Effect of ultraviolet radiation on organic photovoltaic materials and devices

ACS Applied Materials and Interfaces American Chemical Society 11 (2019) 21543-21551

J Patel, P Tiwana, N Seidler, GE Morse, OR Lozman, M Johnston, L 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.

Overcoming zinc oxide interface instability with a methylammonium-free perovskite for high performance solar cells

Advanced Functional Materials Wiley (2019) 1900466

K Schutt, P Nayak, A Ramadan, B Wenger, Y-H Lin, H Snaith

Perovskite solar cells have achieved the highest power conversion efficiencies on metal oxide n‐type layers, including SnO2 and TiO2. Despite ZnO having superior optoelectronic properties to these metal oxides, such as improved transmittance, higher conductivity, and closer conduction band alignment to methylammonium (MA)PbI3, ZnO is largely overlooked due to a chemical instability when in contact with metal halide perovskites, which leads to rapid decomposition of the perovskite. While surface passivation techniques have somewhat mitigated this instability, investigations as to whether all metal halide perovskites exhibit this instability with ZnO are yet to be undertaken. Experimental methods to elucidate the degradation mechanisms at ZnO–MAPbI3 interfaces are developed. By substituting MA with formamidinium (FA) and cesium (Cs), the stability of the perovskite–ZnO interface is greatly enhanced and it is found that stability compares favorably with SnO2‐based devices after high‐intensity UV irradiation and 85 °C thermal stressing. For devices comprising FA‐ and Cs‐based metal halide perovskite absorber layers on ZnO, a 21.1% scanned power conversion efficiency and 18% steady‐state power output are achieved. This work demonstrates that ZnO appears to be as feasible an n‐type charge extraction layer as SnO2, with many foreseeable advantages, provided that MA cations are avoided.

Revealing the nature of photoluminescence emission in the metal-halide double perovskite Cs2AgBiBr6


SJ Zelewski, JM Urban, A Surrente, DK Maude, A Kuc, L Schade, RD Johnson, M Dollmann, PK Nayak, HJ Snaith, P Radaelli, R Kudrawiec, RJ Nicholas, P Plochocka, M Baranowski

Controlling competing photochemical reactions stabilizes perovskite solar cells

NATURE PHOTONICS 13 (2019) 532-+

SG Motti, D Meggiolaro, AJ Barker, E Mosconi, CAR Perini, JM Ball, M Gandini, M Kim, F De Angelis, A Petrozza

Imaging photoinduced surface potentials on hybrid perovskites by real-time Scanning Electron Microscopy.

Micron (Oxford, England : 1993) 121 (2019) 53-65

G Irde, SM Pietralunga, V Sala, M Zani, JM Ball, AJ Barker, A Petrozza, G Lanzani, A Tagliaferri

We introduce laser-assisted Time-Resolved SEM (TR-SEM), joining Scanning Electron Microscopy and laser light excitation, to probe the long-term temporal evolution of optically excited charge distributions at the surface of Metal Ammonium Lead Triiodide (MAPbI3) hybrid perovskite thin films. Laser-assisted TR-SEM relies on the optically induced local modification of Secondary Electron (SE) detection yield to provide mapping of photoexcited potentials and charge dynamics at surfaces, and qualifies as a complementary approach to near-field probe microscopies and nonlinear photoemission spectroscopies for photovoltage measurements. Real-time imaging of evolving field patterns are provided on timescales compatible with SEM scanning rates, so that temporal resolution in the millisecond range can be ultimately envisaged. MAPbI3 is an outstanding light-sensitive material candidate for applications in solar light harvesting and photovoltaics, also appealing as an active system for light generation. In this work, the real time temporal evolution of optically induced SE contrast patterns in MAPbI3 is experimentally recorded, both under illumination by a 405 nm blue laser and after light removal, showing the occurrence of modifications related to photoinduced positive charge fields at surface. The long term evolution of these surface fields are tentatively attributed to ion migration within the film, under the action of the illumination gradient and the hole collecting substrate. This optical excitation is fully reversible in MAPbI3 over timescales of hours and a complete recovery of the system occurs within days. Permanent irradiation damage of the material is avoided by operating the SEM at 5 keV of energy and 1-10 pA of primary current. Optical excitation is provided by intense above-bandgap illumination (up to 50 W/cm2). TR-SEM patterns show a strong dependence on the geometry of SE collection. Measurements are taken at different axial orientations of the sample with respect to the entrance of the in-column detection system of the SEM and compared with numerical modeling of the SE detection process. This enables to single out the information regarding the local potential distribution. Results are interpreted by combining data about the spectral distribution of emitted SEs with the configuration of the electric and magnetic fields in the specimen chamber. The present modeling sets a robust basis for the understanding of photoinduced SE electron contrast.

