Publications/Patents

2017
Tufan Ghosh, Sigalit Aharon, lioz etgar, and Sanford Ruhman. 12/5/2017. “Free carrier emergence and onset of electron-phononcoupling in methylammonium lead halide perovskite films.” Journal of the American Chemical Society, DOI: 10.1021/jacs.7b09508. free_carrier_emergence_and_onset_of_electron-phonon_coupling_in_methylammonium_lead_halide_perovskite_films.pdf
Daniel Amgar, Małgorzata Wierzbowska, Vladimir Uvarov, Vitaly Gutkin, and lioz etgar. 10/23/2017. “Novel Rubidium lead chloride nanocrystals: Synthesisand characterization.” Nano Futures, 1: 021002.Abstract

Alkali ternary lead halides have been studied intensively in the past few years, with great interest
focussed on perovskite materials. In this paper we report on novel rubidium lead chloride nanocrystals
(NCs) with the formula Rb6Pb5Cl16, which adopt a tetragonal symmetry. The NCs were characterized
and found to be active in theUVregion, with a band-gap of∼4.05 eV. The roles of the ligands, oleic
acid and oleylamine, were investigated and found to strongly affect the morphology and composition
of the NCs, through the stabilization of the facilitated crystallization of the ionic precursors. The
effective masses were observed by density functional theory (DFT) calculations, using the dielectric
function, and the the Bohr exciton radius and exciton binding energy of the NCs were estimated.
Moreover, the results were supported by the DFT calculations of the electronic properties and atomic
structure.

novel_rubidium_lead_chloride_nanocrystals.pdf
Stav Rahmany, Michael Layani, Shlomo Magdassi, and lioz etgar. 9/24/2017. “Fully functional semi-transparent perovskitesolar cell fabricated at ambient air.” Energy & Fuels, DOI: 10.1039/c7se00383h.Abstract

Organic–inorganic halide perovskite has excellent properties to function as light harvesters in solar cells
due to the possibility to tune its optical properties and to use it as thin film absorber, at a few hundrednanometer
thicknesses. Herein, we demonstrate the fabrication of perovskite solar cells with controlled
transparency, by the mesh assisted deposition process. Sequential fabrication of perovskite was
performed in air, wherein a PbI2 grid was formed in the first step, and in the second step, the grid
reacted selectively with methylammoniumiodide, resulting in a perovskite grid pattern. The best cells
were obtained with a photoanode composed of mesoporous TiO2 with Al2O3 nanoparticles. The
resulting semi-transparent perovskite solar cells, including a semi-transparent contact composed of
MoO3/Au/MoO3 yielded a power conversion efficiency of 5.5% with an average transparency of 26% and
efficiency of 8% for cells fabricated with a gold contact.

fully_functional_semi-transparent.pdf fully_functional.png
Ravi K. Misra, Bat-El Cohen, Lior Iagher, and lioz etgar. 8/28/2017. “Low-Dimensional Organic–Inorganic Halide Perovskite:Structure, Properties, and Applications.” ChemSusChem, 2017,10: 3712 – 3721.Abstract

Three-dimensional (3D) perovskite has attracted a lot of attention owing to its success in photovoltaic (PV) solar cells. However, one of its major crucial issues lies in its stability, which has limited its commercialization. An important property of organic–inorganic perovskite is the possibility of forming a layered material by using long organic cations that do not fit into the octahedral cage. These long organic cations act as a “barrier” that “caps” 3D perovskite to form the layered material.
Controlling the number of perovskite layers could provide a confined structure with chemical and physical properties that are different from those of 3D perovskite. This opens up a
whole new batch of interesting materials with huge potential for optoelectronic applications. This Minireview presents the synthesis, properties, and structural orientation of low-dimensional perovskite. It also discusses the progress of low-dimensional perovskite in PV solar cells, which, to date, have performance comparable to that of 3D perovskite but with enhanced stability. Finally, the use of low-dimensional perovskite in light-emitting diodes (LEDs) and photodetectors is discussed.
The low-dimensional perovskites are promising candidates for LED devices, mainly because of their high radiative recombination as a result of the confined low-dimensional
quantum well.

