Publications/Patents

2016
Vinay sharma, Sigalit Aharon, Itay Gdor, Chunfan Yang, lioz etgar, and Sanford Ruhman. 2016. “New insights into exciton binding and relaxationfrom high time resolution ultrafast spectroscopy ofCH3NH3PbI3 and CH3NH3PbBr3 films.” J. Mater. Chem. A, 2016,4: 3546-3553.Abstract

High time resolution broadband pump-probe experiments on CH3NH3PbI3 and CH3NH3PbBr3 films are described. The improved time resolution delineates instantaneous and delayed relaxation related effects on sample absorption and assists in clarifying controversial assignment of the underlying mechanisms. Analysis of the data in terms of finite difference spectra and spectral band integrals reveals that photoexcitation is high in the inter-band continuum leading to partial bleaching and red-shifts of the exciton band just below the absorption-edge instantaneously. Increased pump intensity saturates the exciton bleach and progressively reduces inter-band absorption in a broad range extending from the band edge to higher photon energies. Both effects are attributed to reduced Coulomb enhancement due to hot carrier screening. The spectral extent of the inter-band absorption attenuation provides estimated binding energies in the range of 20–30 meV in both materials. Sub-picosecond carrier cooling reverses the initial exciton transition red-shift and induces transmission near the band edge due to state filling and stimulated emission. Finally, 1–100 ps signals are dominated by reverse state filling due to non-geminate recombination. These results demonstrate that both inter-band and exciton absorptions are essential for unraveling photo-induced dynamics in these materials, and that insights obtained from many-body theoretical analysis of dynamic screening are essential for correctly assigning the recorded spectral evolution.

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Bat-El Cohen and lioz etgar. 2016. “Parameters that control and influence the organo-metalhalide perovskite crystallization and morphology.” Front. Optoelectron, 1, 2016,9: 44–52.Abstract

This review discusses various parameters that influence and control the organo-metal halide perovskite crystallization process. The effect of the perovskite morphology on the photovoltaic performance is a critical factor. Moreover, it has a dramatic effect on the stability of the perovskite, which has significant importance for later use of the organo-metal perovskite in assorted applications. In this review, we brought together several research investigations that describe the main parameters that significantly influence perovskite crystallization, for example, the annealing process, the precursor solvent, anti-solvent treatment, and additives to the iteite solutions.mechanisms. Control over morphology is a key parameter to understand this attractive material; morphology control will be an additional step throughout its commercialization process. The review is divided to four parts, presenting various parameters influencing perovskite crystallization and morphology. Section 2 discusses the effect of the annealing process; Section 3 describes the precursor solvent, presenting the possible solvents being used in the deposition process; Section 4 presents the anti-solvent treatment and its effect on the cell properties; and Section 5 discusses additives that can be added to the perovskite solution before deposition.

parameters_that_control_and_influence_the_organo-metal_halide_perovskite_crystallization_and_morphology.pdf
Etgar Lioz. 2016. “Perovskites nanoscrystals (hybrids and inorganic) synthesis, optical and physical properties.” In HANDBOOK OF ORGANIC OPTOELECTRONIC DEVICES. World Scientific.
lioz etgar, Shlomo Magdassi, Sigalit Aharon, and Michael Layani. 2016. “Semi-transparent hole conductor free perovskite based solar cells.” WIPO (World Intellectual Prop Org) WO2016110851 A1.
Yanqi Luo, Shany Gamliel, Sally Nijem, Sigalit Aharon, Martin Holt, Benjamin Stripe, Volker Rose, Mariana I. Bertoni, lioz etgar, and David P. Fenning. 2016. “Spatially Heterogeneous Chlorine Incorporation in Organic−Inorganic Perovskite Solar Cells.” Chemistry of Materials, 18, 2016,28: 6536–6543.Abstract

