FTO Darkening Rate as a Qualitative, High-Throughput Mapping Method for Screening Li-Ionic Conduction in Thin Solid Electrolytes.

We present a high-throughput (combinatorial) method to screen thin ceramic films as Li-ion conductors by mapping an optical effect of Li-ion conduction. The method, while qualitative, is fast and simple to implement, provides a planar (XY) map of Li-ion conductivity through different parts of the film. The effect, FTO darkening, is an optoelectrochemical one that relies on darkening of the FTO (F-doped tin oxide) substrate, onto which the investigated film is deposited. The rate of color change of the FTO reflects the rate of Li-ion migration through the film. The method is validated by testing two model systems, a Li-La-S-O film with uniform composition and varying thickness, and a Li-La-P-O film with varying thickness and lateral composition. The darkening rate, obtained from optical transmission, correlates linearly with inverse film thickness. The darkening rate map can be compared with a resistance map obtained by impedance measurements, showing that only Li conduction is measured. We discuss the conditions required to distinguish between areas with pure ion conductivity and those with mixed conductivity, the reversibility of the darkening effect and artifacts.

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.

Process-Function Data Mining for the Discovery of Solid-State Iron-Oxide PV.

Data mining tools have been known to be useful for analyzing large material data sets generated by high-throughput methods. Typically, the descriptors used for the analysis are structural descriptors, which can be difficult to obtain and to tune according to the results of the analysis. In this Research Article, we show the use of deposition process parameters as descriptors for analysis of a photovoltaics data set. To create a data set, solar cell libraries were fabricated using iron oxide as the absorber layer deposited using different deposition parameters, and the photovoltaic performance was measured. The data was then used to build models using genetic programing and stepwise regression. These models showed which deposition parameters should be used to get photovoltaic cells with higher performance. The iron oxide library fabricated based on the model predictions showed a higher performance than any of the previous libraries, which demonstrates that deposition process parameters can be used to model photovoltaic performance and lead to higher performing cells. This is a promising technique toward using data mining tools for discovery and fabrication of high performance photovoltaic materials.

Surface Polarization Model for the Dynamic Hysteresis of Perovskite Solar Cells.

The dynamic hysteresis of perovskite solar cells consists of the occurrence of significant deviations of the current density-voltage curve shapes depending on the specific conditions of measurement such as starting voltage, waiting time, scan rate, and other factors. Dynamic hysteresis is a serious impediment to stabilized and reliable measurement and operation of the perovskite solar cells. In this Letter, we formulate a model for the dynamic hysteresis based on the idea that the cell accumulates a huge quantity of surface electronic charge at forward bias that is released on voltage sweeping, causing extra current over the normal response. The charge shows a retarded dynamics due to the slow relaxation of the accompanying ionic charge, that produces variable shapes depending on scan rate or poling value and time. We show that the quantitative model provides a consistent description of experimental results and allows us to determine significant parameters of the perovskite solar cell for both the transient and steady-state performance.

Perovskites for Photovoltaics in the Spotlight: Photoinduced Physical Changes and Their Implications.

Organic-inorganic halide perovskites are in consensus to revolutionize the field of photovoltaics and optoelectronic devices due to their superior optical and electronic properties which are unprecedented in comparison to those of other solution processed semiconductors. These hybrid materials are used as light absorbers and also as charge carriers which makes them very versatile to be implemented and studied in a multitude of fields. Traditionally, the working paradigm in solar cells and optoelectronic devices' characterization has been that the properties of photovoltaic materials remain stable following illumination of varying times and intensities. However, recently there has been a growing number of reports on prolonged illumination-dependent physical changes in perovskite films and perovskite based devices. The changes are reversible and range from structural transformations and differences in optical characteristics, to an increase in optoelectronic properties and physical parameters. In this Account, we review the physical changes in three reported model systems which display changes under prolonged illumination of light intensities of ∼0.01-1 sun. The three systems are (i) a free-standing perovskite film on a glass substrate, (ii) a symmetrical system with nonselective electrical contacts, and (iii) a working perovskite solar cell (either a planar or a porous structure). We examine each model system and discuss its photoinduced physical changes and conclude with the implications on future experimentation design, data analysis, and characterization that involve organic-inorganic halide perovskites illumination. Since hybrid perovskites are considered to be mixed ionic-electronic conductors in nature, ions that migrate in the perovskite under electrical fields can influence its properties. Therefore, an important distinction is made between photoinduced effects and photo and electric field induced effects. Thus, photoinduced effects are designated as observed effects in illuminated free-standing films or symmetrical devices without selective contacts. In contrast, photo- and electric field induced effects are designated as observed effects under open-circuit potential or during voltage scanning (internal electrical field exists across the device). In the latter case, the two effects are superimposed and it is difficult to evaluate the relative influence of each one (light or electric field). However, we show that the magnitude and the importance of the photoinduced effect are substantial.

