Surface Regulation via Carboxylate Polymer for Efficient and Stable CsPbI2Br Perovskite Solar Cells.

CsPbI2Br perovskite solar cell (PSC) is a promising candidate for high-efficiency single-junction and tandem solar cells. However, due to the numerous surface defects of the CsPbI2Br film and the mismatch of energy levels at the CsPbI2Br/charge transport layer interface, the power conversion efficiency (PCE) of CsPbI2Br PSC is still significantly lower than the theoretical limits. To alleviate those issues, in this work, a carboxylate-based p-type polymer, TTC-Cl, is employed to modify the surface of CsPbI2Br layer. TTC-Cl can interact with uncoordinated Pb2+, thereby mitigating surficial defects of CsPbI2Br film and reducing non-radiative recombination losses. Furthermore, TTC-Cl also improves the band properties of the CsPbI2Br thin film surface, rendering it more p-type, which facilitates hole transport. Consequently, the CsPbI2Br PSCs with TTC-Cl modification achieve a remarkable PCE of 17.81%, which is notably higher than that of counterpart without TTC-Cl (15.87%). Moreover, CsPbI2Br PSCs with TTC-Cl modification also exhibit better stability. This work highlights the importance of surface regulation via carboxylate polymer for further enhancing the performance of CsPbI2Br PSCs.

Polymer Based on Asymmetrically Halogenated Benzotriazole Enables High Performance Organic Solar Cells Prepared in Nonhalogenated Solvent.

Halogenation on the A unit of the D-π-A-type polymer donor has been proven as an effective strategy to improve the performance of organic solar cells (OSCs). Compared with fluorination, chlorination usually increases the open-circuit voltage because of the downward shift of energy levels, but decreases the charge transport ability due to the large steric hindrance of the chlorine atom. We reported herein a method to balance the energy loss and charge transport through asymmetric halogenation on the benzotriazole (BTA) unit of the polymer. The designed PE3-FCl based on the BTA unit containing fluorine and chlorine atoms rendered the highest power conversion efficiency (PCE) of 17.83% when eC9-2Cl-γ and o-xylene were used as the electron acceptor and solvent, respectively. The performance is obviously higher than that of the polymer PE3 containing a difluorinated BTA unit (16.65%) and polymer PE3-2Cl with dichlorinated BTA (14.65%) due to the manipulated morphology by preaggregation, improved and more balanced charge carrier transport, and reduced recombination loss. Notably, this PCE is a breakthrough for the BTA-based polymers processed by nonhalogenated solvent. This work gives deep insight into the asymmetric halogenation of polymer donors for high-performance green solvent-processed OSCs.

Selenophene-fused Perylene Diimide-Based Cathode Interlayer Enables 19 % Efficiency Binary Organic Solar Cells via Stimulative Charge Extraction.

The cathode interlayer is crucial for the development of organic solar cells (OSCs), but the research on simple and efficient interlayer materials is lagging behind. Here, a donor-acceptor (D-A) typed selenophene-fused perylene diimide (PDI) derivative (SePDI3) is developed as cathode interlayer material (CIM) for OSCs, and a non-fused PDI derivative (PDI3) is used as the control CIM for comparison. Compared to PDI3, SePDI3 shows a stronger self-doping effect and better crystallinity, resulting in better charge transport ability. Furthermore, the interaction between SePDI3 and L8-BO can form an efficient extraction channel, leading to superior charge extraction behavior. Finally, benefitting from significantly enhanced charge transport and extraction capacity, the SePDI3-based device displays a champion PCE of 19.04 % with an ultrahigh fill factor of 81.65 % for binary OSCs based on PM6 : L8-BO active layer, which is one of the top efficiencies reported to date in binary OSCs based novel CIMs. Our work prescribes a facile and effective fusion strategy to develop high-efficiency CIMs for OSCs.

Application Prospect of Ion-Imprinted Polymers in Harmless Treatment of Heavy Metal Wastewater.

