Combining second harmonic generation and multiphoton excited photo-luminescence to investigate TiO2 nanoparticle powders.

Disentangling Second Harmonic Generation (SHG) and Multiphoton Excited Photoluminescence (MEPL) signals in microscopy experiments is not an easy task. Two methods have been so far proposed based either on a time domain or a spectral domain analysis of the collected signals. In this report, a new method based on polarization discrimination is proposed to separate these SHG and MEPL contributions. In order to demonstrate this operation, intensity depth profiles are recorded for an anatase titanium dioxide powder consisting of 22 nm diameter nanoparticles using ultrafast femtosecond laser excitation. Polarization analysis of these intensity depth profiles is therefore performed and demonstrates a polarization angle shift for the SHG intensity contribution as compared to the MEPL one, allowing for the discrimination of the two SHG and MEPL contributions. The fundamental beam is set at two different wavelengths in order to provide a SHG photon energy above and below the anatase TiO2 band-gap of 3.2 eV, leading to a change in the relative intensity weight and a spectral shift between the SHG and MEPL contributions. This operation further demonstrates the potential of the method when the spectral domain disentangling cannot be performed. SHG profiles are by far narrower than those of MEPL. This study where both SHG and MEPL contributions are observed offers perspectives in photonics of powder materials as the different origin and properties of the two processes can be separated.

Lu doping nickel oxide thin films using sol-gel spin coated and density functional theory: optoelectronic and magnetic properties.

For the first time, sol-gel spin coating was used to fabricate thin films of NiO doped with lutetium. The films were characterized to determine their crystalline structure, surface morphology, and optical properties as a function of Lu doping concentration. The investigations revealed that the Lu-doped NiO films consisted of nano-polycrystalline particles with a cubic bunsenite structure and (200) preferential orientation. Optical studies indicated that the optical band gap of pure NiO widened with low levels of Lu incorporation before narrowing with higher concentrations. The Urbach energy value for pure NiO initially decreased with 1 at. % Lu-content, from 224 meV to 190 meV, and then continuously increased to 380 meV with more Lu-level. To investigate the effects of Lu doping on the electronics, magnetic, and optical properties of NiO, first-principle computations were performed. The results showed that bulk magnetization underwent significant modifications due to a high hybridization between the Lu-f/d and Ni-d states. This study suggests that NiO doped with lutetium could be used for spin-polarized transport devices and other spin-dependent applications.

Experimental and theoretical study of catalytic dye degradation and bactericidal potential of multiple phase Bi and MoS2 doped SnO2 quantum dots.

In the present study, different concentrations (1 and 3%) of Bi were incorporated into a fixed amount of molybdenum disulfide (MoS2) and SnO2 quantum dots (QDs) by co-precipitation technique. This research aimed to increase the efficacy of dye degradation and bactericidal behavior of SnO2. The high recombination rate of SnO2 can be decreased upon doping with two-dimensional materials (MoS2 nanosheets) and Bi metal. These binary dopants-based SnO2 showed a significant role in methylene blue (MB) dye degradation in various pH media and antimicrobial potential as more active sites are provided by nanostructured MoS2 and Bi3+ is responsible for producing a variety of different oxygen vacancies within SnO2. The prepared QDs were described via morphology, optical characteristics, elemental composition, functional group, phase formation, crystallinity, and d-spacing. In contrast, antimicrobial activity was checked at high and low dosages against Escherichia coli (E. coli) and the inhibition zone was calculated utilizing a Vernier caliper. Furthermore, prepared samples have expressed substantial antimicrobial effects against E. coli. To further explore the interactions between the MB and Bi/MoS2-SnO2 composite, we modeled and calculated the MB adsorption using density functional theory and the Heyd-Scuseria-Ernzerhof hybrid (HSE06) approach. There is a relatively strong interaction between the MB molecule and Bi/MoS2-SnO2 composite.

Machine Learning for Halide Perovskite Materials ABX3 (B = Pb, X = I, Br, Cl) Assessment of Structural Properties and Band Gap Engineering for Solar Energy.

