Fluorination on cyclopentadithiophene-based hole-transport materials for high-performance perovskite solar cells.

A new class of fluorinated cyclopenta[2,1-b:3,4-b']dithiophene (CPDT)-based small molecules, namely YC-oF, YC-mF, and YC-H, are demonstrated as hole-transporting materials (HTMs) for high-performance perovskite solar cells (PSCs). PSCs employing YC-oF as the HTM delivered an excellent efficiency of 22.41% with encouraging long-term stability.

Photochromic Dithienylethene Monolayer-Modified Gold Nanoparticles as a Tunable Floating Gate in the Fabrication of Nonvolatile Organic Memory.

Nonvolatile memory (NVM) devices were fabricated by implanting a self-assembled monolayer (SAM) of functional dithienylethene (DTE) derivative on the gold nanoparticle (Au-NP) surface in a pentacene-based organic transistor. The Au-NPs and DTE served as a charge-trapping medium and tunneling barrier layer, respectively. The transfer characteristic of the NVM device showed a narrow hysteresis window and wide memory window, indicating that the DTE-SAM served as a variable barrier layer to regulate the trapping and detrapping of external free charges at the Au-NPs. The energy gap introduced by the DTE-SAM is modulated through photoisomerization between a ring-open form and a ring-closed form by absorbing UV or visible light. For a memory device, the ring-closed DTE allows more free charge injection into the trapping sites, and the ring-open one better retains the trapped charges. A longer anchoring alkanethiol chain at the DTE moiety can further extend the device's retention time. For the NVM operation, programming with the ring-closed DTE and then switching the DTE structure to the ring-open form for erasing can facilitate the charge trapping and charge retention with the same molecule compared to operating all in the ring-open form or all in the ring-closed form of DTE. The structural characterization and electronic characteristics of these devices are discussed in detail.

Tailoring Photophysical Properties of Diketopyrrolopyrrole Small Molecules with Electron-Withdrawing Moieties for Efficient Solar Steam Generation.

The development of photothermal materials (PTMs) for solar steam generation (SSG) has gained tremendous attention in response to the global clean water scarcity issue. However, the investigation in employing organic small-molecule PTMs for SSG applications is rarely found due to their narrow optical absorption range to harvest solar energy and insufficient photostability for long-term use. Herein, we employ a diketopyrrolopyrrole (DPP) core unit together with electron-withdrawing (EW) endcaps and siloxane side chains to introduce stronger intramolecular charge transfer (ICT) characteristics as well as the hydrophobic character. The enhanced ICT characteristics of DPP derivatives render a broad optical absorption range, less emission, and a high nonradiative decay rate for efficient solar energy harvesting and photothermal effects. Meanwhile, the hydrophobic nature of these DPP derivatives allows the facile fabrication of novel Janus photothermal membranes for effective water vaporization and solar-to-vapor conversion efficiency. By embedding DPP derivatives to the SSG device, we showed that the solar-to-vapor efficiency can reach up to 71.8% under relatively low visible light power (∼700 W m-2), which is, on average, 2.66 times higher than that of bulk water of similar dimension. Moreover, this report demonstrates the great potential of conjugated small molecules for photothermal applications, owing to their versatility and flexibility in structural engineering and its diminishing radiative decay properties. This may inspire more innovation and advancement in SSG applications.

Toward Large-Area and Fully Solution-Sheared Perovskite Solar Cells.

The solution shearing technique was used to prepare the various layers involved in perovskite solar cells (PSCs), with a device structure of FTO/c-TiO2/mp-TiO2/CH3NH3PbI3/Spiro-OMeTAD/Ag, in an area as large as 6 × 10 cm2. The film morphology and thickness of each layer were optimized by varying respective shearing parameters. The fully solution-sheared PSCs exhibited a champion power conversion efficiency (PCE) of 15.89%. In comparison, the PSCs with only perovskite layer solution-sheared and other layers spin-coated showed a high PCE of 17.27%. These results demonstrate the potential of a simple, rapid, cost-effective, and scalable solution shearing process to fabricate large-area PSCs and modules.

Low-Cost Hole-Transporting Materials Based on Carbohelicene for High-Performance Perovskite Solar Cells.