With the rapid development of industry, the discharge of heavy metal-containing wastewater poses a significant threat to aquatic and terrestrial environments as well as human health. This paper provides a brief introduction to the basic principles of ion-imprinted polymer preparation and focuses on the interaction between template ions and functional monomers. We summarized the current research status on typical heavy metal ions, such as Cu(II), Ni(II), Cd(II), Hg(II), Pb(II), and Cr(VI), as well as metalloid metal ions of the As and Sb classes. Furthermore, it discusses recent advances in multi-ion-imprinted polymers. Finally, the paper addresses the challenges faced by ion-imprinted technology and explores its prospects for application.

Dithienoquinoxalineimide-Based Polymer Donor Enables All-Polymer Solar Cells Over 19 % Efficiency.

All-polymer solar cells (all-PSCs) have been regarded as one of the most promising candidates for commercial applications owing to their outstanding advantages such as mechanical flexibility, light weight and stable film morphology. However, compared to large amount of new-emerging excellent polymer acceptors, the development of high-performance polymer donor lags behind. Herein, a new D-π-A type polymer donor, namely QQ1, was developed based on dithienoquinoxalineimide (DTQI) as the A unit, benzodithiophene with thiophene-conjugated side chains (BDTT) as the D unit, and alkyl-thiophene as the π-bridge, respectively. QQ1 not only possesses a strong dipole moment, but also shows a wide band gap of 1.80 eV and a deep HOMO energy level of -5.47 eV, even without halogen substituents that are commonly indispensable for high-performance polymer donors. When blended with a classic polymer acceptor PY-IT, the QQ1-based all-PSC delivers an outstanding PCE of 18.81 %. After the introduction of F-BTA3 as the third component, a record PCE of 19.20 % was obtained, the highest value reported so far for all-PSCs. The impressive photovoltaic performance originates from broad absorption range, reduced energy loss, and compact π-π stacking. These results provide new insight in the rational design of novel nonhalogenated polymer donors for further development of all-PSCs.

Noncovalent Interaction Boosts Performance and Stability of Organic Solar Cells Based on Giant-Molecule Acceptors.

Designing giant-molecule acceptors is deemed as an up-and-coming strategy to construct stable organic solar cells (OSCs) with high performance. Herein, two giant dimeric acceptors, namely, DYV and DYFV, have been designed and synthesized by linking two Y-series derivatives with a vinyl unit. DYFV exhibits more red-shifted absorption, down-shifted energy levels, and enhanced intermolecular packing than DYV because the intramolecular noncovalent interaction (H···F) of DYFV leads to better coplanarity of the backbone. The D18:DYFV film owns a distinct nanofibrous nanophase separation structure, a more dominant face-on orientation, and more balanced carrier mobilities. Therefore, the D18:DYFV OSC achieves a higher photoelectron conversion efficiency of 17.88% and a longer-term stability with a t80 over 45,000 h compared with the D18:DYV device. The study demonstrates that the intramolecular noncovalent interaction is a superior strategy to design giant-molecule acceptors and boost the photovoltaic performance and stability of the OSCs.

Benzotriazole-Based 3D Four-Arm Small Molecules Enable 19.1 % Efficiency for PM6 : Y6-Based Ternary Organic Solar Cells.

A third component featuring a planar backbone structure similar to the binary host molecule has been the preferred ingredient for improving the photovoltaic performance of ternary organic solar cells (OSCs). In this work, we explored a new avenue that introduces 3D-structured molecules as guest acceptors. Spirobifluorene (SF) is chosen as the core to combine with three different terminal-modified (rhodanine, thiazolidinedione, and dicyano-substituted rhodanine) benzotriazole (BTA) units, affording three four-arm molecules, SF-BTA1, SF-BTA2, and SF-BTA3, respectively. After adding these three materials to the classical system PM6 : Y6, the resulting ternary devices obtained ultra-high power-conversion efficiencies (PCEs) of 19.1 %, 18.7 %, and 18.8 %, respectively, compared with the binary OSCs (PCE=17.4 %). SF-BTA1-3 can work as energy donors to increase charge generation via energy transfer. In addition, the charge transfer between PM6 and SF-BTA1-3 also acts to enhance charge generation. Introducing SF-BTA1-3 could form acceptor alloys to modify the molecular energy level and inhibit the self-aggregation of Y6, thereby reducing energy loss and balancing charge transport. Our success in 3D multi-arm materials as the third component shows good universality and brings a new perspective. The further functional development of multi-arm materials could make OSCs more stable and efficient.

