Showing papers by "Michael Grätzel published in 2014"
TL;DR: A molecularly engineered porphyrin dye is reported, coded SM315, which features the prototypical structure of a donor-π-bridge-acceptor and both maximizes electrolyte compatibility and improves light-harvesting properties.
Abstract: A dye that both maximizes electrolyte compatibility and improves light-harvesting properties has been designed for dye-sensitized solar cells. In cells based on the cobalt(II)/(III) redox mediator, use of the dye resulted in a power-conversion efficiency of 13%, revealing the great potential of porphyrin dyes for future solar cell applications.
3,940 citations
TL;DR: It is revealed that solution-processed organic-inorganic halide perovskites (CH3NH3PbX3), which demonstrated huge potential in photovoltaics, also have promising optical gain and may show electrically driven lasing.
Abstract: Low-temperature solution-processed materials that show optical gain and can be embedded into a wide range of cavity resonators are attractive for the realization of on-chip coherent light sources. Organic semiconductors and colloidal quantum dots are considered the main candidates for this application. However, stumbling blocks in organic lasing include intrinsic losses from bimolecular annihilation and the conflicting requirements of high charge carrier mobility and large stimulated emission; whereas challenges pertaining to Auger losses and charge transport in quantum dots still remain. Herein, we reveal that solution-processed organic-inorganic halide perovskites (CH 3 NH 3 PbX 3 where X = Cl, Br, I), which demonstrated huge potential in photovoltaics, also have promising optical gain. Their ultra-stable amplified spontaneous emission at strikingly low thresholds stems from their large absorption coefficients, ultralow bulk defect densities and slow Auger recombination. Straightforward visible spectral tunability (390-790 nm) is demonstrated. Importantly, in view of their balanced ambipolar charge transport characteristics, these materials may show electrically driven lasing. © 2014 Macmillan Publishers Limited.
2,691 citations
TL;DR: A perovskite solar cell that uses a double layer of mesoporous TiO2 and ZrO2 as a scaffold infiltrated with perovSkite and does not require a hole-conducting layer is fabricated and achieves a certified power conversion efficiency of 12.8%.
Abstract: We fabricated a perovskite solar cell that uses a double layer of mesoporous TiO2 and ZrO2 as a scaffold infiltrated with perovskite and does not require a hole-conducting layer. The perovskite was produced by drop-casting a solution of PbI2, methylammonium (MA) iodide, and 5-ammoniumvaleric acid (5-AVA) iodide through a porous carbon film. The 5-AVA templating created mixed-cation perovskite (5-AVA)x(MA)1- xPbI3 crystals with lower defect concentration and better pore filling as well as more complete contact with the TiO2 scaffold, resulting in a longer exciton lifetime and a higher quantum yield for photoinduced charge separation as compared to MAPbI3. The cell achieved a certified power conversion efficiency of 12.8% and was stable for >1000 hours in ambient air under full sunlight.
2,639 citations
TL;DR: It is shown that a pair of perovskite cells connected in series can power the electrochemical breakdown of water into hydrogen and oxygen efficiently, and the combination of the two yields a water-splitting photocurrent density and a solar-to-hydrogen efficiency of 12.3%.
Abstract: Although sunlight-driven water splitting is a promising route to sustainable hydrogen fuel production, widespread implementation is hampered by the expense of the necessary photovoltaic and photoelectrochemical apparatus. Here, we describe a highly efficient and low-cost water-splitting cell combining a state-of-the-art solution-processed perovskite tandem solar cell and a bifunctional Earth-abundant catalyst. The catalyst electrode, a NiFe layered double hydroxide, exhibits high activity toward both the oxygen and hydrogen evolution reactions in alkaline electrolyte. The combination of the two yields a water-splitting photocurrent density of around 10 milliamperes per square centimeter, corresponding to a solar-to-hydrogen efficiency of 12.3%. Currently, the perovskite instability limits the cell lifetime.
