In this study, we demonstrated for the first time the growth of ZnO nanowires (NWs) decorated with highly crystalline few-layer PbI2 and fabricated two-terminal single-nanowire photodetector devices to investigate the photoelectric properties of the hybrid nanostructures. We developed a novel two-step growth process for uniform crystalline PbI2 nanosheets via reactive magnetron deposition of a lead oxide film followed by subsequent iodination to PbI2 on a ZnO NW substrate, and we compared as-grown hybrid nanostructures with ones prepared via thermal evaporation method. ZnO–PbI2 NWs were characterized by scanning and transmission electron microscopy, X-ray diffraction analysis and photoluminescence measurements. By fabricating two-terminal single-nanowire photodetectors of the as-grown ZnO–PbI2 nanostructures, we showed that they exhibit reduced dark current and decreased photoresponse time in comparison to pure ZnO NWs and have responsivity up to 0.6 A/W. Ab initio calculations of the electronic structure of both PbI2 nanosheets and ZnO NWs have been performed, and show potential for photoelectrocatalytic hydrogen production. The obtained results show the benefits of combining layered van der Waals materials with semiconducting NWs to create novel nanostructures with enhanced properties for applications in optoelectronics or X-ray detectors.
Temperature dependence of the afterglow of persistent luminescence material SrAl2O4:Eu,Dy is a major problem for outdoor low temperature applications. Therefore this publication deals with tailoring the material for better outdoor use by exploring the second mechanism, that is involved in the afterglow – charge tunnelling from the trapping center to the luminescence center. Structure, morphology, emission and thermally stimulated luminescence properties have been measured for SrAl2O4:Eu,Dy samples with different added boron percentage. The results indicate a change in morphology of the samples with increasing boron concentration, as well as a change in afterglow times. The low temperature luminescence intensity and afterglow time dependence of boron addition turns out to be different from the room temperature luminescence intensity and afterglow time dependence from boron concentration. Boron addition in necessary amount plays a key role to creating trapping centers in the material that are located spatially close to the luminescence center thus making the material afterglow possible even in low temperatures.
Photoluminescence and thermally stimulated luminescence of synthetic and natural (morion and smoky) α-quartz crystals doped with aluminum and alkali ions were studied. The samples were examined both untreated and subjected to substitution of alkali ions for copper or silver ions. The photoluminescence spectrum of the untreated crystals is characterized with the main blue band around 400 nm (~3.1 eV). The corresponding luminescence center is based on a defect containing aluminum and alkali as compensators in natural and synthetic quartz crystals. Photoluminescence is subjected to thermal quenching and can be detected at high temperatures above 700 K, however the main intensity decay takes place at 200 K. The thermal quenching activation energy is 0.15 ± 0.05 eV and the frequency factor is 3·107 s−1. In the samples with silver ions the main luminescence band is located at ~260 nm (~4.7 eV) with a time constant of ~37 μs at 80 K, and in the samples with copper ions the PL band is at ~ 360 nm (~3.4 eV) with a time constant ~ 50 μs at 80 K. The initial luminescence of crystals is greatly reduced after introduction of noble ions. The luminescence of noble ions quenches at 700 K without drop in intensity at 200 K. For luminescence associated with silver the energy of thermal quenching is 0.7 ± 0.1 eV with a frequency coefficient of 1 · 101 3 s−1, and for the luminescence related to copper, these parameters are 0.55 ± 0.1 eV and 1 · 101 2 s−1. The differences in intra-center luminescence properties of the same defect containing alkali ions or noble ions are based on differences in electronic transitions. In the case of alkali ions the charge transfer transitions between oxygen and alkali ions. In the case of noble ions absorption – luminescence corresponds to intra ion transitions. Radiation properties are related to trapping of an electron on one valence ion. Created atom moves out of aluminum containing defect. The hole remains on aluminum-oxygen defect. Thermally stimulated luminescence is related to release of atom, it diffusion to aluminum defect with the hole on oxygen and following radiative recombination. Optically stimulated luminescence is explained by the similar process of optical release of excited atom and movement to aluminum defect and recombination of electron with hole.