Recent Advances in Organic Photovoltaic Materials Based on Thiazole-Containing Heterocycles.

Organic solar cells (OSCs) have achieved great progress, driven by the rapid development of wide bandgap electron donors and narrow bandgap non-fullerene acceptors (NFAs). Among a large number of electron-accepting (A) building blocks, thiazole (Tz) and its derived fused heterocycles have been widely used to construct photovoltaic materials, especially conjugated polymers. Benefiting from the electron deficiency, rigidity, high planarity, and enhanced intra/intermolecular interactions of Tz-containing heterocycles, some related photovoltaic materials exhibit proper energy levels, optimized molecular aggregation, and active layer morphology, leading to excellent photovoltaic performance. This review focuses on the progress of Tz-based photovoltaic materials in the field of OSCs. First, the Tz-based donor and acceptor photovoltaic materials are reviewed. Then, the materials based on promising Tz-containing heterocycles, mainly including thiazolo[5,4-d]thiazole (TzTz), benzo[1,2-d:4,5-d']bis(thiazole) (BBTz), and benzo[d]thiazole (BTz) are summarized and discussed. In addition, the new emerging Tz-fused structures and their application in OSCs are introduced. Finally, perspectives and outlooks for the further development of Tz-containing heterocycle-based photovoltaic materials are proposed.

Dithienobenzothiadiazole (DTBT)-Based Polymers Enable Organic Solar Cells with Ultrahigh VOC of ≈1.3 V.

Dithieno[3',2':3,4;2",3":5,6]benzo[1,2-c][1,2,5]thiadiazole (DTBT) is a newly emerging building block to construct effective photovoltaic polymers. Organic solar cells (OSCs) based on DTBT-based polymers have realized power conversion efficiency (PCEs) over 18%, despite their relatively low open-circuit voltage (VOC ) of 0.8-0.95 V. To extend the application of DTBT-based polymers in high-voltage OSCs, herein, D18-Cl and PE55 are used to combine with a wide-bandgap non-fullerene acceptor (NFA), BTA3, and achieve ultrahigh VOC of 1.30 and 1.28 V, respectively. Compared with D18-Cl based on tricyclic benzodithiophene (BDT) segment, PE55 containing the pentacyclic dithienobenzodithiophene (DTBDT) unit possesses better hole mobility, higher charge-transfer efficiency, and more desirable phase separation. Hence, PE55:BTA3 blend exhibits a higher efficiency of 9.36% than that of D18-Cl: BTA3 combination (6.30%), which is one of the highest values for OSCs at ≈1.3 V VOC . This work attests that DTBT-based p-type polymers are ideal for the application in high-voltage OSCs.

Multiple-cation wide-bandgap perovskite solar cells grown using cesium formate as the Cs precursor with high efficiency under sunlight and indoor illumination.

