Manipulating the Crystallization of Tin Halide Perovskites for Efficient Moisture-to-Electricity Conversion.

Manipulating the crystallization of perovskite in thin films is essential for the fabrication of any thin-film-based devices. Fabricating tin-based perovskite films from solution poses difficulties because tin tends to crystallize faster than the commonly used lead perovskite. To achieve optimal device performance in solar cells, the preferred method involves depositing tin perovskite under inert conditions using dimethyl sulfoxide (DMSO), which effectively retards the formation of the tin-bromine network, which is crucial for perovskite assembly. We found that under ambient conditions, a DMSO-based tin perovskite salt solution resulted in the formation of a two-phase system, SnBr4(DMSO)2 and MABr, whereas a dimethylformamide-based solution resulted in the formation of vacancy-ordered double perovskite MA2SnBr6. Humidity is known to solvate MABr to form the solvated ions, and so we used the two-phase system for the application in moisture to electricity conversion. The importance of the presence of the scaffold can be seen with the negligible power output from the vacancy-ordered double perovskite obtained with MA2SnBr6. We have fabricated a device with two-phase system that can generate an open-circuit potential of 520 mV and a short-circuit current density of 30.625 µA/cm2 at 85% RH. Also, the device charges a 10 µF capacitor from 150 mV at 51% RH to 500 mV at 85% RH in 6 s at a rate of 52.5 mV/s. Moreover, the output can be scaled by connecting devices in series and parallel configurations. A 527 nm green LED was powered by connecting five devices in series at 75% RH. This indicates a potential for utilizing these moisture-to-electricity conversion devices in powering low-energy requirement devices.

Self-powered humidity sensors based on zero-dimensional perovskite-like structures with fast response and high stability.

With the rapid development of technology, the development of self-powered sensors has garnered significant attention. The importance of monitoring humidity has grown significantly in various technological contexts, from environmental monitoring to biomedical applications. In this work, we have fabricated a low-cost and self-powered humidity sensor using zero-dimensional perovskite-like structures. Switching tests at different relative humidity levels have shown that the zero-dimensional perovskites have visible coloration at high humidities and discoloration upon reducing the humidity. The humidity sensor was fabricated by spin coating the zero-dimensional perovskites on a patterned fluorine doped tin oxide (FTO) substrate and the sensor not only shows high response values of around 500 mV and few micro amperes of short circuit current densities, but also shows good cycling performance and stability. Also high selectivity to humidity is observed in comparison to different gases and volatile organic compounds. The high selectivity to humidity arises due to the fact that the exclusion of MAI from the MA4PbI6 strucuture does not happen with all the other analytes which has been confirmed from the XRD studies. In addition, due to the low temperature fabrication they can be deposited on flexible substrates and the sensor displayed excellent resistance to bending and durability. Furthermore, the study explored the humidity monitoring capabilities of this sensor, revealing an outstanding response performance to human respiration. This observation suggests that the sensor holds significant potential for practical applications in the monitoring of human health and environmental conditions. This work paves the way for developing organic-inorganic hybrid perovskite materials for self-powered sensing applications.

Exfoliation of Ca3Co4O9 to Two-Dimensional Single-Crystalline Misfit Calcium Cobaltates for Energy Storage Applications.

Layered materials have become indispensable in the development of two-dimensional (2D) systems, offering extensive specific surface area and exceptional electrical, electrochemical, and optical properties critical for diverse applications in energy storage, catalysis, sensing, and optoelectronics. While mono- and biatomic layered materials have demonstrated remarkable characteristics in lower dimensions, the quest for complexity in materials has opened new avenues for tailoring properties to specific requirements. Within this context, misfit-layered compounds (MLCs) stand out as promising candidates. In this study, we present a successful synthesis of few-layered misfit CaCoO2-CoO2 2D nanosheets in bulk quantities from bulk calcium cobalt oxide (CCO-B or CCO). These newly synthesized 2D exfoliated misfit nanosheets demonstrate remarkable 7-fold electrochemical energy storage properties, surpassing their parent bulk CCO, as cathode materials in aqueous Zn-ion batteries. This work addresses the longstanding challenge of exfoliating bulk MLCs to nanostructured, lower dimensional MLCs, opening doors for utilization in advanced energy storage systems and beyond.

