Halogenated 9H-Indeno[1,2-b]Pyrazine-2,3-Dicarbonitrile End Groups Based Asymmetric Non-Fullerene Acceptors for Green Solvent-Processable, Additive-Free, and Stable Organic Solar Cells.

Non-fullerene acceptors (NFAs) significantly enhance photovoltaic performance in organic solar cells (OSCs) using halogenated solvents and additives. However, these solvents are environmentally detrimental and unsuitable for industrial-scale production, and the issue of OSCs' poor long-term stability persists. This report introduces eight asymmetric NFAs (IPCnF-BBO-IC2F, IPCnF-BBO-IC2Cl, IPCnCl-BBO-IC2F, and IPCnCl-BBO-IC2Cl, where n = 1 and 2). These NFAs comprise a 12,13-bis(2-butyloctyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2'',3'':4',5']thieno[2',3':4,5]pyrrolo[3,2-g]thieno[2',3':4,5]thieno-[3,2-b]indole (BBO) core. One end of the core attaches to a mono- or di-halogenated 9H-indeno[1,2-b]pyrazine-2,3-dicarbonitrile (IPC) end group (IPC1F, IPC1Cl, IPC2F, or IPC2Cl), while the other end connects to a 2-(5,6-dihalo-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (IC) end group (IC2F or IC2Cl). The optical and electronic properties of these NFAs can be finely tuned by controlling the number of halogen atoms. Crucially, these NFAs demonstrate excellent compatibility with PM6 even in o-xylene, facilitating the production of additive-free OSCs. The di-halogenated IPC-based NFAs outperform their mono-halogenated counterparts in photovoltaic performance within OSCs. Remarkably, the di-halogenated IPC-based NFAs maintain 94‒98% of their initial PCEs over 2000 h in air without encapsulation, indicating superior long-term device stability. These findings imply that the integration of di-halogenated IPCs in asymmetric NFA design offers a promising route to efficient, stable OSCs manufactured through environmentally friendly processes.

γ-Ray Irradiation Enables Annealing- and Light-Soaking-Free Solution Processable SnO2 Electron Transport Layer for Inverted Organic Solar Cells.

The electrode buffer layer is crucial for high-performance and stable OSCs, optimizing charge transport and energy level alignment at the interface between the polymer active layer and electrode. Recently, SnO2 has emerged as a promising material for the cathode buffer layer due to its desirable properties, such as high electron mobility, transparency, and stability. Typically, SnO2 nanoparticle layers require a postannealing treatment above 150°C in an air environment to remove the surfactant ligands and obtain high-quality thin films. However, this poses challenges for flexible electronics as flexible substrates can't tolerate temperatures exceeding 100°C. This study presents solution-processable and annealing-free SnO2 nanoparticles by employing y-ray irradiation to disrupt the bonding between surfactant ligands and SnO2 nanoparticles. The SnO2 layer treated with y-ray irradiation is used as an electron transport layer in OSCs based on PTB7-Th:IEICO-4F. Compared to the conventional SnO2 nanoparticles that required high-temperature annealing, the y-SnO2 nanoparticle-based devices exhibit an 11% comparable efficiency without postannealing at a high temperature. Additionally, y-ray treatment has been observed to eliminate the light-soaking effect of SnO2 . By eliminating the high-temperature postannealing and light-soaking effect, y-SnO2 nanoparticles offer a promising, cost-effective solution for future flexible solar cells fabricated using roll-to-roll mass processing.

Simplified Y6-Based Nonfullerene Acceptors: In-Depth Study on Molecular Structure-Property Relation, Molecular Dynamics Simulation, and Charge Dynamics.

