Small-molecule Organic Semiconductors Research Articles

Machine learning-assisted chemical space generation of small molecule organic semiconductors for efficient photodetectors

Organic photodetectors (OPDs), the emerging next-generation candidates for light sensing applications, could compensate deficiencies of the traditional inorganic photodetectors. To get OPDs of highly improved performance, and broader applications, machine learning (ML) technique is employed. A chemical space of 20,000 organic semiconductors (OSCs) by RDKit via BRICKS (Breaking Retrosynthetically Interesting Chemical Substructures) method was achieved, from the selected building blocks of the OSC data obtained from the literature, contributing to big data. Out of these, top twenty OSCs were screened based on synthetic accessibility score, chemical similarity analysis, and structural behavior understanding.

A Novel Non-Fullerene D-A Interface with Two Asymmetrical Electron Acceptors Facilitates Charge and Energy Transfer for Effective Carbon Dioxide Reduction.

Converting carbon dioxide (CO2 ) into high-value chemicals using solar energy remains a formidable challenge. In this study, the CSC@PM6:IDT6CN-M:IDT8CN-M non-fullerene small-molecule organic semiconductor is designed with highly efficient electron donor-acceptor (D-A) interface for photocatalytic reduction of CO2 . Atomic Force Microscope and Transmission Electron Microscope images confirmed the formation of an interpenetrating fibrillar network after combination of donor and acceptor. The CO yield from the CSC@PM6:IDT6CN-M:IDT8CN-M reached 1346µmolg-1 h-1 , surpassing those of numerous reported inorganic photocatalysts. The D-A structure effectively facilitated charge separation to enable electrons transfer from the PM6 to IDT6CN-M:IDT8CN-M. Meanwhile, attributing to the dipole moments of the strong intermolecular interactions between IDT6CN-M and IDT8CN-M, the intermolecular forces are enhanced, and laminar stacking and π-π stacking are strengthened, thereby reinforcing energy transfer between acceptor molecules and significantly enhanced charge separation. Moreover, the strong internal electric field in the D-A interface enhanced the excited state lifetime of PM6:IDT6CN-M:IDT8CN-M. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analysis demonstrated that carboxylate (COOH*) is the predominant intermediate during CO2 reduction, and possible pathways of CO2 reduction to CO are deduced. This study presents a novel approach for designing materials with D-A interface to achieve high photocatalytic activity.

LiTFSI-Free Hole Transport Materials for Robust Perovskite Solar Cells and Modules with High Efficiencies.

Lithium bis(trifluoromethane) sulfonamide (LiTFSI) and oxygen-doped organic semiconductors have been frequently used to achieve record power conversion efficiencies of perovskite solar cells (PSCs). However, this conventional doping process is time-consuming and leads to poor device stability due to the incorporation of Li ions. Herein, aiming to accelerate the doping process and remove the Li ions, we report an alternative p-doping process by mixing a new small-molecule organic semiconductor, N2,N2,N7,N7-tetrakis (4-methoxyphenyl)-9-(4-(octyloxy) phenyl)-9H carbazole-2,7-diamine (labeled OH44) and its preoxidized form OH44+(TFSI-). With this method, a champion efficiency of 21.8% has been achieved for small-area PSCs, which is superior to the state-of-the-art EH44 and comparable with LiTFSI and oxygen-doped spiro-OMeTAD. Moreover, the stability of OH44-based PSCs is improved compared with those of EH44, maintaining more than 85% of its initial efficiency after aging in an ambient condition without encapsulation for 1000 h. In addition, we achieved efficiencies of 14.7 and 12.6% for the solar modules measured with a metal mask of 12.0 and 48.0 cm2, respectively, which demonstrated the scalability of this method.

