Revealing Giant Exciton Fine-Structure Splitting in Two-Dimensional Perovskites Using van der Waals Passivation.

Organic-inorganic layered perovskites are currently some of the most promising 2D van der Waals materials. Low crystal quality usually broadens the exciton line width, obscuring the fine structure of the exciton in conventional photoluminescence experiments. Here, we propose a mechanical approach to reducing the effect of spectral diffusion by means of hBN capping on layered perovskites, revealing the exciton fine structure. We used a stochastic model to link the reduction of the spectral line width with the population of charge fluctuation centers present in the organic spacer. van der Waals forces between both lattices cause the partial clamping of the perovskite organic spacer molecules, and hence the amplitude of the overall spectral diffusion effect is reduced. Our work provides a low-cost solution to the problem of accessing important fine-structure excitonic state information, along with an explanation of the important carrier dynamics present in the organic spacer that affect the quality of the optical emission.

Understanding equivalent circuits in perovskite solar cells. Insights from drift-diffusion simulation.

Perovskite solar cells (PSCs) have reached impressively high efficiencies in a short period of time; however, the optoelectronic properties of halide perovskites are surprisingly complex owing to the coupled ionic-electronic charge carrier dynamics. Electrical impedance spectroscopy (EIS) is a widely used characterization tool to elucidate the mechanisms and kinetics governing the performance of PSCs, as well as of many other semiconductor devices. In general, equivalent circuits are used to evaluate EIS results. Oftentimes these are justified via empirical constructions and the real physical meaning of the elements remains disputed. In this perspective, we use drift-diffusion numerical simulations of typical thin-film, planar PSCs to generate impedance spectra avoiding intrinsic experimental difficulties such as instability and low reproducibility. The ionic and electronic properties of the device, such as ion vacancy density, diffusion coefficients, recombination mechanism, etc., can be changed individually in the simulations, so their effects can be directly observed. We evaluate the resulting EIS spectra by comparing two commonly used equivalent circuits with series and parallel connections respectively, which result in two signals with significantly different time constants. Both circuits can fit the EIS spectra and by extracting the values of the elements of one of the circuits, the values of the elements of the other circuit can be unequivocally obtained. Consequently, both can be used to analyse the EIS of a PSC. However, the physical meaning of each element in each circuit could differ. EIS can produce a broad range of physical information. We analyse the physical interpretation of the elements of each circuit and how to correlate the elements of one circuit with the elements of the other in order to have a direct picture of the physical processes occurring in the device.

Correction: A first-principles study of the stability, electronic structure, and optical properties of halide double perovskite Rb2Sn1-xTexI6 for solar cell applications.

Correction for 'A first-principles study of the stability, electronic structure, and optical properties of halide double perovskite Rb2Sn1-xTexI6 for solar cell applications' by Muhammad Faizan et al., Phys. Chem. Chem. Phys., 2021, 23, 4646-4657, DOI: 10.1039/D0CP05827K.

A first-principles study of the stability, electronic structure, and optical properties of halide double perovskite Rb2Sn1-xTexI6 for solar cell applications.

Owing to their emerging role in solar cell technology, lead halide perovskites have aroused significant research interest in the recent past. However, due to its obvious toxicity, looking for a potential alternative to lead is becoming one of the most important pursuits in present times. We present our work based on density functional theory (DFT) investigating lead free defect perovskites (Rb2Sn1-xTexI6 (0 ≤x≤ 1)). In particular, we explore the crystal structure, thermodynamic stability, electronic structure, and optical properties of Rb2Sn1-xTexI6 (0 ≤x≤ 1) as a function of increasing Te concentration. Our results show that the Sn-Te alloyed perovskites exhibit considerable stability, a suitable band gap, small effective mass, and excellent light absorption. Especially, Rb2Sn0.75Te0.25I6 and Rb2Sn0.50Te0.50I6 have a direct band gap of 1.35 and 1.44 eV, respectively, which is highly favorable for use in a single-junction photovoltaic cell. We hope that our work will arouse the interest of experimental as well as theoretical scientists for synthesizing new materials and/or exploring the Sn-Te mix as a potential substitute for lead in photovoltaic materials.

