Naphthalene‐Diimide‐Based Ionenes as Universal Interlayers for Efficient Organic Solar Cells

Self‐doping ionene polymers were efficiently synthesized by reacting functional naphthalene diimide (NDI) with 1,3‐dibromopropane ( NDI‐NI ) or trans‐1,4‐dibromo‐2‐butene ( NDI‐CI ) via quaternization polymerization. These NDI‐based ionene polymers are universal interlayers with random molecular orientation, boosting the efficiencies of fullerene‐based, non‐fullerene‐based, and ternary organic solar cells (OSCs) over a wide range of interlayer thicknesses, with a maximum efficiency of 16.9 %. NDI‐NI showed a higher interfacial dipole (Δ), conductivity, and electron mobility than NDI‐CI , affording solar cells with higher efficiencies. These polymers proved to efficiently lower the work function (WF) of air‐stable metals and optimize the contact between metal electrode and organic semiconductor, highlighting their power to overcome energy barriers of electron injection and extraction processes for efficient organic electronics.     

Efficient Enhancement of Electron Transport and Collection Capability in PTB7:PC71BM‐based Solar Cells Enabled by Sulforhodamine Cathode Interlayers

Development of low‐cost water‐/alcohol‐soluble interfacial materials is a crucial issue to promote the commercialization of polymer solar cells (PSCs). Herein, two derivatives of low‐cost rhodamine, called sulforhodamine 101 (SR101) and sulforhodamine B (SRB), are applied as cathode interfacial layers (CILs) to effectively improve the charge‐carrier transportation and collection, reduce the work function (WF) of Al counter electrode, and decrease the series resistance and charge recombination in the PSCs. As a result, SR101‐based devices show excellent performance with the highest power conversion efficiency (PCE) of 9.10 %, superior to that of both the control devices with MeOH/Al and Ca/Al. Notably, sulforhodamine is commercially available with low cost and great solution‐processability. This work demonstrates that sulforhodamine has a great potential as a CIL material,which is suitable for the large‐area fabrication process and commercialization of highly efficient PSCs.     

Enhanced Charge Transfer,Transport and Photovoltaic Efficiency in All‐Polymer Organic Solar Cells by Polymer Backbone Fluorination

We successfully designed and synthesized two BDT‐BT‐T (BDT=benzo[1,2‐b:4,5‐b']dithiophene, BT‐T=4,7‐dithien‐2‐yl‐2,1,3‐benzothiadiazole) based polymers as the electron donor for application in all‐polymer solar cells (all‐PSCs). By adopting N2200 as the electron acceptor, we systematically investigated the impact of fluorination on the charge transfer, transport, blend morphology and photovoltaic properties of the relevant all‐PSCs. A best power conversion efficiency (PCE) of 3.4% was obtained for fluorinated PT‐BT2F/N2200 (BT2F=difluorobenzo[c][1,2,5]thiadiazole) all‐PSCs in comparison with that of 2.7% in non‐fluorinated PT‐BT/N2200 (BT=benzothiadiazole) based device. Herein, all‐polymers blends adopting either non‐fluorinated PT‐BT or fluorinated PT‐BT2F exhibit similar morphology features. In depth optical spectrum measurements demonstrate that molecular fluorination can further enhance charge transfer between donor and acceptor polymer. Moreover, all‐polymer blends exhibit improved hole mobilities and more balanced carriers transport when adopting fluorinated donor polymer PT‐BT2F. Therefore, although the PCE is relatively low, our findings may become important in understanding how subtle changes in molecular structure impact relevant optoelectronic properties and further improve the performance of all‐PSCSs.     

