Molecular Orientation-Dependent Photonic Polarization Engineering in Organic Single-Crystal-Filled Microcavities.

Designing the polarization degree of freedom of light is crucial in many fields and has widespread application in, for example, all-optical circuits. In this work, we find that in an organic microcavity filled with anisotropic single crystals the cavity modes can be modulated to be elliptically polarized, i.e., partially circularly polarized and partially linearly polarized. The circular polarization component originates from the Rashba-Dresselhaus spin splitting, while the linear polarization component is due to the dislocation of linearly polarized modes. The dislocation of the linear polarizations is ascribed to the orientation of individual molecules and the molecular packing arrangement; hence, the linear polarizations can be controlled by properly structuring the molecular distributions. Our results pave the way for enriching and engineering the polarization properties of individual optical cavity modes in organic microstructures, which may favor the development of polarized lasers with various polarizations.

Molecular Design of Fully Nonfused Acceptors for Efficient Organic Photovoltaic Cells.

The nonfused thiophene-benzene-thiophene (TBT) unit offers advantages in obtaining low-cost organic photovoltaic (OPV) materials due to its simple structure. However, OPV cells, including TBT-based acceptors, exhibit significantly lower energy conversion efficiencies. Here, we introduce a novel approach involving the design and synthesis of three TBT-based acceptors by substituting different position-branched side chains on the TBT unit. In comparison to TBT-10 and TBT-11, TBT-13, which exclusively incorporates α-position branched side chains with a large steric hindrance, demonstrates a more planar and stable conformation. When blended with the donor PBQx-TF, TBT-13-based blend film achieves favorable π-π stacking and aggregation characteristics, resulting in excellent charge transfer performance in the corresponding device. Due to the simultaneous enhancements in short-circuit current density and fill factor, the TBT-13-based OPV cell obtains an outstanding efficiency of 16.1%, marking the highest value for the cells based on fully nonfused acceptors. Our work provides a practical molecular design strategy for high-performance and low-cost OPV materials.

Photochemical Reaction Enabling the Engineering of Photonic Spin-Orbit Coupling in Organic-Crystal Optical Microcavities.

The control and active manipulation of spin-orbit coupling (SOC) in photonic systems are fundamental in the development of modern spin optics and topological photonic devices. Here, we demonstrate the control of an artificial Rashba-Dresselhaus (RD) SOC mediated by photochemical reactions in a microcavity filled with an organic single crystal of photochromic phase-change character. Splitting of the circular polarization components of the optical modes induced by photonic RD SOC is observed experimentally in momentum space. By applying an ultraviolet light beam, we control the spatial molecular orientation through a photochemical reaction, and with that we control the energies of the photonic modes. This way, we realize a reversible conversion of spin splitting of the optical modes with different energies, leading to an optically controlled switching between circularly and linearly polarized optical modes in our device. Our strategy of in situ and reversible engineering of SOC induced by a light field provides a promising approach to actively design and manipulate synthetic gauge fields toward future on-chip integration in photonics and topological photonic devices.

An Ortho-Bisalkyloxylated Benzene-Based Fully Non-fused Electron Acceptor for Efficient Organic Photovoltaic Cells.

To develop the low-cost nonfullerene acceptors (NFAs), two fully non-fused NFAs (TBT-2 and TBT-6) with ortho-bis((2-ethylhexyl)oxy)benzene unit and different side chains onto thiophene-bridges are synthesized through highly efficient synthetic procedures. Both acceptors show good planarity, low optical gaps (≈1.51 eV), and deep highest occupied molecular orbital levels (≤-5.77 eV). More importantly, the single-crystal structure of TBT-2 shows compact molecular arrangement due to the existence of intramolecular interactions between adjacent aromatic units and strong π-π stacking between intermolecular terminal groups. When the two acceptors are fabricated organic photovoltaic (OPV) cells by combining with a wide optical gap polymer donor, the TBT-6 with strong crystallization forms large domain sizes in bulk heterojunction (BHJ) blend. As a result, the TBT-6-based OPV cell shows a low power conversion efficiency (PCE) of 9.53%. In contrast, the TBT-2 with proper crystallization facilitates morphological optimization in the BHJ blend. Consequently, the TBT-2-based OPV cell gives an outstanding PCE of 13.25%, which is one of the best values among OPV cells with similar optical gaps. Overall, this work provides a practical molecular design strategy for developing high-performance and low-cost electron acceptors.