Influence of Excess Conjugated Wrapping Polymer in Semiconducting Single-Walled Carbon Nanotube Dispersions

Single-walled carbon nanotubes (SWNTs) are promising nanomaterials for incorporation into organic electronic devices (OEDs), with the potential to fabricate flexible devices while exploiting inexpensive solution-processing techniques. As-synthesized SWNTs are insoluble and comprised of a mixture of metallic and semiconducting SWNTs (sc-SWNTs), necessitating dispersal and purification before integration into OEDs. Refinement of conjugated polymer extraction techniques has allowed for the isolation of sc-SWNTs from metallic in a reproducible and scalable manner. The availability of highly-pure sc-SWNT materials has facilitated the production of thin-film transistors (TFTs) with very high charge carrier mobilities, outperforming organic small molecule and polymer semiconductors. However, the realization of commercial OED applications of polymer-sorted sc-SWNTs have not yet been achieved, partially due to the prohibitive time and materials costs associated with purifying sc-SWNTs.Current protocols for dispersing sc-SWNTs with conjugated polymers involve three broad steps: (1) dispersion of bulk SWNT material, (2) removal of non-dispersed carbonaceous materials, and (3) removal of excess polymer through filtration or centrifugation. The final step of removal of excess polymer is time-consuming and wasteful, but viewed as necessary for preparing high-performing TFTs, as the conjugated polymer has much lower performance compared to SWNTs.In this study we performed the first systematic investigation of the effect of excess polymer on SWNT TFT performance. Three SWNT concentrations were investigated, with varying ratios of excess polymer added to each. TFT device performance was monitored using several metrics, including: mobility, threshold voltage, on/off ratios and hysteresis. Characterization of large numbers of replicate TFT devices determined that below a threshold amount of excess polymer the presence of excess polymer did not have a negative impact on device performance. Detailed analysis of the sc-SWNT films through Raman spectroscopy and atomic force microscopy (AFM) confirmed that a simple rinsing step was sufficient to remove all the unbound conjugated polymer from the substrate surface without affecting the sc-SWNT network. The volume of solvent required for the rinsing step was substantially lower than that required for filtration or centrifugation steps. Furthermore, at higher SWNT concentrations the excess polymer prevented nanotube bundling, resulting in moderate improvements in both mobility and on/off ratios. Our results were reproducible for two different conjugated polymer sc-SWNT systems, demonstrating the versatility of this procedure.

TCAD simulation of organic field-effect transistors based on spray-coated small molecule organic semiconductor with an insulating polymer blend

TCAD simulation of organic field-effect transistors based on spray-coated small molecule organic semiconductor with an insulating polymer blend

Nanocrystal Array Engineering and Optoelectronic Applications of Organic Small-Molecule Semiconductors.

Organic small-molecule semiconductor materials have attracted extensive attention because of their excellent properties. Due to the randomness of crystal orientation and growth location, however, the preparation of continuous and highly ordered organic small-molecule semiconductor nanocrystal arrays still face more challenges. Compared to organic macromolecules, organic small molecules exhibit better crystallinity, and therefore, they exhibit better semiconductor performance. The formation of organic small-molecule crystals relies heavily on weak interactions such as hydrogen bonds, van der Waals forces, and π-π interactions, which are very sensitive to external stimuli such as mechanical forces, high temperatures, and organic solvents. Therefore, nanocrystal array engineering is more flexible than that of the inorganic materials. In addition, nanocrystal array engineering is a key step towards practical application. To resolve this problem, many conventional nanocrystal array preparation methods have been developed, such as spin coating, etc. In this review, the typical and recent progress of nanocrystal array engineering are summarized. It is the typical and recent innovations that the array of nanocrystal array engineering can be patterned on the substrate through top-down, bottom-up, self-assembly, and crystallization methods, and it can also be patterned by constructing a series of microscopic structures. Finally, various multifunctional and emerging applications based on organic small-molecule semiconductor nanocrystal arrays are introduced.

Highly Ordered Small Molecule Organic Semiconductor Thin-Films Enabling Complex, High-Performance Multi-Junction Devices.

