Identification and Dynamics of Microsecond Long-Lived Charge Carriers for CsPbBr3 Perovskite Quantum Dots, Featuring Ambient Long-Term Stability.

We analyze the stability and photophysical dynamics of CsPbBr3 perovskite quantum dots (PeQDs), fabricated under mild synthetic conditions and embedded in an amorphous silica (SiOx) matrix (CsPbBr3@SiOx), underscoring their sustained performance in ambient conditions for over 300 days with minimal optical degradation. However, this stability comes at the cost of a reduced photoluminescence efficiency. Time-resolved spectroscopic analyses, including flash-photolysis time-resolved microwave conductivity and time-resolved photoluminescence, show that excitons in CsPbBr3@SiOx films decay within 2.5 ns, while charge carriers recombine over approximately 230 ns. This longevity of the charge carriers is due to photoinduced electron transfer to the SiOx matrix, enabling hole retention. The measured hole mobility in these PeQDs is 0.880 cm2 V-1 s-1, underscoring their potential in optoelectronic applications. This study highlights the role of the silica matrix in enhancing the durability of PeQDs in humid environments and modifying exciton dynamics and photoluminescence, providing valuable insights for developing robust optoelectronic materials.

Operando spectroscopic characterization of formamidinium lead iodide perovskite quantum dots for tracking electrochemical reactions.

Multidimensional ABX3 hybrid perovskites three-dimensionally confined dot-shaped structure demonstrate versatile potential to photoelectrochemical cells for water splitting, hydrogen generation, solar cells, and light-emitting diodes. To apply perovskite quantum dots (PQDs) to solar-driven chemistry and optoelectronic devices, understanding the photoinduced charge carrier dynamics of PQDs under electrochemical conditions or applied bias are important. In this study, the detailed transformation mechanism of formamidinium lead iodide perovskite quantum dots under electrochemical conditions was studied by tracking the products of the reaction through cyclic voltammetry, X-ray photoemission spectroscopy, in-situ UV-visible spectroelectrochemistry, etc. Through comprehensive characterizations, the mechanism of irreversible oxidative transformation of perovskite quantum dots was presented. This study provides deeper insight into the electrochemical behavior of PQDs for successful solar-driven chemistry and optoelectronic device applications.

Role of electrochemical reactions in the degradation of formamidinium lead halide hybrid perovskite quantum dots.

Organic-inorganic hybrid perovskites are widely utilized in solar driven chemistry such as photocatalysis, hydrogen evolution, and oxygen reduction. Hybrid perovskites contain various components with high polarity and/or charge values, which undergo transformations due to ion exchange, photoinduced phase segregation, or ion migration. These variable characteristics make perovskites "soft materials". Meanwhile, optoelectronic devices often operate under electrochemical reactions in the presence of an electrical field. To examine the effect of this field on the material/photophysical properties of hybrid perovskites, hybrid FAPbBr3 (FA+: CH(NH2)2+) perovskite quantum dots (PQDs) were synthesized. In this study, we report the spectroelectrochemical investigation of the hybrid FAPbBr3 PQDs to understand the electrochemical stability and degradation process. We also found that the electrochemical condition played an important role in inducing defect-mediated oxidation/reduction reactions, changing the photophysical properties of hybrid PQDs, and causing their irreversible transformations to various lead halide plumbate complexes. These findings can help develop a strategy for enhancing the operational performance of PQDs for the solar driven chemistry.

Effect of PbSO4-Oleate Coverage on Cesium Lead Halide Perovskite Quantum Dots to Control Halide Exchange Kinetics.

The selective control of halide ion exchange in metal halide perovskite quantum dots (PQDs) plays an important role in determining their band gap and composition. In this study, CsPbX3 (X = Cl-, Br-, and I-) PQDs were self-assembled with PbSO4-oleate to form a peapod-like morphology to selectively control halide ion exchange. Considering the distinct absorption and bright luminescence characteristics of these PQDs, in situ UV-Vis. absorption and fluorescence spectroscopies were employed to monitor the time-dependent band gap and compositional changes of the PQDs. We determined that the halide exchange in the capped PQDs is hindered-unlike the rapid anion exchange in noncapped PQDs-by a reduction in the halide exchange kinetic rate depending on the extent of coverage of the PQDs. Thus, we tracked the halide ion exchange kinetics between CsPbBr3 and CsPbI3 PQDs, depending on the coverage, using in situ UV-Vis. absorption/photoluminescence spectroscopy. We regulated the halide exchange reaction rate by varying the capping reaction temperature of the PQDs. The capping hindered the halide exchange kinetics and increased the activation energy. These results will enable the development of white LEDs, photovoltaic cells, and photocatalysts with alternative structural designs based on the divalent composition of CsPbX3 PQDs.

Ligand & band gap engineering: tailoring the protocol synthesis for achieving high-quality CsPbI3 quantum dots.