2,140 citations
TL;DR: The rise of metal halide perovskites as light harvesters has stunned the photovoltaic community and questions on the control of the performance of perovSKite solar cells and on its characterization are being addressed.
Abstract: The rise of metal halide perovskites as light harvesters has stunned the photovoltaic community. As the efficiency race continues, questions on the control of the performance of perovskite solar cells and on its characterization are being addressed.
1,839 citations
TL;DR: In this article, a two-step spin-coating procedure was used to control the size of the cuboid cuboid of CH(3)NH(3)-PbI(3), achieving an average efficiency exceeding 16% and best efficiency of 17%.
Abstract: Perovskite solar cells with submicrometre-thick CH(3)NH(3)PbI(3) or CH(3)NH(3)PbI(3-x)Cl(x) active layers show a power conversion efficiency as high as 15%. However, compared to the best-performing device, the average efficiency was as low as 12%, with a large standard deviation (s.d.). Here, we report perovskite solar cells with an average efficiency exceeding 16% and best efficiency of 17%. This was enabled by the growth of CH(3)NH(3)PbI(3) cuboids with a controlled size via a two-step spin-coating procedure. Spin-coating of a solution of CH(3)NH(3)I with different concentrations follows the spin-coating of PbI(2), and the cuboid size of CH(3)NH(3)PbI(3) is found to strongly depend on the concentration of CH(3)NH(3)I. Light-harvesting efficiency and charge-carrier extraction are significantly affected by the cuboid size. Under simulated one-sun illumination, average efficiencies of 16.4% (s.d. ± 0.35), 16.3% (s.d. ± 0.44) and 13.5% (s.d. ± 0.34) are obtained from solutions of CH(3)NH(3)I with concentrations of 0.038 M, 0.050 M and 0.063 M, respectively. By controlling the size of the cuboids of CH(3)NH(3)PbI(3) during their growth, we achieved the best efficiency of 17.01% with a photocurrent density of 21.64 mA cm(-2), open-circuit photovoltage of 1.056 V and fill factor of 0.741.
1,570 citations
TL;DR: This work shows that the goal of extending the optical-absorption onset of perovskite-based photovoltaics further into the red to enhance solar-light harvesting can be reached by using a mixture of formamidinium and methylammonium cations, which leads to an enhanced short-circuit current and thus superior devices to those based on only CH3 NH3 (+).
Abstract: Hybrid organic–inorganic lead halide perovskite APbX3 pigments, such as methylammonium lead iodide, have recently emerged as excellent light harvesters in solid-state mesoscopic solar cells. An important target for the further improvement of the performance of perovskite-based photovoltaics is to extend their optical-absorption onset further into the red to enhance solar-light harvesting. Herein, we show that this goal can be reached by using a mixture of formamidinium (HN=CHNH3+, FA) and methylammonium (CH3NH3+, MA) cations in the A position of the APbI3 perovskite structure. This combination leads to an enhanced short-circuit current and thus superior devices to those based on only CH3NH3+. This concept has not been applied previously in perovskite-based solar cells. It shows great potential as a versatile tool to tune the structural, electrical, and optoelectronic properties of the light-harvesting materials.
1,152 citations
TL;DR: A fully first-principles investigation on APbI3 perovskites with A = Cs(+), MA, and FA shows evidence that the tetragonal-to-quasi cubic structural evolution observed when moving from MA to FA is due to the interplay of size effects and enhanced hydrogen bonding between the FA cations and the inorganic matrix altering the covalent/ionic character of Pb-I bonds.
Abstract: Organohalide lead perovskites have revolutionized the scenario of emerging photovoltaic technologies. The prototype MAPbI3 perovskite (MA = CH3NH3+) has dominated the field, despite only harvesting photons above 750 nm (∼1.6 eV). Intensive research efforts are being devoted to find new perovskites with red-shifted absorption onset, along with good charge transport properties. Recently, a new perovskite based on the formamidinium cation ((NH2)2CH+ = FA) has shown potentially superior properties in terms of band gap and charge transport compared to MAPbI3. The results have been interpreted in terms of the cation size, with the larger FA cation expectedly delivering reduced band-gaps in Pb-based perovskites. To provide a full understanding of the interplay among size, structure, and organic/inorganic interactions in determining the properties of APbI3 perovskites, in view of designing new materials and fully exploiting them for solar cells applications, we report a fully first-principles investigation on APb...