Organic laser power converter for efficient wireless micro power transfer.

Wireless power transfer with collimated power transmission and efficient conversion provides an alternative charging mode for off-grid and portable micro-power electronics. However, charging micro-power electronics with low photon flux can be challenging for current laser power converters. Here we show laser power converters with organic photovoltaic cells with good performance for application in laser wireless power transfer. The laser selection strategy is established and the upper limit of efficiency is proposed. The organic laser power converters exhibit a 36.2% efficiency at a 660 nm laser with a photon flux of 9.5 mW cm-2 and achieve wireless micro power transfer with an output of 0.5 W on a 2 meter scale. This work shows the good performance of organic photovoltaic cells in constructing organic laser power converters and provides a potential solution for the wireless power transfer of micro-power electronics.

Large Steric Hindrance Enhanced Molecular Planarity for Low-Cost Non-Fused Electron Acceptors.

Designing efficient non-fused ring electron acceptors is of great importance in decreasing the material cost of organic photovoltaic cells (OPVs). It is a challenge to construct a planar molecular skeleton in non-fused molecules as there are many torsions between adjacent units. Here, we design two non-fused electron acceptors based on bithieno[3,2-b]thiophene units as core structures and study the impact of steric hindrance of substituents on molecular planarity. We use 2,4,6-triisopropylphenyl and 4-hexylphenyl groups to prepare ATTP-1 and ATTP-2, respectively. Our results suggest that the enhanced steric hindrance is beneficial for obtaining a more planar molecular configuration, which significantly increases the optical absorption and charge transport properties. The power conversion efficiency (PCE) of PBDB-TF:ATTP-1 combination (11.3%) is superior to that of PBDB-TF:ATTP-2 combination (3.7%). In addition, an impressive PCE of 10.7% is recorded in ATTP-1-based devices when a low-cost polythiophene donor PDCBT is used, which is an outstanding value in OPVs fabricated by non-fused donor/acceptor combinations. Our work demonstrates that modulation of the steric hindrance effect is of great significance to control the molecular planarity and thus obtain excellent photovoltaic performance of low-cost non-fused electron acceptors.

New Method for Preparing ZnO Layer for Efficient and Stable Organic Solar Cells.

Owing to outstanding optoelectronic properties and simple preparation, zinc oxide (ZnO) has widely been used in organic solar cells (OSCs). Although versatile cathode interface materials have been designed in past, ZnO remains indispensable owing to its excellent overall performance. Therefore, solving the persistent problem of residual amine reacting with non-fullerene acceptors will make ZnO superior over other materials, and thus improve the performance and energy budget of OSCs. Herein, a simple, effective, and economical method for removing residual amine in ZnO without distorting ZnO is reported. By accurately comparing the alkalinities of ZnO and residual amine, boric acid (BA) is selected as the amine-removing agent because of its suitable acidic dissociation constant. Moreover, the high water solubility of BA ensures that the post-cleaning process can be easily performed. The work function, electron extraction, and stability of cathode interface layer are optimized through rinsing them with BA. Consequently, the power conversion efficiency (PCE) and stability of OSCs under long-term illumination are significantly improved. The optimal 0.04 and 1.00 cm2  single-junction OSCs are based on PBDB-TF:HDO-4Cl:BTP-eC9 bulk heterojunction output 18.40% and 17.42% efficiencies, respectively. Furthermore, tandem OSCs based on the BA-treated ZnO exhibit a 19.56% PCE, demonstrating the reliability of this method.

A Medium-Bandgap Nonfullerene Acceptor Enabling Organic Photovoltaic Cells with 30% Efficiency under Indoor Artificial Light.