Spatial heterogeneities in the chemical makeup of thin film photovoltaic devices are pivotal in determining device efficiency. We report the in-plane spatial distribution and degree of chlorine incorporation in organic−inorganic lead halide perovskite absorbers by means of nondestructive synchrotronbased nanoprobe X-ray fluorescence. The presence of chlorine is positively identified in CH3NH3PbI3 films synthesized with Clcontaining precursors and as an impurity in some films synthesized with nominally Cl-free precursors. The impurity may be introduced from precursors or as contaminants during film synthesis. The films formed from Cl-containing precursors contain roughly an order of magnitude higher amount of chlorine, with Cl:I values greater than 0.02 found whether Cl is present in either the organic or the inorganic precursor for both one- and two-step fabrication processes. A spatial variation in the Cl incorporation is observed within single particles and as well as between particles within a given film, and the standard deviation of the Cl:I ratio across the films is up to 30% of the average
value. Understanding and controlling the heterogeneous distribution of chlorine in hybrid perovskite layers may offer a path to improve their photovoltaic performance.

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Sigalit Aharon and lioz etgar. 2016. “Two Dimensional Organometal Halide Perovskite Nanorods withTunable Optical Properties.” Nano Lett., 5, 2016,16: 3230–3235.Abstract

Organo-metal halide perovskite is an efficient light harvester in photovoltaic solar cells. Organometal halide perovskite is used mainly in its “bulk” form in the solar cell. Confined perovskite nanostructures could be a promising candidate for efficient optoelectronic devices, taking advantage of the superior bulk properties of organo-metal halideperovskite, as well as the nanoscale properties. In this paper, we present facile low-temperature synthesis of two-dimensional (2D) lead halide perovskite nanorods (NRs). These NRs show a shift to higher energies in the absorbance and in the photoluminescence compared to the bulk material, which supports their 2D structure. X-ray diffraction (XRD) analysis of the NRs demonstrates their 2D nature combined with the tetragonal 3D perovskite structure. In addition, by alternating the halide composition, we were able to tune the optical properties of the NRs. Fast Fourier transform, and electron diffraction show the tetragonal structure of these NRs. By varying the ligands ratio (e.g., octylammonium to oleic acid) in the synthesis, we were able to provide the formation mechanism of these novel 2D perovskite NRs. The 2D perovskite NRs are promising candidates for a variety of optoelectronic applications, such as light-emitting diodes, lasing, solar cells, and sensors.

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Ravi K. Misra, Sigalit Aharon, Michael Layani, Shlomo Magdassi, and lioz etgar. 2016. “A mesoporous–planar hybrid architecture ofmethylammonium lead iodide perovskite basedsolar cells.” J. Mater. Chem. A, 2016,4: 14423-14429.Abstract

We report a hybrid mesoporous–planar architecture of methylammonium lead iodide perovskite based solar cells, to combine the benefits of both the mesoporous and planar architectures in a single device. A mesoporous-TiO2 grid was fabricated on a compact TiO2 layer, through a self-assembly process based on directional wetting, providing regions with and without mesoporous-TiO2, followed by perovskite deposition and back contact evaporation (hybrid cells). The hybrid cells showed up to 10.7% power conversion efficiency (PCE) as compared to 13.5% and 6.3% for their mesoporous and planar counterparts, respectively. Interestingly, the hybrid cells are found to show a short circuit current density
(Jsc) as high as the Jsc of the mesoporous TiO2 based cells and proved to conserve the current density even in the absence of mesoporous-TiO2 from planar parts of the hybrid cells. The cells showed the best fill factor as compared to their mesoporous and planar counterparts. The areal variation in the meso to planar ratio has also been realized by changing the grid size to demonstrate the effect of the architecture on the cell performance. Charge extraction measurements have been used to obtain insight into the recombination inside different solar cells architectures. The hybrid cell structure emerged as a novel promising design for perovskite solar cells.