 

low_dimensional_organic_inorganic.png low-dimensional_organic-inorganic_halide_perovskite.pdf
Bat-El Cohen, Malgorzata Wierzbowska, and lioz etgar. 8/10/2017. “High efficiency quasi 2D lead bromide perovskitesolar cells using various barrier molecules.” Sustainable Energy & Fuels, 2017,1: 1935–1943.Abstract

This work reports on the high power conversion efficiency (PCE) and high open circuit voltage (Voc) of
bromide-based quasi 2D perovskite solar cells. A Voc of more than 1.4 V and, at the same time, a PCE of
9.5% for cells with hole transport material (HTM) were displayed, whereas a Voc value of 1.37 V and a PCE
of 7.9% were achieved for HTM-free cells. Bromide quasi 2D perovskites were synthesized using various
long organic barriers (e.g., benzyl ammonium, BA; phenylethyl ammonium, PEA; and propyl phenyl
ammonium, PPA). The influence of different barrier molecules on the quasi 2D perovskite's properties
was studied using absorbance, X-ray diffraction, and scanning electron microscopy. No change was
observed in the exciton binding energy as a result of changing the barrier molecule. Density functional
theory (DFT) with spin–orbit coupling calculations showed that in the case of BA, holes are delocalized
over the whole molecule, whereas for PEA and PPA, they are delocalized more at the phenyl ring. This
factor influences the electrical conductivity of holes, which is highest for BA in comparison with the
other barriers. In the case of electrons, the energy onset for the nonzero conductivity is lowest for BA.
Both calculations support the better PV performance observed for the quasi 2D perovskite based on BA
as the barrier. Finally, using contact angle measurements, it was shown that the quasi 2D perovskite is
more hydrophobic than the 3D perovskite. Stability measurements showed that cells based on the quasi
2D perovskite are more stable than cells based on the 3D perovskite.

high_efficiency_quasi_2d_lead_bromide_perovskite.pdf high_efficiency_quasi_2d_1.png
Y. Huang, S. Aharon, A. Rolland, L. Pedesseau, O. Durand, L. Etgar, and J. Even. 5/19/2017. “Influence of Schottky contact on the C-V and J-V characteristicsof HTM-free perovskite solar cells.” EPJ Photovoltaics, 2017,8: 85501.Abstract

Abstract The influence of the Schottky contact is studied for hole transport material (HTM) free
CH3NH3PbI3 perovskite solar cells (PSCs), by using drift-diffusion and small signal models. The basic
current-voltage and capacitance-voltage characteristics are simulated in reasonable agreement with experimental
data. The build in potential of the finite CH3NH3PbI3 layer is extracted from a Mott-Schottky
capacitance analysis. Furthermore, hole collector conductors with work-functions of more than 5.5 eV are
proposed as solutions for high efficiency HTM-free CH3NH3PbI3 PSCs.

influence_of_schottky_contact_on_the_c-v_and_j-v_characteristics.pdf
Chongwen Li, Yuanyuan Zhou, Yue Chang Li Wang, Yingxia Zong, lioz etgar, Guanglei Cui, Nitin P. Padture, and Shuping Pang. 5/19/2017. “Methylammonium-Mediated Evolution of Mixed-Organic-CationPerovskite Thin Films: A Dynamic Composition-Tuning Process.” Angew. Chem. Int. Ed., 2017,56: 7674 –7678.Abstract

Methylammonium-mediated phase-evolution
behavior of FA1@xMAxPbI3 mixed-organic-cation perovskite
(MOCP) is studied. It is found that by simply enriching the
MOCP precursor solutions with excess methylammonium
cations, the MOCPs form via a dynamic composition-tuning
process that is key to obtaining MOCP thin films with superior
properties. This simple chemical approach addresses several
key challenges, such as control over phase purity, uniformity,
grain size, composition, etc., associated with the solutiongrowth
of MOCP thin films with targeted compositions.

methylammonium.png methylammonium-mediated_evolution_of_mixed-organic-cation.pdf
Yue Chang, Li Wang, Jiliang Zhang, Zhongmin Zhou, Chongwen Li, Bingbing Chen, lioz etgar, Guanglei Cui, and Shuping Pang. 2/10/2017. “CH3NH2 gas induced (110) preferred cesiumcontainingperovskite films with reduced PbI6octahedron distortion and enhanced moisturestability.” J. Mater. Chem. A, 2017,5: 4803–4808.Abstract

