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At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Polaron and Exciton Delocalization in Oligomers of High-Performance Polymer PTB7

A key characteristic of organic photovoltaic cells is the efficient charge separation in the active layer. Sufficient delocalization of the positive polaron in organic photovoltaics is considered essential for the effective separation of the opposite charges and the suppression of recombination. Here we use light-induced EPR and ENDOR spectroscopy combined with DFT calculations to determine the electronic structure of the positive polaron in PTB7-type oligomers. Utilizing the superior spectral resolution of high-frequency (130 GHz) D-band EPR, the principal components of the g tensors were determined. Pulsed ENDOR spectroscopy at X-band allowed the measurement of H-1 hyperfine coupling constants. A comparison of g tensors and H-1 hyperfine coupling constants of the PTB7-type oligomers with the high-performance PTB7 polymer revealed a delocalization of the positive polaron in the polymer over about four monomeric units, corresponding to about 45 angstrom in length. Our current study thus not only determines the polaron delocalization length in PTB7 but also validates the approach combining EPR/ENDOR spectroscopy with DFT-calculated magnetic resonance parameters. This is of importance in those cases where oligomers of defined length are not easily obtained. In addition, the delocalization of the neutral triplet exciton was also determined in the oligomers and compared with polymer PTB7. The analysis revealed that the neutral triplet exciton is substantially more delocalized than the positive polaron, exceeding 10 monomeric units.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Interfacial and bulk polaron masses in Zn{sub 1−x}Mg{sub x}O/ZnO heterostructures examined by terahertz time-domain cyclotron spectroscopy

The cyclotron resonance of polarons in Zn{sub 1−x}Mg{sub x}O/ZnO heterostructures (with 0.15<x<0.22) was studied by terahertz time-domain spectroscopy. Low-temperature magnetoconductivity spectra of the 2D electron gas at the Zn{sub 1−x}Mg{sub x}O/ZnO interface determined the polaron density, mass, and scattering rate. The cyclotron mass of 2D polarons was found to increase significantly with magnetic field B from 0.24 m{sub e} at B = 2 T to 0.37 m{sub e} at B = 7.5 T. A nonlinear cyclotron frequency with B was also observed for 3D polarons in ZnO. The findings are discussed in the context of polaron mass renormalization driven by the electron-LO-phonon and electron-acoustic phonon interactions.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Effects of the built-in electric field on polaron effects in a wurtzite ZnO/Mg{sub x}Zn{sub 1−x}O quantum well

The effects of the built-in electric field on the polarons in wurtzite ZnO/Mg{sub x}Zn{sub 1−x}O quantum wells are studied numerically via the improved Lee-Low-Pines intermediate coupling variational method. The contributions of the different branches of the optical phonons to the polaron energies of the ZnO/Mg{sub x}Zn{sub 1−x}O quantum wells are calculated as functions of well width d and composition x. The anisotropy effects of the electronic effective masses, the dielectric constants, and the frequencies of the different branches of the phonon modes (including both the longitudinal-like and transverse-like confined optical phonon modes, the interface optical phonon modes and the half-space phonon modes) on the polaron energies are considered in the calculations. Comparisons between the cases with and without the built-in electric field (F ≠ 0 and F = 0) are made for the optical phonon contributions to the polaron energies for the different branches of the phonon modes. The results show that the built-in electric field has marked effects on the contributions of the phonons with the different modes; in detail, it makes positive contributions to the interface and the half-space phonons, but negative contributions to the confined phonons, and thus its effect on the total phonon contribution is not obvious. Detailed comparisons of the contributions of the symmetric and antisymmetric phonon modes to the polaron energies as functions of d and x are also presented and a heuristic argument is provided to explain the numerical results.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

Bond-Peierls polaron: Moderate mass enhancement and current-carrying ground state

We study polarons in the one-dimensional Bond-Peierls electron-phonon model in which phonons on bonds of a lattice modulate the hopping of electrons between lattice sites and contrast the results to those known for the breathing-mode Peierls problem. By inspecting the atomic limit, we show that polaronic dressing and mass enhancement of Bond-Peierls polarons depend on the momentum dependence of the phonons. For dispersionless phonons, Bond-Peierls polarons are perfectly localized in the atomic limit, unlike their breathing-mode counter-parts because the carrier creates a string of phonon excitations that can only be annihilated via processes that retrace the carrier to its original site. Furthermore, inclusion of phonon dispersion leads to a nondivergent polaron mass even in the atomic limit and depending on the form of the phonon dispersion may lead to a transition to a non-zero-momentum ground state akin to that found in the breathing-mode Peierls model.

