Fluorination on cyclopentadithiophene-based hole-transport materials for high-performance perovskite solar cells.

A new class of fluorinated cyclopenta[2,1-b:3,4-b']dithiophene (CPDT)-based small molecules, namely YC-oF, YC-mF, and YC-H, are demonstrated as hole-transporting materials (HTMs) for high-performance perovskite solar cells (PSCs). PSCs employing YC-oF as the HTM delivered an excellent efficiency of 22.41% with encouraging long-term stability.

A star-shaped cyclopentadithiophene-based dopant-free hole-transport material for high-performance perovskite solar cells.

A new cyclopentadithiophene (CPDT)-based organic small molecule serves as an efficient dopant-free hole transport material (HTM) for perovskite solar cells (PSCs). Upon incorporation of two carbazole groups, the resulting CPDT-based HTM (C-CPDT) shows an impressive power conversion efficiency (PCE) of 19.68% with better stability compared with those of spiro-OMeTAD.

Thiophene-Fused Butterfly-Shaped Polycyclic Arenes with a Diphenanthro[9,10-b:9',10'-d]thiophene Core for Highly Efficient and Stable Perovskite Solar Cells.

Two polycyclic heteroarene derivatives, namely, V-1 and V-2, with a diphenanthro[9,10-b:9',10'-d]thiophene (DPT) core tethered with two diphenylaminophenyl or diphenylamino groups were first synthesized and used as hole-transporting materials (HTMs) in perovskite solar cell (PSC) fabrication. The novel HTMs exhibit appropriate energy-level alignment with the perovskite so as to ensure efficient hole transfer from the perovskite to HTMs. V-2 with the diphenylamino substituent on DPT exhibited impressive photovoltaic performance with a power conversion efficiency of 19.32%, which was higher than that of V-1 (18.60%) and the benchmark 2,2',7,7'-tetrakis-(N,N-di-p-methoxyphenyl-amine)-9,9'-spirobifluorene (spiro-OMeTAD) (17.99%), presumably because of a better hole extraction, higher hole mobility, and excellent film-forming ability, which were supported by steady-state photoluminescence (PL), time-resolved PL, the hole mobility experiment, scanning electron microscopy, and atomic force microscopy measurements. Meanwhile, V-2-based PSCs exhibited better long-term durability than that with V-1 and the state-of-the-art spiro-OMeTAD, which is ascribable to the excellent surface morphology and hydrophobicity of the film. This systematic study suggests that DPT-based molecules are good potential candidates as HTMs for achieving high-performance PSCs.

New Helicene-Type Hole-Transporting Molecules for High-Performance and Durable Perovskite Solar Cells.

Three azahelicene derivatives with electron-rich bis(4-methoxyphenyl)amino or bis( p-methoxyphenyl)aminophenyl groups at the terminals were deliberately designed, synthesized, and characterized as hole-transporting materials (HTMs) for perovskite solar cells (PSCs). Optical and thermal properties, energy level alignments, film morphologies, hole extraction ability, and hole mobility were studied in detail. PSCs using the newly synthesized molecules as HTMs were fabricated. A maximum power conversion efficiency (PCE) of 17.34% was observed for the bis( p-methoxyphenyl)amino-substituted derivative (SY1) and 16.10% for the bis( p-methoxyphenyl)aminophenyl-substituted derivative (SY2). Longer-chain substituent such as hexyloxy group greatly diminishes the efficiency. In addition, the dopant-free devices fabricated with SY1 as the HTM shows an average PCE of 12.13%, which is significantly higher than that of spiro-OMeTAD (7.61%). The ambient long-term stability test revealed that after 500 h, the devices prepared from SY1 and SY2 retained more than 96% of its initial performance, which is much improved than the reference device with standard spiro-OMeTAD as the HTM under the same conditions. Detailed material cost analysis reveals that the material cost for SY1 is less than 8% of that for spiro-OMeTAD. These results provide a useful direction for designing a new class of HTMs to prepare highly efficient and more durable PSCs.

Highly efficient and stable semi-transparent perovskite solar modules with a trilayer anode electrode.

Highly efficient and stable semi-transparent CH3NH3PbI3 perovskite photovoltaic cells are realized by using an ITO/MoOx bilayer conductive oxide as the anode electrode with a cyclopenta[2,1-b;3,4-b']dithiophene (CT) based hole-transport material (HTM), which allows bifacial illumination from both sides of the electrodes. The wide bandgap MoOx thin film is not only to be an electron blocking layer, but also to be a passivation layer which can withstand the excessive energy bombardment during the magnetron sputtering process for the deposition of a high-quality ITO thin film. Atomic-force microscopy images, transmittance spectra and water-droplet contact angle images show that the interfacial contact between MoOx and hole transport layer (HTL) strongly influences the short-circuit current density (JSC) and fill factor (FF). The highest power conversion efficiency (PCE) values for the bifacial perovskite solar cells (0.16 cm2) and modules (11.7 cm2) are 16.38% and 14.96%, respectively. In addition, the PCE of the ITO/MoOx/CT-HTM based perovskite solar module decreases slowly toward a stable value (∼11%) for more than 700 h under wet environment conditions (70 ± 5 RH%).

Hole-Transporting Materials Based on Twisted Bimesitylenes for Stable Perovskite Solar Cells with High Efficiency.

A new class of hole-transport materials (HTMs) based on the bimesitylene core designed for mesoporous perovskite solar cells is introduced. Devices fabricated using two of these derivatives yield higher open-circuit voltage values than the commonly used spiro-OMeTAD. Power conversion efficiency (PCE) values of up to 12.11% are obtained in perovskite-based devices using these new HTMs. The stability of the device made using the highest performing HTM (P1) is improved compared with spiro-OMeTAD as evidenced through long-term stability tests over 1000 h.