The exact control of material properties essential for solar applications has been made possible because of perovskites' compositional engineering. However, tackling efficiency, stability, and toxicity at the same time is still a difficulty. Mixed lead-free and inorganic perovskites have lately shown promise in addressing these problems, but their composition space is vast, making it challenging to find good candidates even with high-throughput approaches. We investigated two groups of halide perovskite compound data with the ABX3 formula to investigate the formation energy data for 81 compounds. The structural stability was analyzed over 63 compounds. For these perovskites, we used new library data extracted from a calculation using generalized-gradient approximation within the Perdew-Burke-Ernzerhof (PBE) functional established on density functional theory. As a second step, we built machine learning models, based on a kernel-based naive Bayes algorithm that anticipate a variety of target characteristics, including the mixing enthalpy, different octahedral distortions, and band gap calculations. In addition to laying the groundwork for observing new perovskites that go beyond currently available technical uses, this work creates a framework for finding and optimizing perovskites in a photovoltaic application.

Facile Synthesis of Barium-Doped Cadmium Sulfide Quantum Dots for the Treatment of Polluted Water: Experimental and Computational Investigations.

In this study, cadmium sulfide (CdS) quantum dots (QDs) and barium (Ba) (3 and 6 wt %)-doped CdS QDs were synthesized via a hydrothermal technique. The basic purpose of this work is to degrade methylene blue (MB) dye and evaluate density functional theory (DFT). The synthesized samples were characterized through X-ray powder diffraction (XRD), selected area electron diffraction (SAED), Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM), high-resolution transmission electron microscopy (HR-TEM), UV-vis spectrophotometer, PL, and density functional theory (DFT). The XRD (structural analysis) confirmed that the hexagonal crystal structure and crystallinity increased upon doping. Selected area electron diffraction (SAED) analysis confirmed the polycrystalline nature of the prepared QDs. The functional groups have been investigated using FTIR analysis. The surface and structural morphologies of the synthesized specimen have been investigated by applying TEM and FE-SEM, and it was found to exhibit the topology of QDs. In addition, optical characteristics have been investigated via UV-vis absorption spectroscopy, which exhibited a bathochromic shift (red shift) as a consequence of the reduction of the band-gap energy upon doping from 2.56 to 2.38 eV. PL analysis was used to observe the electron-hole recombination rate. Moreover, the electronic and optical properties of Ba-doped CdS were further explored using density functional theory. Pristine and Ba-doped QDs exhibit sufficient catalytic activity (CA) against the MB dye in all media as 62.59, 70.15, and 72.74% in neutral, basic, and acidic solutions, respectively.

Synthesis of Al/starch co-doped in CaO nanoparticles for enhanced catalytic and antimicrobial activities: experimental and DFT approaches.

In this work, aluminum/starch (St)-doped CaO nanoparticles (NPs) were synthesized by a co-precipitation method to degrade harmful dyes in various pH media. Systematic characterization was performed to investigate the influence of Al/St dopants on the composition, crystal structure, functional groups present, optical characteristics, and morphology of CaO NPs. Further hybrid density functional analyses corroborated that the band gap energy was reduced as the Al concentration in starch-doped CaO is increased. Optical absorption spectra of the synthesized materials revealed a redshift upon doping, which indicated depletion in the band gap energy of Al/St-doped CaO. PL spectroscopy showed that the intensity of CaO was reduced by the incorporation of Al and St assigned to minimum electron-hole pair recombination. Interlayer spacing and morphological features were determined by HR-TEM. HRTEM revealed that the control sample has cubic NPs and the incorporation of St showed overlapping around agglomerated NPs. The d-spacing of CaO was little enhanced by the inclusion of dopants. Experimental outcomes indicated that the addition of Co-dopants improved the catalytic potential of CaO NPs. Al (4%)/St-doped CaO NPs expressed a significant reduction of methylene blue in a basic environment. The maximum bactericidal performance was observed as 10.25 mm and 4.95 mm in the inhibition zone against S. aureus and E. coli, respectively, after the addition of Al and St in CaO.

The enhanced photocatalytic performance and first-principles computational insights of Ba doping-dependent TiO2 quantum dots.

