Lifshitz transition enabling superconducting dome around a charge-order critical point.

Superconductivity often emerges as a dome around a quantum critical point (QCP) where long-range order is suppressed to zero temperature, mostly in magnetically ordered materials. However, the emergence of superconductivity at charge-order QCPs remains shrouded in mystery, despite its relevance to high-temperature superconductors and other exotic phases of matter. Here, we present resistance measurements proving that a dome of superconductivity surrounds the putative charge-density-wave QCP in pristine samples of titanium diselenide tuned with hydrostatic pressure. In addition, our quantum oscillation measurements combined with electronic structure calculations show that superconductivity sets in precisely when large electron and hole pockets suddenly appear through an abrupt change of the Fermi surface topology, also known as a Lifshitz transition. Combined with the known repulsive interaction, this suggests that unconventional s± superconductivity is mediated by charge-density-wave fluctuations in titanium diselenide. These results highlight the importance of the electronic ground state and charge fluctuations in enabling unconventional superconductivity.

Erratum: Fermi Surface Reconstruction and Electron Dynamics at the Charge-Density-Wave Transition in TiSe_{2} [Phys. Rev. Lett. 124, 167602 (2020)].

This corrects the article DOI: 10.1103/PhysRevLett.124.167602.

Charge transfer modulation in charge transfer co-crystals driven by crystal structure morphology.

The electronic properties of a charge-transfer (donor-acceptor) semiconducting organic co-crystal, Perylene:F4-TCNQ (PE:F4) (the donor, D, is PE and the acceptor, A, is 2,3,5,6-tetrafluoro-7,7,8,8 tetracyanoquinodimethane (F4)) in its 3 : 2 stoichiometry, are experimentally and theoretically studied. This is performed by means of electron paramagnetic resonance (EPR) and solid state electrochemical techniques, such as cyclic voltammetry (CV) measurements on single crystals. In particular, solid state electrochemistry proves to be an effective tool to probe, on a macroscopic scale, the electronic characteristics of the co-crystal. However, EPR highlights the presence of spin ½ radicals localized on F4 molecules, possibly linked to defects. The experimental findings are discussed on the basis of density functional theory (DFT) based calculations, carried out using both the projector augmented wave (PAW), with "periodic boundary conditions" (pbc), method and the localized orbitals, molecular cluster, approach. In particular, a satisfying agreement is found between the experimental, 0.336 eV (electrochemical), and theoretical, 0.303 eV (PAW), band gaps. Differences with the reported optical bandgap are discussed considering excitonic effects.

First-Principles Estimation of Core Level Shifts for Hf, Ta, W, and Re.

A simple first-principles approach is used to estimate the core level shifts observed in X-ray photoelectron spectroscopy for the 4f electrons of Hf, Ta, W, and Re; these elements were selected because their 4f levels are relatively close to the Fermi energy. The approach is first tested by modeling the surface core level shifts of low-index surfaces of the four elemental metals, followed by its application to the well-studied material TaSe2 in the commensurate charge density wave (CDW) phase, where agreement with experimental data is found to be good, showing that this approach can yield insights into modifications of the CDW. Finally, unterminated surface core level shifts in the hypothetical MXene Ta3C2 are modeled, and the potential of XPS for the investigation of the surface termination of MXenes is demonstrated.

Fermi Surface Reconstruction and Electron Dynamics at the Charge-Density-Wave Transition in TiSe_{2}.

The evolution of the charge carrier concentrations and mobilities are examined across the charge-density-wave (CDW) transition in TiSe_{2}. Combined quantum oscillation and magnetotransport measurements show that a small electron pocket dominates the electronic properties at low temperatures while an electron and hole pocket contribute at room temperature. At the CDW transition, an abrupt Fermi surface reconstruction and a minimum in the electron and hole mobilities are extracted from two-band and Kohler analysis of magnetotransport measurements. The minimum in the mobilities is associated with the overseen role of scattering from the softening CDW mode. With the carrier concentrations and dynamics dominated by the CDW and the associated bosonic mode, our results highlight TiSe_{2} as a prototypical system to study the Fermi surface reconstruction at a density-wave transition.

Ferrocene Molecular Architectures Grafted on Si(111): A Theoretical Calculation of the Standard Oxidation Potentials and Electron Transfer Rate Constant.