Hot-injection has become the most widespread method used for the synthesis of perovskite quantum dots (QDs) with enormous interest for application in optoelectronic devices. However, there are some aspects of the chemistry involved in this synthesis that have not been completely investigated. In this work, we synthesized ultra-high stable CsPbI3 QDs for more than 15 months by controlling two main parameters: synthesis temperature and the concentration of capping ligands. By increasing the capping ligand concentration during the QD synthesis, we were able to grow CsPbI3 in a broad range of temperatures, improving the photophysical properties of QDs by increasing the synthesis temperature. We achieved the maximum photoluminescence quantum yield (PLQY) of 93% for a synthesis conducted at 185 °C, establishing an efficient surface passivation to decrease the density of non-radiative recombination sites. Under these optimized synthesis conditions, deep red LEDs with an External Quantum Efficiency (EQE) higher than 6% were achieved. The performance of these LEDs is higher than that of the reported CsPbI3 QD-LEDs containing standard capping agents, without additional elements or further element exchange. We show that it is possible to produce stable CsPbI3 QDs with high PLQY and red emission beyond the requirement of the Rec. 2020 standards for red color.

Role of Regeneration of Nanoclusters in Dictating the Power Conversion Efficiency of Metal-Nanocluster-Sensitized Solar Cells.

Metal nanoclusters (NCs) have emerged as feasible alternatives to dyes and quantum dots in light energy conversion applications. Despite the remarkable enhancement in power conversion efficiency (PCE) in recent years and the increase in the number of NCs available as sensitizers, a comprehensive understanding of the various interfacial charge-transfer, transport, and recombination events in NCs is still lacking. This understanding is vital to the establishment of design principles for an efficient photoelectrode that uses NCs. In this work, we carefully design a comparison study of two representative NCs, Au and Ag, based on transient absorption spectroscopy and electrochemical impedance spectroscopy, methods that shed light on the true benefits and limitations of NC sensitizers. Low NC regeneration efficiency is the most critical factor that limits the performance of metal-nanocluster-sensitized solar cells (MCSSCs). The slow regeneration that results from sluggish hole transfer kinetics not only limits photocurrent generation efficiency but also has a profound effect on the stability of MCSSCs. This finding calls for urgent attention to the development of an efficient redox couple that has a great hole-extraction ability and no corrosive nature. This work also reveals different interfacial behaviors of Au and Ag NCs in photoelectrodes, suggesting that utilizing the benefits of both types of NCs simultaneously by cosensitization or using AuAg alloy NCs may be one avenue for further PCE improvement in MCSSCs.

Unravelling the Photocatalytic Behavior of All-Inorganic Mixed Halide Perovskites: The Role of Surface Chemical States.

Within the most mesmerizing materials in the world of optoelectronics, mixed halide perovskites (MHPs) have been distinguished because of the tunability of their optoelectronic properties, balancing both the light-harvesting efficiency and the charge extraction into highly efficient solar devices. This feature has drawn the attention of analogous hot topics as photocatalysis for carrying out more efficiently the degradation of organic compounds. However, the photo-oxidation ability of perovskite depends not only on its excellent light-harvesting properties but also on the surface chemical environment provided during its synthesis. Accordingly, we studied the role of surface chemical states of MHP-based nanocrystals (NCs) synthesized by hot-injection (H-I) and anion-exchange (A-E) approaches on their photocatalytic (PC) activity for the oxidation of ß-naphthol as a model system. We concluded that iodide vacancies are the main surface chemical states that facilitate the formation of superoxide ions, O2●-, which are responsible for the PC activity in A-E-MHP. Conversely, the PC performance of H-I-MHP is related to the appropriate balance between band gap and a highly oxidizing valence band. This work offers new insights on the surface properties of MHP related to their catalytic activity in photochemical applications.

Ag(I)-Thiolate-Protected Silver Nanoclusters for Solar Cells: Electrochemical and Spectroscopic Look into the Photoelectrode/Electrolyte Interface.

Intrinsic low stability and short excited lifetimes associated with Ag nanoclusters (NCs) are major hurdles that have prevented the full utilization of the many advantages of Ag NCs over their longtime contender, Au NCs, in light energy conversion systems. In this report, we diagnosed the problems of conventional thiolated Ag NCs used for solar cell applications and developed a new synthesis route to form aggregation-induced emission (AIE)-type Ag NCs that can significantly overcome these limitations. A series of Ag(0)/Ag(I)-thiolate core/shell-structured NCs with different core sizes were explored for photoelectrodes, and the nature of the two important interfacial events occurring in Ag NC-sensitized solar cells (photoinduced electron transfer and charge recombination) were unveiled by in-depth spectroscopic and electrochemical analyses. This work reveals that the subtle interplay between the light absorbing capability, charge separation dynamics, and charge recombination kinetics in the photoelectrode dictates the solar cell performance. In addition, we demonstrate significant improvement in the photocurrent stability and light conversion efficiency that have not been achieved previously. Our comprehensive understanding of the critical parameters that limit the light conversion efficiency lays a foundation on which new principles for designing Ag NCs for efficient light energy conversion can be built.