971 citations
TL;DR: The role of the temperature used in the annealing process required to convert the as deposited solution into the perovskite material is investigated in this paper, where it is found that the conversion requires sufficiently high temperatures to ensure the vaporization of solvent and the crystallization of the material.
Abstract: Organic-inorganic hybrid perovskites have attracted attention as successful light harvesting materials for mesoscopic solid-state solar cells and led to record breaking efficiencies. The photovoltaic performance of these devices is greatly dependent on the film morphology, which in turn is dependent on the deposition techniques and subsequent treatments employed. In this work the perovskite film is deposited by spin-coating a precursor solution of PbCl2 and CH3NH3I (1 to 3 molar ratio) in dimethylformamide. Here, the role of the temperature used in the annealing process required to convert the as deposited solution into the perovskite material is investigated. It is found that the conversion requires sufficiently high temperatures to ensure the vaporization of solvent and the crystallization of the perovskite material. However, increasing the annealing temperature too high leads to the additional formation of PbI2, which is detrimental to the photovoltaic performance. Furthermore, the effect of the annealing temperature on the film formation, morphology, and composition is examined and correlated with the photovoltaic performance and device working mechanisms.
864 citations
TL;DR: Perovskites are of great interest in photovoltaic devices due to their panchromatic light absorption and ambipolar behavior and it will not be unrealistic to speculate that one day perovskite-based solar cells can match the capability and capacity of existing technologies.
Abstract: It is not often that the scientific community is blessed with a material, which brings enormous hopes and receives special attention. When it does, it expands at a rapid pace and its every dimension creates curiosity. One such material is perovskite, which has triggered the development of new device architectures in energy conversion. Perovskites are of great interest in photovoltaic devices due to their panchromatic light absorption and ambipolar behavior. Power conversion efficiencies have been doubled in less than a year and over 15% is being now measured in labs. Every digit increment in efficiency is being celebrated widely in the scientific community and is being discussed in industry. Here we provide a summary on the use of perovskite for inexpensive solar cells fabrication. It will not be unrealistic to speculate that one day perovskite-based solar cells can match the capability and capacity of existing technologies.
861 citations
TL;DR: For long-term stability and practical applications, electrolytes based on the iodine/triiodine couple also suffer from two other disadvantages: the corrosive effect toward the metal electrodes, and the partial absorption of the visible light by triiodine anions.
Abstract: Among the several approaches for harnessing solar energy and converting it into electricity, dye-sensitized solar cells (DSSC) represent one of the most promising methods for future large-scale power production from renewable energy sources. In these cells, the sensitizer is one of the key components harvesting solar radiation and converting it into electric current. The electrochemical, photophysical, and ground and excited state properties of the sensitizer play an important role for charge transfer dynamics at the semiconductor interface. Moreover, for long-term stability and practical applications, electrolytes based on the iodine/triiodine couple also suffer from two other disadvantages: the corrosive effect toward the metal electrodes, and the partial absorption of the visible light by triiodine anions. These issues hence constitute one of the reasons that have encouraged the development of alternative iodine-free redox couples in liquid electrolytes for DSSCs.
TL;DR: This work demonstrates the application of an effective and cheap inorganic p-type hole-transporting material, copper thiocyanate, on lead halide perovskite-based devices and opens the door for integration of a class of abundant and inexpensive material for photovoltaic application.
