Stable Organic Solar Cells Enabled by Simultaneous Hole and Electron Interlayer Engineering

The development of high-performance organic solar cells(OSCs)with high operational stability is essential to accelerate their commercialization.Unfortunately,our understanding of the origin of instabilities in state-of-the-art OSCs based on bulk heterojunction(BHJ)featuring non-fullerene acceptors(NFAs)remains limited.Herein,we developed NFA-based OSCs using different charge extraction interlayer materials and studied their storage,thermal,and operational stabilities.Despite the high power conversion efficiency(PCE)of the OSCs(17.54%),we found that cells featuring self-assembled monolayers(SAMs)as hole-extraction interlayers exhibited poor stability.The time required for these OSCs to reach 80%of their initial performance(T_(80))was only 6h under continuous thermal stress at 85℃in a nitrogen atmosphere and 1 h under maximum power point tracking(MPPT)in a vacuum.Inserting MoO_(x)between ITO and SAM enhanced the T_(80)to 50 and~15 h after the thermal and operational stability tests,respectively,while maintaining a PCE of 16.9%.Replacing the organic PDINN electron transport layer with ZnO NPs further enhances the cells'thermal and operational stability,boosting the T_(80)to 1000 and 170 h,respectively.Our work reveals the synergistic roles of charge-selective interlayers and device architecture in developing efficient and stable OSCs.

Heteroatom substitution-induced asymmetric A–D–A type non-fullerene acceptor for efficient organic solar cells

Research on asymmetric A–D–A structured non-fullerene acceptors has lagged far behind the development of symmetric counterpart.In this contribution,by simply replacing one sulfur atom in indacenodithiophene unit with a selenium atom,an asymmetric building block Se PT and a corresponding asymmetric non-fullerene acceptor Se PT-IN have been developed.Asymmetric Se PT-IN achieved a high efficiency of 10.20% in organic solar cells when blended with PBT1-C,much higher than that of symmetric TPT-IN counterpart(8.91%).Our results demonstrated an effective heteroatom substitution strategy to develop asymmetric A–D–A structured non-fullerene acceptors.

Regioisomeric Polymer Semiconductors Based on Cyano-Functionalized Dialkoxybithiophenes:Structure-Property Relationship and Photovoltaic Performance

Cyano substitution is vital to the molecular design of polymer semiconductors toward highly efficient organic solar cells.However,how regioselectivity impacts relevant optoelectronic properties in cyano-substituted bithiophene systems remain poorly understood.Three regioisomeric cyano-functionalized dialkoxybithiophenes BT_(HH),BT_(HT),and BT_(TT) with headto-head,head-to-tail,and tail-to-tail linkage,respectively,were synthesized and characterized in this work.The resulting polymer semiconductors(PBDTBTs)based on these building blocks were prepared accordingly.The regiochemistry and property relationships of PBDTBTs were investigated in detail.The BTHH moiety has a higher torsional barrier than the analogs BT_(HT) and BT_(TT),and the regiochemistry of dialkoxybithiophenes leads to fine modulation in the optoelectronic properties of these polymers,such as optical absorption,band gap,and energy levels of frontier molecular orbitals.Organic field-effect transistors based on PBDTBT_(HH) had higher hole mobility(4.4×10^(-3) cm^(2)/(V·s))than those(ca.10^(-4) cm^(2)/(V·s))of the other two polymer analogs.Significantly different short-circuit current densities and fill factors were obtained in polymer solar cells using PBDTBTs as the electron donors.Such difference was probed in greater detail by performing space-charge-limited current mobility,thin-film morphology,and transient photocurrent/photovoltage characterizations.The findings highlight that the BTHH unit is a promising building block for the construction of polymer donors for highperformance organic photovoltaic cells.

