showing 36 related works from this author
Tailoring of the electronic properties of ZnO-polyacrylonitrile nanofibers: Experiment and theory
2017
Abstract We report the study of ZnO-polyacrylonitrile (ZnO-PAN) nanofibers fabricated by the combination of electrospinning and atomic layer deposition. The latter technique enables us to control the size of the surface of ZnO 1D nanostructures and hence its effectiveness for energy and biosensor applications. We observe the tendency of ZnO to form nanograins with increase of the layer thickness, and investigate the influence of the grain size on the electronic properties of the nanofibers. It is demonstrated that the ZnO work function (Φ) is strongly affected by surface band bending in the ZnO layer. The observed change of Φ in ZnO layers results from the curvature of the grain surface as …
Tuning Optical Properties of Al 2 O 3 /ZnO Nanolaminates Synthesized by Atomic Layer Deposition
2014
Nanolaminates are of great interest for their unique properties such as high dielectric constants and advanced mechanical, electrical, and optical properties. Here we report on the tuning of optical and structural properties of Al2O3/ZnO nanolaminates designed by atomic layer deposition (ALD). Structural properties of nanolaminates were studied by SEM, GIXRD, and AFM. Optical characterization was performed by transmittance and photoluminescence (PL) spectroscopy. Complex study of monolayer properties was performed by ellipsometry. Optical constants for Al2O3 and ZnO monolayer were calculated. The band gap of ZnO single layers and the excitonic PL peak position were shifted to the UV region …
Structure and Doping Determined Thermoelectric Properties of Bi2Se3Thin Films Deposited by Vapour–Solid Technique
2019
In this work, a simple catalyst-free vapour-solid deposition method was applied for controlled deposition of two types (planar and disordered) of continuous Bi 2 Se 3 nanostructured thin films on different (fused quartz/glass, mica, graphene) substrates. Characterisation of electron transport (type, concentration and mobility of the main charge carriers) and thermoelectric properties (Seebeck coefficient and power factor) showed that proposed in this work deposition method allows to obtain Bi 2 Se 3 thin films with power factor comparable and even higher than reported for the Bi 2 Se 3 thin films grown by molecular beam epitaxy technique. Power factor of the best obtained thin films can be …
Enhancement of Electronic and Optical Properties of ZnO/Al2O3 Nanolaminate Coated Electrospun Nanofibers
2016
International audience; Nanolaminates are new class of promising nanomaterials with outstanding properties. Here we explored on the tuning of structural properties and the enhancement of electronic and optical properties of 1D PAN ZnO/Al2O3 nanolaminates designed by atomic layer deposition (ALD) and electrospinning. The influence of ZnO/Al2O3 bilayer thicknesses on the fundamental properties of 1D PAN ZnO/Al2O3 nanolaminates has been investigated. Due to the quantum confinement effect, the shift of XPS peaks to higher energies has been observed. Work function of Al2O3 was mostly independent of the bilayers number, whereas the ZnO work function decreased with an increase of the bilayer numbe…
Enhancement of calcium copper titanium oxide photoelectrochemical performance using boron nitride nanosheets
2020
International audience; Photoelectrochemical water splitting under visible light has attracted attention for renewable hydrogen production. Despite prevalent investigations, many challenges still hindered an efficient energy conversion, such as enhancing the reaction efficiency in visible light. Thus controlling the photoelectrode materials is an essential step in designing new materials for water splitting. CaCu3Ti4O12 (CCTO) has received great attention as photocatalyst under solar light due to its combined band gap as result of the presence in its structure of TiO2 active in UV light and CuO active under visible light. In this work, a cubic CCTO with different amount of exfoliated hexago…
Optical and structural properties of Al 2 O 3 doped ZnO nanotubes prepared by ALD and their photocatalytic application
2018
Abstract Al2O3 doped ZnO nanotubes with controlled ratio of Al2O3 were successfully designed by combining the two techniques of atomic layer deposition (ALD) and electrospinnig. In order to study the effect of Al2O3 doping on optical and structural properties of Al2O3 doped ZnO nanotubes, the prepared samples were analyzed by scanning electron microscopy (SEM), X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDX), Fourier-transform infrared (FTIR), reflectance emission and room temperature photoluminescence (PL). The photocatalytic activity and stability of these materials under UV light was studied by the photodegradation of methyl orange (MO). The results indicate that Al2O…