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Shany Gamliel, Inna Popov, Bat-El Cohen, Vladimir Uvarov, and lioz etgar. 2016. “Structural and Quantitative Investigation of Perovskite Pore Filling in Mesoporous Metal Oxides.” Crystals, 2016, 6: 149.Abstract

In recent years, hybrid organic–inorganic perovskite light absorbers have attracted much
attention in the field of solar cells due to their optoelectronic characteristics that enable high power
conversion efficiencies. Perovskite-based solar cells’ efficiency has increased dramatically from
3.8% to more than 20% in just a few years, making them a promising low-cost alternative for
photovoltaic applications. The deposition of perovskite into a mesoporous metal oxide is an
influential factor affecting solar cell performance. Full coverage and pore filling into the porous metal
oxide are important issues in the fabrication of highly-efficient mesoporous perovskite solar cells.
In this work, we carry out a structural and quantitative investigation of CH3NH3PbI3 pore filling
deposited via sequential two-step deposition into two different mesoporous metal oxides—TiO2
and Al2O3. We avoid using a hole conductor in the perovskite solar cells studied in this work to
eliminate undesirable end results. Filling oxide pores with perovskite was characterized by Energy
Dispersive X-ray Spectroscopy (EDS) in Transmission Electron Microscopy (TEM) on cross-sectional
focused ion beam (FIB) lamellae. Complete pore filling of CH3NH3PbI3 perovskite into the metal
oxide pores was observed down to X-depth, showing the presence of Pb and I inside the pores.
The observations reported in this work are particularly important for mesoporous Al2O3 perovskite
solar cells, as pore filling is essential for the operation of this solar cell structure. This work presents
structural and quantitative proof of complete pore filling into mesoporous perovskite-based solar
cells, substantiating their high power conversion efficiency.

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2015
Jon M. Azpiroz, Jesus M. Ugalde, lioz etgar, Ivan Infante, and Filippo De Angelis. 2015. “The effect of TiO2 surface on the electroninjection efficiency in PbS quantum dot solarcells: a first-principles study.” Phys.Chem.Chem.Phys, 2015, 17: 6076--6086.Abstract

We present a density functional theory (DFT) study aimed at understanding the injection and recombination processes that occur at the interface between PbS QDs and TiO2 oxide nanoparticles with different morphologies. The calculated injection rates fall in the picosecond timescale in good agreement with the experiments. In addition, our simulations show that the (101) facet of TiO2 more favourably accommodates the QD, resulting in stronger electronic couplings and faster electron injections than the (001) surfaces. Despite this, the (101) slab is also more prone to faster electron recombination with the valence band of the QD, which can lead to overall lower injection efficiencies than the (001) surface.

the_effect_of_tio2_surface_on_the_electron_injection_efficiency_in_pbs_quantum_dot_solar_cells.pdf
Tzofia Englman, Eyal Terkieltaub, and lioz etgar. 2015. “High Open Circuit Voltage in Sb2S3/Metal Oxide-Based Solar Cells.” J. Phys. Chem. C, 2015, 119: 12904−12909.Abstract

This paper presents for the first time Sb2S3-based solar cells operating on
scaffold film. The scaffolds studied are Al2O3 and ZrO2, for which no electron injection
from the Sb2S3 to the Al2O3 or ZrO2 is possible. As a result, one of the highest open circuit
voltages (Voc) of 0.712 V was observed for this solar cell configuration. Electron dispersive
spectroscopy (EDS) was performed, revealing complete pore filling of the Sb2S3 into the
metal oxide pores (e.g., Al2O3 or ZrO2); the complete pore filling of the Sb2S3 is
responsible for the photovoltaic performance (PV) of this unique solar cell structure. In
addition, intensity modulated photovoltage and photocurrent spectroscopy (IMVS and
IMPS) were performed to extract the electron diffusion length. Electron diffusion length in
the range of 900 nm to 290 nm (depending on the light intensity) was observed, which
further supports the operation of metal oxide/Sb2S3 solar cell configuration. Moreover, the
Al2O3-based cells have longer electron diffusion length than the TiO2-based cells,
supporting the higher open circuit voltage of the noninjected metal oxide-based cells. This
work demonstrates the potential of Sb2S3 to gain high voltage and to perform on a scaffold
substrate without requiring electron injection.