Temperature dependences of the photoluminescence and X-ray excited luminescence intensity and thermally stimulated luminescence glow curves are measured in the 4.2–300 K temperature range for the undoped and Ce3+ – doped Gd3(Ga,Al)5O12 crystals. The conclusion is made that no low-temperature quenching of the Ce3+ – related photoluminescence takes place. In both the undoped and the Ce3+ – doped crystals, temperature dependences of the X-ray excited recombination luminescence intensity correlate with the position and shape of thermally stimulated luminescence glow curve peaks of the hole origin. Low-temperature quenching of the X-ray excited luminescence in these crystals is explained by the fact that at low temperatures, free holes are trapped at oxygen ions while electrons are trapped at various intrinsic defects. In Ce3+ – doped Gd3(Ga,Al)5O12 crystals, thermally stimulated release of the trapped holes and electrons and their subsequent recombination at Ce3+ ions result in the enhancement of the Ce3+ – related electron recombination luminescence with the increasing temperature in the 10–180 K range.
Pyroelectric luminescence was observed in noncentrosymmetrical crystal LiGaO2 with the direct band gap around 6 eV. For the first time spectral and kinetic characteristics of pyroelectric luminescence were obtained. The temporal structure of the PEL signal was determined as a sequence of pulses with duration not longer than several nanoseconds. This allowed proposing of the luminescence mechanism: in vacuum conditions in LiGaO2 crystal pyroelectric luminescence occurs inside the sample due to radiative recombination of electrons with the positively charged intrinsic luminescence centres.
The photoelectric response spectra were studied in a LiGaO2 crystal. The obtained spectra were interpreted as the release and diffusion of charge carriers, as well as external photoemission of electrons. The charge carrier release starts from excitation with a photon with energy greater than the optical gap of the LiGaO2 crystal (∼6 eV). The efficiency of generation of charge carriers exponentially increases up to 8 eV with saturation beginning from 9 eV. The nature of the photoelectric response is attributed to the Dember effect corresponding to the higher mobility of electrons compared to holes. The low yield of the internal photoelectron in the range of the intrinsic absorption band at 6 eV is associated with its exciton nature. Above 9.5–10 eV, an additional response was revealed that was interpreted as external photoelectron emission with a threshold of about Eth = 10.1 ± 0.2 eV. The relative emission yield of electrons increases as (hν – Eth)3, which corresponds to indirect transitions between the valence and conduction bands. The emission of photoelectrons for the direct band-to-band transitions increases linearly with the photon energy and the corresponding threshold is defined as 12.7 ± 0.2 eV.
It was recently reported that more efficient triboelectric nanogenerator (TENG)-like devices can be prepared using inversely polarized ferroelectric films made of same material as the contacting layers. In the present work, a clear correlation between the piezoelectric response of inversely polarized ferroelectric PVDF/BaTiO3 nanocomposite films and the performance of the TENG-like device based on these films is demonstrated. This observation is explained by magnified electrostatic induction that is driven by piezoelectric charges and ferroelectric properties of these films. A double capacitor model is proposed that effectively portrays the interactions between ferroelectric layers during contact-separation and subsequent charge redistributions in the external circuit. The new understanding has allowed the result of 3-fold higher open circuit voltages (2.7 kV from 5 cm2) as compared to that of a state of the art TENG. Furthermore, findings uncover the potential for vast improvement in the field of nanogenerators for mechanical energy harvesting as a significantly better piezoelectric performance of flexible nanogenerators has been reported elsewhere.
Advanced lithium orthosilicate (Li 4 SiO 4 ) pebbles with additions of lithium metatitanate (Li 2 TiO 3 ) as a secondary phase have attracted international attention as an alternative solid-state candidate for the tritium breeding in future nuclear fusion reactors. In this research, the generation of radiation-induced defects in the Li 4 SiO 4 pebbles with various contents of Li 2 TiO 3 was analysed in-situ by X-ray induced luminescence technique. After irradiation with X-rays, the accumulated radiation-induced defects in the Li 4 SiO 4 pebbles were studied by electron spin resonance, thermally stimulated luminescence and absorption spectrometry. On the basis of the obtained results, it is concluded that the generation mechanism and the structure of primary radiation-induced defects (except Ti 3+ centres) in the advanced Li 4 SiO 4 pebbles with additions of Li 2 TiO 3 under exposure to X-rays is similar to the single-phase ceramics. In addition, it is expected that the additions of Li 2 TiO 3 can increase the probability for the recombination processes of primary radiation-induced defects in the advanced Li 4 SiO 4 pebbles during irradiation and thereby reduce the formation of thermally stable radiolysis products, such as colloidal lithium particles.