Optical properties of ZnO deposited by atomic layer deposition (ALD) on Si nanowires
2018
International audience; In this work, we report proof-of-concept results on the synthesis of Si core/ ZnO shell nanowires (SiNWs/ZnO) by combining nanosphere lithography (NSL), metal assisted chemical etching (MACE) and atomic layer deposition (ALD). The structural properties of the SiNWs/ZnO nanostructures prepared were investigated by X-ray diffraction, Raman spectroscopy, scanning and transmission electron microscopies. The X-ray diffraction analysis revealed that all samples have a hexagonal wurtzite structure. The grain sizes are found to be in the range of 7-14 nm. The optical properties of the samples were investigated using reflectance and photoluminescence spectroscopy. The study o…
Visible Photoluminescence of Variable-Length Zinc Oxide Nanorods Embedded in Porous Anodic Alumina Template for Biosensor Applications
2021
Zinc oxide (ZnO) and porous anodic aluminum oxide (PAAO) are technologically important materials, rich with features that are of interest in optical applications, for example, in light-emitting and sensing devices. Here, we present synthesis method of aligned ZnO nanorods (NR) with 40 nm diameter and variable length in 150 to 500 nm range obtained by atomic layer deposition (ALD) of ZnO in pores of continuously variable thickness PAAO. The relative intensity of yellow (1.99 eV), green (2.35 eV), and blue (2.82 eV) photoluminescence (PL) components originating from the different types of defects, varied with non-monotonic dependency on the composite film thickness with a Fabry–Pérot like mod…
Optical biosensors based on ZnO nanostructures: advantages and perspectives. A review
2016
This review article highlights the application of beneficial physico-chemical properties of ZnO nanostructures for the detection of wide range of biological compounds. As the medical diagnostics require accurate, fast and inexpensive biosensors, the advantages inherent optical methods of detection are considered. The crucial points of the immobilization process, responsible for biosensor performance (biomolecule adsorption, surface properties, surface defects role, surface functionalization etc.) along with the interaction mechanism between biomolecules and ZnO are disclosed. The latest achievements in surface plasmon resonance (SPR), surface enhanced Raman spectroscopy (SERS) and photolumi…
Evolution of microstructure and related optical properties of ZnO grown by atomic layer deposition.
2013
A study of transmittance and photoluminescence spectra on the growth of oxygen-rich ultra-thin ZnO films prepared by atomic layer deposition is reported. The structural transition from an amorphous to a polycrystalline state is observed upon increasing the thickness. The unusual behavior of the energy gap with thickness reflected by optical properties is attributed to the improvement of the crystalline structure resulting from a decreasing concentration of point defects at the growth of grains. The spectra of UV and visible photoluminescence emissions correspond to transitions near the band-edge and defect-related transitions. Additional emissions were observed from band-tail states near th…
Application of Thin ZnO ALD Layers in Fiber-Optic Fabry-Pérot Sensing Interferometers
2016
International audience; In this paper we investigated the response of a fiber-optic Fabry-Pérot sensing interferometer with thin ZnO layers deposited on the end faces of the optical fibers forming the cavity. Standard telecommunication single-mode optical fiber (SMF-28) segments were used with the thin ZnO layers deposited by Atomic Layer Deposition (ALD). Measurements were performed with the interferometer illuminated by two broadband sources operating at 1300 nm and 1550 nm. Reflected interference signal was acquired by an optical spectrum analyzer while the length of the air cavity was varied. Thickness of the ZnO layers used in the experiments was 50 nm, 100 nm, and 200 nm. Uncoated SMF…
Surface structure promoted high-yield growth and magnetotransport properties of Bi2Se3 nanoribbons
2019