The correlation between molecular structure and photovoltaic performance is lagging for constructing high-performance indoor organic photovoltaic (OPV) cells. Herein, this relationship is investigated in depth by employing two medium-bandgap nonfullerene acceptors (NFAs). The newly synthesized NFA of FTCCBr exhibits a similar bandgap and molecular energy level, but a much stronger dipole moment and larger average electrostatic potential (ESP) compared with ITCC. After blending with the polymer donor PB2, the PB2:ITCC and PB2:FTCCBr blends exhibit favorable bulk-heterojunction morphologies and the same driving force, but the PB2:FTCCBr blend exhibits a large ESP difference. In OPV cells, the PB2:ITCC-based device produces a power conversion efficiency (PCE) of 11.0%, whereas the PB2:FTCCBr-based device gives an excellent PCE of 14.8% with an open-circuit voltage (VOC ) of 1.05 V, which is the highest value among OPV cells with VOC values above 1.0 V. When both acceptor-based devices work under a 1000 lux of 3000 K light-emitting diode, the PB2:ITCC-based 1 cm2 device yields a good PCE of 25.4%; in contrast, the PB2:FTCCBr-based 1 cm2 device outputs a record PCE of 30.2%. These results suggest that a large ESP offset in photovoltaic materials is important for achieving high-performance OPV cells.

Benchmarking of Density Functionals for the Description of Optical Properties of Newly Synthesized π-Conjugated TADF Blue Emitters.

Computational modeling of the optical characteristics of organic molecules with potential for thermally activated delayed fluorescence (TADF) may assist markedly the development of more efficient emitting materials for organic light-emitting diodes. Recent theoretical studies in this area employ mostly methods from density functional theory (DFT). In order to obtain accurate predictions within this approach, the choice of a proper functional is crucial. In the current study, we focus on testing the performance of a set of DFT functionals for estimation of the excitation and emission energy and the excited singlet-triplet energy gap of three newly synthesized compounds with capacity for TADF. The emitters are designed specifically to enable charge transfer by π-electron conjugation, at the same time possessing high-energy excited triplet states. The functionals chosen for testing are from various groups ranging from gradient-corrected through global hybrids to range-separated ones. The results show that the monitored optical properties are especially sensitive to how the long-range part of the exchange energy is treated within the functional. The accurate functional should also be able to provide well balanced distribution of the π-electrons among the molecular fragments. Global hybrids with moderate (less than 0.4) share of exact exchange (B3LYP, PBE0) and the meta-GGA HSE06 are outlined as the best performing methods for the systems under study. They can predict all important optical parameters correctly, both qualitatively and quantitatively.

A Universal Nonhalogenated Polymer Donor for High-Performance Organic Photovoltaic Cells.

Nonhalogenated polymers have great potential in the commercialization of organic photovoltaic (OPV) cells due to their advantage in low-cost preparation. However, non-halogenated polymers usually have high highest occupied molecular orbital (HOMO) energy levels and inferior self-aggregation properties in solution, thus resulting in low power conversion efficiencies (PCEs). Herein, two nonhalogenated polymers, PB1 and PB2, are prepared. When the polymers are used to fabricate OPV cells with BTP-eC9, the PB1-based device only gives a PCE of 5.3%, while the PB2-based device shows an outstanding PCE of 17.7%. After the introduction of PBDB-TF as the third component, the PB2:PBDB-TF:BTP-eC9-based device with an optimal weight ratio of 0.5:0.5:1 achieves a PCE up to 18.4%. More importantly, PB2 exhibits good compatibility with various nonfullerene acceptors to achieve better PCEs than those of classical polymer (PBDB-T and PBDB-TF)-based devices. When PB2 is combined with a wide-bandgap electron acceptor (F-BTA3), this device shows excellent PCE of 27.1% and 24.6% for 1 and 10 cm2 devices, respectively, under light intensity of 1000 lux light-emitting diode illumination. These results provide new insight in the rational design of novel nonhalogenated polymer donors for further development of low-cost materials and broadening the application of OPV cells.

A High-Performance Nonfused Wide-Bandgap Acceptor for Versatile Photovoltaic Applications.