Abstract: Organo-lead halide perovskites have attracted much attention for solar cell applications due to their unique optical and electrical properties With either low-temperature solution processing or vacuum evaporation, the overall conversion efficiencies of perovskite solar cells with organic hole-transporting material were quickly improved to over 15% during the last 2 years However, the organic hole-transporting materials used are normally quite expensive due to complicated synthetic procedure or high-purity requirement Here, we demonstrate the application of an effective and cheap inorganic p-type hole-transporting material, copper thiocyanate, on lead halide perovskite-based devices With low-temperature solution-process deposition method, a power conversion efficiency of 124% was achieved under full sun illumination This work represents a well-defined cell configuration with optimized perovskite morphology by two times of lead iodide deposition, and opens the door for integration of a class of abundant and inexpensive material for photovoltaic application
TL;DR: The features in the IS responses that are attributed to the ionic and electronic transport properties of the perovskite material and manifest as a slow response at low frequency and an additional RC element at intermediate frequency are explored.
Abstract: Mesoscopic solid-state solar cells based on the inorganic–organic hybrid perovskite CH3NH3PbI3 in conjunction with the amorphous organic semiconductor spiro-MeOTAD as a hole transport material (HTM) are investigated using impedance spectroscopy (IS). A model to interpret the frequency response of these devices is established by expanding and elaborating on the existing models used for the liquid and solid-state dye-sensitized solar cells. Furthermore, the influence of changing the additive concentrations of tert-butylpyridine and LiTFSI in the HTM and varying the HTM overlayer thickness on top of the sub-micrometer thick TiO2 on the extracted IS parameters is investigated. The internal electrical processes of such devices are studied and correlated with the overall device performance. In particular, the features in the IS responses that are attributed to the ionic and electronic transport properties of the perovskite material and manifest as a slow response at low frequency and an additional RC element at...
TL;DR: In this article, a detailed understanding of why perovskite solar cells are so efficient is provided, and the authors use femtosecond laser spectroscopy and microwave photoconductivity measurements to reveal important insights into the photoinduced charge transfer processes and dynamics of such cells.
Abstract: Perovskite solar cells are currently generating great interest in the photovoltaics community, but a detailed understanding of why they are so efficient is lacking. Femtosecond laser spectroscopy and microwave photoconductivity measurements now reveal important insights into the photoinduced charge transfer processes and dynamics of such cells.
TL;DR: In this article, the thermal properties of CH3NH3PbX3 (X = I or Cl) perovskite using thermogravimetric analysis were examined.
Abstract: Recently organic–inorganic hybrid perovskites have attracted attention as light harvesting materials in mesoscopic cells. While a considerable number of deposition and formation methods have been reported for the perovskite crystalline material, most involve an annealing step. As such, the thermal behavior of this material and its individual components is of crucial interest. Here, we examine the thermal properties of the CH3NH3PbX3 (X = I or Cl) perovskite using thermogravimetric analysis. The role of the precursors is exposed, and the effect of the formation of excess organic species is investigated. The sublimation behavior of the organic component is intensively scrutinized. Furthermore, differential scanning calorimetry is employed to probe the crystal phase structure, revealing subtle differences depending on the deposition method.
TL;DR: A simple and scalable technique for the deposition of amorphous molybdenum sulphide films as hydrogen evolution catalyst onto protected copper(I) oxide films, which demonstrates the potential of earth-abundant light-harvesting material and catalysts for solar hydrogen production.
Abstract: Photoelectrochemical water splitting may be used to produce hydrogen using abundant solar energy. Here, the authors fabricate layered films of amorphous molybdenum sulphide on copper(I) oxide and demonstrate the catalytic activity and enhanced stability of these devices made from earth-abundant materials.
TL;DR: The importance of introducing the phenyl group as a spacer between the BTD and the zinc porphyrin in achieving high power-conversion efficiencies is shown.
