Polaron Formation Research Articles

Delocalisation enables efficient charge generation in organic photovoltaics, even with little to no energetic offset.

Organic photovoltaics (OPVs) are promising candidates for solar-energy conversion, with device efficiencies continuing to increase. However, the precise mechanism of how charges separate in OPVs is not well understood because low dielectric constants produce a strong attraction between the charges, which they must overcome to separate. Separation has been thought to require energetic offsets at donor-acceptor interfaces, but recent materials have enabled efficient charge generation with small offsets, or with none at all in neat materials. Here, we extend delocalised kinetic Monte Carlo (dKMC) to develop a three-dimensional model of charge generation that includes disorder, delocalisation, and polaron formation in every step from photoexcitation to charge separation. Our simulations show that delocalisation dramatically increases charge-generation efficiency, partly by enabling excitons to dissociate in the bulk. Therefore, charge generation can be efficient even in devices with little to no energetic offset, including neat materials. Our findings demonstrate that the underlying quantum-mechanical effect that improves the charge-separation kinetics is faster and longer-distance hops between delocalised states, mediated by hybridised states of exciton and charge-transfer character.

Polaron-induced changes in moiré exciton propagation in twisted van der Waals heterostructures.

Twisted transition metal dichalcogenides (TMDs) present an intriguing platform for exploring excitons and their transport properties. By introducing a twist angle, a moiré superlattice forms, providing a spatially dependent exciton energy landscape. Based on a microscopic many-particle theory, we investigate in this work polaron-induced changes in exciton transport properties in the exemplary MoSe2/WSe2 heterostructure. We demonstrate that polaron formation and the associated enhancement of the moiré exciton mass lead to a significant band flattening. As a result, the moiré inter-cell tunneling and the propagation velocity undergo noticeable temperature and twist-angle dependent changes. We predict a reduction of the hopping strength ranging from 80% at a twist angle of 1° to 30% at 3° at room temperature. The provided microscopic insights into the spatio-temporal exciton dynamics in presence of a moiré potential further expand the possibilities to tune charge and energy transport in 2D materials.

Spin polarized electron dynamics enhance water splitting efficiency by yttrium iron garnet photoanodes: a new platform for spin selective photocatalysis.

This work presents a spectroscopic and photocatalytic comparison of water splitting using yttrium iron garnet (Y3Fe5O12, YIG) and hematite (α-Fe2O3) photoanodes. Despite similar electronic structures, YIG significantly outperforms widely studied hematite, displaying more than an order of magnitude increase in photocurrent density. Probing the charge and spin dynamics by ultrafast, surface-sensitive XUV spectroscopy reveals that the enhanced performance arises from (1) reduced polaron formation in YIG compared to hematite and (2) an intrinsic spin polarization of catalytic photocurrents in YIG. Ultrafast XUV measurements show a reduction in the formation of surface electron polarons compared to hematite due to site-dependent electron-phonon coupling. This leads to spin polarized photocurrents in YIG where efficient charge separation occurs on the Td sub-lattice compared to fast trapping and electron/hole pair recombination on the Oh sub-lattice. These lattice-dependent dynamics result in a long-lived spin aligned hole population at the YIG surface, which is directly observed using XUV magnetic circular dichroism. Comparison of the Fe M2,3 and O L1-edges show that spin aligned holes are hybridized between O 2p and Fe 3d valence band states, and these holes are responsible for highly efficient, spin selective water oxidation by YIG. Together, these results point to YIG as a new platform for highly efficient, spin selective photocatalysis.

From molecular salt to layered network: cation-driven tuning of band gap, structure, and charge transport in A3Bi2I9 (A = Cs, Rb) perovskites.

