Fullerene-C60 and PCBM as interlayers in regular and inverted lead-free PSCs using CH3NH3SnI3: an analysis of device performance and defect density dependence by SCAPS-1D.

One of the challenges hindering the commercialization of perovskite solar cells (PSCs) is the presence of toxic metals such as lead in their composition. Simulation studies using SCAPS-1D have already been conducted on lead-free PSCs to find optimized solar cell parameters, having tin as the primary candidate for replacing lead in perovskites. Here, we used fullerene-C60 and its derivative PCBM as interlayers in a lead-free tin-based PSC between the ETL (ZnO) and the perovskite MASI in both regular and inverted configurations of PSCs using SCAPS-1D software. To the best of our knowledge, this is the first simulation study reporting the impact of using fullerene-C60 and PCBM as interlayers in lead-free PSCs. The defect density (Nt) of the perovskite material is varied, allowing us to observe its influence on the power conversion efficiency (PCE). Using an Nt value of 1017 cm-3 without the interlayer, the PCE was 6.90% and 3.72% for regular and inverted devices. Using PCBM as an interlayer improves the efficiency of both simulated PSCs, achieving a maximum PCE of 8.11% and 5.26% for the regular and inverted configurations, respectively. Decreasing the Nt from 1017 cm-3 to 1016 cm-3 caused a significant increase in efficiency, reaching 13.38% (n-i-p) and 10.00% (p-i-n). Finally, using the optimized parameters and an ideal Nt value (1013 cm-3), both PSCs achieved a PCE close to 30%.

In Situ and Operando Characterizations of Metal Halide Perovskite and Solar Cells: Insights from Lab-Sized Devices to Upscaling Processes.

The performance and stability of metal halide perovskite solar cells strongly depend on precursor materials and deposition methods adopted during the perovskite layer preparation. There are often a number of different formation pathways available when preparing perovskite films. Since the precise pathway and intermediary mechanisms affect the resulting properties of the cells, in situ studies have been conducted to unravel the mechanisms involved in the formation and evolution of perovskite phases. These studies contributed to the development of procedures to improve the structural, morphological, and optoelectronic properties of the films and to move beyond spin-coating, with the use of scalable techniques. To explore the performance and degradation of devices, operando studies have been conducted on solar cells subjected to normal operating conditions, or stressed with humidity, high temperatures, and light radiation. This review presents an update of studies conducted in situ using a wide range of structural, imaging, and spectroscopic techniques, involving the formation/degradation of halide perovskites. Operando studies are also addressed, emphasizing the latest degradation results for perovskite solar cells. These works demonstrate the importance of in situ and operando studies to achieve the level of stability required for scale-up and consequent commercial deployment of these cells.

Tiny spots to light the future: advances in synthesis, properties, and application of perovskite nanocrystals in solar cells.

Perovskites are in the hotspot of material science and technology. Outstanding properties have been discovered, fundamental mechanisms of defect formation and degradation elucidated, and applications in a wide variety of optoelectronic devices demonstrated. Advances through adjusting the bulk-perovskite composition, as well as the integration of layered and nanostructured perovskites in the devices, allowed improvement in performance and stability. Recently, efforts have been devoted to investigating the effects of quantum confinement in perovskite nanocrystals (PNCs) aiming to fabricate optoelectronic devices based solely on these nanoparticles. In general, the applications are focused on light-emitting diodes, especially because of the high color purity and high fluorescence quantum yield obtained in PNCs. Likewise, they present important characteristics featured for photovoltaic applications, highlighting the possibility of stabilizing photoactive phases that are unstable in their bulk analog, the fine control of the bandgap through size change, low defect density, and compatibility with large-scale deposition techniques. Despite the progress made in the last years towards the improvement in the performance and stability of PNCs-based solar cells, their efficiency is still much lower than that obtained with bulk perovskite, and discussions about upscaling of this technology are scarce. In light of this, we address in this review recent routes towards efficiency improvement and the up-scaling of PNC solar cells, emphasizing synthesis management and strategies for solar cell fabrication.

Improving the Stability and Efficiency of Perovskite Solar Cells by a Bidentate Anilinium Salt.

