Enhancing the Thermoelectric and Mechanical Properties of p-Type PbS through Band Convergence and Microstructure Regulation.

While lead sulfide shows notable thermoelectric properties, its production costs remain high, and its mechanical hardness is low, which constrains its commercial viability. Herein, we demonstrate a straightforward and cost-effective method to produce PbS nanocrystals at ambient temperature. By introducing controlled amounts of silver, we achieve p-type conductivity and fine-tune the energy band structure and lattice configuration. Computational results show that silver shifts the Fermi level into the valence band, facilitating band convergence and thereby enhancing the power factor. Besides, excess silver is present as silver sulfide, which effectively diminishes the interface barrier and enhances the Seebeck coefficient. Defects caused by doping, along with dislocations and interfaces, reduce thermal conductivity to 0.49 W m-1 K-1 at 690 K. Moreover, the alterations in crystal structure and chemical composition enhance the PbS mechanical properties. Overall, optimized materials show thermoelectric figures of merit approximately 10-fold higher than that of pristine PbS, alongside an average hardness of 1.08 GPa.

Monolithic Two-Terminal Tandem Solar Cells Using Sb2S3 and Solution-Processed PbS Quantum Dots Achieving an Open-Circuit Potential beyond 1.1 V.

Multijunction solar cells have the prospect of a greater theoretical efficiency limit than single-junction solar cells by minimizing the transmissive and thermalization losses a single absorber material has. In solar cell applications, Sb2S3 is considered an attractive absorber due to its elemental abundance, stability, and high absorption coefficient in the visible range of the solar spectrum, yet with a band gap of 1.7 eV, it is transmissive for near-IR and IR photons. Using it as the top cell (the cell where light is first incident) in a two-terminal tandem architecture in combination with a bottom cell (the cell where light arrives second) of PbS quantum dots (QDs), which have an adjustable band gap suitable for absorbing longer wavelengths, is a promising approach to harvest the solar spectrum more effectively. In this work, these two subcells are monolithically fabricated and connected in series by a poly(3,4-ethylene-dioxythiophene) polystyrene sulfonate (PEDOT:PSS)-ZnO tunnel junction as the recombination layer. We explore the surface morphology of ZnO QD films with different spin-coating conditions, which serve as the PbS QD cell's electron transport material. Furthermore, we examine the differences in photogenerated current upon varying the PbS QD absorber layer thickness and the electrical and optical characteristics of the tandem with respect to the stand-alone reference cells. This tandem architecture demonstrates an extended spectral response into the IR with an open-circuit potential exceeding 1.1 V and a power conversion efficiency of 5.6%, which is greater than that of each single-junction cell.

PbS Quantum Dots Ink with Months-Long Shelf-Lifetime Enabling Scalable and Efficient Short-Wavelength Infrared Photodetectors.

The phase-transfer ligand exchange of PbS quantum dots (QDs) has substantially simplified device fabrication giving hope for future industrial exploitation. However, this technique when applied to QDs of large size (>4 nm) gives rise to inks with poor colloidal stability, thus hindering the development of QDs photodetectors in short-wavelength infrared range. Here, it is demonstrated that methylammonium lead iodide ligands can provide sufficient passivation of PbS QDs of size up to 6.7 nm, enabling inks with a minimum of ten-week shelf-life time, as proven by optical absorption and solution-small angle X-ray scattering. Furthermore, the maximum linear electron mobility of 4.7 × 10-2 cm2 V-1 s-1 is measured in field-effect transistors fabricated with fresh inks, while transistors fabricated with the same solution after ten-week storage retain 74% of the average starting electron mobility, demonstrating the outstanding quality both of the fresh and aged inks. Finally, photodetectors fabricated via blade-coating exhibit 76% external quantum efficiency at 1300 nm and 1.8 × 1012 Jones specific detectivity, values comparable with devices fabricated using ink with lower stability and wasteful methods such as spin-coating.

Rapid and large-scale synthesis of MoS2via ultraviolet laser-assisted technology for photodetector applications.