Dye‐Incorporated Polynaphthalenediimide Acceptor for Additive‐Free High‐Performance All‐Polymer Solar Cells

All‐polymer solar cells (all‐PSCs) can offer unique advantages for applications in flexible devices, and naphthalene diimide (NDI)‐based polymer acceptors are the widely used polymer acceptors. However, their power conversion efficiency (PCE) still lags behind that of state‐of‐the‐art polymer solar cells, due to low light absorption, suboptimal energy levels and the strong aggregation of the NDI‐based polymer acceptor. Herein, a rhodanine‐based dye molecule was introduced into the NDI‐based polymer acceptor by simple random copolymerization and showed an improved light absorption coefficient, an up‐shifted lowest unoccupied molecular orbital level and reduced crystallization. Consequently, additive‐free all‐PSCs demonstrated a high PCE of 8.13 %, which is one of the highest performance characteristics reported for all‐PSCs to date. These results indicate that incorporating a dye into the n‐type polymer gives insight into the precise design of high‐performance polymer acceptors for all‐PSCs.     

Naphthalene-Diimide-Based Ionenes as Universal Interlayers for Efficient Organic Solar Cells

Self-doping ionene polymers were efficiently synthesized by reacting functional naphthalene diimide (NDI) with 1,3-dibromopropane ( NDI-NI ) or trans-1,4-dibromo-2-butene ( NDI-CI ) via quaternization polymerization. These NDI-based ionene polymers are universal interlayers with random molecular orientation, boosting the efficiencies of fullerene-based, non-fullerene-based, and ternary organic solar cells (OSCs) over a wide range of interlayer thicknesses, with a maximum efficiency of 16.9 %. NDI-NI showed a higher interfacial dipole (Δ), conductivity, and electron mobility than NDI-CI , affording solar cells with higher efficiencies. These polymers proved to efficiently lower the work function (WF) of air-stable metals and optimize the contact between metal electrode and organic semiconductor, highlighting their power to overcome energy barriers of electron injection and extraction processes for efficient organic electronics.     

Linking Polythiophene Chains Through Conjugated Bridges: A Way to Improve Charge Transport in Polymer Solar Cells

Summary: A series of cross‐linked polythiophene derivatives ( P1 – 4 ) are synthesized by adding different ratio (0, 2, 5, and 10%) of conjugated cross‐linker via a Stille coupling reaction. From P1 – 4 , with the increase of the content of the conjugated bridges, the UV‐visible absorption peaks of the polymers were shifted towards blue and their electrochemical bandgap increased. The hole mobilities of P1 – 4 as determined from the SCLC model are 5.23 × 10⁻⁶, 1.28 × 10⁻⁴, 7.01 × 10⁻³, and 2.34 × 10⁻⁵ cm² · V⁻¹ · s⁻¹, respectively. The PCEs of the polymer solar cells based on P1 – 4 are 0.37, 1.05, 1.26, and 0.78%, respectively. The improvement of PCE of the devices based on P2 – 4 compared with that of P1 may be due to the increase of hole mobility.

Molecular structure of the polythiophene derivatives ( P1 – 4 ).     

富勒烯稠合体与共轭聚合物作为有机太阳能电池材料的研究进展

介绍了有关富勒烯与共轭聚合物超快光诱导电子的研究状况和三种不同光敏层材料制备的太阳能电池的组装和性能,包括:(1)以共轭聚合物/C60或C60衍生物的主体异介质为光敏层,(2)分子水平上的主体异介质:D-A双功能聚合物,(3)单纯以富勒烯稠合体为光敏层,以及国内外这三种太阳能电池研究的进展情况及存在的问题.     

n‐Type Conjugated Polymer Based on Dicyanodistyrylbenzene and Naphthalene Diimide Units for All‐Polymer Solar Cells

All polymer solar cells (all‐PSCs), possessing superior mechanical strength and flexibility, offer the commercialization opportunity of the PSCs for flexible and portable devices. In this work, we designed and synthesized two copolymer acceptors based on dicyanodistyrylbenzene (DCB) and naphthalene diimide (NDI) units. The corresponding copolymer acceptors are denoted as PDCB‐NDI812 and PDCB‐NDI1014. The medium band gap copolymer PBDB‐T was selected as donor material for investigation of the photovoltaic performance. Two all‐PSCs devices showed power conversion efficiencies (PCE) of 4.26% and 3.43% for PDCB‐NDI812 and PDCB‐NDI1014, respectively. The improved PCE was ascribed to the higher short‐circuit current (J_SC), greater charge carrier mobility and higher exciton dissociation probability of the PBDB‐T:PDCB‐NDI812 blend film. These results suggest that DCB unit and NDI unit based copolymer acceptors are promising candidates for high performance all‐PSCs.     

