Designing simple non-fused terthiophene-based electron acceptors for efficient organic solar cells

Low-cost photovoltaic materials are essential for realizing large-scale commercial applications of organic solar cells(OSCs).However,highly efficient OSCs based on low-cost photovoltaic materials are scarce due to a deficiency in understanding the structure-property relationship.Herein,we investigated two low-cost terthiophene-based electron acceptors,namely,3TC8 and 3TEH,with 3,4-bis(octan-3-yloxy)thiophene,differing only in the alkylated thiophene-bridges.Both acceptors exhibit low optical gaps(∼1.43 eV)and possess deep highest occupied molecular orbital(HOMO)levels(∼−5.8 eV).Notably,the single-crystal structure of 3TEH demonstrates highly planar conjugated backbone and strongπ-πstacking between intermolecular terminal groups,attributed to the presence of the bulky alkylated noncovalently conformational locks.Upon utilizing both acceptors to fabricate OSCs,the 3TC8-based device exhibited a power conversion efficiency(PCE)of 11.1%,while the 3TEH-based OSC demonstrated an excellent PCE of 14.4%.This PCE is the highest among OSCs based on terthiophene-containing electron acceptors.These results offer a new strategy for designing low-cost electron acceptors for highly efficient OSCs.

End-group modulation of phenazine based non-fullerene acceptors for efficient organic solar cells with high open-circuit voltage

Phenazine-based non-fullerene acceptors(NFAs)have demonstrated great potential in improving the power conversion efficiency(PCE)of organic solar cells(OSCs).Halogenation is known to be an effective strategy for increasing optical absorption,refining energy levels,and improving molecular packing in organic semiconductors.Herein,a series of NFAs(Pz IC-4H,Pz IC-4F,Pz IC-4Cl,Pz IC-2Br)with phenazine as the central core and with/without halogen-substituted(dicyanomethylidene)-indan-1-one(IC)as the electron-accepting end group were synthesized,and the effect of end group matched phenazine central unit on the photovoltaic performance was systematically studied.Synergetic photophysical and morphological analyses revealed that the PM6:Pz IC-4F blend involves efficient exciton dissociation,higher charge collection and transfer rates,better crystallinity,and optimal phase separation.Therefore,OSCs based on PM6:Pz IC-4F as the active layer exhibited a PCE of 16.48%with an open circuit voltage(Voc)and energy loss of 0.880 V and 0.53 e V,respectively.Accordingly,this work demonstrated a promising approach by designing phenazine-based NFAs for achieving high-performance OSCs.

Rational molecular engineering towards efficient heterojunction solar cells based on organic molecular acceptors

The selection of photoactive layer materials for organic solar cells(OSCs) is essential for the photoelectric conversion process.It is well known that chlorophyll is an abundant pigment in nature and is extremely valuable for photosynthesis.However,there is little research on how to improve the efficiency of chlorophyll-based OSCs by matching chlorophyll derivatives with excellent non-fullerene acceptors to form heterojunctions.Therefore in this study we utilize a chlorophyll derivative,Ce_(6)Me_(3),as a donor material and investigate the performance of its heterojunction with acceptor materials.Through density functional theory,the photoelectric performances of acceptors,i ncluding the fullerene derivative PC_(71)BM and the terminal halogenated non-fullerene DTBCIC series,are compared in detail.It is found that DTBCIC-C1 has better planarity,light absorption,electron affinity,charge reorganization energy and charge mobility than others.Ce_(6)Me_(3) has good energy level matching and absorption spectral complementarity with the investigated acceptor molecules and also shows good electron donor properties.Furthermore,the designed Ce_(6)Me_(3)/DTBCIC interfaces have improved charge separation and reorganization rates(K_(CS)/K_(CR)) compared with the Ce_(6)Me_(3)/PC_(71)BM interface.This research provides a theoretical basis for the design of photoactive layer materials for chlorophyll-based OSCs.