Two-dimensional transition metal dichalcogenide (TMDC) thin films have been extensively employed in microelectronics research. Molybdenum disulfide (MoS2), as one of prominent candidates of this class, has been applied in photodetectors, integrated electronic devices, gas sensing, and electrochemical catalysis, owing to its extraordinary optoelectronic, chemical, and mechanical properties. Synthesis of MoS2crystal film is the key to its application. However, the reported technology revealed several drawbacks, containing limited surface area, prolonged high-temperature environment, and unsatisfying crystallinity. In order to enhance the convenience of MoS2applications, there is a pressing need for optimized fabrication technology, which could be quicker, with a large area, with adequate crystallinity and heat-saving. In this work, we presented an ultraviolet laser-assisted synthesis technology, accomplishing rapid growth (with the growth rate of about 40µm s-1) of centimeter-scale MoS2films at room temperature. To achieve this, we self-assembled a displaceable reaction chamber system, coupled with krypton fluoride ultraviolet pulse laser. The laser motion speed and trajectory could be customized in the software, allowing the maskless patterning of crystal films. As application, we exhibited a photodetector with the integration of synthesized MoS2and lead sulfide colloidal quantum dots (PbS CQDs), displaying broadband photodetection from ultraviolet, visible to near-infrared spectrum (365-1550 nm), with the detectivity of 109-1010Jones, and the rising time of 0.2-0.3 s. This work not only demonstrated a high-process-efficiency synthesis of TMDC materials, but also has opened up new opportunities for ultraviolet laser used in optoelectronics.

Pressurized Back-Junction Doping via Spray-Coating Silver Nanowires Top Electrodes for Efficient Charge Collection in Bifacial Colloidal PbS Quantum Dot Solar Cells.

Colloidal PbS quantum-dot solar cells (QDSCs) have long suffered from inefficient charge collection near the back-junction due to the lack of p-doping strategy, rendering their bifacial photovoltaic applications unsuccessful. Here, we report highly efficient photocarrier collection in bifacial colloidal PbS QDSCs by exploiting spray-coated silver nanowires (AgNWs) top electrodes. During our spray-coating process, pressurized Ag diffusion occurred toward the active layer, which induced effective p-doping and deep-level passivation. By manipulating the spray pressure, optimum AgNWs' stacking morphology enabling an appropriate level of Ag diffusion could be achieved, leading to Jsc over 30 mA/cm2 from the conventional n-i-p structure upon light illumination to the film side. The morphological and electrical behaviors of AgNWs according to the spray pressure are comprehensively explained in relation to the device performance. Finally, 50 bifacial cells were fabricated over 49 cm2 sized glass substrate, demonstrating the large-area processability and functionality of the spray-coated AgNWs with the effective back-junction engineering.

Transient Measurements and Simulations Correlate Exchange Ligand Concentration and Trap States in Colloidal Quantum Dot Photodetectors.

Colloidal quantum dot (CQD) photodetectors (PDs) can detect wavelengths longer than the 1100 nm limit of silicon because of their highly tunable bandgaps. CQD PDs are acutely affected by the ligands that separate adjacent dots in a CQD-solid. Optimizing the exchange solution ligand concentration in the processing steps is crucial to achieving high photodetector performance. However, the complex mix of chemistry and optoelectronics involved in CQD PDs means that the effects of the exchange solution ligand concentration on device physics are poorly understood. Here we report direct correspondence between simulated and experimental transient photocurrent responses in CQD PDs. For both deficient and excess conditions, our model demonstrated the experimental changes to the transient photocurrent aligned with changes in trap state density. Combining transient photoluminescence, absorption, and photocurrent with this simulation model, we revealed that different mechanisms are responsible for the increased trap density induced by excess and deficient active layer ligand concentrations.

Understanding Colloidal Quantum Dot Device Characteristics with a Physical Model.

Colloidal quantum dots (CQDs) are finding increasing applications in optoelectronic devices, such as photodetectors and solar cells, because of their high material quality, unique and attractive properties, and process flexibility without the constraints of lattice match and thermal budget. However, there is no adequate device model for colloidal quantum dot heterojunctions, and the popular Shockley-Quiesser diode model does not capture the underlying physics of CQD junctions. Here, we develop a compact, easy-to-use model for CQD devices rooted in physics. We show how quantum dot properties, QD ligand binding, and the heterointerface between quantum dots and the electron transport layer (ETL) affect device behaviors. We also show that the model can be simplified to a Shockley-like equation with analytical approximate expressions for reverse saturation current, ideality factor, and quantum efficiency. Our model agrees well with the experiment and can be used to describe and optimize CQD device performance.

