On the energy gap determination of organic optoelectronic materials: the case of porphyrin derivatives

A correct determination of the ionization potential (IP) and electron affinity (EA) as wells as the energy gap is essential to properly characterize a series of key phenomena related to...

Benefits of Low Electron-Affinity Material as the N-Type Layer for Cu(In,Ga)S2 Solar Cell

Despite the potential in single- and multi-junction solar cells application, research into the wide band gap CuIn1−xGax(Se1−ySy)2 or CIG(SSe)2 solar cell material, with Eg≥1.5eV, has yet to be extensively performed to date. In this work, we conducted a numerical study into the role of the n-type layers in CIG(SSe)2 heterojunction solar cells, specifically concerning the maximum open-circuit voltage of the devices. In the first part of the study, we derived a new ideal open-circuit voltage equation for a thin-film heterojunction solar cell by taking into account the current contribution from the depletion region. The accuracy of the new equation was validated through a simulation model in the second part of the study. Another simulation model was also used to clarify the design rules of the n-type layer in a wide band gap CIG(SSe)2 solar cell. Our work stressed the importance of a positive conduction band offset on the n-/p-type interface, through the use of a low electron affinity n-type material for a solar cell with a high open-circuit voltage . Through a precise selection of the window layer material, a buffer-free CIG(SSe)2 design is sufficient to fulfill such conditions. We also proposed the specific roles of the n-type layer, i.e., as a passivation layer and selective electron contact, in the operation of CIGS2 solar cells.

O2 and Other High-Energy Molecules in Photosynthesis: Why Plants Need Two Photosystems

The energetics of photosynthesis in plants have been re-analyzed in a framework that represents the relatively high energy of O2 correctly. Starting with the photon energy exciting P680 and “loosening an electron”, the energy transfer and electron transport are represented in a comprehensive, self-explanatory sequence of redox energy transfer and release diagrams. The resulting expanded Z-scheme explicitly shows charge separation as well as important high-energy species such as O2, TyrZ˙, and P680+˙, whose energies are not apparent in the classical Z-scheme of photosynthesis. Crucially, the energetics of the three important forms of P680 and of P700 are clarified. The relative free energies of oxidized and reduced species are shown explicitly in kJ/mol, not encrypted in volts. Of the chemical energy produced in photosynthesis, more is stored in O2 than in glucose. The expanded Z-scheme introduced here provides explanatory power lacking in the classical scheme. It shows that P680* is energetically boosted to P680+˙ by the favorable electron affinity of pheophytin and that Photosystem I (PSI) has insufficient energy to split H2O and produce O2 because P700* is too easily ionized. It also avoids the Z-scheme’s bewildering implication, according to the “electron waterfall” concept, that H2O gives off electrons that spontaneously flow to chlorophyll while releasing energy. The new analysis explains convincingly why plants need two different photosystems in tandem: (i) PSII mostly extracts hydrogen from H2O, producing PQH2 (plastoquinol), and generates the energetically expensive product O2; this step provides little energy directly to the plant; (ii) PSI produces chemical energy for the organism, by pumping protons against a concentration gradient and producing less reluctant hydrogen donors. It also documents that electron transport and energy transfer occur in opposite directions and do not involve redox voltages. The analysis makes it clear that the high-energy species in photosynthesis are unstable, electron-deficient species such as P680+˙ and TyrZ˙, not putative high-energy electrons.

BAl4Mg−/0/+: Global Minima with a Planar Tetracoordinate or Hypercoordinate Boron Atom

We have explored the chemical space of BAl4Mg−/0/+ for the first time and theoretically characterized several isomers with interesting bonding patterns. We have used chemical intuition and a cluster building method based on the tabu-search algorithm implemented in the Python program for aggregation and reaction (PyAR) to obtain the maximum number of possible stationary points. The global minimum geometries for the anion (1a) and cation (1c) contain a planar tetracoordinate boron (ptB) atom, whereas the global minimum geometry for the neutral (1n) exhibits a planar pentacoordinate boron (ppB) atom. The low-lying isomers of the anion (2a) and cation (3c) also contain a ppB atom. The low-lying isomer of the neutral (2n) exhibits a ptB atom. Ab initio molecular dynamics simulations carried out at 298 K for 2000 fs suggest that all isomers are kinetically stable, except the cation 3c. Simulations carried out at low temperatures (100 and 200 K) for 2000 fs predict that even 3c is kinetically stable, which contains a ppB atom. Various bonding analyses (NBO, AdNDP, AIM, etc.) are carried out for these six different geometries of BAl4Mg−/0/+ to understand the bonding patterns. Based on these results, we conclude that ptB/ppB scenarios are prevalent in these systems. Compared to the carbon counter-part, CAl4Mg−, here the anion (BAl4Mg−) obeys the 18 valence electron rule, as B has one electron fewer than C. However, the neutral and cation species break the rule with 17 and 16 valence electrons, respectively. The electron affinity (EA) of BAl4Mg is slightly higher (2.15 eV) than the electron affinity of CAl4Mg (2.05 eV). Based on the EA value, it is believed that these molecules can be identified in the gas phase. All the ptB/ppB isomers exhibit π/σ double aromaticity. Energy decomposition analysis predicts that the interaction between BAl4−/0/+ and Mg is ionic in all these six systems.

Perfluorocycloparaphenylenes: Fully fluorinated carbon nanorings by Ni-mediated one-pot synthesis

Perfluorinated aromatic compounds, the so-called perfluoroarenes, are widely used in materials science owing to their high electron affinity and characteristic intermolecular interactions. However, methods to synthesize highly strained perfluoroarenes have remained elusive so far, which greatly limits their structural diversity. Herein, we report the synthesis and isolation of perfluorocycloparaphenylenes (PFCPPs) as a class of ring-shaped perfluoroarenes. Using macrocyclic nickel complexes, we succeeded in synthesizing PF[n]CPPs (n = 10, 12, 14, 16) in one-pot without noble metals. The molecular structures of PF[n]CPPs (n = 10, 12) were determined by X-ray crystallography to confirm their tubular alignment. Photophysical and electrochemical measurements revealed that PF[n]CPPs (n = 10, 12) exhibit wide HOMO–LUMO gaps, high electron affinity, and strong phosphorescence at low temperature. PFCPPs are not only useful as electron-accepting organic semiconductors but can also be used for accelerating the creation of topologically unique molecular nanocarbon materials.