Quantum dot-sensitized solar cells.

Quantum dot-sensitized solar cells (QDSCs) have emerged as a promising candidate for next-generation solar cells due to the distinct optoelectronic features of quantum dot (QD) light-harvesting materials, such as high light, thermal, and moisture stability, facilely tunable absorption range, high absorption coefficient, multiple exciton generation possibility, and solution processability as well as their facile fabrication and low-cost availability. In recent years, we have witnessed a dramatic boost in the power conversion efficiency (PCE) of QDSCs from 5% to nearly 13%, which is comparable to other kinds of emerging solar cells. Both the exploration of new QD light-harvesting materials and interface engineering have contributed to this fantastically fast improvement. The outstanding development trend of QDSCs indicates their great potential as a promising candidate for next-generation photovoltaic cells. In this review article, we present a comprehensive overview of the development of QDSCs, including: (1) the fundamental principles, (2) a history of the brief evolution of QDSCs, (3) the key materials in QDSCs, (4) recombination control, and (5) stability issues. Finally, some directions that can further promote the development of QDSCs in the future are proposed to help readers grasp the challenges and opportunities for obtaining high-efficiency QDSCs.

Fullerene-Based Materials as Hole-Transporting/Electron-Blocking Layers: Applications in Perovskite Solar Cells.

Here we report for the first time an efficient fullerene-based compound, FU7, able to act as hole-transporting material (HTM) and electron blocking contact. It has been applied on perovskite solar cells (PSCs), obtaining 0.81 times the efficiency of PSCs with the standard HTM, spiro-OMeTAD, with the additional advantage that this performance is reached without any additive introduced in the HTM layer. Moreover, as a proof of concept, we have described for the first time efficient PSCs in which both selective contacts are fullerene derivatives, to obtain unprecedented "fullerene sandwich" PSCs.

Tuning optical/electrical properties of 2D/3D perovskite by the inclusion of aromatic cation.

The employment of bulky aliphatic cations in the manufacture of moisture-stable materials has triggered the development and application of 2D/3D perovskites as sensitizers in moisture-stable solar cells. Although it is true that the moisture stability increases, it is also true that the photovoltaic performance of 2D/3D PVK materials is severely limited owing to quantum and dielectric confinement effects. Accordingly, it is necessary the synthesis and deep optical characterization of materials with an adequate management of dielectric contrast between the layers. Here, we demonstrate the successful tuning of dielectric confinement by the inclusion of a conjugated molecule, as a bulky cation, in the fabrication of the 2D/3D PVK material (C6H5NH3)2(CH3NH3)n-1PbnI3n+1, where n = 3 or 5. The absence of excitonic states related to n ≥ 1 at room temperature, as well as the very low concentration of excitons after 1 ps of excitation of samples in which n ≥ 3, provide strong evidence of an excellent ability to dissociate excitons into free charge carriers. As consequence films with low n, presenting higher stability than standard 3D perovskites, improved significantly their performance, showing one of the highest short circuit current density (Jsc ≈ 13.8) obtained to date for perovskite materials within the 2D limit (n < 10).

Transformation of PbI2, PbBr2 and PbCl2 salts into MAPbBr3 perovskite by halide exchange as an effective method for recombination reduction.