The standard oxidation potential and the electron transfer (ET) rate constants of two silicon-based hybrid interfaces, Si(111)/organic-spacer/Ferrocene, are theoretically calculated and assessed. The dynamics of the electrochemical driven ET process is modeled in terms of the classical donor/acceptor scheme within the framework of "Marcus theory". The ET rate constants, k E T , are determined following calculation of the electron transfer matrix element, V R P , together with the knowledge of the energy of the neutral and charge separated systems. The recently introduced Constrained Density Functional Theory (CDFT) method is exploited to optimize the structure and determine the energy of the charge separated species. Calculated ET rate constants are k E T = 77.8 s - 1 and k E T = 1.3 × 10 - 9 s - 1 , in the case of the short and long organic-spacer, respectively.

An unforeseen polymorph of coronene by the application of magnetic fields during crystal growth.

The continued development of novel drugs, proteins, and advanced materials strongly rely on our ability to self-assemble molecules in solids with the most suitable structure (polymorph) in order to exhibit desired functionalities. The search for new polymorphs remains a scientific challenge, that is at the core of crystal engineering and there has been a lack of effective solutions to this problem. Here we show that by crystallizing the polyaromatic hydrocarbon coronene in the presence of a magnetic field, a polymorph is formed in a ß-herringbone structure instead of the ubiquitous γ-herringbone structure, with a decrease of 35° in the herringbone nearest neighbour angle. The ß-herringbone polymorph is stable, preserves its structure under ambient conditions and as a result of the altered molecular packing of the crystals, exhibits significant changes to the optical and mechanical properties of the crystal.

An Integrated Experimental/Theoretical Study of Structurally Related Poly-Thiophenes Used in Photovoltaic Systems.

In this work, a series of eight thiophene-based polymers (exploited as "donors" in bulk heterojunction photovoltaics cells), whose structures were designed to be suitably tuned with the electronic characteristics of the [6,6]-Phenyl C61 butyric acid methyl ester (PCBM), is considered,. The electronic properties of the mono-, di-, trimeric oligomers are reckoned (at the Hartree-Fock and DFT level of the theory) and compared to experimental spectroscopic and electrochemical results. Indeed, electrochemical and spectroscopic results show a systematic difference whose physical nature is assessed and related to the exciton (electron-hole) binding energy ( J e , h ). The critical comparison of the experimental and theoretical band gaps, i.e., the HOMO-LUMO energy difference, suggests that electrochemical and DFT values are the most suited to being used in the design of a polythiophene-based p-n junction for photovoltaics.

Enhanced Photogeneration of Polaron Pairs in Neat Semicrystalline Donor-Acceptor Copolymer Films via Direct Excitation of Interchain Aggregates.

We investigate the photogeneration of polaron pairs (PPs) in neat films of the semicrystalline donor-acceptor semiconducting copolymer PCPDTBT. Carefully selecting the solution-processing procedures, we obtain films with different amounts of crystallinity and interchain aggregation. We compare the photogeneration of PPs between the films by monitoring their photoinduced absorption in ultrafast pump-probe experiments, selectively exciting nonaggregated or aggregated polymer chains. The direct photoexcitation of interchain π-aggregates results in prompt (<100 fs) charge generation. Compared to the case where nonaggregated chains are excited, we find an 8-fold increase in the prompt PP to singlet-exciton ratio. We also show that highly crystalline lamellar nanostructures not containing π-stacked or any light-absorbing aggregates do not improve the efficiency of PP photogeneration. Our results show that light absorption from interchain aggregates is highly beneficial for charge photogeneration in semiconducting polymers and should be taken into account when optimizing film morphologies for photovoltaic devices.

Electronically coupled hybrid structures by graphene oxide directed self-assembly of Cu(2-x)S nanocrystals.

Here, we describe an electronically coupled hybrid material consisting of graphene oxide (GO) flakes and inorganic Cu(2-x)S nanocrystals (NCs) formed via a self-assembly route. As a result of the amphiphilic nature of the water-dispersible GO flakes, the hydrophobic Cu(2-x)S NCs self-assemble in between the GO flakes, resulting in a large-interface hybrid structure with ordered close-packed NCs. We demonstrate that the optical properties of the hybrid GO/Cu(2-x)S structures are governed by the injection of electrons from the GO flakes to the valence band of the vacancy-doped plasmonic Cu(2-x)S NCs. This leads to a suppression of the plasmon band of the Cu(2-x)S NCs and to a softening of the Raman G-band of the GO flakes. Our results indicate that graphene derivatives can act not only as a self-assembly directing template, but also as a tool to affect the optical properties of self-assembled NCs in a chemical process, enhanced by the high interface area of the composite.

How intermolecular geometrical disorder affects the molecular doping of donor-acceptor copolymers.