Owing to the advantages of adjustable bandgap, low-cost fabrication and superior photovoltaic performance, wide-bandgap (WBG) perovskite solar cells (PSCs) are considered as the promising top-cell for multi-junction solar cells. At the same time, WBG PSCs have also shown great potential for indoor photovoltaic applications. To further improve the performance of WBG PSCs, in this work, we fabricated efficient WBG PSCs via introducing cesium formate (CsFa) as the Cs precursor. Due to the HCOO·Pb+ and HCOOH·Cs+ complex formation and HCOOH volatilization accompanying the crystallization process, the crystallization of the perovskite using the CsFa precursor (CsFa-perovskite) is promoted. Compared to the perovskite prepared using the CsBr precursor (CsBr-perovskite), the WBG CsFa-perovskite shows better perovskite crystallization, reduced trap-state density, and better phase stability under light illumination. Finally, the 1.63 eV WBG PSCs based on the CsFa-perovskite achieve a significant PCE of 20.01% under one sun illumination (AM 1.5G, 100 mW cm-2), which is higher than that of PSCs based on the CsBr-perovskite (18.27%). Moreover, the PCE of CsFa-perovskite PSCs also under indoor warm-white 2700 K LED light illumination (1000 lux) is as high as 38.52%. Our results demonstrate that CsFa as the Cs precursor is a promising candidate to promote the device performance of WBG PSCs.

Side-chain engineering of copolymers based on benzotriazole (BTA) and dithieno[2,3-d;2',3'-d']benzo[1,2-b;4,5-b']dithiophenes (DTBDT) enables a high PCE of 14.6.

Dithieno[2,3-d;2',3'-d']benzo[1,2-b;4,5-b']dithiophenes (DTBDT) is a kind of prospective candidate for constructing donor-π-acceptor (D-π-A) copolymer donors applied in organic solar cells but is restricted due to its relatively poor photovoltaic performance compared with benzo[1,2-b;4,5-b']dithiophenes (BDT)-based analog. Herein, three conjugated polymers (PE51,PE52andPE53)-based DTBDT and benzo[d][1,2,3]triazole (BTA) bearing different lengths of alkyl side chain were designed and synthesized. The change in alkyl chain length can obviously affect the energy level distribution, molecular stacking, miscibility and morphology with the non-fullerene acceptor ofY6. PolymerPE52with a moderate alkyl chain realized the highest short-current density (JSC) and fill factor (FF) of 25.36 mA cm-2and 71.94%, respectively. Compared with BDT-based analogJ52-Cl, the significantly enhanced crystallinity and intermolecular interaction ofPE52had effectively boosted the charge transport characteristic and optimized the surface morphology, thereby increasing the power conversion efficiency from 12.3% to an impressive 14.6%, which is the highest value among DTBDT-based and BTA-based polymers. Our results show that not only could high efficiency be achieved via using DTBDT as a D unit, but the length of the alkyl chain on BTA has a significant impact on the photovoltaic performance.

Effects of Oxygen Atoms Introduced at Different Positions of Non-Fullerene Acceptors in the Performance of Organic Solar Cells with Poly(3-hexylthiophene).

With the development of large-area fabrication technologies for organic solar cells (OSCs), poly(3-hexylthiophene) (P3HT) is the best choice as a photovoltaic donor polymer because it can be easily synthesized in the scale of kilograms at low cost. However, non-fullerene acceptors (NFAs) matching with P3HT for high performance OSCs are very rare. Herein, by introducing oxygen atoms into the side chains or the fused-ring core of indaceno[1,2-b:5,6-b']dithiophene, we synthesized two new A2-A1-D-A1-A2 type NFAs, where benzotriazole (BTA) and 2-(1,1-dicyanomethylene)rhodanine were used as the bridged A1 and terminal A2, respectively. The final NFAs, named BTA43 and BTA53, show wider absorption spectra and enhanced intermolecular/intramolecular interaction in comparison with their analogue BTA3 without oxygen atoms. The photovoltaic devices based on P3HT:BTA43 and P3HT:BTA53 can achieve a high power conversion efficiency of 6.56 and 6.31%, respectively, which are obviously higher than that of BTA3 (5.64%). Our results provide a simple and effective strategy to design promising NFAs to pair with the classic photovoltaic polymer P3HT.

High-Performance Inverted Planar Perovskite Solar Cells Enhanced by Thickness Tuning of New Dopant-Free Hole Transporting Layer.