We report improvement in the perovskite solar cell efficiency and stability after passivation with an organic molecule decorated with two anilinium cations. We compare this salt with its neutral analog and found that the change in the electron density distribution upon protonation and the presence of the halide anion are key to explaining the better passivation ability of the salt. In addition, we show that the counteranion has a significant impact on the performance of the device.

Double Perovskite Single-Crystal Photoluminescence Quenching and Resurge: The Role of Cu Doping on its Photophysics and Crystal Structure.

Cs2AgBiBr6 is a potential lead-free double perovskite candidate for optoelectronic applications; however, its large and indirect band gap imposes limitations. Here, single crystals of Cs2AgBiBr6 are doped with Cu2+ cations to increase the absorption range from the visible region up to 0.5 eV in the near-infrared region. Inductively coupled plasma spectroscopy confirms the presence of 1.9% of copper in the Cs2AgBiBr6 structure. Structural and optical changes caused by Cu doping were studied by Raman spectroscopy combined with X-ray diffraction, heat capacity measurements, and low-temperature photoluminescence spectroscopy. Along with the 1.9 eV emission typical of the pristine Cs2AgBiBr6 single crystals, we report a novel low-energy emission at 0.9 eV related to deep defects. In the doped crystals, these peaks are quenched, and a new emission band at 1.3 eV is visible. This new emission band appears only above 120 K, showing that thermal energy is necessary to trigger the copper-related emission.

Introduction to celebrating Latin American talent in chemistry.

In celebration of the excellence and breadth of Latin American research achievements across the chemical sciences, we are delighted to present an introduction to the themed collection, Celebrating Latin American talent in chemistry.

In Situ Analysis Reveals the Role of 2D Perovskite in Preventing Thermal-Induced Degradation in 2D/3D Perovskite Interfaces.

Engineering 2D/3D perovskite interfaces is a common route to realizing efficient and stable perovskite solar cells. Whereas 2D perovskite's main function in trap passivation has been identified and is confirmed here, little is known about its 2D/3D interface properties under thermal stress, despite being one of the main factors that induces device instability. In this work, we monitor the response of two typical 2D/3D interfaces under a thermal cycle by in situ X-ray scattering. We reveal that upon heating, the 2D crystalline structure undergoes a dynamical transformation into a mixed 2D/3D phase, keeping the 3D bulk underneath intact. The observed 3D bulk degradation into lead iodide is blocked, revealing the paramount role of 2D perovskite in engineering stable device interfaces.

Revealing the Role of Tin(IV) Halides in the Anisotropic Growth of CsPbX3 Perovskite Nanoplates.

CsPbX3 perovskite nanoplates (PNPLs) were formed in a synthesis driven by SnX4 (X=Cl, Br, I) salts. The role played by these hard Lewis acids in directing PNPL formation is addressed. Sn4+ disturbs the acid-base equilibrium of the system, increasing the protonation rate of oleylamine and inducing anisotropic growth of nanocrystals. Sn4+ cations influence the reaction dynamics owing to complexation with oleylamine molecules. By monitoring the photoluminescence excitation and photoluminescence (PL) spectra of the PNPLs grown at different temperatures, the influence of the thickness on their optical properties is mapped. Time-resolved and spectrally resolved PL for colloidal dispersions with different optical densities reveals that the dependence of the overall PL lifetime on the emission wavelength do not originate from energy transfer between PNPLs but from the contribution of PNPLs with distinct thickness, indicating that thicker PNPLs exhibit longer PL lifetimes.

Progress on Electrolytes Development in Dye-Sensitized Solar Cells.

Dye-sensitized solar cells (DSSCs) have been intensely researched for more than two decades. Electrolyte formulations are one of the bottlenecks to their successful commercialization, since these result in trade-offs between the photovoltaic performance and long-term performance stability. The corrosive nature of the redox shuttles in the electrolytes is an additional limitation for industrial-scale production of DSSCs, especially with low cost metallic electrodes. Numerous electrolyte formulations have been developed and tested in various DSSC configurations to address the aforementioned challenges. Here, we comprehensively review the progress on the development and application of electrolytes for DSSCs. We particularly focus on the improvements that have been made in different types of electrolytes, which result in enhanced photovoltaic performance and long-term device stability of DSSCs. Several recently introduced electrolyte materials are reviewed, and the role of electrolytes in different DSSC device designs is critically assessed. To sum up, we provide an overview of recent trends in research on electrolytes for DSSCs and highlight the advantages and limitations of recently reported novel electrolyte compositions for producing low-cost and industrially scalable solar cell technology.

