Non-Halogenated Solvents Processed Efficient ITO-Free Flexible Organic Solar Cells with Upscaled Area.

Organic solar cells (OSCs) show the potential to harness solar energy at a lower cost and in a greener way with the merits of mechanical flexibility and potential low-cost upscaling production with solution processing. Meanwhile, the common use of toxic halogenated solvents causes pollution to the natural environment, and thus, needs to be avoided. Following the authors' previous work on the design of top-illuminated ultrathin Ag-based device structure highlighting most merits of OSC, herein non-halogen solvent and additive processing OSCs are presented, which exhibit high power conversion efficiency (PCE) of 17.64%, close to the best PCE with the commonly used halogen solvent. Interestingly, it is observed that the additive and the multicomponent strategy (blending third component BTP-S2 into PM6:L8-BO binary blend) synergistically affect the optimal morphology and device performance. Finally, OSC devices featuring green solvent processing, indium tin oxide-free, flexibility, and upscaling merits are fabricated and exhibit the best PCE of 13.76% with high mechanical robustness and good stability against heat or light illumination. This work provides a prospective potential for manufacturing the OSC toward practical applications.

Correction: Optical and electrical effects of plasmonic nanoparticles in high-efficiency hybrid solar cells.

Correction for 'Optical and electrical effects of plasmonic nanoparticles in high-efficiency hybrid solar cells' by Wei-Fei Fu et al., Phys. Chem. Chem. Phys., 2013, 15, 17105-17111, DOI: 10.1039/C3CP52723A.

Vertically Oriented 2D Layered Perovskite Solar Cells with Enhanced Efficiency and Good Stability.

Vertically oriented highly crystalline 2D layered (BA)2 (MA)n-1 Pbn I3n+1 (BA = CH3 (CH2 )3 NH3 , MA = CH3 NH3 , n = 3, 4) perovskite thin-films are fabricated with the aid of ammonium thiocyanate (NH4 SCN) additive through one-step spin-coating process. The humidity-stability of the film is certified by the almost unchanged X-ray diffraction patterns after exposed to humid atmosphere (Hr = 55 ± 5%) for 40 d. The photovoltaic devices with the structure of indium tin oxide(ITO)/poly(3,4-ethylenedioxythiophene):poly(styrene-sulfonate)/(BA)2 (MA)n-1 Pbn I3n+1 (n = 3,4)/[6,6]-phenyl-C61 -butyric acid methyl ester/Bathocuproine/Ag are fabricated. The devices based on (BA)2 (MA)2 Pb3 I10 perovskite (n = 3) with the precursor composition of BAI:methylammonium iodide:PbI2 :NH4 SCN = 2:2:3:1 (by molar ratio) show an averaged power conversion efficiency (PCE) of 6.82%. In the case of (BA)2 (MA)3 Pb4 I13 (n = 4), a higher PCE of 8.79% is achieved. Both of the unsealed devices perform unique stability with almost unchanged PCE during the period of storage in purified N2 glove box. This work provides a simple and effective method to enhance the efficiency of the 2D perovskite solar cell.

Dopant-Free Hole-Transporting Material with a C3h Symmetrical Truxene Core for Highly Efficient Perovskite Solar Cells.

Herein we present a new structural design of hole-transporting material, Trux-OMeTAD, which consists of a C3h Truxene-core with arylamine terminals and hexyl side-chains. This planar, rigid, and fully conjugated molecule exhibits excellent hole mobility and desired surface energy to the perovskite uplayer. Perovskite solar cells fabricated using the p-i-n architecture with Trux-OMeTAD as the p-layer, show a high PCE of 18.6% with minimal hysteresis.

Enhanced photovoltaic performance of CH3NH3PbI3 perovskite solar cells through interfacial engineering using self-assembling monolayer.