A new perspective to develop regiorandom polymer acceptors with high active layer ductility,excellent device stability,and high efficiency approaching 17%

The recently reported efficient polymerized small-molecule acceptors(PSMAs)usually adopt a regioregular backbone by polymerizing small-molecule acceptors precursors with a low-reactivity 5-brominated 3-(dicyanomethylidene)indan-1-one(IC)end group or its derivatives,leading to low molecular weight,and thus reduce active layer mechanical properties.Herein,a series of newly designed chlorinated PSMAs originating from isomeric IC end groups are developed by adjusting chlorinated positions and copolymerized sites on end groups to achieve high molecular weight,favorable intermolecular interaction,and improved physicochemical properties.Compared with regioregular PY2Se-Cl-o and PY2Se-Cl-m,regiorandom PY2Se-Cl-ran has a similar absorption profile,moderate lowest unoccupied molecular orbital level,and favorable intermolecular packing and crystallization properties.Moreover,the binary PM6:PY2Se-Cl-ran blend achieves better ductility with a crack-onset strain of 17.5% and improved power conversion efficiency(PCE)of 16.23% in all-polymer solar cells(all-PSCs)due to the higher molecular weight of PY2Se-Cl-ran and optimized blend morphology,while the ternary PM6:J71:PY2Se-Cl-ran blend offers an impressive PCE approaching 17% and excellent device stability,which are all crucial for potential practical applications of all-PSCs in wearable electronics.To date,the efficiency of 16.86% is the highest value reported for the regiorandom PSMAs-based all-PSCs and is also one of the best values reported for the all-PSCs.Our work provides a new perspective to develop efficient all-PSCs,with all high active layer ductility,impressive PCE,and excellent device stability,towards practical applications.

Banana-shaped electron acceptors with an electron-rich core fragment and 3D packing capability

The emergence of Y6-type nonfullerene acceptors has greatly enhanced the power conversion efficiency(PCE)of organic solar cells(OSCs).However,which structural feature is responsible for the excellent photovoltaic performance is still under debate.In this study,two Y6-like acceptors BDOTP-1 and BDOTP-2 were designed.Different from previous Y6-type acceptors featuring an A–D–Aʹ–D–A structure,BDOTP-1,and BDOTP-2 have no electron-deficient Aʹfragment in the core unit.Instead,there is an electron-rich dibenzodioxine fragment in the core.Although this modification leads to a marked change in the molecular dipole moment,electrostatic potential,frontier orbitals,and energy levels,BDOTP acceptors retain similar three-dimensional packing capability as Y6-type acceptors due to the similar banana-shaped molecular configuration.BDOTP acceptors show good performance in OSCs.High PCEs of up to 18.51%(certified 17.9%)are achieved.This study suggests that the banana-shaped configuration instead of the A–D–Aʹ–D–A structure is likely to be the determining factor in realizing high photovoltaic performance.

Green‑Solvent Processed Blade‑Coating Organic Solar Cells with an Efficiency Approaching 19%Enabled by Alkyl‑Tailored Acceptors

Power-conversion-efficiencies(PCEs)of organic solar cells(OSCs)in laboratory,normally processed by spin-coating technology with toxic halogenated solvents,have reached over 19%.However,there is usually a marked PCE drop when the bladecoating and/or green-solvents toward large-scale printing are used instead,which hampers the practical development of OSCs.Here,a new series of N-alkyl-tailored small molecule acceptors named YR-SeNF with a same molecular main backbone are developed by combining selenium-fused central-core and naphthalene-fused endgroup.Thanks to the N-alkyl engineering,NIR-absorbing YR-SeNF series show different crystallinity,packing patterns,and miscibility with polymeric donor.The studies exhibit that the molecular packing,crystallinity,and vertical distribution of active layer morphologies are well optimized by introducing newly designed guest acceptor associated with tailored N-alkyl chains,providing the improved charge transfer dynamics and stability for the PM6:L8-BO:YRSeNF-based OSCs.As a result,a record-high PCE approaching 19%is achieved in the blade-coating OSCs fabricated from a greensolvent o-xylene with high-boiling point.Notably,ternary OSCs offer robust operating stability under maximum-power-point tracking and well-keep>80%of the initial PCEs for even over 400 h.Our alkyl-tailored guest acceptor strategy provides a unique approach to develop green-solvent and blade-coating processed high-efficiency and operating stable OSCs,which paves a way for industrial development.