Modeling and implementation of tandem polymer solar cells using wide-bandgap front cells

Tandem device architectures offer a route to greatly increase the maximum possible power conversion efficiencies(PCEs)of polymer solar cells,however,the complexity of tandem cell device fabrication(such as selecting bandgaps of the front and back cells,current matching,thickness,and recombination layer optimization)often result in lower PCEs than are observed in single-junction devices.In this study,we analyze the influence of front cell and back cell bandgaps and use transfer matrix modeling to rationally design and optimize effective tandem solar cell structures before actual device fabrication.Our approach allows us to estimate tandem device parameters based on known absorption coefficients and open-circuit voltages of different active layer materials and design devices without wasting valuable time and materials.Using this approach,we have investigated a series of wide bandgap,high voltage photovoltaic polymers as front cells in tandem devices with PTB7-Th as a back cell.In this way,we have been able to demonstrate tandem devices with PCE of up to 12.8%with minimal consumption of valuable photoactive materials in tandem device optimization.This value represents one of the highest PCE values to date for fullerene-based tandem solar cells.

Optimization of solvent swelling for efficient organic solar cells via sequential deposition

Compared to bulk heterojunction(BHJ)organic solar cells(OSCs)prepared by the blend casting in“one step process”,sequential deposition(SD)processed OSCs can realize an ideal profile of vertical component distribution due to the swelling of polymer films.Herein,we did trials on several kinds of second solvents for swelling the polymer layer,and investigated the packing structure and morphology of the swollen films and the performance of the resulting devices.We found that an optimized morphology can be achieved by solvent swelling while using orthodichlorobenzene(o-DCB)as the second layer processing-solvent,with polymer donor PffBT-3 as bottom layer,PC71BM as top layer and bicontinuous networks in the middle.Such solvent swelling process also makes the SD method exempt from thermal annealing treatment.The device based on SD yields a power conversion effi-ciency(PCE)up to 8.7%without any post-treatment,outperforming those from the devices based on SD using other solvents and that(7.06%)from BHJ device,respectively.We also extended the use of this approach to allpolymer blend system,and successfully improved the efficiency from 4.72%(chloroform)to 9.35%(o-DCB),which is among the highest PCEs in all-polymer-based OSCs fabricated with SD method.The results demonstrate that the swelling of the polymer by the second layer solvent is a necessity for SD,paving the way towards additivefree high-performance OSCs.

Over 18.2% efficiency of layer–by–layer all–polymer solar cells enabled by homoleptic iridium(Ⅲ)carbene complex as solid additive

The vertical phase distribution of active layers plays a vital role in balancing exciton dissociation and cha rge transport for achieving efficient polymer solar cells(PSCs).The layer-by-layer(LbL)PSCs are commonly prepared by using sequential spin-coating method from donor and acceptor solutions with distinct solvents and solvent additives.The enhanced exciton dissociation is expected in the LbL PSCs with efficient charge transport in the relatively neat donor or acceptor layers.In this work,a series of LbL all-polymer solar cells(APSCs)were fabricated with PM6 as donor and PY-DT as acceptor,and triplet material m-Ir(CPmPB)_(3)is deliberately incorporated into PY-DT layer to prolong exciton lifetimes of active layers.The power conversion efficiency(PCE)of LbL APSCs is improved to 18.24%from 17.32%by incorporating 0.3 wt%m-Ir(CPMPB)_(3)in PY-DT layer,benefiting from the simultaneously enhanced short-circuit current density(Isc)of 25.17 mA cm^(-2)and fill factor(FF)of 74.70%.The enhancement of PCE is attributed to the efficient energy transfer of m-Ir(CPmPB)_(3)to PM6 and PY-DT,resulting in the prolonged exciton lifetime in the active layer and the increased exciton diffusion distance.The efficient energy transfer from m-Ir(CPmPB)_(3)to PM6 and PY-DT layer can be confirmed by the increased photoluminescence(PL)intensity and the prolonged PL lifetime of PM6 and PY-DT in PM6+m-Ir(CPmPB)_(3)and PY-DT+m-Ir(CPmPB)_(3)films.This study indicates that the triplet material as solid additive has great potential in fabricating efficient LbL APSCs by prolonging exciton lifetimes in active layers.

