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Solution-processed organic photovoltaic cells (OPVs) hold great promise to enable roll-to-roll printing of environmentally friendly, mechanically flexible and cost-effective photovoltaic devices. Nevertheless, many high-performing systems show best power conversion efficiencies (PCEs) with a thin active layer (thickness is ~100 nm) that is difficult to translate to roll-to-roll processing with high reproducibility. Here we report a new molecular donor, benzodithiophene terthiophene rhodanine (BTR), which exhibits good processability, nematic liquid crystalline behaviour and excellent optoelectronic properties. A maximum PCE of 9.3% is achieved under AM 1.5G solar irradiation, with fill factor reaching 77%, rarely achieved in solution-processed OPVs. Particularly promising is the fact that BTR-based devices with active layer thicknesses up to 400 nm can still afford high fill factor of ~70% and high PCE of ~8%. Together, the results suggest, with better device architectures for longer device lifetime, BTR is an ideal candidate for mass production of OPVs. Despite recent developments in solid-state photovoltaic devices,,, bulk-heterojunction (BHJ) organic photovoltaics (OPVs) continue to be a promising low-cost renewable energy technology.

The reasons for this outlook include the versatility of organic semiconducting materials and simple device architectures that can be constructed from a variety of printing techniques. The development of the BHJ OPVs has been rapid in recent years driven by a combination of organic material design, interface engineering and improvements in device geometry. The reported power conversion efficiency (PCE) of single-junction small-area devices is now routinely in the 6–8% range.

Published reports of single-junction BHJ OPVs over 9% PCE are still rare. A handful of polymeric electron donor materials and only one molecular donor have been reported in devices that reached this benchmark,,. Molecular OPVs are an attractive alternative to polymer-based OPVs. Higher material purity can be achieved with the well-defined discrete structure of molecules and this should ensure greater reproducibility in devices. To achieve high photovoltaic conversion efficiency, the material should be capable of forming good films with high molecular order. This can be achieved by smart molecular design and control over crystallization processes. For molecular semiconductors, conjugated flat and rigid backbones are preferred for easy packing via π–π interactions.

Good solubility is conferred through employment of the appropriate number, type and length of side chains, without hindering the packing of the backbones. The desirable donor phase in BHJ OPVs needs well-ordered nanocrystals with sizes comparable to the exciton diffusion length for efficient charge generation. Strategies simultaneously to enhance molecular order and restrict crystal size have been reported, including thermal annealing, solvent additives, solid additives and solvent vapour annealing (SVA),,,.

Recent reports showed that the rapid SVA treatment was particularly useful in achieving high fill factor (FF) and PCE in molecular OPVs. Solvent selection rules for SVA treatment were identified in our previous study. Despite the important progress achieved in small-area OPV devices fabricated in laboratories, the successful commercialization of OPV technology relies on the application of solution-processed roll-to-roll techniques for large-scale printing. One of the challenges in printing OPV devices is in printing the optimal active layer thickness of 80–120 nm that many of the high-performing material systems require, while obtaining pinhole-free thin films reproducibly at high printing speed. This problem can be relieved by printing thick films with thickness over 200 nm.

Unfortunately, due to limited charge diffusion length, thick-film OPV devices often experience severe bimolecular recombination and space charge effect, leading to reduced FF and PCE. So far only a few studies have achieved high photovoltaic performance on polymer-based OPVs, with active layers above 200 nm. No report has been found for molecular OPVs. In this work, a new molecular electron donor material, benzodithiophene terthiophene rhodanine (BTR), with a benzo[1,2- b:4,5- b′]dithiophene (BDT) core and rhodanine peripheral units was developed and used in OPV devices giving PCEs >9%.

While its π-conjugated structure is analogous to a high-performance compound reported previously,, the strategic placement of the side chains provided BTR with strong intermolecular interactions, as evidenced by its liquid crystalline (LC) behaviour. Such interactions translated successfully into excellent hole transport properties; hole mobilities up to 0.1 and 1.6 × 10 −3 cm 2 V −1 s −1 were recorded by organic field-effect transistor (OFET) and space-charge-limited current (SCLC) methods, respectively. Thus, BTR-based OPVs with thick active layers (300–400 nm) could still afford PCEs of over 8% with high FF of ~70%. Normal cell architecture employed in this study showed a moderate device lifetime. With better cell architectures or proper encapsulation for longer device lifetime, it is believed that BTR is a very attractive candidate for roll-to-roll printed OPV modules. Physical properties of BTR The BTR molecule was synthesized in two steps from known precursors in a good yield ().