AbstractIn the present work, a catalyst-free physical vapour deposition method is used to synthesize high yield of Bi2Se3 nanoribbons. By replacing standard glass or quartz substrates with aluminium covered with ultrathin porous anodized aluminium oxide (AAO), the number of synthesized nanoribbons per unit area can be increased by 20–100 times. The mechanisms of formation and yield of the nanoribbons synthesized on AAO substrates having different arrangement and size of pores are analysed and discussed. It is shown that the yield and average length of the nanoribbons can base tuned by adjustment of the synthesis parameters. Analysis of magnetotransport measurements for the individual Bi2Se3…
The influence of localized plasmons on the optical properties of Au/ZnO nanostructures
2015
Optical and structural experiments have been carried out on Si/ZnO thin films modified with ultra-thin gold layers of different thicknesses. ZnO was produced via Atomic Layer Deposition (ALD) and Au via Physical Vapor Deposition (sputtering). The structural properties of nanostructures were studied by XRD and AFM. Optical characterization was performed by absorbance, photoluminescence (PL) and spectroscopic ellipsometry (SE). A transition from cluster-to-thin films with the increase of Au thickness has been revealed from an analysis of optical and structural parameters. The analysis of optical features of the system has shown that slight changes of the localized plasmon absorption peaks in …
Highly textured boron/nitrogen co-doped TiO2 with honeycomb structure showing enhanced visible-light photoelectrocatalytic activity
2020
International audience; In this work, we report a novel photocatalyst based on boron and nitrogen co-doped TiO2 rutile (1 1 0) honeycomb structures. The photocatalyst has been prepared by simultaneously oxidizing and doping a Ti-foil substrate at 750 degrees C. The unit cell volume and the crystallite size of grown TiO2 films were measured by Rietveld refinement analysis. The co-doping by boron and nitrogen was achieved simultaneously with the oxidation of the titanium, resulting in a rutile (1 1 0) textured TiO2 film. X-ray photoelectron spectroscopy analysis revealed the presence of Ti-O-N and Ti-O-B-N bonds, and the presence of crystal defects in the lattice was detected and displayed by…
Improved Crystalline Structure and Enhanced Photoluminescence of ZnO Nanolayers in Bi2Se3/ZnO Heterostructures
2019
The Bi2Se3/ZnO heterostructure is a new combination of high- and low-band-gap nanomaterials that can be implemented for optoelectronic devices. The influence of the Bi2Se3 substrate on crystallizat...
ALD thin ZnO layer as an active medium in a fiber-optic Fabry–Perot interferometer
2015
Abstract A novel optical fiber sensor of temperature using a thin ZnO layer fabricated by atomic layer deposition (ALD) is demonstrated for the first time. The thin ZnO layer was grown on the face of a standard optical telecommunication fiber SMF-28 and operates as a Fabry–Perot interferometer sensitive to temperature. The interferometer characterization was made in the temperature range extending from 50 to 300 °C with resolution equal to 1 °C. The output signal was analyzed by measurement of the shift of the maxima in spectral pattern. The sensitivity of temperature measurement is about 0.05 nm/°C. Furthermore, very good linearity of the sensor was achieved with correlation coefficient R2…
Tuning of ZnO 1D nanostructures by atomic layer deposition and electrospinning for optical gas sensor applications
2015
We explored for the first time the ability of a three-dimensional polyacrylonitrile/ZnO material—prepared by a combination of electrospinning and atomic layer deposition (ALD) as a new material with a large surface area—to enhance the performance of optical sensors for volatile organic compound (VOC) detection. The photoluminescence (PL) peak intensity of these one-dimensional nanostructures has been enhanced by a factor of 2000 compared to a flat Si substrate. In addition, a phase transition of the ZnO ALD coating from amorphous to crystalline has been observed due to the properties of a polyacrylonitrile nanofiber template: surface strain, roughness, and an increased number of nucleation …
Photoelectrocatalysis of paracetamol on Pd–ZnO/ N-doped carbon nanofibers electrode
2021
Abstract The presence of pharmaceuticals in water bodies has become a major concern in recent years. An efficient and innovative way of eliminating these pollutants is through photoelectrocatalytic (PEC) degradation owing to its environmental sustainability and its ability to remove recalcitrant pollutants. In this study, palladium loaded zinc oxide/carbon nanofibers (CZnO–Pd) were employed as a novel photoanode for PEC degradation of paracetamol. The CZnO–Pd composite was prepared through electrospinning and atomic layer deposition (ALD). The obtained materials were characterized. Photoelectrochemical studies were carried out with linear sweep voltammetry and chronoamperometry. The removal…
