Pinning energies of organic semiconductors in high-efficiency organic solar cells

With the emergence of new materials for high-efficiency organic solar cells(OSCs),understanding and finetuning the interface energetics become increasingly important.Precise determination of the so-called pinning energies,one of the critical characteristics of the material to predict the energy level alignment(ELA)at either electrode/organic or organic/organic interfaces,are urgently needed for the new materials.Here,pinning energies of a wide variety of newly developed donors and nonfullerene acceptors(NFAs)are measured through ultraviolet photoelectron spectroscopy.The positive pinning energies of the studied donors and the negative pinning energies of NFAs are in the same energy range of 4.3−4.6 eV,which follows the design rules developed for fullerene-based OSCs.The ELA for metal/organic and inorganic/organic interfaces follows the predicted behavior for all of the materials studied.For organic-organic heterojunctions where both the donor and the NFA feature strong intramolecular charge transfer,the pinning energies often underestimate the experimentally obtained interface vacuum level shift,which has consequences for OSC device performance.

In-situ/operando characterization techniques for organic semiconductors and devices

The increasing demands of multifunctional organic electronics require advanced organic semiconducting materials to be developed and significant improvements to be made to device performance. Thus, it is necessary to gain an in-depth understanding of the film growth process, electronic states, and dynamic structure-property relationship under realistic operation conditions, which can be obtained by in-situ/operando characterization techniques for organic devices. Here, the up-todate developments in the in-situ/operando optical, scanning probe microscopy, and spectroscopy techniques that are employed for studies of film morphological evolution, crystal structures, semiconductor-electrolyte interface properties, and charge carrier dynamics are described and summarized. These advanced technologies leverage the traditional static characterizations into an in-situ and interactive manipulation of organic semiconducting films and devices without sacrificing the resolution, which facilitates the exploration of the intrinsic structure-property relationship of organic materials and the optimization of organic devices for advanced applications.

Unsymmetrical donor—acceptor—donor—acceptor type indoline based organic semiconductors with benzothiadiazole cores for solution-processed bulk heterojunction solar cells

Bulk heterojunction(BHJ) solar cells based on small molecules have attracted potential attention due to their promise of conveniently defined structures, high absorption coefficients, solution process-ability and easy fabrication. Three D—A—D—A type organic semiconductors(WS-31,WS-32 and WS-52) are synthesized, based on the indoline donor and benzotriazole auxiliary acceptor core, along with either bare thiophene or rigid cyclopentadithiophene as π bridge, rhodanine or carbonocyanidate as end-group. Their HOMO orbitals are delocalized throughout the whole molecules. Whereas the LUMOs are mainly localized on the acceptor part of structure, which reach up to benzothiadiazole, but no distribution on indoline donor. The first excitations for WS-31 and WS-32 are mainly originated by electron transition from HOMO to LUMO level, while for WS-52, partly related to transition between HOMO and LUMO+1 level. The small organic molecules are applied as donor components in bulk heterojunction(BHJ) organic solar cells, using PC_(61)BM as acceptor material to check their photovoltaic performances. The BHJ solar cells based on blended layer of WS-31:PC_(61)BM and WS-32:PC_(61)BM processed with chloroform show overall photoelectric conversion efficiency(PCE) of 0.56% and 1.02%, respectively. WS-32 based BHJ solar cells show a higher current density originated by its relatively larger driving force of photo-induced carrier in photo-active layer to LUMO of PC_(61)BM.

2D organic semiconductors, the future of green nanotechnology

The discovery of 2D organic semiconductors of atomically thin structures has attracted great attention due to their emerging optical, electronic, optoelectronic and mechatronic properties. Recent progress in such organic nanostructures has opened new opportunities for engineering material properties in many ways, such as, 0D/1D/2D nanoparticles hybridization, strain engineering, atomic doping etc. Moreover, 2D organic nanostructures exhibit a unique feature of bio–functionality and are highly sensitive to bio-analytes. Such peculiar behavior in 2D organics can be utilized to design highly-efficient bio-sensors. Also, a bio-molecular integrated electronic/optoelectronic device with enhanced performance can be attained. Furthermore, the bio-degradable, biocompatible, biometabolizable, non-toxic behaviour and natural origin of organic nanomaterials can address the current ecological concerns of increasing inorganic material based electronic waste. This review highlights the benefits of 2D organic semiconductors. Considering the importance of strategic techniques for growing thin 2D organic layers,this review summarizes progress towards this direction. The possible challenges for long-time stability and future research directions in 2D organic nano electronics/optoelectronics are also discussed. We believe that this review article provides immense research interests in organic 2D nanotechnology for exploiting green technologies in the future.