Halide perovskite derivatives present unprecedented physical phenomena among those materials which are suitable for photovoltaics, such as a fast ion diffusion coefficient. In this paper it is reported how the benefits of this property can be used during the growth of halide perovskites in order to control the morphological and optoelectronic properties of the final thin film. Using a large enough halide reservoir, the nature of the halides present in the final perovskite layer can be exchanged and this depends on the initial salt used in the two-step deposition method. In particular, the preparation of a methylammonium lead bromide (MAPbBr3) thin film is reported, using a two-step method based on the transformation of lead(ii) iodide (PbI2), lead(ii) bromide (PbBr2) and lead(ii) chloride (PbCl2) salts into MAPbBr3 perovskite after dipping in a methylammonium bromide (MABr) solution. The films prepared from different salts present different properties in terms of morphology and optoelectronic properties, thus providing significantly different performance when they are used for the preparation of photovoltaic devices. Interestingly, the use of PbI2 and PbCl2 salts reduce the charge recombination and increase the open circuit potential obtained, especially in the former case. However, the highest photocurrent is obtained when PbBr2 is used. For PbI2 and PbCl2 salts no traces of the former salt are observed in the MAPbBr3 layer obtained after 10 minutes of dipping time, however, the presence of PbBr2 has still been detected (using X-ray diffraction) when this salt has been employed.

Boosting power conversion efficiencies of quantum-dot-sensitized solar cells beyond 8% by recombination control.

At present, quantum-dot-sensitized solar cells (QDSCs) still exhibit moderate power conversion efficiency (with record efficiency of 6-7%), limited primarily by charge recombination. Therefore, suppressing recombination processes is a mandatory requirement to boost the performance of QDSCs. Herein, we demonstrate the ability of a novel sequential inorganic ZnS/SiO2 double layer treatment onto the QD-sensitized photoanode for strongly inhibiting interfacial recombination processes in QDSCs while providing improved cell stability. Theoretical modeling and impedance spectroscopy reveal that the combined ZnS/SiO2 treatment reduces interfacial recombination and increases charge collection efficiency when compared with conventional ZnS treatment alone. In line with those results, subpicosecond THz spectroscopy demonstrates that while QD to TiO2 electron-transfer rates and yields are insensitive to inorganic photoanode overcoating, back recombination at the oxide surface is strongly suppressed by subsequent inorganic treatments. By exploiting this approach, CdSe(x)Te(1-x) QDSCs exhibit a certified record efficiency of 8.21% (8.55% for a champion cell), an improvement of 20% over the previous record high efficiency of 6.8%, together with an additional beneficial effect of improved cell stability.

Classification of solar cells according to mechanisms of charge separation and charge collection.

In the last decade, photovoltaics (PV) has experienced an important transformation. Traditional solar cells formed by compact semiconductor layers have been joined by new kinds of cells that are constituted by a complex mixture of organic, inorganic and solid or liquid electrolyte materials, and rely on charge separation at the nanoscale. Recently, metal organic halide perovskites have appeared in the photovoltaic landscape showing large conversion efficiencies, and they may share characteristics of the two former types. In this paper we provide a general description of the photovoltaic mechanisms of the single absorber solar cell types, combining all-inorganic, hybrid and organic cells into a single framework. The operation of the solar cell relies on a number of internal processes that exploit internal charge separation and overall charge collection minimizing recombination. There are two main effects to achieve the required efficiency, first to exploit kinetics at interfaces, favouring the required forward process, and second to take advantage of internal electrical fields caused by a built-in voltage and by the distribution of photogenerated charges. These principles represented by selective contacts, interfaces and the main energy diagram, form a solid base for the discussion of the operation of future types of solar cells. Additional effects based on ferroelectric polarization and ionic drift provide interesting prospects for investigating new PV effects mainly in the perovskite materials.

General working principles of CH3NH3PbX3 perovskite solar cells.

Organometal halide perovskite-based solar cells have recently realized large conversion efficiency over 15% showing great promise for a new large scale cost-competitive photovoltaic technology. Using impedance spectroscopy measurements we are able to separate the physical parameters of carrier transport and recombination in working devices of the two principal morphologies and compositions of perovskite solar cells, viz. compact thin films of CH3NH3PbI(3-x)Clx and CH3NH3PbI3 infiltrated on nanostructured TiO2. The results show nearly identical spectral characteristics indicating a unique photovoltaic operating mechanism that provides long diffusion lengths (1 µm). Carrier conductivity in both devices is closely matched, so that the most significant differences in performance are attributed to recombination rates. These results highlight the central role of the CH3NH3PbX3 semiconductor absorber in carrier collection and provide a new tool for improved optimization of perovskite solar cells. We report for the first time a measurement of the diffusion length in a nanostructured perovskite solar cell.