Nitrogen- and sulfur-codoped carbon catalysts were prepared as electrocatalytic materials for the oxygen reduction reaction (ORR). Herein, we propose a novel and effective one-pot synthetic approach to prepare a NS-doped carbon catalyst by using the mixture of graphene oxide and multi-walled carbon nanotubes as a carbon support. Successful NS-doping of carbon and formation of the catalytically active sites were confirmed by X-ray photoelectron spectroscopy and with energy dispersion spectroscopy. The ORR activity of NS-codoped carbon was investigated by using a rotating disc electrode method. The NS-doped carbon shows superior ORR performance in alkaline media, and the electrocatalytic mechanism for the reduction of oxygen was well explained by density functional theory calculations of graphene sheets.
For decades, plasma electrolytic oxidation (PEO) coatings are actively studied and applied to protect the surface of various valve metals from chemical or mechanical damage. However, over the last couple of years intense research is being done to explore additional possibilities of the PEO coatings apart from their classical application. One of the possible additional uses is thermostimulated luminescence dosimetry that is already widely applied for environmental and health monitoring. This research proposes a method to produce a novel functional coating on aluminium surface exhibiting intense thermostimulated luminescence signal that could be used for dosimetry of ionizing radiation. The result was achieved using plasma electrolytic oxidation with modified electrolyte to introduce carbon ions into the oxide thus inducing defects in the crystalline structure of the coating. Al6082 aluminium alloy was used as a substrate, KOH and ethanol mixture as an electrolyte. A bipolar pulsed regime was used for 15 min. The obtained coating combines the desired luminescence properties with a good mechanical stability due to the relatively hard cubic phase of the coating. Scalability of the technology and low production cost makes the coatings prospective for various practical applications.
The effects of indium concentration influence on the morphology, luminescence spectra and luminescence decay kinetics of ZnO:In nanocrystals prepared by the solar physical vapour deposition method are investigated. While undoped ZnO nanocrystals exhibit tetrapod-like morphology, with increasing indium concentration the tetrapods are transformed into particles whose average size decreases with increasing indium concentration. The results of time-resolved luminescence studies of undoped and indium doped ZnO nanocrystals showed that by increasing indium concentration the decay time falls and luminescence intensity decreases.
The search for engineering approaches to improve the scintillation properties of Gd 3 Al 2 Ga 3 O 12 crystals and enable their production technology is of current interest. This crystal, while doped with Ce, is considered a good multi-purpose scintillation material for detecting gamma-quanta and neutrons. It is observed that co-doping with Mg affected intrinsic defects in the crystal structure that create shallow electronic traps. Other point structure defects, which are based on local variations of the crystal stoichiometry, are significantly diminished by use of a co-precipitated raw material. Nano-structuring of the raw material enables production of a homogeneous precursor mixture for growing a crystal with minimal evaporation of Ga from the melt. The demonstrated nano-engineering approach increased the light yield from the crystal by approximately 20%, enabling its applications in well logging.
ZnO nanocrystals, undoped and doped with Iridium or Indium were prepared by solar irradiation in Heliotron reactor in PROMES CNRS facilities, France. The comparative analysis of the excitonic spectra of ZnO single crystal and ZnO nanocrystals (NCs) doped with In and Ir was performed. It is shown that the excitonic processes in Ir doped nanocrystals coincide well with electronic processes in undoped NC and single crystal; however, the electronic processes in In-doped nanocrystals are significantly different from those in single crystal. The radioluminescence spectra of ZnO:In was analysed and additional luminescence band at ∼3.18 eV was detected due to In-doping. The luminescence decay time depends on In concentration in nanocrystals and is significantly less in ZnO:In compared with undoped nanocrystals. The fast scintillation of ZnO:In makes this material promising for application.