The increasing demand for eco-friendly and stable optoelectronic materials has led to interest in all-inorganic lead-free halide perovskites. This study reports the synthesis of A3Bi2I9 (A = Cs, Rb) perovskites via a solvothermal technique. The materials crystallize in hexagonal and monoclinic structures, with micrometer-sized particles. Optical investigations reveal direct band-gaps of 2.03 eV for Cs3Bi2I9 and 1.90 eV for Rb3Bi2I9. Raman spectroscopy highlights distinct vibrational modes, influenced by their structural differences. Space charge limited current (SCLC) measurements indicate varying threshold voltages and trap densities. Impedance spectroscopy and Jonscher's power law analysis reveal different polaron tunneling mechanisms in each compound. Ultrafast transient absorption spectroscopy shows the formation of self-trapped states upon photoexcitation, linked to lattice distortion and the formation of small polarons, which affect electrical conductivity.

A transparent p-type semiconductor designed via a polarizability-enhanced strongly correlated insulator oxide matrix.

Electron-transporting transparent conducting oxides (TCOs) are a commercial reality, however, hole-transporting counterparts are far more challenging because of limited material design. Here, we propose a strategy for enhancing the hole conductivity without deteriorating the band gap (Eg) and workfunction (Φ) by Cu incorporation in a strongly correlated NiWO4 insulator. The optimal Cu-doped NiWO4 (Cu0.185Ni0.815WO4) exhibits a resistivity reduction of ∼109 times versus NiWO4 as well as band-like charge transport with the hole mobility approaching 7 cm2 V-1 s-1 at 200 K, a deep Φ of 5.77 eV, and Eg of 2.8 eV. Experimental and theoretical data reveal that the strength of the electron correlation in NiWO4 is unaffected by Cu incorporation, while the promoted polarizability weakens electron-phonon coupling, promoting the formation of large polarons. Quantum dot light-emitting and oxide p/n junction devices incorporating Cu0.185Ni0.815WO4 exhibit remarkable performances, demonstrating that our approach can be deployed to discover new p-type TCOs.

Particularities of polaron formation in the extended Holstein model with next nearest neighbor transfer

Particularities of polaron formation in the extended Holstein model with next nearest neighbor transfer

Time-Domain View of Polaron Dynamics in Metal Oxide Photocatalysts.

The polaron is a fundamental physical phenomenon in transition metal oxides (TMOs), and it has been studied extensively for decades. However, the implication of a polaron on photochemistry is still ambiguous. As such, understanding the fundamental properties and controlling the dynamics of polarons at the atomistic level is desired. In this Perspective, we seek to highlight the recent advances in studying small polarons in TMOs, with a particular focus on nonadiabatic molecular dynamics at the ab initio level, and discuss the implications for photocatalysis from the aspects of the structure, intrinsic physical properties, formation, migration, and recombination of small polarons. Finally, various methods were proposed to advance our understanding of manipulating the small-polaron dynamics, and strategies to design high-performance TMO-based photoelectrodes were discussed.

Engineering lattice oxygen defects and polaronic transport in vanadium pentoxide via isovalent phosphorus doping

Oxygen vacancies are equilibrium defects in the vanadium pentoxide system that give rise to polaronic hopping transport via V4+ charge compensating defect. In this paper, we report the tunability of polaron formation, the hopping process, and their magnetic signature by substitution of isovalent (5+) phosphorus ions in the V5+ site. The powder x-ray diffraction data show a monotonous shift in lattice parameters with progressive P-doping, confirming the presence of a substitutional dopant. The polaron hopping energy reduced from 0.307 to 0.290 eV depicting a lower defect concentration in P-doping in V2O5. At low temperatures, it is found to obey the Efros–Shklovskii variable range hopping mechanism. The estimated hopping range increased to 1.6 ± 0.1 nm in doped V2O5 in contrast to ∼1.3 nm in the undoped one. The electron spin resonance measurements show a diminishing broad ferromagnetic signal and rising paramagnetic signal (g = 1.97) with progressive P-doping depicting predominant isolated electronic spins in the doped sample. The same is corroborated in room temperature M–H with a distinct hysteresis that diminishes with P-doping and a rise of a paramagnetic slope. Moreover, the reduced oxygen defects and lower V4+ relative occupancy together with fermi level fall toward intrinsic position are substantiated by photoelectron emission studies.