高效率窄带隙聚合物太阳能电池材料

太阳能电池能够将太阳能直接转化为电能,是利用太阳能资源的一种非常有效的手段。聚合物太阳能电池因成本低、重量轻、制备方便和可制成柔性器件的优点,已经成为该领域的研究热点之一。基于窄带隙共轭聚合物给体/富勒烯受体复合材料体系制得的太阳能电池的最高转换效率已经达到8.3%,而寻找性能更优异的聚合物给体材料是进一步提高光伏性能的关键因素。本文综述了近几年关于高效率窄带隙聚合物太阳能电池给体材料的研究进展,着重介绍了苯并噻二唑类共聚物、稠环噻吩类共聚物和吡嗪类共聚物等窄带隙聚合物给体材料体系及相应光伏器件的性能,分析了各种材料的优点和不足,并对今后这一领域的发展做了展望。     

Silaindacenodithiophene‐Based Fused‐Ring Non‐Fullerene Electron Acceptor for Efficient Polymer Solar Cells

In this work, a new A‐D‐A type nonfullerene small molecular acceptor SiIDT‐IC, with a fused‐ring silaindacenodithiophene (SiIDT) as D unit and 2‐(3‐oxo‐2,3‐dihydroinden‐1‐ylidene)malononitrile (INCN) as the end A unit, was design and synthesized. The SiIDT‐IC film shows absorption peak and edge at 695 and 733 nm, respectively. The HOMO and LUMO of SiIDT‐IC are of −5.47 and −3.78 eV, respectively. Compared with carbon‐bridging, the Si‐bridging can result in an upper‐lying LUMO level of an acceptor, which is benefit to achieve a higher open‐circuit voltage in polymer solar cells (PSCs). Complementary absorption and suitable energy level alignment between SiIDT‐IC and wide bandgap polymer donor PBDB‐T were found. For the PBDB‐T:SiIDT‐IC based inverted PSCs, a D/A ratio of 1: 1 was optimal to achieve a power conversion efficiency (PCE) of 7.27%. With thermal annealing (TA) of the blend film, a higher PCE of 8.16% could be realized due to increasing of both short‐circuit current density and fill factor. After the TA treatment, hole and electron mobilities were elevated to 3.42 × 10⁻⁴ and 1.02 × 10⁻⁴ cm²·V⁻¹·s⁻¹, respectively. The results suggest that the SiIDT, a Si‐bridged fused ring, is a valuable D unit to construct efficient nonfullerene acceptors for PSCs.     

An Isoindigo‐Based “Double‐Cable” Conjugated Polymer for Single‐ Component Polymer Solar Cells

An isoindigo‐based “double‐cable” conjugated polymer bearing perylene bisimide side units was developed via Stille polymerization for application in single‐component polymer solar cells, in which a power conversion efficiency of 1% with broad photo‐response from 300 nm to 800 nm was achieved. There is no evidence of large phase separation confirmed by AFM images and photoluminescence (PL) spectra. The space charge limit current measurements and light intensity dependence measurements indicate that the low electron mobility and the significant recombination of photogenerated charge carriers in active layer mainly account for the low performance of our solar cells. Our results suggest that these “double‐cable” are promising candidates for use in single‐component polymer solar cells with NIR photoresponse.     