Wide-bandgap (WBG) nonfullerene acceptors (NFAs) with nonfused conjugated structures play a critical role in organic photovoltaic (OPV) cells. Here, NFAs named GS-OEH, GS-OC6, and GS-ISO, with optical bandgaps larger than 1.70 eV, are synthesized without using the fused ring structures. Compared with GS-OEH and GS-OC6, GS-ISO exhibits much stronger crystallinity, leading to a smaller energetic disorder and a larger exciton diffusion coefficient. GS-ISO also possesses a higher electroluminescence external quantum efficiency of 1.0 × 10-2 . The OPV cell based on PBDB-TF:GS-ISO demonstrates a power conversion efficiency (PCE) of 11.62% under the standard one sun illumination. Besides, the PBDB-TF:GS-ISO-based cell with effective area of 1.0 cm2  exhibits a PCE of 28.37% under 2700 K illumination of 500 lux. A tandem OPV cell using PBDB-TF:GS-ISO as the front subcell shows an outstanding efficiency of 19.10%. Importantly, the GS-ISO-based OPV cell exhibits promising stability under the continuous illumination of simulated sunlight. This study indicates that the molecular design strategy demonstrated in this work has great superiority in developing nonfused NFAs and also that GS-ISO is a promising WBG acceptor for versatile photovoltaic applications.

A Sulfhydryl Azobenzene-Modified Polyaniline/Silver Electrode and Its Photoswitching Electrochemical Performance.

In this work, a sulfhydryl-functionalized azobenzene derivative (Azo) was synthesized and polyaniline/silver was modified (PANI/Ag) to make a nanocomposite (PANI/Ag/Azo). A series of characterization techniques like1HNMR, UV-vis absorption spectra, Raman spectra, FT-IR, XRD, SEM, TEM, and TGA was employed to study Azo, PANI/Ag, and PANI/Ag/Azo. Electrochemical properties were measured by cyclic voltammetry (CV) and galvanostatic charging/discharging (GCD). CV showed that UV and blue light had hardly any effect on PANI/Ag. However, with the prolonged exposure time of UV light, the maximum CV current density of PANI/Ag/Azo rose from 1.24 to 2.72 A g-1. Then, after 20 min of blue light irradiation, the maximum current density gradually recovered (from 2.72 to 1.26 A g-1). The GCD also obtained similar results. After formula calculation, the specific capacitance of PANI/Ag/Azo also presented a reversible trend under the alternating irradiation of UV light and blue light. All the results show that PANI/Ag/Azo has a good photoelectric response, and its electrochemical performance can be reversibly adjusted by light. This result provides a new design idea for developing electrode materials with real-time electrochemical properties.

Reduced Nonradiative Recombination Energy Loss Enabled Efficient Polymer Solar Cells via Tuning Alkyl Chain Positions on Pendent Benzene Units of Polymers.

Nonradiative recombination energy loss (ΔE3) plays a key role in enhancing device efficiencies for polymer solar cells (PSCs). Until now, there is no clear resolution for reducing ΔE3 via molecular design. Herein, we report two conjugated polymers, PBDB-P-p and PBDB-P-m, which are integrated from benzo[1,2-b:4,5-b']dithiophene with alkylthio chain substituted at para- or meta-position on pendent benzene and benzo[1,2-c:4,5-c']dithiophene-4,8-dione. Both the polymers have different temperature-dependent aggregation properties but similar molecular energy levels. When BO-4Cl was used as an acceptor to fabricate PSCs, the device of PBDB-P-p:BO-4Cl displayed a maximal power conversion efficiency (PCE) of 13.83%, while the best device of PBDB-P-m:BO-4Cl exhibited a higher PCE of 14.12%. The close JSCs and fill factors in both PSCs are attributed to their formation of effective nanoscale phase separation as confirmed by atomic force microscopy measurements. We find that the PBDB-P-m-based device has 1 order of magnitude higher electroluminescence quantum efficiency (EQEEL) than in the PBDB-P-p-based one, which could arise from the relatively weak aggregation in the PBDB-P-m-based film. Thus, the PBDB-P-m-based device has a remarkably enhanced VOC of 0.86 V in contrast to 0.80 V in the PBDB-P-p-based device. This study offers a feasible structural optimization way on the alkylthio side chain substitute position on the conjugated polymer to enhance VOC by reducing nonradiative recombination energy loss in the resulting PSCs.