Molecular doping of conjugated polymers represents an important strategy for improving organic electronic devices. However, the widely reported low efficiency of doping remains a crucial limitation to obtain high performance. Here we investigate how charge transfer between dopant and donor-acceptor copolymers is affected by the spatial arrangement of the dopant molecule with respect to the copolymer repeat unit. We p-dope a donor-acceptor copolymer and probe its charge-sensitive molecular vibrations in films by infrared spectroscopy. We find that, compared with a related homopolymer, a four times higher dopant/polymer molar ratio is needed to observe signatures of charges. By DFT methods, we simulate the vibrational spectra, moving the dopant along the copolymer backbone and finding that efficient charge transfer occurs only when the dopant is close to the donor moiety. Our results show that the donor-acceptor structure poses an obstacle to efficient doping, with the acceptor moiety being inactive for p-type doping.

Carrier lifetime in exfoliated few-layer graphene determined from intersubband optical transitions.

We report a femtosecond transient spectroscopy study in the near to middle infrared range, 0.8-0.35 eV photon energy, on graphene and few layer graphene single flakes. The spectra show an evolving structure of photoinduced absorption bands superimposed on the bleaching caused by Pauli blocking of the interband optically coupled states. Supported by tight-binding model calculations, we assign the photoinduced absorption features to intersubband transitions as the number of layers is increased. Interestingly, the intersubband photoinduced resonances show a longer dynamics than the interband bleaching, because of their independence from the absolute energy of the carriers with respect to the Dirac point. The dynamic of these intersubband transitions reflects the lifetime of the hot carriers and provides an elegant method to access it in this important class of semimetals.

Charge photogeneration in donor-acceptor conjugated materials: influence of excess excitation energy and chain length.

We investigate the role of excess excitation energy on the nature of photoexcitations in donor-acceptor π-conjugated materials. We compare the polymer poly(2,6-(4,4-bis(2-ethylhexyl)-4H-cyclopenta[1,2-b;3,4-b']dithiophene)-4,7-benzo[2,1,3]thiadiazole) (PCPDTBT) and a short oligomer with identical constituents at different excitation wavelengths, from the near-infrared up to the ultraviolet spectral region. Ultrafast spectroscopic measurements clearly show an increased polaron pair yield for higher excess energies directly after photoexcitation when compared to the exciton population. This effect, already observable in the polymer, is even more pronounced for the shorter oligomer. Supported by quantum chemical simulations, we show that excitation in high-energy states generates electron and hole wave functions with reduced overlap, which likely act as precursors for the polaron pairs. Interestingly, in the oligomer we observe a lifetime of polaron pairs which is one order of magnitude longer. We suggest that this behavior results from the intermolecular nature of polaron pairs in oligomers. The study excludes the presence of carrier multiplication in these materials and highlights new aspects in the photophysics of donor-acceptor small molecules when compared to polymers. The former are identified as promising materials for efficient organic photovoltaics.

Increasing organic solar cell efficiency with polymer interlayers.

We demonstrate how organic solar cell efficiency can be increased by introducing a pure polymer interlayer between the PEDOT:PSS layer and the polymer:fullerene blend. We observe an increase in device efficiency with three different material systems over a number of devices. Using both electrical characterization and numerical modeling we show that the increase in efficiency is caused by optical absorption in the pure polymer layer and hence efficient charge separation at the polymer bulkheterojunction interface.

Spectral signatures of polarons in conjugated co-polymers.

We study electronic and optical properties of the low-bandgap co-polymer PCPDT-BT (poly-cyclopentadithiophene-co-benzothiadiazole) and compare it with the corresponding homo-polymer PCPDT (poly-cyclopentadithiophene). We investigate the linear absorptivity in these systems for neutral molecules and for their singly charged ions based on quantum-chemical calculations and experiments. One of our main findings is that the ions of the homo-polymer show a polaron absorption that is symmetric between anion and cation, whereas for polaron excitations in the co-polymer this symmetry is strongly lifted. We demonstrate that this asymmetry can be attributed to the absence of symmetry between the high-lying occupied and low-lying unoccupied molecular orbitals in the co-polymer with type-II orbital alignment between the moieties constituting the chain. This notion is of importance for the qualitative and quantitative interpretation of spectroscopic polaron data and is not specific to the system studied here but similarly applies to other co-polymers.

Structural correlations in the generation of polaron pairs in low-bandgap polymers for photovoltaics.