Semicrystalline Unfused Polymer Donors with Backbone Halogenation toward Cost-Effective Organic Solar Cells

Developing novel unfused building blocks with simple synthesis and low cost is essential to advance and enrich cost-effective poly-mer donors;however,it remains a challenge due to the lack of efficient molecular strategies.Herein,a class of low-cost and fully unfused polymer donors with precisely regulated backbone planarity via halogenation was designed and synthesized,namely PDTBTBz-2H,PDTBTBz-2F,and PDTBTBz-2Cl.These polymer donors possess a four-step synthesis route with over 80%yield from cheap raw chemicals comparable to existing low-cost polymer donors,such as PTQ10.Benefitting from the planar backbone via in-corporating the F…S non-covalent interactions,PDTBTBz-2F exhibits more robust J-type aggregation in solution and a long-ranged molecular stacking in film relative to PDTBTBz-2H and PDTBTBz-2Cl.Moreover,the systematical study of PDTBTBz-based organic so-lar cells(OSCs)reveals the close relationship between optimized molecular self-assembly and charge separation/transport regarding backbone halogenation when paired with the non-fullerene acceptor(Y6-BO-4F).As a result,the photovoltaic devices based on semicrystalline PDTBTBz-2F achieved a promising power conversion efficiency(PCE)of 12.37%.Our work highlighted the influence of backbone halogenation on the molecular self-assembly properties and a potential unfused backbone motif for further developing cost-effective OSCs.

Engineering of dendritic dopant-free hole transport molecules:enabling ultrahigh fill factor in perovskite solar cells with optimized dendron construction

Developing dopant-free hole-transporting materials(HTMs)for high-performance perovskite solar cells(PVSCs)has been a very active research topic in recent years since HTMs play a critical role in optimizing interfacial charge carrier kinetics and in turn determining device performance.Here,a novel dendritic engineering strategy is first utilized to design HTMs with a D-A type molecular framework,and diphenylamine and/or carbazole is selected as the building block for constructing dendrons.All HTMs show good thermal stability and excellent film morphology,and the key optoelectronic properties could be fine-tuned by varying the dendron structure.Among them,MPA-Cz-BTI and MCz-Cz-BTI exhibit an improved interfacial contact with the perovskite active layer,and non-radiative recombination loss and charge transport loss can be effectively suppressed.Consequently,high power conversion efficiencies(PCEs)of 20.8%and 21.35%are achieved for MPA-Cz-BTI and MCz-Cz-BTI based devices,respectively,accompanied by excellent long-term storage stability.More encouragingly,ultrahigh fill factors of 85.2%and 83.5%are recorded for both devices,which are among the highest values reported to date.This work demonstrates the great potential of dendritic materials as a new type of dopant-free HTMs for high-performance PVSCs with excellent FF.

Over 16% efficiency all-polymer solar cells by sequential deposition

All-polymer solar cells(all-PSCs) have received extensive attention due to their excellent mechanical robustness and performance stability. However, the power conversion efficiency(PCE) of all-PSCs still lags behind those of organic solar cells(OSCs)based on non-fullerene small molecule acceptors. Herein, we report highly efficient all-PSCs via sequential deposition(SD) with donor and acceptor layers coated sequentially to optimize the film microstructure. Compared with the bulk heterojunction(BHJ)all-PSCs, an optimized morphology with vertical component distribution was achieved for the SD-processed all-PSCs due to the synergistic effect of swelling of polymer films and using additive. Such strategy involves using chlorobenzene as the first layer processing-solvent for polymer donor, chloroform as the second processing-solvent for polymer acceptor with trace 1-chloronaphthalene, efficiently promoting exciton dissociation and charge extraction and reducing trap-assisted recombination.Consequently, over 16% all-PSCs fabricated via SD method was realized for the first time, which is much higher than that(15.2%) of its BHJ counterpart and also among the highest PCEs in all-PSCs. We have further demonstrated the generality of this approach in various all-polymer systems. This work indicates that the SD method can yield excellent all-PSCs and provides a facile approach to fabricating high-performance all-PSCs.