Two hole-transporting materials (HTMs) based on carbohelicene cores, CH1 and CH2, are developed and used in fabricating efficient and stable perovskite solar cells (PSCs). Owing to the rigid conformation of the helicene core, both compounds possess unique CH-π interactions in the crystalline packing pattern and good phase stability, which are distinct from the π-π intermolecular interactions of conventional planar and spiro-type molecules. PSCs based on CH1 and CH2 as HTMs deliver excellent device efficiencies of 19.36 and 18.71%, respectively, outperforming the control device fabricated with spiro-OMeTAD (18.45%). Furthermore, both PSCs exhibit better ambient stability, with 90% of initial performance retained after aging with a 50-60% relative humidity at 25 °C for 500 h. Due to the low production cost of both compounds, these newly designed carbohelicene-type HTMs have the potential for the future commercialization of PSCs.

Coronenes, Benzocoronenes and Beyond: Modern Aspects of Their Syntheses, Properties, and Applications.

In recent years, a variety of new designs of coronene-based polycyclic aromatic hydrocarbons (PAHs) with diverse functions have emerged to serve as complementary materials in organic chemistry and materials chemistry. In the present review, we highlight the modern aspects of syntheses related to or different from the strategies used in the early era of coronene research. Systematic extension and expansion of coronene backbones to wide categories of angular PAHs are covered. The substitution and extension of coronene architectures, by incorporating functional groups and by fusing small and large conjugated units, advatangeously enrich their photophysical, electrochemical, self-assembling, and other properties, of which are discussed to demostrate their impact in materials chemistry. While the highly symmetric coronenes, tribenzocoronenes and hexabenzocoronenes conceived wide potential in charge-transporting, electroluminescent, sensing, and other applications, other related derivatives such as dibenzo, tetrabenzo and pentabenzocoronenes also displayed their potentials as exemplified by their use as charge-conduction channel in transistor application.

Thiophene-Fused Butterfly-Shaped Polycyclic Arenes with a Diphenanthro[9,10-b:9',10'-d]thiophene Core for Highly Efficient and Stable Perovskite Solar Cells.

Two polycyclic heteroarene derivatives, namely, V-1 and V-2, with a diphenanthro[9,10-b:9',10'-d]thiophene (DPT) core tethered with two diphenylaminophenyl or diphenylamino groups were first synthesized and used as hole-transporting materials (HTMs) in perovskite solar cell (PSC) fabrication. The novel HTMs exhibit appropriate energy-level alignment with the perovskite so as to ensure efficient hole transfer from the perovskite to HTMs. V-2 with the diphenylamino substituent on DPT exhibited impressive photovoltaic performance with a power conversion efficiency of 19.32%, which was higher than that of V-1 (18.60%) and the benchmark 2,2',7,7'-tetrakis-(N,N-di-p-methoxyphenyl-amine)-9,9'-spirobifluorene (spiro-OMeTAD) (17.99%), presumably because of a better hole extraction, higher hole mobility, and excellent film-forming ability, which were supported by steady-state photoluminescence (PL), time-resolved PL, the hole mobility experiment, scanning electron microscopy, and atomic force microscopy measurements. Meanwhile, V-2-based PSCs exhibited better long-term durability than that with V-1 and the state-of-the-art spiro-OMeTAD, which is ascribable to the excellent surface morphology and hydrophobicity of the film. This systematic study suggests that DPT-based molecules are good potential candidates as HTMs for achieving high-performance PSCs.

Self-Assembly Behavior of Diacetylenic Acid Molecules upon Vapor Deposition: Odd-Even Effect on the Film Morphology.

A series of linear carboxylic acids containing diacetylenic units at different positions along the chain (C12 H25 (C≡C)2 (CH2 )n COOH, n=7-11) were vacuum-deposited on clean silica substrates. The morphologies of the initial films after UV irradiation were studied. A clear odd-even effect on the morphology of the initial film was observed in that, depending on the spacer length between the diacetylenic unit and carboxyl head group, rings or dendrites of acid dimer layers were obtained. A molecular dynamic simulation of the aggregation process suggests that two competing intermolecular interactions and thus aggregation directions are involved and modulated by the odd or even carbon chain length. Further modulation of the interaction by substitution of a phenyl group at the terminus of the chain or by changing the carboxyl head group to an amidobenzoic acid head group led to a similar odd-even effect but with different dimensions or trends, which can be rationalized similarly. These results give the opportunity to create aligned conjugated polymer chains of different dimensions through self-assembly for applications in molecular/organic electronics.

Alignment and Photopolymerization of Hexa-peri-hexabenzocoronene Derivatives Carrying Diacetylenic Side Chains for Charge-Transporting Application.