Three-Dimensional Superlattice of PbS Quantum Dots in Flakes.

In the last two decades, many experiments were conducted in self-organization of nanocrystals into two- and three-dimensional (3D) superlattices and the superlattices were synthesized and characterized by different techniques, revealing their unusual properties. Among all characterization techniques, X-ray diffraction (XRD) is the one that has allowed the confirmation of the 3D superlattice formation due to the presence of sharp and intense diffraction peaks. In this work, we study self-organized superlattices of quantum dots of PbS prepared by dropping a monodispersed colloidal solution on a glass substrate at different temperatures. We showed that the intensity of the low-angle XRD peaks depends strongly on the drying time (substrate temperature). We claim that the peaks are originated from the 3D superlattice. Scanning electron microscopy images show that this 3D superlattice (PbS quantum dots) is formed in flake's shape, parallel to the substrate surface and randomly oriented in the perpendicular planes.

Correction to "Three-Dimensional Superlattice of PbS Quantum Dots in Flakes".

[This corrects the article DOI: 10.1021/acsomega.7b01791.].

Nanocrystalline anatase TiO2/reduced graphene oxide composite films as photoanodes for photoelectrochemical water splitting studies: the role of reduced graphene oxide.

Nanocrystalline TiO2 and reduced graphene oxide (TiO2/RGO) composite films were prepared by combining a sol-gel method with hydrothermal treatment, employing titanium isopropoxide (Ti(O(i)Pr)4) and graphene oxide (GO) as starting materials. Although several reports in the literature have explored the benefits of RGO addition in titania films for photocatalysis and water splitting reactions, the role of RGO in the composite is always described as that of a material that is able to act as an electron acceptor and transport electrons more efficiently. However, in most of these reports, no clear evidence for this "role" is presented, and the main focus is deviated to the improved efficiency and not to the reasons for said efficiency. In this study, we employed several techniques to definitively present our understanding of the role of RGO in titania composite films. The TiO2/RGO composite films were characterized by X ray diffraction, Raman spectroscopy, microscopy and electrochemical techniques. In photoelectrochemical water splitting studies, the TiO2/RGO(0.1%) photoelectrodes showed the highest photocurrent density values (0.20 mA cm(-2) at 1.23 VRHE) compared to other electrodes, with an increase of 78% in relation to pristine TiO2 film (0.11 mA cm(-2) at 1.23 VRHE). The transient absorption spectroscopy (TAS) results indicated increases in the lifetime and yield of both the photogenerated holes and electrons. Interestingly, the TiO2/RGO(0.1%) film exhibited the best charge generation upon excitation, corroborating the photoelectrochemical data. We proposed that in films with lower concentrations (<0.1 wt%), the RGO sheets are electron acceptors, and a decrease in the charge recombination processes is the immediate consequence. Thus, both holes and electrons live longer and contribute more effectively to the photocurrent density.

Efficient dye-sensitized solar cells based on the combination of ZnO nanorods and microflowers.

Well-aligned ZnO nanorod films were grown onto transparent conducting substrates by using an aqueous solution route. The presence of some reflections in the X-ray diffraction pattern of the ZnO films indicates the vertical alignment of the nanorods along the c axis of the wurtzite hexagonal structure. Well-aligned ZnO nanorods were observed by scanning electron microscopy. The presence of top ZnO microflower layers over the ZnO nanorod film was observed for all growth times studied. The ZnO nanorods with ZnO microflower top layers were applied as photoelectrodes in dye-sensitized solar cells. Higher photocurrent densities and photovoltages were observed with longer nanorod growth times. The high performance of the dye-sensitized solar cells might be associated to the combination of ZnO nanorods and microflowers in the same photoelectrode.