Organic semiconductors have opened up many new electronic applications, enabled by properties like flexibility, low-cost manufacturing, and biocompatibility, as well as improved ecological sustainability due to low energy use during manufacturing. Most current devices are made of highly disordered thin-films, leading to poor transport properties and, ultimately, reduced device performance as well. Here, we discuss techniques to prepare highly ordered thin-films of organic semiconductors to realize fast and highly efficient devices as well as novel device types. We discuss the various methods that can be implemented to achieve such highly ordered layers compatible with standard semiconductor manufacturing processes and suitable for complex devices. A special focus is put on approaches utilizing thermal treatment of amorphous layers of small molecules to create crystalline thin-films. This technique has first been demonstrated for rubrene─an organic semiconductor with excellent transport properties─and extended to some other molecular structures. We discuss recent experiments that show that these highly ordered layers show excellent lateral and vertical mobilities and can be electrically doped to achieve high n- and p-type conductivities. With these achievements, it is possible to integrate these highly ordered layers into specialized devices, such as high-frequency diodes or completely new device principles for organics, e.g., bipolar transistors.

Are Coarse-Grained Structures as Good as Atomistic Ones for Calculating the Electronic Properties of Organic Semiconductors?

The quality of amorphous molecular morphologies obtained with a recently introduced coarse-grained model, representing molecules in terms of connected anisotropic beads (Phys. Chem. Chem. Phys. 2019, 21, 26195), is benchmarked against reference atomistic data. Typical small-molecule organic semiconductors in their pristine and doped forms are chosen as a challenging and technologically relevant case study for our comparison, which includes both structural features and the resulting electronic properties, such as charge carrier energy levels, energetic disorder, and intermolecular charge transfer couplings. Our analysis shows that our accurate coarse-grained model leads to molecular glasses that are very similar to native atomistic samples, with the discrepancy being further reduced upon back-mapping. The electronic properties computed for back-mapped morphologies are almost indistinguishable from the atomistic reference, especially for multibranched poly(hetero)cyclic hydrocarbons usually employed as organic semiconductors. This study provides a proof of principle for highly accurate large-scale simulations of complex molecular systems at a reduced computational cost.

Sensitive photodetection below silicon bandgap using quinoid-capped organic semiconductors.

High-sensitivity organic photodetectors (OPDs) with strong near-infrared (NIR) photoresponse have attracted enormous attention due to potential applications in emerging technologies. However, few organic semiconductors have been reported with photoelectric response beyond ~1.1 μm, the detection limit of silicon detectors. Here, we extend the absorption of organic small-molecule semiconductors to below silicon bandgap, and even to 0.77 eV, through introducing the newly designed quinoid-terminals with high Mulliken-electronegativity (5.62 eV). The fabricated photodiode-type NIR OPDs exhibit detectivity (D*) over 1012 Jones in 0.41 to 1.2 μm under zero bias with a maximum of 2.9×1012 Jones at 1.02 μm, which is the highest D* for reported OPDs in photovoltaic-mode with response spectra beyond 1.1 μm. The high D* in 0.9 to 1.2 μm is comparable to those of commercial InGaAs photodetectors, despite the detection limit of our OPDs is shorter than InGaAs (~1.7 μm). A spectrometer prototype with a wide measurable region (0.4 to 1.25 μm) and NIR imaging under 1.2-μm illumination are demonstrated successfully in OPDs.

3D-Printed Organic Conjugated Trimer for Visible-Light-Driven Photocatalytic Applications.