Abstract: Porphyrins have drawn much attention as sensitizers owing to the large absorption coefficients of their Soret and Q bands in the visible region. In a donor and acceptor zinc porphyrin we applied a new strategy of introducing 2,1,3-benzothiadiazole (BTD) as a pi-conjugated linker between the anchoring group and the porphyrin chromophore to broaden the absorption spectra to fill the valley between the Soret and Q bands. With this novel approach, we observed 12.75% power-conversion efficiency under simulated one-sun illumination (AM1.5G, 100 mW cm(-2)). In this study, we showed the importance of introducing the phenyl group as a spacer between the BTD and the zinc porphyrin in achieving high power-conversion efficiencies. Time-resolved fluorescence, transient-photocurrent-decay, and transient-photovoltage-decay measurements were employed to determine the electron-injection dynamics and the lifetime of the photogenerated charge carriers.
TL;DR: Two new molecularly engineered push-pull dyes, i.e., YA421 and YA422, based on substituted quinoxaline as a π-conjugating linker and bulky-indoline moiety as donor are reported, compared with reported IQ4 dye.
Abstract: We report two new molecularly engineered push–pull dyes, i.e., YA421 and YA422, based on substituted quinoxaline as a π-conjugating linker and bulky-indoline moiety as donor and compared with reported IQ4 dye. Benefitting from increased steric hindrance with the introduction of bis(2,4-dihexyloxy)benzene substitution on the quinoxaline, the electron recombination between redox electrolyte and the TiO2 surface is reduced, especially in redox electrolyte employing Co(II/III) complexes as redox shuttles. It was found that the open circuit photovoltages of IQ4, YA421, and YA422 devices with cobalt-based electrolyte are higher than those with iodide/triiodide electrolyte by 34, 62, and 135 mV, respectively. Moreover, the cells employing graphene nanoplatelets on top of gold spattered film as a counter electrode (CE) show lower charge-transfer resistance compared to platinum as a CE. Consequently, YA422 devices deliver the best power conversion efficiency due to higher fill factor, reaching 10.65% at AM 1.5 sim...
TL;DR: Low-temperature (70 °C) solution processing of TiO2/CH3NH3PbI3 based solar cells is demonstrated, resulting in impressive power conversion efficiency (PCE) of 13.7%.
Abstract: We demonstrate low-temperature (70 °C) solution processing of TiO2/CH3NH3PbI3 based solar cells, resulting in impressive power conversion efficiency (PCE) of 13.7%. Along with the high efficiency, a strikingly high open circuit potential (VOC) of 1110 mV was realized using this low-temperature chemical bath deposition approach. To the best of our knowledge, this is so far the highest VOC value for solution-processed TiO2/CH3NH3PbI3 solar cells. We deposited a nanocrystalline TiO2 (rutile) hole-blocking layer on a fluorine-doped tin oxide (FTO) conducting glass substrate via hydrolysis of TiCl4 at 70 °C, forming the electron selective contact with the photoactive CH3NH3PbI3 film. We find that the nanocrystalline rutile TiO2 achieves a much better performance than a planar TiO2 (anatase) film prepared by high-temperature spin coating of TiCl4, which produces a much lower PCE of 3.7%. We attribute this to the formation of an intimate junction of large interfacial area between the nanocrystalline rutile TiO2 ...
TL;DR: This is the first heterocycle-containing material achieving >10 % efficiency in such devices, and has great potential to replace the expensive spiro-OMeTAD given its much simpler and cheaper synthesis.
Abstract: We report a novel electron-rich molecule based on 3,4-ethylenedioxythiophene (H101). When used as the hole-transporting layer in a perovskite-based solar cell, the power-conversion efficiency reached 13.8% under AM 1.5G solar simulation. This result is comparable with that obtained using the well-known hole transporting material 2,2,7,7-tetrakis(N,N-di-p-methoxyphenylamine)-9,9-spirobifluorene (spiro-OMeTAD). This is the first heterocycle-containing material achieving >10% efficiency in such devices, and has great potential to replace the expensive spiro-OMeTAD given its much simpler and cheaper synthesis.
TL;DR: Three complementary techniques are employed to address the kinetic competition between electron-hole recombination and water oxidation for one of the most widely studied photoanode systems: nanostructured hematite thin films, and for the first time, quantitative agreement is shown between all three techniques.