Segregation of copper oxide on calcium copper titanate surface induced by Graphene Oxide for Water splitting applications
2020
Abstract Photoelectrochemical cells (PEC) are promising devices for hydrogen production via sunlight energy. One of the important challenges in this area is to design photoactive electrodes able to absorb visible light. A good photoelectrochemical behavior depends on the presence of surface active sites to photogenerate current at the lower possible potential for water splitting. Recent investigations in this field are focusing on perovskite materials such as CaCu3Ti4O12 (CCTO) as visible light active electrode due its outstanding structure in which CCTO encloses in its structure a visible light absorbance component (CuO). The presence CuO on the material surface is mainly responsible for t…
Photoluminescence: A very sensitive tool to detect the presence of anatase in rutile phase electrospun TiO 2 nanofibers
2015
Abstract This paper reports on the synthesis and the characterization of titanium dioxide (TiO2) nanofibers prepared by electrospinning. The samples were annealed at various temperatures in air for 4 h. The as-spun and annealed TiO2/PVP composite nanofibers were characterized by scanning electron microscopy (SEM), Energy-dispersive X-ray spectroscopy analysis (EDX), X-ray diffraction (XRD), Raman spectroscopy and photoluminescence (PL). The results show that the heat treatment has an effect on the crystallization process. Even if the XRD data shows a complete anatase-to-rutile transition in the TiO2 nanofibers at 900 °C, photoluminescence reveals a small portion of anatase in rutile sample.…
Thickness-dependent properties of ultrathin bismuth and antimony chalcogenide films formed by physical vapor deposition and their application in ther…
2021
This work was supported by the European Regional Development Fund (ERDF) project No 1.1.1.1/16/A/257. J. A. acknowledges the ERDF project No. 1.1.1.2/1/16/037. Institute of Solid State Physics, University of Latvia, Latvia as the Center of Excellence has received funding from the European Union's Horizon 2020 Framework Programme H2020-WIDESPREAD-01-2016-2017 TeamingPhase2 under grant agreement No. 739508, project CAMART2 . The raw/processed data required to reproduce these findings cannot be shared at this time as the data also form a part of an ongoing study.
High-Yield Growth and Tunable Morphology of Bi2Se3 Nanoribbons Synthesized on Thermally Dewetted Au
2021
The yield and morphology (length, width, thickness) of stoichiometric Bi2Se3 nanoribbons grown by physical vapor deposition is studied as a function of the diameters and areal number density of the Au catalyst nanoparticles of mean diameters 8–150 nm formed by dewetting Au layers of thicknesses 1.5–16 nm. The highest yield of the Bi2Se3 nanoribbons is reached when synthesized on dewetted 3 nm thick Au layer (mean diameter of Au nanoparticles ~10 nm) and exceeds the nanoribbon yield obtained in catalyst-free synthesis by almost 50 times. The mean lengths and thicknesses of the Bi2Se3 nanoribbons are directly proportional to the mean diameters of Au catalyst nanoparticles. In contrast, the me…
Photoluminescence Study of Defects in ZnO-Coated Polyacrylonitrile Nanofibers
2020
International audience; Core-shell nanostructures of one-dimensional (1D) polyacrylonitrile (PAN)/zinc oxide (ZnO) were obtained by combining atomic layer deposition (ALD) and electrospinning. Nanofibers with different ZnO thicknesses were synthesized and investigated. The present work offers novel information about 1D ZnO structural defects and activation energies (Ea) by performing photoluminescence (PL) measurements. PL measurements of 1D ZnO/PAN samples were investigated from 77 K to 273 K (room temperature). By analyzing the obtained data of the emission spectrum, Ea and temperature coefficients were calculated. The results let us suggest an approximate model of defects in 1D ZnO/PAN s…
Mesoporous ZnFe2O4@TiO2 Nanofibers Prepared by Electrospinning Coupled to PECVD as Highly Performing Photocatalytic Materials
2017
International audience; Zinc ferrite @ titanium dioxide (ZnFe2O4@TiO2) composite nanofibers were elaborated by combining the two different techniques: electrospinning and plasma-enhanced chemical vapor deposition (PECVD). The nanofiber compositions were controlled using different ratios of zinc to iron. Their structural, morphological, and optical properties were analyzed by scanning electron microscopy, X-ray diffraction, energy-dispersive X-ray spectroscopy, BET surface area, Raman spectroscopy, and UV–visible spectrophotometry. The photocatalytic activity has been investigated by the degradation of methylene blue under visible light. The results indicate that the combination of spinel st…