1-dimensional systems↗
DOE OSTI2023

Delocalized polaron and Burstein-Moss shift induced by Li in α–V 2 O 5 : A DFT + DMFT study

For this work, we performed density functional theory (DFT)+U and dynamical mean field theory (DMFT) calculations with a continuous-time quantum Monte Carlo impurity solver to investigate the electronic properties of V 2 O 5 and Li x V 2 O 5 (x = 0.125 and 0.25). Pristine V 2 O 5 is a charge-transfer insulator with strong O p–V d hybridization, and it exhibits a large band gap (E gap ) as well as a nonzero conduction-band (CB) gap.We show that the band gap, the number of d electrons of vanadium, N d , and the CB gap for V 2 O 5 obtained from our DMFT calculations are in excellent agreement with the experimental values. While the DFT +U approach replicates the experimental band gap, it overestimates the value of N d and underestimates the CB gap. In the presence of low Li doping, the electronic properties of V 2 O 5 are mainly driven by a polaronic mechanism, and electron spin resonance and electron nuclear double resonance spectroscopies observed the coexistence of free and bound polarons. Notably, our DMFT results identify both polaron types, with the bound polaron being energetically preferred, while the DFT +U method only predicts the free polaron. Our DMFT analysis also reveals that increased Li doping leads to electron filling in the conduction band, shifting the Fermi level. This result is consistent with the observed Burstein-Moss shift upon enhanced Li doping, and we thus demonstrate that the DFT + DMFT approach can be used for an accurate and realistic description of strongly correlated materials.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Magnetic polarons and spin-glass behavior in insulating La 1-x Sr x CoO 3 (x = 0.125 and 0.15)

The evolution of magnetic polarons in Sr doped La Co O 3 ( La 1 - x Sr x Co O 3 ) single crystal and polycrystalline samples are investigated by employing dc and ac magnetic measurement and small angle neutron scattering (SANS) techniques. The effect of magnetic field and temperature on magnetic polarons is experimentally studied for La 0.875 Sr 0.125 Co O 3 and La 0.85 Sr 0.15 Co O 3 compounds that belong to the spin glass insulating regime of the broader compositional phase diagram of this system. Langevin analyses of the isothermal magnetization curves in the notional paramagnetic regime prove the existence of magnetic polarons with large moments. The dc field superimposed ac susceptibility data and the analysis of the glassy dynamics prove that the size of polarons in 15% Sr doped crystal increase as the field is increased while the field effect is not visible in the 12.5% Sr doped crystal. A polycrystalline sample of La 0.85 Sr 0.15 Co O 3 is analyzed by SANS experiments, which confirm nonzero correlation length at temperatures far above the macroscopic ordering temperature and hence the presence of magnetic polarons.

36 MATERIALS SCIENCE↗
DOE OSTI2015

On the dynamics of a polaron in a classical chain with finite temperature

In today’s literature, polaron states in classical molecular chains are mostly calculated at zero temperature. It is assumed that the properties of these states change little if the temperature is different from zero but is much less than the characteristic energy equal to the depth of the polaron level. By numerical experiments, we demonstrate that the temperature decay of a polaron depends on the chain length. The longer the chain, the lower the critical temperature above which the charge is in a delocalized state, and, conversely, the shorter the chain, the higher the decay temperature of a polaron. The results of numerical experiments lead to a conclusion that, in an indefinitely long chain, polaron states decay at temperatures differing arbitrarily little from zero.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2018

Influence of the Diagonal and Off-Diagonal Electron–Phonon Interactions on the Formation of Local Polarons and Their Band Structure in Materials with Strong Electron Correlations

For systems with strong electron correlations and strong electron–phonon interaction, we analyze the electron–phonon interaction in local variables. The effects of the mutual influence of electron–electron and electron–phonon interactions that determine the structure of local Hubbard polarons are described. Using a system containing copper–oxygen layers as an example, we consider the competition between the diagonal and off-diagonal interactions of electrons with the breathing mode as the polaron band structure is formed within a corrected formulation of the polaron version of the generalized tight-binding method. The band structure of Hubbard polarons is shown to depend strongly on the temperature due to the excitation of Franck–Condon resonances. For an undoped La{sub 2}CuO{sub 4} compound we have described the evolution of the band structure and the spectral function from the hole dispersion in an antiferromagnetic insulator at low temperatures with the valence band maximum at point (π/2, π/2) to the spectrum with the maximum at point (π, π) typical for the paramagnetic phase. The polaron line width at the valence band top and its temperature dependence agree qualitatively with angle-resolved photoemission spectroscopy for undoped cuprates.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2017