Thin films of four discotic liquid-crystalline hexa-peri-hexabenzocoronene (HBC) derivatives carrying three diacetylenic side chains and three saturated alkyl chains at different positions around the central HBC core were prepared on phenyltrichlorosilane-modified SiO2 substrate by the Chinese brush-coating method. The brush-coated films of molecules with D3h symmetry and C1 symmetry all exhibited anisotropic alignment with an edge-on orientation and molecular π-π stacking along the coating direction on the surface, in contrast to the spin-coated films, where a mixture of face-on and edge-on orientations was obtained. Hexagonally packed columnar structure or lamella-like columnar structure was obtained, depending on the location of the diacetylenic unit along the chain. UV irradiation of the films resulted in cross-linking/polymerization of the molecular columns. Among them, the lamella-like structure with a diacetylene unit closer to the HBC core gave more closely packed and ordered HBC arrays with the poly(ene-yne) backbones stretching along the column direction, based on a variety of experimental evidence. A thin-film transistor based on this irradiated film gave a highest mobility of 1.5 cm2 V-1 s-1 along the column direction, which is a 3 orders of magnitude improvement over that of the monomeric film. However, for those with a diacetylenic unit extended farther away from the core, cross-linking between neighboring columns was suggested to occur and no mobility can be measured for devices based on those films.

Synergy of Ionic and Dipolar Effects by Molecular Design for pH Sensing beyond the Nernstian Limit.

Knowledge of interfacial interactions between analytes and functionalized sensor surfaces, from where the signal originates, is key to the development and application of electronic sensors. The present work explores the tunability of pH sensitivity by the synergy of surface charge and molecular dipole moment induced by interfacial proton interactions. This synergy is demonstrated on a silicon-nanoribbon field-effect transistor (SiNR-FET) by functionalizing the sensor surface with properly designed chromophore molecules. The chromophore molecules can interact with protons and lead to appreciable changes in interface dipole moment as well as in surface charge state. In addition, the dipole moment can be tuned not only by the substituent on the chromophore but also by the anion in the electrolyte interacting with the protonated chromophore. By designing surface molecules to enhance the surface dipole moment upon protonation, an above-Nernstian pH sensitivity is achieved on the SiNR-FET sensor. This finding may bring an innovative strategy for tailoring the sensitivity of the SiNR-FET-based pH sensor toward a wide range of applications.

n-Type Thin-Film Transistors Based on Diketopyrrolopyrrole Derivatives: Role of Siloxane Side Chains and Electron-Withdrawing Substituents.

The physical properties, packing, morphology, and semiconducting performance of a planar π-conjugated system can be effectively modified by introducing side chains and substituent groups, both of which can be complementary to the π framework in changing the intermolecular association, frontier molecular orbital energy, optical band gap, and others. We herein show that installation of end-capped electron-withdrawing groups (EWGs), such as dicyanovinyl (-DCV), 3-ethylrhodanine (-RD), and 2-(3-oxo-indan-1-ylidene)-malononitrile (-INCN), together with siloxane side chains to the backbones of dithienyldiketopyrrolopyrrole (DPPT), such as DPPT-Si-DCV, DPPT-Si-RD, and DPPT-Si-INCN, can greatly improve its solubility, air stability, and film morphology to serve as an n-channel in thin-film transistor fabrication. The EWGs attached to the DPPT core narrowed the optical band gap (Egopt) and changed the highest occupied molecular orbital and the lowest unoccupied molecular orbital energies (EHOMO and ELUMO), making them suitable for n-channel field-effect transistor (FET) applications. The benefits of introducing siloxane side chains to the DPPT core include enhanced solubility, low crystallization barrier, enantiotropic phase behavior, and much improved FET performance. The DPPT-Si-INCN film displayed low-lying HOMO (-5.82 eV) and LUMO (-4.60 eV) energy levels and an optical band gap as low as 1.22 eV, all of which suggest that this derivative can be quite resistant toward aerial oxidation. Thin films of these derivatives were prepared by the solution-shear method. A comparison of the solution-sheared films indicated that the molecular packing motif of DPPT-Si-INCN film was somehow different from that of DPPT-Si-DCV and DPPT-Si-RD, in which the π-π stacking tended to align orthogonally to the shearing direction. This specific π-π stacking alignment could have an impact on the electron mobility (µe) values in transistors based on the solution-sheared films.

Benzophenanthrothiophenes: Syntheses, Crystal Structures, and Properties.