Photocatalytic water splitting by N-TiO2 on MgO(111) with exceptional quantum efficiencies at elevated temperature

Nature Communications Springer Nature 10 (2019) 4421

Y Li, Y-K Peng, L Hu, J Zheng, D Prabhakaran, S Wu, TJ Puchtler, M Li, K-Y Wong, R Taylor, SCE Tsang

Photocatalytic water splitting is attracting enormous interest for the storage of solar energy but no practical method has yet been identified. In the past decades, various systems have been developed but most of them suffer from low activities, a narrow range of absorption and poor quantum efficiencies (Q.E.) due to fast recombination of charge carriers. Here we report a dramatic suppression of electron-hole pair recombination on the surface of N-doped TiO2 based nanocatalysts under enhanced concentrations of H+ and OH−, and local electric field polarization of a MgO (111) support during photolysis of water at elevated temperatures. Thus, a broad optical absorption is seen, producing O2 and H2 in a 1:2 molar ratio with a H2 evolution rate of over 11,000 μmol g−1 h−1 without any sacrificial reagents at 270 °C. An exceptional range of Q.E. from 81.8% at 437 nm to 3.2% at 1000 nm is also reported.

Tuning the circumference of six-porphyrin nanorings

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

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

<p>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 × 10<sup>9</sup>, to a value of ca. 10<sup>38</sup> M<sup>–1</sup>, 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<sup>–1</sup>, 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 S<sub>1</sub> excited state are preserved in the low-symmetry macrocycles.</p>

Heterogeneous photon recycling and charge diffusion enhance charge transport in quasi-2D lead-halide perovskite films

Nano Letters American Chemical Society 19 (2019) 3953-3960

S Motti, T Crothers, R Yang, Y Cao, R Li, M Johnston, J Wang, L Herz

<p>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 MAPbI<sub>3</sub> 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.</p>

Impurity tracking enables enhanced control and reproducibility of hybrid perovskite vapour deposition

ACS Applied Materials and Interfaces American Chemical Society 11 (2019) 28851-28857

J Borchert, I Levchuk, L Snoek, M Rothmann, R Haver, H Snaith, CJ Brabec, L Herz, M Johnston

Metal halide perovskite semiconductors have the potential to enable low-cost, flexible and efficient solar cells for a wide range of applications. Physical vapour deposition by co-evaporation of precursors is a method which results in very smooth and pin-hole-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) has proved extremely challenging. We show that the established method of controlling the evaporation-rate of MAI with quartz micro balances (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 MAI batch-to-batch 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 solar cell performance. Our results indicate that as long as precursor deposition rates are well controlled, physical vapour deposition will allow high solar cell device yields even if the purity of precursors change from run to run.

Charge-carrier dynamics, mobilities and diffusion lengths of 2D-3D hybrid butylammonium-caesium-formamidinium lead halide perovskites

Advanced Functional Materials Wiley (2019)