Morphology control is critical to achieve high efficiency CH3NH3PbI3 perovskite solar cells (PSC). The surface properties of the substrates on which crystalline perovskite thin films form are expected to affect greatly the crystallization and, thus, the resulting morphology. However, this topic is seldom examined in PSC. Here we developed a facile but efficient method of modifying the ZnO-coated substrates with 3-aminopropanioc acid (C3-SAM) to direct the crystalline evolution and achieve the optimal morphology of CH3NH3PbI3 perovskite film. With incorporation of the C3-SAM, highly crystalline CH3NH3PbI3 films were formed with reduced pin-holes and trap states density. In addition, the work function of the cathode was better aligned with the conduction band minimum of perovskite for efficient charge extraction and electronic coupling. As a result, the PSC performance remarkably increased from 9.81(±0.99)% (best 11.96%) to 14.25(±0.61)% (best 15.67%). We stress the importance of morphology control through substrate surface modification to obtain the optimal morphology and device performance of PSC, which should generate an impact on developing highly efficient PSC and future commercialization.

Solution-grown organic single-crystalline donor-acceptor heterojunctions for photovoltaics.

Organic single crystals are ideal candidates for high-performance photovoltaics due to their high charge mobility and long exciton diffusion length; however, they have not been largely considered for photovoltaics due to the practical difficulty in making a heterojunction between donor and acceptor single crystals. Here, we demonstrate that extended single-crystalline heterojunctions with a consistent donor-top and acceptor-bottom structure throughout the substrate can be simply obtained from a mixed solution of C60 (acceptor) and 3,6-bis(5-(4-n-butylphenyl)thiophene-2-yl)-2,5-bis(2-ethylhexyl)pyrrolo[3,4-c]pyrrole-1,4-dione (donor). 46 photovoltaic devices were studied with the power conversion efficiency of (0.255±0.095)% under 1 sun, which is significantly higher than the previously reported value for a vapor-grown organic single-crystalline donor-acceptor heterojunction (0.007%). As such, this work opens a practical avenue for the study of organic photovoltaics based on single crystals.

A direct arylation-derived DPP-based small molecule for solution-processed organic solar cells.

A diketo-pyrrolo-pyrrole (DPP) oligomer containing three DPP cores (Ph4Th4(DPP)3) was synthesized via direct arylation of C-H bonds (DACH). Ph4Th4(DPP)3 has good solubility in many organic solvents, and shows a broad absorption band from the visible to near-infrared region as well as a field-effect hole mobility as high as 0.006 cm(2) V(-1) s(-1). Solution-processed bulk heterojunction organic solar cells based on blends of Ph4Th4(DPP)3 as electron donor and fullerene derivative as electron acceptor were fabricated. An optimized power conversion efficiency of 3.76% with a high open-circuit voltage of 0.85 V was achieved after finely tuning the morphology by changing the blend ratio and by adding additives. These results indicate that DACH is an effective way to produce π-conjugated oligomers for organic solar cells.

Thorough Optimization for Intrinsically Stretchable Organic Photovoltaics.

The development of intrinsically stretchable organic photovoltaics (is-OPVs) with a high efficiency is of significance for practical application. However, their efficiencies lag far behind those of rigid or even flexible counterparts. To address this issue, an advanced top-illuminated OPV is designed and fabricated, which is intrinsically stretchable and has a high performance, through systematic optimizations from material to device. First, the stretchability of the active layer is largely increased by adding a low-elastic-modulus elastomer of styrene-ethylene-propylene-styrene tri-block copolymer (SEPS). Second, the stretchability and conductivity of the opaque electrode are enhanced by a conductive polymer/metal (denoted as M-PH1000@Ag) composite electrode strategy. Third, the optical and electrical properties of a sliver nanowire transparent electrode are improved by a solvent vapor annealing strategy. High-performance is-OPVs are successfully fabricated with a top-illuminated structure, which provides a record-high efficiency of 16.23%. Additionally, by incorporating 5-10% elastomer, a balance between the efficiency and stretchability of the is-OPVs is achieved. This study provides valuable insights into material and device optimizations for high-efficiency is-OPVs, with a low-cost production and excellent stretchability, which indicates a high potential for future applications of OPVs.