Enhanced photocatalytic performance of novel electrospun BN/TiO 2 composite nanofibers
2017
International audience; High activity boron nitride/titanium dioxide (BN/TiO2) composite nanofiber photocatalysts were synthesized for the first time via the electrospinning technique. The as-spun nanofibers with a controlled ratio of boron nitride nanosheets (BN) were calcined under air at 500 °C for 4 hours. Their morphological, structural and optical properties were studied by scanning electron microscopy (SEM), X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDX), BET surface area, Fourier-transform infrared (FTIR), Raman spectroscopy, UV-Visible spectrophotometry and room temperature photoluminescence (PL). The effect of loading different BN sheet amounts on the photocat…
BN/GdxTi(1-x)O(4-x)/2 nanofibers for enhanced photocatalytic hydrogen production under visible light
2019
Abstract BN/GdxTi(1-x)O(4-x)/2 nanofibers were elaborated via electrospinning technique. The properties of the prepared nanofibers were controlled using different ratios of gadolinium. All the prepared nanofibers exhibit the tetragonal structure of anatase TiO2 phase. An increase in the unit cell volume and a decrease in the crystallite size were observed with increasing the doping amount of Gd3+ as revealed by Rietveld refinement analysis. The defect in TiO2 lattice was observed by Raman. The Gd3+ incorporation inside TiO2 lattice, which is accompanied by the creation of Ti-O-Gd bond, was characterized by the X-ray photoelectron spectra. Scanning electron microscopy demonstrates that the a…
Tuning of Structural and Optical Properties of Graphene/ZnO Nanolaminates
2016
International audience; Zinc Oxide (ZnO) and graphene (G) have been extensively studied because of their unique physical properties. Here, Graphene-Zinc Oxide (G/ZnO) nanolaminates were fabricated, respectively, by chemical vapor deposition and low temperature atomic layer deposition technique. The number of obtained G/ZnO layers was tuned from 1 to 11 with a total thickness of 100 nm for all prepared nanolaminates. The structure, optical properties and interaction between G and ZnO were studied by X-ray methods, TEM, AFM, Raman and optical spectroscopy. The obtained results were interpreted and analysed taking into account strain and charge effects of graphene in G/ZnO nanostructures. We d…
Natural payload delivery of the doxorubicin anticancer drug from boron nitride oxide nanosheets
2019
International audience; We studied the behavior of doxorubicin (DOX; an anticancer drug) molecules loaded on a boron nitride oxide nanosheet (BNO-NS) using the density functional theory (DFT), time-dependent density functional theory (TDDFT), and molecular dynamic (MD) simulation methods. We found that DOX molecules in pi-pi or covalent interaction with BNO-NS preserve their optical properties in water. Moreover, the BNO-NS vector allowed stabilizing the DOX molecules on a cellular membrane contrary to isolated DOX that randomly moved in the solvent box without any interaction with the cell membrane. From these results, we conclude that hydrophilic BNO-NS represents a good candidate for DOX…
Magnetotransport Studies of Encapsulated Topological Insulator Bi2Se3 Nanoribbons
2022
This research was funded by the Latvian Council of Science, project “Highly tunable surface state transport in topological insulator nanoribbons”, No. lzp-2020/2-0343, and by the European Union’s Horizon 2020 research and innovation program, Grant Agreement No. 766714/ HiTIMe. Institute of Solid-State Physics, University of Latvia as the Center of Excellence has received funding from the European Union’s Horizon 2020 Framework Programme H2020-WIDESPREAD-01-2016-2017-TeamingPhase2 under grant agreement No. 739508, project CAMART2.
Optical and structural properties of Al 2 O 3 /ZnO nanolaminates deposited by ALD method
2014
International audience; We report on the investigation of optical and structural properties of Al2O3/ZnO nanolaminates. The nanolaminates were deposited on Si and glass substrates by Atomic layer deposition method. Structural properties of nanolaminates were studied by SEM, GIXRD, and AFM. Optical characterization was performed by transmittance and photoluminescence spectroscopy. Complex analysis of monolayer properties was done by ellipsometry. Optical constants for Al2O3 and ZnO monolayer were calculated.