We report here the discovery of a fancy interaction between cesium iodide (CsI) and methylamine (CH3NH2) due to the presence of the hydrogen bond. The formed CsI$xCH3NH2 is a liquid phase, which facilitates the large scale fabrication of highly uniform cesium-containing perovskite films with strong (110) preferred orientation by the CH3NH2 gas healing process. With this method, at most 10% nonpolar Cs cations could fully dope into the crystal lattice and extremely enhance the interaction of the inorganic framework with a more
symmetrical PbI6 octahedron, resulting in obvious improvement in moisture stability under continuous illumination.

ch3nh2_gas_induced_110_preferred_cesiumcontaining.pdf ch3.png
Bat-El Cohen, Małgorzata Wierzbowska, and lioz etgar. 2/3/2017. “High Efficiency and High Open Circuit Voltage in Quasi 2DPerovskite Based Solar Cells.” Advanced Functional Materials, 2017: 1604733.Abstract

An important property of hybrid layered perovskite is the possibility to reduce
its dimensionality to provide wider band gap and better stability. In this work,
2D perovskite of the structure (PEA)2(MA)n–1PbnBr3n+1 has been sensitized,
where PEA is phenyl ethyl-ammonium, MA is methyl-ammonium, and using
only bromide as the halide. The number of the perovskite layers has been
varied (n) from n = 1 through n = ∞. Optical and physical characterization
verify the layered structure and the increase in the band gap. The photovoltaic
performance shows higher open circuit voltage (Voc) for the quasi 2D perovskite
(i.e., n = 40, 50, 60) compared to the 3D perovskite. Voc of 1.3 V without
hole transport material (HTM) and Voc of 1.46 V using HTM have been
demonstrated, with corresponding efficiency of 6.3% and 8.5%, among the
highest reported. The lower mobility and transport in the quasi 2D perovskites
have been proved effective to gain high Voc with high efficiency, further
supported by ab initio calculations and charge extraction measurements. Bromide
is the only halide used in these quasi 2D perovskites, as mixing halides
have recently revealed instability of the perovskite structure. These quasi 2D
materials are promising candidates for use in optoelectronic applications that
simultaneously require high voltage and high efficiency.

high_efficiency_and_high_open_circuit_voltage.png hight_efficiency_and_hight.pdf
Daniel Amgar, Avigail Stern, Dvir Rotem, Danny Porath, and lioz etgar. 1/17/2017. “Tunable Length and Optical Properties of CsPbX3 (X = Cl, Br, I)Nanowires with a Few Unit Cells.” Nano Letters, 2017, 17: 1007−1013.Abstract

Perovskite nanostructures, both hybrid organo−metal
and fully inorganic perovskites, have gained a lot of interest in the past
few years for their intriguing optical properties in the visible region. We
report on inorganic cesium lead bromide (CsPbBr3) nanowires (NWs)
having quantum confined dimensions corresponding to 5 unit cells. The
addition of various hydrohalic acids (HX, X = Cl, Br, I) was found to
highly affect the NW length, composition, and optical properties.
Hydrochloric (HCl) and hydroiodic (HI) acids mixed in the reaction
solution influence the crystal structure and optical properties and
shorten the NWs, while the hydrobromic acid (HBr) addition results
solely in shorter NWs, without any structural change. The addition of HX increases the acidity of the reaction solution, resulting
in protonation of the oleylamine ligands from oleylamine into oleyl-ammonium cations that behave similarly to Cs+ during
crystallization. Therefore, the positions of the Cs+ at the growing surface of the NWs are taken by the oleyl-ammonium cations,
thus blocking further growth in the favored direction. The emission of the NWs is tunable between ∼423−505 nm and possesses
a potential in the optoelectronic field. Moreover, electrical conductivity measurements

