Publications by Henry Snaith

Publisher Correction: Deciphering photocarrier dynamics for tuneable high-performance perovskite-organic semiconductor heterojunction phototransistors.

Nature communications 11 (2020) 2956-

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

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

CsI-antisolvent adduct formation in all-inorganic metal halide perovskites

Advanced Energy Materials Wiley 10 (2020) 1903365

T Moot, A Marshall, L Wheeler, S Habisreutinger, T Schloemer, CC Boyd, D Dikova, G Pach, M McGehee, A Hazarika, H Snaith, J Luther

The excellent optoelectronic properties demonstrated by hybrid organic/inorganic metal halide perovskites are all predicated on precisely controlling the exact nucleation and crystallization dynamics that occur during film formation. In general, high‐performance thin films are obtained by a method commonly called solvent engineering (or antisolvent quench) processing. The solvent engineering method removes excess solvent, but importantly leaves behind solvent that forms chemical adducts with the lead‐halide precursor salts. These adduct‐based precursor phases control nucleation and the growth of the polycrystalline domains. There has not yet been a comprehensive study comparing the various antisolvents used in different perovskite compositions containing cesium. In addition, there have been no reports of solvent engineering for high efficiency in all‐inorganic perovskites such as CsPbI3. In this work, inorganic perovskite composition CsPbI3 is specifically targeted and unique adducts formed between CsI and precursor solvents and antisolvents are found that have not been observed for other A‐site cation salts. These CsI adducts control nucleation more so than the PbI2–dimethyl sulfoxide (DMSO) adduct and demonstrate how the A‐site plays a significant role in crystallization. The use of methyl acetate (MeOAc) in this solvent engineering approach dictates crystallization through the formation of a CsI–MeOAc adduct and results in solar cells with a power conversion efficiency of 14.4%.

A piperidinium salt stabilizes efficient metal-halide perovskite solar cells.

Science (New York, N.Y.) Nature Research 369 (2020) 96-102

Y-H Lin, N Sakai, P Da, J Wu, HC Sansom, AJ Ramadan, S Mahesh, J Liu, RDJ Oliver, J Lim, L Aspitarte, K Sharma, P Madhu, AB Morales-Vilches, PK Nayak, S Bai, F Gao, CRM Grovenor, MB Johnston, JG Labram, JR Durrant, JM Ball, B Wenger, B Stannowski, HJ Snaith

Longevity has been a long-standing concern for hybrid perovskite photovoltaics. We demonstrate high-resilience positive-intrinsic-negative perovskite solar cells by incorporating a piperidinium-based ionic compound into the formamidinium-cesium lead-trihalide perovskite absorber. With the bandgap tuned to be well suited for perovskite-on-silicon tandem cells, this piperidinium additive enhances the open-circuit voltage and cell efficiency. This additive also retards compositional segregation into impurity phases and pinhole formation in the perovskite absorber layer during aggressive aging. Under full-spectrum simulated sunlight in ambient atmosphere, our unencapsulated and encapsulated cells retain 80 and 95% of their peak and post-burn-in efficiencies for 1010 and 1200 hours at 60° and 85°C, respectively. Our analysis reveals detailed degradation routes that contribute to the failure of aged cells.

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.

Facile synthesis of stable and highly luminescent methylammonium lead halide nanocrystals for efficient light emitting devices

Journal of the American Chemical Society American Chemical Society 141 (2019) 1269–1279-

Y Hassan, OJ Ashton, JH Park, G Li, N Sakai, B Wenger, A-A Haghighirad, NK Noel, MH Song, BR Lee, RH Friend, HJ Snaith

Metal halide perovskites are promising candidates for use in light emitting diodes (LEDs), due to their potential for color tunable and high luminescence efficiency. While recent advances in perovskite-based light emitting diodes have resulted in external quantum efficiencies exceeding 12.4% for the green emitters, and infrared emitters based on 3D/2D mixed dimensional perovskites have exceeded 20%, the external quantum efficiencies of the red and blue emitters still lag behind. A critical issue to date is creating highly emissive and stable perovskite emitters with the desirable emission band gap to achieve full-color displays and white LEDs. Herein, we report the preparation and characterization of a highly luminescent and stable suspension of cubic-shaped methylammonium lead triiodide (CH3NH3PbI3) perovskite nanocrystals, where we synthesize the nanocrystals via a ligand-assisted reprecipitation technique, using an acetonitrile/methylamine compound solvent system to solvate the ions and toluene as the antisolvent to induce crystallization. Through tuning the ratio of the ligands, the ligand to toluene ratio, and the temperature of the toluene, we obtain a solution of CH3NH3PbI3 nanocrystals with a photoluminescence quantum yield exceeding 93% and tunable emission between 660 and 705 nm. We also achieved red emission at 635 nm by blending the nanocrystals with bromide salt and obtained perovskite-based light emitting diodes with maximum electroluminescent external quantum efficiency of 2.75%.

