Modeling of Charge Injection, Recombination, and Diffusion in Complete Perovskite Solar Cells on Short Time Scales.

A model of charge population decay upon ultrafast optical pulse excitation in complete, working perovskite solar cells is proposed. The equation, including charge injections (extractions) from perovskite to contact materials, charge diffusion, and charge recombination via first-, second-, and third-order processes, is solved using numerical simulations. Results of simulations are positively verified by broadband transient absorption results of mixed halide, triple-cation perovskite (FA0.76MA0.19Cs0.05Pb(I0.81Br0.19)3). The combined analytical and experimental findings reveal the best approaches for the proper determination of the crucial parameters that govern charge transfer dynamics in perovskite solar cells on picosecond and single nanosecond time scales. Measurements from both electron and hole transporting layer sides under different applied bias potentials (zero and close to open circuit potential) and different pump fluence (especially below 5 µJ/cm2), followed by fitting of parameters using numerical modeling, are proposed as the optimal methodology for describing the processes taking place in efficient devices.

Synergistic Effect of Precursor and Interface Engineering Enables High Efficiencies in FAPbI3 Perovskite Solar Cells.

Formamidinium lead iodide (FAPbI3)-based perovskite solar cells have gained immense popularity over the last few years within the perovskite research community due to their incredible opto-electronic properties and the record power conversion efficiencies (PCEs) achieved by the solar cells. However, FAPbI3 is vulnerable to phase transitions even at room temperature, which cause structural instability and eventual device failure during operation. We performed post-treatment of the FAPbI3 surface with octyl ammonium iodide (OAI) in order to stabilize the active phase and preserve the crystal structure of FAPbI3. The formation of a 2D perovskite at the interface depends on the stoichiometry of the precursor. By optimizing the precursor stoichiometry and the concentration of OAI, we observe a synergistic effect, which results in improved power conversion efficiencies, reaching the best values of 22% on a glass substrate. Using physical and detailed optical analysis, we verify the presence of the 2D layer on the top of the 3D surface of the perovskite film.

Template-Assisted Synthesis of a Large-Area Ordered Perovskite Nanowire Array for a High-Performance Photodetector.

One-dimensional (1D) organic-inorganic hybrid perovskite nanowires (NWs) with well-defined structures possess superior optical and electrical properties for optoelectronic applications. However, most of the perovskite NWs are synthesized in air, which makes the NWs susceptible to water vapor, resulting in large amounts of grain boundaries or surface defects. Here, a template-assisted antisolvent crystallization (TAAC) method is designed to fabricate CH3NH3PbBr3 NWs and arrays. It is found that the as-synthesized NW array has designable shapes, low crystal defects, and ordered alignment, which is attributed to the sequestration of water and oxygen in air by the introduction of acetonitrile vapor. The photodetector based on the NWs exhibits an excellent response to light illumination. Under the illumination of a 532 nm laser with 0.1 µW and a bias of -1 V, the responsivity and detectivity of the device reach 1.55 A/W and 1.21 × 1012 Jones, respectively. The transient absorption spectrum (TAS) shows a distinct ground state bleaching signal only at 527 nm, which corresponds to the absorption peak induced by the interband transition of CH3NH3PbBr3. Narrow absorption peaks (a few nanometers) indicate that the energy-level structures of CH3NH3PbBr3 NWs only have a few impurity-level-induced transitions leading to additional optical loss. This work provides an effective and simple strategy to achieve high-quality CH3NH3PbBr3 NWs, which exhibit potential application in photodetection.

Co-Sensitization Effects of Indoline and Carbazole Dyes in Solar Cells and Their Neutral-Anion Equilibrium in Solution.