Photocatalytic and Photoelectrochemical Degradation of Organic Compounds with All-Inorganic Metal Halide Perovskite Quantum Dots.

Inspired by the outstanding optoelectronic properties reported for all-inorganic halide perovskite quantum dots (QDs), we have evaluated the potential of these materials toward the photocatalytic and photoelectrochemical degradation of organic compounds, taking the oxidation of 2-mercaptobenzothiazole (MBT) as a proof-of-concept. First, we determined electrochemically the energy levels of dispersions of perovskite QDs with different band gaps induced by the different ratios between halides (Br and I) and metallic cations (Pb and Sn). Then, we selected CsPbBr3 QDs to demonstrate the photocatalytic and photoelectrochemical oxidation of MBT, confirming that hole injection takes place from CsPbBr3 QDs to MBT, resulting in the total degradation of MBT as evidenced by electrospray mass spectrometry analyses. Although the stability and toxicity of these QDs are major issues to address in the near future, the results obtained in the present study open promising perspectives for the implementation of solar-driven catalytic strategies based on these fascinating materials.

Controlling the Phase Segregation in Mixed Halide Perovskites through Nanocrystal Size.

Mixed halide perovskites are one of the promising candidates in developing solar cells and light-emitting diodes (LEDs), among other applications, because of their tunable optical properties. Nonetheless, photoinduced phase segregation, by formation of segregated Br-rich and I-rich domains, limits the overall applicability. We tracked the phase segregation with increasing crystalline size of CsPbBr3-x I x and their photoluminescence under continuous-wave laser irradiation (405 nm, 10 mW cm-2) and observed the occurrence of the phase segregation from the threshold size of 46 ± 7 nm. These results have an outstanding agreement with the diffusion length (45.8 nm) calculated also experimentally from the emission lifetime and segregation rates. Furthermore, through Kelvin probe force microscopy, we confirmed the correlation between the phase segregation and the reversible halide ion migration among grain centers and boundaries. These results open a way to achieve segregation-free mixed halide perovskites and improve their performances in optoelectronic devices.

Author Correction: Rationalizing the light-induced phase separation of mixed halide organic-inorganic perovskites.

The original version of this Article contained an error in the spelling of the author Joseph S. Manser, which was incorrectly given as Joseph M. Manser. This has now been corrected in both the PDF and HTML versions of the Article.

Rationalizing the light-induced phase separation of mixed halide organic-inorganic perovskites.

Mixed halide hybrid perovskites, CH3NH3Pb(I1-x Br x )3, represent good candidates for low-cost, high efficiency photovoltaic, and light-emitting devices. Their band gaps can be tuned from 1.6 to 2.3 eV, by changing the halide anion identity. Unfortunately, mixed halide perovskites undergo phase separation under illumination. This leads to iodide- and bromide-rich domains along with corresponding changes to the material's optical/electrical response. Here, using combined spectroscopic measurements and theoretical modeling, we quantitatively rationalize all microscopic processes that occur during phase separation. Our model suggests that the driving force behind phase separation is the bandgap reduction of iodide-rich phases. It additionally explains observed non-linear intensity dependencies, as well as self-limited growth of iodide-rich domains. Most importantly, our model reveals that mixed halide perovskites can be stabilized against phase separation by deliberately engineering carrier diffusion lengths and injected carrier densities.Mixed halide hybrid perovskites possess tunable band gaps, however, under illumination they undergo phase separation. Using spectroscopic measurements and theoretical modelling, Draguta and Sharia et al. quantitatively rationalize the microscopic processes that occur during phase separation.

Direct Imaging of Long-Range Exciton Transport in Quantum Dot Superlattices by Ultrafast Microscopy.

Long-range charge and exciton transport in quantum dot (QD) solids is a crucial challenge in utilizing QDs for optoelectronic applications. Here, we present a direct visualization of exciton diffusion in highly ordered CdSe QDs superlattices by mapping exciton population using ultrafast transient absorption microscopy. A temporal resolution of ∼200 fs and a spatial precision of ∼50 nm of this technique provide a direct assessment of the upper limit for exciton transport in QD solids. An exciton diffusion length of ∼125 nm has been visualized in the 3 ns experimental time window and an exciton diffusion coefficient of (2.5 ± 0.2) × 10(-2) cm(2) s(-1) has been measured for superlattices constructed from 3.6 nm CdSe QDs with center-to-center distance of 6.7 nm. The measured exciton diffusion constant is in good agreement with Förster resonance energy transfer theory. We have found that exciton diffusion is greatly enhanced in the superlattices over the disordered films with an order of magnitude higher diffusion coefficient, pointing toward the role of disorder in limiting transport. This study provides important understandings on energy transport mechanisms in both the spatial and temporal domains in QD solids.