Vapor and healing treatment for CH3NH3PbI(3-x)Cl(x) films toward large-area perovskite solar cells.

Hybrid methyl-ammonium lead trihalide perovskites are promising low-cost materials for use in solar cells and other optoelectronic applications. With a certified photovoltaic conversion efficiency record of 20.1%, scale-up for commercial purposes is already underway. However, preparation of large-area perovskite films remains a challenge, and films of perovskites on large electrodes suffer from non-uniform performance. Thus, production and characterization of the lateral uniformity of large-area films is a crucial step towards scale-up of devices. In this paper, we present a reproducible method for improving the lateral uniformity and performance of large-area perovskite solar cells (32 cm(2)). The method is based on methyl-ammonium iodide (MAI) vapor treatment as a new step in the sequential deposition of perovskite films. Following the MAI vapor treatment, we used high throughput techniques to map the photovoltaic performance throughout the large-area device. The lateral uniformity and performance of all photovoltaic parameters (V(oc), J(sc), Fill Factor, Photo-conversion efficiency) increased, with an overall improved photo-conversion efficiency of ∼100% following a vapor treatment at 140 °C. Based on XRD and photoluminescence measurements, We propose that the MAI treatment promotes a "healing effect" to the perovskite film which increases the lateral uniformity across the large-area solar cell. Thus, the straightforward MAI vapor treatment is highly beneficial for large scale commercialization of perovskite solar cells, regardless of the specific deposition method.

A combined computational and experimental investigation of Mg doped α-Fe2O3.

In the current work, pristine α-Fe2O3 metal oxide was doped with Mg in an attempt to modulate its electronic properties. To this end, we employed an experimental high throughput strategy, including scanning XRD and optical spectroscopy, which were complimented by atomistic density functional theory (DFT) calculations. The combined study reveals that at Mg/Fe atomic ratios up to ∼1/3, the bandgaps of the hematite-Mg composite materials are similar to that of the pure material. The observed bandgaps are rationalized by electronic band structure and density of states calculations. Additional rationale for the similar bandgaps in pure and doped hematite is provided by topological Bader charge analyses, which indicate that the Mg and Fe ions in the hematite matrix have similar partial atomic charges. Nonetheless, the small charge density difference between the Mg and Fe ions induces a slight spin polarization on both oxygen and Fe ions, resulting in changes in the band edges. Further charge density analyses, using charge density maps and chemical-bonding analyses with the crystal orbital Hamiltonian population scheme, indicate that Mg forms ionic bonds with the neighboring oxygen atoms. This change from iron-oxygen covalent bonds to a more ionic nature for magnesium-oxygen bonds is probably responsible for the reduction observed in the computed bulk modulus of α-Mg(0.17)Fe(1.83)O3 (193 GPa) compared to α-Fe2O3 (202 GPa).

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.

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.

Utilizing pulsed laser deposition lateral inhomogeneity as a tool in combinatorial material science.

Pulsed laser deposition (PLD) is widely used in combinatorial material science, as it enables rapid fabrication of different composite materials. Nevertheless, this method was usually limited to small substrates, since PLD deposition on large substrate areas results in severe lateral inhomogeneity. A few technical solutions for this problem have been suggested, including the use of different designs of masks, which were meant to prevent inhomogeneity in the thickness, density, and oxidation state of a layer, while only the composition is allowed to be changed. In this study, a possible way to take advantage of the large scale deposition inhomogeneity is demonstrated, choosing an iron oxide PLD-deposited library with continuous compositional spread (CCS) as a model system. An Fe2O3-Nb2O5 library was fabricated using PLD, without any mask between the targets and the substrate. The library was measured using high-throughput scanners for electrical, structural, and optical properties. A decrease in electrical resistivity that is several orders of magnitude lower than pure α-Fe2O3 was achieved at ∼20% Nb-O (measured at 47 and 267 °C) but only at points that are distanced from the center of the PLD plasma plume. Using hierarchical clustering analysis, we show that the PLD inhomogeneity can be used as an additional degree of freedom, helping, in this case, to achieve iron oxide with much lower resistivity.

Data Mining and Machine Learning Tools for Combinatorial Material Science of All-Oxide Photovoltaic Cells.

