Abstract: All-polymer solar cells (all-PSCs) offer unique morphology stability for the application as flexible devices, but the lack of high-performance polymer acceptors limits their power conversion efficiency (PCE) to a value lower than those of the PSCs based on fullerene derivative or organic small molecule acceptors. We herein demonstrate a strategy to synthesize a high-performance polymer acceptor PZ1 by embedding an acceptor–donor–acceptor building block into the polymer main chain. PZ1 possesses broad absorption with a low band gap of 1.55 eV and high absorption coefficient (1.3×105 cm−1). The all-PSCs with the wide-band-gap polymer PBDB-T as donor and PZ1 as acceptor showed a record-high PCE of 9.19 % for the all-PSCs. The success of our polymerization strategy can provide a new way to develop efficient polymer acceptors for all-PSCs.

Abstract: We have developed a kind of novel fused-ring small molecular acceptor, whose planar conformation can be locked by intramolecular noncovalent interaction. The formation of planar supramolecular fused-ring structure by conformation locking can effectively broaden its absorption spectrum, enhance the electron mobility, and reduce the nonradiative energy loss. Polymer solar cells (PSCs) based on this acceptor afforded a power conversion efficiency (PCE) of 9.6%. In contrast, PSCs based on similar acceptor, which cannot form a flat conformation, only gave a PCE of 2.3%. Such design strategy, which can make the synthesis of small molecular acceptor much easier, will be promising in developing a new acceptor for high efficiency polymer solar cells.

Abstract: Emissive molecules comprising a donor and an acceptor bridged by 9,9-dimethylxanthene, were studied (XPT, XCT, and XtBuCT). The structures position the donor and acceptor with cofacial alignment at distances of 3.3–3.5 A wherein efficient spatial charge transfer can occur. The quantum yields were enhanced by excluding molecular oxygen and thermally activated delayed fluorescence with lifetimes on the order of microseconds was observed. Although the molecules displayed low quantum yields in solution, higher quantum yields were observed in the solid state. Crystal structures revealed π–π intramolecular interactions between a donor and an acceptor, however, the dominant intermolecular interactions were C—H···π, which likely restrict the molecular dynamics to create aggregation-induced enhanced emission. Organic light emitting devices using XPT and XtBuCT as dopants displayed electroluminescence external quantum efficiencies as high as 10%.

Abstract: A fused hexacyclic electron acceptor, IHIC, based on strong electron-donating group dithienocyclopentathieno[3,2-b]thiophene flanked by strong electron-withdrawing group 1,1-dicyanomethylene-3-indanone, is designed, synthesized, and applied in semitransparent organic solar cells (ST-OSCs). IHIC exhibits strong near-infrared absorption with extinction coefficients of up to 1.6 × 105 m-1 cm-1 , a narrow optical bandgap of 1.38 eV, and a high electron mobility of 2.4 × 10-3 cm2 V-1 s-1 . The ST-OSCs based on blends of a narrow-bandgap polymer donor PTB7-Th and narrow-bandgap IHIC acceptor exhibit a champion power conversion efficiency of 9.77% with an average visible transmittance of 36% and excellent device stability; this efficiency is much higher than any single-junction and tandem ST-OSCs reported in the literature.

Abstract: Ternary polymer solar cells are fabricated based on one donor PBDB-T and two acceptors (a methyl-modified small-molecular acceptor (IT-M) and a bis-adduct of Bis[70]PCBM). A high power conversion efficiency of 12.2% can be achieved. The photovoltaic performance of the ternary polymer solar cells is not sensitive to the composition of the blend.

Abstract: We demonstrate novel molecular design for thermally activated delayed fluorescence (TADF) polymers based on a nonconjugated polyethylene backbone with through-space charge transfer effect between pendant electron donor (D) and acceptor (A) units. Different from conventional conjugated D–A polymers with through-bond charge transfer effect, the nonconjugated architecture avoids direct conjugation between D and A units, enabling blue emission. Meanwhile, spatial π–π interaction between the physically separated D and A units results in both small singlet–triplet energy splitting (0.019 eV) and high photoluminescence quantum yield (up to 60% in film state). The resulting polymer with 5 mol % acceptor unit gives efficient blue electroluminescence with Commission Internationale de l’Eclairage coordinates of (0.176, 0.269), together with a high external quantum efficiency of 12.1% and low efficiency roll-off of 4.9% (at 1000 cd m–2), which represents the first example of blue TADF nonconjugated polymer.