π-Extension and chlorination of non-fullerene acceptors enable more readily processable and sustainable high-performance organic solar cells

Organic solar cells(OSCs)processed without halogenated solvents and complex treatments are essential for future commercialization.Herein,we report three novel small molecule acceptors(NFAs)consisting of a Y6-like core but withπ-extended naphthalene with progressively more chlorinated end-capping groups and a longer branched chain on the Nitrogen atom.These NFAs exhibit good solubilities in nonchlorinated organic solvents,broad optical absorptions,closeπ-πstacking distances(3.63–3.84A),and high electron mobilities(~10^(-3)cm^(2)V^(-1)s^(-1)).The o-xylene processed and as-cast binary devices using PM6 as the donor polymer exhibit a PCE increasing upon progressive chlorination of the naphthalene end-capping group from 8.93%for YN to 14.38%for YN-Cl to 15.00%for YN-2Cl.Furthermore similarly processed ternary OSCs were fabricated by employing YN-Cl and YN-2Cl as the third component of PM6:CH1007 blends(PCE=15.75%).Compared to all binary devices,the ternary PM6:CH1007:YN-Cl(1:1:0.2)and PM6:CH1007:YN-2Cl(1:1:0.2)cells exhibit significantly improved PCEs of 16.49%and15.88%,respectively,which are among the highest values reported to date for non-halogenated solvent processed OSCs without using any additives and blend post-deposition treatments.

Alkyl chain modulation of asymmetric hexacyclic fused acceptor synergistically with wide bandgap third component for high efficiency ternary organic solar cells

Herein,two asymmetric hexacyclic fused small molecule acceptors(SMAs),namely BP4F-HU and BP4F-UU,were synthesized.The elongated outside chains in the BP4F-UU molecule played a crucial role in optimizing the morphology of blend film,thereby improving charge mobility and reducing energy loss within the corresponding film.Notably,the PM6:BP4F-UU device exhibited a higher open-circuit voltage(V_(oc))of 0.878 V compared to the PM6:BP4F-HU device with a V_(oc)of 0.863 V.Further,a new wide bandgap SMA named BTP-TA was designed and synthesized as the third component to the PM6:BP4F-UU host binary devices,which showed an ideal complementary absorption spectrum in PM6:BP4F-UU system.In addition,BTP-TA can achieve efficient intermolecular energy transfer to BP4F-UU by fluorescence resonance energy transfer(FRET)pathway,due to the good overlap between the photoluminescence(PL)spectrum of BTP-TA and the absorption region of BP4F-UU.Consequently,ternary devices with 15wt%BTP-TA exhibits broader photon utilization,optimal blend morphology,and reduced charge recombination compared to the corresponding binary devices.Consequently,PM6:BP4F-UU:BTP-TA ternary device achieved an optimal power conversion efficiency(PCE)of 17.83%with simultaneously increased V_(oc)of 0.905 V,short-circuit current density(J_(sc))of 26.14 mA/cm^(2),and fill factor(FF)of 75.38%.

Molecular-level proton acceptor boosts oxygen evolution catalysis to enable efficient industrial-scale water splitting

Industrial water splitting has long been suppressed by the sluggish kinetics of the oxygen evolution reaction(OER),which requires a catalyst to be efficient.Herein,we propose a molecular-level proton acceptor strategy to produce an efficient OER catalyst that can boost industrial-scale water splitting.Molecular-level phosphate(-PO_(4))group is introduced to modify the surface of PrBa_(0.5)Ca_(0.5)Co_(2)O_(5)+δ(PBCC).The achieved catalyst(PO_(4)-PBCC)exhibits significantly enhanced catalytic performance in alkaline media.Based on the X-ray absorption spectroscopy results and density functional theory(DFT)calculations,the PO_(4)on the surface,which is regarded as the Lewis base,is the key factor to overcome the kinetic limitation of the proton transfer process during the OER.The use of the catalyst in a membrane electrode assembly(MEA)is further evaluated for industrial-scale water splitting,and it only needs a low voltage of 1.66 V to achieve a large current density of 1 A cm^(-2).This work provides a new molecular-level strategy to develop highly efficient OER electrocatalysts for industrial applications.