Co-sensitization of two or more light-absorbing compounds on a TiO2 surface has recently become one of the most successful strategies in the development of dye-sensitized solar cells (DSSCs). The specific structure of the dyes for DSSCs implies that they can partly exist in anionic forms in popular solvents used for sensitization. Our study concerns the above two issues being analyzed in detail using the example of the popular carbazole (MK2) and indoline (D205) dyes, studied by stationary absorption and emission, femtosecond transient absorption (in complete cells and in the solutions), current-voltage measurements, DFT and TD-DFT theoretical calculations. After the addition of D205 to DSSC with MK2, the fill factor of the cells was improved, and the electron recombination between TiO2 and the dyes was blocked (observed on sub-nanosecond time scales). Thus, the active co-adsorbent can take the role of the typically used passive additive, like chenodeoxycholic acid. Evidence of the concentration-dependent equilibrium between neutral and anionic forms of dyes with different lifetimes was found in acetonitrile solutions (the best for sensitization), while in ethanol solution the dominant form was the anion (worse for sensitization). Our findings should help in better understanding the operation and optimization of DSSC.

Impact of improvements in mesoporous titania layers on ultrafast electron transfer dynamics in perovskite and dye-sensitized solar cells.

Improvement in the performance of perovskite solar cells (PSC) and dye-sensitized solar cells (DSSC) upon modifications of mesoporous titania layers has been studied. For PSC with triple cation perovskite (FA0.76 MA0.19 Cs0.05 Pb (I0.81 Br0.19)3) about 40% higher photocurrent (up to ∼24 mA cm-2) was found for more homogenous, made of larger particles (30 nm) and thinner (150-200 nm) titania layer. For DSSC (both with liquid cobalt-based electrolyte as well as with solid state hole transporter - spiro-OMeTAD), a greater dye loading, rise in photovoltage, and the enhancement in relative photocurrent were observed for the cells prepared from the diluted titania paste (2 : 1 w/w ratio) with respect to those prepared from undiluted one. The impact of these improvements in titania layers on charge transfer dynamics in the complete solar cells as well as in pristine TiO2 layers was investigated by femtosecond transient absorption. Shorter photocarriers lifetime in perovskite material observed in better PSC, indicated that faster electron transfer at the titania interface was responsible for the higher photocurrent. Moreover, the photoinduced changes close to TiO2 interface were revealed in better PSC, which may indicate that in the efficient devices halide segregation takes place in perovskite material. In liquid DSSC, the fast component of unwanted recombination was slower in the samples with the diluted titania paste than in those made with undiluted ones. In solid state DSSC, hole injection from MK2 dye to spiro-OMeTAD takes place on the very fast ps time scale (comparable to that of electron injection) and the evidence of better penetration of spiro-OMeTAD into thinner and more porous titania layers was provided.

Understanding the Interfaces between Triple-Cation Perovskite and Electron or Hole Transporting Material.

The properties of efficient solar cells fabricated with triple-cation perovskite placed between a mesoporous titania layer and a spiro-OMeTAD layer are studied by using devices either prepared under water-free drybox conditions or fabricated under ambient room humidity. The morphological studies indicate that the content of unreacted PbI2 phase in the perovskite structure is much higher near the interface with titania than near the interface with spiro-OMeTAD. The stationary emission spectra and transient bleach peaks of perovskites show additional long-wavelength features close to the titania side. Time-resolved techniques ranging from femtoseconds to seconds reveal further differences in charge dynamics at both interfaces. The population decay is significantly faster at the titania side than at the spiro-OMeTAD side for the cells prepared under ambient conditions. An increased hole injection rate correlates with higher photocurrent seen in the devices prepared under drybox conditions. The charge recombination loss on the millisecond time scale is found to be slower at the interface with titania than at the interface with spiro-OMeTAD. The ideality factor of the cells is found to increase with increasing DMSO content in the precursor solution, indicating a change in recombination mechanism from bulk to surface recombination. We also found that the charge dynamics are not uniform within the whole perovskite layer. This feature has significant implications for understanding the operation and optimizing the performance of solar devices based on mixed cation perovskites.

The Effect of Chloride Anions on Charge Transfer in Dye-Sensitized Photoanodes for Water Splitting.

