Publications by Laura Herz


How β-Phase Content Moderates Chain Conjugation and Energy Transfer in Polyfluorene Films.

The journal of physical chemistry letters (2019) 1729-1736

HJ Eggimann, F Le Roux, LM Herz

Poly(9,9-dioctylfluorene) (PFO) is a blue-light-emitting polymer exhibiting two distinct phases, namely, the disordered "glassy" phase and a more ordered β-phase. We investigate how a systematic increase in the fraction of β-phase present in PFO films controls chain conformation, photoluminescence quantum efficiency (PLQE), and the resonant energy transfer from the glassy to the β-phase. All films are prepared by the same technique, using paraffin oil as an additive to the spin-coating solution, allowing systematic tuning of the β-phase fraction. The PFO films exhibit high PLQE with values increasing to 0.72 for increasing fractions of β-phase present, with the β-phase chain conformation becoming more planar and including more repeat units. Differences in Förster radii calculated from the overlap of steady-state absorptance and emission spectra and from time-resolved ultrafast photoluminescence transients indicate that exciton diffusion within the glassy phase plays an important role in the energy transfer process.


Structural and Optical Properties of Cs2AgBiBr6 Double Perovskite

ACS ENERGY LETTERS 4 (2019) 299-305

L Schade, AD Wright, RD Johnson, M Dollmann, B Wenger, PK Nayak, D Prabhakaran, LM Herz, R Nicholas, HJ Snaith, PG Radaelli


Aromaticity and Antiaromaticity in the Excited States of Porphyrin Nanorings.

The journal of physical chemistry letters (2019) 2017-2022

MD Peeks, JQ Gong, K McLoughlin, T Kobatake, R Haver, LM Herz, HL Anderson

Aromaticity can be a useful concept for predicting the behavior of excited states. Here we show that π-conjugated porphyrin nanorings exhibit size-dependent excited-state global aromaticity and antiaromaticity for rings containing up to eight porphyrin subunits, although they have no significant global aromaticity in their neutral singlet ground states. Applying Baird's rule, even rings ([4 n] π-electrons) are aromatic in their lowest excited states, whereas the lowest excited states of odd rings ([4 n + 2] π-electrons) are antiaromatic. These predictions are borne out by density functional theory (DFT) studies of the nucleus-independent chemical shift (NICS) in the T1 triplet state of each ring, which reveal the critical importance of the triplet delocalization to the emergence of excited-state aromaticity. The singlet excited states (S1) are explored by measurements of the radiative rate and fluorescence peak wavelength, revealing a subtle odd-even alternation as a function of ring size, consistent with symmetry breaking in antiaromatic excited states.


Electronic Traps and Phase Segregation in Lead Mixed-Halide Perovskite

ACS ENERGY LETTERS 4 (2019) 75-84

AJ Knight, AD Wright, JB Patel, DP McMeekin, HJ Snaith, MB Johnston, LM Herz


Raman Spectrum of the Organic-Inorganic Halide Perovskite CH3NH3PbI3 from First Principles and High-Resolution Low-Temperature Raman Measurements

JOURNAL OF PHYSICAL CHEMISTRY C 122 (2018) 21703-21717

MA Perez-Osorio, Q Lin, RT Phillips, RL Milot, LM Herz, MB Johnston, F Giustino


High Electron Mobility and Insights into Temperature-Dependent Scattering Mechanisms in InAsSb Nanowires.

Nano letters 18 (2018) 3703-3710

JL Boland, F Amaduzzi, S Sterzl, H Potts, LM Herz, A Fontcuberta I Morral, MB Johnston

InAsSb nanowires are promising elements for thermoelectric devices, infrared photodetectors, high-speed transistors, as well as thermophotovoltaic cells. By changing the Sb alloy fraction the mid-infrared bandgap energy and thermal conductivity may be tuned for specific device applications. Using both terahertz and Raman noncontact probes, we show that Sb alloying increases the electron mobility in the nanowires by over a factor of 3 from InAs to InAs0.65Sb0.35. We also extract the temperature-dependent electron mobility via both terahertz and Raman spectroscopy, and we report the highest electron mobilities for InAs0.65Sb0.35 nanowires to date, exceeding 16,000 cm2 V-1 s-1 at 10 K.


Temperature-Dependent Refractive Index of Quartz at Terahertz Frequencies

JOURNAL OF INFRARED MILLIMETER AND TERAHERTZ WAVES 39 (2018) 1236-1248

CL Davies, JB Patel, CQ Xia, LM Herz, MB Johnston


Modification of the fluorinated tin oxide/electron-transporting material interface by a strong reductant and its effect on perovskite solar cell efficiency

MOLECULAR SYSTEMS DESIGN & ENGINEERING 3 (2018) 741-747

F Pulvirenti, B Wegner, NK Noel, G Mazzotta, R Hill, JB Patel, LM Herz, MB Johnston, MK Riede, HJ Snaith, N Koch, S Barlow, SR Marder


How Lattice Dynamics Moderate the Electronic Properties of Metal-Halide Perovskites.