π-Extended giant dimeric acceptor as a third component enables highly efficient ternary organic solar cells with efficiency over 19.2%

Ternary strategy with a suitable third component is a successful strategy to improve the photovoltaic performance of organic solar cells(OSCs).Very recently,Y-series based giant molecule acceptors or oligomerized acceptors have emerged as promising materials for achieving highly efficient and stable binary OSCs,while application as third component for ternary OSCs is limited.Here a novelπ-extended giant dimeric acceptor,GDF,is developed based on central Y series core fusion and rigid BDT as linker,and then incorporated into the state-of-the-art PM1:PC6 system to construct ternary OSCs.The GDF has a near planar backbone,resulting in increasedπ-conjugation,excellent crystallinity,and good electron transport capacity.When GDF is introduced into the PM1:PC6 system,it ensues in a cascade like the lowest unoccupied molecular orbitals(LUMO)energy level alignment,a complementary absorption band with PM1 and PC6,higher and balanced hole and electron mobility,slightly smaller domain size,and a higher exciton dissociation probability for PM1:PC6:GDF(1:1.1:0.1)blend film.As a consequence,the PM1:PC6:GDF(1:1.1:0.1)ternary OSC achieves a champion PCE of 19.22%,with a significantly higher open-circuit voltage and short-circuit current density,compared to 18.45%for the PM1:PC6(1:1.2)binary OSC.Our findings show that employing aπ-extended giant dimeric acceptor as a third component significantly improves the photovoltaic performance of ternary OSCs.

Enhancing efficiency and stability of organic solar cells through a simplified four-step synthesis of fully non-fused ring electron acceptor

Design and synthesis of superior cost-effective non-fullerene acceptors(NFAs)are still big challenges for facilitating the commercialization of organic solar cells(OSCs),yet to be realized.Herein,two medium bandgap fully non-fused ring electron acceptors(NFREAs,medium bandgap,i,e.,1,3-1,8 eV),namely PTR-2Cl and PTR-4Cl are synthesized with only four steps by using intramolecular noncovalent interaction central core,structured alkyl side chain orientation linking units and flanking with different electron-withdrawing end group.Among them,PTR-4C1 exhibits increased average electrostatic potential(ESP)difference with polymer donor,enhanced crystallinity and compactπ-πstacking compared with the control molecule PTR-2CI.As a result,the PTR-4Cl-based OSC achieved an impressive power conversion efficiency(PCE)of 14.72%,with a much higher open-circuit voltage(V_(OC))of 0.953 V and significantly improved fill factor(FF)of 0.758,demonstrating one of the best acceptor material in the top-performing fully NFREA-based OSCs with both high PCE and V_(OC).Notably,PTR-4Cl-based cells maintain a good T_80lifetime of its initial PCE after over 936 h under a continuous thermal annealing treatment and over1300 h T_(80)lifetime without encapsulation.This work provides a cost-effective design strategy for NFREAs on obtaining high V_(OC),efficient exciton dissociation,and ordered molecular packing and thus high-efficiency and stable OSCs.

Photophysical Properties and Photovoltaic Performance of Sensitizers with a Bipyrimidine Acceptor

Molecular engineering is a crucial strategy for improving the photovoltaic performance of dye-sensitized solar cells(DSSCs). Despite the common use of the donor-π bridge-acceptor architecture in designing sensitizers, the underlying structure-performance relationship remains not fully understood. In this study, we synthesized and characterized three sensitizers: MOTP-Pyc, MOS_(2)P-Pyc, and MOTS_(2)P-Pyc, all featuring a bipyrimidine acceptor. Absorption spectra, cyclic voltammetry, and transient photoluminescence spectra reveal a photo-induced electron transfer(PET) process in the excited sensitizers. Electron spin resonance spectroscopy confirmed the presence of charge-separated states. The varying donor and π-bridge structures among the three sensitizers led to differences in their conjugation effect, influencing light absorption abilities and PET processes and ultimately impacting the photovoltaic performance. Among the synthesized sensitizers, MOTP-Pyc demonstrated a DSSC efficiency of 3.04%. Introducing an additional thienothiophene block into the π-bridge improved the DSSC efficiency to 4.47% for MOTS_(2)P-Pyc. Conversely, replacing the phenyl group with a thienothiophene block reduced DSSC efficiency to 2.14% for MOS_(2)P-Pyc. Given the proton-accepting ability of the bipyrimidine module, we treated the dye-sensitized TiO_(2) photoanodes with hydroiodic acid(HI), significantly broadening the light absorption range. This treatment greatly enhanced the short-circuit current density of DSSCs owing to the enhanced electron-withdrawing ability of the acceptor. Consequently, the HI-treated MOTS_(2)P-Pyc-based DSSCs achieved the highest power conversion efficiency of 7.12%, comparable to that of the N719 dye at 7.09%. This work reveals the positive role of bipyrimidine in the design of organic sensitizers for DSSC applications.