L Buizza, T Crothers, Z Wang, P Jay, R Milot, H Snaith, M Johnston, L Herz

Perovskite solar cells (PSCs) have improved dramatically over the past decade, increasing in efficiency and gradually overcoming hurdles of temperature‐ and humidity‐induced instability. Materials that combine high charge‐carrier lifetimes and mobilities, strong absorption, and good crystallinity of 3D perovskites with the hydrophobic properties of 2D perovskites have become particularly promising candidates for use in solar cells. In order to fully understand the optoelectronic properties of these 2D–3D hybrid systems, the hybrid perovskite BAx(FA0.83Cs0.17)1‐xPb(I0.6Br0.4)3 is investigated across the composition range 0 ≤ x ≤ 0.8. Small amounts of butylammonium (BA) are found that help to improve crystallinity and appear to passivate grain boundaries, thus reducing trap‐mediated charge‐carrier recombination and enhancing charge‐carrier mobilities. Excessive amounts of BA lead to poor crystallinity and inhomogeneous film formation, greatly reducing effective charge‐carrier mobility. For low amounts of BA, the benevolent effects of reduced recombination and enhanced mobilities lead to charge‐carrier diffusion lengths up to 7.7 µm for x = 0.167. These measurements pave the way for highly efficient, highly stable PSCs and other optoelectronic devices based on 2D–3D hybrid materials.

Aromaticity and antiaromaticity in the excited states of porphyrin nanorings

Journal of Physical Chemistry Letters American Chemical Society 10 (2019) 2017-2022

M Peeks, JQ 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 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.

Oxidative passivation of metal halide perovskites

Joule Cell Press 3 (2019) 2716-2731

J Godding, A Ramadan, Y-H Lin, K Schutt, HJ Snaith, B Wenger

Metal halide perovskites have demonstrated extraordinary potential as materials for next-generation optoelectronics including photovoltaics and light-emitting diodes. Nevertheless, our understanding of this material is still far from complete. One remaining puzzle is the phenomenon of perovskite “photo-brightening”: the increase in photoluminescence during exposure to light in an ambient atmosphere. Here, we propose a comprehensive mechanism for the reactivity of the archetypal perovskite, MAPbI3, in ambient conditions. We establish the formation of lead-oxygen bonds by hydrogen peroxide as the key factor leading to perovskite photo-brightening. We demonstrate that hydrogen peroxide can be applied directly as an effective “post-treatment” to emulate the process and substantially improve photoluminescence quantum efficiencies. Finally, we show that the treatment can be incorporated into photovoltaic devices to give a 50 mV increase in open-circuit voltage, delivering high 19.2% steady-state power conversion efficiencies for inverted perovskite solar cells of the mixed halide, mixed cation perovskite FA0.83Cs0.17Pb(I0.9Br0.1)3.

Planar perovskite solar cells with long-term stability using ionic liquid additives

Nature Springer Nature 571 (2019) 245–250-

S Bai, P Da, C Li, Z Wang, Y Zhongcheng, F Fan, K Maciej, L Xianjie, N Sakai, JT-W Wang, S Huetter, S Bucheler, M Fahlman, F Gao, H Snaith

Solar cells based on metal halide perovskites are one of the most promising photovoltaic technologies1,2,3,4. Over the past few years, the long-term operational stability of such devices has been greatly improved by tuning the composition of the perovskites5,6,7,8,9, optimizing the interfaces within the device structures10,11,12,13, and using new encapsulation techniques14,15. However, further improvements are required in order to deliver a longer-lasting technology. Ion migration in the perovskite active layer—especially under illumination and heat—is arguably the most difficult aspect to mitigate16,17,18. Here we incorporate ionic liquids into the perovskite film and thence into positive–intrinsic–negative photovoltaic devices, increasing the device efficiency and markedly improving the long-term device stability. Specifically, we observe a degradation in performance of only around five per cent for the most stable encapsulated device under continuous simulated full-spectrum sunlight for more than 1,800 hours at 70 to 75 degrees Celsius, and estimate that the time required for the device to drop to eighty per cent of its peak performance is about 5,200 hours. Our demonstration of long-term operational, stable solar cells under intense conditions is a key step towards a reliable perovskite photovoltaic technology.

Giant Fine Structure Splitting of the Bright Exciton in a Bulk MAPbBr3 Single Crystal.