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lioz etgar. 2015. “Hole-transport material-freeperovskite-based solar cells.” MRS Bulletin, 8, 2015,40: 674-680.Abstract

Recent discoveries have revealed a breakthrough in the photovoltaics (PVs) ! eld using
organometallic perovskites as light harvesters in the solar cell. The organometal perovskite
arrangement is self-assembled as alternate layers via a simple low-cost procedure. These
organometal perovskites promise several bene! ts not provided by the separate constituents.
This overview concentrates on implementing perovskites in PV cells such that the perovskite
layers are used as the light harvester as well as the hole-conducting component. Eliminating
hole-transport material (HTM) in this solar-cell structure avoids oxidation, reduces costs, and
provides better stability and consistent results. Aspects of HTM-free perovskite solar cells
discussed in this article include (1) depletion regions, (2) high voltages, (3) panchromatic
responses, (4) chemical modi! cations, and (5) contacts in HTM-free perovskite solar cells.
Elimination of HTM could expand possibilities to explore new interfaces in these solar
cells, while over the long term, these uniquely structured HTM-free solar cells could offer
valuable bene! ts for future PV and optoelectronics applications.

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Elham Ghadiri, Bin Liu, Jacques-E. Moser, Michael Grätzel, and lioz etgar. 2015. “Investigation of Interfacial Charge Separation at PbS QDs/(001) TiO2 Nanosheets Heterojunction Solar Cell.” Part. Part. Syst. Charact., 2015, 32: 483–488.Abstract

In the recent years, the heterojunction solar cells based on quantum dots (QDs) have attracted attention due to strong light absorbing characteristics and the size effect on the bandgap tuning. This paper reports on the kinetics of interfacial charge separation of PbS QDs/(001) TiO 2 nanosheets heterojunction solar cells. PbS QDs are deposited using a bifunctional linker molecule on two different TiO 2 fi lms, i.e., TiO 2 nanosheets (with 001 dominant exposed facet) and TiO 2 nanoparticles (with 101 dominant exposed facet). Upon bandgap excitation, electrons are transferred from the PbS QDs conduction band to the lower lying conduction band of TiO 2 . Based on the ultrafast pump-probe laser spectroscopy technique, the kinetics of charge separation is scrutinized at the PbS/TiO 2 interface. The interfacial charge separation at PbS/TiO 2 nanosheets films made of (001) dominant exposed facets is fi ve times faster than that on (101) dominant exposed facets TiO 2 nanoparticles. The quantum yields for charge injection are higher for the (001) TiO 2 nanosheets than the (101) TiO 2 nanoparticles due to enhanced interfacial interaction with (001) surface compared to the (101) nanoparticles. The superior interfacial charge separation at PbS/(001) nanosheets respect to PbS/(101) nanoparticles is consistent with the higher photocurrent and enhanced power conversion effi ciency in the PbS QDs/(001) TiO 2 heterojunction solar cell. The use of (001) TiO 2 nanosheets can be a better alternative to conventional mesoporous TiO 2 fi lms in QD heterojunction solar cells and perovskites-based heterojunction solar cells.

investigation_of_interfacial_charge_separation_at_pbs_qds.pdf
Shany Gamliel, Alex Dymshits, Sigalit Aharon, Eyal Terkieltaub, and lioz etgar. 2015. “Micrometer Sized Perovskite Crystals in Planar Hole Conductor FreeSolar Cells.” J. Phys. Chem. C, 2015, 119: 19722−19728.Abstract

In this work we demonstrate the planar configuration on hole conductor (HTM) free perovskite based solar cells. The CH3NH3PbI3 perovskite was deposited using the spray technique to achieve micrometer size perovskite crystals. The number of spray passes changes the CH3NH3PbI3 film thickness; for example, 10 spray passes achieved a film thickness of 3.4 μm of perovskite. Surprisingly, power conversion efficiency of 6.9% was demonstrated for this novel, simple solar cell structure with thick perovskite film that has no HTM. Capacitance−voltage measurements reveal charge accumulation at the CH3NH3PbI3/Au interface while the compact TiO2/CH3NH3PbI3 junction showed a space charge region, which inhibits the recombination. Studying these interfaces is key to understanding the operation mechanism of this unique solar cell structure. This simple planar HTM free perovskite solar cell demonstrates the potential to make large-scale solar cells while maintaining a simple, low-cost architecture.