Growth in energy demands, coupled with the need for clean energy, are likely to make solar cells an important part of future energy resources. In particular, cells entirely made of metal oxides (MOs) have the potential to provide clean and affordable energy if their power conversion efficiencies are improved. Such improvements require the development of new MOs which could benefit from combining combinatorial material sciences for producing solar cells libraries with data mining tools to direct synthesis efforts. In this work we developed a data mining workflow and applied it to the analysis of two recently reported solar cell libraries based on Titanium and Copper oxides. Our results demonstrate that QSAR models with good prediction statistics for multiple solar cells properties could be developed and that these models highlight important factors affecting these properties in accord with experimental findings. The resulting models are therefore suitable for designing better solar cells.

Four-point probe electrical resistivity scanning system for large area conductivity and activation energy mapping.

The electrical properties of metal oxides play a crucial role in the development of new photovoltaic (PV) systems. Here we demonstrate a general approach for the determination and analysis of these properties in thin films of new metal oxide based PV materials. A high throughput electrical scanning system, which facilitates temperature dependent measurements at different atmospheres for highly resistive samples, was designed and constructed. The instrument is capable of determining conductivity and activation energy values for relatively large sample areas, of about 72 × 72 mm(2), with the implementation of geometrical correction factors. The efficiency of our scanning system was tested using two different samples of CuO and commercially available Fluorine doped tin oxide coated glass substrates. Our high throughput tool was able to identify the electrical properties of both resistive metal oxide thin film samples with high precision and accuracy. The scanning system enabled us to gain insight into transport mechanisms with novel compositions and to use those insights to make smart choices when choosing materials for our multilayer thin film all oxide photovoltaic cells.

Quantum efficiency and bandgap analysis for combinatorial photovoltaics: sorting activity of Cu-O compounds in all-oxide device libraries.

All-oxide-based photovoltaics (PVs) encompass the potential for extremely low cost solar cells, provided they can obtain an order of magnitude improvement in their power conversion efficiencies. To achieve this goal, we perform a combinatorial materials study of metal oxide based light absorbers, charge transporters, junctions between them, and PV devices. Here we report the development of a combinatorial internal quantum efficiency (IQE) method. IQE measures the efficiency associated with the charge separation and collection processes, and thus is a proxy for PV activity of materials once placed into devices, discarding optical properties that cause uncontrolled light harvesting. The IQE is supported by high-throughput techniques for bandgap fitting, composition analysis, and thickness mapping, which are also crucial parameters for the combinatorial investigation cycle of photovoltaics. As a model system we use a library of 169 solar cells with a varying thickness of sprayed titanium dioxide (TiO2) as the window layer, and covarying thickness and composition of binary compounds of copper oxides (Cu-O) as the light absorber, fabricated by Pulsed Laser Deposition (PLD). The analysis on the combinatorial devices shows the correlation between compositions and bandgap, and their effect on PV activity within several device configurations. The analysis suggests that the presence of Cu4O3 plays a significant role in the PV activity of binary Cu-O compounds.

Relaxation of Electron Carriers in the Density of States of Nanocrystalline TiO2.

Band gap localized states and surface states play a dominant role in the application of nanocrystalline metal oxides to photovoltaics and solar fuel production. Electrons injected in nanocrystalline TiO2 by voltage or photogeneration are mainly located in band gap states. Therefore, charging a nanoparticulate semiconductor network allows one to recover the density of states (DOS) in the energy axis. However, shallow traps remain in equilibrium with the conduction band electrons, while deep traps do not. We show that the characteristic peak of the apparent DOS mixes an exponential DOS and a monoenergetic surface state. A model that incorporates the trap's kinetics proves to be very efficient to assess the important parameters that determine both contributions via variation of charging rate. Contrary to the common theory, we demonstrate that the peculiar capacitance peak of nanocrystalline TiO2 can be mainly attributed, in some cases, to deep traps in the exponential distribution.

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.

Photophysics of Voltage Increase by Photoinduced Dipole Layers in Sensitized Solar Cells.

Significant overpotentials between the sensitizer and both the electron and hole conductors hamper the performance of sensitized solar cells, leading to a reduced photovoltage. We show that by using properly designed type-II quantum dots (QDs) between the sensitizer and the hole conductor in thin absorber cells, it is possible to increase the open circuit voltage (Voc) by more than 100 mV. This increase is due to the formation of a photoinduced dipole (PID) layer. Photogenerated holes in the type-II QDs are retained in the core for a relatively long time, allowing for the accumulation of a positively charged layer. Negative charges are, in turn, injected and accumulated in the TiO2 anode, creating a dipole moment, which negatively shifts the TiO2 conduction band relative to the electrolyte. We study this phenomenon using a unique TiO2/CdSe/(ZnSe:Te/CdS)/polysulfide system, where the formation of a PID depends on the color of the illumination. The PID concept thus introduces a new design strategy, where the operating parameters of the solar cell can be manipulated separately.