Recent progress in wide bandgap conjugated polymer donors for high-performance nonfullerene organic photovoltaics.

In the last five years, the tremendous progress achieved in the field of polymer solar cells (PSCs) has attracted extensive attention to this emerging technology for exploiting renewable energy. Owing to their excellent optoelectronic features and outstanding manufacturability for film deposition, wide bandgap (WBG) polymer donors have become a leading component in bulk heterojunction layers and thus, a correlative review focusing on their molecular design, aggregation behavior and photovoltaic properties is necessary. In this feature article, we summarize our recent efforts in developing WBG polymer donors and understanding the charge separation and non-radiative recombination energy loss in high-performance non-fullerene (NF) PSCs. We also discuss the opportunities and challenges towards the realization of the commercialization of NF PSCs based on WBG polymer donors.

Single-Junction Organic Photovoltaic Cells with Approaching 18% Efficiency.

Optimizing the molecular structures of organic photovoltaic (OPV) materials is one of the most effective methods to boost power conversion efficiencies (PCEs). For an excellent molecular system with a certain conjugated skeleton, fine tuning the alky chains is of considerable significance to fully explore its photovoltaic potential. In this work, the optimization of alkyl chains is performed on a chlorinated nonfullerene acceptor (NFA) named BTP-4Cl-BO (a Y6 derivative) and very impressive photovoltaic parameters in OPV cells are obtained. To get more ordered intermolecular packing, the n-undecyl is shortened at the edge of BTP-eC11 to n-nonyl and n-heptyl. As a result, the NFAs of BTP-eC9 and BTP-eC7 are synthesized. The BTP-eC7 shows relatively poor solubility and thus limits its application in device fabrication. Fortunately, the BTP-eC9 possesses good solubility and, at the same time, enhanced electron transport property than BTP-eC11. Significantly, due to the simultaneously enhanced short-circuit current density and fill factor, the BTP-eC9-based single-junction OPV cells record a maximum PCE of 17.8% and get a certified value of 17.3%. These results demonstrate that minimizing the alkyl chains to get suitable solubility and enhanced intermolecular packing has a great potential in further improving its photovoltaic performance.

Organic photovoltaic cell with 17% efficiency and superior processability.

The development of organic photoactive materials, especially the newly emerging non-fullerene electron acceptors (NFAs), has enabled rapid progress in organic photovoltaic (OPV) cells in recent years. Although the power conversion efficiencies (PCEs) of the top-performance OPV cells have surpassed 16%, the devices are usually fabricated via a spin-coating method and are not suitable for large-area production. Here, we demonstrate that the fine-modification of the flexible side chains of NFAs can yield 17% PCE for OPV cells. More crucially, as the optimal NFA has a suitable solubility and thus a desirable morphology, the high efficiencies of spin-coated devices can be maintained when using scalable blade-coating processing technology. Our results suggest that optimization of the chemical structures of the OPV materials can improve device performance. This has great significance in larger-area production technologies that provide important scientific insights for the commercialization of OPV cells.

Tailoring and Modifying an Organic Electron Acceptor toward the Cathode Interlayer for Highly Efficient Organic Solar Cells.

With the rapid advance of organic photovoltaic materials, the energy level structure, active layer morphology, and fabrication procedure of organic solar cells (OSCs) are changed significantly. Thus, the photoelectronic properties of many traditional electrode interlayers have become unsuitable for modifying new active layers; this limits the further enhancement in OSC efficiencies. Herein, a new design strategy of tailoring the end-capping unit, ITIC, to develop a cathode interlayer (CIL) material for achieving high power conversion efficiency (PCE) in OSCs is demonstrated. The excellent electron accepting capacity, suitable energy level, and good film-forming ability endow the S-3 molecule with an outstanding electron extraction property. A device with S-3 shows a PCE of 16.6%, which is among the top values in the field of OSCs. More importantly, it is demonstrated that the electrostatic potential difference between the CIL molecule and the polymer donor plays a crucial role in promoting exciton dissociation at the CIL/active layer interface, contributing to additional charge generation; this is crucial for enhancement of the current density. The results of this work not only develop a new design strategy for high-performance CIL, but also demonstrate a reliable approach of density functional theory (DFT) calculation to predict the effect of the CIL chemical structure on exciton dissociation in OSCs.