Phase-breaking effect on polaron transport in organic conjugated polymers

Despite intense investigations and many accepted viewpoints on theory and experiment, the coherent and incoherent carrier transport in organic semiconductors remains an unsettled topic due to the strong electron-phonon coupling. Based on the tight-binding Su-Schrieffer-Heeger (SSH) model combined with a non-adiabatic dynamics method, we study the effect of phase-breaking on polaron transport by introducing a group of phase-breaking factors into π-electron wave-functions in organic conjugated polymers. Two approaches are applied: the modification of the transfer integral and the phase-breaking addition to the wave-function. Within the former, it is found that a single site phase-breaking can trap a polaron. However, with a larger regular phase-breaking a polaron becomes more delocalized and lighter. Additionally, a group of disordered phase-breaking factors can make the polaron disperse in transport process. Within the latter approach, we show that the phase-breaking can render the delocalized state in valence band discrete and the state in the gap more localized. Consequently, the phase-breaking frequency and intensity can reduce the stability of a polaron. Furthermore, the phase-breaking in organic systems is the main factor that degrades the coherent transport and destroys the carrier stability.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Geometry Distortion and Small Polaron Binding Energy Changes with Ionic Substitution in Halide Perovskites

Halide perovskites have demonstrated remarkable performance in optoelectronic applications. Despite extraordinary progress, questions remain about device stability. We report an in-depth computational study of small polaron formation, electronic structure, charge density, and reorganization energies of several experimentally relevant halide perovskites using isolated clusters. Local lattice symmetry, electronic structure, and electron-phonon coupling are interrelated in polaron formation in these materials. To illustrate this, first principles calculations are performed on (MA/Cs/FA)Pb(I/Br) 3 and MASnI 3 . Across the materials studied, electron small polaron formation is manifested by Jahn-Teller like distortions in the central octahedron, with apical PbI bonds expanding significantly more than the equatorial bonds. In contrast, hole polarons cause the central octahedron to uniformly contract. This difference in manifestation of electron and hole polaron formation can be a tool to determine what is taking place in individual systems to systematically control performance. Other trends as the anion and cations are changed, are established for optimization in specific optoelectronic applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Polaron catastrophe within quantum acoustics

The quantum acoustic framework has recently emerged as a nonperturbative, coherent approach to electron–lattice interactions, uncovering rich physics often obscured by perturbative methods with incoherent scattering events. Here, we model the strongly coupled dynamics of electrons and acoustic lattice vibrations within this framework, representing lattice vibrations as coherent states and electrons as quantum wave packets, in a manner distinctively different from tight-binding or discrete hopping-based approaches. We derive and numerically implement electron backaction on the lattice, providing both visual and quantitative insights into electron wave packet evolution and the formation of acoustic polarons. We investigate polaron binding energies across varying material parameters and compute key observables—including mean square displacement, kinetic energy, potential energy, and vibrational energy—over time. Our findings reveal the conditions that favor polaron formation, which is enhanced by low temperatures, high deformation potential constants, slow sound velocities, and high effective masses. Additionally, we explore the impact of external electric and magnetic fields, showing that while polaron formation remains robust under moderate fields, it is weakly suppressed at higher field strengths. These results deepen our understanding of polaron dynamics and pave the way for future studies into nontrivial transport behavior in quantum materials.

Science & Technology - Other Topics↗
DOE OSTI2020

Coherent band-edge oscillations and dynamic longitudinal-optical phonon mode splitting as evidence for polarons in perovskites