Dynamics of interfacial charge transfer between CsPbBr3perovskite nanocrystals and molecular acceptors for photodetection application.

Perovskite nanocrystals (NCs) recently emerged as a suitable candidate for optoelectronic applications because of its simplistic synthesis approach and superior optical properties. For better device performance, the effective absorption of incident photons and the understanding of charge transfer (CT) process are the basic requirements. Herein, we investigate the interfacial charge transfer dynamics of CsPbBr3NCs in the presence of different molecular acceptors; 7,7,8,8-Tetracyanoquinodimethane (TCNQ) and 11,11,12,12 tetracyanonaphtho-2,6-quinodimethane (TCNAQ). The vivid change in CT dynamics at the interfaces of NCs and two different molecular acceptors (TCNQ and TCNAQ) has been observed. The results demonstrate that the ground state complex formation in the presence of TCNQ acts as additional driving force to accelerate the charge transfer between the NCs and molecular acceptor. Moreover, this donor (NCs)-acceptor (TCNQ, TCNAQ) system results in the higher absorption of incident photons. Finally, the photo detector based on CsPbBr3-TCNQ system was fabricated for the first time. The device exhibited a high on-off ratio (104). Furthermore, the CsPbBr3-TCNQ photodetector shows a fast photoresponse times of 180 ms/110 ms (rise/decay time) with a specific detectivity (D*) of 5.2 × 1011Jones. The simple synthesis and outstanding photodetection abilities of this perovskite NCs-molecular acceptor system make them potential candidates for optoelectronic applications.

Lattice Dynamics and Electron-Phonon Coupling in Lead-Free Cs2AgIn1-xBixCl6 Double Perovskite Nanocrystals.

Recently, lead free all-inorganic double perovskites have revolutionized photovoltaic research, showing promising light emitting efficiency and tunability via modification of inherent structural and chemical properties. Here, we report a combined experimental and theoretical study on the variation of carrier-lattice interaction and optoelectronic properties of Cs2AgIn1-xBixCl6 double perovskite nanocrystals with varying alloying concentrations. Our UV-vis study confirms the parity allowed first direct transition for x ≤ 0.25. Using a careful analysis of Raman spectra assisted with first-principles simulations, we assign the possible three types of active modes to intrinsic atomic vibrations; 2 T2g modes (one for translational motion of "Cs" and other for octahedral breathing), 1 Eg and 1 A1g mode for various stretching of Ag-Cl octahedra. Ab-initio simulation reveals dominant carrier-phonon scattering via Fröhlich mechanism near room temperature, with longitudinal optical phonons being effectively activated around 230 K. We observe a noticeable increase in hole mobility (∼4 times) with small Bi alloying, attributed to valence band (VB) maxima acquiring Bi-s orbital characteristics, thus resulting in a dispersive VB. We believe that our results should help to gain a better understanding of the intrinsic electronic and lattice dynamical properties of these compounds and provide a base toward improving the overall performance of double perovskite nanocrystals.

ZnX2 mediated post-synthetic transformation of zero dimensional Cs4PbBr6 nanocrystals for opto-electronic applications.