Two new Y6 derivatives of symmetrical YBO-2O and asymmetrical YBO-FO nonfullerene acceptors (NFAs) are prepared with a simplified synthetic procedure by incorporating octyl and fluorine substituents onto the terminal 2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (INCN) moiety. By moving the alkyl substituents on the Y6 core to the terminal INCN moiety, the lowest unoccupied molecular orbital of the YBO NFAs increases without decreasing solubility, resulting in high open-circuit voltages of the devices. Molecular dynamics simulation shows that YBO-2O/-FO preferentially form core-core and terminal-terminal dimeric interactions, demonstrating their tighter packing structure and higher electron mobility than Y6, which is consistent with 2D grazing incidence X-ray scattering and space charge limited current measurements. In blend films, the hole transfer (HT) from YBO-2O/-FO to the polymer donor PM6 is studied in detail by transient absorption spectroscopy, demonstrating efficient HT from YBO-FO to PM6 with their suitable energy level alignment. Despite the simplified synthesis, YBO-FO demonstrates photovoltaic performance similar to that of Y6, exhibiting a power conversion efficiency of 15.01%. Overall, this design strategy not only simplifies the synthetic procedures but also adjusts the electrical properties by modifying the intermolecular packing and energy level alignment, suggesting a novel simplified molecular design of Y6 derivatives.

Inverted Polymer Solar Cells with Annealing-Free Solution-Processable NiO.

Nickel oxide (NiO) offers intrinsic p-type behavior and high thermal and chemical stability, making it promising as a hole transport layer (HTL) material in inverted organic solar cells. However, its use in this application has been rare because of a wettability problem caused by use of water as base solvent and high-temperature annealing requirements. In the present work, an annealing-free solution-processable method for NiO deposition is developed and applied in both conventional and inverted non-fullerene polymer solar cells. To overcome the wettability problem, the typical DI water solvent is replaced with a mixed solvent of DI water and isopropyl alcohol with a small amount of 2-butanol additive. This allows a NiO nanoparticle suspension (s-NiO) to be deposited on a hydrophobic active layer surface. An inverted non-fullerene solar cell based on a blend of p-type polymer PTB7-Th and non-fullerene acceptor IEICO-4F exhibits the high efficiency of 11.23% with an s-NiO HTL, comparable to the efficiency of an inverted solar cell with a MoOx HTL deposited by thermal evaporation. Conventionally structured devices including this s-NiO layer show efficiency comparable to that of a conventional device with a PEDOT:PSS HTL.

Controlled Crystal Growth of All-Inorganic CsPbI2Br via Sequential Vacuum Deposition for Efficient Perovskite Solar Cells.

Vacuum deposition of perovskites is a promising method for scale-up fabrication and uniform film growth. However, improvements in the photovoltaic performance of perovskites are limited by the fabrication of perovskite films, which are not optimized for high device efficiency in the vacuum evaporation process. Herein, we fabricate CsPbI2Br perovskite with high crystallinity and larger grain size by controlling the deposition sequence between PbI2 and CsBr. The nucleation barrier for perovskite formation is significantly lowered by first evaporating CsBr and then PbI2 (CsBr-PbI2), followed by the sequential evaporation of multiple layers. The results show that the reduced Gibbs free energy of CsBr-PbI2, compared with that of PbI2-CsBr, accelerates perovskite formation, resulting in larger grain size and reduced defect density. Furthermore, surface-modified homojunction perovskites are fabricated to efficiently extract charge carriers and enhance the efficiency of perovskite solar cells (PeSCs) by modulating the final PbI2 thickness before thermal annealing. Using these strategies, the best PeSC exhibits a power conversion efficiency of 13.41% for a small area (0.135 cm2), the highest value among sequential thermal deposition inorganic PeSCs, and 11.10% for a large area PeSC (1 cm2). This study presents an effective way to understand the crystal growth of thermally deposited perovskites and improve their performance in optoelectronic devices.

Enhancing Performance and Stability of Sn-Pb Perovskite Solar Cells with Oriented Phenyl-C61-Butyric Acid Methyl Ester Layer via High-Temperature Annealing.