Structure-determined thermoelectric properties of Bi2Se3 thin films deposited by vapour-solid technique
2018
International audience; In this work, a simple catalyst-free vapour-solid deposition method is applied for controlled obtaining of two types (planar and disordered) continuous Bi2Se3 nanostructured thin films on different (fused quartz/glass, mica, graphene) substrates. Performed for the deposited thin films transport and thermoelectric characterization (type, concentration and mobility of the main charge carriers, Seebeck coefficient and power factor) showed that proposed deposition method allows to fabricate “low-doped” Bi2Se3 thin films with power factor comparable and even higher than reported for the Bi2Se3 thin films fabricated by molecular beam epitaxy technique.
Synthesis of novel ZnO/ZnAl2O4 multi co-centric nanotubes and their long-term stability in photocatalytic application
2016
Based on the Kirkendall effect, novel double, triple and quadruple co-centric nanotubes of ZnO/ZnAl2O4 have been successfully fabricated by combining the two techniques of electrospinning and atomic layer deposition. The as-prepared samples were annealed at 900 °C under air. Their morphological, structural and optical properties were studied by Scanning Electron Microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Energy-Dispersive X-ray spectroscopy (EDX), UV-visible spectrophotometry, Raman spectroscopy, photoluminescence (PL) and reflectance emission. The performances and long-term stability of these multi co-centric nanotubes for photocatalytic applications…
Effect of graphene substrate type on formation of Bi2Se3 nanoplates
2019
AbstractKnowledge of nucleation and further growth of Bi2Se3 nanoplates on different substrates is crucial for obtaining ultrathin nanostructures and films of this material by physical vapour deposition technique. In this work, Bi2Se3 nanoplates were deposited under the same experimental conditions on different types of graphene substrates (as-transferred and post-annealed chemical vapour deposition grown monolayer graphene, monolayer graphene grown on silicon carbide substrate). Dimensions of the nanoplates deposited on graphene substrates were compared with the dimensions of the nanoplates deposited on mechanically exfoliated mica and highly ordered pyrolytic graphite flakes used as refer…
High photodegradation and antibacterial activity of BN–Ag/TiO 2 composite nanofibers under visible light
2018
To develop material with good photocatalytic properties for organic compound degradation and bacterial removal, we produced Ag/TiO2 and BN–Ag/TiO2 composite nanofibers that included controlled amounts of boron nitride (BN) nanosheets and silver (Ag). After annealing at 500 °C under air, we used scanning electron microscopy, transmission electron microscopy, Brunauer–Emmet–Teller analysis, X-ray diffraction, energy-dispersive X-ray spectroscopy, Raman spectroscopy, UV-visible reflectance spectroscopy and room temperature photoluminescence to investigate the morphological, structural and optical properties of all samples. The photocatalytic tests using methylene blue under visible light, in r…
Review article: recommended reading list of early publications on atomic layer deposition - outcome of the "virtual Project on the History of ALD"
2017
Atomic layer deposition (ALD), a gas-phase thin film deposition technique based on repeated, self-terminating gas-solid reactions, has become the method of choice in semiconductor manufacturing and many other technological areas for depositing thin conformal inorganic material layers for various applications. ALD has been discovered and developed independently, at least twice, under different names: atomic layer epitaxy (ALE) and molecular layering. ALE, dating back to 1974 in Finland, has been commonly known as the origin of ALD, while work done since the 1960s in the Soviet Union under the name "molecular layering" (and sometimes other names) has remained much less known. The virtual proj…
Influence of ZnO/graphene nanolaminate periodicity on their structural and mechanical properties
2018
International audience; Structural, electronic and mechanical properties of ZnO/Graphene (ZnO/G) nanolaminates fabricated by low temperature atomic layer deposition (ALD) and chemical vapor deposition (CVD) were investigated. We performed scanning and transmission electron microscopy (SEM/TEM), X-ray diffraction (XRD), electron energy loss spectroscopy (EELS), Raman spectroscopy, X-Ray photoelectron spectroscopy (XPS) and nanoindentation to characterize the ZnO/G nanolaminates. The main structural and mechanical parameters of ZnO/G nanolaminates were calculated. The obtained results were analyzed and interpreted taking into account mechanical interaction and charge effects occurring at the …