Publications


Control over crystal size in vapor deposited metal-halide perovskite films

ACS Energy Letters American Chemical Society (ACS) 5 (2020) 0c00183

KB Lohmann, JB Patel, MU Rothmann, CQ Xia, RDJ Oliver, LM Herz, HJ Snaith, MB Johnston

Understanding and controlling grain growth in metal halide perovskite polycrystalline thin films is an important step in improving the performance of perovskite solar cells. We demonstrate accurate control of crystallite size in CH3NH3PbI3 thin films by regulating substrate temperature during vacuum co-deposition of inorganic (PbI2) and organic (CH3NH3I) precursors. Films co-deposited onto a cold (−2 °C) substrate exhibited large, micrometer-sized crystal grains, while films that formed at room temperature (23 °C) only produced grains of 100 nm extent. We isolated the effects of substrate temperature on crystal growth by developing a new method to control sublimation of the organic precursor, and CH3NH3PbI3 solar cells deposited in this way yielded a power conversion efficiency of up to 18.2%. Furthermore, we found substrate temperature directly affects the adsorption rate of CH3NH3I, thus impacting crystal formation and hence solar cell device performance via changes to the conversion rate of PbI2 to CH3NH3PbI3 and stoichiometry. These findings offer new routes to developing efficient solar cells through reproducible control of crystal morphology and composition.


Understanding the Performance-Limiting Factors of Cs2AgBiBr6 Double-Perovskite Solar Cells

ACS ENERGY LETTERS 5 (2020) 2200-2207

G Longo, S Mahesh, LRV Buizza, AD Wright, AJ Ramadan, M Abdi-Jalebi, PK Nayak, LM Herz, HJ Snaith


Three-dimensional cross-nanowire networks recover full terahertz state

Science American Association for the Advancement of Science 368 (2020) 510-513

K Peng, D Jevtics, F Zhang, S Sterzl, D Damry, M Rothmann, B Guilhabert, MJ Strain, HH Tan, LM Herz, L Fu, MD Dawson, A Hurtado, C Jagadish, M Johnston

Terahertz radiation encompasses a wide band of the electromagnetic spectrum, spanning from microwaves to infrared light, and is a particularly powerful tool for both fundamental scientific research and applications such as security screening, communications, quality control, and medical imaging. Considerable information can be conveyed by the full polarization state of terahertz light, yet to date, most time-domain terahertz detectors are sensitive to just one polarization component. Here we demonstrate a nanotechnology-based semiconductor detector using cross-nanowire networks that records the full polarization state of terahertz pulses. The monolithic device allows simultaneous measurements of the orthogonal components of the terahertz electric field vector without cross-talk. Furthermore, we demonstrate the capabilities of the detector for the study of metamaterials.


Postpassivation of Multication Perovskite with Rubidium Butyrate

ACS Photonics American Chemical Society (ACS) (2020) acsphotonics.0c00878

JC Germino, R Szostak, SG Motti, RF Moral, PE Marchezi, HS Seleghini, LG Bonato, FL de Araújo, TDZ Atvars, LM Herz, D Fenning, A Hagfeldt, AF Nogueira


Impact of Tin Fluoride Additive on the Properties of Mixed Tin-Lead Iodide Perovskite Semiconductors

Advanced Functional Materials (2020)

KJ Savill, AM Ulatowski, MD Farrar, MB Johnston, HJ Snaith, LM Herz

© 2020 Wiley-VCH GmbH Mixed tin-lead halide perovskites are promising low-bandgap absorbers for all-perovskite tandem solar cells that offer higher efficiencies than single-junction devices. A significant barrier to higher performance and stability is the ready oxidation of tin, commonly mitigated by various additives whose impact is still poorly understood for mixed tin-lead perovskites. Here, the effects of the commonly used SnF2 additive are revealed for FA0.83Cs0.17SnxPb1−xI3 perovskites across the full compositional lead-tin range and SnF2 percentages of 0.1–20% of precursor tin content. SnF2 addition causes a significant reduction in the background hole density associated with tin vacancies, yielding longer photoluminescence lifetimes, decreased energetic disorder, reduced Burstein–Moss shifts, and higher charge-carrier mobilities. Such effects are optimized for SnF2 addition of 1%, while for 5% SnF2 and above, additional nonradiative recombination pathways begin to appear. It is further found that the addition of SnF2 reduces a tetragonal distortion in the perovskite structure deriving from the presence of tin vacancies that cause strain, particularly for high tin content. The optical phonon response associated with inorganic lattice vibrations is further explored, exhibiting a shift to higher frequency and significant broadening with increasing tin fraction, in accordance with lower effective atomic metal masses and shorter phonon lifetimes.