The coherence of collective modes, such as phonons and polarons, and their modulation of electronic states is long sought in complex systems, which is a crosscutting issue in photovoltaics and quantum electronics. In photovoltaic cells and lasers based on metal halide perovskites, the presence of polarons, i.e., photocarriers dressed by the macroscopic motion of charged lattice, assisted by terahertz (THz) longitudinal-optical (LO) phonons, has been intensely studied yet is still debated. This may be key for explaining the remarkable properties of the perovskite materials, e.g., defect tolerance, long charge lifetimes, and diffusion lengths. In this work we use the intense single-cycle THz pulse with peak electric field up to E THz = 1000 kV/cm to drive coherent polaronic band-edge oscillations at room temperature in CH 3 NH 3 PbI 3 (MAPbI 3 ). We reveal the oscillatory behavior is dominated by a specific quantized lattice vibration mode at $ω$ LO ~ 4 THz, which is both dipole and momentum forbidden. THz-driven coherent polaron dynamics exhibits distinguishing features: room temperature coherent oscillations at ω LO longer than 1 ps in both single crystals and thin films, mode-selective modulation of different band-edge states assisted by electron-phonon interaction, and dynamic mode splitting at low temperature due to entropy and anharmonicity of organic cations. Our results demonstrate intense THz-driven coherent band-edge modulation is a powerful probe of electron-lattice coupling phenomena and polaronic quantum control in perovskites.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Polarons and electrical leakage in BaZrO 3 and BaCeO 3

The proton conductors barium zirconate (BaZrO 3 , or BZO), barium cerate (BaCeO 3 , or BCO), and their alloys have attracted considerable interest as solid-state electrolytes in solid-oxide fuel and electrolysis cells. However, the reasons for their non-negligible electrical conductivity, which can limit their performance, are not fully understood. To address that question, we use first-principles calculations based on density functional theory to study the properties of hole and electron polarons in BZO and BCO. We confirm that hole polarons form in both materials, slightly more favorably in BCO. Electron polarons, on the other hand, are stable only in BCO and in Ce-containing alloys; in pure BZO, electron polaron states are unfavorable relative to free carriers, though they become accessible when Ce impurities are introduced. In general, doped BZO and BCO will have negligible electron concentrations, but larger concentrations of holes and hole polarons may be present. Avoiding extreme O-rich conditions and limiting dopant concentrations are key strategies for reducing significant p -type electrical leakage. Furthermore, our results provide physical insights into the different electronic behaviors of BZO and BCO, which can be used to optimize their performance as pure ionic conductors.

08 HYDROGEN↗
DOE OSTI2017

Large polarons in lead halide perovskites

Lead halide perovskites show marked defect tolerance responsible for their excellent optoelectronic properties. These properties might be explained by the formation of large polarons, but how they are formed and whether organic cations are essential remain open questions. We provide a direct time domain view of large polaron formation in single-crystal lead bromide perovskites CH 3 NH 3 PbBr 3 and CsPbBr 3 . We found that large polaron forms predominantly from the deformation of the PbBr 3 - frameworks, irrespective of the cation type. The difference lies in the polaron formation time, which, in CH 3 NH 3 PbBr 3 (0.3 ps), is less than half of that in CsPbBr3 (0.7 ps). First-principles calculations confirm large polaron formation, identify the Pb-Br-Pb deformation modes as responsible, and explain quantitatively the rate difference between CH 3 NH 3 PbBr 3 and CsPbBr 3 . The findings reveal the general advantage of the soft [PbX 3 ] - sublattice in charge carrier protection and suggest that there is likely no mechanistic limitations in using all-inorganic or mixed-cation lead halide perovskites to overcome instability problems and to tune the balance between charge carrier protection and mobility.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Direct and Inverse Photoelectron Spectroscopy Evidence for a Revised Picture of Electronic States of Negative Polarons in n‐Doped C 60

Abstract Determining the electronic levels associated with polarons, the fundamental charge carriers in organic semiconductors, is key to understanding the charge transport properties of these materials. Recent findings challenge the traditional view of these electronic levels by highlighting the importance of intra‐molecular Coulomb interactions in polarons. Experimental evidence was previously presented for a revised model of the negative polaron in the case of the polymer semiconductor poly(NDI2OD‐T 2 ); there, the addition of an excess electron was seen to lead to the emergence of a singly occupied state within the energy gap of the undoped material and an unoccupied state above the edge of the conduction states . Here, focus is on a small‐molecule semiconductor, C 60 , and spectral evidence is provided of a similar picture for the new states appearing upon polaron formation. Specifically, direct and inverse photoemission spectroscopy is used to investigate the density of states in C 60 films n‐doped with two dimeric dopants. The Coulomb interaction energy (Hubbard U ) of the C 60 anion is experimentally determined to be ≈1.1 eV, a value that aligns closely with theoretical predictions.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Optical absorption induced by small polaron formation in transition metal oxides: The case of Co 3 O 4

