge transport properties to various degrees depending on the actual crystal structure.     

Bismuth Interfacial Doping of Organic Small Molecules for High Performance n‐type Thermoelectric Materials

Development of chemically doped high performance n‐type organic thermoelectric (TE) materials is of vital importance for flexible power generating applications. For the first time, bismuth (Bi) n‐type chemical doping of organic semiconductors is described, enabling high performance TE materials. The Bi interfacial doping of thiophene‐diketopyrrolopyrrole‐based quinoidal (TDPPQ) molecules endows the film with a balanced electrical conductivity of 3.3 S cm^?1 and a Seebeck coefficient of 585 μV K^?1. The newly developed TE material possesses a maximum power factor of 113 μW m^?1 K^?2, which is at the forefront for organic small molecule‐based n‐type TE materials. These studies reveal that fine‐tuning of the heavy metal doping of organic semiconductors opens up a new strategy for exploring high performance organic TE materials.     

Sterically-Hindered Molecular p-Dopants Promote Integer Charge Transfer in Organic Semiconductors

Molecular p-dopants designed to undergo electron transfer with organic semiconductors are typically planar molecules with high electron affinity. However, their planarity can promote the formation of ground-state charge transfer complexes with the semiconductor host and results in fractional instead of integer charge transfer, which is highly detrimental to doping efficiency. Here, we show this process can be readily overcome by targeted dopant design exploiting steric hindrance. To this end, we synthesize and characterize the remarkably stable p-dopant 2,2′,2′′-(cyclopropane-1,2,3-triylidene)tris(2-(perfluorophenyl)acetonitrile) comprising pendant functional groups that sterically shield its central core while retaining high electron affinity. Finally, we demonstrate it outperforms a planar dopant of identical electron affinity and increases the thin film conductivity by up to an order of magnitude. We believe exploiting steric hindrance represents a promising design strategy towards molecular dopants of enhanced doping efficiency.     

Surface transfer doping of semiconductors

Surface transfer doping relies on charge separation at interfaces, and represents a valuable tool for the controlled and nondestructive doping of nanostructured materials or organic semiconductors at the nanometer-scale. It cannot be easily achieved by the conventional implantation process with energetic ions. Surface transfer doping can effectively dope semiconductors and nanostructures at relatively low cost, thereby facilitating the development of organic and nanoelectronics. The aim of this review is to highlight recent advances of surface transfer doping of semiconductors. Special focus is given to the effective doping of diamond, epitaxial graphene thermally grown on SiC, and organic semiconductors. The doping mechanism of various semiconductors and their possible applications in nanoelectronic devices will be discussed, including the interfacial charge transfer and the energy level alignment mechanisms.     

Approaching the Integer‐Charge Transfer Regime in Molecularly Doped Oligothiophenes by Efficient Decarboxylative Cross‐Coupling

A library of symmetrical linear oligothiophene was prepared employing decarboxylative cross‐coupling reaction as the key transformation. Thiophene potassium carboxylate salts were used as cross‐coupling partners without the need of co‐catalyst, base, or additives. This method demonstrates complete chemoselectivity and is a comprehensive greener approach compared to the existing methods. The modularity of this approach is demonstrated with the preparation of discreet oligothiophenes with up to 10 thiophene repeat units. Symmetrical oligothiophenes are prototypical organic semiconductors where their molecular electrical doping as a function of the chain length can be assessed spectroscopically. An oligothiophene critical length for integer charge transfer was observed to be 10 thiophene units, highlighting the potential use of discrete oligothiophenes as doped conduction or injection layers in organic electronics applications.     

Secondary doping in poly(3,4‐ethylenedioxythiophene):Poly(4‐styrenesulfonate) thin films

The electrical and structural properties of poly(3,4‐ethylenedioxythiophene):poly(4‐styrenesulfonate) (PEDOT:PSS) thin films deposited from aqueous dispersion using different concentrations of selected secondary dopants are studied in detail. An improvement of the electrical conductivity by three orders of magnitude is achieved for dimethyl sulfoxide, sorbitol, ethylene glycol, and N,N‐dimethylformamide, and the secondary dopant concentration dependence of the conductivity exhibits almost identical behavior for all investigated secondary dopants. Detailed analysis of the surface morphology and Raman spectra reveals no presence of the secondary dopant in fabricated films, and thus the dopants are truly causing the secondary doping effect. Although the ratio of benzenoid and quinoid vibrations in Raman spectra is unaffected by doping, the phase transition in PEDOT:PSS films owing to doping is confirmed. Further analysis of temperature‐dependent conductivity reveals 1D variable range hopping (VRH) charge transport for undoped PEDOT:PSS, whereas highly conductive doped PEDOT:PSS films exhibit 3D VRH charge transport. We demonstrate that the charge ‐ hopping dimensionality change should be a fundamental reason for the conductivity enhancement. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1139–1146     