Thermal cycle and polaron formation in structured bosonic environments

Thermal cycle and polaron formation in structured bosonic environments

Exciton-polaron interactions in metal halide perovskite nanocrystals revealed via two-dimensional electronic spectroscopy.

Metal halide perovskite nanocrystals have been under intense investigation for their promise in optoelectronic devices due to their remarkable physics, such as liquid/solid duality. This liquid/solid duality may give rise to their defect tolerance and other such useful properties. This duality means that the electronic states are fluctuating in time, on a distribution of timescales from femtoseconds to picoseconds. Hence, these lattice induced energy fluctuations that are connected to polaron formation are also connected to exciton formation and dynamics. We observe these correlations and dynamics in metal halide perovskite nanocrystals of CsPbI3 and CsPbBr3 using two-dimensional electronic (2DE) spectroscopy, with its unique ability to resolve dynamics in heterogeneously broadened systems. The 2DE spectra immediately reveal a previously unobserved excitonic splitting in these 15nm NCs that may have a coarse excitonic structure. 2D lineshape dynamics reveal a glassy response on the 300fs timescale due to polaron formation. The lighter Br system shows larger amplitude and faster timescale fluctuations that give rise to dynamic line broadening. The 2DE signals enable 1D transient absorption analysis of exciton cooling dynamics. Exciton cooling within this doublet is shown to take place on a slower timescale than within the excitonic continuum. The energy dissipation rates are the same for the I and Br systems for incoherent exciton cooling but are very different for the coherent dynamics that give rise to line broadening. Exciton cooling is shown to take place on the same timescale as polaron formation, revealing both as coupled many-body excitation.

Signatures of Polaron Dynamics in Photoexcited MAPbBr3 by Infrared Spectroscopy.

Hybrid organic-inorganic perovskites (HOIPs) have attracted considerable attention in the past years as photoactive materials for low-cost, high-performance photovoltaics. Polaron formation through electron-phonon coupling has been recognized as the leading mechanism governing charge carrier transport and recombination in HOIPs. In this work, two types of MAPbBr3 film samples deposited on different substrates (transparent insulating SrTiO3 and a heterostructure mimicking a functioning photovoltaic cell) were photoexcited with above-bandgap radiation at 450 nm, and the effects of illumination on the sample were analyzed in the infrared region. The infrared absorbance detected at different powers of the photoexciting laser allowed us to obtain an estimate of the characteristic decay time of photoexcited polaron population of the order of 100-1000 ns. When focusing on the absorption features of the MA molecular cation in the region of the NH stretching modes, we observed the influence of hydrogen bonding and the effect of the polaron dynamics on the cation reorientation.

Bayesian optimization approach to quantify the effect of input parameter uncertainty on predictions of numerical physics simulations

An understanding of how input parameter uncertainty in the numerical simulation of physical models leads to simulation output uncertainty is a challenging task. Common methods for quantifying output uncertainty, such as performing a grid or random search over the model input space, are computationally intractable for a large number of input parameters represented by a high-dimensional input space. It is, therefore, generally unclear as to whether a numerical simulation can reproduce a particular outcome (e.g., a set of experimental results) with a plausible set of model input parameters. Here, we present a method for efficiently searching the input space using Bayesian optimization to minimize the difference between the simulation output and a set of experimental results. Our method allows explicit evaluation of the probability that the simulation can reproduce the measured experimental results in the region of input space defined by the uncertainty in each input parameter. We apply this method to the simulation of charge-carrier dynamics in the perovskite semiconductor methyl-ammonium lead iodide (MAPbI3), which has attracted attention as a light harvesting material in solar cells. From our analysis, we conclude that the formation of large polarons, quasiparticles created by the coupling of excess electrons or holes with ionic vibrations, cannot explain the experimentally observed temperature dependence of electron mobility.