Nano letters (2019)

M Baranowski, K Galkowski, A Surrente, JM Urban, Ł Klopotowski, S Mackowski, DK Maude, R Ben Aich, K Boujdaria, M Chamarro, C Testelin, P Nayak, M Dollmann, HJ Snaith, RJ Nicholas, P Plochocka

Exciton fine structure splitting in semiconductors reflects the underlying symmetry of the crystal and quantum confinement. Since the latter factor strongly enhances the exchange interaction, most work has focused on nanostructures. Here, we report on the first observation of the bright exciton fine structure splitting in a bulk semiconductor crystal, where the impact of quantum confinement can be specifically excluded, giving access to the intrinsic properties of the material. Detailed investigation of the exciton photoluminescence and reflection spectra of a bulk methylammonium lead tribromide single crystal reveals a zero magnetic field splitting as large as ~200μeV. This result provides an important starting point for the discussion of the origin of the large bright exciton fine structure observed in perovskite nanocrystals.

Unveiling Temperature-Dependent Scattering Mechanisms in Semiconductor Nanowires Using Optical-Pump Terahertz-Probe Spectroscopy

International Conference on Infrared, Millimeter, and Terahertz Waves, IRMMW-THz 2019-September (2019)

JL Boland, F Amaduzzi, S Sterzl, H Potts, G Tutuncuoglu, LM Herz, AFI Morral, MB Johnston

© 2019 IEEE. Optical-pump terahertz-probe (OPTP) spectroscopy is a powerful, non-contact tool for extracting the electrical conductivity within a material. In this work, we show how OPTP spectroscopy can be used to extract the temperature-dependent electron mobility and photoconductivity lifetime within semiconductor nanowires (NWs), in order to reveal the underlying scattering mechanisms governing carrier transport in these materials.

Charge-carrier cooling and polarization memory loss in formamidinium tin triiodide

Journal of Physical Chemistry Letters American Chemical Society 10 (2019) 6038-6047

K Savill, M Klug, RL Milot, H Snaith, L Herz

<p>Combination of a cryogenic ion-trap machine, operated at 4.7 K, with the free-electron-laser FELIX allows the first experimental characterization of the unusually bright antisymmetric stretch (ν<sub>3</sub>) and π-bending (ν<sub>2</sub>) fundamentals of the He–X<sup>+</sup>–He (X = H, D) chromophore of the in situ prepared HHe<sub><em>n</em></sub><sup>+</sup> and DHe<sub><em>n</em></sub><sup>+</sup> (<em>n</em> = 3–6) complexes. The band origins obtained are fully supported by first-principles quantum-chemical computations, performed at the MP2, the CCSD(T), and occasionally the CCSDTQ levels employing extended basis sets. Both the experiments and the computations are consistent with structures for the species with <em>n</em> = 3 and 6 being of T-shaped <em>C</em><sub>2<em>v</em></sub> and of <em>D</em><sub>4<em>h</em></sub> symmetry, respectively, while the species with <em>n</em> = 4 are suggested to exhibit interesting dynamical phenomena related to large-amplitude motions.</p>

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

Nanoscale Royal Society of Chemistry 11 (2019) 14276

ES Parrott, J Patel, AA Haghighirad, H Snaith, M Johnston, L 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.

Interfacial charge-transfer doping of metal halide perovskites for high performance photovoltaics

Energy and Environmental Science Royal Society of Chemistry (2019)

N Noel, Habisreutinger, A Pellaroque, F Pulvirenti, B Wenger, F Zhang, Y-H Lin, OG Reid, J Leisen, Y Zhang, S Barlow, Marder, A Kahn, HJ Snaith, CB Arnold, BP Rand

<p>We demonstrate a method for controlled p-doping of the halide perovskite surface using molecular dopants, resulting in reduced non-radiative recombination losses and improved device performance.</p>

III-V compounds as single photon emitters

Journal of Semiconductors IOP Publishing 40 (2019) 071906

X Wang, L Xu, Z Yin, C Chan, C Deng, R Taylor

Deciphering photocarrier dynamics for tuneable high-performance perovskite-organic semiconductor heterojunction phototransistors

Nature Communications Springer Nature 10 (2019) 4475

Y-H Lin, W Huang, P Pattanasattayavong, J Lim, R Li, N Sakai, J Panidi, MJ Hong, C Ma, N Wei, N Wehbe, Z Fei, M Heeney, JG Labram, TD Anthopoulos, HJ Snaith