Phenyl-C61-butyric acid methyl ester (PCBM) can be used as a passivation material in perovskite solar cells (PeSCs) in order to reduce the trap site of the perovskite. Here, we show that a thick PCBM layer can form a smoother surface on the SnO2 substrate, improving the grain size and reducing the microstrain of the perovskite. High-temperature annealing treatment of PCBM layer not only increases its solvent resistance to perovskite precursor or antisolvent, but also enhances its molecular alignment, resulting in improved conductivity as an electron transport layer. High-temperature annealed PCBM (HT-PCBM) effectively minimizes trap-assisted nonradiative recombination by reducing trap density in perovskite and improving the electrical properties at the interface between SnO2 and perovskite layers. This HT-PCBM process significantly enhances the performance of the PeSCs, including the open-circuit voltage (VOC) from 0.39 to 0.77 V, fill factor from 52% to 65%, and power conversion efficiency (PCE) from 6.03% to 15.50%, representing substantial improvements compared to devices without PCBM. This PCE is the highest efficiency among conventional (n-i-p) Sn-Pb PeSCs reported to date. Moreover, passivating the trap sites of SnO2 and separating the interface between the Sn-containing perovskite and the substrate effectively have improved the stability of the Sn-Pb perovskite in the n-i-p structure. The optimized best device with HT-PCBM has maintained an efficiency of over 90% for more than 300 h at 85 °C and 5000 h at room temperature in a glovebox atmosphere.

High-Performance Organic Electrochemical Transistors Achieved by Optimizing Structural and Energetic Ordering of Diketopyrrolopyrrole-Based Polymers.

For optimizing steady-state performance in organic electrochemical transistors (OECTs), both molecular design and structural alignment approaches must work in tandem to minimize energetic and microstructural disorders in polymeric mixed ionic-electronic conductor films. Herein, a series of poly(diketopyrrolopyrrole)s bearing various lengths of aliphatic-glycol hybrid side chains (PDPP-mEG; m = 2-5) is developed to achieve high-performance p-type OECTs. PDPP-4EG polymer with the optimized length of side chains exhibits excellent crystallinity owing to enhanced lamellar and backbone interactions. Furthermore, the improved structural ordering in PDPP-4EG films significantly decreases trap state density and energetic disorder. Consequently, PDPP-4EG-based OECT devices produce a mobility-volumetric capacitance product ([µC*]) of 702 F V-1 cm-1 s-1 and a hole mobility of 6.49 ± 0.60 cm2 V-1 s-1 . Finally, for achieving the optimal structural ordering along the OECT channel direction, a floating film transfer method is employed to reinforce the unidirectional orientation of polymer chains, leading to a substantially increased figure-of-merit [µC*] to over 800 F V-1 cm-1 s-1 . The research demonstrates the importance of side chain engineering of polymeric mixed ionic-electronic conductors in conjunction with their anisotropic microstructural optimization to maximize OECT characteristics.

Improved photovoltaic performance and stability of perovskite solar cells by adoption of an n-type zwitterionic cathode interlayer.

Recently, inverted perovskite solar cells (PeSCs) have witnessed significant advancements; however, their long-term stability remains a challenge because of the oxidation of silver cathodes to form AgI by mobile iodides. To overcome this problem, we propose the integration of an electron-deficient naphthalene diimide-based zwitterion (NDI-ZI) as the cathode interlayer. Compared to the physical ion-blocking layer, it effectively captures ions by forming ionic bonds via electrostatic Coulombic interaction to suppress the migration of iodide and Ag ions. The NDI-ZI interlayer also suppresses the shunt paths and modulates the work function of the Ag electrode by forming interface dipoles, thereby enhancing charge extraction. FA0.85Cs0.15PbI3 based PeSCs incorporating NDI-ZI exhibited a noticeably high power conversion efficiency of up to 23.3% and outstanding stability, maintaining ∼80% of their initial performance over 1500 h at 85 °C and over 500 h under continuous 1-sun illumination. This study highlights the potential of a zwitterionic cathode interlayer in diverse perovskite optoelectronic devices, leading to their improved efficiency and stability.