Herein we demonstrate a facile approach for the synthesis of all inorganic cesium lead halide perovskite nanocrystal composites CsPbX3 (X = Cl, Br, I) with high quantum yield by post-synthetic modulation of zero dimensional Cs4PbBr6 nanocrystals with ZnX2 salts. The transformation of Cs4PbBr6 nanocrystals into CsPbBr3 takes place in two steps, the first step being the surface modification of the Cs4PbBr6 nanocrystals with Zn2+ ions and the second step being extraction of CsBr by the Zn2+ ions resulting in the formation of composite Cs4PbBr6/CsPbBr3 nanocrystals. The transformed composite nanocrystals were found to have a PL QY exceeding 90% and the shape of the nanocrystals also changed from hexagonal to cubic shaped. Owing to the highly ionic nature of the nanocrystals, complete anion exchange could be also realized using ZnI2 salt. In the case of the iodide post-treated samples, nanorods were obtained which exhibited bright red photoluminescence. Photodetectors based on the ZnI2 treated Cs4PbBr6 NCs were fabricated, and the photodetectors exhibited a high on/off ratio with a fast response time. The excellent optoelectronic properties make this treatment versatile for a wide range of functional optoelectronic devices like light emitting diodes and photovoltaic devices.

Interface engineering through electron transport layer modification for high efficiency organic solar cells.

In the present study, we have compared the device performance of poly[4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b;4,5-b']dithiophene-2,6-diyl-alt-(4-(2-ethylhexyl)-3-fluorothieno[3,4-b]thio-phene-)-2-carb-oxylate-2-6-diyl)] (PTB7-Th):phenyl-C71-butyric acid methyl ester (PCBM) organic solar cells (OSCs) in an inverted geometry with ZnO, a bilayer of ZnO and Ba(OH)2 [ZnO/Ba(OH)2] and a nanocomposite of ZnO and Ba(OH)2 [ZnO:Ba(OH)2] as electron transport layers (ETLs). Our study reveals that the performance of the devices with the ZnO/Ba(OH)2 and ZnO:Ba(OH)2 nanocomposite as ETL supersedes that of devices with only ZnO as ETL. The plausible reasons for the improved performance of these devices are identified using morphological studies, contact angle measurements, X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS) and photo-electrochemical impedance spectroscopy (EIS) measurements. It is observed that films of ZnO/Ba(OH)2 and ZnO:Ba(OH)2 nanocomposites have a low work function and are slightly more smooth and hydrophobic than ZnO films. This might have suppressed the charge recombination and thereby improved the charge collection as has been confirmed by EIS measurements.

Molecular Design Principles for Near-Infrared Absorbing and Emitting Indolizine Dyes.

Desirable components for dye-sensitzed solar cell (DSC) sensitizers and fluorescent imaging dyes include strong donating building blocks coupled with well-balanced acceptor functionalities for absorption beyond the visible range. We have evaluated the effects of increasing acceptor strengths and incorporation of dye morphology controlling groups on molar absorptivity and absorption breadth with indolizine donor-based dyes. Indolizine-based D-A and D-π-A sensitizers incorporating bis-rhodanine, tricyanofuran (TCF), and cyanoacrylic acid functionalities were analyzed for performance in DSC devices. The TCF derivatives were also evaluated as near-infrared (NIR)-emissive materials with the AH25 emissions extending past 1000 nm.

Unraveling the Dual Character of Sulfur Atoms on Sensitizers in Dye-Sensitized Solar Cells.

Cyclometalated ruthenium sensitizers have been synthesized that differ with number of thiophene units on the auxiliary ligands. Sensitizers possessing four (SA25, SA246, and SA285) or none (SA282) sulfur atoms in their structures, were tested in solar cell devices employing I3-/I- redox mediator, enabling an estimation of the influence of sulfur-iodine/iodide interactions on dye-sensitized solar cell (DSC) performance. Power conversion efficiencies over 6% under simulated AM 1.5 illumination (1 Sun) were achieved with all the sensitizers. Consistently higher open-circuit voltage (VOC) and fill factor (FF) values were measured using SA282. Scrutinizing the DSCs with these dyes by transient absorption spectroscopy (TAS) and electrochemical impedance spectroscopy (EIS) indicate that sulfur atom induced recombination cancels favorable increased regeneration resulting in decreased power conversion efficiencies (PCEs). The data indicate that, to reduce charge recombination channels, the use of sulfur-containing aromatic rings should be avoided if possible in the dye structure when I3-/I- redox mediator is used.