Degradation in the presence of visible light is essential for successfully removing dyes from industrial wastewater, which is pivotal for environmental and ecological safety. In recent years, photocatalysis has emerged as a prominent technology for wastewater treatment. This study aimed to improve the photocatalytic efficiency of synthesized TiO2 quantum dots (QDs) under visible light by barium (Ba) doping. For this, different weight ratios (2% and 4%) of Ba-doped TiO2 QDs were synthesized under ambient conditions via a simple and modified chemical co-precipitation approach. The QD crystal structure, functional groups, optical features, charge-carrier recombination, morphological properties, interlayer spacing, and presence of dopants were analyzed. The results showed that for 4% Ba-doped TiO2, the effective photocatalytic activity in the degradation process of methylene blue (MB) dye was 99.5% in an alkaline medium. Density functional theory analysis further corroborated that the band gap energy was reduced when Ba was doped into the TiO2 lattice, implying a considerable redshift of the absorption edge due to in-gap states near the valence band.

Hybrid Density Functional Investigation of Cu Doping Impact on the Electronic Structures and Optical Characteristics of TiO2 for Improved Visible Light Absorption.

We report a theoretical investigation of the influence of Cu doping into TiO2 with various concentrations on crystal structure, stability, electronic structures and optical absorption coefficient using density functional theory via the hybrid formalism based on Heyd Scuseria Ernzerhof. Our findings show that oxygen-rich environments are better for fabricating Cu-doped materials and that the energy of formation for Cu doping at the Ti site is lower than for Cu doping at the O site under these environments. It is found that Cu doping introduces intermediate bands into TiO2, narrowing the band gap. Optical absorption curves show that the Cu-doped TiO2 can successfully harvest visible light. The presence of widely intermediate bands above the valence-band edge could explain the increase in the visible light absorption range. However, the intensity of visible light absorption rises with the increase in doping concentration.

Novel Ta/chitosan-doped CuO nanorods for catalytic purification of industrial wastewater and antimicrobial applications.

Novel tantalum (Ta) and chitosan (CS)-doped CuO nanorods (NRs) were synthesized using a single step co-precipitation route. Different concentrations (2 and 4%) of Ta were used in fixed amounts of CS and CuO to examine their catalytic activity and antimicrobial potential. For critical analysis, synthesized NRs were systematically examined using XRD, FTIR HRTEM, EDS, UV-Vis and PL spectroscopy. The XRD technique revealed the monoclinic structure of CuO while an increase in its crystallite size (from 15.5 to 18.5 nm) was observed upon doping. FTIR spectra were examined to study the functional groups of CuO where peaks at 514 cm-1 and 603 cm-1 confirmed the formation of CuO NRs. PL spectra depicted the charge transfer efficiency of the synthesized samples. The presence of dopants (Ta and CS) and constituent elements (Cu, O) was detected using EDS spectra. Additionally, the pH based catalytic performance of fabricated NRs revealed 99.7% dye degradation of toxic methylene blue (MB) dye in neutral media, 99.4% in basic media and 99.5% in acidic media along with promising antibacterial activities for Gram negative/positive bacteria, respectively upon doping of Ta (4%) into CS/CuO. The adsorption energies of CuO co-doped with CS/Ta led to the creation of stable structures that were investigated theoretically using density functional theory.

Experimental and Computational Study of Zr and CNC-Doped MnO2 Nanorods for Photocatalytic and Antibacterial Activity.

Cellulose nanocrystals (CNC), MnO2, CNC-doped MnO2, and Zr/CNC-doped MnO2 were prepared with a hydrothermal method to assess their photocatalytic and antibacterial properties. Various characterizations were undertaken to determine the phase composition, the existence of functional units, optical characteristics, elemental analysis, surface topography, and microstructure of the prepared materials. Sample crystallinity was improved, whereas a decrease in crystallite size was observed with increasing amounts of dopants. Incorporation of dopants (CNC and Zr) into MnO2 instigated a transformation in morphology from nanoclusters to nanorods with different diameters. Furthermore, photocatalytic activity experiments indicated a more effective degradation of methylene blue (MB) dye with CNC-doped MnO2 and Zr/CNC-codoped MnO2 while enhancing the bacterial efficacy for both G +ve and G -ve. Density functional theory was utilized to model the structures and elucidate their bonding and charge transfer mechanisms. The Zr/CNC-MnO2 system showed charge depletion around Mn atoms, while charges were observed to accumulate around oxygen atoms.

Structural Transition-Induced Raman Enhancement in Bioinspired Diphenylalanine Peptide Nanotubes.