How Lead Halide Complex Chemistry Dictates the Composition of Mixed Halide Perovskites.

Varying the halide ratio (e.g., Br(-):I(-)) is a convenient approach to tune the bandgap of organic lead halide perovskites. The complexation between Pb(2+) and halide ions is the primary step in dictating the overall composition, and optical properties of the annealed perovskite structure. The complexation between Pb(2+) and Br(-) is nearly 7 times greater than the complexation between Pb(2+) and I(-), thus making Br(-) a dominant binding species in mixed halide systems. Emission and transient absorption measurements show a strong dependence of excited state behavior on the composition of halide ions employed in the precursor solution. When excess halide (X = Br(-) and I(-)) are present in the precursor solution (0.3 M PbX2 and 0.9 M CH3NH3X), the exclusive binding of Pb(2+) with Br(-) results in the formation of CH3NH3PbBr3 perovskites as opposed to mixed halide perovskite.

Enhanced photovoltaic performance of Cu-based metal-organic frameworks sensitized solar cell by addition of carbon nanotubes.

In the present work, TiO2 nanoparticle and multi-walled carbon nanotubes composite powder is prepared hydrothermally. After doctor blading the paste from composite powder, the resulted composite film is sensitized with Cu-based metal-organic frameworks using a layer-by-layer deposition technique and the film is characterized using FE-SEM, EDX, XRD, UV/Visible spectrophotometry and photoluminescence spectroscopy. The influence of the carbon nanotubes in photovoltaic performance is studied by constructing a Grätzel cell with I3(-)/I(-) redox couple containing electrolyte. The results demonstrate that the introduction of carbon nanotubes accelerates the electron transfer, and thereby enhances the photovoltaic performance of the cell with a nearly 60% increment in power conversion efficiency.

WGS catalysis and in situ studies of CoO(1-x), PtCo(n)/Co3O4, and Pt(m)Co(m')/CoO(1-x) nanorod catalysts.

Water-gas shift (WGS) reactions on Co3O4 nanorods and Co3O4 nanorods anchoring singly dispersed Pt atoms were explored through building correlation of catalytic performance to surface chemistry of catalysts during catalysis using X-ray absorption spectroscopy, ambient pressure X-ray photoelectron spectroscopy (AP-XPS), and environmental TEM. The active phase of pure Co3O4 during WGS is nonstoichiometric cobalt monoxide with about 20% oxygen vacancies, CoO0.80. The apparent activation energy (Ea) in the temperature range of 180-240 °C is 91.0 ± 10.5 kJ mol(-1). Co3O4 nanorods anchoring Pt atoms (Pt/Co3O4) are active for WGS with a low Ea of 50.1 ± 5.0 kJ mol(-1) in the temperature range of 150-200 °C. The active surface of this catalyst is singly dispersed Pt1Co(n) nanoclusters anchored on Co3O4 (Pt1/Co3O4), evidenced by in situ studies of extended X-ray absorption fine structure spectroscopy. In the temperature range of 200-300 °C, catalytic in situ studies suggested the formation of Pt(m)Co(m') nanoclusters along with the reduction of Co3O4 substrate to CoO(1-x). The new catalyst, Pt(m)Co(m')/CoO(1-x) is active for WGS with a very low Ea of 24.8 ± 3.1 kJ mol(-1) in the temperature range of 300-350 °C. The high activity could result from a synergy of Pt(m)Co(m') nanoclusters and surface oxygen vacancies of CoO(1-x).

Structural and optical properties of chemically deposited CuInSe2 thin film in acidic medium.

Thin films of nanocrystalline CuInSe2 were prepared on glass substrates using chemical bath deposition in acidic medium at room temperature. Thickness of the chemically deposited CuInSe2 thin films was approximately 100 nm which composed of closely packed irregular grains of approximately 100-120 nm in diameter. X-ray diffraction pattern of CuInSe2 thin films showed nanocrystalline structure with (112) preferential orientation. The films exhibited faint black and direct band gap energy was 0.96 eV.

Interfacially treated dye-sensitized solar cell with in situ photopolymerized iodine doped polythiophene.

A thin film of iodine doped polythiophene was grown photoelectrochemically around the dye-sensitized TiO(2) nanoparticles in a Grätzel cell, and the effect of iodine doping level on the cell performance was investigated using X-ray photoelectron spectroscopy, electrochemical impedance spectroscopy, and photovoltage decay. At an optimum doping level, the cell demonstrated the enhanced energy conversion efficiency by 27.52% compared to the cell without polythiophene.