Publications


Effect of Ultraviolet Radiation on Organic Photovoltaic Materials and Devices.

ACS applied materials & interfaces 11 (2019) 21543-21551

JB Patel, P Tiwana, N Seidler, GE Morse, OR Lozman, MB Johnston, LM Herz

Organic photovoltaics are a sustainable and cost-effective power-generation technology that may aid the move to zero-emission buildings, carbon neutral cities, and electric vehicles. While state-of-the-art organic photovoltaic devices can be encapsulated to withstand air and moisture, they are currently still susceptible to light-induced degradation, leading to a decline in the long-term efficiency of the devices. In this study, the role of ultraviolet (UV) radiation on a multilayer organic photovoltaic device is systematically uncovered using spectral filtering. By applying long-pass filters to remove different parts of the UV portion of the AM1.5G spectrum, two main photodegradation processes are shown to occur in the organic photovoltaic devices. A UV-activated process is found to cause a significant decrease in the photocurrent across the whole spectrum and is most likely linked to the deterioration of the charge extraction layers. In addition, a photodegradation process caused by UV-filtered sunlight is found to change the micromorphology of the bulk heterojunction material, leading to a reduction in photocurrent at high photon energies. These findings strongly suggest that the fabrication of inherently photostable organic photovoltaic devices will require the replacement of fullerene-based electron transporter materials with alternative organic semiconductors.


Aromaticity and Antiaromaticity in the Excited States of Porphyrin Nanorings

(2019)

M Peeks, J Gong, K McLoughlin, T Kobatake, R Haver, L Herz, H 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 law, odd rings ([4n] π-electrons) are aromatic in their excited states, whereas the excited states of even rings ([4n+2] π-electrons) are antiaromatic. These predictions are borne out by density functional theory (DFT) studies of the nucleus-independent chemical shift 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.


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

The journal of physical chemistry letters 10 (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.


Tuning the Circumference of Six-Porphyrin Nanorings.

Journal of the American Chemical Society 141 (2019) 7965-7971

R Haver, L Tejerina, H-W Jiang, M Rickhaus, M Jirasek, I Grübner, HJ Eggimann, LM Herz, HL Anderson

Most macrocycles are made from a simple repeat unit, resulting in high symmetry. Breaking this symmetry allows fine-tuning of the circumference, providing better control of the host-guest behavior and electronic structure. Here, we present the template-directed synthesis of two unsymmetrical cyclic porphyrin hexamers with both ethyne (C2) and butadiyne (C4) links, and we compare these nanorings with the symmetrical analogues with six ethyne or six butadiyne links. Inserting two extra carbon atoms into the smaller nanoring causes a spectacular change in binding behavior: the template affinity increases by a factor of 3 × 109, to a value of ca. 1038 M-1, and the mean effective molarity is ca. 830 M. In contrast, removing two carbon atoms from the largest nanoring results in almost no change in its template-affinity. The strain in these nanorings is 90-130 kJ mol-1, as estimated both from DFT calculation of homodesmotic reactions and from comparing template affinities of linear and cyclic oligomers. Breaking the symmetry has little effect on the absorption and fluorescence behavior of the nanorings: the low radiative rates that are characteristic of a circular delocalized S1 excited state are preserved in the low-symmetry macrocycles.


Heterogeneous Photon Recycling and Charge Diffusion Enhance Charge Transport in Quasi-2D Lead-Halide Perovskite Films.