High-performance Ti-doped V2O5 coating on the Ni-rich layered cathode: Construction and theoretical calculation

Surface coating had been widely acknowledged as an effective method to improve the electrochemical performance of the cathodes for lithium-ion batteries (LiBs). In this study, a high-conductivity Ti0.05V1.96O5 (TVO) coating was successfully deposited on the surface of Li(Ni0.8Co0.1Mn0.1)O2 (NCM811) particles. The crystal structure, micro morphology and element composition of the resulted NCM811 @TVO samples were evaluated using X-ray diffractometer (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM) and X-ray photoelectron spectroscopy (XPS) analysis. Subsequently, the electrochemical performance of NCM811 @TVO cathodes were evaluated by galvanostatic charge/discharge tests (GCDT) and electrochemical impedance spectroscopy (EIS). The experimental results suggested that incorporating a TVO coating on the NCM811 cathode effectively enhanced both the rate capability and the cycling stability. Furthermore, first-principles calculation based on the density functional theory (DFT) were performed to elucidate the distinct electronic structure and Li ion migration behavior of V2O5 and TVO. The DFT calculation demonstrated that the introduction of Ti ions into the V2O5 leaded to the formation of small polarons and excessive free electrons, while significantly reduced the energy barrier for Li+ migration along [100] direction.

Size effects on polaron formation in lead chloride perovskite thin films

Lead halide perovskites (LHP) are of interest for light-emitting applications due to the tunability of their bandgap across the visible and near-infrared spectrum (IR) coupled with efficient photoluminescence quantum yields (PLQY). It is widely speculated that photoexcited electrons and holes spatially separate into large negative (electron) and positive (hole) polarons. Polarons are expected to be optically active. With the observed optoelectronic signatures expecting to show potential excited states within the polaronic potential well. From the polaron excited-state we predict that large polarons should be capable of spontaneous emission, photoluminescence, in the mid-IR to far-IR regime based on the concept of inverse occupations within the polaron potential well. Here we use density functional theory (DFT), including spin–orbit coupling interactions, for calculations on a two-dimensional Dion-Jacobson (DJ) lead chloride perovskite atomistic model of various sizes as a host material for either negative or positive polarons to examine the effects of size on polaron formation. This work provides computational evidence that polaron formation through selective charge injection does not show the same level of localisation for positive and negative polarons.

Exploring polaron formation in PEDOT oligomers through Advanced DFT analysis

In this short communication, we delve into the intriguing electronic structure of Poly(3,4-ethylenedioxythiophene) (PEDOT) to explore the formation of polarons. Through density functional theory approaches, the formation of polarons in PEDOT oligomers was explored, shedding light on their unique characteristics. The ωB97XD/6-311G(d,p) level of theory was adopted to investigate the oxidized states q = 0, q = 1, and q = 2 to understand their geometry optimization in different oxidation states. By calculating vibrational mode spectra, molecular orbital energies, Wiberg bond indices, and formal atomic charges, valuable insights into the intricate details of polaron formation were obtained. Our proposal of using Natural Bond Orbitals analysis, resulted in the conclusion that Wiberg Bond Indexes are a robust alternative for characterizing non-covalent interactions, providing a localized description of electron pairs and facilitating the interpretation of complex quantum mechanical electronic structures.

Thermoelectric Power (TEP) of Semiconducting Cobalt–Tellurite Glasses

The TEP, or Seebeck coefficient (S), for five bulk glasses in different compositions of binary semiconducting CoO–TeO2 glasses has been measured in the temperature range 304–490K. The glasses were prepared by melting dry mixtures of analytical reagent grads of CoO and TeO2 at a temperature of 1000 °C for 1h using quenching form the melt technique. TEP measurements have been performed utilizing specifically designed sample holders on annealed samples. The glasses were found to be n–type semiconductors with S in the range from –293 to –460 μV/K. S was found to be independent of temperature for all glass compositions, and Heikes’ formula adequately satisfied the TEP experimental results. The analyses provide evidence on the polaron formation and the disorder energy due to random fields.