The journal of physical chemistry letters (2018) 6853-6863

LM Herz

Metal-halide perovskites have emerged as highly promising semiconductors with excellent optoelectronic properties. This Perspective outlines how the dynamic response of the ionic lattice affects key electronic properties such as exciton binding energies and charge-carrier mobilities in hybrid perovskites. Such links are shown to derive from the frequency-dependence of the dielectric function, which is governed by contributions from electronic interband transitions, polar vibrations of the metal-halide sublattice, organic cation collective reorientations, and ionic movement. The influence of each of these contributions to charge-carrier screening and carrier-lattice interactions is discussed, which allows for general trends with material composition to be revealed. Overall, this Perspective highlights the challenges and questions arising from the peculiar combination of a soft polar metal-halide sublattice interspersed with rotationally mobile dipolar molecules that is encountered in hybrid metal-halide perovskites.


Bimolecular recombination in methylammonium lead triiodide perovskite is an inverse absorption process.

Nature communications 9 (2018) 293-

CL Davies, MR Filip, JB Patel, TW Crothers, C Verdi, AD Wright, RL Milot, F Giustino, MB Johnston, LM Herz

Photovoltaic devices based on metal halide perovskites are rapidly improving in efficiency. Once the Shockley-Queisser limit is reached, charge-carrier extraction will be limited only by radiative bimolecular recombination of electrons with holes. Yet, this fundamental process, and its link with material stoichiometry, is still poorly understood. Here we show that bimolecular charge-carrier recombination in methylammonium lead triiodide perovskite can be fully explained as the inverse process of absorption. By correctly accounting for contributions to the absorption from excitons and electron-hole continuum states, we are able to utilise the van Roosbroeck-Shockley relation to determine bimolecular recombination rate constants from absorption spectra. We show that the sharpening of photon, electron and hole distribution functions significantly enhances bimolecular charge recombination as the temperature is lowered, mirroring trends in transient spectroscopy. Our findings provide vital understanding of band-to-band recombination processes in this hybrid perovskite, which comprise direct, fully radiative transitions between thermalized electrons and holes.


Hybrid Perovskites: Prospects for Concentrator Solar Cells.

Advanced science (Weinheim, Baden-Wurttemberg, Germany) 5 (2018) 1700792-1700792

Q Lin, Z Wang, HJ Snaith, MB Johnston, LM Herz

Perovskite solar cells have shown a meteoric rise of power conversion efficiency and a steady pace of improvements in their stability of operation. Such rapid progress has triggered research into approaches that can boost efficiencies beyond the Shockley-Queisser limit stipulated for a single-junction cell under normal solar illumination conditions. The tandem solar cell architecture is one concept here that has recently been successfully implemented. However, the approach of solar concentration has not been sufficiently explored so far for perovskite photovoltaics, despite its frequent use in the area of inorganic semiconductor solar cells. Here, the prospects of hybrid perovskites are assessed for use in concentrator solar cells. Solar cell performance parameters are theoretically predicted as a function of solar concentration levels, based on representative assumptions of charge-carrier recombination and extraction rates in the device. It is demonstrated that perovskite solar cells can fundamentally exhibit appreciably higher energy-conversion efficiencies under solar concentration, where they are able to exceed the Shockley-Queisser limit and exhibit strongly elevated open-circuit voltages. It is therefore concluded that sufficient material and device stability under increased illumination levels will be the only significant challenge to perovskite concentrator solar cell applications.


High irradiance performance of metal halide perovskites for concentrator photovoltaics (vol 3, pg 855, 2018)

NATURE ENERGY 3 (2018) 1013-1013

Z Wang, Q Lin, B Wenger, MG Christoforo, Y-H Lin, MT Klug, MB Johnston, LM Herz, HJ Snaith


Impact of the Organic Cation on the Optoelectronic Properties of Formamidinium Lead Triiodide.

The journal of physical chemistry letters 9 (2018) 4502-4511

CL Davies, J Borchert, CQ Xia, RL Milot, H Kraus, MB Johnston, LM Herz

Metal halide perovskites have proven to be excellent light-harvesting materials in photovoltaic devices whose efficiencies are rapidly improving. Here, we examine the temperature-dependent photon absorption, exciton binding energy, and band gap of FAPbI3 (thin film) and find remarkably different behavior across the β-γ phase transition compared with MAPbI3. While MAPbI3 has shown abrupt changes in the band gap and exciton binding energy, values for FAPbI3 vary smoothly over a range of 100-160 K in accordance with a more gradual transition. In addition, we find that the charge-carrier mobility in FAPbI3 exhibits a clear T-0.5 trend with temperature, in excellent agreement with theoretical predictions that assume electron-phonon interactions to be governed by the Fröhlich mechanism but in contrast to the T-1.5 dependence previously observed for MAPbI3. Finally, we directly observe intraexcitonic transitions in FAPbI3 at low temperature, from which we determine a low exciton binding energy of only 5.3 meV at 10 K.


