Photoluminescent Silicon Nanoparticles: Fluorescent Cellular Imaging Applications and Photoluminescence (PL) Behavior Study

Molecular fluorophores and semiconductor quantum dots (QDs) have been used as cellular imaging agents for biomedical research, but each class has challenges associated with their use, including poor photostability or toxicity. Silicon is a semiconductor material that is inexpensive and relatively environmental benign in comparison to heavy metal-containing quantum dots. Thus, red-emitting silicon nanoparticles (Si NPs) are desirable to prepare for cellular imaging application to be used in place of more toxic QDs. However, Si NPs currently suffer poorly understood photoinstability, and furthermore, the origin of the PL remains under debate. This dissertation first describes the use of diatomaceous earth as a new precursor for the synthesis of photoluminescent Si NPs. Second, the stabilization of red PL from Si NPs in aqueous solution via micellar encapsulation is reported. Thirdly, red to blue PL conversion of decane-terminated Si NPs in alcohol dispersions is described and the origins (i.e., color centers) of the emission events were studied with a comprehensive characterization suite including FT-IR, UV-vis, photoluminescence excitation, and time-resolved photoluminescence spectroscopies in order to determine size or chemical changes underlying the PL color change. In this study, the red and blue PL was determined to result from intrinsic and surface states, respectively. Lastly, we determined that the blue emission band assigned to a surface state can be introduced by base addition in originally red-emitting silicon nanoparticles, and that red PL can be restored by subsequent acid addition. This experimentally demonstrates blue PL is surface state related and can overcome the intrinsic state related excitonic recombination pathway in red PL event. Based on all the data collected and analyzed, we present a simple energy level diagram detailing the multiple origins of Si NP PL, which are related to both size and surface chemistry

Aqueous Red-Emitting Silicon Nanoparticles for Cellular Imaging: Consequences of Protecting Against Surface Passivation by Hydroxide and Water for Stable Red Emission

Stable, aqueous, red-to-near infrared emission is critical for the use of silicon nanoparticles (Si NPs) in biological fluorescence assays, but such Si NPs have been difficult to attain. We report a synthesis and surface modification strategy that protects Si NPs and preserves red photoluminescence (PL) in water for more than 6 mo. The Si NPs were synthesized via high temperature reaction, liberated from an oxide matrix, and functionalized via hydrosilylation to yield hydrophobic particles. The hydrophobic Si NPs were phase transferred to water using the surfactant cetyltrimethylammonium bromide (CTAB) with retention of red PL. CTAB apparently serves a double role in providing stable, aqueous, red-emitting Si NPs by (i) forming a hydrophobic barrier between the Si NPs and water and (ii) providing aqueous colloidal stability via the polar head group. We demonstrate preservation of the aqueous red emission of these Si NPs in biological media and examine the effects of pH on emission color

Маркетинг навколишнього середовища

The photophysical properties of silicon semiconductor nanocrystals (SiNCs) are extremely sensitive to the presence of surface chemical defects, many of which are easily produced by oxidation under ambient conditions. The diversity of chemical structures of such defects and the lack of tools capable of probing individual defects continue to impede understanding of the roles of these defects in SiNC photophysics. We use scanning tunneling spectroscopy to study the impact of surface defects on the electronic structures of hydrogen-passivated SiNCs supported on the Au(111) surface. Spatial maps of the local electronic density of states (LDOS) produced by our measurements allowed us to identify locally enhanced defect-induced states as well as quantum-confined states delocalized throughout the SiNC volume. We use theoretical calculations to show that the LDOS spectra associated with the observed defects are attributable to Si-O-Si bridged oxygen or Si-OH surface defects

Demographic and Clinical Characteristics of Patients with Severe Asthma in the Asian Pacific Region : data from the International Severe Asthma Registry (ISAR)

Peer reviewe

Electrochemically Deposited MoS2 and MnS Multilayers on Nickel Substrates in Inverse Opal Structure as Supercapacitor Microelectrodes

High-dispersion polystyrene (PS) microspheres with monodispersity were successfully synthesized by the non-emulsification polymerization method, and three-dimensional (3D) photonic crystals of PS microspheres were fabricated by electrophoretic self-assembly (EPSA). The metal nickel inverse opal structure (IOS) photonic crystal, of which the structural thickness can be freely adjusted via electrochemical deposition (ECD), and subsequently, MnS/MoS2/Ni-IOS specimens were also prepared by ECD. Excellent specific capacitance values (1880 F/g) were obtained at a charge current density of 5 A/g. The samples in this experiment were tested for 2000 cycles of cycle life and still retained a reasonably good level of 76.6% of their initial capacitance value. In this study, the inverse opal structure photonic crystal substrate was used as the starting point, and then the microelectrode material for the MnS/MoS2/Ni-IOS supercapacitor was synthesized. Our findings show that the MnS/MoS2/Ni-IOS microelectrode makes a viable technical contribution to the design and fabrication of high-performance supercapacitors

Recent Configurational Advances for Solid-State Lithium Batteries Featuring Conversion-Type Cathodes