The design of nanoparticle delivery materials possessing biological activities is an attractive strategy for the development of various therapies. In this study, 11 cationic amphiphilic 4-(N-alkylpyridinium)-1,4-dihydropyridine (1,4-DHP) derivatives differing in alkyl chain length and propargyl moiety/ties number and position were selected for the study of their self-assembling properties, evaluation of their cytotoxicity in vitro and toxicity on microorganisms, and the characterisation of their interaction with phospholipids. These lipid-like 1,4-DHPs have been earlier proposed as promising nanocarriers for DNA delivery. We have revealed that the mean diameter of freshly prepared nanoparticles varied from 58 to 513 nm, depending upon the 4-(N-alkylpyridinium)-1,4-DHP structure. Additionally, we have confirmed that only nanoparticles formed by 4-(N-dodecylpyridinium)-1,4-DHP derivatives 3 and 6, and by 4-(N-hexadecylpyridinium)-1,4-DHP derivatives 10 and 11 were stable after two weeks of storage. The nanoparticles of these compounds were found to be homogenous in size distribution, ranging from 124 to 221 nm. The polydispersity index (PDI) values of 1,4-DHPs samples 3, 6, 10, and 11 were in the range of 0.10 to 0.37. We also demonstrated that the nanoparticles formed by 4-(N-dodecylpyridinium)-1,4-DHP derivatives 3, 6, and 9, and 4-(N-hexadecylpyridinium)-1,4-DHP derivatives 10 and 11 had zeta-potentials from +26.07 mV (compound 6) to +62.80 mV (compound 11), indicating a strongly positive surface charge and confirming the relative electrostatic stability of these nanoparticle solutions. Transmission electron microscopy (TEM) images of nanoaggregates formed by 1,4-DHPs 3 and 11 confirmed liposome-like structures with diameters around 70 to 170 nm. The critical aggregation concentration (CAC) value interval for 4-(N-alkylpyridinium)-1,4-DHP was from 7.6 µM (compound 11) to 43.3 µM (compound 6). The tested 4-(N-alkylpyridinium)-1,4-DHP derivatives were able to quench the fluorescence of the binary 1,6-diphenyl-1,3,5-hexatriene (DPH)—1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) system, demonstrating hydrophobic interactions of 1,4-DHPs with phospholipids. Thus, 4-(N-dodecylpyridinium)-1,4-DHP derivative 3 quenched the fluorescence of the DPH–DPPC system more efficiently than the other 4-(N-alkylpyridinium)-1,4-DHP derivatives. Likewise the compound 3, also 4-(N-dodecylpyridinium)-1,4-DHP derivative 9 interacted with the phospholipids. Moreover, we have established that increasing the length of the alkyl chain at the quaternised nitrogen of the 4-(N-alkylpyridinium)-1,4-DHP molecule or the introduction of propargyl moieties in the 1,4-DHP molecule significantly influences the cytotoxicity on HT-1080 (human fibrosarcoma) and MH-22A (mouse hepatocarcinoma) cell lines, as well as the estimated basal cytotoxicity. Additionally, it was demonstrated that the toxicity of the 4-(N-alkylpyridinium)-1,4-DHP derivatives on the Gram-positive and Gram-negative bacteria species and eukaryotic microorganism depended on the presence of the alkyl chain length at the N-alkyl pyridinium moiety, as well as the number of propargyl groups. These lipid-like compounds may be proposed for the further development of drug formulations to be used in cancer treatment.
In this study, a new approach for producing phosphorescent aluminum coatings was studied. Using the plasma electrolytic oxidation (PEO) process, a porous oxide coating was produced on the Al6082 aluminum alloy substrate. Afterwards, activated strontium aluminate (SrAl2O4: Eu2+, Dy3+) powder was filled into the cavities and pores of the PEO coating, which resulted in a surface that exhibits long-lasting luminescence. The structural and optical properties were studied using XRD, SEM, and photoluminescence measurements. It was found that the treatment time affects the morphology of the coating, which influences the amount of strontium aluminate powder that can be incorporated into the coating and the resulting afterglow intensity.