Structural and optical properties of Cs2AgBiBr6 double perovskite

ACS Energy Letters American Chemical Society 4 (2018) 299-305

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

We present a comprehensive study of the relationship between the crystal structure and optoelectronic properties of the double perovskite Cs2AgBiBr6, which has emerged as a promising candidate for photovoltaic devices. On the basis of single-crystal/powder X-ray diffraction and neutron powder diffraction, we have revealed the presence of a structural phase transition at Ts ≈ 122 K between the room-temperature cubic structure (space group Fm3̅m) and a new low-temperature tetragonal structure (I4/m). From reflectivity measurements we found that the peak exciton energy Eex ≈ 2.85 eV near the direct gap shifts proportionally to the tetragonal strain, which is consistent with the Eex being primarily controlled by a rotational degree of freedom of the crystal structure, thus by the angle Bi−Ag−Br. We observed the time-resolved photoluminescence kinetics and we found that, among the relaxation channels, a fast one is mainly present in the tetragonal phase, suggesting that its origin may lie in the formation of tetragonal twin domains.

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.

Infrared light management using a nanocrystalline silicon oxide interlayer in monolithic perovskite/silicon heterojunction tandem solar cells with efficiency above 25%

Advanced Energy Materials Wiley 9 (2019) 1803241

L Mazzarella, S Kirner, Morales-Vilches, L Korte, S Albrecht, E Crossland, B Stannowski, C Case, H Snaith, R Schlatmann, Y-H Lin

Perovskite/silicon tandem solar cells are attractive for their potential for boosting cell efficiency beyond the crystalline silicon (Si) single-junction limit. However, the relatively large optical refractive index of Si, in comparison to that of transparent conducting oxides and perovskite absorber layers, results in significant reflection losses at the internal junction between the cells in monolithic (two-terminal) devices. Therefore, light management is crucial to improve photocurrent absorption in the Si bottom cell. Here it is shown that the infrared reflection losses in tandem cells processed on a flat silicon substrate can be significantly reduced by using an optical interlayer consisting of nanocrystalline silicon oxide. It is demonstrated that 110 nm thick interlayers with a refractive index of 2.6 (at 800 nm) result in 1.4 mA cm − ² current gain in the silicon bottom cell. Under AM1.5G irradiation, the champion 1 cm 2 perovskite/silicon monolithic tandem cell exhibits a top cell + bottom cell total current density of 38.7 mA cm −2 and a certified stabilized power conversion efficiency of 25.2%.

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

Surface modified fullerene electron transport layers for stable and reproducible flexible perovskite solar cells

NANO ENERGY 49 (2018) 324-332

S Song, R Hill, K Choi, K Wojciechowski, S Barlow, J Leisen, HJ Snaith, SR Marder, T Park

Aligned and Graded Type-II Ruddlesden-Popper Perovskite Films for Efficient Solar Cells


J Qing, X-K Liu, M Li, F Liu, Z Yuan, E Tiukalova, Z Yan, M Duchamp, S Chen, Y Wang, S Bai, J-M Liu, HJ Snaith, C-S Lee, TC Sum, F Gao

The effect of ionic composition on acoustic phonon speeds in hybrid perovskites from Brillouin spectroscopy and density functional theory

Journal of Materials Chemistry C Royal Society of Chemistry 6 (2018) 3861-3868

IV Kabakova, I Azuri, Z Chen, P Nayak, H Snaith, L Kronik, C Paterson, AA Bakulin, DA Egger

Hybrid organic–inorganic perovskites (HOIPs) have recently emerged as highly promising solution-processable materials for photovoltaic (PV) and other optoelectronic devices. HOIPs represent a broad family of materials with properties highly tuneable by the ions that make up the perovskite structure as well as their multiple combinations. Interestingly, recent high-efficiency PV devices using HOIPs with substantially improved long-term stability have used combinations of different ionic compositions. The structural dynamics of these systems are unique for semiconducting materials and are currently argued to be central to HOIPs stability and charge-transport properties. Here, we studied the impact of ionic composition on phonon speeds of HOIPs from Brillouin spectroscopy experiments and density functional theory calculations for FAPbBr3, MAPbBr3, MAPbCl3, and the mixed halide MAPbBr1.25Cl1.75. Our results show that the acoustic phonon speeds can be strongly modified by ionic composition, which we explain by analysing the lead-halide sublattice in detail. The vibrational properties of HOIPs are therefore tuneable by using targeted ionic compositions in the perovskite structure. This tuning can be rationalized by non-trivial effects, for example, considering the influence of the shape and dipole moment of organic cations. This has an important implications for further improvements in the stability and charge-transport properties of these systems.