Optical and electrical effects of plasmonic nanoparticles in high-efficiency hybrid solar cells.

Plasmonics have been proven to be an effective way to harness more incident light to achieve high efficiency in photovoltaic devices. Herein, we explore the possibility that plasmonics can be utilized to enhance light trapping and power conversion efficiency (PCE) for polymer-quantum dot (QD) hybrid solar cells (HSCs). Based on a low band-gap polymer poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']-dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (PCPDTBT) and a CdSe QD bulk-heterojunction (BHJ) system, gold nanoparticles were doped at different locations of the devices. Successfully, an improved PCE of 3.20 ± 0.22% and 3.16 ± 0.15% was achieved by doping the hole transporting layer and the active layer, respectively, which are among the highest values reported for CdSe QD based HSCs. A detailed study of processing, characterization, microscopy, and device fabrication is conducted to understand the underlying mechanism for the enhanced device performance. The success of this work provides a simple and generally applicable approach to enhance light harnessing of polymer-QD hybrid solar cells.

High efficiency hybrid solar cells using post-deposition ligand exchange by monothiols.

High-performance hybrid solar cells (HSCs) based on P3HT : CdSe QD blends are achieved through post-deposition ligand exchange by n-butanethiol (n-BT) with a high power conversion efficiency of 3.09%. The mechanism by which n-BT modifies the surface structures of CdSe QDs and thus improves the HSCs performance is investigated.

Balancing the Selective Absorption and Photon-to-Electron Conversion for Semitransparent Organic Photovoltaics with 5.0% Light-Utilization Efficiency.

Efficiently converting invisible light while allowing full visible light transmission is key to achieving high-performance semitransparent organic photovoltaics (ST-OPVs). Here, a detailed balance strategy is explored to optimize the ST-OPV via taking both absorption and carrier dynamics into consideration. Based on this principle, comprehensive optimizations are carried out, including a ternary strategy, donor:acceptor blend ratio, thickness, antireflection, etc., to compromise the invisible energy conversion and visible transmission for high-performance ST-OPVs. As a result, the opaque OPV device exhibits a champion power conversion efficiency of 19.35% (certificated 19.07%), and most strikingly, the best ST-OPV shows a remarkably high light-utilization efficiency of 5.0%, where the efficiency and the average visible transmission are 12.95% and 38.67%, respectively. An efficiency of 12.09% is achieved on the upscaled device with an area of 1.05 cm2 , demonstrating its promise for large-area fabrication. These results are among the best values for ST-OPVs. Besides, it is demonstrated that the ST-OPV exhibits good infrared light-reflection capability for thermal control. This work provides a rational design of balancing the absorbing selectivity and photon-to-electron conversion for high-performance ST-OPVs, and may pave the way toward the practical application of solar windows.

Multiphase Morphology with Enhanced Carrier Lifetime via Quaternary Strategy Enables High-Efficiency, Thick-Film, and Large-Area Organic Photovoltaics.

With the continuous breakthrough of the efficiency of organic photovoltaics (OPVs), their practical applications are on the agenda. However, the thickness tolerance and upscaling in recently reported high-efficiency devices remains challenging. In this work, the multiphase morphology and desired carrier behaviors are realized by utilizing a quaternary strategy. Notably, the exciton separation, carrier mobility, and carrier lifetime are enhanced significantly, the carrier recombination and the energy loss (Eloss ) are reduced, thus beneficial for a higher short-circuit density (JSC ), fill factor (FF), and open-circuit voltage (VOC ) of the quaternary system. Moreover, the intermixing-phase size is optimized, which is favorable for constructing the thick-film and large-area devices. Finally, the device with a 110 nm-thick active layer shows an outstanding power conversion efficiency (PCE) of 19.32% (certified 19.35%). Furthermore, the large-area (1.05 and 72.25 cm2 ) devices with 110 nm thickness present PCEs of 18.25% and 12.20%, and the device with a 305 nm-thick film (0.0473 cm2 ) delivers a PCE of 17.55%, which are among the highest values reported. The work demonstrates the potential of the quaternary strategy for large-area and thick-film OPVs and promotes the practical application of OPVs in the future.