Polymeric semiconductors are materials where unique optical and electronic properties often originate from a tailored chemical structure. This allows for synthesizing conjugated macromolecules with ad hoc functionalities for organic electronics. In photovoltaics, donor-acceptor co-polymers, with moieties of different electron affinity alternating on the chain, have attracted considerable interest. The low bandgap offers optimal light-harvesting characteristics and has inspired work towards record power conversion efficiencies. Here we show for the first time how the chemical structure of donor and acceptor moieties controls the photogeneration of polaron pairs. We show that co-polymers with strong acceptors show large yields of polaron pair formation up to 24% of the initial photoexcitations as compared with a homopolymer (η=8%). π-conjugated spacers, separating the donor and acceptor centre of masses, have the beneficial role of increasing the recombination time. The results provide useful input into the understanding of polaron pair photogeneration in low-bandgap co-polymers for photovoltaics.

Tuning the excitonic and plasmonic properties of copper chalcogenide nanocrystals.

The optical properties of stoichiometric copper chalcogenide nanocrystals (NCs) are characterized by strong interband transitions in the blue part of the spectral range and a weaker absorption onset up to ~1000 nm, with negligible absorption in the near-infrared (NIR). Oxygen exposure leads to a gradual transformation of stoichiometric copper chalcogenide NCs (namely, Cu(2-x)S and Cu(2-x)Se, x = 0) into their nonstoichiometric counterparts (Cu(2-x)S and Cu(2-x)Se, x > 0), entailing the appearance and evolution of an intense localized surface plasmon (LSP) band in the NIR. We also show that well-defined copper telluride NCs (Cu(2-x)Te, x > 0) display a NIR LSP, in analogy to nonstoichiometric copper sulfide and selenide NCs. The LSP band in copper chalcogenide NCs can be tuned by actively controlling their degree of copper deficiency via oxidation and reduction experiments. We show that this controlled LSP tuning affects the excitonic transitions in the NCs, resulting in photoluminescence (PL) quenching upon oxidation and PL recovery upon subsequent reduction. Time-resolved PL spectroscopy reveals a decrease in exciton lifetime correlated to the PL quenching upon LSP evolution. Finally, we report on the dynamics of LSPs in nonstoichiometric copper chalcogenide NCs. Through pump-probe experiments, we determined the time constants for carrier-phonon scattering involved in LSP cooling. Our results demonstrate that copper chalcogenide NCs offer the unique property of holding excitons and highly tunable LSPs on demand, and hence they are envisaged as a unique platform for the evaluation of exciton/LSP interactions.

Reduced charge transfer exciton recombination in organic semiconductor heterojunctions by molecular doping.

We investigate the effect of molecular doping on the recombination of electrons and holes localized at conjugated-polymer-fullerene interfaces. We demonstrate that a low concentration of p-type dopant molecules (<4% weight) reduces the interfacial recombination via charge transfer excitons and results in a favored formation of separated carriers. This is observed by the ultrafast quenching of photoluminescence from charge transfer excitons and the increase in photoinduced polaron density by ~70%. The results are consistent with a reduced formation of emissive charge transfer excitons, induced by state filling of tail states.

Formation of a defect-free π-electron system in single ß-phase polyfluorene chains.

Single-molecule spectroscopy can help to uncover the underlying heterogeneity of conjugated polymers used in organic electronics, revealing the most effective molecules in an ensemble in terms of the transport of charge and excitation energy. We demonstrate that ß-phase polyfluorene chains can form a near-perfect π-electron system, whereas conventional polymers exhibit chromophoric localization due to perturbation of the conjugation. Broad-band excitation spectroscopy demonstrates that only one absorbing and emitting unit is present on the polymer chain with an average length of ∼500 repeat units, illustrating that the material effectively behaves as a molecular quantum wire with strong electronic coupling throughout the entire system.

Multiexcitonic dual emission in CdSe/CdS tetrapods and nanorods.

CdSe/CdS semiconductor nanocrystal heterostructures are currently of high interest for the peculiar electronic structure offering unique optical properties. Here, we show that nanorods and tetrapods made of such material combination enable efficient multiexcitonic emission, when the volume of the nanoparticle is maximized. This condition is fulfilled by tetrapods with an arm length of 55 nm and results in a dual emission with comparable intensities from the CdS arms and CdSe core. The relative intensities of the dual emission, originating from exciton phase-space filling and reduced Auger recombination, can be effectively modulated by the photon fluence of the pump laser. The results, obtained under steady-state detection conditions, highlight the properties of tetrapods as multiexciton dual-color emitters.