n‐Type Organic Semiconductors in Organic Electronics

Organic semiconductors have been the subject of intensive academic and commercial interest over the past two decades, and successful commercial devices incorporating them are slowly beginning to enter the market. Much of the focus has been on the development of hole transporting, or p‐type, semiconductors that have seen a dramatic rise in performance over the last decade. Much less attention has been devoted to electron transporting, or so called n‐type, materials, and in this paper we focus upon recent developments in several classes of n‐type materials and the design guidelines used to develop them.     

High‐Efficiency All‐Small‐Molecule Organic Solar Cells Based on an Organic Molecule Donor with Alkylsilyl‐Thienyl Conjugated Side Chains

Two medium‐bandgap p‐type organic small molecules H21 and H22 with an alkylsily‐thienyl conjugated side chain on benzo[1,2‐b:4,5‐b′]dithiophene central units are synthesized and used as donors in all‐small‐molecule organic solar cells (SM‐OSCs) with a narrow‐bandgap n‐type small molecule 2,2′‐((2Z,2′Z)‐((4,4,9,9‐tetrahexyl‐4,9‐dihydro‐s‐indaceno[1,2‐b:5,6‐b′]dithiophene‐2,7‐diyl)bis(methanylylidene))bis(3‐oxo‐2,3‐dihydro‐1H‐indene‐2,1‐diylidene))dimalononitrile (IDIC) as the acceptor. In comparison to H21 with 3‐ethyl rhodanine as the terminal group, H22 with cyanoacetic acid esters as the terminal group shows blueshifted absorption, higher charge‐carrier mobility and better 3D charge pathway in blend films. The power conversion efficiency (PCE) of the SM‐OSCs based on H22:IDIC reaches 10.29% with a higher open‐circuit voltage of 0.942 V and a higher fill factor of 71.15%. The PCE of 10.29% is among the top efficiencies of nonfullerene SM‐OSCs reported in the literature to date.     

N‐Type 2D Organic Single Crystals for High‐Performance Organic Field‐Effect Transistors and Near‐Infrared Phototransistors

Organic field‐effect transistors and near‐infrared (NIR) organic phototransistors (OPTs) have attracted world's attention in many fields in the past decades. In general, the sensitivity, distinguishing the signal from noise, is the key parameter to evaluate the performance of NIR OPTs, which is decided by responsivity and dark current. 2D single crystal films of organic semiconductors (2DCOS) are promising functional materials due to their long‐range order in spite of only few molecular layers. Herein, for the first time, air‐stable 2DCOS of n‐type organic semiconductors (a furan‐thiophene quinoidal compound, TFT‐CN) with strong absorbance around 830 nm, by the facile drop‐casting method on the surface of water are successfully prepared. Almost millimeter‐sized TFT‐CN 2DCOS are obtained and their thickness is below 5 nm. A competitive field‐effect electron mobility (1.36 cm² V^?1 s^?1) and high on/off ratio (up to 10⁸) are obtained in air. Impressively, the ultrasensitive NIR phototransistors operating at the off‐state exhibit a very low dark current of ≈0.3 pA and an ultrahigh detectivity (D*) exceeding 6 × 10¹⁴ Jones because the devices can operate in full depletion at the off‐state, superior to the majority of the reported organic‐based NIR phototransistors.     

Recent Progress in n‐Channel Organic Thin‐Film Transistors

Particular attention has been focused on n‐channel organic thin‐film transistors (OTFTs) during the last few years, and the potentially cost‐effective circuitry‐based applications in flexible electronics, such as flexible radiofrequency identity tags, smart labels, and simple displays, will benefit from this fast development. This article reviews recent progress in performance and molecular design of n‐channel semiconductors in the past five years, and limitations and practicable solutions for n‐channel OTFTs are dealt with from the viewpoint of OTFT constitution and geometry, molecular design, and thin‐film growth conditions. Strategy methodology is especially highlighted with an aim to investigate basic issues in this field.     

White‐Emissive Self‐Assembled Organic Microcrystals

Organic semiconductor micro‐/nanocrystals with regular shapes have been demonstrated for many applications, such as organic field‐effect transistors, organic waveguide devices, organic solid‐state lasers, and therefore are inherently ideal building blocks for the key circuits in the next generation of miniaturized optoelectronics. In the study, blue‐emissive organic molecules of 1,4‐bis(2‐methylstyryl)benzene (o‐MSB) can assemble into rectangular microcrystals at a large scale via the room‐temperature solution‐exchange method. Because of the Förster resonance energy transfer, the energy of the absorbed photons by the host matrix organic molecules of o‐MSB can directly transfer to the dopant organic molecules of tetracene or 1,2:8,9‐dibenzopentacene (DBP), which then emit visible photons in different colors from blue to green, and to yellow. More impressively, by modulating the doping molar ratios of DBP to o‐MSB, bright white‐emissive organic microcrystals with well‐preserved rectangular morphology can be successfully achieved with a low doping ratio of 1.5%. These self‐assembled organic semiconductor microcrystals with multicolor emissions can be the white‐light sources for the integrated optical circuits at micro‐/nanoscale.     

High‐Performance Vertical Organic Transistors

Vertical organic thin‐film transistors (VOTFTs) are promising devices to overcome the transconductance and cut‐off frequency restrictions of horizontal organic thin‐film transistors. The basic physical mechanisms of VOTFT operation, however, are not well understood and VOTFTs often require complex patterning techniques using self‐assembly processes which impedes a future large‐area production. In this contribution, high‐performance vertical organic transistors comprising pentacene for p‐type operation and C₆₀ for n‐type operation are presented. The static current–voltage behavior as well as the fundamental scaling laws of such transistors are studied, disclosing a remarkable transistor operation with a behavior limited by injection of charge carriers. The transistors are manufactured by photolithography, in contrast to other VOTFT concepts using self‐assembled source electrodes. Fluorinated photoresist and solvent compounds allow for photolithographical patterning directly and strongly onto the organic materials, simplifying the fabrication protocol and making VOTFTs a prospective candidate for future high‐performance applications of organic transistors.