Low-temperature processed electron collection layers of graphene/TiO2 nanocomposites in thin film perovskite solar cells.

The highest efficiencies in solution-processable perovskite-based solar cells have been achieved using an electron collection layer that requires sintering at 500 °C. This is unfavorable for low-cost production, applications on plastic substrates, and multijunction device architectures. Here we report a low-cost, solution-based deposition procedure utilizing nanocomposites of graphene and TiO2 nanoparticles as the electron collection layers in meso-superstructured perovskite solar cells. The graphene nanoflakes provide superior charge-collection in the nanocomposites, enabling the entire device to be fabricated at temperatures no higher than 150 °C. These solar cells show remarkable photovoltaic performance with a power conversion efficiency up to 15.6%. This work demonstrates that graphene/metal oxide nanocomposites have the potential to contribute significantly toward the development of low-cost solar cells.

High-efficiency "green" quantum dot solar cells.

Semiconductor quantum dots (QDs) are extremely interesting materials for the development of photovoltaic devices, but currently the present the drawback is that the most efficient devices have been prepared with toxic heavy metals of Cd or Pb. Solar cells based on "green" QDs--totally free of Cd or Pb--present a modest efficiency of 2.52%. Herein we achieve effective surface passivation of the ternary CuInS2 (CIS) QDs that provides high photovoltaic quality core/shell CIS/ZnS (CIS-Z) QDs, leading to the development of high-efficiency green QD solar cells that surpass the performance of those based on the toxic cadmium and lead chalcogenides QDs. Using wide absorption range QDs, CIS-Z-based quantum dot sensitized solar cell (QDSC) configuration with high QD loading and with the benefit of the recombination reduction with type-I core/shell structure, we boost the power conversion efficiency of Cd- and Pb-free QDSC to a record of 7.04% (with certified efficiency of 6.66%) under AM 1.5G one sun irradiation. This efficiency is the best performance to date for QDSCs and also demonstrates that it is possible to obtain comparable or even better photovoltaic performance from green CIS QDs to the toxic cadmium and lead chalcogenides QDs.

Charge separation at disordered semiconductor heterojunctions from random walk numerical simulations.

Many recent advances in novel solar cell technologies are based on charge separation in disordered semiconductor heterojunctions. In this work we use the Random Walk Numerical Simulation (RWNS) method to model the dynamics of electrons and holes in two disordered semiconductors in contact. Miller-Abrahams hopping rates and a tunnelling distance-dependent electron-hole annihilation mechanism are used to model transport and recombination, respectively. To test the validity of the model, three numerical "experiments" have been devised: (1) in the absence of constant illumination, charge separation has been quantified by computing surface photovoltage (SPV) transients. (2) By applying a continuous generation of electron-hole pairs, the model can be used to simulate a solar cell under steady-state conditions. This has been exploited to calculate open-circuit voltages and recombination currents for an archetypical bulk heterojunction solar cell (BHJ). (3) The calculations have been extended to nanostructured solar cells with inorganic sensitizers to study, specifically, non-ideality in the recombination rate. The RWNS model in combination with exponential disorder and an activated tunnelling mechanism for transport and recombination is shown to reproduce correctly charge separation parameters in these three "experiments". This provides a theoretical basis to study relevant features of novel solar cell technologies.

Synthesis of Hybrid Tin-Based Perovskite Microcrystals for LED Applications.