Isoindigo-based small molecules for high-performance solution-processed organic photovoltaic devices: the electron donating effect of the donor group on photo-physical properties and device performance.

Five solution processable isoindigo-based donor-acceptor-donor (D-A-D) small molecules with different electron donating strengths have been designed and synthesized. The variation in the electron donating strength of the donor group strongly affected the optical, thermal, electrochemical and photovoltaic device performances of the isoindigo organic materials. The highest power conversion efficiency of ~3.2% was achieved in the bulk heterojunction photovoltaic device consisting of ID3T as the donor and PC70BM as the acceptor. This work demonstrates the potential of isoindigo moieties as electron-deficient units and presents guidelines for the synthesis of D-A-D small molecules for producing highly efficient, solution-processed organic photovoltaic devices.

Asymmetric Polymer Additive for Morphological Regulation and Thermally Stable Organic Solar Cells.

High thermal stability is crucial for the commercialization of organic solar cells (OSCs). The thermal stability of OSCs has been improved using the tailoring blend morphology of bulk heterojunctions (BHJs). Herein, we demonstrated thermally stable OSCs in a ternary blended system containing low-crystalline semiconducting polymers (asy-PNDI1FTVT and PTB7-Th) and a non-fullerene acceptor (Y6). The asymmetric n-type semiconducting polymer (asy-PNDI1FTVT) differed from general symmetric semiconducting polymers as it randomly substituted fluorine atoms at the donor moiety (TVT), resulting in significantly lower crystallinity. asy-PNDI1FTVT in PTB7-Th:Y6 exhibited a well-mixed morphology at the BHJ and efficiently facilitated the charge dissociation process with an enhanced fill factor and power conversion efficiency. Furthermore, the ternary system of PTB7-Th:Y6:asy-PNDI1FTVT suppressed phase separation with negligible burn-in loss and performance degradation under thermal stress. The experiments showed that our devices without encapsulation retained over 90% of their initial efficiencies after 100 h at 65 °C. These results show significant potential for the development of thermally stable OSCs with reasonable efficiency.

Efficient and Moisture-Stable Inverted Perovskite Solar Cells via n-Type Small-Molecule-Assisted Surface Treatment.

Defect states at the surface and grain boundaries of perovskite films have been known to be major determinants impairing the optoelectrical properties of perovskite films and the stability of perovskite solar cells (PeSCs). Herein, an n-type conjugated small-molecule additive based on fused-unit dithienothiophen[3,2-b]-pyrrolobenzothiadiazole-core (JY16) is developed for efficient and stable PeSCs, where JY16 possesses the same backbone as the widely used Y6 but with long-linear n-hexadecyl side chains rather than branched side chains. Upon introducing JY16 into the perovskite films, the electron-donating functional groups of JY16 passivate defect states in perovskite films and increase the grain size of perovskite films through Lewis acid-base interactions. Compared to Y6, JY16 exhibits superior charge mobility owing to its molecular packing ability and prevents decomposition of perovskite films under moisture conditions owing to their hydrophobic characteristics, improving the charge extraction ability and moisture stability of PeSCs. Consequently, the PeSC with JY16 shows a high power conversion efficiency of 21.35%, which is higher than those of the PeSC with Y6 (20.12%) and without any additive (18.12%), and outstanding moisture stability under 25% relative humidity, without encapsulation. The proposed organic semiconducting additive will prove to be crucial for achieving highly efficient and moisture stable PeSCs.

Poly(dimethylsiloxane)-block-PM6 Polymer Donors for High-Performance and Mechanically Robust Polymer Solar Cells.