Abstract: The kinetic competition between electron–hole recombination and water oxidation is a key consideration for the development of efficient photoanodes for solar driven water splitting. In this study, we employed three complementary techniques, transient absorption spectroscopy (TAS), transient photocurrent spectroscopy (TPC), and electrochemical impedance spectroscopy (EIS), to address this issue for one of the most widely studied photoanode systems: nanostructured hematite thin films. For the first time, we show a quantitative agreement between all three techniques. In particular, all three methods show the presence of a recombination process on the 10 ms to 1 s time scale, with the time scale and yield of this loss process being dependent upon applied bias. From comparison of data between these techniques, we are able to assign this recombination phase to recombination of bulk hematite electrons with long-lived holes accumulated at the semiconductor/electrolyte interface. The data from all three techniques...
TL;DR: This work attempts to make a one-to-one comparison of the photovoltaic performance and the electron transfer dynamics involved in DSCs, with ZnO and TiO2 as photoanodes, and reveals that at an optimal thickness ZNO exhibits photovvoltaic performances similar toTiO2, but the internal electron transfer properties differ.
Abstract: Mesoporous TiO2 nanoparticle films are used as photoanodes for high-efficiency dye-sensitized solar cells (DSCs). In spite of excellent photovoltaic power conversion efficiencies (PCEs) displayed by titanium dioxide nanoparticle structures, the transport rate of electrons is known to be low due to low electron mobility. So the alternate oxides, including ZnO, that possesses high electron mobility are being investigated as potential candidates for photoanodes. However, the PCE with ZnO is still lower than with TiO2, and this is typically attributed to the low internal surface area. In this work, we attempt to make a one-to-one comparison of the photovoltaic performance and the electron transfer dynamics involved in DSCs, with ZnO and TiO2 as photoanodes. Previously such comparative investigations were hampered due to the morphological differences (internal surface area, pore diameter, porosity) that exist between zinc oxide and titanium dioxide films. We circumvent this issue by depositing different thickn...
TL;DR: Kelvin probe force microscopy is used to study the real-space cross-sectional distribution of the internal potential within high efficiency mesoscopic methylammonium lead tri-iodide solar cells and shows that the electric field is homogeneous through these devices, similar to that of a p-i-n type junction.
Abstract: Perovskite-sensitized solar cells have reached power conversion efficiencies comparable to commercially available solar cells used for example in solar farms. In contrast to silicon solar cells, perovskite-sensitized solar cells can be made by solution processes from inexpensive materials. The power conversion efficiency of these cells depends substantially on the charge transfer at interfaces. Here we use Kelvin probe force microscopy to study the real-space cross-sectional distribution of the internal potential within high efficiency mesoscopic methylammonium lead tri-iodide solar cells. We show that the electric field is homogeneous through these devices, similar to that of a p-i-n type junction. On illumination under short-circuit conditions, holes accumulate in front of the hole-transport layer as a consequence of unbalanced charge transport in the device. After light illumination, we find that trapped charges remain inside the active device layers. Removing these traps and the unbalanced charge injection could enable further improvements in performance of perovskite-sensitized solar cells.
TL;DR: In this paper, the contribution of each layer is analyzed by means of electrochemical impedance spectroscopy, with the aim of obtaining a general understanding of surface and interface modifications and their influence on the hematite photoanode performance.
Abstract: Recent research on photoanodes for photoelectrochemical water splitting has introduced the concept of under- and overlayers for the activation of ultrathin hematite films. Their effects on the photocatalytic behavior were clearly shown; however, the mechanism is thus far not fully understood. Herein, the contribution of each layer is analyzed by means of electrochemical impedance spectroscopy, with the aim of obtaining a general understanding of surface and interface modifications and their influence on the hematite photoanode performance. This study shows that doping of the hematite from the underlayer and surface passivation from annealing treatments and an overlayer are key parameters to consider for the design of more efficient iron oxide electrodes. Understanding the contribution of these layers, a new design for ultrathin hematite films employing a combination of a gallium oxide overlayer with thin niobium oxide and silicon oxide underlayers is shown to achieve a photocurrent onset potential for the photoelectrochemical oxidation of water more negative than 750 mV versus the reversible hydrogen electrode (RHE) at pH 13.6, utilizing Co-Pi as a water oxidation catalyst. It is demonstrated that multilayer hematite thin film photoanodes are a strategy to reduce the overpotential for this material, thereby facilitating more efficient tandem cells.