tunable_length_and_optical_properties_of_few.png tunable_length_and_optical_properties_of_cspbx3.pdf
lioz etgar and Sigalit Aharon. 2017. “TWO DIMENSIONAL ORGANO-METAL HALIDE PEROVSKITENANORODS.” WIPO (World Intellectual Prop Org) WO 2017/153994 Al.
David P. Fenning, Mariana I. Bertoni, Yang Shao-Horn, lioz etgar, and Shany Gamliel. 2017. “Environmental sensors using metal halide perovskites.” United States of America Provisional application.
lioz etgar and Daniel Amgar. 2017. “Rubidium Lead Chloride Nanocrystals.” United States of America Provisional.
2016
Hadas Naor, Yiftach Divon, Lior Iagher, lioz etgar, and David Avnir. 11/14/2016. “Conductive molecularly doped gold films.” J. Mater. Chem. C, 2016,4: 11548--11556.Abstract

We describe a general synthesis of conductive gold thin films doped with entrapped organic molecules,
and demonstrate, for the first time, the immobilization of a redox couple within an electrode in a single
step. The resulting film is of dual properties: conductivity arising from the gold, and redox behavior
originating from the entrapped molecule. Faster electron-transfer rates are found for the entrapped
case, compared to adsorption. The conductivity of the film affects the organic molecule–metal interactions,
as seen in resistivity measurements, in Raman spectroscopy of the metal-entrapped molecules and from
a remarkable red shift of 30 nm in emission spectroscopy. Doping is found to affect the work function
of gold. Thin conductive doped metal films are of relevance to a variety of applications such as
electrochemical detectors, electrode materials for electrochemical impedance spectroscopy, micro and
nano electronics interconnects for packaging and for printed circuit boards. The ability to fine-tune the
work function opens the possibility to design the desired energy level gaps for optoelectronic applications
such as light emitting diodes (LEDs), solar cells and transistors.

conductive_molecularly_doped_gold_films.pdf conductive_molecularly_doped_gold_films.png
Ravi K. Misra, Laura Ciammaruchi, Sigalit Aharon, Dmitry Mogilyansky, lioz etgar, Iris Visoly-Fisher, and Eugene A. Katz. 2016. “Effect of Halide Composition on the PhotochemicalStability of Perovskite Photovoltaic Materials.” ChemSusChem, 2016, 9: 1 – 7.Abstract

The photochemical stability of encapsulated films of mixed halide perovskites with a range of MAPb(I1xBrx)3 (MA=methylammonium) compositions (solid solutions) was investigated under accelerated stressing using concentrated sunlight. The relevance of accelerated testing to standard operational conditions of solar cells was confirmed by comparison to degradation experiments under outdoor sunlight exposure. We found that MAPbBr3 films exhibited no degradation, while MAPbI3 and mixed halide MAPb(I1xBrx)3 films decomposed yielding crystallization of inorganic PbI2 accompanied by degradation of the perovskite solar light absorption, with faster absorption degradation in mixed halide films. The crystal coherence length was found to correlate with the stability of the films. We postulate that the introduction of Br into the mixed halide solid solution stressed its structure and induced more structural defects and/or grain boundaries compared to pure halide perovskites, which might be responsible for the accelerated degradation. Hence, the cause for accelerated degradation may be the increased defect density rather than the chemical composition of the perovskite materials.

effect_of_halide_composition_on_the_photochemical.png effect_of_halide_composition_on_the_photochemical_stability.pdf
Sigalit Aharon and lioz etgar. 2016. “Hole Conductor Free Organometal Halide Perovskite Solar Cells: Properties and Different Architectures: Principle, Materials and Devices.” In Perovskite Solar Cells, 111-146. World Scientific Publishing Company.
lioz etgar. 2016. Hole Conductor Free Perovskite-based Solar Cells. Springer International Publishing.
Bat-El Cohen, Sigalit Aharon, Alex Dymshits, and lioz etgar. 2016. “Impact of Antisolvent Treatment on Carrier Density in Efficient Hole-Conductor-Free Perovskite-Based Solar Cells.” J. Phys. Chem. C, 2016, 120: 142-147.Abstract