A new class of polycyclic heteroarenes based on benzo[3,4]phenanthro[1,2-b]benzo[3,4]phenanthro[2,1-d]thiophene (BPBPT) was prepared from polyaryl thiophenes via regioselective Scholl reactions. The molecular frameworks of these compounds exhibited twisted bridges and near-cofacial packing motifs with oppositely or parallel π-stacked structures depending on the substituents on the periphery. Theoretical calculation of electronic coupling and charge mobility was carried out on the basis of the single-crystal structures. Single crystals of selected benzophenanthrothiophenes were used in p-channel field-effect transistor device fabrication, from which the highest mobility was measured as 2.03 cm2 V-1 s-1 from Flu-BPBPT.

Polysubstituted Hexa-cata-hexabenzocoronenes: Syntheses, Characterization, and Their Potential as Semiconducting Materials in Transistor Applications.

A series of tetra- and octa-substituted hexa-cata-hexabenzocoronenes (cata-HBCs) were synthesized from tetraryl olefins via iodine- and iron chloride-catalyzed oxidative cyclodehydrogenation reactions. The substitutions on the periphery of the parent HBC serve to modify the photophysical properties, highest occupied molecular orbital-lowest unoccupied molecular orbital gaps, and thermal stabilities of the respective derivatives. The crystal structures were determined to display multiple twists in the framework, resulting in different packing motifs depending on the position, type, and number of functional groups on the hexabenzocoronene framework. Nearly perfect co-facial packing to marginally or extensively shifted co-facial stacks were obtained due to substitution. The single crystals of parent HBC were used to fabricate single-crystal field-effect transistors, from which the highest p-channel mobility of 0.51 cm2 V-1 s-1 was measured. Thin-film transistors of selected HBCs were also prepared, and 0.61 cm2 V-1 s-1 was obtained for MeHBC-2. These results attest the potential of these materials as semiconducting materials.

Molecularly Aligned Hexa- peri-hexabenzocoronene Films by Brush-Coating and Their Application in Thin-Film Transistors.

The facile Chinese brush-coating method was used to prepare oriented thin films of hexa- peri-hexabenzocoronene (HBC) derivatives on the silicon substrate. As a result of the directional solution-coating, the D3 h-symmetry (HBC-1,3,5-Ph-C12) and the C1-symmetry (HBC-1,2,4-Ph-C12) derivatives displayed an anisotropic alignment, with mostly edge-on orientation on SiO2 surfaces modified with various silane-based monolayers. On these silane-modified surfaces, the higher symmetry molecule HBC-1,3,5-Ph-C12 developed a hexagonally packed superstructure, which provided greater π orbital overlap and presumably the electronic coupling between neighboring molecules. In particular, the use of an octyltrichlorosilane (OTS)-modified surface enabled brush-coated thin films to have higher anisotropic orientation, crystallinity, and favorable molecular arrangement. In contrast, the growth of the hexagonal packing of low-symmetry derivative HBC-1,2,4-Ph-C12 was only achieved on the phenyltrichlorosilane and OTS surfaces. Thin-film transistors based on these brush-coated films gave a maximum mobility of 0.1 and 0.056 cm2 V-1 s-1, which are 2 orders of magnitude improvement over the devices with unoriented films prepared by spin-coating. The results indicate that the molecular packing of discotic liquid crystals on the silane-modified surface is sensitively influenced by the molecular symmetry, which affects intermolecular interactions as well as molecule/surface interactions. This study provides a simple way to fabricate aligned films for HBC derivatives for transistor application.

New Helicene-Type Hole-Transporting Molecules for High-Performance and Durable Perovskite Solar Cells.

Three azahelicene derivatives with electron-rich bis(4-methoxyphenyl)amino or bis( p-methoxyphenyl)aminophenyl groups at the terminals were deliberately designed, synthesized, and characterized as hole-transporting materials (HTMs) for perovskite solar cells (PSCs). Optical and thermal properties, energy level alignments, film morphologies, hole extraction ability, and hole mobility were studied in detail. PSCs using the newly synthesized molecules as HTMs were fabricated. A maximum power conversion efficiency (PCE) of 17.34% was observed for the bis( p-methoxyphenyl)amino-substituted derivative (SY1) and 16.10% for the bis( p-methoxyphenyl)aminophenyl-substituted derivative (SY2). Longer-chain substituent such as hexyloxy group greatly diminishes the efficiency. In addition, the dopant-free devices fabricated with SY1 as the HTM shows an average PCE of 12.13%, which is significantly higher than that of spiro-OMeTAD (7.61%). The ambient long-term stability test revealed that after 500 h, the devices prepared from SY1 and SY2 retained more than 96% of its initial performance, which is much improved than the reference device with standard spiro-OMeTAD as the HTM under the same conditions. Detailed material cost analysis reveals that the material cost for SY1 is less than 8% of that for spiro-OMeTAD. These results provide a useful direction for designing a new class of HTMs to prepare highly efficient and more durable PSCs.