A High Dielectric N-Type Small Molecular Acceptor Containing Oligoethyleneglycol Side-Chains for Organic Solar Cellst

We report a new small molecular acceptor, ITIC-OEG, which is based on indacenodithieno[3,2-b]thiophene and 1,1-（dicyanomethylene）-3- indanone including oligoethyleneglycol （OEG） side-chains. ITIC-OEG was found to have higher dielectric constant （ε1=5.6} than that of a reference molecule of ITIC with normal alkyl substituents （ε1=3.9）. The dielectric constant of medium influences significantly the exciton binding energy and the resulting charge separation and recombination. The optical, electrochemical and morphological properties of ITIC-OEG and its photovoltaic characteristics were investigated by blending with a semi-crystalline donor polymer, PPDT2FBT, with comparison to those of ITIC. ITIC-OEG shows more red-shifted absorption and stronger crystalline packing than ITIC. However, the lower photovoltaic performance （with 1.58% power conversion efficiency, PCE） was measured for PPDT2FBT-ITIC-OEG, compared to PPDT2FBT：ITIC （5..52% PCE）. The incompatibility between PPDT2FBT and ITIC-OEG （due to high hydrophilic nature of OEG chains） resulted in poor intermixing with large domain separation over 300 nm, showing inefficient charge separation and significant charge recombination. Therefore, to investigate the effect of dielectric constant of the materials on the charge separation and recombination, the blend morphology of the PPDT2FBT：ITIC-OEG should be optimized first by improving their miscibility and phase separation.

High-efficiency organic solar cells enabled by an alcohol-washable solid additive

The solvent additive strategy has been widely utilized to boost the power conversion efficiency(PCE)of organic solar cells(OSCs).However,the residual solvent additive in the active layer tends to induce a gradual morphology degradation and further influences the long-term stability of OSCs.Here,a solid additive,1,4-diiodobenzene(DIB),was introduced to fabricate efficient OSCs.We found that the treatment of DIB can lead to optimized morphology to form a bicontinuous network with intensified intermolecular packing in the donor and acceptor phases.Notably,DIB can be easily removed from the active layer via a simple alcohol washing process and no further post-thermal annealing is needed,which is desirable for large-scale manufacturing of OSCs.As a result,high efficiencies of 17.47%for PM6:Y6 and 18.13%(certified as 17.7%)for PM6:BTP-eC9 binary OSCs are achieved,which are among the highest efficiencies reported for binary OSCs thus far.Moreover,OSCs fabricated with DIB also exhibit superior stability compared with the as-cast and traditional solvent additive processed devices.Additionally,DIB was successfully applied in different active layers,manifesting its general applicability.This work provides a feasible approach to enhance both the efficiency and stability of OSCs.

Germinant ZnO nanorods as a charge-selective layer in organic solar cells

A facile method was introduced and demonstrated to synthesize zinc oxide(ZnO) nanorods(NRs) as an electron transporting layer(ETL) for organic solar cells(OSCs).Hydrothermal synthesis of the NRs showed a constant growth rate of 5.5 nm min-1 from germination to sub-micrometer length.The properties were characterized using scanning electron microscopy(SEM),transmission electron microscopy(TEM),absorption spectrophotometry and so on.Based on these measurements,the germinant growth mechanism and its corresponding orientation characteristics were investigated.As an ETL of the OSCs,ZnO NRs enhance the charge extraction from the active layer due to their increased interfacial surface area,but there is an optimal length because of the shunt path formation and UV absorption of long ZnO NRs.As a re sult,the OSC with the ZnO NRs as ETL shows power conversion efficiency(PCE) up to 6.2%.The J-V characteristics and incident photon-to-current conversion efficiency(IPCE) measurement also reveal that the efficiency enhancement is an assembly of individual results from optical,physical and electrical characteristic of the ZnO NRs.

Organic solar cells based on chlorine functionalized benzo[1,2-b:4,5-b′]difuran-benzo[1,2-c:4,5-c′]dithiophene-4,8-dione copolymer with efficiency exceeding 13%

Benzo[1,2-b:4,5-b′]dithiophene(BDT) has been widely used to construct donor-acceptor(D-A) copolymers in organic solar cells(OSCs). However, benzo[1,2-b:4,5-b′]difuran(BDF), an analogue of BDT, has received less attention than BDT. The photovoltaic performance of BDF copolymers has lagged behind that of BDT copolymers. Here, we designed and synthesized two BDF copolymers, PBF1-C and PBF1-C-2Cl. PBF1-C-2Cl, which is composed of BDF and benzo[1,2-c:4,5-c′]dithiophene-4,8-dione connected by a chlorinated thiophene π-bridge, displays a low-lying highest occupied molecular orbital energy level,which helps in yielding a high open-circuit voltage(Voc) in OSCs. As a result, when blended with Y6, PBF1-C-2Cl-based devices showed a high Voc of 0.83 V and a power conversion efficiency(PCE) of 13.10%. To the best of our knowledge, the PCE of 13.10% is among the highest efficiency values for OSCs based on BDF copolymers.