Abstract: The performance of organic solar cells is determined by the delicate, meticulously optimized bulk-heterojunction microstructure, which consists of finely mixed and relatively separated donor/acceptor regions. Here we demonstrate an abnormal strong burn-in degradation in highly efficient polymer solar cells caused by spinodal demixing of the donor and acceptor phases, which dramatically reduces charge generation and can be attributed to the inherently low miscibility of both materials. Even though the microstructure can be kinetically tuned for achieving high-performance, the inherently low miscibility of donor and acceptor leads to spontaneous phase separation in the solid state, even at room temperature and in the dark. A theoretical calculation of the molecular parameters and construction of the spinodal phase diagrams highlight molecular incompatibilities between the donor and acceptor as a dominant mechanism for burn-in degradation, which is to date the major short-time loss reducing the performance and stability of organic solar cells.

Abstract: A new polymer acceptor, naphthodiperylenetetraimide-vinylene (NDP-V), featuring a backbone of altenating naphthodiperylenetetraimide and vinylene units is designed and applied in all-polymer solar cells (all-PSCs). With this polymer acceptor, a new record power-conversion efficiencies (PCE) of 8.59% has been achieved for all-PSCs. The design principle of NDP-V is to reduce the conformational disorder in the backbone of a previously developed high-performance acceptor, PDI-V, a perylenediimide-vinylene polymer. The chemical modifications result in favorable changes to the molecular packing behaviors of the acceptor and improved morphology of the donor-acceptor (PTB7-Th:NDP-V) blend, which is evidenced by the enhanced hole and electron transport abilities of the active layer. Moreover, the stronger absorption of NDP-V in the shorter-wavelength range offers a better complement to the donor. All these factors contribute to a short-circuit current density (J sc ) of 17.07 mA cm-2 . With a fill factor (FF) of 0.67, an average PCE of 8.48% is obtained, representing the highest value thus far reported for all-PSCs.

Abstract: Low-bandgap polymers/molecules are an interesting family of semiconductor materials, and have enabled many recent exciting breakthroughs in the field of organic electronics, especially for organic photovoltaics (OPVs) Here, such a low-bandgap (143 eV) non-fullerene electron acceptor (BT-IC) bearing a fused 7-heterocyclic ring with absorption edge extending to the near-infrared (NIR) region was specially designed and synthesized Benefitted from its NIR light harvesting, high performance OPVs were fabricated with medium bandgap polymers (J61 and J71) as donors, showing power conversion efficiencies of 96% with J61 and 105% with J71 along with extremely low energy loss (056 eV for J61 and 053 eV for J71) Interestingly, femtosecond transient absorption spectroscopy studies on both systems show that efficient charge generation was observed despite the fact that the highest occupied molecular orbital (HOMO)–HOMO offset (ΔEH) in the blends was as low as 010 eV, suggesting that such a small ΔEH is not a crucial limitation in realizing high performance of NIR non-fullerene based OPVs Our results indicated that BT-IC is an interesting NIR non-fullerene acceptor with great potential application in tandem/multi-junction, semitransparent, and ternary blend solar cells

Abstract: A kind of new fused-ring electron acceptor, IDT-OB, bearing asymmetric side chains, is synthesized for high-efficiency thick-film organic solar cells The introduction of asymmetric side chains can increase the solubility of acceptor molecules, enable the acceptor molecules to pack closely in a dislocated way, and form favorable phase separation when blended with PBDB-T As expected, PBDB-T:IDT-OB-based devices exhibit high and balanced hole and electron mobility and give a high power conversion efficiency (PCE) of 1012% More importantly, the IDT-OB-based devices are not very sensitive to the film thickness, a PCE of 917% can still be obtained even the thickness of active layer is up to 210 nm

Abstract: A novel-small molecular acceptor with electron-deficient 1,3,5-triazine as the core and perylene diimides as the arms is developed as the acceptor material for efficient bulk heterojunction organic solar cells with an efficiency of 9.15%.