Synergistic Effects of Chlorination and Branched Alkyl Side Chain on the Photovoltaic Properties of Simple Non-Fullerene Acceptors with Quinoxaline as the Core.

To date, the fused-ring electron acceptors show the best photovoltaic performances, and the development of simple non-fullerene acceptors via intramolecular noncovalent interactions can reduce synthetic costs. In this work, four simple non-fullerene acceptors with an A-D-A'-D-A configuration (QCIC1, QCIC2, QCIC3, and QCIC4) were synthesized. They contained the same conjugated backbone (A': quinoxaline; D: cyclopentadithiophene; A: dicyano-indanone) but different halogen atoms and alkyl side chains. Due to the chlorination on the end-groups and the most and/or longest branched alkyl side chains on the backbone, the blended film composed of QCIC3 and donor poly{[2,6'-4,8-di(5-ethylhexylthienyl)benzo [1,2-b : 4,5-b']dithiophene]-alt-[5,5-(1',3'-di-2-thienyl-5',7'-bis(2-ethylhexyl)benzo[1',2'-c : 4',5'-c']dithiophene-4,8-dione)]} (PBDB-T) exhibited the strongest π-π stacking and the most suitable phase-separation domains among the four blended films. Therefore, the QCIC3-based organic solar cells yielded the highest power conversion efficiency of 10.55 %. This work provides a pathway to optimize the molecular arrangements and enhance the photovoltaic property of simple electron acceptors through subtle chemical modifications.

Oriented Perovskite Growth Regulation Enables Sensitive Broadband Detection and Imaging of Polarized Photons Covering 300-1050 nm.

Photodetectors selective to the polarization empower breakthroughs in sensing technology for target identification. However, the realization of polarization-sensitive photodetectors based on intrinsically anisotropic crystal structure or extrinsically anisotropic device pattern requires complicated epitaxy and etching processes, which limit scalable production and application. Here, solution-processed PEA2 MA4 (Sn0.5 Pb0.5 )5 I16 (PEA= phenylethylammonium, MA= methylammonium) polycrystalline film is probed as photoactive layer toward sensing polarized photon from 300 to 1050 nm. The growth of the PEA2 MA4 (Sn0.5 Pb0.5 )5 I16 crystal occurs in confined crystallographic orientation of the (202) facet upon the assistance of NH4 SCN and NH4 Cl, enhancing anisotropic photoelectric properties. Therefore, the photodetector achieves a polarization ratio of 0.41 and dichroism ratio (Imax /Imin ) of 2.4 at 900 nm. At 520 nm, the Imax /Imin even surpasses the one of the perovskite crystalline films, 1.8 and ≈1.2, respectively. It is worth noting that the superior figure-of-merits possess a response width of 900 kHz, Ion /Ioff ratio of ≈3 × 108 , linear dynamic range from 0.15 nW to 12 mW, noise current of 8.28 × 10-13 A × Hz-0.5 , and specific detectivity of 1.53 × 1012 Jones, which demonstrate high resolution and high speed for weak signal sensing and imaging. The proof of concept in polarized imaging confirms that the polarization-sensitive photodetector meets the requirements for practical application in target recognition.

Highly Efficient Semitransparent Solar Cells with Selective Absorption and Tandem Architecture.