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Sigalit Aharon, Michael Layani, Bat-El Cohen, Efrat Shukrun, Shlomo Magdassi, and lioz etgar. 2015. “Self-Assembly of Perovskite for Fabrication ofSemitransparent Perovskite Solar Cells.” Adv. Mater. Interfaces, 2015, 2: 1500118.Abstract

This work reports on the preparation of semitransparent perovskite solar cells. The cells transparency is achieved through a unique wet deposition technique that creates perovskite grids with various dimensions. The perovskite grid is deposited on a mesoporous TiO 2 layer, followed by hole transport material deposition and evaporation of a semitransparent gold fi lm. Control of the transparency of the solar cells is achieved by changing the perovskite solution concentration and the mesh openings. The semitransparent cells demonstrate 20–70% transparency with a power conversion effi ciency of 5% at 20% transparency. This is the fi rst demonstration of the possibility to create a controlled perovskite pattern using a direct mesh-assisted assembly deposition method for fabrication of a semitransparent perovskite-based
solar cell.

full_paperc_2015_wiley-vch_verlag_gmbh_co._kgaa_weinheim1_of_6_1500118wileyonlinelibrary.com_self-assembly_of_perovskite_for_fabrication_of_semitransparent_perovskite_solar_cells.pdf
Ravi K. Misra, Sigalit Aharon, Baili Li, Dmitri Mogilyansky, Iris Visoly-Fisher, lioz etgar, and Eugene A. Katz. 2015. “Temperature- and Component-Dependent Degradation ofPerovskite Photovoltaic Materials under Concentrated Sunlight.” J. Phys. Chem. Lett., 2015, 6: 326−330.Abstract

We report on accelerated degradation testing of MAPbX3 films (X = I or Br) by exposure to concentrated sunlight of 100 suns and show that the evolution of light absorption and the corresponding structural modifications are dependent on the type of halide ion and the exposure temperature. One hour of such exposure provides a photon dose equivalent to that of one sun exposure for 100 hours. The degradation in absorption of MAPbI3 films after exposure to 100 suns for 60 min at elevated sample temperature (∼45−55 °C), due to decomposition of the hybrid perovskite material, is documented. No degradation was observed after exposure to the same sunlight concentration but at a lower sample temperature (∼25 °C). No photobleaching or decomposition of MAPbBr3 films was observed after exposure to similar stress conditions (light intensity, dose, and temperatures). Our results indicate that the degradation is highly dependent on the hybrid perovskite composition and can be light- and thermally enhanced.

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Alex Dymshits, Alex Henning, Gideon Segev, Yossi Rosenwaks, and lioz etgar. 2015. “The electronic structure of metal oxide/organo metal halide perovskite junctionsin perovskite based solar cells.” Nature Scientific Reports, 2015, 5: 8704.Abstract

Cross-sections of a hole-conductor-free CH3NH3PbI3 perovskite solar cell were characterized with Kelvin probe force microscopy. A depletion region width of about 45 nm was determined from the measured potential profiles at the interface between CH3NH3PbI3 and nanocrystalline TiO2, whereas a negligible depletion was measured at the CH3NH3PbI3/Al2O3 interface. A complete solar cell can be realized with the CH3NH3PbI3 that functions both as light harvester and hole conductor in combination with a metal oxide. The band diagrams were estimated from the measured potential profile at the interfaces, and are critical findings for a better understanding and further improvement of perovskite based solar cells.

