Bright and fast-response perovskite light-emitting diodes with an ICBA:modified-C60 nanocomposite electrical confinement layer.

Bright and fast-response CH3NH3PbBr3 perovskite light-emitting diodes (PeLEDs) are realized by using ICBA:modified C60 (MC60) nanocomposites as the hole blocking layer (HBL) and electron transport layer (ETL). The photoluminescence spectrum shows that the use of hydrophilic MC60 in the ETL helps the surface passivation of the perovskite layer. In addition, the photoelectron spectra and water-droplet contact angle images show that the use of the ICBA:MC60 nanocomposite ETL can simultaneously confine the electrons and holes in the perovskite layer, which boosts the injected electron-hole radiative recombination efficiency and thereby increases the electroluminescence from 1 cd m-2 to 2080 cd m-2 at 6 V when the ICBA:3,5OEC60 nanocomposite ETL is used. In addition, the operational frequency of the optimal PeLED is up to 1.5 MHz.

Functional graded fullerene derivatives for improving the fill factor and device stability of inverted-type perovskite solar cells.

A graded fullerene derivative thin film was used as a dual-functional electron transport layer (ETL) in CH3NH3PbI3 (MAPbI3) solar cells, to improve the fill factor (FF) and device stability. The graded ETL was made by mixing phenyl-C61-butyric acid methyl ester (PCBM) molecules and C60-diphenylmethanofullerene-oligoether (C60-DPM-OE) molecules using the spin-coating method. The formation of the graded ETLs can be due to the phase separation between hydrophobic PCBM and hydrophilic C60-DPM-OE, which was confirmed by XPS depth-profile analysis and an electron energy-loss spectroscope. Comprehensive studies were carried out to explore the characteristics of the graded ETLs in MAPbI3 solar cells, including the surface properties, electronic energy levels, molecular packing properties and energy transfer dynamics. The elimination of the s-shape in the current density-voltage curves results in an increase in the FF, which originates from the smooth contact between the C60-DPM-OE and hydrophilic MAPbI3 and the formation of the more ordered ETL. There was an improvement in device stability mainly due to the decrease in the photothermal induced morphology change of the graded ETLs fabricated from two fullerene derivatives with distinct hydrophilicity. Consequently, such a graded ETL provides dual-functional capabilities for the realization of stable high-performance MAPbI3 solar cells.

Linear oligoarylamines: electrochemical, EPR, and computational studies of their oxidative states.

A series of straight-chain oligoarylamines were synthesized and examined by electrochemical, spectroelectrochemical, electron paramagnetic resonance techniques, and density functional theory (DFT) calculation. Depending on their electrochemical characteristics, these oligoarylamines were classified into two groups: one containing an odd number and the other an even number of redox centers. In the systems with odd redox centers (N1, N3, and N5), each oxidation was associated with the loss of one electron. As for the systems with even redox centers (N2, N4, and N6), oxidation occurred by taking N2 as a unit. Absorption spectra of linear oligoarylamines at various oxidative states were obtained to investigate their charge transfer behaviors. Moreover, DFT-computed isotropic hyperfine coupling constants and spin density were in accordance with the EPR experiment, and gave a close examination of oligoarylamines at charged states.

Electrochemically controlled multiple hydrogen bonding between triarylamines and imidazoles.

By increasing the number of amino substituents on triarylamine, the extent of hydrogen bonding between the oxidized form of triarylamine and imidazole could be electrochemically controlled. Three behaviors, depending on the interaction between oxidized amine and imidazole, were obtained in CV patterns. DFT calculation was used to confirm that the electron density of protons of the amino group decreased as the amino moiety increased.

Studies on the structure of N-phenyl-substituted hexaaza[1(6)]paracyclophane: synthesis, electrochemical properties, and theoretical calculation.

The N-phenyl-substituted hexaaza[1(6)]paracyclophane (3, hexamer) has been synthesized successfully in two steps and the noncoplanar conformation was calculated by gaussian program. The electrochemical properties exhibited lots of interesting results and each overlapping oxidative wave contained two-electron transfer.

Redox potential inversion by ionic hydrogen bonding between phenylenediamines and pyridines.

In electrochemical oxidations, the second oxidation potential of phenylenediamines (PD) varies because of hydrogen-bonding formation for PD(+•) with pyridines. A linear relationship was obtained for the potential shift as a function of pK(a) of the protonated pyridines and potential inversion could be observed. The oxidized PD(+•) could also form hydrogen bonding with alcohols and the shift of potential exhibits a different pattern.

Electrochemically controlled ligand shuttling between zinc porphyrin and meso-phenylenediamine substituent.

ZnTMP-PD was synthesized and fully characterized; by using electrochemical and spectroelectrochemical methods, ligand shuttling between the zinc porphyrin and the meso-phenylenediamine substituent could be monitored; EPR results indicated that the charge was delocalized on ZnTMP-PD.

Novel spectral and electrochemical characteristics of triphenylamine-bound zinc porphyrins and their intramolecular energy and electron transfer.

Porphine bearing triphenylamine (TPA) pendant groups and their zinc complexes, zinc meso-tetra-p-(di-p-phenylamino)phenylporphyrin (ZnTDPAPP) and zinc meso-tetra-p-(di-p-tolylamino)phenylporphyrin (ZnTDTAPP) are synthesized and their spectral and electrochemical characteristics are studied. Zinc meso-tetraphenylporphyrin (ZnTPP) and zinc meso-tetra-p-aminophenylporphyrin (ZnTAPP) are also used as reference complexes. The B and Q bands of ZnTDPAPP and ZnTDTAPP are located at higher wavelengths and the bandwidths become broader compared with those of ZnTPP and ZnTAPP, indicating the peripheral TPA affects the electronic configuration of zinc porphyrins. Upon excitation in CH2Cl2 at room temperature, the compounds exhibit intramolecular singlet energy transfer from the TPA to the porphyrin core, and emission from the porphyrins are observed. Both ZnTDPAPP and ZnTDTAPP are easier to be oxidized and harder to be reduced than ZnTPP, in agreement with the strong electron-donating effect of the TPA groups. Extra waves corresponding to the oxidation of TPA substituents are also observed. The cation radical ZnTDTAPP+* exhibits an absorption spectrum very different from the typical spectra for porphyrin cation radicals. The NIR absorption band at 1296 nm indicates the electron transfer occurs intramolecularly. The above results evince the ability of TPA to modulate the electronic structure of zinc porphyrins.

Photophysical and electrochemical properties of 1,7-diaryl-substituted perylene diimides.

Substituent effects on the photophysical and electrochemical properties of 1,7-diaryl-substituted perylene diimides (1,7-Ar(2)PDIs) have been carefully explored. Progressive red-shifts of the absorption and emission maxima were observed when the electron-donating ability of these substituents was increased. Linear Hammett correlations of 1/lambda(max) versus sigma(+) were observed in both spectral analyses. The positive slopes of the Hammett plots suggested that the electronic transitions carry certain amounts of photoinduced intramolecular charge-transfer (PICT) character from the aryl substituents to the perylene diimide core which leads to the reduction of the electron density on the substituents. The substituent electronic effects originated mainly from the perturbation of the core PDI HOMO energy level by the substituents. This conclusion was supported by PM3 analyses and confirmed by cyclic voltammetry experiments. More interestingly, the Ph(2)NC(6)H(4)-substituted PDI, 4i, showed an unusual dual-band absorption that spans from 450 to 750 nm. We tentatively assigned these two bands as the charge-transfer band and the PDI core absorption, respectively.