High Detectivity of PbS Films Deposited on Quartz Substrates: The Role of Enhanced Photogenerated Carrier Separation.

PbS films grown on quartz substrates by the chemical bath deposition method were annealed in an O2 atmosphere to investigate the role of oxygen in the sensitization process at different annealing temperatures. The average grain size of the PbS films gradually increased as the annealing temperature increased from 400 °C to 700 °C. At an annealing temperature of 650 °C, the photoresponsivity and detectivity reached 1.67 A W-1 and 1.22 × 1010 cm Hz1/2 W-1, respectively. The role of oxides in the sensitization process was analyzed in combination with X-ray diffraction and scanning electron microscopy results, and a three-dimensional network model of the sensitization mechanism of PbS films was proposed. During the annealing process, O functioned as a p-type impurity, forming p+-type PbS layers with high hole concentrations on the surface and between the PbS grains. As annealing proceeds, the p+-type PbS layers at the grain boundaries interconnect to form a three-dimensional network structure of hole transport channels, while the unoxidized p-type PbS layers act as electron transport channels. Under bias, photogenerated electron-hole pairs were efficiently separated by the formed p+-p charge separation junction, thereby reducing electron-hole recombination and facilitating a higher infrared response.

Enhanced performance of lead sulfide quantum dot-sensitized solar cells by controlling the thickness of metal halide perovskite shells.

The metal halide perovskite CH3NH3PbI3 (MAP) can be applied as the shell layer of lead sulfide quantum dots (PbS QDs) for improving solar power conversion efficiency. However, basic physics for this PbS core/MAP shell QD system is still unclear and needs to be clarified to further improve efficiency. Therefore, in this study, we investigate how MAP shell thickness affects device performance and dynamics of charge carriers for PbS QD-sensitized solar cells. Covering the PbS QDs with the MAP shell layers of an appropriate thickness around 0.34 nm greatly suppresses charge carrier recombination at surface defects along with improved carrier transport to neighboring oxide and polymer layers. Therefore, this MAP shell thickness provides the highest open-circuit voltage, short-circuit current density, and fill factor for solar cells. Overall power conversion efficiencies of these solar cells reached about 4.1%, which is about six-fold higher than that for solar cells without MAP (about 0.7%). Additionally, use of the MAP shell layers can prevent oxidation of PbS QDs and, therefore, makes a degradation of solar cell performance slower in air.

BSA-assisted ultrasound synthesis of water stable CsPbBr3 nanocrystals for sensitive fluorescent detection of hydrogen sulfide in human serum.

A bovine serum albumin (BSA)-assisted ultrasonication strategy was developed for the synthesis of CsPbBr3 nanocrystals (NCs) with stable fluorescence properties in aqueous solution. Such a preparation method is simple, fast and does not require complex equipment. The results show that the synthesized CsPbBr3 NCs are homogeneous in particle size and have good solubility and stability in water. The CsPbBr3 NCs have been utilized as fluorescence probe for rapid detection of hydrogen sulfide (H2S) in human serum. The reaction of H2S with the lead sites on the surface of CsPbBr3 NCs produces lead sulfide (PbS), resulting in the decrease of fluorometric intensity of CsPbBr3 NCs. Our designed fluorescent assay has a linear S2- detecting range of 10 ~ 800 nM with a detection limit of 7.05 nM. The assay was used to determine H2S in human serum with spiked recoveries ranging from 94.98% to 102.69%. This work opens new avenues for the application of halide lead perovskite in different biosensing areas.

Controlling Electronic Coupling of Acene Chromophores on Quantum Dot Surfaces through Variable-Concentration Ligand Exchange.