A new hole transporting material (HTM) named DMZ is synthesized and employed as a dopant-free HTM in inverted planar perovskite solar cells (PSCs). Systematic studies demonstrate that the thickness of the hole transporting layer can effectively enhance the morphology and crystallinity of the perovskite layer, leading to low series resistance and less defects in the crystal. As a result, the champion power conversion efficiency (PCE) of 18.61% with JSC = 22.62 mA cm-2 , VOC = 1.02 V, and FF = 81.05% (an average one is 17.62%) is achieved with a thickness of ≈13 nm of DMZ (2 mg mL-1 ) under standard global AM 1.5 illumination, which is ≈1.5 times higher than that of devices based on poly(3,4-ethylenedioxythiophene)/poly(styrene sulfonic acid) (PEDOT:PSS). More importantly, the devices based on DMZ exhibit a much better stability (90% of maximum PCE retained after more than 556 h in air (relative humidity ≈ 45%-50%) without any encapsulation) than that of devices based on PEDOT:PSS (only 36% of initial PCE retained after 77 h in same conditions). Therefore, the cost-effective and facile material named DMZ offers an appealing alternative to PEDOT:PSS or polytriarylamine for highly efficient and stable inverted planar PSCs.

Fluorination Triggered New Small Molecule Donor Materials for Efficient As-Cast Organic Solar Cells.

Solution-processable small molecules (SMs) have attracted intense attention due to their definite molecular structures, less batch-to-batch variation, and easier structure control. Herein, two new SM donors based on substituted isatin unit (DI3T, DI3T-2F) are synthesized and applied as electron donors with the mixture of PC71 BM to construct organic photovoltaics. As a result, 5,6-difluoro isatin derivative (DI3T-2F) obtains a power conversion efficiency of 7.80% by a simple solution spin-coating fabrication process without any additives, solvent, or thermal annealing process. More intuitively, due to stronger intermolecular interaction and higher hole mobility after the incorporation of fluorine atoms in end units, the devices present good tolerance to active layer thickness. The results indicate that DI3T-2F shows promising potential for large-scale printing processes and flexible application of efficient small molecule organic solar cells.

Impact of over distraction on occurrence of axial symptom after anterior cervical discectomy and fusion.

OBJECTIVE: A retrospective review was undertaken to evaluate the impact of over distraction on cervical axial symptoms (AS) after anterior cervical discectomy and fusion (ACDF). METHODS: The retrospective review included 421 patients who underwent ACDF for one or two segments. Of these, 78 patients for whom complete follow-up data were available were selected for inclusion in the analysis. X-rays of the cervical vertebra were performed immediately after the surgery, 3 months postsurgery, and at a final follow up (6-24 months). According to the presence/absence of AS, the patients were divided into a symptom group (Group S) and a nonsymptom group (Group N). The ratio of intervertebral height change, change in the overall cervical curvature, change in the local curvature of the surgical segment, cervical total range of motion (ROM), and Japanese Orthopaedic Association (JOA) recovery rate were compared and analyzed. A linear regression analysis of the ratio of intervertebral height change and the symptom and severity of the AS according to the Visual Analogue Scale (VAS) was carried out. RESULTS: The total incidence of AS was 33.97%. C5 nerve root palsy occurred in one case in Group S after the surgery. The neurologic symptoms of both groups were significantly alleviated after the surgery. The ratio of intervertebral height change in Group S was significantly higher than that in Group N at the last follow-up (P < 0.05). However, the changes in the overall cervical curvature, local curvature of the surgical segment, cervical ROM, and JOA recovery rates were not statistically significant (P > 0.05). In Group S, 37% of the patients had symptoms that occurred in the chest area, and the ratio of intervertebral height change was significantly positively correlated with the VAS score of the AS (r = 0.893). CONCLUSIONS: The occurrence of postoperative AS will significantly increase if the ratio of intervertebral height change of the surgical segment after ACDF is over 10%.