Shay Tirosh

Extremely Slow Photoconductivity Response of CH3NH3PbI3 Perovskites Suggesting Structural Changes under Working Conditions

Photoconductivity measurements of CH3NH3PbI3 deposited between two dielectric-protected Au electrodes show extremely slow response. The CH3NH3PbI3, bridging a gap of ∼2000 nm, was subjected to a DC bias and cycles of 5 min illumination and varying dark duration. The approach to steady -state photocurrent lasted tens of seconds with a strong dependence on the dark duration preceding the illumination. On the basis of DFT calculations, we propose that under light + bias the methylammonium ions are freed to rotate and align along the electric field, thus modifying the structure of the inorganic scaffold. While ions alignment is expected to be fast, the adjustment of the inorganic scaffold seems to last seconds as reflected in the extremely slow photoconductivity response. We propose that under working conditions a modified, photostable, perovskite structure is formed, depending on the bias and illumination parameters. Our findings seem to clarify the origin of the well-known hysteresis in perovskite solar cells.

Photoinduced Reversible Structural Transformations in Free-Standing CH3NH3PbI3 Perovskite Films

In the pursuit to better understand the mechanisms of perovskite solar cells we performed Raman and photoluminescence measurements of free-standing CH3NH3PbI3 films, comparing dark with working conditions. The films, grown on a glass substrate and sealed by a thin glass coverslip, were measured subsequent to dark and white-light pretreatments. The extremely slow changes we observe in both the Raman and photoluminescence cannot be regarded as electronic processes, which are much faster. Thus, the most probable explanation is of slow photoinduced structural changes. The CH3NH3PbI3 transformation between the dark and the light structures is reversible, with faster rates for the changes under illumination. The results seem to clarify several common observations associated with solar cell mechanisms, like performance improvement under light soaking. More important is the call for solar-cell-related investigation of CH3NH3PbI3 to take the photoinduced structural changes into consideration when measuring and interpreting the results.

Design Rules for High-Efficiency Quantum-Dot-Sensitized Solar Cells: A Multilayer Approach

The effect of multilayer sensitization in quantum-dot (QD)-sensitized solar cells is reported. A series of electrodes, consisting of multilayer CdSe QDs were assembled on a compact TiO2 layer. Photocurrent measurements along with internal quantum efficiency calculation reveal similar electron collection efficiency up to a 100 nm thickness of the QD layers. Moreover, the optical density and the internal quantum efficiency measurements reveal that the desired surface area of the TiO2 electrode should be increased only by a factor of 17 compared with a compact electrode. We show that the sensitization of low-surface-area TiO2 electrode with QD layers increases the performance of the solar cell, resulting in 3.86% efficiency. These results demonstrate a conceptual difference between the QD-sensitized solar cell and the dye-based system in which dye multilayer decreases the cell performance. The utilization of multilayer QDs opens new opportunities for a significant improvement of quantum-dot-sensitized solar cells via innovative cell design.

Influence of the porosity on diffusion and lifetime in porous TiO2 layers

Photocurrent transients were investigated on pressed and sintered porous TiO2 layers which were immersed in electrolyte during the measurements. Unpressed porous TiO2 layers were prepared by electrophoretic deposition. The porosity of the layers was changed systematically by pressing. The surfaces of the TiO2 nanoparticles and the intimate contact between them were identically conditioned by sintering in air at 450°C after pressing. With decreasing porosity, the diffusion coefficient increased while the electron lifetime decreased. The results are discussed on the base of the change of the mean coordination number between TiO2 nanoparticles.

Open circuit potential build-up in perovskite solar cells from dark conditions to 1 sun.