The impact of reabsorption effect on composition analysis of organic semiconductors

Reabsorption is one of the most fundamental optical phenomena,but it has rarely been considered in spectroscopy-based composition analysis for organic semiconductors.Here,we take four state-of-the-art organic solar cell(OSC)materials as examples,and systematically investigate the influence of reabsorption on photoluminescence emission and excitation spectra by both experimental studies and optical simulations.We find that the overlap between absorption and emission spectra of these OSC materials is strong enough for them to be affected by the reabsorption effect,and the effect becomes more obvious between different species in the multi-components systems.Moreover,three features of the reabsorption effect and the reabsorption strength are identified,with which we have successfully analyzed the composition in a range of OSC materials in both solution and solid-state films.Our work not only provides an important understanding of the largely overlooked feature of reabsorption in the widely used spectroscopic techniques but also offers an effective toolbox for the composition analysis of organic semiconductors.

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.

1,2,5,6-Naphthalene Diimides:A Class of Promising Building Blocks for Organic Semiconductors

Organic semiconductors have drawn extensive atten-tion due to their optoelectronic properties and wide applications in organic optoelectronics.In comparison with the popular 1,4,5,8-naphthalene diimides(1,4,5,8-NDIs),the angular-shaped 1,2,5,6-NDIs have exhibited tunable photophysical properties,self-as-sembly behaviors and charge transporting properties.Due to these unique features,1,2,5,6-NDIs show great potential for construction of high performance n-func-tional materials.In this review,we highlight the recent advances and future prospects of 1,2,5,6-NDI-basedπ-systems in the field of organic optoelectronics,in-cluding molecular design,synthesis,structure-prop-erty relationships as well as the applications in high performance organic field-effect transistors,organic photovoltaics,perovskite solar cells,and so on.

Multilayered organic semiconductors for high performance optoelectronic stimulation of cells

The efficiency of devices for bioelectronic applications,including cell and tissue stimulation,is heavily dependent on the scale and the performance level.With miniaturization of stimulation electrodes,achieving a sufficiently high current pulse to elicit action potentials becomes an issue.Herein we report on our approach of vertically stacking organic p-n junctions to create highlyefficient multilayered organic semiconductor(MOS)photostimulation device.A tandem arrangement substantially increases the photovoltage and charge density without sacrificing lateral area,while not exceeding 200-500 nm of thickness.These devices generate 4 times higher voltages and at least double the charge densities over single p-n junction devices,which allow using lower light intensities for stimulation.MOS devices show an outstanding stability in the electrolyte that is extremely important for forthcoming in vivo experiments.Finally,we have validated MOS devices performance by photostimulating fibroblasts and neuroblasts,and found that using tandem devices leads to more effective action potential generation.As a result,we obtained up to 4 times enhanced effect in cell growth density using 3 p-n layered devices.These results corroborate the conclusion that MOS technology not only can achieve parity with state-of-the-art silicon devices,but also can exceed them in miniaturization and performance for biomedical applications.

The surface electron transfer strategy promotes the hole of PDI release and enhances emerging organic pollutant degradation

In semiconductor photocatalysts,the easy recombination of photogenerated carriers seriously affects the application of photocatalytic materials in water treatment.To solve the serious problem of electron−hole pair recombination in perylene diimide(PDI)organic semiconductors,we loaded ferric hydroxyl oxide(FeOOH)on PDI materials,successfully prepared novel FeOOH@PDI photocatalytic materials,and constructed a photo-Fenton system.The system was able to achieve highly efficient degradation of BPA under visible light,with a degradation rate of 0.112 min^(−1)that was 20 times higher than the PDI system,and it also showed universal degradation performances for a variety of emerging organic pollutants and anti-interference ability.The mechanism research revealed that the FeOOH has the electron trapping property,which can capture the photogenerated electrons on the surface of PDI,effectively reducing the compounding rate of photogenerated carriers of PDI and accelerating the iron cycling and H2O2 activation on the surface of FeOOH at the same time.This work provides new insights and methods for solving the problem of easy recombination of carriers in semiconductor photocatalysts and degrading emerging organic pollutants.