Small polarons (SPs) are known to exist in most important transition metal oxides; however, the nature of small polaron formation remains enigmatic, and a fundamental understanding of how SPs impact the intrinsic electronic structure and optical properties of these materials is largely lacking. In this work, we employ first-principles calculations to investigate SP formation in Co 3 O 4 , a highly promising material for a wide range of emerging energy applications, and we resolve the conflicting findings that have been reported on the electronic structure of the system. We confirm that the intrinsic band gap of Co 3 O 4 is 1.6 eV, and we show that the formation of small hole polarons significantly influences the optical absorption spectra, leading to a 0.8 eV transition that is often misinterpreted as the band edge that defines the fundamental gap. In addition, we discuss how uniaxial strain can be utilized to probe the Jahn-Teller distortion of SP states and, in turn, effect their optical transitions. Beyond Co 3 O 4 , our study suggests a general roadmap for establishing a first-principles computational approach that can simultaneously achieve an accurate description of SP states, electronic band structure, and optical transitions of polaronic magnetic oxides.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Polaron and Spin Dynamics in Organic–Inorganic Lead Halide Perovskite Nanocrystals

Long-lived carrier population and spin-based behavior in lead halide perovskite nanocrystals (NCs) are very interesting for implementing photovoltaic devices with efficiencies exceeding the Shockley–Queisser limit and quantum information processing, respectively. However, a comprehensive understanding of polaron-mediated charge carrier interactions and an accurate description of the spin-polarized states for spintronics are still lacking. Herein, the carrier and spin interactions are studied under controlled conditions in FAPbI 3 and Cs 0.01 FA 0.99 Pb(Br 0.11 I 0.89 ) 3 NCs through ultrafast transient absorption (TA) spectroscopy. At early timescales, TA spectrum shows an asymmetric derivative feature originating from the hot carrier-induced spectral redshift in FAPbI 3 NCs (55 ± 3 meV) and Cs0.01FA0.99Pb(Br0.11I0.89)3 NCs (54 ± 2 meV) at the bandedges that stabilizes to 9 ± 1 and 11 ± 2 meV, respectively, at 1 ps due to the polaron formation. The kinetic analysis indicates that the polaron populations in FAPbI3 and Cs 0.01 FA 0.99 Pb(Br 0.11 I 0.89 ) 3 NCs decay with an average lifetime of 657 ± 34 and 532 ± 28 ps, respectively. The circular polarization-resolved TA reveals that polaron formation can control spin relaxation in NCs, thus providing a powerful tool to explore the development of their prospective applications in spintronics.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Polarons induced electronic transport, dielectric relaxation and magnetodielectric coupling in spin frustrated Ba{sub 2}FeWO{sub 6}

Highlights: • Ordered double perovskite Ba{sub 2}FeWO{sub 6} synthesized in reducing atmosphere possess a tetragonal I4/m crystal structure with mixed valent Fe/W cations. • Ba{sub 2}FeWO{sub 6} has an antiferromagnetic structure with T{sub N} at 19 K. • Insulating Ba{sub 2}FeWO{sub 6} shows different conducting mechanisms at different temperature regions and dielectric relaxation. • The polarons invoked by the mixed valence state of cations and their disordered arrangements are solely responsible for the various physical phenomena observed in Ba{sub 2}FeWO{sub 6}. - Abstract: Mixed valent double perovskite Ba{sub 2}FeWO{sub 6}, with tetragonal crystal structure, synthesized in a highly controlled reducing atmosphere, shows antiferromagnetic transition at T{sub N} = 19 K. A cluster glass-like transition is observed around 30 K arising from the competing interactions between inhomogeneous magnetic states. The structural distortion leads to the formation of polarons that are not contributing to DC conduction below charge ordering temperature, T{sub CO} = 279 K. Above T{sub CO}, small polarons will start to hop by exploiting thermal energy and participate in the conduction mechanism. The polarons are also responsible for the dielectric relaxor behavior, in which the dielectric relaxation time follows non-linearity in temperature as proposed by Fulcher. The material also exhibits a small room temperature magnetoresistance of 1.7% at 90 kOe. An intrinsic magnetodielectric coupling of ∼4% near room temperature and at lower temperatures, as well as an extrinsic magnetodielectric coupling change from +4% to −6% at around 210 K are reported.

36 MATERIALS SCIENCE↗