Single-wall carbon nanotubes chemically modified with cysteamine and their application in polymer solar cells: influence of the chemical modification on device performance.

In order to improve the dispersion of single-wall carbon nanotubes in a matrix of poly(3-hexylthiophene), this paper reports the modification of single-wall carbon nanotubes with COOH groups followed by reaction with cysteamine that introduced thiol groups along the tubes. The resulting modified single-wall carbon nanotubes were characterized by high resolution transmission electron microscopy, thermogravimetric analysis, X-ray photoelectron spectroscopy and Raman spectroscopy. The modified carbon nanotubes were applied, in combination with poly(3-hexylthiophene), in a bulk heterojunction solar cell. After passing through a post-treatment process to obtain debundied modified single-wall carbon nanotubes, solar cells with improved performance were obtained. After the treatment sequence, both the open circuit voltage and short-circuit current increased in comparison to the non-treated modified single-wall carbon nanotubes polymer solar cells.

Synthesis and characterization of ZnO and ZnO:Ga films and their application in dye-sensitized solar cells.

Highly crystalline ZnO and Ga-modified zinc oxide (ZnO:Ga) nanoparticles containing 1, 3 and 5 atom% of Ga3+ were prepared by precipitation method at low temperature. The films were characterized by XRD, BET, XPS and SEM. No evidence of zinc gallate formation (ZnGa2O4), even in the samples containing 5 atom% of gallium, was detected by XRD. XPS data revealed that Ga is present into the ZnO matrix as Ga3+, according to the characteristic binding energies. The particle size decreased as the gallium level was increased as observed by SEM, which might be related to a faster hydrolysis reaction rate. The smaller particle size provided films with higher porosity and surface area, enabling a higher dye loading. When these films were applied to dye-sensitized solar cells (DSSCs) as photoelectrodes, the device based on ZnO:Ga 5 atom% presented an overall conversion efficiency of 6% (at 10 mW cm(-2)), a three-fold increase compared to the ZnO-based DSSCs under the same conditions. To our knowledge, this is one of the highest efficiencies reported so far for ZnO-based DSSCs. Transient absorption (TAS) study of the photoinduced dynamics of dye-sensitized ZnO:Ga films showed that the higher the gallium content, the higher the amount of dye cation formed, while no significant change on the recombination dynamics was observed. The study indicates that Ga-modification of nanocrystalline ZnO leads to an improvement of photocurrent and overall efficiency in the corresponding device.

Enhancement of photocurrent generation and open circuit voltage in dye-sensitized solar cells using Li+ trapping species in the gel electrolyte.

The influence of the addition of 12-crown-4 ether in a gel polymer electrolyte based to a PEO copolymer and its application in dye sensitized solar cells were investigated. Introduction of these Li+ trapping species brought beneficial contributions to both V(oc) and J(sc) values, increasing the device's performance.

Conduction and photoelectrochemical properties of monomeric and electropolymerized tetraruthenated porphyrin films.

The influence of the preparation method on the structure, conduction and photoelectrochemical properties of monomeric and polymeric tetraruthenated porphyrin films on ITO glass and nanocrystalline TiO2 has been investigated. The films were characterized by STM, MAC mode SFM, cyclic voltammetry, electrochemical impedance spectroscopy (EIS) and combined electro-/photoelectrochemical techniques. The electronic diffusion coefficient D(e)C(m)2 of the films differed by three to four orders of magnitude depending on the procedure employed for the deposition process. The photoelectrochemical properties were evaluated either: by depositing the films directly on transparent ITO electrodes, under an applied bias potential and presence of O2 as electron acceptor; or by depositing the porphyrin material on nanocrystalline TiO2 in a Grätzel-type cell. In the first case the porphyrin films exhibited a typical p-type semiconductor behavior described by a Schottky junction model, while in the second the films behaved as a sensitizer of an n-type semiconductor. The photoelectrochemical properties of the porphyrin films and their performance as sensitizer in Grätzel-type cells were found to be strongly dependent on the conductivity and packing characteristics of the material. Semi-empirical calculations were performed by modified MM2 and ZINDO/S methods, in order to simulate the packing and electronic structures of the tetraruthenated porphyrin.