CsPbBr3 nanocrystal films: Deviations from bulk vibrational and optoelectronic properties

Advanced Functional Materials Wiley (2020) 1909904

SG Motti, F Krieg, AJ Ramadan, JB Patel, HJ Snaith, MV Kovalenko, MB Johnston, LM Herz

Metal‐halide perovskites (MHP) are highly promising semiconductors for light‐emitting and photovoltaic applications. The colloidal synthesis of nanocrystals (NCs) is an effective approach for obtaining nearly defect‐free MHP that can be processed into inks for low‐cost, high‐performance device fabrication. However, disentangling the effects of surface ligands, morphology, and boundaries on charge‐carrier transport in thin films fabricated with these high‐quality NCs is inherently difficult. To overcome this fundamental challenge, terahertz (THz) spectroscopy is employed to optically probe the photoconductivity of CsPbBr3 NC films. The vibrational and optoelectronic properties of the NCs are compared with those of the corresponding bulk polycrystalline perovskite and significant deviations are found. Charge‐carrier mobilities and recombination rates are demonstrated to vary significantly with the NC size. Such dependences derive from the localized nature of charge carriers within NCs, with local mobilities dominating over interparticle transport. It is further shown that the colloidally synthesized NCs have distinct vibrational properties with respect to the bulk perovskite, exhibiting blue‐shifted optical phonon modes with enhanced THz absorption strength that also manifest as strong modulations in the THz photoconductivity spectra. Such fundamental insights into NC versus bulk properties will guide the optimization of nanocrystalline perovskite thin films for optoelectronic applications.


Preventing phase segregation in mixed-halide perovskites: a perspective

Energy & Environmental Science Royal Society of Chemistry (RSC) (2020)

AJ Knight, LM Herz

<p>Halide segregation represents a severe stability problem for certain mixed-halide perovskites. Here we explore a myriad of methods for mitigating halide segregation, including several largely unexplored approaches that show significant promise.</p>


Charge-Carrier Trapping Dynamics in Bismuth-Doped Thin Films of MAPbBr3 Perovskite.

The journal of physical chemistry letters American Chemical Society (ACS) 11 (2020) 3681-3688

AM Ulatowski, AD Wright, B Wenger, LRV Buizza, SG Motti, HJ Eggimann, KJ Savill, J Borchert, HJ Snaith, MB Johnston, LM Herz

Successful chemical doping of metal halide perovskites with small amounts of heterovalent metals has attracted recent research attention because of its potential to improve long-term material stability and tune absorption spectra. However, some additives have been observed to impact negatively on optoelectronic properties, highlighting the importance of understanding charge-carrier behavior in doped metal halide perovskites. Here, we present an investigation of charge-carrier trapping and conduction in films of MAPbBr3 perovskite chemically doped with bismuth. We find that the addition of bismuth has no effect on either the band gap or exciton binding energy of the MAPbBr3 host. However, we observe a substantial enhancement of electron-trapping defects upon bismuth doping, which results in an ultrafast charge-carrier decay component, enhanced infrared emission, and a notable decrease of charge-carrier mobility. We propose that such defects arise from the current approach to Bi-doping through addition of BiBr3, which may enhance the presence of bromide interstitials.


Charge‐Carrier Trapping and Radiative Recombination in Metal Halide Perovskite Semiconductors

Advanced Functional Materials Wiley (2020) 2004312-2004312

MJ Trimpl, AD Wright, K Schutt, LRV Buizza, Z Wang, MB Johnston, HJ Snaith, P Müller‐Buschbaum, LM Herz


Trap states, electric fields, and phase segregation in mixed-halide perovskite photovoltaic devices

Advanced Energy Materials Wiley 10 (2020) 1903488

A Knight, J Patel, H Snaith, M Johnston, L Herz

Mixed-halide perovskites are essential for use in all-perovskite or perovskite–silicon tandem solar cells due to their tunable bandgap. However, trap states and halide segregation currently present the two main challenges for efficient mixed-halide perovskite technologies. Here photoluminescence techniques are used to study trap states and halide segregation in full mixed-halide perovskite photovoltaic devices. This work identifies three distinct defect species in the perovskite material: a charged, mobile defect that traps charge-carriers in the perovskite, a charge-neutral defect that induces halide segregation, and a charged, mobile defect that screens the perovskite from external electric fields. These three defects are proposed to be MA+ interstitials, crystal distortions, and halide vacancies and/or interstitials, respectively. Finally, external quantum efficiency measurements show that photoexcited charge-carriers can be extracted from the iodide-rich low-bandgap regions of the phase-segregated perovskite formed under illumination, suggesting the existence of charge-carrier percolation pathways through grain boundaries where phase-segregation may occur.