Infrared Photodetectors and Image Arrays Made with Organic Semiconductors

Combining the strategies of introducing larger heteroatom,regio-regular backbone and extended branching position of side-chain,we developed polymer semiconductors(PPCPD)with narrow band-gap to construct the photosensing layer of thin-film photodiodes and image arrays.The spectral response of the resulting organic photodiodes spans from the near ultra-violet to short-wavelength infrared region.The performance of these short-wavelength infrared photodiodes in 900–1200 nm range achieved a level competitive with that of indium gallium arsenide-based inorganic crystalline detectors,exhibiting a specific detectivity of 5.55×1012 Jones at 1.15µm.High photodetectivity and quantum efficiency in photodiode with amorphous/nanocrystalline thin-films of 100–200 nm thickness enabled high pixel-density image arrays without pixel-level-patterning in the sensing layer.1×256 linear diode arrays with 25µm×25µm pixel pitch were achieved,enabling high pixel-density short-wavelength infrared imaging at room temperature.

Greater than 10 cm^(2) V^(−1) s ^(−1) : A breakthrough of organic semiconductors for field-effect transistors

Organic semiconductors have been receiving intensive attention due to the specific advantages of low-temperature processing ability,low-fabrication cost,flexibility,and so forth.The charge carrier mobility of higher than 10 cm^(2) V^(−1) s ^(−1)for organic semiconductors is of great importance to be studied since it presents a future promising research direction toward commercial microelectronic applications.With the significant progress of the discovery of novel organic molecules and the further improvements of device fabrication technology,some organic molecules can break the limit of our knowledge and show very high mobilities.In this review,organic polymers and small molecules with mobilities above 10 cm^(2) V^(−1) s ^(−1) are first introduced to provide the readers with a general understanding of the features and characteristics of high-performance organic semiconductors.Then,some important parameters,including the molecular structures,the device configurations,and the performance,are discussed in detail.Finally,the clues to obtain high mobility are summarized,and the perspective toward the future possible research directions are also provided.

Noncovalent conformational locks in organic semiconductors

Highly planar conformation is considered to be one of the most important properties for high performance organic semiconductors. Among all kinds strategies for designing highly performing materials, noncovalent conformational locks （NCLs） have been widely used to increase the planarity and rigidity for x-conjugated systems. This review summarizes π-conjugated small molecules and polymers by employing various NCLs for controlling molecular conformation in the past two years. The optoelectronic properties of the conjugated materials, together with their applications on organic field-effect transistors （OFETs） and organic photovoltaics （OPVs） are discussed. Besides, the outlook and challenges in this field are also presented. It is obvious that NCLs play an important role in the design and synthesis of high-performance organic semiconductors.

One-dimensional(1D) micro/nanostructures of organic semiconductors for field-effect transistors

Organic semiconductors have gradually become the super stars on the stage of optoelectronic materials, due to their low cost, flexibility and solution processability. Numerous organic semiconductors, including small molecules and conjugated polymers, have been designed and synthesized to explore the potential of organic materials in optoelectronic industry. One-dimensional micro/nanostructures of organic semiconductors generally have more ordered packing structure with fewer defects compared with thin films, and are thus thought to show intrinsic carrier mobility of organic materials. Moreover, the packing structure in micro/nanostructures is clear and relatively easy to analyze, which makes these micro/nanostructures a good platform to study structure-property relationship. Therefore, design of suitable organic molecules to form micro-/nanostructures and methods to obtain ideal micro/nanostructures for functional devices will be fully discussed in this mini review. Finally, the perspective and opportunity of 1D micro/nanostructured organic materials based OFETs in the near future are also addressed.

Chlorine gas sensors using hybrid organic semiconductors of PANI/ZnPcCl_(16)

PANI/ZnPcCl_（16）（polyaniline doped with sulfosalicylic acid/hexadecachloro zinc phthalocyanine） powders were vacuum co-deposited onto Si substrates,where Pt interdigitated electrodes were made by micromachining.The PANI/ZnPcCl_（16） films were characterized and analyzed by SEM,and the influencing factors on its intrinsic performance were analyzed and sensitivities of the sensors were investigated by exposure to chlorine（Cl_2） gas.The results showed that powders prepared with a stoichiometric ratio of（ZnPcCl_（16））_（0.6）（PANI）_（0.4） had a preferential sensitivity to Cl_2 gas, superior to those prepared otherwise;the optimal vacuum co-deposition conditions for the films are a substrate temperature of 160℃,an evaporation temperature of 425℃and a film thickness of 75 nm;elevating the operation temperature （above 100℃） or increasing the gas concentration（over 100 ppm） would improve the response characteristics,but there should be upper levels for each.Finally,the gas sensing mechanism of PANI/ZnPcCl_（16） films was also discussed.