Organic Semiconductor/Gold Interface Interactions: From Physisorption on Planar Surfaces to Chemical Reactions with Metal Nanoparticles

The interaction of gold nanoparticles (AuNPs) with prototypical organic semiconductors used in optoelectronics, namely, tris(8‐hydroxyquinoline)aluminium (Alq₃) and 4,4‐bis[N‐(1‐naphthyl)‐N‐phenylamino]diphenyl (α‐NPD), is investigated in situ by X‐ray photoelectron spectroscopy (XPS). These AuNPs‐on‐molecule experiments are compared with the reversed molecule‐on‐Au cases. The molecules‐on‐Au systems show only weak interactions, and the evolution of the XP spectra is dominated by final‐state effects. In contrast, in the AuNPs‐on‐molecules cases, both initial‐state effects and final‐state effects occur. Spectral features arising for both molecules and metal indicate charge transfer and the formation of organometallic complexes (initial‐state effects). The energy shift in the metal emission underlines the size‐induced nanometric nature of the molecule/Au interaction (final‐state effects). Consequently, the chemical interaction between metals and organic semiconductors likely depends strongly on the deposition sequence in general.     

Organic soluble deoxyribonucleic acid (DNA) bearing carbazole moieties and its blend with phosphorescent Ir(III) complexes

A functionalized deoxyribonucleic acid (Cz‐DNA) was prepared with carbazolyl ammonium lipid as a triplet host material for phosphorescent material system. It is soluble in organic solvents, which facilitates the sample preparation for the absorption and luminescent properties in solid states. A highly soluble iridium complex, Ir(Cz‐ppy)₃ with carbazolyl‐substituted 2‐phenylpyridine ligands was employed for studying the phosphorescence in Cz‐DNA. There is a good overlap between the photoluminescence spectrum of Cz‐DNA and the metal‐to‐ligand charge transfer (MLCT) absorption bands of the iridium complex. This overlap enables efficient energy transfer from the excited state in the host to the MLCT band of Ir(Cz‐ppy)₃. In addition, photoluminescence quantum yield of Cz‐DNA was found to be relatively larger than the copolymer (PCzSt) with vinylcarbazole and styrene. Thus, Cz‐DNA was employed as a triplet host material for fabricating multilayered electrophosphorescence devices via modification of its property by doping 5,4‐tert‐butylhexyl‐1,3,4‐oxadiazole (PBD). After doping 30 wt % PBD and 10 wt % Ir(Cz‐ppy)₃ into Cz‐DNA, we achieved much improvement in electron injection/transport from an adjacent carrier transport layer, resulting in much improved device performances. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1913–1918, 2010     

Alternant molecular orbitals (amo's) for some organic semiconductors: Ion radical salts from 7, 7, 8, 8-tetracyanoquinodimethane (TCNQ) and chloranil/ para-phenylenediamine (PDC) charge transfer complex

We report an attempt of ab initio computation for the ground-state wave-function of a few organic semiconductors (namely TCNQ salts and the PDC charge transfer complex) for which we show that electrical conduction appears to look strongly like that of a band-gap semiconductor.     

Energy‐level alignment at metal–organic and organic–organic interfaces

This article reports on the electronic structure at interfaces found in organic semiconductor devices. The studied organic materials are C₆₀ and poly (para‐phenylenevinylene) (PPV)‐like oligomers, and the metals are polycrystalline Au and Ag. To measure the energy levels at these interfaces, ultraviolet photoelectron spectroscopy has been used. It is shown how the energy levels at interfaces deviate from the bulk. Furthermore, it is demonstrated that the vacuum levels do not align at the studied interfaces. The misalignment is caused by an electric field at the interface. Several effects are presented that influence the energy alignment at interfaces, such as screening effects, dipole layer formation, charge transfer, and chemical interaction. The combination of interfaces investigated here is similar to interfaces found in polymer light‐emitting diodes and organic bulk heterojunction photovoltaic devices. The result, the misalignment of the vacuum levels, is expected to influence charge‐transfer processes across these interfaces, possibly affecting the electrical characteristics of organic semiconductor devices that contain similar interfaces. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2549–2560, 2003     