Reaction-based colorimetric and ratiometric fluorescence sensor for detection of cyanide in aqueous media.

A stilbene-based compound (1) has been prepared and was highly selective for the detection of cyanide anion in aqueous media even in the presence of other anions, such as F(-), Cl(-), Br(-), I(-), ClO(4)(-), H(2)PO(4)(-), HSO(4)(-), NO(3)(-), and CH(3)CO(2)(-). A noticeable change in the color of the solution, along with a prominent fluorescence enhancement, was observed upon the addition of cyanide. The color change was observed upon the nucleophilic addition of the cyanide anion to the electron-deficient cyanoacrylate group of 1. The spectral changes induced by the reaction were analyzed by comparison with two model compounds, such as compound 2 with dimethyl substituents and compound 3 without a cyanoacrylate group. An intramolecular charge-transfer (ICT) mechanism played a key role in the sensing properties, and the mechanism was supported by DFT/TDDFT calculations.

A pentiptycene-derived molecular brake: photochemical E→Z and electrochemical Z→E switching of an enone module.

The synthesis and brakelike performance of a new molecular system (1) consisting of a pentiptycene rotor and a 2-methyleneindanone brake are reported. The rotation kinetics of the rotor was probed by both variable-temperature (1)H and (13)C NMR spectroscopy and DFT calculations, and the switching between the brake-on and brake-off states was conducted by a combination of photochemical and electrochemical isomerization. Because of the greater steric hindrance between the rotor and the brake units in the Z form ((Z)-1) than in the E form ((E)-1), rotation of the rotor is slowed down 500-fold at room temperature (298 K) on going from (E)-1 to (Z)-1, corresponding to the brake-off and brake-on states, respectively. The (E)-1→(Z)-1 photoisomerization in acetonitrile is efficient and reaches an (E)-1/(Z)-1 ratio of 11:89 in the photostationary state upon excitation at 290 nm, attributable to a much larger isomerization quantum efficiency for (E)-1 versus (Z)-1. An efficient (Z)-1→(E)-1 isomerization (96%) was also achieved by electrochemical treatment through the radical anionic intermediates. Consequently, the reversibility of the E-Z switching of 1 is as high as 85%. The repeated E-Z switching of 1 with alternating photochemical and electrochemical treatments is also demonstrated.

Synthesis, dual fluorescence, and fluoroionophoric behavior of dipyridylaminomethylstilbenes.

The synthesis, dual fluorescence, and fluoroionophoric behavior of two donor-sigma spacer-acceptor (D-s-A) compounds, trans-4-(N,N-bis(2-pyridyl)amino)methylstilbene (1H) and trans-4-(N,N-bis(2-pyridyl)amino)methyl-4'-cyanostilbene (1CN), are reported and compared to that of trans-4-(N,N-bis(2-pyridyl)amino)methyl-4'-(N,N-dimethylamino)stilbene (1DPA). To gain insights into the dual fluorescence properties for 1H and 1CN in polar but not in nonpolar solvents, model compounds resulting from a replacement of the stilbene group by alkyl (2R) or xylyl (2X) groups or from a replacement of the dipyridylamino (dpa) group by dianisoleamino (3AA), diethylamino (3EE), methylanilino (3MP), or diphenylamino (3PP) groups also have been investigated. In addition to 1H and 1CN, all four compounds of 3 display dual fluorescence. The locally excited (LE) fluorescence mainly results from the stilbene group and the ICT fluorescence from the through-bond interactions between the amino donor and the stilbene acceptors. In the presence of transition metal ions such as Zn(II), Ni(II), Cu(II), and Cd(II), the ICT processes are switched from dpa (D) --> stilbene (A) in 1H and 1CN to stilbene (D) --> dpa/metal ion (A) in their complexes. Whereas the ICT states for the complexes are generally nonfluorescent, an exception was found for the case of 1H/Zn(II). As a result, substituent-dependent fluoroionophoric behavior has been demonstrated by 1H, 1CN, and 1DPA in response to Zn(II).

Zn(II)-induced ground-state pi-deconjugation and excited-state electron transfer in N,N-bis(2-pyridyl)amino-substituted arenes.

The synthesis and X-ray crystal structures of two N,N-bis(2-pyridyl)amino (dpa)-substituted aromatic systems (Ar-dpa) 1 (Ar = 4,4'-disubstituted trans-stilbene) and 2 (Ar = 1,4-disubstituted benzene) and their ZnCl(2) complexes (1/ZnCl(2) and 2/ZnCl(2)) are reported. The fluoroionophoric behavior of 1-2 in response to Zn(II) in acetonitrile also has been investigated. In addition, compound 3DPA has been prepared and served as a pi-deconjugated model for 1DPA. The observed crystal structures for 1/ZnCl(2) and 2/ZnCl(2) could be divided into two distinct types, the planar and the twisted forms, depending on the aryl-dpa (C(ph)-NC(3)) dihedral angle. The twisted form is more favorable for these complexes unless the arene has a strong "push-pull" character. Nonetheless, the degree of pi-conjugation between the N-pyridyl and the N-aryl group is reduced in both complex forms when compared with the free ligands. Such a Zn(II)-induced pi-deconjugation not only directly affects the internal charge transfer (ICT) fluorescence of the dpa-substituted stilbenes but also facilitates the occurrence of photoinduced electron transfer (PET) from the stilbene donor to the dpa/Zn(II) acceptor. The PET process is particularly important in accounting for the observed Zn(II)-induced fluorescence quenching for 1DPA as well as 3DPA.