Semi-crystalline photovoltaic polymers with siloxane-terminated hybrid side-chains

Three types of semi-cry stalline photovoltaic polymers were synthesized by incorporating a siloxane-terminated organic/inorganic hybrid side-chain and changing the number of fluorine substituents.A branch point away from a polymer main backbone in the siloxane-containing side-chains and the intra-and/or interchain noncovalent coulombic interactions enhance a chain planarity and facile interchain organization.The resulting polymers formed strongly agglomerated films with high roughness,suggesting strong intermolecular interactions.The optical band gap of ca.1.7 eV was measured for all polymers with a pronounced shoulder peak due to tight π-π stacking.With increasing the fluorine substituents,the frontier energy levels decreased and preferential face-on orientation was observed.The siloxane-terminated side-chains and fluorine substitution promoted the intermolecular packing,showing well resolved lamellar scatterings up to(300) for this series of polymers in the grazing incidence wide angle X-ray scattering measurements.The PPsiDTBT,PPsiDTFBT and PPsiDT2 FBT devices showed a power conversion efficiency of 3.16%,4.40%and 5.65%,respectively,by blending with PC_(71)BM.Langevin-type bimolecular charge recombination was similar for three polymeric solar cells.The main loss in the photocurrent generation for PPsiDTBT:PC_(71)BM was interpreted to originate from the trap assisted charge recombination by measuring light-intensity dependent short-circuit current density(J_(SC)) and open-circuit voltage(V_(Oc)).Our results provide a new insight into the rational selection of solubilizing substituents for optimizing crystalline interchain packing with appropriate miscibility with PC71 BM for further optimizing polymer solar cells.

Organic solar cells for indoor power generation

During last decades,organic solar cells(OSCs)have achieved remarkable advancements via extensive studies on the optimization of photovoltaic donor/acceptor(D/A)materials,device fabrication,and the D/A bulk heterojunction morphologies.Power conversion efficiencies(PCEs)up to〜16%for single junction cells and over 17%PCEs were successfully demonstrated for tandem OSC devices[1,2].OSCs may find real industrial applications soon,including building integrated photovoltaics,portable power sources and indoor power generation for low power consumption electronic devices(i.e.,internet of things(IOT)sensors).Among them,indoor applications have great potentials because OSCs can convert indoor lights into electricity more efficiently compared to inorganic counterparts[3].

Improvement of photovoltaic properties of benzo[1,2-b:4,5-b′]difuran-conjugated polymer by side-chain modification

The development of polymer solar cells(PSCs)for the donor materials based on benzo[1,2-b:4,5-b′]dithiophene(BDT)has significantly boosted the power conversion efficiency(PCE).However,the PCE of polymer donor materials for benzo[1,2-b:4,5-b′]difuran(BDF)-based lags far behind that of their BDT analogs.To further explore efficient copolymers based on BDF units,a two-dimensional(2D)side-chain strategy was proposed to investigate the atom-changing effects on the copolymer donors for the properties of electron and optical.In this study,we designed and synthesized three new BDF-based copolymer donor materials,named PBDF-C,PBDF-O,and PBDF-S.Owing to the balanced charge transport and favorable phase separation of PBDF-S:Y6,a high PCE of 13.4%,a short-circuit current(J sc)of 25.48 mA cm−2,an open-circuit voltage(V oc)of 0.721 V,and a fill factor(FF)of 72.6%was obtained.This research demonstrates that the BDF building block has great potential for constructing conjugated copolymer donors for high-performance PSCs and that 2D side-chain modification is a facile approach for designing high-performance BDF-based copolymer materials.