The high open-circuit potential (Voc) achieved by perovskite solar cells (PSCs) is one of the keys to their success. The Voc analysis is essential to understand their working mechanisms. A large number of CH3NH3PbI3-xClx PSCs were fabricated on single large-area substrates and their Voc dependencies on illumination intensity, I0, were measured showing three distinctive regions. Similar results obtained in Al2O3 based PSCs relate the effect to the compact TiO2 rather than the mesoporous oxide. We propose that two working mechanisms control the Voc in PSCs. The rise of Voc at low I0 is determined by the employed semiconductor n-type contact (TiO2 or MgO coated TiO2). In contrast, at I0 close to AM1.5G, the employed oxide does not affect the achieved voltage. Thus, a change of regime from an oxide-dominated EFn (as in the dye sensitized solar cells) to an EFn, directly determined by the CH3NH3PbI3-xClx absorber is suggested.

Influence of sintering temperature, pressing, and conformal coatings on electron diffusion in electrophoretically deposited porous TiO2

The electrophoretic deposition of nanoporous TiO2 layers allows us to investigate separately the influence of sintering temperature, porosity, and conformal surface coatings on the effective diffusion coefficient (Deff) of excess electrons in porous layers. Photocurrent transients were measured to obtain Deff in nanoporous TiO2 layers immersed in aqueous electrolyte. The applied treatments control parameters such as the contact between interconnected nanoparticles, the coordination of nanoparticles in the porous network, and the surface passivation of TiO2 nanoparticles. The hierarchy of the different factors for transport optimization in porous TiO2 is discussed. Under fixed geometry of the nanoporous network, trapping on surface states can strongly limit electron diffusion in porous TiO2.

Cs+ incorporation into CH3NH3PbI3 perovskite: substitution limit and stability enhancement

In this study we systematically explored the mixed cation perovskite Csx(CH3NH3)1−xPbI3. We exchanged the A-site cation by dipping MAPbI3 films into a CsI solution, thereby incrementally replacing the MA+ in a time-resolved dipping process and analysed the resulting thin-films with UV-Vis, XRD, EDAX, SEM and optical depth-analysis in a high-throughput fashion. Additional in situ UV-Vis and time-resolved XRD measurements allowed us to look at the kinetics of the formation process. The results showed a discontinuity during the conversion. Firstly, small amounts of Cs+ are incorporated into the structure. After a few minutes, the Cs content approaches a limit and grains of δ-CsPbI3 occur, indicating a substitution limit. We compared this cation exchange to a one-step crystallisation approach and found the same effect of phase segregation, which shows that the substitution limit is an intrinsic feature rather than a kinetic effect. Optical and structural properties changed continuously for small Cs incorporations. Larger amounts of Cs result in phase segregation. We estimate the substitution limit of CsxMA1−xPbI3 to start at a Cs ratio x = 0.13, based on combined measurements of EDAX, UV-Vis and XRD. The photovoltaic performance of the mixed cation perovskite shows a large increase in device stability from days to weeks. The initial efficiency of mixed CsxMA1−xPbI3 devices decreases slightly, which is compensated by stability after a few days.

How Transparent Oxides Gain Some Color: Discovery of a CeNiO3 Reduced Bandgap Phase As an Absorber for Photovoltaics

In this work, we describe the formation of a reduced bandgap CeNiO3 phase, which, to our knowledge, has not been previously reported, and we show how it is utilized as an absorber layer in a photovoltaic cell. The CeNiO3 phase is prepared by a combinatorial materials science approach, where a library containing a continuous compositional spread of Ce xNi1- xO y is formed by pulsed laser deposition (PLD); a method that has not been used in the past to form Ce-Ni-O materials. The library displays a reduced bandgap throughout, calculated to be 1.48-1.77 eV, compared to the starting materials, CeO2 and NiO, which each have a bandgap of ∼3.3 eV. The materials library is further analyzed by X-ray diffraction to determine a new crystalline phase. By searching and comparing to the Materials Project database, the reduced bandgap CeNiO3 phase is realized. The CeNiO3 reduced bandgap phase is implemented as the absorber layer in a solar cell and photovoltages up to 550 mV are achieved. The solar cells are also measured by surface photovoltage spectroscopy, which shows that the source of the photovoltaic activity is the reduced bandgap CeNiO3 phase, making it a viable material for solar energy.