Dithienobenzothiadiazole‐Based Conjugated Polymer: Processing Solvent‐Relied Interchain Aggregation and Device Performances in Field‐Effect Transistors and Polymer Solar Cells

DTfBT‐Th₃, a new conjugated polymer based on dithienobenzothiadiazole and terthiophene, possesses a bandgap of ≈1.86 eV and a HOMO level of −5.27 eV. Due to strong interchain aggregation, DTfBT‐Th₃ can not be well dissolved in chloro­benzene (CB) and o‐dichlorobenzene (DCB) at room temperature (RT), but the polymer can be processed from hot CB and DCB solutions of ≈100 °C. In CB, with a lower solvation ability, a certain polymer chain aggregation can be preserved, even in hot solution. DTfBT‐Th₃ displays a field‐effect hole mobility of 0.55 cm² V⁻¹ s⁻¹ when fabricated from hot CB solution, which is higher than that of the device processed from hot DCB (0.16 cm² V⁻¹ s⁻¹). In DTfBT‐Th₃‐based polymer solar cells, a good power conversion efficiency from 5.37% to 6.67% can be achieved with 150−300 nm thick active layers casted from hot CB solution, while the highest efficiency for hot DCB‐processed solar cells is only 5.07%. The results demonstrate that using a solvent with a lower solvation ability, as a “wet control” process, is beneficial to preserve strong interchain aggregation of a conjugated polymer during solution processing, showing great potential to improve its performances in optoelectronic devices.

     

聚合物太阳能电池高效共轭聚合物给体和富勒烯受体光伏材料

聚合物太阳能电池（PSC）由共轭聚合物给体和富勒烯衍生物受体的共混膜（活性层）夹在ITO透明导电玻璃正极和低功函数金属负极之间所组成,具有制备过程简单、成本低、重量轻、可制备成柔性器件等突出优点,近年来成为国内外研究前沿和热点。当前研究的焦点是提高器件的光电能量转换效率,而提高效率的关键是高效共轭聚合物给体和富勒烯衍生...     

Planar Conjugated Polymers Containing 9,10‐Disubstituted Phenanthrene Units for Efficient Polymer Solar Cells

Four novel conjugated polymers ( P1‐4 ) with 9,10‐disubstituted phenanthrene (PhA) as the donor unit and 5,6‐bis(octyloxy)benzothiadiazole as the acceptor unit are synthesized and characterized. These polymers are of medium bandgaps (2.0 eV), low‐lying HOMO energy levels (below −5.3 eV), and high hole mobilities (in the range of 3.6 × 10⁻³ to 0.02 cm² V⁻¹ s⁻¹). Bulk heterojunction (BHJ) polymer solar cells (PSCs) with P1‐4 :PC₇₁BM blends as the active layer and an alcohol‐soluble fullerene derivative (FN‐C60) as the interfacial layer between the active layer and cathode give the best power conversion efficiency (PCE) of 4.24%, indicating that 9,10‐disubstituted PhA are potential donor materials for high‐efficiency BHJ PSCs.

     

Crystalline Conjugated Polymers for Organic Solar Cells: From Donor,Acceptor to Single‐Component

Organic solar cells have made rapid progress in the last two decades due to the innovation of conjugated materials and photovoltaic devices. Microphase separation that connects with materials and devices plays a crucial role in the charge generation process. In this account, we summary our recent works of developing new crystalline conjugated polymers to control the microphase separation in thin films in order to realize high performance in solar cells, including crystalline diketopyrrolopyrrole‐based donor polymers, perylene bisimide‐based electron acceptors, and “double‐cable” conjugated polymers that contain covalently‐linked crystalline donor and acceptor in one material for single‐component organic solar cells.     