Controlling the binding of functional organic molecules on quantum dot (QD) surfaces and the resulting ligand/QD interfacial structure determines the resulting organic-inorganic hybrid behavior. In this study, we vary the binding of tetracenedicarboxylate ligands bound to PbS QDs cast in thin films by performing solid-state ligand exchange of as-produced bound oleate ligands. We employ comprehensive Fourier-transform infrared (FTIR) analysis coupled with ultraviolet-visible (UV-vis) spectrophotometric measurements, transient absorption, and Density Functional Theory (DFT) simulations to study the QD/ligand surface structure and resulting optoelectronic properties. We find that there are three primary QD/diacid structures, each with a distinct binding mode dictated by the QD-ligand and ligand-ligand intermolecular and steric interactions. They can be accessed nearly independently of one another via different input ligand concentrations. Low concentrations produce mixed oleate/tetracene ligand structures where the tetracene carboxylates tilt toward QD surfaces. Intermediate concentrations produce mixed oleate/tetracene ligand structures with ligand-ligand interactions through intramolecular hydrogen bonding with the ligands perpendicular to the QD surface and weaker QD/ligand electronic interactions. High concentrations result in full ligand exchange, and the ligands tilt toward the surface while the QD film compacts. When the tetracene ligands tilt or lie flat on the QD surface, the benzene ring π-system interacts strongly with the p-orbitals at the PbS surface and produces strong QD-ligand interactions evidenced through QD/ligand state mixing, with a coupling energy of ≈700 meV.

Both biogenic and chemically synthesized metal sulfide nanoparticles induce oxidative stress and enhance lipid accumulation in Rhodococcus opacus.

Metallic nanoparticles (NPs) find applications in many different industrial sectors. However, the fate of these NPs in the environment and their potential impact on organisms living in different ecosystems are not fully known. In this work, the individual effect of biogenic and chemically synthesized lead sulfide nanoparticles (PbSNPs) and cadmium sulfide nanoparticles (CdSNPs) on the activity of the oleaginous bacterium Rhodococcus opacus PD630 which belongs to an ecologically important genus Rhodococcus was investigated. A dose-dependent increase in PbSNPs and CdSNPs uptake by the bacterium was observed upto a maximum of 16.4 and 15.6 mg/g cell, corresponding to 98% and 95% uptake. In the case of chemically synthesized NPs, the specific PbSNPs and CdSNPs uptake were slightly less [15.5 and 14.8 mg/g cell], corresponding to 93.2% and 88.4% uptake. Both biogenic and chemically synthesized PbSNPs and CdSNPs did not affect the bacterial growth. On the other hand, the triacylglycerol (biodiesel) content in the bacterium increased from 30% to a maximum of 75% and 73% CDW due to oxidative stress induced by biogenic PbSNPs and CdSNPs. The results of induced oxidative stress by biogenic metal nanoparticle were similar to that induced by the chemically synthesized NPs.

Optimizing the Infrared Photoelectric Detection Performance of Pbs Quantum Dots through Solid-State Ligand Exchange.

Lead sulfide (PbS) quantum dots (QDs) have attracted a great deal of attention in recent decades, due to their value for applications in optoelectronic devices. However, optimizing the performance of optoelectronic devices through ligand engineering has become a major challenge, as the surfactants that surround quantum dots impede the transport of electrons. In this paper, we prepared PbS QD films and photoconductive devices with four different ligands: 1,2-ethylenedithiol (EDT), tetrabutylammonium iodide (TBAI), hexadecyl trimethyl ammonium bromide (CTAB), and sodium sulfide (Na2S). A series of characterization studies confirmed that using the appropriate ligands in the solid-state ligand exchange step for thin film fabrication can significantly improve the responsivity. The devices treated with sodium sulfide showed the best sensitivity and a wider detection from 400 nm to 2300 nm, compared to the other ligand-treated devices. The responsivity of the champion device reached 95.6 mA/W under laser illumination at 980 nm, with an intensity of 50 mW/cm2.

Heteroepitaxy of Large-Area, Monocrystalline Lead Halide Perovskite Films on Gallium Arsenide.

Lead halide perovskite materials have been emerging as promising candidates for high-performance optoelectronic devices. Significant efforts have sought to realize monocrystalline perovskite films on a large scale. Here, we epitaxially grow monocrystalline methylammonium lead tribromide (MAPbBr3) films on lattice-matched gallium arsenide (GaAs) substrates on a centimeter scale. In particular, a solution-processed lead(II) sulfide (PbS) layer provides a lattice-matched and chemical protective interface for the solid-gas reaction to form MAPbBr3 films on GaAs. Structure characterizations identify the crystal orientations in the trilayer MAPbBr3/PbS/GaAs epistructure and confirm the monocrystalline nature of MAPbBr3 on PbS/GaAs. The dynamic evolution of surface morphologies during the growth indicates a two-step epitaxial process. These fundamental understandings and practical growth techniques offer a viable guideline to approach high-quality perovskite films for previously inaccessible applications.