Interplay of Structural and Optoelectronic Properties in Formamidinium Mixed Tin-Lead Triiodide Perovskites

ADVANCED FUNCTIONAL MATERIALS 28 (2018) ARTN 1802803

ES Parrott, T Green, RL Milot, MB Johnston, HJ Snaith, LM Herz


Engineering III-V nanowires for optoelectronics: from epitaxy to terahertz photonics

QUANTUM DOTS AND NANOSTRUCTURES: GROWTH, CHARACTERIZATION, AND MODELING XV 10543 (2018)

HJ Joyce, C Uswachoke, SA Baig, SO Adeyemo, JL Boland, DA Damry, CL Davies, J Wong-Leung, HH Tan, C Jagadish, LM Herz, MB Johnston


The Effects of Doping Density and Temperature on the Optoelectronic Properties of Formamidinium Tin Triiodide Thin Films.

Advanced materials (Deerfield Beach, Fla.) 30 (2018) e1804506-

RL Milot, MT Klug, CL Davies, Z Wang, H Kraus, HJ Snaith, MB Johnston, LM Herz

Optoelectronic properties are unraveled for formamidinium tin triiodide (FASnI3 ) thin films, whose background hole doping density is varied through SnF2 addition during film fabrication. Monomolecular charge-carrier recombination exhibits both a dopant-mediated part that grows linearly with hole doping density and remnant contributions that remain under tin-enriched processing conditions. At hole densities near 1020 cm-3 , a strong Burstein-Moss effect increases absorption onset energies by ≈300 meV beyond the bandgap energy of undoped FASnI3 (shown to be 1.2 eV at 5 K and 1.35 eV at room temperature). At very high doping densities (1020 cm-3 ), temperature-dependent measurements indicate that the effective charge-carrier mobility is suppressed through scattering with ionized dopants. Once the background hole concentration is nearer 1019 cm-3 and below, the charge-carrier mobility increases with decreasing temperature according to ≈T-1.2 , suggesting that it is limited mostly by intrinsic interactions with lattice vibrations. For the lowest doping concentration of 7.2 × 1018 cm-3 , charge-carrier mobilities reach a value of 67 cm2 V-1 s-1 at room temperature and 470 cm2 V-1 s-1 at 50 K. Intraexcitonic transitions observed in the THz-frequency photoconductivity spectra at 5 K reveal an exciton binding energy of only 3.1 meV for FASnI3 , in agreement with the low bandgap energy exhibited by this perovskite.


Photocurrent Spectroscopy of Perovskite Solar Cells Over a Wide Temperature Range from 15 to 350 K.

The journal of physical chemistry letters 9 (2018) 263-268

JB Patel, Q Lin, O Zadvorna, CL Davies, LM Herz, MB Johnston

Solar cells based on metal halide perovskite thin films show great promise for energy generation in a range of environments from terrestrial installations to space applications. Here we assess the device characteristics of the prototypical perovskite solar cells based on methylammonium lead triiodide (CH3NH3PbI3) over a broad temperature range from 15 to 350 K (-258 to 77 °C). For these devices, we observe a peak in the short-circuit current density and open-circuit voltage at 200 K (-73 °C) with decent operation maintained up to 350 K. We identify the clear signature of crystalline PbI2 contributing directly to the low-temperature photocurrent spectra, showing that PbI2 plays an active role (beyond passivation) in CH3NH3PbI3 solar cells. Finally we observe a blue-shift in the photocurrent spectrum with respect to the absorption spectrum at low temperature (15 K), allowing us to extract a lower limit on the exciton binding energy of 9.1 meV for CH3NH3PbI3.


Template-Directed Synthesis of a Conjugated Zinc Porphyrin Nanoball.

Journal of the American Chemical Society 140 (2018) 5352-5355

J Cremers, R Haver, M Rickhaus, JQ Gong, L Favereau, MD Peeks, TDW Claridge, LM Herz, HL Anderson

We report the template-directed synthesis of a π-conjugated 14-porphyrin nanoball. This structure consists of two intersecting nanorings containing six and 10 porphyrin units. Fluorescence upconversion spectroscopy experiments demonstrate that electronic excitation delocalizes over the whole three-dimensional π system in less than 0.3 ps if the nanoball is bound to its templates or over 2 ps if the nanoball is empty.


High irradiance performance of metal halide perovskites for concentrator photovoltaics

NATURE ENERGY 3 (2018) 855-861

Z Wang, Q Lin, B Wenger, MG Christoforo, Y-H Lin, MT Klug, MB Johnston, LM Herz, HJ Snaith


Highly Crystalline Methylammonium Lead Tribromide Perovskite Films for Efficient Photovoltaic Devices

ACS ENERGY LETTERS 3 (2018) 1233-1240

NK Noel, B Wenger, SN Habisreutinger, JB Patel, T Crothers, Z Wang, RJ Nicholas, MB Johnston, LM Herz, HJ Snaith

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