Formation of binary magnon polaron in a two-dimensional artificial magneto-elastic crystal

We observed strong tripartite magnon-phonon-magnon coupling in a two-dimensional periodic array of magnetostrictive nanomagnets deposited on a piezoelectric substrate, forming a 2D magnetoelastic “crystal”; the coupling occurred between two Kittel-type spin wave (magnon) modes and a (non-Kittel) magnetoelastic spin wave mode caused by a surface acoustic wave (SAW) (phonons). The strongest coupling occurred when the frequencies and wavevectors of the three modes matched, leading to perfect phase matching. We achieved this condition by carefully engineering the frequency of the SAW, the nanomagnet dimensions and the bias magnetic field that determined the frequencies of the two Kittel-type modes. The strong coupling (cooperativity factor exceeding unity) led to the formation of a new quasi-particle, called a binary magnon-polaron, accompanied by nearly complete (~100%) transfer of energy from the magnetoelastic mode to the two Kittel-type modes. This coupling phenomenon exhibited significant anisotropy since the array did not have rotational symmetry in space. The experimental observations were in good agreement with the theoretical simulations.

Direct observation of topological magnon polarons in a multiferroic material

Magnon polarons are novel elementary excitations possessing hybrid magnonic and phononic signatures, and are responsible for many exotic spintronic and magnonic phenomena. Despite long-term sustained experimental efforts in chasing for magnon polarons, direct spectroscopic evidence of their existence is hardly observed. Here, we report the direct observation of magnon polarons using neutron spectroscopy on a multiferroic Fe2Mo3O8 possessing strong magnon-phonon coupling. Specifically, below the magnetic ordering temperature, a gap opens at the nominal intersection of the original magnon and phonon bands, leading to two separated magnon-polaron bands. Each of the bands undergoes mixing, interconverting and reversing between its magnonic and phononic components. We attribute the formation of magnon polarons to the strong magnon-phonon coupling induced by Dzyaloshinskii-Moriya interaction. Intriguingly, we find that the band-inverted magnon polarons are topologically nontrivial. These results uncover exotic elementary excitations arising from the magnon-phonon coupling, and offer a new route to topological states by considering hybridizations between different types of fundamental excitations.

Quantum fluctuation of ferroelectric order in polar metals

The polar metallic phase is an unusual metallic phase of matter containing long-range ferroelectric (FE) order in the electronic and atomic structure. Distinct from the typical FE insulating phase, this phase spontaneously breaks the inversion symmetry without global polarization. Unexpectedly, the FE order is found to be dramatically suppressed and destroyed at moderate ~ 10% carrier density. Here, we propose a general mechanism based on carrier-induced quantum fluctuations to explain this puzzling phenomenon. The quantum kinetic effect would drive the formation of polaronic quasi-particles made of the carriers and their surrounding dipoles. The disruption in dipolar directions can therefore weaken or even destroy the FE order. We demonstrate such polaron formation and the associated FE suppression via a concise model using exact diagonalization, perturbation, and quantum Monte Carlo approaches. This quantum mechanism also provides an intuitive picture for many puzzling experimental findings, thereby facilitating new designs of multifunctional FE electronic devices augmented with quantum effects.

Understanding Effects of Alkyl Side-Chain Density on Polaron Formation Via Electrochemical Doping in Thiophene Polymers.

Polarons exist when charges are injected into organic semiconductors due to their strong coupling with the lattice phonons, significantly affecting electronic charge-transport properties. Understanding the formation and (de)localization of polarons is therefore critical for further developing organic semiconductors as a future electronics platform. However, there are very few studies reported in this area. In particular, there is no direct in situ monitoring of polaron formation and identification of its dependence on molecular structure and impact on electrical properties, limiting further advancement in organic electronics. Herein, how a minor modification of side-chain density in thiophene-based conjugated polymers affects the polaron formation via electrochemical doping, changing the polymers' electrical response to the surrounding dielectric environment for gas sensing, is demonstrated. It is found that the reduction in side-chain density results in a multistep polaron formation, leading to an initial formation of localized polarons in thiophene units without side chains. Reduced side-chain density also allows the formation of a high density of polarons with fewer polymer structural changes. More numerous but more localized polarons generate a stronger analyte response but without the selectivity between polar and non-polar solvents, which is different from the more delocalized polarons that show clear selectivity. The results provide important molecular understanding and design rules for the polaron formation and its impact on electrical properties.