Impact of Organic Hole Transporting Material and Doping on the Electrical Response of Perovskite Solar Cells

The hole transport material (HTM) layer is a key component of the perovskite solar cells (PSCs) that must be optimized to reach high efficiency. The development of new HTMs alternative to Spiro-OMeTAD and the understanding of the role of doping agents on these layers are important research axes in the field. It requires the use of appropriate characterization tools enabling us to discriminate the bulk and interface effects. In the present paper, we fully analyze the effect of HTM doping and of the material on the impedance response of PSCs. The approach has been implemented on two different molecular HTMs, Spiro-OMeTAD and a new molecular carbazole HTM, called B186, and with various doping levels. We show that limitations by poor doping are characterized by an extra high frequency impedance loop for which capacitance and resistance analysis gives the dielectric constant and conductivity of the material, respectively. However, the low-frequency part of the spectra provides important information on the charge accumulation/outflow and on the recombination levels. More generally, the presented approach is of high practical interest for the development of new organic HTMs and for the optimization of the layer doping

Processable Star-Shaped Molecules with Triphenylamine Core as Hole-Transporting Materials: Experimental and Theoretical Approach

In this study we report on the characterization of five star-shaped π-conjugated molecules by means of UV–vis absorption spectroscopy and electrochemical cyclic voltammetry. These molecules, with triphenylamine (TPA) core bearing one thienothiophene moiety and a different number of thiophene ones, are designed as hole-transporting materials for dye-sensitized solar cell (DSSC) applications. Theoretical calculations employing the B3LYP functional are also carried out in order to understand the structure–property relationships. UV–vis absorption measurements and time-dependent density functional theory (TDDFT) calculations show the presence of intense UV–vis bands for all compounds. These bands are dominated by two degenerate π–π* excitations mostly involving the HOMO → LUMO and HOMO → LUMO+1 transitions. Electrochemical cyclic voltammetry and DFT calculations show the HOMO (LUMO) energy levels increasing (decreasing) with the number of conjugated heterocyclic rings in these molecules. The HOMO energies have been found to vary between −5.38 and −5.13 eV thus showing good positioning with respect to the Fermi level of gold electrode (DSSC applications). The calculated internal reorganization energies (λ_i) suggest for these materials promising hole-transport properties. The analysis of the space extension of the HOMO orbitals as a function of the number of conjugated rings in these molecules gives useful information on their design

Panchromatic Photopolymerizable Cationic Films Using Indoline and Squaraine Dye Based Photoinitiating Systems

The photoinitiating abilities of indoline and squaraine dyes (D102 and SQ02) incorporated in multicomponent systems for the cationic polymerization of an epoxide or a vinyl ether have been investigated. The polymerizable films exhibit a panchromatic character as revealed by their photosensitivity to a halogen lamp (370–800 nm); household LED bulbs centered at 462 nm (blue), 514 nm (green), 591 nm (yellow), and 630 nm (red); and laser diodes at 457, 473, 532, and 635 nm. SQ02 is particularly efficient in the 520–700 nm range, while D102 exhibits a good efficiency in the 400–580 nm region. The radical photopolymerization of an acrylate can also be observed particularly at 635 nm or upon a halogen lamp. The photochemical mechanisms are studied by steady state photolysis, fluorescence, cyclic voltammetry, electron spin resonance spin trapping, and laser flash photolysis techniques

Nanographene Coupled with Interfacial Pyrene Derivatives for Thermally Stable Perovskite Solar Cells

Although high-efficiency perovskite solar cells (PSCs) have been achieved using a hole-extracting material, spiro-MeOTAD, thermal stability has been unattainable due to the low glass transition temperature of spiro-MeOTAD and additives therein. Here, we report on the use of nanographene-based hole-transporting materials coupled with a pyrene derivative as an interface modifier for thermally stable and high efficiency PSCs. Asymmetric methyl and methoxy groups are introduced in the diphenyl­amino group that is attached to the hexa-peri-hexabenzo­coronene (HBC) nanographene core, coded HBC-DPAMeOMe. 1-Pyrene­methyl­ammonium iodide is coupled to enhance the chemical interaction between perovskite and HBC-DPAMeOMe, which leads to a power conversion efficiency over 23%. A thermal stability test at 85 °C for 1000 h reveals that 83.6% of the initial efficiency (23.04% → 19.25%) is maintained for the device with HBC-DPAMeOMe, while a significant degradation from 20.69% to 5.08% is observed for the device with spiro-MeOTAD. Nanographene-based hole conductors shed light on the thermal stability issue in PSCs