Three-dimensional cross-nanowire networks recover full terahertz state.

Science (New York, N.Y.) 368 (2020) 510-513

K Peng, D Jevtics, F Zhang, S Sterzl, DA Damry, MU Rothmann, B Guilhabert, MJ Strain, HH Tan, LM Herz, L Fu, MD Dawson, A Hurtado, C Jagadish, MB Johnston

Terahertz radiation encompasses a wide band of the electromagnetic spectrum, spanning from microwaves to infrared light, and is a particularly powerful tool for both fundamental scientific research and applications such as security screening, communications, quality control, and medical imaging. Considerable information can be conveyed by the full polarization state of terahertz light, yet to date, most time-domain terahertz detectors are sensitive to just one polarization component. Here we demonstrate a nanotechnology-based semiconductor detector using cross-nanowire networks that records the full polarization state of terahertz pulses. The monolithic device allows simultaneous measurements of the orthogonal components of the terahertz electric field vector without cross-talk. Furthermore, we demonstrate the capabilities of the detector for the study of metamaterials.


Metal composition influences optoelectronic quality in mixed-metal lead-tin triiodide perovskite solar absorbers

ENERGY & ENVIRONMENTAL SCIENCE 13 (2020) 1776-1787

MT Klug, RL Milot, JB Patel, T Green, HC Sansom, MD Farrar, AJ Ramadan, S Martani, Z Wang, B Wenger, JM Ball, L Langshaw, A Petrozza, MB Johnston, LM Herz, HJ Snaith

© The Royal Society of Chemistry. Current designs for all-perovskite multi-junction solar cells require mixed-metal Pb-Sn compositions to achieve narrower band gaps than are possible with their neat Pb counterparts. The lower band gap range achievable with mixed-metal Pb-Sn perovskites also encompasses the 1.3 to 1.4 eV range that is theoretically ideal for maximising the efficiency of single-junction devices. Here we examine the optoelectronic quality and photovoltaic performance of the ((HC(NH2)2)0.83Cs0.17)(Pb1-ySny)I3 family of perovskite materials across the full range of achievable band gaps by substituting between 0.001% and 70% of the Pb content with Sn. We reveal that a compositional range of "defectiveness"exists when Sn comprises between 0.5% and 20% of the metal content, but that the optoelectronic quality is restored for Sn content between 30-50%. When only 1% of Pb content is replaced by Sn, we find that photoconductivity, photoluminescence lifetime, and photoluminescence quantum efficiency are reduced by at least an order of magnitude, which reveals that a small concentration of Sn incorporation produces trap sites that promote non-radiative recombination in the material and limit photovoltaic performance. While these observations suggest that band gaps between 1.35 and 1.5 eV are unlikely to be useful for optoelectronic applications without countermeasures to improve material quality, highly efficient narrower band gap absorber materials are possible at or below 1.33 eV. Through optimising single-junction photovoltaic devices with Sn compositions of 30% and 50%, we respectively demonstrate a 17.6% efficient solar cell with an ideal single-junction band gap of 1.33 eV and an 18.1% efficient low band gap device suitable for the bottom absorber in all-perovskite multi-junction cells.


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.


Time-resolved THz spectroscopy of metal-halide perovskite single crystals and polycrystalline thin films

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

CQ Xia, Q Lin, JB Patel, AD Wright, TW Crothers, RL Milot, LM Herz, MB Johnston

© 2019 IEEE. In this study the photoconductivity and charge-carrier dynamics of the metal-halide perovskite MAPbI3 is investigated via optical-pump-THz-probe spectroscopy (OPTPS). We perform OPTPS on polycrystalline MAPbI3 thin films in both transmission and reflection modes, and demonstrate the consistency of extracted mobility and recombination parameters between the two geometries. Furthermore, we performed OPTP measurement on MAPbI3 single crystal in reflection and compare the mobility and charge recombination dynamics between the polycrystalline thin films and perovskite single crystals. Finally, the consequence of our results for future metal halide optoelectronic devices are discussed.


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.


Dual-source co-evaporation of low-bandgap FA1-xCsxSn1-yPbyI3 perovskites for photovoltaics

ACS Energy Letters American Chemical Society 4 (2019) 2748-2756

JM Ball, L Buizza, HC Sansom, Farrar, MT Klug, J Borchert, J Patel, LM Herz, M Johnston, H Snaith


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.

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