TL;DR: A low band gap quinolizino acridine based molecule was designed and synthesized as new hole transporting material for organic-inorganic hybrid lead halide perovskite solar cells and showed an effective hole mobility in the same range of the state-of-the-art spiro-MeOTAD and an appropriate oxidation potential vs the vacuum level.
Abstract: A low band gap quinolizino acridine based molecule was designed and synthesized as new hole transporting material for organic-inorganic hybrid lead halide perovskite solar cells. The functionalized quinolizino acridine compound showed an effective hole mobility in the same range of the state-of-the-art spiro-MeOTAD and an appropriate oxidation potential of 5.23 eV vs the vacuum level. The device based on this new hole transporting material achieved high power conversion efficiency of 12.8% under the illumination of 98.8 mW cm(-2), which was better than the well-known spiro-MeOTAD under the same conditions. Moreover, this molecule could work alone without any additives, thus making it to be a promising candidate for solid-state photovoltaic application.
TL;DR: Transient absorption spectroscopy on subpicosecond to second time scales is used to investigate photogenerated charge carrier recombination in Si-doped nanostructured hematite (α-Fe2O3) photoanodes as a function of applied bias.
Abstract: Transient absorption spectroscopy on subpicosecond to second time scales is used to investigate photogenerated charge carrier recombination in Si-doped nanostructured hematite (α-Fe2O3) photoanodes as a function of applied bias. For unbiased hematite, this recombination exhibits a 50% decay time of ∼6 ps, ∼103 times faster than that of TiO2 under comparable conditions. Anodic bias significantly retards hematite recombination dynamics, and causes the appearance of electron trapping on ps−μs time scales. These ultrafast recombination dynamics, their retardation by applied bias, and the associated electron trapping are discussed in terms of their implications for efficient water oxidation.
TL;DR: It is shown for the first time that amorphous molybdenum sulfide is a highly active hydrogen evolution catalyst in basic medium and photoelectrochemical hydrogen production in alkaline solutions is reported, which is more favorable than acidic solutions for the complementary oxygen evolution half-reaction.
Abstract: The splitting of water into hydrogen and oxygen molecules using sunlight is an attractive method for solar energy storage. Until now, photoelectrochemical hydrogen evolution is mostly studied in acidic solutions, in which the hydrogen evolution is more facile than in alkaline solutions. Herein, we report photoelectrochemical hydrogen production in alkaline solutions, which are more favorable than acidic solutions for the complementary oxygen evolution half-reaction. We show for the first time that amorphous molybdenum sulfide is a highly active hydrogen evolution catalyst in basic medium. The amorphous molybdenum sulfide catalyst and a Ni-Mo catalyst are then deposited on surface-protected cuprous oxide photocathodes to catalyze sunlight-driven hydrogen production in 1M KOH. The photocathodes give photocurrents of -6.3mAcm(-2) at the reversible hydrogen evolution potential, the highest yet reported for a metal oxide photocathode using an earth-abundant hydrogen evolution reaction catalyst.
TL;DR: In this paper, two types of pinholes in the blocking layers are classified, and their effective area is quantified, and frequency-independent Mott-Schottky plots are fitted from electrochemical impedance spectroscopy.