Semiconducting materials are increasingly proposed as alternatives to noble metal nanomaterials to enhance Raman scattering. We demonstrate that bioinspired semiconducting diphenylalanine peptide nanotubes annealed through a reported structural transition can support Raman detection of 10-7 M concentrations for a range of molecules including mononucleotides. The enhancement is attributed to the introduction of electronic states below the conduction band that facilitate charge transfer to the analyte molecule. These results show that organic semiconductor-based materials can serve as platforms for enhanced Raman scattering for chemical sensing. As the sensor is metal-free, the enhancement is achieved without the introduction of electromagnetic surface-enhanced Raman spectroscopy.

Low-Cost Inorganic Strontium Ferrite a Novel Hole Transporting Material for Efficient Perovskite Solar Cells.

Perovskite solar cells attract significant interest due to their high-power conversion efficiencies. The replacement of charge-transporting layers using inorganic materials is an effective approach for improving stability and performance, as these materials are low-cost, highly durable, and environmentally friendly. This work focuses on the inorganic hole and electron transport layers (HTL and ETL), strontium ferrite (SrFe2O4), and zinc oxide (ZnO), respectively, to enhance the efficiency of perovskite solar cells. Favorable band alignment and high charge-collection capability make these materials promising. Experimental and computational studies revealed that the power conversion efficiency of the fabricated device is 7.80% and 8.83%, respectively. Investigating electronic properties and interface charge transfer through density functional theory calculations further corroborated that SrFe2O4 is a good HTL candidate. Our numerical device modeling reveals the importance of optimizing the thickness (100 nm and 300 nm) of the HTL and perovskite layers and defect density (1016 cm-3) of the absorber to achieve better solar cell performance.

Impact of Bi Doping into Boron Nitride Nanosheets on Electronic and Optical Properties Using Theoretical Calculations and Experiments.

In the present work, boron nitride (BN) nanosheets were prepared through bulk BN liquid phase exfoliation while various wt. ratios (2.5, 5, 7.5 and 10) of bismuth (Bi) were incorporated as dopant using hydrothermal technique. Our findings exhibit that the optical investigation showed absorption spectra in near UV region. Density functional theory calculations indicate that Bi doping has led to various modifications in the electronic structures of BN nanosheet by inducing new localized gap states around the Fermi level. It was found that bandgap energy decrease with the increase of Bi dopant concentrations. Therefore, in analysis of the calculated absorption spectra, a redshift has been observed in the absorption edges, which is consistent with the experimental observation. Additionally, host and Bi-doped BN nanosheets were assessed for their catalytic and antibacterial potential. Catalytic activity of doped free and doped BN nanosheets was evaluated by assessing their performance in dye reduction/degradation process. Bactericidal activity of Bi-doped BN nanosheets resulted in enhanced efficiency measured at 0-33.8% and 43.4-60% against S. aureus and 0-38.8% and 50.5-85.8% against E. coli, respectively. Furthermore, In silico molecular docking predictions were in good agreement with in-vitro bactericidal activity. Bi-doped BN nanosheets showed good binding score against DHFR of E. coli (- 11.971 kcal/mol) and S. aureus (- 8.526 kcal/mol) while binding score for DNA gyrase from E. coli (- 6.782 kcal/mol) and S. aureus (- 7.819 kcal/mol) suggested these selected enzymes as possible target.

Liquid-phase exfoliated MoS2 nanosheets doped with p-type transition metals: a comparative analysis of photocatalytic and antimicrobial potential combined with density functional theory.