The photoelectrochemical behavior of dye-sensitized photoelectrochemical cells based on a TiO2 layer sensitized with ruthenium components, including an absorber, ruthenium(II)bis(2,2'-bipyridine)([2,2'-bipyridine]-4,4'-diylbis(phosphonic acid)) dibromide (RuP), and a catalyst, ruthenium(II) tris(4-methylpyridine)(4-(4-(2,6-bis((l1-oxidanyl)carbonyl)pyridin-4-yl)phenyl) pyridine-2,6-dicarboxylic acid) (RuOEC), was investigated in the following water-based electrolyte configurations: KCl (pH ≈ 5), HCl (pH ≈ 3), ethylphoshonic acid (pH ≈ 3) with a different KCl concentration, and a standard phosphate buffer (pH ≈ 7). The rate of charge transfer on the photoanode's surface was found to increase in line with the increase in the concentration of chloride anions (Cl-) in the low pH electrolyte. This effect is discussed in the context of pH influence, ionic strength, and specific interaction, studied by cyclic voltammetry (CV) in dark conditions and upon illumination of the photoanodes. The correlations between photocurrent decay traces and CV studies were also observed.

Understanding the Effect of Different Synthesis Conditions on the Physicochemical Properties of Mixed-Ion Perovskite Solar Cells.

Perovskite solar cells, composed of a mixture of methylammonium (MA) and formamidinium (FA) cations [in the benchmark proportions of (FAPbI3 )0.85 (MAPbBr3 )0.15 ] and titania as an electron-accepting material, are prepared under different conditions, with the objective of finding correlations between the solar cell performance and several important stationary and dynamical parameters of the material. The effects of humidity, oxygen, the use of anti-solvent, and the presence and quality of a mesoporous titania layer are investigated. It is found that an increase in the photocurrent corresponds to a higher content of the desired cubic perovskite phase and to increased long-wavelength absorption of the sample. On the contrary, for poorer-quality cells, additional short-wavelength bands in both absorption and emission spectra are present. Furthermore, a higher photocurrent of the cells is correlated with faster interfacial charge-transfer dynamics. For the highest photocurrent of >20 mA cm-2 , the characteristic times of about 1 µs are observed by electrochemical impedance spectroscopy, and emission half-lifetimes of about 6 ns by time-resolved fluorescence spectroscopy (upon excitation with 420 nm pulses of ≈0.5 mW power). Both first- and second-order rate constants, extracted from the emission measurements, are greater for the cells showing higher photocurrents, probably owing to a more rapid charge injection.

Comparison of charge transfer dynamics in polypyridyl ruthenium sensitizers for solar cells and water splitting systems.

Standard ruthenium components of dye-sensitized solar cells (sensitizer N719) and dye-sensitized photoelectrochemical cells (sensitizer RuP and water oxidation catalyst RuOEC) are investigated in the same solar cell configuration to compare their photodynamics and charge separation efficiency. The samples are studied on time scales from femtoseconds to seconds by means of transient absorption, time-resolved emission and electrochemical impedance measurements. RuP shows significantly slower electron injection into a mesoporous titania electrode and enhanced fast (sub-ns) electron recombination with respect to those of N719. Moreover, RuOEC is found to be responsible for partial light absorption and electron injection with low efficiency. The obtained results reveal new insights into the reasons for the lower charge separation efficiency in water splitting systems with respect to that in solar cells. The important role of the initial processes occurring at the dye-titania interface within the first nanoseconds in this efficiency is emphasized.

Differences in photoinduced optical transients in perovskite absorbers for solar cells.

Methylammonium lead iodide films and powdered crystals were studied by time-resolved absorption and emission spectroscopy on the time scales from femtoseconds to nanoseconds. Strikingly different transient absorption signals were observed, changing from strong long-wavelength band-edge bleach to weak signatures of band-shift, which depended on the absorber form (films or polycrystals) and preparation method (stoichiometric or non-stoichiometric). The observed differences were correlated with the variation in absorption and emission spectra, changes in photo-induced carrier lifetimes and solar cell efficiency. These differences also pointed out that similar perovskite absorbers can provide significantly different transient responses and emphasize that special care must be taken when interpolating the obtained findings to the processes occurring in the most efficient devices.