A Carbonylated Terthiophene-Based Twisted Polymer for Efficient Ternary Polymer Solar Cells.

In polymer solar cells (PSCs), it is difficult for twisted conjugated polymers to achieve high power-conversion efficiency (PCE) as donors due to their low charge carrier mobilities and poor bulk heterojunction morphologies. In this work, a new twisted conjugated polymer (P3TCO-1) with excellent solubilities (above 30 mg mL-1 ) in common organic solvents at room temperature is reported. UV-visible absorption spectra and cyclic voltammetry indicate that P3TCO-1 has a wide optical bandgap of 1.90 eV and deep HOMO level of -5.39 eV. In binary PSCs, P3TCO-1:ITIC-based device shows a PCE of 10.11%, with JSC of 17.05 mA cm-2 and FF of 62.89%; P3TCO-1:PC71 BM-based device gives a PCE of 6.67% with JSC of 12.31 mA cm-2 and FF of 58.00%. When the two acceptors of ITIC and PC71 BM are combined, the twisted P3TCO-1-based ternary PSCs exhibit a significantly boosted PCE of up to 11.41%, with a simultaneously improved JSC of 18.16 mA cm-2 and FF of 66.78%. These results can guide the improvement of PCE for twisted conjugated polymer-based PSCs.

Three-Dimensional Pyrene-Fused N-Heteroacenes.

Four three-dimensional (3D) pyrene-fused N-heteroacenes (P1-P4) are designed and synthesized. From P1 to P4, their lengths are extended in an iterative way, where the thiadiazole unit can be reduced to diamine and the obtained diamines can be further condensed with the diketones with a thiadiazole unit. Compared to their two-dimensional counterparts, the solubility of these 3D pyrene-fused N-heteroacenes is improved by this 3D covalent linkage with two-dimensional units. The diameters of P1-P4 are 3.66, 6.06, 8.48 and 10.88 nm, respectively, and these 3D molecules are characterized by 1H, 13C and 2D NMR, MS, UV-vis, PL and CV spectra. Our strategy shows a promising way to large 3D pyrene-fused N-heteroacenes.

Asymmetric Wide-Bandgap Polymers Simultaneously Improve the Open-Circuit Voltage and Short-Circuit Current for Organic Photovoltaics.

A trade-off between open-circuit voltage (V OC ) and high short-circuit (J SC ) becomes one of the most vital problems limiting further improvement in polymer solar cells' (PSCs) efficiency. In this work, two asymmetric polymer donors PBDT-F-2TC and PBDT-SF-2TC are designed and synthesized. When blended with a state-of-the-art acceptor IT-4F with low lowest-unoccupied molecular orbital level, simultaneously high V OC (up to 0.94 V) and J SC (up to 20.73 mA cm-2 ) are obtained for both copolymers. Note that the V OC value of 0.94 V is the highest value of PSCs based on IT-4F reported so far. The simultaneously improved V OC and J SC in resulting devices are discovered from the deep highest-occupied molecular orbital levels (-5.5 to -5.7 eV) and the hyperchromic effect of the polymers, the small driving force, and the small energy loss during the charge transfer, due to the synergistic effect of asymmetric carboxylate unit and fluorine/sulfur atoms. More importantly, thanks to the asymmetric 2TC, both PBDT-F-2TC- and PBDT-SF-2TC-based PSCs can be successfully processed by non-halogenated solvent 1,2,4-trimethylbenzene (TMB) to yield device efficiencies of 10.29% and 10.39%, respectively, which are the maximum values for non-fullerene PSCs fabricated using the eco-friendly solvent TMB.