Boosting inverted perovskite solar cell performance by using 9,9-bis(4-diphenylaminophenyl)fluorene functionalized with triphenylamine as a dopant-free hole transporting material

In this study, two newly developed small molecules based on 9,9-bis(4-diphenylaminophenyl)fluorene functionalized with triphenylamine moieties, namely TPA-2,7-FLTPA-TPA and TPA-3,6-FLTPA-TPA, are designed, synthesized and characterized. The electrochemical, optical and thermal properties of both materials are investigated using various techniques. Afterwards, these materials are employed as dopant-free hole transporting materials (HTMs) in planar inverted perovskite solar cell devices with the aim of determining the device performance and studying their stability in comparison with reference N-4,N-4,N-4,N-4-tetra([1,10-biphenyl]-4-yl)-[1,1:4,1-terphenyl]-4,4-diamine (TaTm)-based devices. Under 1 sun conditions, TPA-3,6-FLTPA-TPA-based devices achieve a power conversion efficiency (PCE) of 13.9% whereas TPA-2,7-FLTPA-TPA-based devices exhibit the highest PCE of 17.1% mainly due to an improvement in the fill factor (FF). Meanwhile, the devices prepared using TaTm as the reference HTM exhibit an overall efficiency of 15.9%. In addition to the higher efficiency, our newly developed HTM TPA-2,7-FLTPA-TPA-based devices demonstrate good stability which is comparable to those with TaTm under similar aging test conditions

All‐Rounder Low‐Cost Dopant‐Free D‐A‐D Hole‐Transporting Materials for Efficient Indoor and Outdoor Performance of Perovskite Solar Cells

A novel biphenyl fumaronitrile as an acceptor and triphenylamine as donor conjugated building blocks are used for the first time to successfully synthesize donor–acceptor–donor molecule (D-A-D) 2,3-bis(4′-(bis(4-methoxyphenyl)amino)-[1,1′-biphenyl]-4-yl)fumaronitrile (TPA-BPFN-TPA). The new TPA-BPFN-TPA with low-lying HOMO is used as a dopant-free hole-transporting material (HTM) in mesoporous perovskite solar cells. The performance of the solar cells using this new HTM is compared with the traditional 2,2′,7,7′-tetrakis(N,N′-di-p-methoxyphenylamino)- 9,9′-spirobifluorene (Spiro-OMeTAD) HTM based devices for outdoor and indoor performance evaluation. Under 1 sun illumination, dopant-free TPA-BPFN-TPA HTM based devices exhibit a power conversion efficiency (PCE) of 18.4%, which is the record efficiency to date among D-A-D molecular design based dopant-free HTMs. Moreover, the stability of unencapsulated TPA-BPFN-TPA-based devices shows improvement over Spiro-OMeTAD-based devices in harsh relative humidity condition of 70%. Another exciting feature of the newly developed HTM is that the TPA-BPFN-TPA-based devices exhibit improved PCE of 30% and 20.1% at 1000 lux and 200 lux illuminations, respectively. This new finding provides a solution to fabricate low indoor (low light) and outdoor (1 sun) perovskite solar cell devices with high efficiency for cutting-edge energy harvesting technology.</p

Correction: Naphthalene flanked diketopyrrolopyrrole based organic semiconductors for high performance organic field effect transistors (New Journal of Chemistry (2018) 42 (12374–12385) DOI: 10.1039/C8NJ01453A)

The authors would like to correct the Acknowledgements section. The Acknowledgements section should read: Qian Liu is thankful to QUT for offering here QUTPRA scholarship to conduct his research. P. S. is thankful to QUT for the financial support from the Australian Research Council (ARC) for the Future Fellowship (FT130101337) and QUT core funding (QUT/322120-0301/07). S. M. is supported by the Ministry of Education of Singapore. Some of the data reported in this paper were obtained at the Central Analytical Research Facility (CARF) operated by the Institute for Future Environments (QUT). Access to CARF is supported by generous funding from the Science and Engineering Faculty (QUT). This study was supported by the Center for Advanced Soft-Electronics (2013M3A6A5073183) through the NRF grant funded by the Korean government. The Royal Society of Chemistry apologises for these errors and any consequent inconvenience to authors and readers

Correction: Naphthalene flanked diketopyrrolopyrrole based organic semiconductors for high performance organic field effect transistors (New Journal of Chemistry (2018) 42 (12374–12385) DOI: 10.1039/C8NJ01453A)