Photochemistry and Photophysics in Silica-Based Materials: Ultrafast and Single Molecule Spectroscopy Observation.

Silica-based materials (SBMs) are widely used in catalysis, photonics, and drug delivery. Their pores and cavities act as hosts of diverse guests ranging from classical dyes to drugs and quantum dots, allowing changes in the photochemical behavior of the confined guests. The heterogeneity of the guest populations as well as the confinement provided by these hosts affect the behavior of the formed hybrid materials. As a consequence, the observed reaction dynamics becomes significantly different and complex. Studying their photobehavior requires advanced laser-based spectroscopy and microscopy techniques as well as computational methods. Thanks to the development of ultrafast (spectroscopy and imaging) tools, we are witnessing an increasing interest of the scientific community to explore the intimate photobehavior of these composites. Here, we review the recent theoretical and ultrafast experimental studies of their photodynamics and discuss the results in comparison to those in homogeneous media. The discussion of the confined dynamics includes solvation and intra- and intermolecular proton-, electron-, and energy transfer events of the guest within the SBMs. Several examples of applications in photocatalysis, (photo)sensors, photonics, photovoltaics, and drug delivery demonstrate the vast potential of the SBMs in modern science and technology.

Insights into the limitations of solar cells sensitized with ruthenium dyes revealed in time-resolved spectroscopy studies.

The substitution of iodide electrolytes with cobalt ones has led to the current champion laboratory efficiencies for dye-sensitized solar cells (DSSCs). However, unlike with organic dyes, this strategy does not work with classical ruthenium dyes. Therefore, we compare DSSCs sensitized with a popular Ru dye (N719) using both types of electrolytes by exploring the electron dynamics occurring from sub-ps to seconds. An important limitation in the photocurrent of cobalt-based cells is revealed to be due to electron recombination between titania and oxidized Ru dyes, which is much higher than that in iodide-based cells and occurs on the time scale of tens and hundreds of ps. Electron recombination between titania and the electrolyte, taking place on the millisecond time scale, is responsible for further lowering of the photovoltage and fill factor of cobalt-based cells. Ruthenium dyes also exhibit lower absorption coefficients with respect to their organic counterparts. For this reason, we also investigate the effect of the changes in the titania layer thickness, addition of scattering nanoparticles and modifications in the TiCl4 treatment on DSSC performance.

Effects of Post-Assembly Molecular and Atomic Passivation of Sensitized Titania Surface: Dynamics of Electron Transfer Measured from Femtoseconds to Seconds.

The dynamics of electron transfer at the dye-titania and titania-electrolyte interfaces is investigated in two post-sensitization processes: (i) atomic layer deposition of blocking alumina coating and (ii) hierarchical molecular multicapping. To measure the electron transfer dynamics, time-resolved spectroscopic methods (femtosecond transient absorption on the time scale from femtoseconds to nanoseconds and electrochemical impedance spectroscopy on the time scale from milliseconds to seconds) are applied to the complete dye-sensitized solar cells with cobalt-based electrolyte and champion ADEKA-1 dye (with silyl-anchor unit) or its popular carboxyl-anchor analogue, MK-2 dye. Both molecular capping and alumina blocking layers slow down the electron injection process (the average rate constant decreases from 1.1 ps-1 to 0.4 ps-1) and partial sub-nanosecond back electron transfer from titania to the dye (from ca. 10 ns-1 to 5 ns-1). Very small alumina layers (of 0.1 nm thickness) have the highest impact on reducing the rate constants of these electron transfer processes, and for the thicknesses greater than 0.3 nm the rate constants hardly change. In contrast, the electron recombination between titania and electrolyte, occurring on the millisecond time scale, starts to be significantly suppressed for the blocking layers of 0.3 nm or more in thickness (up to ca. 20 times for 0.5 nm thickness with respect to that for untreated sample), improving open circuit voltage and fill factor of the cells. The amplitude of the relative photocurrent (short circuit current per number of absorbed photons) is found to depend almost exclusively on the ultrafast and fast processes taking place in the first nanoseconds after dye excitation. The positive impact of coadsorbents on the solar cells performance for both ADEKA-1 and MK-2 is also studied.