Small molecule organic semiconductors (SMOSs) have emerged as a new class of photocatalysts that exhibit visible light absorption, tunable bandgap, good dispersion, and solubility. However, the recovery and reusability of such SMOSs in consecutive photocatalytic reactions is challenging. This work concerns a 3D-printed hierarchical porous structure based on an organic conjugated trimer, named EBE. Upon manufacturing, the photophysical and chemical properties of the organic semiconductor are maintained. The 3D-printed EBE photocatalyst shows a longer lifetime (11.7 ns) compared to the powder-state EBE (1.4 ns). This result indicates a microenvironment effect of the solvent (acetone), a better dispersion of the catalyst in the sample, and reduced intermolecular π-π stacking, which results in improved separation of the photogenerated charge carriers. As a proof-of-concept, the photocatalytic activity of the 3D-printed EBE catalyst is evaluated for water treatment and hydrogen production under sun-like irradiation. The resulting degradation efficiencies and hydrogen generation rates are higher than those reported for the state-of-the-art 3D-printed photocatalytic structures based on inorganic semiconductors. The photocatalytic mechanism is further investigated, and the results suggest that hydroxyl radicals (HO⋅) are the main reactive radicals responsible for the degradation of organic pollutants. Moreover, the recyclability of the EBE-3D photocatalyst is demonstrated in up to 5 uses. Overall, these results indicate the great potential of this 3D-printed organic conjugated trimer for photocatalytic applications.

Recent Research Progress of Organic Small-Molecule Semiconductors with High Electron Mobilities.

Organic electronics has made great progress in the past decades, which is inseparable from the innovative development of organic electronic devices and the diversity of organic semiconductor materials. It is worth mentioning that both of these great advances are inextricably linked to the development of organic high-performance semiconductor materials, especially the representative n-type organic small-molecule semiconductor materials with high electron mobilities. The n-type organic small molecules have the advantages of simple synthesis process, strong intermolecular stacking, tunable molecular structure, and easy to functionalize structures. Furthermore, the n-type semiconductor is a remarkable and important component for constructing complementary logic circuits and p-n heterojunction structures. Therefore, n-type organic semiconductors play an extremely important role in the field of organic electronic materials and are the basis for the industrialization of organic electronic functional devices. This review focuses on the modification strategies of organic small molecules with high electron mobility at molecular level, and discusses in detail the applications of n-type small-molecule semiconductor materials with high mobility in organic field-effect transistors, organic light-emitting transistors, organic photodetectors, and gas sensors.

Applying of C8-BTBT-Based EGOFETs at Different pH Values of the Electrolyte

Electrolyte-gated organic field-effect transistors (EGOFETs) is a popular platform for numerous sensing and biosensing applications in aqueous media. In this work, the variation of electrical characteristics of EGOFETs based on small-molecule organic semiconductor C8-BTBT and polystyrene blend in water solutions at different pH values was investigated. A positive shift of the threshold voltage with near-Nernstian pH sensitivity was demonstrated in the pH range from 4.9 to 2.8, while no measurable pH dependence in the range from 4.9 to 8.6 pH was registered. These results indicate chemical doping of the molecules of organic semiconductors by protons from the electrolyte in the acidic region. In order to check the applicability of the EGOFETs in a flow mode, a flow chamber was designed and assembled. The preliminary results obtained in the flow mode measurements showed a fast response to pH variation.

Insights into the kinetics and self-assembly order of small-molecule organic semiconductor/quantum dot blends during blade coating.

Organic-inorganic nanocomposite films formed from blends of small-molecule organic semiconductors and colloidal quantum dots are attractive candidates for high efficiency, low-cost solar energy harvesting devices. Understanding and controlling the self-assembly of the resulting organic-inorganic nanocomposite films is crucial in optimising device performance, not only at a lab-scale but for large-scale, high-throughput printing and coating methods. Here, in situ grazing incidence X-ray scattering (GIXS) gives direct insights into how small-molecule organic semiconductors and colloidal quantum dots self-assemble during blade coating. Results show that for two blends separated only by a small difference in the structure of the small molecule forming the organic phase, crystallisation may proceed down two distinct routes. It either occurs spontaneously or is mediated by the formation of quantum dot aggregates. Irrespective of the initial crystallisation route, the small-molecule crystallisation acts to exclude the quantum dot inclusions from the growing crystalline matrix phase. These results provide important fundamental understanding of structure formation in nanocomposite films of organic small molecules and colloidal quantum dots prepared via solution processing routes. It highlights the fundamental difference to structural evolution which can be made by seemingly small changes in system composition. It provides routes for the structural design and optimisation of solution-processed nanocomposites that are compatible with the large-scale deposition manufacturing techniques that are crucial in driving their wider adoption in energy harvesting applications.