Features of Recombination Radiation of GaAs Type Semiconductors with the Participation of Fine Acceptor Levels in a Magnetic Field

Using the method of Picus and Beer invariants, general expressions are obtained for the total intensity I and the degree of circular polarization Рcirc.of the luminescence of GaAs-type semiconductors with the participation of shallow acceptor levels in a longitudinal magnetic field H. Special cases are analyzed depending on the value and direction of the magnetic field strength, as well as on the constants of the g-factor of the acceptor g1,g2and the conduction band electron ge. In the case of a strong magnetic field H// [100], [111], [110], a numerical calculation of the angular dependence of the quantities I and Рcirc.was performed for some critical values of g2/g1, at which Рcirc.exhibits a sharp anisotropy in the range from −100% to +100%, and the intensity of the crystal radiation along the magnetic field tends to a minimum value.

A 3-D Hybrid Framework {[(dafone)PbI_2](dafone)_2}_n Constructed from Weak Interactions by Introducing Aromatic H-bond Acceptors: Synthesis and Theoretical Study

A new 3-D hybrid framework {[（dafone）PbI2]（dafone）2}n 1 （dafone = 4,5-diazafluoren-9-one） has been prepared and structurally determined. 1 crystallizes in the monoclinic system, space group C2/c with a = 24.109（8）, b = 16.596（8）, c = 7.983（3）A, β = 91.590（15）°, V = 3193（2）A^3, Z = 4, C33H18I2N6O3Pb, Mr = 1007.53, Dc = 2.096 g/cm^3, F（000） = 1880, μ（MoKα） = 7.262 mm^-1, the final R = 0.0352 and wR = 0.0951 for 3198 observed reflections with I 〉 2σ（I）. In the [（dafone）PbI2]n chain, the Pb center adopts a distorted octahedral coordination geometry and shares an edge to give a one-dimensional polymer. The 3-D arrangement of 1 constructs from H-bonds among dafone molecules and π-π stacking interactions among dissociative dafone molecules. These weak interactions contribute to the stability of the title compound. DFT calculation was carried out to reveal its electronic structure.

Polymer acceptors for all-polymer solar cells

Bulk-heterojunction polymer solar cells(PSCs)as a clean and renewable energy resource have attracted great attention from both academia and industry[1−20].Recently non-fullerene PSCs based on polymer donors(PDs)and small molecule acceptors(SMAs)have achieved remarkable success with the power conversion efficiencies(PCEs)over 18%[21−26].

Non-fullerene small molecule electron acceptors for high-performance organic solar cells

Fullerenes and their derivatives are important types of electron acceptor materials and play a vital role in organic solar cell devices. However, the fullerene acceptor material has some difficulties to overcome the intrinsic shortcomings, such as weak absorption in the visible range, difficulty in modification and high cost, which limit the performance of the device and the large-scale application of this type of acceptors. In recent years, non-fullerene electron acceptor material has attracted the attention of scientists due to the advantages of adjustable energy level, wide absorption, simple synthesis, low processing cost and good solubility. Researchers can use the rich chemical means to design and synthesize organic small molecules and their oligomers with specific aggregation morphology and excellent optoelectronic prop- erties. Great advances in the field of synthesis, device engineering, and device physics of non-fullerene acceptors have been achieved in the last few years. At present, non-fullerene small molecules based photovoltaic devices achieve the highest efficiency more than 13% and the efficiency gap between fullerenetype and non-fullerene-type photovoltaic devices is gradually narrowing. In this review, we explore recent progress of non-fullerene small molecule electron acceptors that have been developed and led to highefficiency photovoltaic devices and put forward the prospect of development in the future.