三(五氟苯基)硼烷掺杂有机/高分子半导体的研究进展

有机/高分子共轭聚合物的结构设计是制备高性能有机半导体的有效策略,但该过程存在着设计合成周期长、制备步骤复杂和产率偏低等问题。为了克服这些问题,近年来人们越来越关注对有机/高分子半导体的掺杂。然而,传统电荷转移掺杂剂(如卤族单质I₂、金属氧化物Fe₃O₄、小分子F4TCNQ等)存在掺杂效率低、溶解度差和掺杂条件苛刻等问题。相比之下,三(五氟苯基)硼烷具有溶解度高、掺杂效率高、广泛适应性等优点。本文结合相关文献综述了三(五氟苯基)硼烷掺杂有机半导体的物理机制,并探讨了掺杂有机半导体的性质;此外,还总结了三(五氟苯基)硼烷掺杂在不同光电功能器件中的应用并明确了今后的研究方向。     

Photoinduced Charge Separation in Molecular Silicon

Interest in molecular silicon semiconductors arises from the properties shared with bulk silicon like earth abundance and the unique architectures accessible from a structure distinctly different than rigid π‐conjugated organic semiconductors. We report ultrafast spectroscopic evidence for direct, photoinduced charge separation in molecular silicon semiconductors that supports the viability of molecular silicon as donor materials in optoelectronic devices. The materials in this study are σ–π hybrids, in which electron‐deficient aromatic acceptors flank a σ‐conjugated silicon chain. Transient absorption and femtosecond‐stimulated Raman spectroscopy (FSRS) techniques revealed signatures consistent with direct, optical charge transfer from the silane chain to the acceptor; these signatures were only observed by probing excited‐state structure. Our findings suggest new opportunities for controlling charge separation in molecular electronics.     

Dicarboxylic imide‐substituted poly(p‐phenylene vinylenes) with high electron affinity

Synthesis of n‐type organic semiconductors with high electron mobilities, good environmental stability, and good processability is an urgent task in current organic electronics. This is because most of π‐conjugated materials are p‐type and prefer to transport positive hole carriers. In this article, a series of new dicarboxylic imide‐substituted poly(p‐phenylene vinylenes) (DI‐PPVs) were first synthesized. They exhibited a high electron affinity of 3.60 eV and thus are able to transport electrons. The polymers showed tunable solubility in common organic solvents and high chemical and thermal stability. They remain rigidity of the PPV backbone, and strong interchain π‐stacking was observed in thin films by X‐ray diffraction measurement. All these suggested that these polymers could serve as good candidates as n‐type semiconductors in organic electronic devices such as n‐channel field‐effect transistors and all polymer‐based solar cells. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 186–194, 2010     

Effects of alkyl side chains positioning and presence of fused aromatic units in the backbone of low‐bandgap diketopyrrolopyrrole copolymers on the optoelectronic properties of organic solar cells

The systematic optimization of the chemical structure of low‐bandgap (LBG) donor‐acceptor polymeric semiconductors is a challenging task for which accurate guidelines are yet to be determined. Several different structural and molecular parameters are crucial ingredients for obtaining LBG polymers that simultaneously possess high power conversion efficiencies, good processability in common organic solvents, and enhanced stability in organic photovoltaic devices. In this work, we present an extensive structure–optoelectronic properties–solar cell performance study on the emerging class of diketopyrrolopyrrole‐based LBG polymers. In particular, we investigate alkyl side chain positioning by introducing linear alkyl side chains into two different positions (α‐ and β‐), and the distance of the electron rich and electron deficient monomers within the repeat units of the polymer chain. We demonstrate that anchoring linear alkyl side chains to the α‐positions and introducing fused moieties into the polymer backbone, can be beneficial toward maintaining photocurrents similar to the unsubstituted derivative, and concurrently exhibit better processabiliy in common organic solvents. These results can provide a design rationale towards further optimization of semiconducting polymers. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 138–146     

A Three‐Dimensional Porous Organic Semiconductor Based on Fully sp2‐Hybridized Graphitic Polymer

Dimensionality plays an important role in the charge transport properties of organic semiconductors. Although three‐dimensional semiconductors, such as Si, are common in inorganic materials, imparting electrical conductivity to covalent three‐dimensional organic polymers is challenging. Now, the synthesis of a three‐dimensional π‐conjugated porous organic polymer (3D p‐POP) using catalyst‐free Diels–Alder cycloaddition polymerization followed by acid‐promoted aromatization is presented. With a surface area of 801 m² g^?1, full conjugation throughout the carbon backbone, and an electrical conductivity of 6(2)×10^?4 S cm^?1 upon treatment with I₂ vapor, the 3D p‐POP is the first member of a new class of permanently porous 3D organic semiconductors.     