PbS and PbO Thin Films via E-Beam Evaporation: Morphology, Structure, and Electrical Properties.

Thin films of lead sulfide (PbS) are being extensively used for the fabrication of optoelectronic devices for commercial and military applications. In the present work, PbS films were fabricated onto a soda lime glass substrate by using an electron beam (e-beam) evaporation technique at a substrate temperature of 300 °C. Samples were annealed in an open atmosphere at a temperature range of 200-450 °C for 2 h. The deposited films were characterized for structural, optical, and electrical properties. Structural properties of PbS have been studied by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), energy dispersive spectroscopy (EDS), and Rutherford backscattering spectrometry (RBS). The results of XRD showed that the PbS thin film was crystalline in nature at room temperature with cubic crystal structure (galena) and preferential (111) and orientation (022). The morphology of the thin films was studied by FESEM, which also showed uniform and continuous deposition without any peel-off and patches. EDS analysis was performed to confirm the presence of lead and sulfur in as-deposited and annealed films. The thickness of the PbS film was found to be 172 nm, which is slightly greater than the intended thickness of 150 nm, determined by RBS. Ultraviolet-Visible-Near-Infrared (UV-Vis-NIR) spectroscopy revealed the maximum transmittance of ~25% for as-deposited films, with an increase of 74% in annealed films. The band gap of PbS was found in the range of 2.12-2.78 eV for as-deposited and annealed films. Hall measurement confirmed the carriers are p-type in nature. Carrier concentration, mobility of the carriers, conductivity, and sheet resistance are directly determined by Hall-effect measurement. The as-deposited sample showed a conductivity of 5.45 × 10-4 S/m, which gradually reduced to 1.21 × 10-5 S/m due to the composite nature of films (lead sulfide along with lead oxide). Furthermore, the present work also reflects the control of properties by controlling the amount of PbO present in the PbS films which are suitable for various applications (such as IR sensors).

Highly Photosensitive Lead Sulfide Thin Films Grown by H2 S Free MOCVD Using a Single Source Metal-Organic Precursor.

High-quality lead sulfide (PbS) films are deposited on selected substrate chemistries by an H2 S-free metal-organic chemical vapor deposition (MOCVD) process using a single-source metal-organic complex (Pb(dmampS)2 ). The complex is synthesized via a salt metathesis reaction between PbCl2  and lithium 1-(dimethylamino)-2-methylpropane-2-thiolate (Li(dmampS)) in diethyl ether. Subsequent film deposition is conducted by a simple thermolysis process in the absence of H2 S, yet chemical and structural analysis confirm chemically stoichiometric and homogenous films. Mechanistic studies with electron impact mass spectroscopy (EIMS) and gas chromatography mass spectroscopy (GCMS) suggest the selective cleavage of C-S bonds in the complex as the reason for the facile PbS formation with negligible impurity incorporation. The high crystallinity, low hole concentrations, and charge transport properties comparable and in many cases superior to films produced by atomic layer deposition (ALD) testify to the quality of the films. Lastly, rigid and flexible photodetectors fabricated with the PbS films exhibit considerably high photocurrents, reliable switching characteristics, and high sensitivity over a broad spectral bandwidth, highlighting the potential for realizing practical broadband photodetectors.

Nanostructured PbS-Doped Inorganic Film Synthesized by Sol-Gel Route.

IV-VI semiconductor quantum dots embedded into an inorganic matrix represent nanostructured composite materials with potential application in temperature sensor systems. This study explores the optical, structural, and morphological properties of a novel PbS quantum dots (QDs)-doped inorganic thin film belonging to the Al2O3-SiO2-P2O5 system. The film was synthesized by the sol-gel method, spin coating technique, starting from a precursor solution deposited on a glass substrate in a multilayer process, followed by drying of each deposited layer. Crystalline PbS QDs embedded in the inorganic vitreous host matrix formed a nanocomposite material. Specific investigations such as X-ray diffraction (XRD), optical absorbance in the ultraviolet (UV)-visible (Vis)-near infrared (NIR) domain, NIR luminescence, Raman spectroscopy, scanning electron microscopy-energy dispersive X-ray (SEM-EDX), and atomic force microscopy (AFM) were used to obtain a comprehensive characterization of the deposited film. The dimensions of the PbS nanocrystallite phase were corroborated by XRD, SEM-EDX, and AFM results. The luminescence band from 1400 nm follows the luminescence peak of the precursor solution and that of the dopant solution. The emission of the PbS-doped film in the NIR domain is a premise for potential application in temperature sensing systems.