Nano letters 19 (2019) 3953-3960

SG Motti, T Crothers, R Yang, Y Cao, R Li, MB Johnston, J Wang, LM Herz

The addition of large hydrophobic cations to lead halide perovskites has significantly enhanced the environmental stability of photovoltaic cells based on these materials. However, the associated formation of two-dimensional structures inside the material can lead to dielectric confinement, higher exciton binding energies, wider bandgaps and limited charge-carrier mobilities. Here we show that such effects are not detrimental to the charge transport for carefully processed films comprising a self-assembled thin layer of quasi-two-dimensional (2D) perovskite interfaced with a 3D MAPbI3 perovskite layer. We apply a combination of time-resolved photoluminescence and photoconductivity spectroscopy to reveal the charge-carrier recombination and transport through the film profile, when either the quasi-2D or the 3D layers are selectively excited. Through modeling of the recorded dynamics, we demonstrate that while the charge-carrier mobility is lower within the quasi-2D region, charge-carrier diffusion to the 3D phase leads to a rapid recovery in photoconductivity even when the quasi-2D region is initially photoexcited. In addition, the blue-shifted emission originating from quasi-2D regions overlaps significantly with the absorption spectrum of the 3D perovskite, allowing for highly effective "heterogeneous photon recycling". We show that this combination fully compensates for the adverse effects of electronic confinement, yielding quasi-2D perovskites with highly efficient charge transporting properties.


Impurity Tracking Enables Enhanced Control and Reproducibility of Hybrid Perovskite Vapor Deposition.

ACS applied materials & interfaces 11 (2019) 28851-28857

J Borchert, I Levchuk, LC Snoek, MU Rothmann, R Haver, HJ Snaith, CJ Brabec, LM Herz, MB Johnston

Metal halide perovskite semiconductors have the potential to enable low-cost, flexible, and efficient solar cells for a wide range of applications. Physical vapor deposition by co-evaporation of precursors is a method that results in very smooth and pinhole-free perovskite thin films and allows excellent control over film thickness and composition. However, for a deposition method to become industrially scalable, reproducible process control and high device yields are essential. Unfortunately, to date, the control and reproducibility of evaporating organic precursors such as methylammonium iodide (MAI) have proved extremely challenging. We show that the established method of controlling the evaporation rate of MAI with quartz microbalances (QMBs) is critically sensitive to the concentration of the impurities MAH2PO3 and MAH2PO2 that are usually present in MAI after synthesis. Therefore, controlling the deposition rate of MAI with QMBs is unreliable since the concentration of such impurities typically varies from one batch of MAI to another and even during the course of a deposition. However once reliable control of MAI deposition is achieved, we find that the presence of precursor impurities during perovskite deposition does not degrade the solar cell performance. Our results indicate that as long as precursor deposition rates are well controlled, physical vapor deposition will allow high solar cell device yields even if the purity of precursors changes from one run to another.


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


Charge-Carrier Dynamics, Mobilities, and Diffusion Lengths of 2D-3D Hybrid Butylammonium-Cesium-Formamidinium Lead Halide Perovskites

ADVANCED FUNCTIONAL MATERIALS 29 (2019) ARTN 1902656

LRV Buizza, TW Crothers, Z Wang, JB Patel, RL Milot, HJ Snaith, MB Johnston, LM Herz


Aromaticity and Antiaromaticity in the Excited States of Porphyrin Nanorings.

The journal of physical chemistry letters 10 (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.


Solution-Processed All-Perovskite Multi-junction Solar Cells

Joule 3 (2019) 387-401

DP McMeekin, S Mahesh, NK Noel, MT Klug, JC Lim, JH Warby, JM Ball, LM Herz, MB Johnston, HJ Snaith