Abstract: Thin compact layers of TiO2 are grown by thermal oxidation of Ti, by spray pyrolysis, by electrochemical deposition, and by atomic layer deposition. These layers are used in dye-sensitized solar cells to prevent recombination of electrons from the substrate (FTO or Ti) with the hole-conducting medium at this interface. The quality of blocking is evaluated electrochemically by methylviologen, ferro/ferricyanide, and spiro-OMeTAD as the model redox probes. Two types of pinholes in the blocking layers are classified, and their effective area is quantified. Frequency-independent Mott–Schottky plots are fitted from electrochemical impedance spectroscopy. Certain films of the thicknesses of several nanometers allow distinguishing the depletion layer formation both in the TiO2 film and in the FTO substrate underneath the titania film. The excellent blocking function of thermally oxidized Ti, electrodeposited film (60 nm), and atomic-layer-deposited films (>6 nm) is documented by the relative pinhole area of less...
TL;DR: Despite the presence of chloride ions in the reaction mixture, scanning transmission electron microscopy- energy dispersive spectroscopy (STEM-EDS) reveals that the CH3NH3PbI3 perovskites formed are chloride-free.
Abstract: As the photovoltaic performance of a device is strongly influenced by the morphology of perovskite, achieving precise control over the crystal formation of organic–inorganic halide perovskites synthesized in the ambience of chloride ions has garnered much attention. Although the resulting morphology dictates the performance of the device considerably, the understanding of the role of chloride ions has been scant. To unravel this mystery, we investigated three different organic–inorganic halide perovskite materials grown from the chloride-containing precursors under different but optimized conditions. Despite the presence of chloride ions in the reaction mixture, scanning transmission electron microscopy- energy dispersive spectroscopy (STEM-EDS) reveals that the CH3NH3PbI3 perovskites formed are chloride-free. Moreover bright field transmission electron microscopy indicates that chloride ions effect the growth of the CH3NH3PbI3.
TL;DR: In this paper, a perovskite solar cell based on rutile TiO2 film was prepared and its photovoltaic performance was compared to an anataseTiO2-based perovsite solar cells.
Abstract: A perovskite solar cell based on rutile TiO2 film was prepared and its photovoltaic performance was compared to an anatase TiO2-based perovskite solar cell. Rutile TiO2 nanoparticles with aspect ratio of 0.2 (20 nm wide and 100 nm long) were prepared by hydrolysis of TiCl4 at ambient temperature. Anatase TiO2 nanoparticles with diameter of about 50 nm were hydrothermally synthesized. The annealed rutile film showed porosity of 60.6%, while lower porosity of 49.1% was detected in the anatase TiO2 film. CH3NH3PbI3 perovskite was deposited on TiO2 film using either a one-step spin coating or two-step dipping method. 2,2′,7,7′-Tetrakis(N,N-p-dimethoxy-phenylamino)-9,9′-spirobifluorene (spiro-MeOTAD) was used as a hole transporting material. One-step deposition led to average power conversion efficiency (PCE) of 8.19% from the rutile-perovskite solar cells and 7.23% from the anatase-perovskite solar cells, while two-step deposition resulted in higher average PCE of 13.75% for the former device and 13.99% for the latter one. Regardless of the deposition methodologies, the rutile–perovskite solar cell showed generally higher Jsc and lower Voc. Slower electron transport and longer electron lifetime were observed for the rutile-based perovskite solar cell than for the anatase-based one. Although the same perovskite material was used for both rutile and anatase TiO2, the difference in electronic behavior indicates that photo-excited electrons are in part injected to TiO2 and the extent of electron injection can be influenced by the crystal phase of TiO2. Despite longer electron lifetime, the slightly lower voltage of the rutile-based device might be due to the fact that the amount of injected electrons was relatively larger for rutile than anatase, leading to a lower Fermi energy level at equilibrium between TiO2 and perovskite. Using a 260 nm-thick rutile TiO2 film, the highest PCE of 14.46% was achieved by depositing CH3NH3PbI3 using a two-step method, in which photocurrent density of 20.02 mA cm−2, open-circuit voltage of 1.022 V and fill factor of 0.71 were demonstrated.