Abstract: Improving the fill factor (FF) is known as a challenging issue in organic solar cells (OSCs). Herein, a strategy of extending the conjugated area of end-group is proposed for the molecular design of acceptor-donor-acceptor (A-D-A)-type small molecule acceptor (SMA), and an indaceno[1,2-b:5,6-b']dithiophene-based SMA, namely IDTN, by end-capping with the naphthyl fused 2-(3-oxocyclopentylidene)malononitrile is synthesized. Benefiting from the π-conjugation extension by fusing two phenyls, IDTN shows stronger molecular aggregation, more ordered packing structure, thus over one order of magnitude higher electron mobility relative to its counterpart. By utilizing the fluorinated polymer (PBDB-TF) as the electron donor, the corresponding device exhibits a high efficiency of 12.2% with a record-high FF of 0.78, which is approaching the theoretical limit of OSCs. Compared with the reference molecule, such a high FF in the IDTN system can be mainly attributed to the more ordered π-π packing of acceptor aggregates, higher domain purity and symmetric carrier transport in the blend. Hence, enlarging the conjugated area of the terminal-group in these A-D-A-type SMAs is a promising approach not only for enhancing the electron mobility, but also for improving the blend morphology, and both of them are conducive to the fill-factor breakthrough.

Abstract: The challenge of continuous printing in high-efficiency large-area organic solar cells is a key limiting factor for their widespread adoption. A materials design concept for achieving large-area, solution-coated all-polymer bulk heterojunction solar cells with stable phase separation morphology between the donor and acceptor is presented. The key concept lies in inhibiting strong crystallization of donor and acceptor polymers, thus forming intermixed, low crystallinity, and mostly amorphous blends. Based on experiments using donors and acceptors with different degree of crystallinity, the results show that microphase separated donor and acceptor domain sizes are inversely proportional to the crystallinity of the conjugated polymers. This methodology of using low crystallinity donors and acceptors has the added benefit of forming a consistent and robust morphology that is insensitive to different processing conditions, allowing one to easily scale up the printing process from a small-scale solution shearing coater to a large-scale continuous roll-to-roll (R2R) printer. Large-area all-polymer solar cells are continuously roll-to-roll slot die printed with power conversion efficiencies of 5%, with combined cell area up to 10 cm2. This is among the highest efficiencies realized with R2R-coated active layer organic materials on flexible substrate.

Abstract: Suppression of carrier recombination is critically important in realizing high-efficiency polymer solar cells. Herein, it is demonstrated difluoro-substitution of thiophene conjugated side chain on donor polymer can suppress triplet formation for reducing carrier recombination. A new medium bandgap 2D-conjugated D-A copolymer J91 is designed and synthesized with bi(alkyl-difluorothienyl)-benzodithiophene as donor unit and fluorobenzotriazole as acceptor unit, for taking the advantages of the synergistic fluorination on the backbone and thiophene side chain. J91 demonstrates enhanced absorption, low-lying highest occupied molecular orbital energy level, and higher hole mobility, in comparison with its control polymer J52 without fluorination on the thiophene side chains. The transient absorption spectra indicate that J91 can suppress the triplet formation in its blend film with n-type organic semiconductor acceptor m-ITIC (3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone)-5,5,11,11-tetrakis(3-hexylphenyl)-dithieno[2,3-d:2,3'-d']-s-indaceno[1,2-b:5,6-b']-dithiophene). With these favorable properties, a higher power conversion efficiency of 11.63% with high VOC of 0.984 V and high JSC of 18.03 mA cm-2 is obtained for the polymer solar cells based on J91/m-ITIC with thermal annealing. The improved photovoltaic performance by thermal annealing is explained from the morphology change upon thermal annealing as revealed by photoinduced force microscopy. The results indicate that side chain engineering can provide a new solution to suppress carrier recombination toward high efficiency, thus deserves further attention.