The chemical structure of BTR is shown in. The backbone consisting of the BDT unit, two terthiophenes and two rhodanine groups formed a coplanar structure.

In comparison with analogous structures in the literature,, the side chains of BTR were shortened and positioned at the terthiophene building blocks in a regioregular manner to facilitate side-chain interdigitation. In combination with the additional hexyl group on the thienyl-BDT unit, the side chains of BTR imparted LC behaviour (vide infra) that was not observed in previous reports. ( a) Chemical structure of BTR.

( b) Normalized UV–vis absorption spectra of BTR in chloroform (5 mg ml −1) and in a spin-cast film. ( c) DSC thermogram of BTR in nitrogen at a ramp rate of 10 °C min −1. The lower trace is from the heating cycle and upper trace from the cooling cycle.

( d) BTR thin film sandwiched in between two glass slides observed under a polarized optical microscope (POM) at a stage temperature of 185 °C. ( e) The POM image of the same BTR thin film at the same settings when the stage temperature rises to 195 °C. ( f) The POM image taken at a stage temperature of 197 °C. ( a) Schematic diagram of a normal cell architecture used in this study.

( b) J–V characteristics of BTR:PC 71BM BHJ solar cells with or without THF solvent vapour annealing tested in air under 98 mW cm −2 AM1.5G illumination. Inset: dark current plotted in a semi-log scale of the two solar cells. ( c) EQE spectra of optimized BTR-based solar cells with or without THF SVA treatment. ( d) J–V curve of the most efficient BTR:PC 71BM BHJ solar cell after 15 s of THF SVA measured by an independent research institute in nitrogen atmosphere under an illumination of 100 mW cm −2. The BTR-based OPVs with an optimal active layer thickness of 250 nm were encapsulated and tested in air.

The current density ( J)–voltage ( V) curves of the best devices are shown in, with the photovoltaic parameters summarized in. Without SVA treatment, the highest performance for the as-cast OPVs showed short-circuit current density ( J sc)=11.64 mA cm −2, V oc=0.96 V, FF=47% and PCE=5.2%. SVA treatment significantly enhanced the photovoltaic performance. OPVs with 15 s of THF SVA exhibited J sc=13.52 mA cm −2, V oc=0.89 V, FF=73% and PCE=8.7%. Device assembly was reproducible with around 60 SVA-treated OPV devices having an average PCE of 8.3±0.2%. Thermal annealing was found to diminish the device performance, due to the overgrowth of the phases (). The causes for the enhanced FF after SVA treatment were investigated by measuring dark currents (inset of ).

Compared with an as-cast molecular OPV, the SVA-treated sample displayed notably higher current density under positive bias. In great contrast, the current density was one order of magnitude smaller in reverse bias. To further understand the SVA treatment effect, series resistance ( R s) and shunt resistance ( R sh) were extracted at 1. The Sims 4 Free For Pc Full Version here. 5 and 0 V of the dark curves (). Without SVA treatment, the OPV had a R s of 14.0 Ω cm 2 and a R sh of 5.5 MΩ cm 2. SVA treatment led to a reduction of R s by six times and a slight increase of R sh. Together, the results suggest the SVA treatment can suppress leakage current and improve the diode behaviour.

The slight improvement in J sc after SVA treatment was monitored by external quantum efficiency (EQE) measurement (). A high EQE of over 60% was measured in the visible region from 400 to 650 nm for the non-annealed OPV. The J sc calculated by integrating the product of photon flux and EQE at each wavelength was 11.70 mA cm −2, which was in good agreement with the measured J sc (11.64 mA cm −2). The SVA treatment lifted the EQE in the entire absorption range. In particular, the EQE stayed above 70% between 400 and 650 nm, and a shoulder was found at 640 nm.

As a result, the calculated J sc increased to 13.53 mA cm −2. The EQE result clearly indicates SVA treatment plays a positive role in charge generation, transport and/or collection.

Bearing in mind that OPVs with normal cell architecture are not stable in air, we fabricated a batch of 20 devices in Singapore and 8 devices in Australia and tested them under inert atmosphere using the facilities at Solar Energy Research Institute of Singapore and the Commonwealth Scientific and Industrial Research Organisation, respectively. The best BTR-based OPV fabricated in Singapore exhibited a record efficiency of 9.3%, with J sc=13.90 mA cm −2, V oc=0.90 V and FF=74.1% (; ). The results were highly reproducible. The same PCE of 9.3% with a J sc of 13.40 mA cm −2, a V oc of 0.90 V and an extremely high FF of 77.0% was achieved in Australia (). This result demonstrates molecular OPVs can achieve comparable efficiencies attainable by polymer-based OPVs.