Solid-state lithium metal batteries offer superior energy density, longer lifespan, and enhanced safety compared to traditional liquid-electrolyte batteries. Their development has the potential to revolutionize battery technology, including the creation of electric vehicles with extended ranges and smaller more efficient portable devices. The employment of metallic lithium as the negative electrode allows the use of Li-free positive electrode materials, expanding the range of cathode choices and increasing the diversity of solid-state battery design options. In this review, we present recent developments in the configuration of solid-state lithium batteries with conversion-type cathodes, which cannot be paired with conventional graphite or advanced silicon anodes due to the lack of active lithium. Recent advancements in electrode and cell configuration have resulted in significant improvements in solid-state batteries with chalcogen, chalcogenide, and halide cathodes, including improved energy density, better rate capability, longer cycle life, and other notable benefits. To fully leverage the benefits of lithium metal anodes in solid-state batteries, high-capacity conversion-type cathodes are necessary. While challenges remain in optimizing the interface between solid-state electrolytes and conversion-type cathodes, this area of research presents significant opportunities for the development of improved battery systems and will require continued efforts to overcome these challenges

Low-Temperature Nitrogen Doping in Ammonia Solution for Production of N-Doped TiO2-Hybridized Graphene as a Highly Efficient Photocatalyst for Water Treatment

To facilitate the potential application of TiO2 as an efficient photocatalyst, the modulation of its band gap and electrical structure is of great significance. Herein, we report a very simple nitrogen (N)-doping method to obtain N-doped TiO2, which is hybridized with graphene sheets at a temperature as low as 180 °C and using an ammonia solution as the N source and reaction medium. X-ray photoelectron spectroscopy analysis revealed that the atomic N level could reach 2.4 atomic percent when the reaction time was 14 h. Photoluminescence (PL) emission spectra indicated that N-doped TiO2/graphene composites have drastically suppressed TiO2 PL intensity when compared to undoped TiO2, confirming the lower recombination rate of electron–hole pairs in the N-doped TiO2. Additionally, photodegradation data showed that the decomposition rate of methylene blue with our N-doped TiO2/graphene photocatalyst is twice as fast as a commercial Degussa P25 catalyst. Furthermore, density functional theory (DFT) calculations demonstrate that N doping creates empty states in the band gap of the TiO2 that are below the Fermi energy of graphene. Thus, when N-doped TiO2 is brought into contact with graphene, these states become filled by electrons from the graphene, shifting the TiO2 bands upward relative to the graphene. Such a shift in band alignment across the TiO2/graphene heterojunction makes transfer of the photoexcited electron more energetically favorable. This work provides a very convenient chemical route to the scalable production of N-doped TiO2/graphene photocatalyst for potential applications in wastewater treatment

The Effect of Annealing on the Optoelectronic Properties and Energy State of Amorphous Pyrochlore Y₂Ti₂O₇ Thin Layers by Sol–Gel Synthesis

Pyrochlore titanate (Y2Ti2O7) is a promising material for a wide range of applications in optoelectronics and photocatalysis due to its advantageous chemical, mechanical, and optical properties. To enhance its potential for such uses, however, a high-quality and scalable synthesis method is required. We here investigate the crystallization of sol–gel produced Y2Ti2O7 layers. We observe a transition of the amorphous pyrochlore phase at annealing temperatures below 700 °C. The transmittances of the Y2Ti2O7 thin layers annealed at 400 to 700 °C are approximately 92.3%. The refractive indices and packing densities of Y2Ti2O7 thin layers annealed at 400–700 °C/1 h vary from 1.931 to 1.954 and 0.835 to 0.846, respectively. The optical bandgap energies of Y2Ti2O7 thin layers annealed at 400–700 °C/1 h reduce from 4.356 to 4.319 eV because of the Moss–Burstein effect. These good electronic and optical properties make Y2Ti2O7 thin layers a promising host material for many potential applications

Low-Temperature Nitrogen Doping in Ammonia Solution for Production of N‑Doped TiO₂‑Hybridized Graphene as a Highly Efficient Photocatalyst for Water Treatment

To facilitate the potential application of TiO₂ as an efficient photocatalyst, the modulation of its band gap and electrical structure is of great significance. Herein, we report a very simple nitrogen (N)-doping method to obtain N-doped TiO₂, which is hybridized with graphene sheets at a temperature as low as 180 °C and using an ammonia solution as the N source and reaction medium. X-ray photoelectron spectroscopy analysis revealed that the atomic N level could reach 2.4 atomic percent when the reaction time was 14 h. Photoluminescence (PL) emission spectra indicated that N-doped TiO₂/graphene composites have drastically suppressed TiO₂ PL intensity when compared to undoped TiO₂, confirming the lower recombination rate of electron–hole pairs in the N-doped TiO₂. Additionally, photodegradation data showed that the decomposition rate of methylene blue with our N-doped TiO₂/graphene photocatalyst is twice as fast as a commercial Degussa P25 catalyst. Furthermore, density functional theory (DFT) calculations demonstrate that N doping creates empty states in the band gap of the TiO₂ that are below the Fermi energy of graphene. Thus, when N-doped TiO₂ is brought into contact with graphene, these states become filled by electrons from the graphene, shifting the TiO₂ bands upward relative to the graphene. Such a shift in band alignment across the TiO₂/graphene heterojunction makes transfer of the photoexcited electron more energetically favorable. This work provides a very convenient chemical route to the scalable production of N-doped TiO₂/graphene photocatalyst for potential applications in wastewater treatment