Molecularly Engineered Ru(II) Sensitizers Compatible with Cobalt(II/III) Redox Mediators for Dye-Sensitized Solar Cells.

Thiocyanate-free isoquinazolylpyrazolate Ru(II) complexes were synthesized and applied as sensitizers in dye-sensitized solar cells (DSCs). Unlike most other successful Ru sensitizers, Co-based electrolytes were used, and resulting record efficiency of 9.53% was obtained under simulated sunlight with an intensity of 100 mW cm(-2). Specifically, dye 51-57dht.1 and an electrolyte based on Co(phen)3 led to measurement of a JSC of 13.89 mA cm(-2), VOC of 900 mV, and FF of 0.762 to yield 9.53% efficiency. The improved device performances were achieved by the inclusion of 2-hexylthiophene units onto the isoquinoline subunits, in addition to lengthening the perfluoroalkyl chain on the pyrazolate chelating group, which worked to increase light absorption and decrease recombination effects when using the Co-based electrolyte. As this study shows, Ru(II) sensitizers bearing sterically demanding ligands can allow successful utilization of important Co electrolytes and high performance.

A low recombination rate indolizine sensitizer for dye-sensitized solar cells.

A sensitizer incorporating a heavily alkylated surface blocking indolizine donor exhibits excellent light absorption and diminished recombination rates in dye-sensitized solar cells (DSCs). DSC device efficiencies (up to 8%) using either I(-)/I3(-) or Co(bpy)3(2+/3+) redox shuttles were obtained, which compare favourably to the known excellent surface coverage co-sensitization dye, .

Ligand Engineering for the Efficient Dye-Sensitized Solar Cells with Ruthenium Sensitizers and Cobalt Electrolytes.

Over the past 20 years, ruthenium(II)-based dyes have played a pivotal role in turning dye-sensitized solar cells (DSCs) into a mature technology for the third generation of photovoltaics. However, the classic I3(-)/I(-) redox couple limits the performance and application of this technique. Simply replacing the iodine-based redox couple by new types like cobalt(3+/2+) complexes was not successful because of the poor compatibility between the ruthenium(II) sensitizer and the cobalt redox species. To address this problem and achieve higher power conversion efficiencies (PCEs), we introduce here six new cyclometalated ruthenium(II)-based dyes developed through ligand engineering. We tested DSCs employing these ruthenium(II) complexes and achieved PCEs of up to 9.4% using cobalt(3+/2+)-based electrolytes, which is the record efficiency to date featuring a ruthenium-based dye. In view of the complicated liquid DSC system, the disagreement found between different characterizations enlightens us about the importance of the sensitizer loading on TiO2, which is a subtle but equally important factor in the electronic properties of the sensitizers.

Thieno[3,4-b]pyrazine as an Electron Deficient π-Bridge in D-A-π-A DSCs.

Thieno[3,4-b]pyrazine (TPz) is examined as an electron deficient π-bridge enabling near-infrared (NIR) spectral access in dye-sensitized solar cells (DSCs). Seven dissymmetric dyes for DSCs were synthesized (NL2-NL8) with TPz as the π-bridge utilizing palladium catalyzed C-H activation methodology. C-H bond cross-coupling was uniquely effective among the cross-couplings and electrophilic aromatic substitution reactions analyzed in monofunctionalizing the TPz building block. The TPz-based NL2-NL8 dyes examine the effects of various donors, π-spacers, and acceptors within the donor-π bridge-acceptor (D-π-A) dye design. Proaromatic TPz stabilizes the excited-state oxidation potential (E(s+/s*)) of the dyes by maintaining aromaticity upon excitation of the dye molecule. This leads to concise conjugated systems capable of accessing the NIR region. Through judicious structural modifications, dye band gaps were reduced to 1.48 eV, and power conversion efficiencies (PCEs) reached 7.1% in this first generation TPz-dye series.