Abstract: Through judicious molecular engineering, novel dopant-free star-shaped D–π–A type hole transporting materials coded KR355, KR321, and KR353 were systematically designed, synthesized and characterized. KR321 has been revealed to form a particular face-on organization on perovskite films favoring vertical charge carrier transport and for the first time, we show that this particular molecular stacking feature resulted in a power conversion efficiency over 19% in combination with mixed-perovskite (FAPbI3)0.85(MAPbBr3)0.15. The obtained 19% efficiency using a pristine hole transporting layer without any chemical additives or doping is the highest, establishing that the molecular engineering of a planar donor core, π-spacer and periphery acceptor leads to high mobility, and the design provides useful insight into the synthesis of next-generation HTMs for perovskite solar cells and optoelectronic applications.

Abstract: B. Xiao, Dr. A. Tang, Dr. J. Zhang, A. Mahmood, Prof. Z. Wei, Prof. E. Zhou CAS Key Laboratory of Nanosystem and Hierarchical Fabrication CAS Center for Excellence in Nanoscience National Center for Nanoscience and Technology Beijing 100190, P. R. China E-mail: zhouej@nanoctr.cn B. Xiao University of Chinese Academy of Sciences Beijing 100049, P. R. China Prof. E. Zhou Yangtze River Delta Academy of Nanotechnology and Industry Development Research Jiaxing City, Zhejiang Province, 314000, P. R. China

Abstract: In recent years, great progress has been achieved in the field of non-fullerene organic solar cells. In particular, the power conversion efficiencies for the photovoltaic devices based on A–π–A fused-ring electron acceptors, e.g. ITIC, can catch up with or even surpass the fullerene-based ones. However, the detailed molecular packing structures and charge transport properties of these acceptors are rarely studied and still unclear, which has become the major obstacle for rational molecular design to further improve the photovoltaic performance. Here, we have unravelled the intermolecular arrangements in the ITIC film via atomistic molecular dynamics simulations. The simulated results point to that three-dimensional molecular packing is formed in the ITIC film through local intermolecular π–π stacking between the terminal acceptor units. In sharp contrast, the ITIC crystal grown by the slow solvent vapor diffusion approach exhibits a one-dimensional edge-to-face stacking structure. Consequently, excellent isotropic electron mobilities along three dimensions are found for the film and unprecedentedly, the overall mobility is even higher than that of the crystal. Our work suggests that judicious modulation of the terminal acceptor unit to increase local intermolecular π–π interaction would be an effective way to improve the electron mobilities and photovoltaic performance of the A–π–A electron acceptors.

Abstract: In this article, we designed and synthesized a novel small molecule acceptor of ITCPTC with thiophene-fused ending group by employing a new active methylene precursor of CPTCN. The ITCPTC-based polymer solar cells with PBT1-EH as a donor achieved very high power conversion efficiencies (PCEs) of up to 11.8% with a remarkably enhanced fill factor (FF) of 0.751, a near 20% boost in PCE with respect to the ITIC-based control device. These values are among the highest PCEs and FFs for polymer solar cells (PSCs). In the whole study, we made contrasts with ITIC to understand the reasons of excellent performance of ITCPTC-based PSCs through various measurements, such as GIXD and RSoXS. We revealed that the simple modification of ITIC into ITCPTC not only change the material electronic structure, but also mediates the material interactions and crystallization, which contribute together to the excellent performance of ITCPTC-based PSCs.