Two multifunctional benzoquinone derivatives as small molecule organic semiconductors for bulk heterojunction and perovskite solar cells

Two novel quinone derivatives (NN3 and NN4) were synthesized in this work and they were characterized to be used as small organic semiconductor molecules in different types of photovoltaic applications. To make accessible compounds, three simple steps were followed to prepare NN3 and NN4 compounds. Furthermore, energy levels of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) were determined for the computationally optimized models of the investigated compounds. The obtained optical and electrochemical results of this work indicated that NN3 and NN4 compounds were good candidates for application in the fields of bulk heterojunction (BHJ) and perovskite solar cells. Indeed, investigating new energy resources has been seen an important topic of research for producing clean energies and portable storage systems.

Organic small molecule semiconductor materials for OFET-based biosensors

Biosensors is an advanced detection and monitoring device for the development of biotechnology, and is also a rapid and microanalytical device at the molecular level. Demands for high sensitivity, high flexibility, good biocompatibility, easy chemical modification and low cost offer incentive for exploring new materials to develop the next-generation biosensors. With the vigorous development of organic electronics, the performances of organic devices have been effectively improved, leading to organic semiconductor materials with low cost, good flexibility, easy chemical modification and good biocompatibility for biosensors. Biosensors based on organic field-effect transistors (OFETs) have become one of the most advanced biosensor platforms because of their inherent ability to amplify received signals. Furthermore, OFET-based biosensors have been widely used in the detection of DNA, protein, cell, glucose and other biological substances due to its high sensitivity, fast analysis speed, label-free detection, small size and simple operation. This mini review briefly discusses the organic small molecule semiconductor materials, device configurations, basic principles and application fields of OFETs-based biosensors.

Electron affinities of small-molecule organic semiconductors: Comparison among cyclic voltammetry, conventional inverse photoelectron spectroscopy, and low-energy inverse photoelectron spectroscopy

The electron affinity ( A ) of an organic semiconductor is an energy parameter representing the electron transport level. The precise value of A in a solid is indispensable for examining and designing organic semiconductor devices. In principle, A in a solid can be determined by inverse photoelectron spectroscopy (IPES). However, because IPES is normally available only for specialists of IPES, A is often estimated from the reduction potential E red measured in solution using a more easily available method, cyclic voltammetry (CV). Thus, the conversion relation from E red into A is practically important in the research of organic semiconductors. On the other hand, previous IPES data may have errors of about 0.3–0.5 eV owing to sample damage and low energy resolution. In 2012, one of the authors developed low-energy inverse photoelectron spectroscopy (LEIPS), which enables the determination of A with the precision of 0.1 eV. In this work, we establish the correlation between CV data E red and solid-state A based on LEIPS data and suggest the relation A = (1.24 ± 0.07) × e E red + (5.06 ± 0.15) eV. We also discuss the reliability of the A values determined by the previous IPES and the present LEIPS in terms of the LUMO spectral onset and the vacuum level. • Electron affinities of 30 small-molecule organic semiconductors. • Correlation between electron affinity and reduction potential. • Electron affinities determined by low-energy inverse photoelectron spectroscopy. • Comparison between conventional and low-energy inverse photoelectron spectroscopies.