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.

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.

Selenium-containing core-expanded naphthalene diimides for high performance n-type organic semiconductors

The incorporation of heavy atoms into molecular backbone is an extremely straightforward strategy for fine-tuning the optoelectronic properties of organic semiconductors.However,it is rarely studied in n-type small molecules.Herein,by selenium substitution of NDI3 HU-DTYM2,two Se-decorated core-expanded naphthalene diimides(NDI)derivatives DTYM-NDI3 HUDSYM(1)and NDI3 HU-DSYM2(2)were synthesized.In comparison with the reference S-containing compound NDI3 HUDTYM2,the highest occupied molecular orbital(HOMO)and lowest unoccupied molecular orbital(LUMO)energy levels of 1 and 2 were fine-tuned with?HOMO of about 0.2 e V,?LUMO of 0.1 e V and the narrowed HOMO-LUMO gaps.More surprisingly,the as-spun organic thin film transistors(OTFTs)based on 1 and 2 both showedμe,satvalues as high as1.0 cm2 V-1 s-1,which are 2-fold higher than that of NDI3 HU-DTYM2 with the same device structure and measurement conditions.In addition,the single crystal OFET devices based on Se-containing compound NDI2 BO-DSYM2 showed a highμe,satvalue of 1.30 cm2 V-1 s-1.The molecular packing of NDI2 BO-DSYM2 in single crystals(two-dimensional supramolecular structure formed by intermolecular Se···Se interactions)is quite different from that of a S-containing compound NDI-DTYM2(one dimensional supramolecular structure formed by intermolecularπ-πstacking).Therefore,the Se substitution can cause dramatic change about molecular stacking model,giving rise to high n-type OTFT performance.Our results demonstrated an effective strategy of the heavy atom effect for designing novel organic semiconductors.

Acceptor-Donor-Acceptor Type Small Molecular Low Band Gap Organic Semiconductors Containing 2-Dicyanomethylen- 3-cya n o-4, 5, 5-t rim ethyl-d i hyd rofu ran

Acceptor-donor-acceptor type compounds WI--W3 were designed and synthesized. These compounds had the same donor moiety of 2,6-di（tbiophen-2-yl）dithieno[3,2-b：2＇,3＇-d]thiophene and different acceptor groups of 2-dicyanomethylen-3-cyano-4,5,5-trimethyl-2,5-dihydrofuran （TCF）, dicyanovinyl （DCV） and 3-ethyl-2-thioxothia- zolidin-4-one. Experimental results showed all compounds had high thermal stability and strong absorption in the visible light region. Among them, compound Wl with TCF as acceptor group displayed the lowest LUMO energy level of-3.74 eV and the smallest HOMO-LUMO band gap of 1.74 eV, suggesting the potential applications of TCF unit in low band gap organic semiconductors.

High mobility organic semiconductors for field-effect transistors

Organic field-effect transistors(OFETs) are attracting more and more attention due to their potential applications in low-cost, large-area and flexible electronic products. Organic semiconductors(OSCs) are the key components of OFETs and basically determine the device performance. The past five years have witnessed great progress of OSCs. OSCs used for OFETs have made rapid progress, with field-effect mobility much larger than that of amorphous silicon(0.5?1.0 cm2/(V s)) and of up to 10 cm2/(V s) or even higher. In this review, we demonstrate the latest progress of OSCs for OFETs, where more than 50 representative OSCs are highlighted and analyzed to give some valuable insights for this important but challenging field.

Realization of vertical and lateral van der Waals heterojunctions using two-dimensional layered organic semiconductors

Van der Waals （vdW） heterojunctions based on two-dimensional （2D） atomic crystals have been extensively studied in recent years. Herein, we show that both vertical and lateral vdW heterojunctions can be realized with layered molecular crystals using a two-step physical vapor transport （PVT） process. Both types of heterojunctions show clean and sharp interfaces without phase mixing under atomic force microscopy （AFM）. They also exhibit a strong interfacial built-in electric field similar to that of their inorganic counterparts. These heterojunctions have greater potential for device applications than individual materials. The lateral heterojunction （LHJ） devices show rectifying characteristics due to the asymmetric energy barrier for holes at the interface, while the vertical heterojunction （VHJ） devices behave like metal-insulator-semiconductor tunnel junctions, with pronounced negative differential conductance （NDC）. Our work extends the concept of vdW heterojunctions to molecular materials, which can be generalized to other layered organic semiconductors （OSCs） to obtain new device functionalities.