Factors Affecting the Performance of Champion Silyl-Anchor Carbazole Dye Revealed in the Femtosecond to Second Studies of Complete ADEKA-1 Sensitized Solar Cells.

Record laboratory efficiencies of dye-sensitized solar cells have been recently reported using an alkoxysilyl-anchor dye, ADEKA-1 (over 14 %). In this work we use time-resolved techniques to study the impact of key preparation factors (dye synthesis route, addition of co-adsorbent, use of cobalt-based electrolytes of different redox potential, creation of insulating Al2 O3 layers and molecule capping passivation of the electrode) on the partial charge separation efficiencies in ADEKA-1 solar cells. We have observed that unwanted fast recombination of electrons from titania to the dye, probably associated with the orientation of the dyes on the titania surface, plays a crucial role in the performance of the cells. This recombination, taking place on the sub-ns and ns time scales, is suppressed in the optimized dye synthesis methods and upon addition of the co-adsorbent. Capping treatment significantly reduces the charge recombination between titania and electrolyte, improving the electron lifetime from tens of ms to hundreds of ms, or even to single seconds. Similar increase in electron lifetime is observed for homogenous Al2 O3 over-layers on titania nanoparticles, however, in this case the total solar cells photocurrent is decreased due to smaller electron injection yield from the dye. Our studies should be important for a broader use of very promising silyl-anchor dyes and the further optimization and development of dye-sensitized solar cells.

Determination of Interfacial Charge-Transfer Rate Constants in Perovskite Solar Cells.

A simple protocol to study the dynamics of charge transfer to selective contacts in perovskite solar cells, based on time-resolved laser spectroscopy studies, in which the effect of bimolecular electron-hole recombination has been eliminated, is proposed. Through the proposed procedure, the interfacial charge-transfer rate constants from methylammonium lead iodide perovskite to different contact materials can be determined. Hole transfer is faster for CuSCN (rate constant 0.20 ns(-1) ) than that for 2,2',7,7'-tetrakis-(N,N-di-4-methoxyphenylamino)-9,9'-spirobifluorene (spiro-OMeTAD; 0.06 ns(-1) ), and electron transfer is faster for mesoporous (0.11 ns(-1) ) than that for compact (0.02 ns(-1) ) TiO2 layers. Despite more rapid charge separation, the photovoltaic performance of CuSCN cells is worse than that of spiro-OMeTAD cells; this is explained by faster charge recombination in CuSCN cells, as revealed by impedance spectroscopy. The proposed direction of studies should be one of the key strategies to explore efficient hole-selective contacts as an alternative to spiro-OMeTAD.

Carbazole Dye-Sensitized Solar Cells Studied from Femtoseconds to Seconds-Effect of Additives in Cobalt- and Iodide-Based Electrolytes.

Comprehensive studies of all charge-separation processes in efficient carbazole dye-sensitized solar cells are correlated with their photovoltaic parameters. An important role of partial, fast electron recombination from the semiconductor nanoparticles to the oxidized dye is revealed; this takes place on the picosecond and sub-nanosecond timescales. The charge-transfer dynamics in cobalt tris(bipyridyl) based electrolytes and iodide-based electrolyte is observed to depend on potential-determining additives in a similar way. Upon addition of 0.5 M 4-tert-butylpiridine to both types of electrolytes, the stability of the cells is greatly improved; the cell photovoltage increases by 150-200 mV, the electron injection rate decreases about five times (from 5 to 1 ps(-1) ), and fast recombination slows down about two to three times. Dye regeneration proceeds at a rate of about 1 µs(-1) in all electrolytes. Electron recombination from titania to cobalt electrolytes is much faster than that to iodide ones.

Optimization of absorption bands of dye-sensitized and perovskite tandem solar cells based on loss-in-potential values.