It is worth noting that the FF of 77.0% is among the highest FF value reported in the literature for solution-processed molecular OPVs. The average photovoltaic parameters for the 28 devices were J sc=13.49±0.28 mA cm −2, V oc=0.89±0.01 V, FF=74±1% and PCE=8.9±0.2% (). OPVs of a thick active layer The high FF values suggest that the BTR-based OPVs can accommodate a greater range of active layer thicknesses.

This is particularly important in roll-to-roll printing of very thin films, which are difficult to be precisely controlled, and pinholes are often found in thin-film devices. We were motivated to explore the thickness-dependent solar cell performance using the BTR molecule.

Active layers with different thicknesses ranging from 80 to 400 nm were fabricated by tuning the solution concentrations and spin rates. And show that BTR-based OPVs maintain a nearly constant V oc between 0.87 and 0.90 V. The average J sc increases from ~10 to ~13 mA cm −2 as the active layer thickness increases from 80 to 250 nm and then it saturates around 13 mA cm −2 when the thickness further increases to 400 nm. Surprisingly, the FF values for BTR-based OPVs remain high and close to 70% even at thicknesses up to 400 nm. This is not commonly observed in thick-film OPVs, whether it is a molecular OPV or a polymer-based solar cell,. As a result, the overall PCEs formed a flat bell curve with a minimum average value of 6.8% and maximum average value of 8.3% at an active layer thickness of 250 nm.

The large tolerance for the active layer thickness makes the BTR molecule a strong candidate for printed OPVs. Solvent vapour annealing To understand the effect of SVA treatment on the photovoltaic performance of BTR-based OPVs, we carried out studies on active layer morphology and the optoelectronic properties. The surface topography of the active layer was recorded by atomic force microscopy (AFM) operated in the tapping mode.

Before the SVA treatment, depicts a rather smooth surface, with root-mean-square roughness ( R rms) of 0.61 nm. Fine crystal domains co-exist with random pinholes, which are believed to be related with the escaping of processing solvent.

After a short THF SVA treatment of 15 s, the active layer exhibits a coarser surface (). The R rms value almost doubles to 1.04 nm. Transmission electron microscopy (TEM) is able to provide morphological information inside the active layer. The bright-field TEM images () suggest THF SVA treatment leads to larger and more well-defined domains. Because of the sharp contrast in the TEM images, we were able to obtain TEM tomograms and computer models to view the morphological change in 3D (; ).

Both the TEM tomograms and their computer models show that fine-sized domains in the as-cast active layer () evolve into larger domains that are inter-connected to form networks throughout the entire active layer after THF SVA for 15 s (). Such networks resemble ‘3D charge highways’ that are beneficial to fast charge transport. The feature size on TEM images is verified by low-energy high-angle angular dark-field scanning TEM (HAADF STEM) images (). ( a) AFM image shows the topography of an as-cast BTR:PC 71BM (1:1 weight ratio) blend film. ( b) TEM bright-field image of the as-cast film taken at a defocusing range of 3 μm. ( c) Computer model generated from the TEM tomogram of the as-cast film.

( d) Low-energy HAADF STEM image of the as-cast film at focus using a beam energy of 15 keV. ( e) AFM image of the BTR:PC 71BM blend film after THF SVA for 15 s. ( f) TEM bright-field image of the SVA-treated film at a defocusing range of 3 μm.

( g) Computer model of the THF SVA film. ( h) HAADF STEM image of the blend film after SVA treatment. In summary, we present a new molecular donor, BTR, which possesses a rigid and flat backbone and a large number of flexible side chains that could work synergistically to provide excellent processability, nematic liquid crystal behaviour and optoelectronic properties.

The neat BTR film exhibited hole mobilities up to 0.1 cm 2 V −1 s −1 in OFET devices. The solution-processed single-junction BHJ solar cells based on BTR and PC 71BM demonstrated a reproducible record efficiency of 9.3%. The blend film also supported a high FF of 77% and a high SCLC hole mobility of 1.6 × 10 −3 cm 2 V −1 s −1 after SVA with THF. Thick-film molecular solar cells with an active layer thickness up to 400 nm were demonstrated, showing a low thickness dependence of photovoltaic performance.

Together, the results suggest BTR is an ideal candidate for printed OPVs. Moreover, enhancing the intermolecular interaction through side-chain modification is a viable way further to enhance the efficiency of molecular solar cells in excess of 10%. Sequential deposition as a route to high-performance perovskite-sensitized solar cells. Nature 499, 316–319 (2013). Liu, M., Johnston, M. Efficient planar heterojunction perovskite solar cells by vapour deposition. Nature 501, 395–398 (2013).

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