Considerable focus on tin-based perovskites lies on substitution to leadhalide perovskites for the fabrication of eco-friendly optoelectronic devices.The major concern related to tin-based perovskite devices are mainly thestability and the efficiency. However, thinking on the final commercializationscope, other considerations such as precursor stability and cost are majorfactors to carry about. In this regard, this work presents a robust and facilesynthesis of 2D A2SnX4 (A = 4-fluorophenethylammonium(4-FPEA); X = I, Br, I/Br) and 3D FASnI3 perovskite microcrystals followinga developed synthesis strategy with low-cost starting materials. In thisdeveloped methodology, acetic acid is used as a solvent, which helps to protectfrom water by making a hydrophobic network over the perovskite surface, andhence provides sufficient ambient and long-term inert atmosphere stability ofthe microcrystals. Further, the microcrystals are recrystallized in thin filmsfor LED application, allowing the fabrication of orange, near-infrared and purered emitting LEDs. The two-step recrystallized devices show better performanceand stability in comparison to the reference devices made by using commercialprecursors. Importantly, the developed synthesis methodology is defined as ageneric method for the preparation of varieties of hybrid tin-based perovskitesmicrocrystals and application in optoelectronic devices.

Tailoring Single-Mode Random Lasing of Tin Halide Perovskites Integrated in a Vertical Cavity.

The development of random lasing (RL) with predictable and controlled properties is an important step to make these cheap optical sources stable and reliable. However, the design of tailored RL characteristics (emission energy, threshold, number of modes) is only obtained with complex photonic structures, while the simplest optical configurations able to tune the RL are still a challenge. This work demonstrates the tuning of the RL characteristics in spin-coated and inkjet-printed tin-based perovskites integrated into a vertical cavity with low quality factor. When the cavity mode is resonant with the photoluminescence (PL) peak energy, standard vertical lasing is observed. More importantly, single mode RL operation with the lowest threshold and a quality factor as high as 1 000 (twenty times the quality factor of the resonator) is obtained if the cavity mode lies above the PL peak energy due to higher gain. These results can have important technological implications toward the development of low-cost RL sources without chaotic behavior.

Microwave-Mediated Synthesis of Lead-Free Cesium Titanium Bromide Double Perovskite: A Sustainable Approach.

Theoretical studies have identified cesium titanium bromide (Cs2TiBr6), a vacancy-ordered double perovskite, as a promising lead-free and earth-abundant candidate to replace Pb-based perovskites in photovoltaics. Our research is focused on overcoming the limitations associated with the current Cs2TiBr6 syntheses, which often involve high-vacuum and high-temperature evaporation techniques, high-energy milling, or intricate multistep solution processes conducted under an inert atmosphere, constraints that hinder industrial scalability. This study presents a straightforward, low-energy, and scalable solution procedure using microwave radiation to induce the formation of highly crystalline Cs2TiBr6 in a polar solvent. This methodology, where the choice of the solvent plays a crucial role, not only reduces the energy costs associated with perovskite production but also imparts exceptional stability to the resulting solid, in comparison with previous reports. This is a critical prerequisite for any technological advancement. The low-defective material demonstrates unprecedented structural stability under various stimuli such as moisture, oxygen, elevated temperatures (over 130 °C), and continuous exposure to white light illumination. In summary, our study represents an important step forward in the efficient and cost-effective synthesis of Cs2TiBr6, offering a compelling solution for the development of eco-friendly, earth-abundant Pb-free perovskite materials.

Enabling white color tunability in complex 3D-printed composites by using lead-free self-trapped exciton 2D perovskite/carbon quantum dot inks.