MoS2 nanosheets were developed by undertaking the liquid-phase exfoliation of bulk counterparts. In order to enhance its photocatalytic properties, the host material was doped with p-type transition metals (i.e., Ag, Co, Bi, and Zr). The hydrothermal technique was used to produce samples doped with 7.5 wt% transition metals (TM). X-ray diffraction detected the existence of 2H-phase by mirroring its reflection at 2θ ∼ 14°, while the peak distribution revealed the degree of exfoliation in samples. Low PL intensities indicated a lower recombination of electron-hole pairs, as corroborated by a high degree of photocatalytic action. Raman analysis was undertaken to identify molecular vibrations. The A1g mode in Raman spectra consistently showed a blueshift in all samples and the E12g mode was only slightly affected, which is evidence of the p-type doping in the MoS2 nanosheets. In the XPS spectrum, two characteristic peaks of Mo 3d appeared at 229.87 and 233.03 eV assigned to Mo-3d5/2 and Mo-3d3/2, respectively. Furthermore, a microstructural examination with HR-TEM and FESEM divulged a thin-layered structure of MoS2 consisting of flat, gently curved or twisted nanosheets. Diverse morphologies were observed with a non-uniform distribution of the dopant. Photocatalytic action of the TM-doped products effectively degraded methylene blue (MB) concentrations of up to 94 percent (for Ag-MoS2). The synergistic effect of doped MoS2 nanosheets against S. aureus in comparison to E. coli bacteria was also evaluated. The efficacy % age improved from (0-31.7%) and (23.5-55.2%) against E. coli, and (0-34.2%) and (8.3-69.23%) against S. aureus. Moreover, results from first principles calculations indicate that substitutional doping of TM atoms is indeed advantageous. Theoretical calculations confirmed that doping with Ag, Co, Bi, and Zr leads to a decrease in the band gap to a certain degree, in which the conduction band edge shifts toward lower energy, while the valence band shifts closer to the high energy end. It can be concluded that Ag, Co, and Bi impurities can lead to beneficial p-type doping in MoS2 monolayered structures. With regards to doping with Zr, the acceptor levels are formed above the edge of the valence band, revealing an introduction of the p-type character.

Synthesis and Studies of Electro-Deposited Yttrium Arsenic Selenide Nanofilms for Opto-Electronic Applications.

Nanocomposite films grown by incorporating varying concentrations of Yttrium, a d-block rare-earth ion, into the binary chalcogenide Arsenic selenide host matrix is here presented. Films were grown via the wet-chemical electro-deposition technique and characterized for structural, optical, surface morphology, and photoluminescence (PL) properties. The X-ray Diffraction (XRD) result of the host matrix (pristine film) showed films of monoclinic structure with an average grain size of 36.2 nm. The composite films, on the other hand, had both cubic YAs and tetragonal YSe structures with average size within 36.5-46.8 nm. The fairly homogeneous nano-sized films are shown by the Scanning Electron Microscopy (SEM) micrographs while the two phases of the composite films present in the XRD patterns were confirmed by the Raman shifts due to the cleavage of the As-Se host matrix and formation of new structural units. The refractive index peaked at 2.63 within 350-600 nm. The bandgap energy lies in the range of 3.84-3.95 eV with a slight decrease with increasing Y addition; while the PL spectra depict emission bands across the Vis-NIR spectral regions. Theoretically, the density functional theory (DFT) simulations provided insight into the changes induced in the structure, bonding, and electronic properties. Besides reducing the bandgap of the As2Se3, the yttrium addition has induced a lone pair p-states of Se contributing nearby to Fermi energy level. The optical constants, and structural and electronic features of the films obtained present suitable features of film for IR applications as well as in optoelectronics.

Insights into the Impact of Yttrium Doping at the Ba and Ti Sites of BaTiO3 on the Electronic Structures and Optical Properties: A First-Principles Study.

We reported a systematic study of the effects of Y doping BaTiO3 at Ba and Ti sites. We assessed the structural, electronic, and optical properties by employing first-principles calculations within the Tran-Blaha-modified Becke-Johnson (TB-mBJ) potential and generalized gradient approximation + U approaches. We calculated the lattice constants and bond lengths for pure and Y-doped BaTiO3. We explored the consequences of electronic structure and optical property modification because of Y doping in BaTiO3. Indeed, Y doping has led to various modifications in the electronic structures of BaTiO3 by inducing a shift of the conduction band through lower energies for the Ba site and higher energies for the Ti site. It was found that Y doping, either at Ba or at Ti sites, strongly enhanced the BaTiO3 dielectric constant properties. The transformation in bonding was explored via the charge density contours and Born effective charges. We used the state of art of polarization theory based on finite difference and Berry-phase approaches to investigate piezoelectricity. Y doping has increased the dielectric constants but canceled the piezoelectricity as they changed to metallic nature. We could look into the future for potential doping, preserving the semiconductor nature of BaTiO3 and increasing the permittivity with large dielectric loss.