The authors would like to correct the Acknowledgements section. The Acknowledgements section should read: Qian Liu is thankful to QUT for offering here QUTPRA scholarship to conduct his research. P. S. is thankful to QUT for the financial support from the Australian Research Council (ARC) for the Future Fellowship (FT130101337) and QUT core funding (QUT/322120-0301/07). S. M. is supported by the Ministry of Education of Singapore. Some of the data reported in this paper were obtained at the Central Analytical Research Facility (CARF) operated by the Institute for Future Environments (QUT). Access to CARF is supported by generous funding from the Science and Engineering Faculty (QUT). This study was supported by the Center for Advanced Soft-Electronics (2013M3A6A5073183) through the NRF grant funded by the Korean government. The Royal Society of Chemistry apologises for these errors and any consequent inconvenience to authors and readers

Switched photocurrent on tin sulfide-based nanoplate photoelectrodes

A new type of SnS2 nanoplate photoelectrode is prepared by using a mild wet-chemical method. Depending on the calcination temperatures, SnS2-based photoelectrodes can either retain their n-type nature with greatly enhanced anodic photocurrent density (ca. 1.2 mA cm(-2) at 0.8V vs. Ag/AgCl) or be completely converted into p-type SnS to generate approximately 0.26 mA cm(-2) cathodic photocurrent density at -0.8 V vs. Ag/AgCl. The dominance of sulfur and tin vacancies are found to account for the dramatically different photoelectrochemical behaviors of n-type SnS2 and p-type SnS photoelectrodes. In addition, the band structures of n-type SnS2 and p-type SnS photoelectrodes are also deduced, which may provide an effective strategy for developing SnS2/SnS films with controllable energy-band levels through a simple calcination treatment

Deducing transport properties of mobile vacancies from perovskite solar cell characteristics

The absorber layers in perovskite solar cells possess a high concentration of mobile ion vacancies. These vacancies undertake thermally activated hops between neighboring lattice sites. The mobile vacancy concentration N 0 is much higher and the activation energy E A for ion hops is much lower than is seen in most other semiconductors due to the inherent softness of perovskite materials. The timescale at which the internal electric field changes due to ion motion is determined by the vacancy diffusion coefficient D v and is similar to the timescale on which the external bias changes by a significant fraction of the open-circuit voltage at typical scan rates. Therefore, hysteresis is often observed in which the shape of the current-voltage, J-V, characteristic depends on the direction of the voltage sweep. There is also evidence that this defect migration plays a role in degradation. By employing a charge transport model of coupled ion-electron conduction in a perovskite solar cell, we show that E A for the ion species responsible for hysteresis can be obtained directly from measurements of the temperature variation of the scan-rate dependence of the short-circuit current and of the hysteresis factor H. This argument is validated by comparing E A deduced from measured J-V curves for four solar cell structures with density functional theory calculations. In two of these structures, the perovskite is MAPbI 3, where MA is methylammonium, CH 3 NH 3; the hole transport layer (HTL) is spiro (spiro-OMeTAD, 2,2 ′,7,7 ′- tetrakis[N,N-di(4-methoxyphenyl) amino]-9,9 ′-spirobifluorene) and the electron transport layer (ETL) is TiO 2 or SnO 2. For the third and fourth structures, the perovskite layer is FAPbI 3, where FA is formamidinium, HC (NH 2) 2, or MAPbBr 3, and in both cases, the HTL is spiro and the ETL is SnO 2. For all four structures, the hole and electron extracting electrodes are Au and fluorine doped tin oxide, respectively. We also use our model to predict how the scan rate dependence of the power conversion efficiency varies with E A, N 0, and parameters determining free charge recombination. </p

Molecular Engineering Using an Anthanthrone Dye for Low-Cost Hole Transport Materials: A Strategy for Dopant-Free, High-Efficiency, and Stable Perovskite Solar Cells