Effects of bromination on anthryl-capped DPP-based semiconductor materials: Improved electrical characteristics of organic field-effect transistors

Diketopyrrolopyrrole (DPP), typically flanked with thiophene rings as π-spacers, has been regarded as a promising electron-acceptor unit for constructing donor-acceptor-donor (D-A-D) type small molecule organic semiconductors. Exploring the relationships between its conjugation structure and semiconducting property is of great importance for both molecular design and device fabrication of such DPP materials. Herein we describe the synthesis, self-assembly, and transistor characteristics of two novel N- and N′− 2-octyldodecylated DPP derivatives which were modified with native anthracene (An) and brominated anthracene (Br-An) at 5-, 5′-position of the flanked thiophenes, respectively, namely An-DPP and Br-An-DPP. Attributing to the self-assembly behaviors, they exhibit enormous difference in hole transport characteristics on interdigitated-electrode based organic field-effect transistor (OFET) devices even though there is only two atoms’ discrepancy in accordance with their molecular structures. The characterization of OFETs with interdigitated-electrodes based on Br-An-DPP reveals p-channel operation with highest field-effect mobility of 0.2 cm2·V−1·s−1, which is 107 times higher than that of An-DPP (4.8 × 10−8 cm2·V−1·s−1), and with a threshold voltage of - 2.5 V. X-ray diffraction, atomic force microscopy, scanning electron microscopy, and optical absorption studies reveal the presence of crystalline films caused by bromination on anthracene-modified alkylated DPP (i.e., Br-An-DPP), while An-DPP exhibits completely amorphous phase.

A high mobility air-stable n-type organic small molecule semiconductor with high UV–visible-to-NIR photoresponse

An organic semiconductor with high carrier mobility and efficient light absorption over a wide spectral range is of the most important yet challenging material for constructing a broadband responsive organic photodetector. However, the development of such organic semiconductors, especially for air-stable n-type organic small molecule semiconductors, is still at an early stage. Here we report the fabrication of high-performance n-type semiconducting crystalline nanosheets and the development of air-stable field-effect transistors, phototransistors, with high response over a broad spectrum. The n-type small molecule semiconductor is assembled into a crystalline nanosheet based on the solvent-phase interfacial self-assembly method. N-type field-effect transistors with high electron mobility are fabricated and their electrical performances exhibit excellent air stability. Impressively, the demonstrated phototransistors exhibit an ultrahigh responsivity over a wide spectral range from 365 to 940 nm, with a maximum photoresponsivity of 9.2 × 105 A W−1 and specific detectivity of 5.26 × 1013 Jones, which is the best performance among the reported n-type organic small molecule-based phototransistors.

(Invited) Probing Charge Carrier Dynamics in Porphyrin-Based Bulk Heterojunction Thin Films with Time-Resolved Terahertz Spectroscopy