Prospects of NIR fluorescent nanosensors for green detection of SARS-CoV-2.

The pandemic of the novel coronavirus disease 2019 (COVID-19) is continuously causing hazards for the world. Effective detection of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) can relieve the impact, but various toxic chemicals are also released into the environment. Fluorescence sensors offer a facile analytical strategy. During fluorescence sensing, biological samples such as tissues and body fluids have autofluorescence, giving false-positive/negative results because of the interferences. Fluorescence near-infrared (NIR) nanosensors can be designed from low-toxic materials with insignificant background signals. Although this research is still in its infancy, further developments in this field have the potential for sustainable detection of SARS-CoV-2. Herein, we summarize the reported NIR fluorescent nanosensors with the potential to detect SARS-CoV-2. The green synthesis of NIR fluorescent nanomaterials, environmentally compatible sensing strategies, and possible methods to reduce the testing frequencies are discussed. Further optimization strategies for developing NIR fluorescent nanosensors to facilitate greener diagnostics of SARS-CoV-2 for pandemic control are proposed.

Matching Charge Extraction Contact for Infrared PbS Colloidal Quantum Dot Solar Cells.

Infrared solar cells (IRSCs) can supplement silicon or perovskite SCs to broaden the utilization of the solar spectrum. As an ideal infrared photovoltaic material, PbS colloidal quantum dots (CQDs) with tunable bandgaps can make good use of solar energy, especially the infrared region. However, as the QD size increases, the energy level shrinking and surface facet evolution makes us reconsider the matching charge extraction contacts and the QD passivation strategy. Herein, different to the traditional sol-gel ZnO layer, energy-level aligned ZnO thin film from a magnetron sputtering method is adopted for electron extraction. In addition, a modified hybrid ligand recipe is developed for the facet passivation of large size QDs. As a result, the champion IRSC delivers an open circuit voltage of 0.49 V and a power conversion efficiency (PCE) of 10.47% under AM1.5 full-spectrum illumination, and the certified PCE is over 10%. Especially the 1100 nm filtered efficiency achieves 1.23%. The obtained devices also show high storage stability. The present matched electron extraction and QD passivation strategies are expected to highly booster the IR conversion yield and promote the fast development of new conception QD optoelectronics.

Bis(4-methylpiperidine-1-carbodithioato)-lead(II) and Bis(4-benzylpiperidine-1-carbodithioato)-lead(II) as Precursors for Lead Sulphide Nano Photocatalysts for the Degradation of Rhodamine B.

Bis(4-methylpiperidine-1-carbodithioato)-lead(II) and bis(4-benzylpiperidine-1-carbodithioato)-lead(II) were prepared and their molecular structures elucidated using single crystal X-ray crystallography and spectroscopic techniques. The compounds were used as precursors for the preparation of lead sulphide nano photocatalysts for the degradation of rhodamine B. The single crystal structures of the lead(II) dithiocarbamate complexes show mononuclear lead(II) compounds in which each lead(II) ion coordinates two dithiocarbamato anions in a distorted tetrahedral geometry. The compounds were thermolyzed at 180 ℃ in hexadecylamine (HDA), octadecylamine (ODA), and trioctylphosphine oxide (TOPO) to prepare HDA, ODA, and TOPO capped lead sulphide (PbS) nanoparticles. Powder X-ray diffraction (pXRD) patterns of the lead sulphide nanoparticles were indexed to the rock cubic salt crystalline phase of lead sulphide. The lead sulphide nanoparticles were used as photocatalysts for the degradation of rhodamine B with ODA-PbS1 achieving photodegradation efficiency of 45.28% after 360 min. The photostability and reusability studies of the as-prepared PbS nanoparticles were studied in four consecutive cycles, showing that the percentage degradation efficiency decreased slightly by about 0.51-1.93%. The results show that the as-prepared PbS nanoparticles are relatively photostable with a slight loss of photodegradation activities as the reusability cycles progress.