© 2019 Multi-junction device architectures can increase the power conversion efficiency (PCE) of photovoltaic (PV) cells beyond the single-junction thermodynamic limit. However, these devices are challenging to produce by solution-based methods, where dissolution of underlying layers is problematic. By employing a highly volatile acetonitrile(CH 3 CN)/methylamine(CH 3 NH 2 ) (ACN/MA) solvent-based perovskite solution, we demonstrate fully solution-processed absorber, transport, and recombination layers for monolithic all-perovskite tandem and triple-junction solar cells. By combining FA 0.83 Cs 0.17 Pb(Br 0.7 I 0.3 ) 3 (1.94 eV) and MAPbI 3 (1.57 eV) junctions, we reach two-terminal tandem PCEs of more than 15% (steady state). We show that a MAPb 0.75 Sn 0.25 I 3 (1.34 eV) narrow band-gap perovskite can be processed via the ACN/MA solvent-based system, demonstrating the first proof-of-concept, monolithic all-perovskite triple-junction solar cell with an open-circuit voltage reaching 2.83 V. Through optical and electronic modeling, we estimate the achievable PCE of a state-of-the-art triple-junction device architecture to be 26.7%. Our work opens new possibilities for large-scale, low-cost, printable perovskite multi-junction solar cells. Silicon-based solar cells are dominating today's solar energy market. However, their efficiencies will soon reach their maximum practical limit. Without any gains in efficiency, price reductions will become increasingly difficult to achieve. Tandem and multi-junction architectures can overcome this single-junction efficiency limit. Perovskite materials offer both band-gap tunability and solution processability. This unique combination of properties allows for fabrication of multi-junction solar cells using high-throughput deposition techniques such as blade coating, roll-to-roll, gravure coating or inkjet printing. However, these solar cells have yet to be fabricated using these deposition techniques due to difficulties in sequentially depositing these semiconductors. By utilizing an acetonitrile/methylamine-based solvent, we demonstrate the first monolithic all-perovskite multi-junction solar cells fabricated via solution processing of all active layers, apart from the electrodes. Perovskite solar cells can be processed using solution-based methods. Furthermore, perovskite solar cells can tune their band gap to absorb different portions of the solar spectrum. This property allows for fabrication of multi-junction solar cell, which can offer higher power conversion efficiencies than single-junction architecture. Here, we combine both features to fabricate the first solution-processed, monolithic, all-perovskite tandem and triple-junction solar cells.


Dual-Source Coevaporation of Low-Bandgap FA(1-x)Cs(x)Sn(1-y)Pb(y)I(3) Perovskites for Photovoltaics

ACS ENERGY LETTERS 4 (2019) 2748-2756

JM Ball, L Buizza, HC Sansom, MD Farrar, MT Klug, J Borchert, J Patel, LM Herz, MB Johnston, HJ Snaith


Charge-Carrier Cooling and Polarization Memory Loss in Formamidinium Tin Triiodide.

The journal of physical chemistry letters 10 (2019) 6038-6047

KJ Savill, MT Klug, RL Milot, HJ Snaith, LM Herz

Reports of slow charge-carrier cooling in hybrid metal halide perovskites have prompted hopes of achieving higher photovoltaic cell voltages through hot-carrier extraction. However, observations of long-lived hot charge carriers even at low photoexcitation densities and an orders-of-magnitude spread in reported cooling times have been challenging to explain. Here we present ultrafast time-resolved photoluminescence measurements on formamidinum tin triiodide, showing fast initial cooling over tens of picoseconds and demonstrating that a perceived secondary regime of slower cooling instead derives from electronic relaxation, state-filling, and recombination in the presence of energetic disorder. We identify limitations of some widely used approaches to determine charge-carrier temperature and make use of an improved model which accounts for the full photoluminescence line shape. Further, we do not find any persistent polarization anisotropy in FASnI3 within 270 fs after excitation, indicating that excited carriers rapidly lose both polarization memory and excess energy through interactions with the perovskite lattice.


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


Growth modes and quantum confinement in ultrathin vapour-deposited MAPbI3 films.

Nanoscale 11 (2019) 14276-14284

ES Parrott, JB Patel, A-A Haghighirad, HJ Snaith, MB Johnston, LM Herz

Vapour deposition of metal halide perovskite by co-evaporation of precursors has the potential to achieve large-area high-efficiency solar cells on an industrial scale, yet little is known about the growth of metal halide perovskites by this method at the current time. Here, we report the fabrication of MAPbI3 films with average thicknesses from 2-320 nm by co-evaporation. We analyze the film properties using X-ray diffraction, optical absorption and photoluminescence (PL) to provide insights into the nucleation and growth of MAPbI3 films on quartz substrates. We find that the perovskite initially forms crystallite islands of around 8 nm in height, which may be the cause of the persistent small grain sizes reported for evaporated metal halide perovskites that hinder device efficiency and stability. As more material is added, islands coalesce until full coverage of the substrate is reached at around 10 nm average thickness. We also find that quantum confinement induces substantial shifts to the PL wavelength when the average thickness is below 40 nm, offering dual-source vapour deposition as an alternative method of fabricating nanoscale structures for LEDs and other devices.


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 9 (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.


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


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.


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

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