Organic photovoltaic (OPV) solar cells have attracted much attention in recent years because of the low production cost and ease of device fabrication. However, the power conversion efficiency is still low compared to the silicon and perovskite solar cells so that further research is necessary to improve their performance. In particular, understanding of the detailed mechanisms of charge carrier generation, recombination and carrier transport process is very important for developing design principles of new compounds for OPVs. Until now, polymer-based compounds have been widely used for p-type semiconductors. However, it is not easy to obtain information on how the microscopic structure of bulk heterojunction (BHJ) blend of donor and acceptor materials affect the charge carrier dynamics because one cannot easily control the molecular weight and conformational distributions of polymer compounds. On the other hand, small molecule-based semiconductors have several unique advantages such well-defined chemical structures, ease of purification and small batch-to-batch variations.Tetrabenzoporphyrin (BP) has been frequently used as a small-molecule organic semiconductor. Recently, Yamada and coworkers synthesized diketopyrrolopyrrole-linked tetrabenzoporphyrin (DPP-BP) conjugates that have linear alkyl groups on the DPP moieties whose chain length is defined as n, namely, Cn-DPP-BP (n=4, 6, 8, or 10). For DPP-BP based solar cells, they demonstrated that alkyl chain length affects the power conversion efficiency. Therefore, it is very interesting to see how the local BHJ structures of DPP-BP based thin films affect the initial step of the charge carrier dynamics because such studies are difficult to perform for polymer-based systems. We can take advantage of small molecule-based systems to study the relationship between the local structure and the charge carrier dynamics.In this work, we used time-resolved terahertz (THz) spectroscopy to investigate the charge carrier dynamics of DPP-BP BHJ thin films blended with [6,6]-phenyl-C61-butyric acid methyl ester (PC61BM). Time-resolved THz spectroscopy is a unique method to quantify charge carrier mobility with very fast time resolution (less than picosecond). This spectroscopy reflects the charge carrier dynamics in the local spatial region because of the high-frequency nature of the THz electric field. We chose C4-DPP-BP:PC61BM and C10-DPP-BP:PC61BM thin films for the THz measurements. In the previous study, it was found that C4-DPP-BP molecule prefers to take a face-on geometry on the substrate. A grain size of the aggregates was around 100 nm or smaller which were measured by atomic force microscopy. In such a structure, one can expect that charge transport takes place very efficiently to the electrode. Actually, power conversion efficiency is 5.2 % which is highest among a series of DPP-BP chromophores. On the other hand, C10-DPP-BP adopts an edge-on geometry on the substrate and forms micrometer-sized aggregates. In this structure, molecular stacking is oriented perpendicular to the electrode so that power conversion efficiency decreases to 0.19%.In contrast to the other measurements, the THz spectroscopy has sensitivity to in-plane motion of the charge carriers with respect to the substrate, we expect to observe higher in-plane mobility of the charge carriers in the C10-DPP-BP:PC61BM BHJ films compared to C4-DPP-BP based films. In contrast to our intuitive expectation, we found that the product of the carrier mobility and the yield of the photo-generated charge carriers is similar to each other. We consider that the similarity of the charge carrier dynamics results from the high-frequency nature of the local mobility of the polarons because most of the polarons are confined in less than a 10-nm length scale. Furthermore, the lowest limit of the carrier mobility obtained from our results is about 1.0 cm2V-1s-1 when the quantum yield of the charge carrier generation is assumed to be unity. This value is much higher than those obtained by space-charge-limited current method. We expect that charge separation occurs very efficiently when the local mobility of the charge carrier is high.In this contribution, we will present importance of the local mobility of the charge carriers and difference of charge transport between short and long length scales in DPP-BP based solar cells.

Deciphering Photoinduced Charge Transfer Dynamics in a Cross-Linked Graphene-Dye Nanohybrid.

The search for synthetic materials that mimic natural photosynthesis by converting solar energy into other more useful forms of energy is an ever-growing research endeavor. Graphene-based materials, with their exceptional electronic and optical properties, are exemplary candidates for high-efficiency solar energy harvesting devices. High photoactivity can be conveniently achieved by functionalizing graphene with small molecule organic semiconductors whose band-gaps can be tuned by structural modification, leading to interactions between the π-conjugated electronic systems in both the semiconductor and graphene. Here we investigate the ultrafast transient optical properties of a cross-linked graphene–dye (diphenyl-dithiophenediketopyrrolopyrrole) nanohybrid material, in which oligomers of the organic semiconductor dye are covalently bound to a random network of few-layer graphene flakes, and compare the results to those obtained for the reference dye monomer. Using a combination of ultrafast transient absorption and two-dimensional electronic spectroscopy, we provide substantial evidence for photoinduced charge transfer that occurs within 18 ps in the nanohybrid system. Notably, subpicosecond photoinduced torsional relaxation observed in the constituent dye monomer is absent in the cross-linked nanohybrid system. Through density functional theory calculations, we compare the competing effects of covalent bonding, increasing conjugation length, and the presence of multiple graphene flakes. We find evidence that the observed ultrafast charge transfer process occurs through a superexchange mechanism in which the oligomeric dye bridge provides virtual states enabling charge transfer between graphene–dye covalent bond sites.