13.34 % Efficiency Non‐Fullerene All‐Small‐Molecule Organic Solar Cells Enabled by Modulating the Crystallinity of Donors via a Fluorination Strategy

Non‐fullerene all‐small‐molecule organic solar cells (NFSM‐OSCs) have shown potential as OSCs, owing to their high purity, easy synthesis and good reproducibility. However, challenges in the modulation of phase separation morphology have limited their development. Herein, two novel small molecular donors, BTEC‐1F and BTEC‐2F, derived from the small molecule DCAO3TBDTT, are synthesized. Using Y6 as the acceptor, devices based on non‐fluorinated DCAO3TBDTT showed an open circuit voltage (V_oc) of 0.804 V and a power conversion efficiency (PCE) of 10.64 %. Mono‐fluorinated BTEC‐1F showed an increased V_oc of 0.870 V and a PCE of 11.33 %. The fill factor (FF) of di‐fluorinated BTEC‐2F‐based NFSM‐OSC was improved to 72.35 % resulting in a PCE of 13.34 %, which is higher than that of BTEC‐1F (61.35 %) and DCAO3TBDTT (60.95 %). To our knowledge, this is the highest PCE for NFSM‐OSCs. BTEC‐2F had a more compact molecular stacking and a lower crystallinity which enhanced phase separation and carrier transport.     

Anthracene‐Containing Wide‐Band‐Gap Conjugated Polymers for High‐Open‐Circuit‐Voltage Polymer Solar Cells

The synthesis, characterization, and photophysical and photovoltaic properties of two anthracene‐containing wide‐band‐gap donor and acceptor (D–A) alternating conjugated polymers ( P1 and P2 ) are described. These two polymers absorb in the range of 300–600 nm with a band gap of about 2.12 eV. Polymer solar cells with P1 :PC₇₁BM as the active layer demonstrate a power conversion efficiency (PCE) of 2.23% with a high V_oc of 0.96 V, a J_sc of 4.4 mA cm⁻², and a comparable fill factor (FF) of 0.53 under simulated solar illumination of AM 1.5 G (100 mW cm⁻²). In addition, P2 :PC₇₁BM blend‐based solar cells exhibit a PCE of 1.42% with a comparable V_oc of 0.89 V, a J_sc of 3.0 mA cm⁻², and an FF of 0.53.

     

Direct Dynamic Evidence of Charge Separation in a Dye‐Sensitized Solar Cell Obtained under Operando Conditions by Raman Spectroscopy

Interfaces play an important role in enhancing the energy conversion performance of dye‐sensitized solar cells (DSCs). The interface effects have been studied by many techniques, but most of the studies only focused on one part of a DSC, rather than on a complete solar cell. Hence, monitoring the interface evolution of a DSC is still very challenging. Here, in situ/operando resonance Raman (RR) spectroscopic analyses were carried out to monitor the dynamics of the photovoltaic conversion processes in a DSC. We observed the creation of new species (i.e., polyiodide and iodine aggregates) in the photosensitization process. We also obtained molecular‐scale dynamic evidence that the bands from the C=C and C=N bonds of 2,2′‐bipyridyl (bpy), the S=C=N bonds of the NCS ligand, and photochemical products undergo reasonably strong intensity and frequency changes, which clearly demonstrates that they are involved in charge separation. Furthermore, RR spectroscopy can also be used to quickly evaluate the performance of DSCs.     

Isoindigo‐3,4‐Difluorothiophene Polymer Acceptors Yield “All‐Polymer” Bulk‐Heterojunction Solar Cells with over 7 % Efficiency

Poly(isoindigo‐alt‐3,4‐difluorothiophene) (PIID[2F]T) analogues used as “polymer acceptors” in bulk‐heterojunction (BHJ) solar cells achieve >7 % efficiency when used in conjunction with the polymer donor PBFTAZ (model system; copolymer of benzo[1,2‐b:4,5‐b′]dithiophene and 5,6‐difluorobenzotriazole). Considering that most efficient polymer‐acceptor alternatives to fullerenes (e.g. PC₆₁BM or its C₇₁ derivative) are based on perylenediimide or naphthalenediimide motifs thus far, branched alkyl‐substituted PIID[2F]T polymers are particularly promising non‐fullerene candidates for “all‐polymer” BHJ solar cells.