SrAl2O4:Eu,Dy is a very efficient long afterglow phosphor with wide range of possible applications. The luminescence properties and the possible luminescence mechanism of this material have been studied extensively, but there is almost no information available about the undoped material. Therefore, this article deals with the luminescence and thermally stimulated luminescence of an undoped SrAl2O4, revealing the possible defects that might be involved in the creation of the long afterglow in doped material. We conclude that undoped material exhibits some luminescence under X-ray irradiation in low temperature; close to room temperatures luminescence is almost fully thermally quenched in comparison to low temperatures. We can observe F and F2 center luminescence as well as trace metal luminescence in the emission spectrum. TSL glow curve yields the peaks that are close to those observed in material with Eu and Dy doping; therefore these peaks are clearly related to intrinsic defects. The peak at around 400 K, that is shifting with rare earth doping, might be due to dopant interaction with intrinsic defects.
The main aim of this work was to obtain conductive polymer-based materials by incorporation of different amounts of multiwalled carbon nanotubes (MWCNTs) into poly(lactide)(PLA) using the electrospinning technique. Fiber-based nonwovens with 0.2, 0.5, 1, and 3 wt% of MWCNTs were characterized regarding conductivity, morphology, thermal, and mechanical properties. It was confirmed that an increase of the MWCNTs content does not influence the increase of the material conductivity, since the conductivity was 170 ohm sq−1 for all composites. Scanning electron microscopy and transmission electron microscopy analyses revealed that smooth and beadless fibers were obtained, but also average diameters of composite nanofibers decreased with the increase of the MWCNTs content. Differential scanning calorimetry analysis showed that the presence of MWCNTs in the PLA matrix had a significant influence on the crystallization behavior of PLA nanofibers, because the decrease in crystallization temperature (Tc) was detected. Also, the incorporation of MWCNTs into PLA fibers affected the melting process, enabling the generation of α′ form, while had no influence on ordered α crystal. The enthalpy of composite degradation decreased, because MWCNTs are well-known for good heat conductivity, and with that the second step of degradation slowed down, as it was confirmed by thermogravimetric analysis. The addition of MWCNTs improved mechanical properties of composite fibers and caused the increase of both elasticity and tensile strengths of nanofibers. © The Author(s) 2019.
Projekta ERAF Projekts Nr.184.108.40.206/16/A/182 ietvaros publicēts jauns raksts par fundamentāliem procesiem fosforescentos materiālos.
Projekta ERAF Projekts Nr.220.127.116.11/16/A/182 ietvaros publicēts jauns raksts par fundamentāliem procesiem fosforescentos materiālos.
Krisjanis Smits, Dags Olsteins, Aleksejs Zolotarjovs, Katrina Laganovska, Donats Millers, Reinis Ignatans & Janis Grabis
Zirconia is a relatively new material with many promising practical applications in medical imaging, biolabeling, sensors, and other fields. In this study we have investigated lanthanide and niobium doped zirconia by luminescence and XRD methods. It was proven that charge compensation in different zirconia phases determines the incorporation of intrinsic defects and activators. Thus, the structure of zirconia does not affect the Er luminescence directly; however, it strongly affects the defect distribution around lanthanide ions and the way in which activator ions are incorporated in the lattice. Our results demonstrate the correlation between the crystalline phase of zirconia and charge compensation, as well as the contribution of different nanocrystal grain sizes. In addition, our experimental results verify the theoretical studies of metastable (tetragonal, cubic) phase stabilization determined using only oxygen vacancies. Moreover, it was found that adding niobium drastically increases activator luminescence intensity, which makes Ln3+doped zirconia even more attractive for various practical applications. Although this study was based on the luminescence of the Er ion, the phase stabilization, charge compensation, and luminescence properties described in our results are expected to be similar for other lanthanide elements. Our results suggest that the luminescence intensity of other oxide matrices where lanthanides incorporate in place of tetravalent cations could be increased by addition of Nb ions.
Scientific Reports 7, Article number: 44453
Great work! Krisjanis Smits took his part in this unique research.