Abstract: A comparison of the efficiency, stability, and photophysics of organic solar cells employing poly[(5,6-difluoro-2,1,3-benzothiadiazol-4,7-diyl)-alt-(3,3'″-di(2-octyldodecyl)-2,2';5',2″;5″,2'″-quaterthiophen-5,5'″-diyl)] (PffBT4T-2OD) as a donor polymer blended with either the nonfullerene acceptor EH-IDTBR or the fullerene derivative, [6,6]-phenyl C71 butyric acid methyl ester (PC71 BM) as electron acceptors is reported. Inverted PffBT4T-2OD:EH-IDTBR blend solar cell fabricated without any processing additive achieves power conversion efficiencies (PCEs) of 9.5 ± 0.2%. The devices exhibit a high open circuit voltage of 1.08 ± 0.01 V, attributed to the high lowest unoccupied molecular orbital (LUMO) level of EH-IDTBR. Photoluminescence quenching and transient absorption data are employed to elucidate the ultrafast kinetics and efficiencies of charge separation in both blends, with PffBT4T-2OD exciton diffusion kinetics within polymer domains, and geminate recombination losses following exciton separation being identified as key factors determining the efficiency of photocurrent generation. Remarkably, while encapsulated PffBT4T-2OD:PC71 BM solar cells show significant efficiency loss under simulated solar irradiation ("burn in" degradation) due to the trap-assisted recombination through increased photoinduced trap states, PffBT4T-2OD:EH-IDTBR solar cell shows negligible burn in efficiency loss. Furthermore, PffBT4T-2OD:EH-IDTBR solar cells are found to be substantially more stable under 85 °C thermal stress than PffBT4T-2OD:PC71 BM devices.

Abstract: Acceptor alloys based on n-type small molecular and fullerene derivatives are used to fabricate the ternary solar cell. The highest performance of optimized ternary device is 10.4%, which is the highest efficiency for one donor/two acceptors-based ternary systems. Three important parameters, JSC , VOC , and FF, of the optimized ternary device are all higher than the binary reference devices.

Abstract: Highly efficient long-wavelength thermally activated delayed fluorescence (TADF) materials are developed using 2,3-dicyanopyrazino phenanthrene (DCPP) as the electron acceptor (A), and carbazole (Cz), diphenylamine (DPA), or 9,9-dimethyl-9,10-dihydroacridine (DMAC) as the electron donor (D). Because of the large, rigid π-conjugated structure and strong electron-withdrawing capability of DCPP, TADF molecules with emitting colors ranging from yellow to deep-red are realized with different electron-donating groups and π-conjugation length. The connecting modes between donor and acceptor, that is, with or without the phenyl ring as π-bridge, are also investigated to study the π-bridge effect on the thermal, photophysical, electrochemical, and electroluminescent properties. Yellow, orange, red, and deep-red organic light-emitting diodes (OLEDs) based on DCPP derivatives exhibit high efficiencies of 47.6 cd A–1 (14.8%), 34.5 cd A–1 (16.9%), 12.8 cd A–1 (10.1%), and 13.2 cd A–1 (15.1%), with Commission Internati...

Abstract: A novel nonfullerene small molecular acceptor (BZIC) based on a ladder-type thieno[3,2-b]pyrrolo-fused pentacyclic benzotriazole core (dithieno[3,2-b]pyrrolobenzotriazole, BZTP) and end-capped with 1,1-dicyanomethylene-3-indanone (INCN) has been first reported in this work. Through introducing multifused benzotriazole and INCN, BZIC could maintain a high-lying lowest unoccupied molecular orbital (LUMO) energy level of −3.88 eV. Moreover, BZIC shows a low optical bandgap of 1.45 eV with broad and efficient absorption band from 600 to 850 nm due to increased π–π interactions by the covalently locking thiophene and benzotriazole units. A power conversion efficiency of 6.30% is delivered using BZIC as nonfullerene acceptor and our recently synthesized hexafluoroquinoxaline-based polymer HFQx-T as donor. This is the first time to synthesize mutifused benzotriazole-based molecules as nonfullerene electron acceptor up to date. The preliminary results demonstrate that the mutifused benzotriazole derivatives hold ...

Abstract: A perylenediimide-based (PDI-based) small molecular (SM) acceptor with both an extended π-conjugation and a three-dimensional structure concurrently is critical for achieving high-performance PDI-based fullerene-free organic solar cells (OSCs). Herein, a novel PDI-based SM acceptor has been successfully synthesized through fusing PDI units with a spiro core 4,4′-spirobi[cyclopenta[2,1-b;3,4-b′]dithiophene (SCPDT) together via β-position coupling with thiophene bridges. An enhanced absorption from 350 to 520 nm has been observed. Moreover, compared with previously reported acceptor SCPDT-PDI4, in which the PDI units and SCPDT are not fused together, the LUMO energy level of FSP (the new SCPDT-based molecule) increases. OSCs containing PTB7-Th as a donor and FSP as an acceptor have been demonstrated to show an excellent performance with a power conversion efficiency as high as 8.89%. This result might be attributed to the efficient and complementary photoabsorption, balanced carrier mobilities, and favorabl...