 

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lioz etgar. 2015. “Perovskite schottky type solar cell.” WIPO (World Intellectual Prop Org) WO 2014/097299 Al.
Sigalit Aharon, Alexander Dymshits, Amit Rotem, and lioz etgar. 2015. “Temperature dependence of hole conductor freeformamidinium lead iodide perovskite based solarcells.” J. Mater. Chem. A, 2015, 3: 9171-9178.Abstract

Organometal halide perovskite is a promising material in photovoltaic (PV) cells. Within a short time, its performance has increased dramatically to become a real competitor to silicon solar cells. Here we report on the temperature dependence (annealing temperature and the dependence of the photovoltaic parameters on temperature) of formamidinium (FA) lead iodide (FAPbI3), methylammonium (MA) lead iodide (MAPbI3) and their mixture (MAPbI3 : FAPbI3) in hole conductor free perovskite solar cells. These three types of perovskites function both as light harvesters and as hole conductors. Surface photovoltage and optical characterization reveal the p-type behavior and the band gap of the different perovskites. We observed that the ratio between the MA and FA cations might change during the annealing process, affecting the band gap and the stability of the layers. The PV parameters at different temperatures show better stability for the pure MAPbI3 and FAPbI3 solar cells compared to their mixture. Using intensity modulated photovoltage/photocurrent spectroscopy, we found that the diffusion length is weakly dependent on the light intensity, while the charge collection efficiency drops with light intensity for the FAPbI3-based cells. However, for MAPbI3 and the mixture, the charge collection efficiency remains constant for a wide range of light intensities.

temperature_dependence_of_hole_conductor_free_formamidinium_lead_iodide_perovskite_based_solar_cells.pdf
2014
Alex Dymshits, Amit Rotem, and lioz etgar. 2014. “High voltage in hole conductor free organo metalhalide perovskite solar cells.” J. Mater. Chem. A, 2014, 2: 20776.Abstract

Organo metal halide perovskite has attracted considerable attention recently due to its distinctive properties that make it especially useful in photovoltaic solar cells. In this work we demonstrate high open circuit voltage of 1.35 V using Al2O3/CH3NH3PbBr3 perovskite solar cells without a hole conductor. The contact potential difference under light measured by surface photovoltage spectroscopy of CH3NH3PbBr3 was more than twice that of CH3NH3PbI3, which results in smaller surface potential for the Al2O3/CH3NH3PbBr3 cells. Incident modulated photovoltage spectroscopy shows a longer recombination lifetime for the Al2O3/CH3NH3PbBr3 cells than for the TiO2/CH3NH3PbI3 cells or for the TiO2/CH3NH3PbBr3 cells, further supporting the high open circuit voltage. The possibility to gain high open circuit voltage even without a hole transport material in perovskite solar cells shows that the perovskite/metal oxide interface has a major effect on the open circuit voltage in perovskite based solar cells.

high_voltage_in_hole_conductor_free_organo_metal_halide_perovskite_solar_cells.pdf
Sigalit Aharon, Bat El Cohen, and lioz etgar. 2014. “Hybrid Lead Halide Iodide and Lead Halide Bromide in Efficient HoleConductor Free Perovskite Solar Cell.” J. Phys. Chem. C, 2014, 118: 17160−17165.Abstract

In this work we used CH3NH3PbInBr3−n (where 0 ≤ n ≤ 3) as hole conductor and light harvester in the solar cell. Various concentrations of methylammonium iodide and methylammonium bromide were studied which reveal that any composition of the hybrid CH3NH3PbInBr3−n can conduct holes. The hybrid perovskite was deposited in two steps, separating it to two precursors to allow better control of the perovskite composition and efficient tuning of its band gap. The X-ray diffraction reveals the change in the lattice parameter due to the introducing of the Br− ions. The hybrid iodide/bromide perovskite hole conductor free solar cells show very good stability, their power conversion efficiency achieved 8.54% under 1 sun illumination with current density of 16.2 mA/cm2. The results of this work open the possibility for graded structure of perovskite solar cells without the need for hole conductor.

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