High power conversion efficiency (PCE) and stretchability are the dual requirements for the wearable application of polymer solar cells (PSCs). However, most efficient photoactive films are mechanically brittle. In this work, highly efficient (PCE = 18%) and mechanically robust (crack-onset strain (COS) = 18%) PSCs are acheived by designing block copolymer (BCP) donors, PM6-b-PDMSx (x = 5k, 12k, and 19k). In these BCP donors, stretchable poly(dimethylsiloxane) (PDMS) blocks are covalently linked with the PM6 blocks to effectively increase the stretchability. The stretchability of the BCP donors increases with a longer PDMS block, and PM6-b-PDMS19k :L8-BO PSC exhibits a high PCE (18%) and 9-times higher COS value (18%) compared to that (COS = 2%) of the PM6:L8-BO-based PSC. However, the PM6:L8-BO:PDMS12k ternary blend shows inferior PCE (5%) and COS (1%) due to the macrophase separation between PDMS and active components. In the intrinsically stretchable PSC, the PM6-b-PDMS19k :L8-BO blend exhibits significantly greater mechanical stability PCE80% ((80% of the initial PCE) at 36% strain) than those of the PM6:L8-BO blend (PCE80% at 12% strain) and the PM6:L8-BO:PDMS ternary blend (PCE80% at 4% strain). This study suggests an effective design strategy of BCP PD to achieve stretchable and efficient PSCs.

An Efficient Green Approach to Constructing Adenine Sulfate-Derived Multicolor Sulfur- and Nitrogen-Codoped Carbon Dots and Their Bioimaging Applications.

A cost-effective and environmentally friendly approach is proposed for producing N- and S-codoped multicolor-emission carbon dots (N- and S-codoped MCDs) at a mild reaction temperature (150 °C) and relatively short time (3 h). In this process, adenine sulfate acts as a novel precursor and doping agent, effectively reacting with other reagents such as citric acid, para-aminosalicylic acid, and ortho-phenylenediamine, even during solvent-free pyrolysis. The distinctive structures of reagents lead to the increased amount of graphitic nitrogen and sulfur doping in the N- and S-codoped MCDs. Notably, the obtained N- and S-codoped MCDs exhibit considerable fluorescence intensities, and their emission color can be adjusted from blue to yellow. The observed tunable photoluminescence can be attributed to variations in the surface state and the amount of N and S contents. Furthermore, due to the favorable optical properties, good water solubility and biocompatibility, and low cytotoxicity, these N- and S-codoped MCDs, especially green carbon dots, are successfully applied as fluorescent probes for bioimaging. The affordable and environmentally friendly synthesis method employed to create N- and S-codoped MCDs, combined with their remarkable optical properties, offers a promising avenue for their use in various fields, particularly in biomedical applications.

Investigation of Hole-Transfer Dynamics through Simple EL De-Convolution in Non-Fullerene Organic Solar Cells.

In conventional fullerene-based organic photovoltaics (OPVs), in which the excited electrons from the donor are transferred to the acceptor, the electron charge transfer state (eECT) that electrons pass through has a great influence on the device's performance. In a bulk-heterojunction (BHJ) system based on a low bandgap non-fullerene acceptor (NFA), however, a hole charge transfer state (hECT) from the acceptor to the donor has a greater influence on the device's performance. The accurate determination of hECT is essential for achieving further enhancement in the performance of non-fullerene organic solar cells. However, the discovery of a method to determine the exact hECT remains an open challenge. Here, we suggest a simple method to determine the exact hECT level via deconvolution of the EL spectrum of the BHJ blend (ELB). To generalize, we have applied our ELB deconvolution method to nine different BHJ systems consisting of the combination of three donor polymers (PM6, PBDTTPD-HT, PTB7-Th) and three NFAs (Y6, IDIC, IEICO-4F). Under the conditions that (i) absorption of the donor and acceptor are separated sufficiently, and (ii) the onset part of the external quantum efficiency (EQE) is formed solely by the contribution of the acceptor only, ELB can be deconvoluted into the contribution of the singlet recombination of the acceptor and the radiative recombination via hECT. Through the deconvolution of ELB, we have clearly decided which part of the broad ELB spectrum should be used to apply the Marcus theory. Accurate determination of hECT is expected to be of great help in fine-tuning the energy level of donor polymers and NFAs by understanding the charge transfer mechanism clearly.