Present status and future prospects of perovskite photovoltaics.

Nature materials 17 (2018) 372-376

HJ Snaith

Publisher Correction: High irradiance performance of metal halide perovskites for concentrator photovoltaics

Nature Energy Springer Nature America, Inc (2018)

Z Wang, Q Lin, B Wenger, M Christoforo, Y-H Lin, MT Klug, MICHAEL Johnston, LAURA Herz, HJ Snaith

© 2018, Springer Nature Limited. When this Article was originally published, an old version of the associated Supplementary Information file was uploaded. This has now been replaced.

Perovskite/Colloidal Quantum Dot Tandem Solar Cells: Theoretical Modeling and Monolithic Structure

ACS ENERGY LETTERS 3 (2018) 869-874

A Karani, L Yang, S Bai, MH Futscher, HJ Snaith, B Ehrler, NC Greenham, D Di

Nonspiro, Fluorene-Based, Amorphous Hole Transporting Materials for Efficient and Stable Perovskite Solar Cells.

Advanced science (Weinheim, Baden-Wurttemberg, Germany) 5 (2018) 1700811-

Š Daškevičiū Tė, N Sakai, M Franckevičius, M Daškevičienė, A Magomedov, V Jankauskas, HJ Snaith, V Getautis

Novel nonspiro, fluorene-based, small-molecule hole transporting materials (HTMs) V1050 and V1061 are designed and synthesized using a facile three-step synthetic route. The synthesized compounds exhibit amorphous nature with a high glass transition temperature, a good solubility, and decent thermal stability. The planar perovskite solar cells (PSCs) employing V1050 generated an excellent power conversion efficiency of 18.3%, which is comparable to 18.9% obtained with the state-of-the-art Spiro-OMeTAD. Importantly, the devices based on V1050 and V1061 show better stability compared to devices based on Spiro-OMeTAD when aged without any encapsulation under uncontrolled humidity conditions (relative humidity around 60%) in the dark and under continuous full sun illumination.

Enabling reliability assessments of pre-commercial perovskite photovoltaics with lessons learned from industrial standards

NATURE ENERGY 3 (2018) 459-465

HJ Snaith, P Hacke

Correction to "Exciton-Dominated Core-Level Absorption Spectra of Hybrid Organic-Inorganic Lead Halide Perovskites".

The journal of physical chemistry letters 9 (2018) 3193-

C Vorwerk, C Hartmann, C Cocchi, G Sadoughi, SN Habisreutinger, R Félix, RG Wilks, HJ Snaith, M Bär, C Draxl

Enhanced photovoltage for inverted planar heterojunction perovskite solar cells

Science American Association for the Advancement of Science 360 (2018) 1442-1446

D Luo, W Yang, Z Wang, A Sadhanala, Q Hu, R Su, R Shivanna, GF Trindade, JF Watts, Z Xu, T Liu, K Chen, F Ye, P Wu, L Zhao, J Wu, Y Tu, Y Zhang, X Yang, W Zhang, RH Friend, Q Gong, HJ Snaith, R Zhu

The highest power conversion efficiencies (PCEs) reported for perovskite solar cells (PSCs) with inverted planar structures are still inferior to those of PSCs with regular structures, mainly because of lower open-circuit voltages (Voc). Here we report a strategy to reduce nonradiative recombination for the inverted devices, based on a simple solution-processed secondary growth technique. This approach produces a wider bandgap top layer and a more n-type perovskite film, which mitigates nonradiative recombination, leading to an increase in Voc by up to 100 millivolts. We achieved a high Voc of 1.21 volts without sacrificing photocurrent, corresponding to a voltage deficit of 0.41 volts at a bandgap of 1.62 electron volts. This improvement led to a stabilized power output approaching 21% at the maximum power point.

Exciton-Dominated Core-Level Absorption Spectra of Hybrid Organic-Inorganic Lead Halide Perovskites.

The journal of physical chemistry letters 9 (2018) 1852-1858

C Vorwerk, C Hartmann, C Cocchi, G Sadoughi, SN Habisreutinger, R Félix, RG Wilks, HJ Snaith, M Bär, C Draxl

In a combined theoretical and experimental work, we investigate X-ray absorption near-edge structure spectroscopy of the I L3 and the Pb M5 edges of the methylammonium lead iodide (MAPbI3) hybrid inorganic-organic perovskite and its binary phase PbI2. The absorption onsets are dominated by bound excitons with sizable binding energies of a few hundred millielectronvolts and pronounced anisotropy. The spectra of both materials exhibit remarkable similarities, suggesting that the fingerprints of core excitations in MAPbI3 are essentially given by its inorganic component, with negligible influence from the organic groups. The theoretical analysis complementing experimental observations provides the conceptual insights required for a full characterization of this complex material.