Nonlinear Polyfused Aromatics with Extended π-Conjugation from Phenanthrotriphenylene, Tetracene, and Pentacene: Syntheses, Crystal Packings, and Properties.

New classes of nonlinear polyaromatics with extended conjugation at lateral and longitudinal directions from triphenylene, tetracene, and pentacene backbones are reported. These planar and twisted polyfused aromatics are obtained through specific and selective multifold Scholl reactions from predesigned polyaryls. These derivatives displayed shifted or perfect cofacial packing motifs. Single crystals of one derivative, phenanthro[9,10: b]triphenylene, were used as p-channel materials in fabricating transistor devices, which exhibited an average mobility of 0.38 cm2 V-1 s-1 and a maximum mobility reaching 1.15 cm2 V-1 s-1.

Contorted Naphtho- and Fluorenocoronenes: Syntheses and Properties of Polycyclic Aromatics beyond Benzo- and Thiophenocoronenes.

Selective oxidative cyclodehydrogenation reactions on olefins carrying larger aromatic units are described to offer modular access to contorted polyaromatics of naphtho- and fluorenocoronenes, which are more extended frameworks than the known benzocoronenes. The annulation proceeded regioselectively when more than one mode was possible, based either on electronic or steric effect. The single-crystal field-effect transistor based on one of the derivatives, dinaphtho[ a, d]coronene, gave a p-carrier mobility of 0.04 cm2/(V s) and on/off current ratio of 102-103.

Compact TiO2 films with sandwiched Ag nanoparticles as electron-collecting layer in planar type perovskite solar cells: improvement in efficiency and stability.

Fabrication of perovskite solar cells (PSCs) in a simple way with high efficiency and stability remains a challenge. In this study, silver nanoparticles (Ag NPs) were sandwiched between two compact TiO2 layers through a facile process of spin-coating an ethanolic AgNO3 solution, followed by thermal annealing. The presence of Ag NPs in the electron-transporting layer of TiO2 improved the light input to the device, the morphology of the perovskite film prepared on top, and eliminated leakage current. Photoluminescence and electron mobility studies revealed that the incorporation of Ag NPs in the ETL of the planar PSC device facilitated the electron-hole separation and promoted charge extraction and transport from perovskite to ETL. Hysteresis-free devices with incorporated Ag NPs gave a high average short-circuit current density (J sc) of 22.91 ± 0.39 mA cm-2 and maximum power conversion efficiency of 17.25%. The devices also showed enhanced stability versus a control device without embedded Ag NPs. The possible reasons for the improvement are analyzed and discussed.

Synthesis and Characterization of Contorted Pentabenzo-Fused Coronenes as Semiconducting Materials.

Here, we report the synthesis and characterization of a series of contorted, yet noncentrosymmetrical, polycyclic aromatic hydrocarbons with a pentabenzo-fused coronene as the core framework. The parent pentabenzo[a,d,g,j,m]coronene (PBC) compound is shown to exhibit a shifted and rotated type of π-π stacking interactions, which render this series a semiconducting material. Single-crystal-based field-effect transistor devices of PBC exhibited efficient charge transport behavior, giving a p-channel field-effect mobility of 0.42 cm2 V-1 s-1 and an on/off ratio of 105.

Effect of Bending on the Electrical Characteristics of Flexible Organic Single Crystal-based Field-effect Transistors.

The charge transport in an organic semiconductor depends highly on the molecular packing in the crystal, which influences the electronic coupling immensely. However, in soft electronics, in which organic semiconductors play a critical role, the devices will be bent or folded repeatedly. The effect of bending on the crystal packing and thus the charge transport is crucial to the performance of the device. In this manuscript, we describe the protocol to bend a single crystal of 5,7,12,16-tetrachloro-6,13-diazapentacene (TCDAP) in the field-effect transistor configuration and to obtain reproducible I-V characteristics upon bending the crystal. The results show that bending a field-effect transistor prepared on a flexible substrate results in nearly reversible yet opposite trends in charge mobility, depending on the bending direction. The mobility increases when the device is bent toward the top gate/dielectric layer (upward, compressive state) and decreases when bent toward the crystal/substrate side (downward, tensile state). The effect of bending curvature was also observed, with greater mobility change resulting from higher bending curvature. It is suggested that the intermolecular π-π distance changes upon bending, thereby influencing the electronic coupling and the subsequent carrier transport ability.