Experimental spectral characterization, Hirshfeld surface analysis, DFT/TD-DFT calculations and docking studies of (2Z,5Z)-5-(4-nitrobenzylidene)-3-N(2-methoxyphenyl)-2-N'(2-methoxyphenylimino) thiazolidin-4-one.

We reported an experimental and theoretical spectroscopic studies of (2Z,5Z)-5-(4-nitrobenzylidene)-3-N (2-methoxyphenyl)-2-N' (2-methoxyphenylimino) thiazolidin-4-one (C24H19N3O5S) molecule, using FT-IR, NMR spectroscopy, and density functional theory (DFT) via time-dependent schema (TD-DFT) respectively. The molecular inter-contacts were explored using Hirshfeld surfaces (HS) analysis method. Vibrational frequencies, gauge-independent atomic orbital (GIAO)1H and13C NMR chemical shift values and frontier molecular orbitals (FMOs) have been calculated from the optimized structure of the molecule by DFT/B3LYP functional with 6-31G(d, p) basis set. Our theoretical results show a good agreement with the experimental data. The calculated UV-visible spectrum employing TD-DFT shows electronic transitions at 388 nm and 495 nm. To get insight on the charge interaction happening inside the molecule, HOMO and LUMO were scrutinized and their calculated energy gap was found to be 2.96 eV. The molecular docking was analyzed via interplay study ofacetyl cholinesterase, and Butyrylcholinesterase using molecular docking methodology.

Toward a better understanding of the enhancing/embrittling effects of impurities in Nickel grain boundaries.

The fracture path follows grain boundaries (GB) in most metallic system under tensile test. In general, impurities, even in ppm concentration, that segregate to these boundaries can remarkably change materials mechanical properties. Predicting impurities segregation effects in Nickel super-alloys might not be seen as intuitive and perhaps more fundamental understanding is needed. We performed a density functional theory calculation to elucidate the effect of eight light elements (B, C, N, O, Al, Si, P and S) and twelve transition metal elements (Tc, Ti, V, Cr, Mn, Zr, Nb, Mo, Hf, Ta, W, Re) on Nickel ∑5(210) grain boundary formation and its Ni free surface. The effect of impurities was carefully examined by calculating different properties such as segregation, binding and cohesive energies, strengthening/embrittling potency and the theoretical tensile strength. Additionally, we employed the electron density differences and magnetic effects to explain why and how impurities such as B, S, V, Nb, Mn and W affect Nickel ∑5 GB. We used the generated data calculated on equal footing, to develop a fundamental understanding on impurity effect. A clear and strong correlation is found between difference in magnetic moment change between isolated and imbedded impurity atom on one hand and the tensile strength on the other hand. The higher the loss of the magnetic moment, the more the impurity consolidates the GB.

Electronic and optical properties of functionalized zigzag ZnO nanotubes.

The present paper reports the analysis of surface decoration on the structural, electronic, and optical properties of (n,0) ZnO nanotubes, performed by means of a density function theory based ab-initio approach. Fe functionalization induced buckling in ZnO nanotubes affects its electronic and optical properties. Increase in Fe functionalization leads to better stability of ZnO nanotube and shows enhanced metallic character. The possibility of its use in optoelectronics has been analyzed in terms of dielectric constant, absorption coefficient, and refractive index. In another observation, the high sensitivity of the HCN molecule for the Fe-incorporated ZnO nanotube suggests it as a potential gas sensor. Graphical abstract HCN-adsorbed Fe-ZnO nanotube, electron difference density, and PDOS analysis of different orbitals.

The origin of magnetism in transition metal-doped ZrO2 thin films: experiment and theory.

We have investigated the magnetic properties of Fe/Co/Ni-doped ZrO2 laser ablated thin films in comparison with the known results of Mn-doped ZrO2, which is thought to be a promising material for spintronics applications. It is found that doping with a transition metal can induce room temperature ferromagnetism in 'fake' diamond. Theoretical analysis based on density functional theory confirms the experimental measurements, by revealing that the magnetic moments of Mn- and Ni-doped ZrO2 thin films are much larger than that of Fe- or Co-doped ZrO2 thin films. Most importantly, our calculations confirm that Mn- and Ni-doped ZrO2 show a ferromagnetic ground state in comparison to Co- and Fe-doped ZrO2, which favor an antiferromagnetic ground state.