Dependence of electrical performance on structural organization in polymer field effect transistors

Organic semiconductors (OSCs) are strong contenders for use in printed, flexible electronics. Although organic electronic materials have been studied for many years, the physics of charge transport is still under investigation. This is in part due to variability resulting from the large variety of molecules that can be synthesized and inconsistency in electrical characterization due to device and processing conditions. Molecular ordering in OSCs is known to alter the charge transport characteristics and attention to long range and short range ordering provides clues as to the nature of transport pathways. Here, we study ordered regioregular poly(3‐hexylthiophene‐2,5‐diyl) films carefully prepared to obtain a set of three samples with incrementally increasing order on identical transistor architectures. Ordering was characterized using a variety of short and long range techniques to probe the coherence and number of crystallites formed during processing, and the correlation between these different measures of order are quantified. We observe three changes in transistor behavior that show a shift from non‐ideal to more textbook‐like characteristics with increasing order: reduction of the contact resistance, shift to field‐independent mobility, and a shift from a diode‐like (S‐shaped) to linear response at low lateral fields. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1063–1074     

Influence of Intermolecular N?H⋅⋅⋅π Interactions on Molecular Packing and Field‐Effect Performance of Organic Semiconductors

Charge transport in organic semiconductors is strongly dependent on their molecular packing modes in the solid state. Therefore, understanding the relationship between molecular packing and charge transport is imperative, both experimentally and theoretically. However, so far, the fundamental effects of solid‐state packing and molecular interactions (e.g. N? H ??? π) on charge transport need further elucidation. Herein, indolo[3,2‐b]carbazole (ICZ) and a derivative thereof are used as examples to approach this scientific target. An interesting insight obtained thereby is that N? H ??? π interactions among ICZ molecules facilitate charge transport for higher mobility. Subtle changes in the of N? H ??? π interactions can significantly influence both the molecular packing and the charge‐transport properties. Therefore, a method for exploiting intermolecular N? H ??? π interactions would yield novel molecular systems with designable characteristics.     

Charge transport and structure in semimetallic polymers

Owing to changes in their chemistry and structure, polymers can be fabricated to demonstrate vastly different electrical conductivities over many orders of magnitude. At the high end of conductivity is the class of conducting polymers, which are ideal candidates for many applications in low‐cost electronics. Here, we report the influence of the nature of the doping anion at high doping levels within the semi‐metallic conducting polymer poly(3,4‐ethylenedioxythiophene) (PEDOT) on its electronic transport properties. Hall effect measurements on a variety of PEDOT samples show that the choice of doping anion can lead to an order of magnitude enhancement in the charge carrier mobility > 3 cm²/Vs at conductivities approaching 3000 S/cm under ambient conditions. Grazing Incidence Wide Angle X‐ray Scattering, Density Functional Theory calculations, and Molecular Dynamics simulations indicate that the chosen doping anion modifies the way PEDOT chains stack together. This link between structure and specific anion doping at high doping levels has ramifications for the fabrication of conducting polymer‐based devices. © 2017 The Authors. Journal of Polymer Science Part B: Polymer Physics Published by Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 97–104     

Experimental techniques and the underlying device physics

This review, which has a very deep tutorial nature to it, aims to collect a range of experimental techniques that are relevant to charge transport and place them all under one device‐physics framework. The types of semiconductors in mind are low mobility ones with an emphasis toward organic semiconductors. As this contribution needs to have a finite length, there are many important methods or techniques not covered in this review. My hope is that by covering methods that are very different in nature, it would make it easier to extend the understanding or intuition collected through this review to methods/techniques not mentioned. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1119–1152     

Controlling open‐shell loading in norbornene‐based radical polymers modulates the solid‐state charge transport exponentially

Radical polymers are an emerging class of electronically active macromolecules; however, the fundamental mechanism by which charge is transferred in these polymers has yet to be established in full. To address this issue, well‐defined norbornene‐based nitroxide radical polymers were synthesized using the controlled ring‐opening metathesis polymerization technique. These polymers were blended in solution with a quenched, electrically insulating hydroxylamine derivative to dilute the radical content of the system. Electron paramagnetic resonance spectroscopy data were used to characterize the radical content as well as to reveal that hydrogen atom transfer occurred between the open‐shell and closed‐shell polynorbornene derivatives when they were blended in solution. Using these platform macromolecules, we demonstrate that the systematic manipulation of the radical content in open‐shell macromolecules leads to exponential changes in the macroscopic electrical conductivity. When coupled with the fact that these materials show a clear temperature‐independent charge transport behavior, a picture emerges that charge transfer in radical polymers is dictated by a tunneling mechanism between localized donor and acceptor sites within the redox‐active thin films. These results constitute the first experimental insight into the mechanism of solid‐state electrical conduction in radical polymers, and this provides a design paradigm for open‐shell macromolecular charge transport. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1516–1525