A numerical study of optimal bandgaps of light absorbers in tandem solar cell configurations is presented with the main focus on dye-sensitized solar cells (DSSCs) and perovskite solar cells (PSCs). The limits in efficiency and the expected improvements of tandem structures are investigated as a function of total loss-in-potential (V(L)), incident photon to current efficiency (IPCE) and fill factor (FF) of individual components. It is shown that the optimal absorption onsets are significantly smaller than those derived for multi-junction devices. For example, for double-cell devices the onsets are at around 660 nm and 930 nm for DSSCs with iodide based electrolytes and at around 720 nm and 1100 nm for both DSSCs with cobalt based electrolytes and PSCs. Such configurations can increase the total sunlight conversion efficiency by about 35% in comparison to single-cell devices of the same VL, IPCE and FF. The relevance of such studies for tandem n-p DSSCs and for a proposed new configuration for PSCs is discussed. In particular, it is shown that maximum total losses of 1.7 V for DSSCs and 1.4 V for tandem PSCs are necessary to give any efficiency improvement with respect to the single bandgap device. This means, for example, a tandem n-p DSSC with TiO2 and NiO porous electrodes will hardly work better than the champion single DSSC. A source code of the program used for calculations is also provided.

Comparison of TiO2 and ZnO solar cells sensitized with an indoline dye: time-resolved laser spectroscopy studies of partial charge separation processes.

Time-resolved laser spectroscopy techniques in the time range from femtoseconds to seconds were applied to investigate the charge separation processes in complete dye-sensitized solar cells (DSC) made with iodide/iodine liquid electrolyte and indoline dye D149 interacting with TiO2 or ZnO nanoparticles. The aim of the studies was to explain the differences in the photocurrents of the cells (3-4 times higher for TiO2 than for ZnO ones). Electrochemical impedance spectroscopy and nanosecond flash photolysis studies revealed that the better performance of TiO2 samples is not due to the charge collection and dye regeneration processes. Femtosecond transient absorption results indicated that after first 100 ps the number of photoinduced electrons in the semiconductor is 3 times higher for TiO2 than for ZnO solar cells. Picosecond emission studies showed that the lifetime of the D149 excited state is about 3 times longer for ZnO than for TiO2 samples. Therefore, the results indicate that lower performance of ZnO solar cells is likely due to slower electron injection. The studies show how to correlate the laser spectroscopy methodology with global parameters of the solar cells and should help in better understanding of the behavior of alternative materials for porous electrodes for DSC and related devices.

Photochromic cycle of 2'-hydroxyacetophenone azine studied by absorption and emission spectroscopy in different solvents.

This paper reports on the investigations of the synthesized di-(o-hydroxyaryl ketoimine) compound by the steady state absorption and emission techniques as well as picosecond time resolved emission and femtosecond transient absorption methods in different solvents. The results of the experimental observation have been supported by the theoretical DFT and TD-DFT calculations. The theoretical data have revealed the completed influence of the environmental polarity on particular conformers of studied compound. Dependencies between the activation rate constant and polarizability function as well as Kamlet-Abbond-Taft hydrogen-bonding parameter have been obtained in different solvent. The mechanism of photodynamic changes of di-(o-hydroxyaryl ketoimine) is presented.

Dynamics of local Stark effect observed for a complete D149 dye-sensitized solar cell.

A complete, functioning dye-sensitized solar cell made of popular indoline D149 sensitizer is studied by means of transient absorption in visible light in the time scale of nanoseconds to seconds. Photocurrent and photovoltage decays are also measured under the same experimental conditions. A local electric field causing a Stark shift of the D149 absorption band is found to strongly influence the transient spectra and kinetics. The presence of electrons in titania has a major contribution to the Stark shift and the effect disappears over many time scales with an average rate of 5 × 10(3) s(-1). This is much slower than the decay of the oxidized dye (2 × 10(6) s(-1)) but, on the other hand, significantly faster than the decay of electrons in titania nanoparticles (3 × 10(2) s(-1) at standard AM1.5 irradiation and open circuit conditions). Possible explanations of this phenomenon are discussed. Electron recombination from the titania conduction band to the oxidized dyes proceeds at an average rate of 2-16 × 10(4) s(-1), depending on the excitation energy density, and does not influence the efficiency of dye regeneration.