In this report, highly efficient and humidity-resistant perovskite solar cells (PSCs) using two new small molecule hole transporting materials (HTM) made from a cost-effective precursor anthanthrone (ANT) dye, namely, 4,10-bis(1,2-dihydroacenaphthylen-5-yl)-6,12-bis(octyloxy)-6,12-dihydronaphtho[7,8,1,2,3-nopqr]tetraphene (ACE-ANT-ACE) and 4,4′-(6,12-bis(octyloxy)-6,12-dihydronaphtho[7,8,1,2,3-nopqr]tetraphene-4,10-diyl)bis(N,N-bis(4-methoxyphenyl)aniline) (TPA-ANT-TPA) are presented. The newly developed HTMs are systematically compared with the conventional 2,2′,7,7′-tetrakis(N,N′-di-p-methoxyphenylamino)-9,9′-spirbiuorene (Spiro-OMeTAD). ACE-ANT-ACE and TPA-ANT-TPA are used as a dopant-free HTM in mesoscopic TiO2/CH3NH3PbI3/HTM solid-state PSCs, and the performance as well as stability are compared with Spiro-OMeTAD-based PSCs. After extensive optimization of the metal oxide scaffold and device processing conditions, dopant-free novel TPA-ANT-TPA HTM-based PSC devices achieve a maximum power conversion efficiency (PCE) of 17.5% with negligible hysteresis. An impressive current of 21 mA cm−2 is also confirmed from photocurrent density with a higher fill factor of 0.79. The obtained PCE of 17.5% utilizing TPA-ANT-TPA is higher performance than the devices prepared using doped Spiro-OMeTAD (16.8%) as hole transport layer at 1 sun condition. It is found that doping of LiTFSI salt increases hygroscopic characteristics in Spiro-OMeTAD; this leads to the fast degradation of solar cells. While, solar cells prepared using undoped TPA-ANT-TPA show dewetting and improved stability. Additionally, the new HTMs form a fully homogeneous and completely covering thin film on the surface of the active light absorbing perovskite layers that acts as a protective coating for underlying perovskite films. This breakthrough paves the way for development of new inexpensive, more stable, and highly efficient ANT core based lower cost HTMs for cost-effective, conventional, and printable PSCs

Utilizing energy transfer in binary and ternary bulk heterojunction organic solar cells

Energy transfer has been identified as an important process in ternary organic solar cells. Here, we develop kinetic Monte Carlo (KMC) models to assess the impact of energy transfer in ternary and binary bulk heterojunction systems. We used fluorescence and absorption spectroscopy to determine the energy disorder and Förster radii for poly(3-hexylthiophene-2,5-diyl), [6,6]-phenyl-C61-butyric acid methyl ester, 4-bis[4-(N,N-diisobutylamino)-2,6-dihydroxyphenyl]squaraine (DIBSq), and poly(2,5-thiophene-<i>alt</i>-4,9-bis(2-hexyldecyl)-4,9-dihydrodithieno[3,2-c:3′,2′-<i>h</i>][1,5]naphthyridine-5,10-dione). Heterogeneous energy transfer is found to be crucial in the exciton dissociation process of both binary and ternary organic semiconductor systems. Circumstances favoring energy transfer across interfaces allow relaxation of the electronic energy level requirements, meaning that a cascade structure is not required for efficient ternary organic solar cells. We explain how energy transfer can be exploited to eliminate additional energy losses in ternary bulk heterojunction solar cells, thus increasing their open-circuit voltage without loss in short-circuit current. In particular, we show that it is important that the DIBSq is located at the electron donor–acceptor interface; otherwise charge carriers will be trapped in the DIBSq domain or excitons in the DIBSq domains will not be able to dissociate efficiently at an interface. KMC modeling shows that only small amounts of DIBSq (<5% by weight) are needed to achieve substantial performance improvements due to long-range energy transfer

Naphthalene flanked diketopyrrolopyrrole based organic semiconductors for high performance organic field effect transistors

Here, we design and synthesize three new diketopyrrolopyrrole (DPP) derivatives with naphthalene, possessing large-scaled p-delocalized electronic structure, as the flanking groups and both linear (n-decyl and n-dodecyl) and branched (2-hexyldecyl)alkyl chains as substitutions as active layer for high performance organic field-effect transistors (OFETs). The thermal, photophysical properties, energy levels and solid state molecular stacking have been studied in detail. All the materials show excellent thermal stability with a decomposition temperature of 400 °C, high semi-crystallinity feature, suitable HOMO & LUMO energy levels, and varying crystalline domain sizes in thin films. Bottom-contact/top-gate transistor devices are thus fabricated to investigate the mobility. Encouragingly, all compounds function well in OFET devices and show significant potential as p-type semiconducting materials. The monomer with the n-decyl alkyl chain (D-DPPN) shows the highest mobility of 0.019 cm2V-1s-1, with the Ion/Ioffratio reaching 106. We for the first time synthesize naphthalene flanked DPP monomers and achieve high mobility in OFET devices when using these monomers without any further functionalization as semiconductors directly. The primary result that high mobility is observed for monomers only opens a new way for further DPP application and provides more possibilities for constructing high performance polymeric and small molecular semiconductors based on this new DPP dye