Materials and interfaces in quantum dot sensitized solar cells: challenges, advances and prospects.

In recent years, quantum dot-sensitized solar cells (QDSSCs) have emerged as attractive candidates for constructing efficient third-generation photoelectrochemical solar cells. Despite a starting point of relatively low performing solar cells, we have been witnessing a boost in scientific research conducted both from the material and the physical points of view, leading to a huge leap in our understanding of the operational mechanisms of QDSSCs followed by a significant improvement of their conversion efficiencies to about 7%. In this feature article, we give an overview of the four main materials and interfaces constructing the QDSSC: (1) sensitizer materials, (2) TiO2/QDs/electrolyte interface, (3) redox electrolyte, and (4) counter electrode. We focus on the scientific challenges associated with each one of the materials/interfaces while highlighting the recent advances achieved in overcoming those obstacles. Finally, we discuss possible future directions for this field of research with an aim toward highly efficient QD-sensitized solar cells.

Photo-induced dipoles: a new method to convert photons into photovoltage in quantum dot sensitized solar cells.

A high photovoltage is an essential ingredient for the construction of a high-efficiency quantum dot sensitized solar cell (QDSSC). In this paper we present a novel configuration of QDSSC which incorporates the photoinduced dipole (PID) phenomenon for improved open circuit voltage (Voc). This configuration, unlike previously studied ones with molecular dipoles, is based on a dipole moment which is created only under illumination and is a result of exciton dissociation. The generation of photodipoles was achieved by the creation of long-lived trapped holes inside a core of type-II ZnSe/CdS colloidal core/shell QDs, which are placed on top of the standard CdS QD sensitizer layer. Upon photoexcitation, the created photodipole negatively shifts the TiO2 energy bands, resulting in a photovoltage that is higher by ∼100 mV compared to the standard cell, without type-II QDs. The extra photovoltage gained diminishes the excessive overpotential losses caused by the energetic difference between the CdS sensitizer layer and the TiO2, without harming the charge injection processes. Moreover, we show that the extent of the additional photovoltage is controlled by the illumination intensity. This work provides new understanding regarding the operation mechanisms of photoelectrochemical cells, while presenting a new strategy for constructing a high-voltage QDSSCs. In addition, the PID effect has the potential to be implemented in other promising photovoltaic technologies.

Characterization and control of the electronic properties of a NiO based dye sensitized photocathode.

One compartment tandem DSSCs are based on two photoactive electrodes which are mediated by a redox electrolyte. Electron accumulation in the photoanode (n-type DSSC) alongside hole accumulation in the photocathode (p-type DSSC) should generate high photovoltage using different parts of the solar spectrum. While impressive efficiencies are reported for n-type DSSCs, the performance of the p-type analogue is very low due to insufficient understanding and a lack of materials. Electrochemical impedance spectroscopy of the p-type DSSC reveals that hole transport within the NiO mesoporous photocathode is the performance limiting factor. Modification of the NiO electrode with molecular dipoles significantly increases the cell photovoltage but has no significant effect on the photocurrent of the p-DSSC. Consequently, the development of better hole conducting materials in conjunction with surface dipole modification can lead to high photovoltage, high photocurrent p-DSSCs and thus to efficient tandem DSSCs.

The importance of the TiO2/quantum dots interface in the recombination processes of quantum dot sensitized solar cells.

Quantum dot sensitized solar cells (QDSSCs) present a promising technology for next generation photovoltaic cells, having exhibited a considerable leap in performance over the last few years. However, recombination processes occurring in parallel at the TiO(2)-QDs-electrolyte triple junction constitute one of the major limitations for further improvement of QDSSCs. Reaching higher conversion efficiencies necessitates gaining a better understanding of the mechanisms of charge recombination in these kinds of cells; this will essentially lead to the development of new solutions for inhibiting the described losses. In this study we have systematically examined the contribution of each interface formed at the triple junction to the recombination of the solar cell. We show that the recombination of electrons at the TiO(2)/QDs interface is as important as the recombination from TiO(2) and QDs to the electrolyte. By applying conformal MgO coating both above and below the QD surface, recombination rates were significantly reduced, and an improvement of more than 20% in cell efficiency was recorded.