Nanomorphology in A–D–A type small molecular acceptors-based bulk heterojunction polymer solar cells

Recent developments in acceptor–donor–acceptor(A–D–A) type non-fullerene acceptors have led to substantial improvements in bulk-heterojunction polymer solar cells efficiency. The device performance strongly depends on photoactive layer morphology, as the molecular packing, donor–acceptor interface and phase separation significantly affect the charge-transfer states and charge carrier dynamics. In this review, we start with a brief introduction of the techniques most effectively utilized to characterize multiphase morphology. Then, we summarize recent progress in A–D–A type acceptors, with the emphasis on understanding the molecular structure–morphology–performance relationships. Finally, an outlook on correlating morphological characteristics with photovoltage losses is presented for further improving device performance.

Effects of Flexible Conjugation-Break Spacers of Non-Conjugated Polymer Acceptors on Photovoltaic and Mechanical Properties of All-Polymer Solar Cells

All-polymer solar cells(all-PSCs)possess attractive merits including superior thermal stability and mechanical flexibility for large-area roll-to-roll processing.Introducing flexible conjugation-break spacers(FCBSs)into backbones of polymer donor(P_(D))or polymer acceptor(P_(A))has been demonstrated as an efficient approach to enhance both the photovoltaic(PV)and mechanical properties of the all-PSCs.However,length dependency of FCBS on certain all-PSC related properties has not been systematically explored.In this regard,we report a series of new non-conjugated P_(A)s by incorporating FCBS with various lengths(2,4,and 8 carbon atoms in thioalkyl segments).Unlike com-mon studies on so-called side-chain engineering,where longer side chains would lead to better solubility of those resulting polymers,in this work,we observe that the solubilities and the resulting photovoltaic/mechanical properties are optimized by a proper FCBS length(i.e.,C2)in P_(A) named PYTS-C2.Its all-PSC achieves a high efficiency of 11.37%,and excellent mechanical robustness with a crack onset strain of 12.39%,significantly superior to those of the other P_(A)s.These results firstly demonstrate the effects of FCBS lengths on the PV performance and mechanical properties of the all-PSCs,providing an effective strategy to fine-tune the structures of P_(A)s for highly efficient and mechanically robust PSCs.

Effect of electron acceptors H_2O_2 and O_2 on the generated reactive oxygen species ~1O_2 and OH~· in TiO_2-catalyzed photocatalytic oxidation of glycerol

The effect of the electron acceptors H2O2 and O2 on the type of generated reactive oxygen species（ROS）,and glycerol conversion and product distribution in the TiO2-catalyzed photocatalytic oxidation of glycerol was studied at ambient conditions.In the absence of an electron acceptor,only HO^·radicals were generated by irradiated UV light and TiO2.However,in the presence of the two electron acceptors,both HO^· radical and ^1O2 were produced by irradiated UV light and TiO2 in different concentrations that depended on the concentration of the electron acceptor.The use of H2O2 as an electron acceptor enhanced glycerol conversion more than O2.The type of generated value-added compounds depended on the concentration of the generated ROS.

Recent advances and prospects of asymmetric non-fullerene small molecule acceptors for polymer solar cells

Recently,polymer solar cells developed very fast due to the application of non-fullerence acceptors.Substituting asymmetric small molecules for symmetric small molecule acceptors in the photoactive layer is a strategy to improve the performance of polymer solar cells.The asymmetric design of the molecule is very beneficial for exciton dissociation and charge transport and will also fine-tune the molecular energy level to adjust the open-circuit voltage(Voc)further.The influence on the absorption range and absorption intensity will cause the short-circuit current density(Jsc)to change,resulting in higher device performance.The effect on molecular aggregation and molecular stacking of asymmetric structures can directly change the microscopic morphology,phase separation size,and the active layer's crystallinity.Very recently,thanks to the ingenious design of active layer materials and the optimization of devices,asymmetric non-fullerene polymer solar cells(A-NF-PSCs)have achieved remarkable development.In this review,we have summarized the latest developments in asymmetric small molecule acceptors(A-NF-SMAs)with the acceptor-donor-acceptor(A-D-A)and/or acceptor-donor-acceptor-donor-acceptor(A-D-A-D-A)structures,and the advantages of asymmetric small molecules are explored from the aspects of charge transport,molecular energy level and active layer accumulation morphology.