Semitransparent (ST) photovoltaics (PVs) with selective absorption in the UV or/and near-infrared (NIR) range(s) and reduced energy losses, are critical for high-efficiency solar-window applications. Here, a high-performance tandem ST-PV with selected absorption in the desirable regions of the solar spectrum is demonstrated. An ultralarge-bandgap perovskite film (FAPbBr2.43 Cl0.57 , Eg ≈ 2.36 eV) is first developed to fulfil efficient selective absorption in the UV region. After optimization, the corresponding ST single junction (SJ) PV exhibits an averaged transmittance (AVT) of ≈68% and an efficiency of ≈7.5%. By sequentially reducing the visible absorbing component in a low-bandgap organic bulk-heterojunction layer, an ST-PV with selective absorption in the NIR is achieved with a power conversion efficiency (PCE) of 5.9% and a high AVT of 62%. The energy loss associated with the SJ ST-PVs is further reduced with a tandem architecture, which affords a high PCE of 10.7%, an AVT of 52.91%, and a light utilization efficiency up to 5.66%. These results represent the best balance of AVT and PCE among all ST-PVs reported so far, and this design should pave the road for solar windows of high performance.

Improved performance and stability of perovskite solar cells with bilayer electron-transporting layers.

Zinc oxide nanoparticles (NPs) are very promising in replacing the phenyl-C61-butyric acid methyl ester (PC61BM) as electron-transporting materials due to the high carrier mobilities, superior stability, low cost and solution processability at low temperatures. The perovskite/ZnO NPs heterojunction has also demonstrated much better stability than perovskite/PC61BM, however it shows lower power conversion efficiency (PCE) compared to the state-of-art devices based on perovskite/PCBM heterojunction. Here, we demonstrated that the insufficient charge transfer from methylammonium lead iodide (MAPbI3) to ZnO NPs and significant interface trap-states lead to the poor performance and severe hysteresis of PSC with MAPbI3/ZnO NPs heterojunction. When PC61BM/ZnO NPs bilayer electron transporting layers (ETLs) were used with a device structure of ITO/poly(bis(4-phenyl)(2,4,6-trimethylphenyl)amine) (PTAA)/MAPbI3/PC61BM/ZnO NPs/Al, which can combine the advantages of efficient charge transfer from MAPbI3 to PC61BM and excellent blocking ability of ZnO NPs against oxygen, water and electrodes, highly efficient PSCs with PCE as high as 17.2% can be achieved with decent stability.

Synthesis and fast transfer of monolayer MoS2 on reusable fused silica.

Atomically thin, two-dimensional materials ranging from superconductors, metals, semiconductors to insulators are emerging as potential candidates for the next-generation digital electronics and optoelectronic applications. Their synthesis on a commonly used substrate and fast transfer to a plenty of desired substrates need to be addressed to meet the industrialization criteria for practical applications. In this study, fused silica, which is amorphous, transparent, and inexpensive, was examined as a substrate for MoS2 synthesis. The MoS2 growth behavior on fused silica and its crystal quality were evaluated. In addition, a novel way was developed to quickly peel off MoS2 from the fused silica surface within 15 s (i.e., etching in an acidic solution to detach the edge and completing the delamination via a capillary force at the interface between air and water). The fused silica could be reused at least three times. Moreover, the produced MoS2 domains showed no obvious degradation of quality. These results support the feasibility of MoS2 synthesis on amorphous and recyclable substrates and also the time-saving transfer for the cost-effective and high-quality production of other two-dimensional materials.

Donor-Acceptor Conjugated Macrocycles: Synthesis and Host-Guest Coassembly with Fullerene toward Photovoltaic Application.