The generation of stable white light emission using lead-free perovskites remains a huge challenge in the development of future display and lighting technologies, due to fast material deterioration and the decrease of the color quality. In this work, we report a combination of diverse types of 2D A2SnX4 (A = bulky cation, X = Br, I) perovskites exhibiting self-trapped exciton (STE) emission and blue luminescent carbon quantum dots (CQDs), with the purpose of generating A2SnX4/CQD inks with a broadband emission in the visible region and a tunable white light color. By varying the concentration of the 2D perovskite, the white emission of the mixtures is modulated to cool, neutral, and warm tonalities, with a PL quantum yield up to 45%. From the combinations, the PEA2SnI4/CQD-based ink shows the longest stability, due to suitable surface ligand passivation provided by the capping ligands covering the CQDs, compensating the defect sites in the perovskite. Then, by incorporating the PEA2SnI4/CQDs inks into an acrylate polymer matrix, the quenching of the PL component from the perovskite was restrained, being stable for >400 h under ambient conditions and at a relative humidity of ∼50%, and allowing the preparation of complex 3D-printed composites with stable white emission tonalities. This contribution offers an application of STE-based Sn-perovskites to facilitate the future fabrication of lead-free white-light optoelectronic devices.

Core/shell colloidal quantum dot exciplex states for the development of highly efficient quantum-dot-sensitized solar cells.

Searching suitable panchromatic QD sensitizers for expanding the light-harvesting range, accelerating charge separation, and retarding charge recombination is an effective way to improve power conversion efficiency (PCE) of quantum-dot-sensitized solar cells (QDSCs). One possible way to obtain a wide absorption range is to use the exciplex state of a type-II core/shell-structured QDs. In addition, this system could also provide a fast charge separation and low charge-recombination rate. Herein, we report on using a CdTe/CdSe type-II core/shell QD sensitizer with an absorption range extending into the infrared region because of its exciplex state, which is covalently linked to TiO2 mesoporous electrodes by dropping a bifunctional linker molecule mercaptopropionic acid (MPA)-capped QD aqueous solution onto the film electrode. High loading and a uniform distribution of QD sensitizer throughout the film electrode thickness have been confirmed by energy dispersive X-ray (EDX) elemental mapping. The accelerated electron injection and retarded charge-recombination pathway in the built CdTe/CdSe QD cells in comparison with reference CdSe QD-based cells have been confirmed by impedance spectroscopy, fluorescence decay, and intensity-modulated photocurrent/photovoltage spectroscopy (IMPS/IMVS) analysis. With the combination of the high QD loading and intrinsically superior optoelectronic properties of type-II core/shell QD (wide absorption range, fast charge separation, and slow charge recombination), the resulting CdTe/CdSe QD-based regenerative sandwich solar cells exhibit a record PCE of 6.76% (J(sc) = 19.59 mA cm(-2), V(oc) = 0.606 V, and FF = 0.569) with a mask around the active film under a full 1 sun illumination (simulated AM 1.5), which is the highest reported to date for liquid-junction QDSCs.

High performance PbS Quantum Dot Sensitized Solar Cells exceeding 4% efficiency: the role of metal precursors in the electron injection and charge separation.

Here we report the preparation of high performance Quantum Dot Sensitized Solar Cells (QDSCs) based on PbS-CdS co-sensitized nanoporous TiO2 electrodes. QDs were directly grown on the TiO2 mesostructure by the Successive Ionic Layer Absorption and Reaction (SILAR) technique. This method is characterized by a fast deposition rate which involves random crystal growth and poor control of the defect states and lattice mismatch in the QDs limiting the quality of the electrodes for photovoltaic applications. In this work we demonstrate that the nature of the metallic precursor selected for SILAR has an active role in both the QD's deposition rate and the defect's distribution in the material, with important consequences for the final photovoltaic performance of the device. For this purpose, acetate and nitrate salts were selected as metallic precursors for the SILAR deposition and films with similar absorption properties and consequently with similar density of photogenerated carriers were studied. Under these conditions, ultrafast carrier dynamics and surface photovoltage spectroscopy reveal that the use of acetate precursors leads to higher injection efficiency and lower internal recombination due to contribution from defect states. This was corroborated in a complete cell configuration with films sensitized with acetate precursors, achieving unprecedented photocurrents of ~22 mA cm(-2) and high power conversion efficiency exceeding 4%, under full 1 sun illumination.