This work demonstrates antisolvent treatment of organo-metal halide perovskite film in hole conductor-free perovskite-based solar cell, achieving impressive power conversion efficiency of 11.2% for hole-conductor-free cells with gold contact. We found that antisolvent (toluene) surface treatment affects the morphology of the perovskite layer, and importantly, it also affects the electronic properties of the perovskite. Conductive atomic force microscopy (cAFM) and surface photovoltage show that the perovskite film becomes more conductive after antisolvent treatment. Moreover, the antisolvent treatment suppresses the hysteresis commonly obtained for perovskite-based solar cells. When the perovskite alone is characterized, a I−V plot of a single perovskite grain measured by cAFM shows that hysteresis vanishes after toluene treatment. During toluene treatment, excess halide and methylammonium ions are removed from the perovskite surface, leading to a net positive charge on the Pb atoms, resulting in a more conductive perovskite surface, which is beneficial for the hole-conductor-free solar cell structure. The reliability of the surface treatment was proved by calculating the statistical parameters Z score and p value, which were 2.5 and 0.012, respectively. According to these values, it can be concluded
with 95% confidence that the average efficiency of cells fabricated via surface treatment is greater than the average efficiency of cells without surface treatment. The statistical data support the impact of surface treatment on the photovoltaic performance of perovskite solar cells.

impact_of_antisolvent_treatment_on_carrier_density_in_efficient_hole-.png impact_of_antisolvent_treatment_on_carrier_density_in_efficient_holeconductor-free.pdf
Daniel Amgar, Sigalit Aharon, and lioz etgar. 2016. “Inorganic and Hybrid Organo-Metal PerovskiteNanostructures: Synthesis, Properties, and Applications.” Advanced Functional Materials, 2016,26: 8576–8593.Abstract

Hybrid perovskite and all-inorganic perovskite have attracted much attention
in recent years owing to their successful use in the photovoltaic field.
Usually the perovskite is used in its bulk form, although recently, perovskites’
nanocrystalline form has received increased attention. Recent developments
in the evolving research field of nanomaterial-based perovskite are reviewed.
Both hybrid organic-inorganic and all-inorganic perovskite nanostructures are
discussed, as well as approaches to tune the optical properties by controlling
the size and shape of perovskite nanostructures. In addition, chemical modifications
can change the perovskite nanostructures’ band-gap, similar to their
bulk counterpart. Several applications, including light-emitting diodes, lasers,
and detectors, demonstrate the latent potential of perovskite nanostructures.

inorganic_and_hybrid_organo-metal_perovskite.pdf
Miriam Koolyk, Daniel Amgar, Sigalit Aharon, and lioz etgar. 2016. “Kinetics of cesium lead halide perovskitenanoparticle growth; focusing andde-focusing of size distribution.” Nanoscale, 2016,8: 6403-6409.Abstract

In this work we study the kinetics of cesium lead halide perovskite nanoparticle (NP) growth; the focusing and de-focusing of the NP size distribution. Cesium lead halide perovskite NPs are considered to be attractive materials for optoelectronic applications. Understanding the kinetics of the formation of these all-inorganic perovskite NPs is critical for reproducibly and reliably generating large amounts of uniformly sized NPs. Here we investigate different growth durations for CsPbI3 and CsPbBr3 NPs, tracking their growth by high-resolution transmission electron microscopy and size distribution analysis. As a result, we are able to provide a detailed model for the kinetics of their growth. It was observed that the CsPbI3 NPs exhibit focusing of the size distribution in the first 20 seconds of growth, followed by de-focusing over longer growth durations, while the CsPbBr3 NPs show de-focusing of the size distribution starting from the beginning of the growth. The monomer concentration is depleted faster in the case of CsPbBr3 than in the case of CsPbI3, due to faster diffusion of the monomers, which increases the critical radius and results in de-focusing of the population. Accordingly, focusing is not observed within 40 seconds of growth in the case of CsPbBr3. This study provides important knowledge on how to achieve a narrow size distribution of cesium lead halide perovskite NPs when generating large amounts of these promising, highly luminescent NPs.

kinetics_of_cesium_lead_halide_perovskite_nanoparticle_growth_focusing_and_de-focusing_of_size_distribution.png kinetics_of_cesium_lead_halide_perovskite_nanoparticle_growth_focusing_and_de-focusing_of_size_distribution.pdf

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