Electron-rich (donor) and electron-deficient (acceptor) units to construct donor-acceptor (D-A) conjugated macrocycles were investigated to elucidate their interactions with electron-deficient fullerene. Triphenylamine and 4,7-bisthienyl-2,1,3-benzothiadiazole were alternately linked through acetylene, as the donor and acceptor units, respectively, for pentagonal 3B2A and hexagonal 4B2A macrocycles. As detected by scanning tunneling microscopy, both D-A macrocycles were found to form an interesting concentration-controlled nanoporous monolayer on highly oriented pyrolytic graphite, which could effectively capture fullerene. Significantly, the fullerene filling was cavity-size-dependent with only one C70 or PC71BM molecule accommodated by 3B2A, while two were accommodated by 4B2A. Density functional theory calculations were also utilized to gain insight into the host-guest systems and indicted that the S···π contact is responsible for stabilizing these host-guest systems. Owing to the ellipsoidal shape of C70, C70 molecules are standing or lying in molecular cavities depending on the energy optimization. For the 3B2A/PC71BM blended film, PC71BM was intercalated into the cavity formed by the macrocycle 3B2A and provided excellent power conversion efficiency despite the broad band gap (2.1 eV) of 3B2A. This study of D-A macrocycles incorporating fullerene provides insights into the interaction mechanism and electronic structure in the host-guest complexes. More importantly, this is a representative example using D-A macrocycles as a donor to match with the spherical fullerene acceptor for photovoltaic applications, which offer a good approach to achieve molecular scale p-n junctions for substantially enhanced efficiencies of organic solar cells through replacing linear polymer donors by cyclic conjugated oligomers.

Solution-Processed 8-Hydroquinolatolithium as Effective Cathode Interlayer for High-Performance Polymer Solar Cells.

Solution-processed 8-hydroxyquinolinatolithium (s-Liq) was successfully applied as an efficient cathode interlayer in bulk heterojunction polymer solar cells (PSCs), giving rise to enhancement in device performance. The ultraviolet photoelectron spectra results revealed that the presence of s-Liq could lower work function of Al cathode, allowing for the ohmic contacts with the fullerene acceptor for better electron extraction and also a larger work function difference between the two electrodes, which leads to an increase in open-circuit voltage (V(oc)). Scanning Kelvin probe microscopy study on the surface potential of active layers suggested that an interfacial dipole was formed in the s-Liq interlayer between the active layer and the Al cathode, which enhanced the intrinsic built-in potential in the device for better charge transportation and extraction. Consequently, the V(oc), fill factor, and current density of the device can be improved by the introduction of s-Liq interlayer, leading to a power conversion efficiency (PCE) improvement. With PTB7 (or PTB7-Th) as the donor and PC71BM as the acceptor, the s-Liq-based PSC devices exhibited a PCE of 8.37% (or 9.04%), much higher than those of devices with the evaporated Liq (7.62%) or commonly used PFN (8.14%) as the cathode interlayer. Moreover, the s-Liq-based devices showed good stability, maintaining 75% (in N2) and 45% (in air) of the initial PCE after 7 days, respectively. These results suggest the great potential of s-Liq as cathode interlayer material for high-performance solar cells application.

Effects of heteroatom substitution in spiro-bifluorene hole transport materials.

Three new spirofluorene-based hole transport materials, Spiro-S, Spiro-N, and Spiro-E, are synthesized by replacing the para-methoxy substituent in 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenylamine)-9,9'-spirobifluorene (Spiro-MeOTAD) with methylsulfanyl, N,N-dimethylamino and ethyl groups. Their properties as hole transport materials in perovskite solar cells are investigated. The impact of replacing the para-methoxy substituent on bulk properties, such as the photophysical properties, HOMO/LUMO energy level, hole extraction properties and morphologies of perovskite thin films are investigated. Their optoelectronic and charge-transport properties and performance in perovskite solar cells are compared with the current benchmarked and structurally-related hole transport material (HTM) Spiro-MeOTAD. Surprisingly, the methylsulfanyl substituted spirofluorene shows the highest power conversion efficiency of 15.92% among the investigated spirofluorenes, which is an over 38% increase in PCE compared with that of Spiro-MeOTAD under similar device fabrication conditions.