An Optically Transparent Iron Nickel Oxide Catalyst for Solar Water Splitting.

Sunlight-driven water splitting to produce hydrogen fuel is an attractive method for renewable energy conversion. Tandem photoelectrochemical water splitting devices utilize two photoabsorbers to harvest the sunlight and drive the water splitting reaction. The absorption of sunlight by electrocatalysts is a severe problem for tandem water splitting devices where light needs to be transmitted through the larger bandgap component to illuminate the smaller bandgap component. Herein, we describe a novel method for the deposition of an optically transparent amorphous iron nickel oxide oxygen evolution electrocatalyst. The catalyst was deposited on both thin film and high-aspect ratio nanostructured hematite photoanodes. The low catalyst loading combined with its high activity at low overpotential results in significant improvement on the onset potential for photoelectrochemical water oxidation. This transparent catalyst further enables the preparation of a stable hematite/perovskite solar cell tandem device, which performs unassisted water splitting.

Near-IR photoresponse of ruthenium dipyrrinate terpyridine sensitizers in the dye-sensitized solar cells.

Coordination of bidentate 5-pentafluorophenyldipyrrinate (pfpdp) or 5-(2-thienyl)dipyrrinate (2-tdp) to a Ru(II) center bearing 2,2':6',2″-terpyridine-4,4',4″-tricarboxylate (tctpy) and a NCS(-) ligand results in strongly light-absorbing complexes [Ru(tctpy)(L)(NCS)] (L = pfpdp or 2-tdp). Anchored to a mesoporous TiO2 electrode, these complexes afford a photoaction spectral response at wavelengths of up to 950 nm, one of the most red-shifted values reported to date for molecular dyes in the dye-sensitized solar cell (DSSC).

Nanocrystalline rutile electron extraction layer enables low-temperature solution processed perovskite photovoltaics with 13.7% efficiency.

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 and the CH3NH3PbI3 layer, which is much more effective in extracting photogenerated electrons than the planar anatase film. Since the complete fabrication of the solar cell is carried out below 100 °C, this method can be easily extended to plastic substrates.

Quantum-confined ZnO nanoshell photoanodes for mesoscopic solar cells.

We present a photoanode for dye-sensitized solar cell (DSC) based on ZnO nanoshell deposited by atomic layer deposition at 150 °C on a mesoporous insulating template. An ultrathin layer of ZnO between 3 and 6 nm, which exhibits quantum confinement effect, is found to be sufficient to transport the photogenerated electrons to the external contacts and exhibits near-unity collection efficiency. A 6 nm ZnO nanoshell on a 2.5 µm mesoporous nanoparticle Al2O3 template yields photovoltaic power conversion efficiency (PCE) of 4.2% in liquid DSC. Perovskite absorber (CH3NH3PbI3) based solid state solar cells made with similar ZnO nanostructures lead to a high PCE of 7%.

Dye-sensitized solar cells with 13% efficiency achieved through the molecular engineering of porphyrin sensitizers.

Dye-sensitized solar cells have gained widespread attention in recent years because of their low production costs, ease of fabrication and tunable optical properties, such as colour and transparency. Here, we report a molecularly engineered porphyrin dye, coded SM315, which features the prototypical structure of a donor-π-bridge-acceptor and both maximizes electrolyte compatibility and improves light-harvesting properties. Linear-response, time-dependent density functional theory was used to investigate the perturbations in the electronic structure that lead to improved light harvesting. Using SM315 with the cobalt(II/III) redox shuttle resulted in dye-sensitized solar cells that exhibit a high open-circuit voltage VOC of 0.91 V, short-circuit current density JSC of 18.1 mA cm(-2), fill factor of 0.78 and a power conversion efficiency of 13%.

Molecular engineering of push-pull porphyrin dyes for highly efficient dye-sensitized solar cells: the role of benzene spacers.

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 π-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.