Freestanding Oxide Membranes for Epitaxial Ferroelectric Heterojunctions.

Since facile routes to fabricate freestanding oxide membranes were previously established, tremendous efforts have been made to further improve their crystallinity, and fascinating physical properties have been also reported in heterointegrated freestanding membranes. Here, we demonstrate our synthetic recipe to manufacture highly crystalline perovskite SrRuO3 freestanding membranes using new infinite-layer perovskite SrCuO2 sacrificial layers. To accomplish this, SrRuO3/SrCuO2 bilayer thin films are epitaxially grown on SrTiO3 (001) substrates, and the topmost SrRuO3 layer is chemically exfoliated by etching the SrCuO2 template layer. The as-exfoliated SrRuO3 membranes are mechanically transferred to various nonoxide substrates for the subsequent BaTiO3 film growth. Finally, freestanding heteroepitaxial junctions of ferroelectric BaTiO3 and metallic SrRuO3 are realized, exhibiting robust ferroelectricity. Intriguingly, the enhancement of piezoelectric responses is identified in freestanding BaTiO3/SrRuO3 heterojunctions with mixed ferroelectric domain states. Our approaches will offer more opportunities to develop heteroepitaxial freestanding oxide membranes with high crystallinity and enhanced functionality.

Build-up of symmetry breaking using a titanium suboxide in bulk-heterojunction solar cells.

The importance of symmetry breaking was investigated in bulk heterojunction solar cells with a conventional device structure. Artificial symmetry breaking was built up by introducing a titanium suboxide. With sufficient symmetry breaking, the influence of the cathode work-function can be diminished, thereby extracting the same level of open circuit voltage regardless of metal work-function.

Metallic transport in polyaniline.

Despite nearly three decades of materials development, the transport properties in the 'metallic state' of the so-called conducting polymers are still not typical of conventional metals. The hallmark of metallic resistivity--a monotonic decrease in resistivity with temperature--has not been obtained at temperatures over the full range below room temperature; and a frequency dependent conductivity, sigma(omega), typical of metals has also not been observed. In contrast, the low-temperature behaviour of 'metallic' polymers has, in all previous cases, exhibited an increase in resistivity as temperature is further decreased, as a result of disorder-induced localization of the charge carriers. This disorder-induced localization also changes the infrared response such that sigma(omega) deviates from the prediction of Drude theory. Here we report classic metallic transport data obtained from truly metallic polymers. With polyaniline samples prepared using self-stabilized dispersion polymerization, we find that for samples having room-temperature conductivities in excess of 1,000 S cm(-1), the resistivity decreases monotonically as the temperature is lowered down to 5 K, and that the infrared spectra are characteristic of the conventional Drude model even at the lowest frequencies measured.

Symmetry-Induced Ordered Assembly of a Naphthobisthiadiazole-Based Nonfused-Ring Electron Acceptor Enables Efficient Organic Solar Cells.