Abstract: In this work, we revealed a new approach for the development of efficient violet-blue emitting materials featuring a hybrid local and charge transfer (HLCT) excited state through the incorporation of naphthyl group(s) as a weak n-type π spacer in a donor–π–acceptor (D–π–A) system. The resulting materials (TPINCz and TPIBNCz) show improved intramolecular charge transfer properties and highly efficient violet-blue fluorescence. It is demonstrated that the pattern of the π spacers has significant influence on the photophysical properties. The incorporation of a naphthyl/binaphthyl spacer between the donor and acceptor moieties can alleviate the common dilemma that enhancing device performance by increasing the charge transfer excited properties often leads to red-shifted emissions. A device using TPINCz as an emissive dopant shows a violet-blue emission with CIE coordinates of (0.153, 0.059) and a record high EQE of 6.56 ± 0.11% at a brightness of 1000 cd m−2. To the best of our knowledge, this performance is the highest among the reported devices with CIEy ≤0.08. Our study provides a new pathway for the design of high-performance violet-blue emitters with a D–π–A architecture in organic electroluminescence applications.

Abstract: A new non-fullerene small molecule with an acceptor-donor-acceptor (A-D-A) structure, FDNCTF, incorporating fluorenedicyclopentathiophene as core and naphthyl-fused indanone as end groups, was designed and synthesized. Compared with the previous molecule FDICTF with the phenyl-fused indanone as the end groups, the extended π-conjugation at the end group has only little impact on its molecular orbital energy levels, and thus, the open-circuit voltage (Voc) of its solar cell devices has been kept high. However, its light absorption and mobility, together with the short-current density (Jsc) and the fill factor (FF), of its devices have been all improved simultaneously. Through morphology, transient absorption, and theoretical studies, it is believed that these favorable changes are caused by (1) the appropriately enhanced molecular interaction between donor/acceptor which makes the charge separation at the interface more efficient, and (2) enhanced light absorption and more ordered packing at solid state, a...

Abstract: The gallium vacancy, an intrinsic acceptor, is identified in β-Ga2O3 using electron paramagnetic resonance (EPR) Spectra from doubly ionized ( V G a 2 −) and singly ionized ( V G a −) gallium vacancies are observed at room temperature, without photoexcitation, after an irradiation with high-energy neutrons The V G a 2 − centers (with S = 1/2) have a slight angular variation due to a small anisotropy in the g matrix (principal values are 20034, 20097, and 20322) The V G a 2 − centers also exhibit a resolved hyperfine structure due to equal and nearly isotropic interactions with the 69,71Ga nuclei at two Ga sites (the hyperfine parameters are 128 and 163 mT for the 69Ga and 71Ga nuclei, respectively, when the field is along the a direction) Based on these g-matrix and hyperfine results, the model for the ground state of the doubly ionized vacancy ( V G a 2 −) has a hole localized on one threefold-coordinated oxygen ion The vacancy is located at one of the three neighboring gallium sites, and the r

Abstract: With applications in high performance electronics, photovoltaics and catalysis, two-dimensional transition metal dichalcogenides (TMDs) attract strong attention. Isolated TMDs, which are already remarkably complex, can stack in sequence to make even more complex heterostructures. Surprisingly, charge separation is ultrafast in layered TMD heterostructures, even though the interlayer interaction is weak. Also surprisingly, the charge separated state is long-lived, despite the close proximity of electron and hole. Using real-time time-dependent density functional theory combined with nonadiabatic (NA) molecular dynamics, we model hole and electron transfer, and electron–hole recombination at a MoS2/WS2 heterojunction. Hole transfer is ultrafast, in excellent agreement with the experiment, due to significant delocalization of the photoexcited state between the donor and acceptor materials. Electron transfer is 1 order of magnitude longer, due to weaker donor–acceptor and NA couplings, lower density of accept...