Nonfused-ring electron acceptors (NFREAs) have received increasing attention for use in organic solar cells (OSCs) because of their synthetic simplicity and tunable optical spectra. However, their fundamental molecular interactions and the mechanism by which they govern the property-function relations of OSCs remain elusive. Here, to investigate the effects of the structural symmetry of NFREAs, two acceptor-donor-acceptor'-donor-acceptor (A-D-A'-D-A)-type NFREAs, 2,2'-(((naphtho[1,2-c:5,6-c']bis[1,2,5]thiadiazole-5,10-diylbis(4,4-bis(2-butyloctyl)-4H-cyclopenta[2,1-b:3,4-b']dithiophene-6,2-diyl))bis(methaneylylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile (NTz-4F) and 2,2'-(((benzo[c][1,2,5]thiadiazole-4,7-diylbis(4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b']dithiophene-6,2-diyl))bis(methaneylylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile (BT-4F), are designed and synthesized. They have different A' cores: NTz-4F has a modified centrosymmetric NTz core, whereas BT-4F has a modified axisymmetric BT core. In pristine films, the NTz-4F, which has a centrosymmetric core, shows substantially enhanced intermolecular interaction and microstructural crystalline ordering compared with BT-4F, which has an axisymmetric core. Even in blends with poly[(2,6-(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)-benzo[1,2-b:4,5-b']dithiophene))-alt-(5,5-(1',3'-di-2-thienyl-5',7'-bis(2-ethylhexyl)benzo[1',2'-c:4',5'-c']dithiophene-4,8,-dione))] (PBDB-T), NTz-4F retains its highly crystalline structure, whereas BT-4F loses crystalline packing. These changes in NTz-4F result in increased electron transport and suppressed nonradiative voltage loss, resulting in a power conversion efficiency of 9.14% for PBDB-T:NTz-4F vs 7.18% for PBDB-T:BT-4F. This work demonstrates that centrosymmetric-structured cores are promising building blocks for high-performance NFREA-based OSCs.

Conformal quantum dot-SnO2 layers as electron transporters for efficient perovskite solar cells.

Improvements to perovskite solar cells (PSCs) have focused on increasing their power conversion efficiency (PCE) and operational stability and maintaining high performance upon scale-up to module sizes. We report that replacing the commonly used mesoporous-titanium dioxide electron transport layer (ETL) with a thin layer of polyacrylic acid-stabilized tin(IV) oxide quantum dots (paa-QD-SnO2) on the compact-titanium dioxide enhanced light capture and largely suppressed nonradiative recombination at the ETL-perovskite interface. The use of paa-QD-SnO2 as electron-selective contact enabled PSCs (0.08 square centimeters) with a PCE of 25.7% (certified 25.4%) and high operational stability and facilitated the scale-up of the PSCs to larger areas. PCEs of 23.3, 21.7, and 20.6% were achieved for PSCs with active areas of 1, 20, and 64 square centimeters, respectively.

Copolymers comprising 2,7-carbazole and bis-benzothiadiazole units for bulk-heterojunction solar cells.

On the basis of theoretical considerations of the intramolecular charge transfer (ICT) effect, we have designed a series of donor (D)-acceptor (A) conjugated polymers based on bis-benzothiadiazole (BBT). A PPP-type copolymer of electron-rich 2,7-carbazole (CZ) and electron-deficient BBT units poly[N-(2-decyltetradecyl)-2,7-carbazole-co-7,7'-{4,4'-bis-(2,1,3-benzothiadiazole)}] (PCZ-BBT), a PPV-type copolymer poly[N-(2-decyltetradecyl)-2,7-carbazolevinylene-co-7,7'-{4,4'-bis-(2,1,3-benzothiadiazolevinylene)}] (PCZV-BBTV), and a tercopolymer based on carbazole, thiophene, and BBT poly[N-(2-decyltetradecyl)-2,7-(di-2-thienyl)carbazole-co-7,7'-{4,4'-bis-(2,1,3-benzothiadiazole)}] (PDTCZ-BBT) have been synthesized to understand the influence of BBT acceptor structure and linkage on the photovoltaic characteristics of the resulting materials. Both the HOMO and LUMO of the resulting polymers are found to be deeper-lying than those of benzothiadiazole-based polymers. The measured electrochemical band gaps (eV) are in the following order: PDTCZ-BBT (1.65 eV) < PCZV-BBTV (1.69 eV) < PCZ-BBT (1.75 eV). All the polymers provide a photovoltaic response when blended with a fullerene derivative as an electron acceptor. The best cell reaches a power conversion efficiency of 2.07 % estimated under standard solar light conditions (AM1.5G, 100 mW cm(-2)). We demonstrate for the first time that BBT-based polymers are promising materials for use in bulk-heterojunction solar cells.