|
“Recent breakthroughs in scanning transmission electron microscopy of small species”. van den Bos KHW, Altantzis T, De Backer A, Van Aert S, Bals S, Advances in Physics: X 3, 1480420 (2018). http://doi.org/10.1080/23746149.2018.1480420
Abstract: Over the last decade, scanning transmission electron microscopy has become one of the most powerful tools to characterise nanomaterials at the atomic scale. Often, the ultimate goal is to retrieve the three-dimensional structure, which is very challenging since small species are typically sensitive to electron irradiation. Nevertheless, measuring individual atomic positions is crucial to understand the relation between the structure and physicochemical properties of these (nano)materials. In this review, we highlight the latest approaches that are available to reveal the 3D atomic structure of small species. Finally, we will provide an outlook and will describe future challenges where the limits of electron microscopy will be pushed even further.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Times cited: 8
DOI: 10.1080/23746149.2018.1480420
|
|
|
“Controlled Growth of Supported ZnO Inverted Nanopyramids with Downward Pointing Tips”. Barreca D, Carraro G, Maccato C, Altantzis T, Kaunisto K, Gasparotto A, Crystal growth &, design , acs.cgd.8b00198 (2018). http://doi.org/10.1021/acs.cgd.8b00198
Abstract: High purity porous ZnO nanopyramids with controllable properties are grown on their tips on
Si(100) substrates by means of a catalyst-free vapor phase deposition route in a wet oxygen
reaction environment. The system degree of preferential [001] orientation, as well as
nanopyramid size, geometrical shape and density distribution, can be finely tuned by varying the
growth temperature between 300 and 400°C, whereas higher temperatures lead to more compact
systems with a three-dimensional (3D) morphology. A growth mechanism of the obtained ZnO
nanostructures based on a self-catalytic vapor-solid (VS) mode is proposed, in order to explain
the evolution of nanostructure morphologies as a function of the adopted process conditions. The
results obtained by a thorough chemico-physical characterization enable to get an improved
control over the properties of ZnO nanopyramids grown by this technique. Taken together, they
are of noticeable importance not only for fundamental research on ZnO nanomaterials with
controlled nano-organization, but also to tailor ZnO functionalities in view of various potential
applications.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 4.055
Times cited: 6
DOI: 10.1021/acs.cgd.8b00198
|
|
|
“Do Binary Supracrystals Enhance the Crystal Stability?”.Yang Z, Altantzis T, Bals S, Tendeloo GV, Pileni M-P, The journal of physical chemistry: C : nanomaterials and interfaces 122, 13515 (2018). http://doi.org/10.1021/acs.jpcc.7b12373
Abstract: We study the oxygen thermal stability of two binary
systems. The larger particles are magnetic amorphous Co (7.2 nm) or
Fe3O4 (7.5 nm) nanocrystals, whereas the smaller ones (3.7 nm) are
Au nanocrystals. The nanocrystal ordering as well as the choice of the
magnetic nanoparticles very much influence the stability of the binary
system. A perfect crystalline structure is obtained with the Fe3O4/Au
binary supracrystals. For the Co/Au binary system, oxidation of Co
results in the chemical transformation from Co to CoO, where the size
of the amorphous Co nanoparticles increases from 7.2 to 9.8 nm in
diameter. During the volume expansion of the Co nanoparticles, Au
nanoparticles within the binary assemblies coalesce and are at the
origin of the instability of the binary nanoparticle supracrystals. On the
other hand, for the Fe3O4/Au binary system, the oxidation of Fe3O4 to
γ-Fe2O3 does not lead to a size change of the nanoparticles, which
maintains the stability of the binary nanoparticle supracrystals. A similar behavior is observed for an AlB2-type Co−Ag binary
system: The crystalline structure is maintained, whereas in disordered assemblies, coalescence of Ag nanocrystals is observed.
Keywords: A1 Journal article; Engineering sciences. Technology; Electron microscopy for materials research (EMAT)
Impact Factor: 4.536
Times cited: 5
DOI: 10.1021/acs.jpcc.7b12373
|
|
|
“Multimode Electron Tomography as a Tool to Characterize the Internal Structure and Morphology of Gold Nanoparticles”. Winckelmans N, Altantzis T, Grzelczak M, Sánchez-Iglesias A, Liz-Marzán LM, Bals S, The journal of physical chemistry: C : nanomaterials and interfaces 122, 13522 (2018). http://doi.org/10.1021/acs.jpcc.7b12379
Abstract: Three dimensional (3D) characterization of structural defects in nanoparticles by transmission electron microscopy is far from straightforward. We propose the use of a dose-efficient approach, so-called multimode tomography, during which tilt series of low and high angle annular dark field scanning transmission electron microscopy projection images are acquired simultaneously. In this manner, not only reliable information can be obtained concerning the shape of the nanoparticles, but also the twin planes can be clearly visualized in 3D. As an example, we demonstrate the application of this approach to identify the position of the seeds with respect to the twinning planes in anisotropic gold nanoparticles synthesized using a seed mediated growth approach.
Keywords: A1 Journal article; Engineering sciences. Technology; Electron microscopy for materials research (EMAT)
Impact Factor: 4.536
Times cited: 23
DOI: 10.1021/acs.jpcc.7b12379
|
|
|
“Tunable porous nanoallotropes prepared by post-assembly etching of binary nanoparticle superlattices”. Udayabhaskararao T, Altantzis T, Houben L, Coronado-Puchau M, Langer J, Popovitz-Biro R, Liz-Marzán LM, Vuković, L, Král P, Bals S, Klajn R, Science 358, 514 (2017). http://doi.org/10.1126/science.aan6046
Abstract: Self-assembly of inorganic nanoparticles has been used to prepare hundreds of different colloidal crystals, but almost invariably with the restriction that the particles must be densely packed. Here,we show that non–close-packed nanoparticle arrays can be fabricated through the selective removal of one of two components comprising binary nanoparticle superlattices. First, a variety of binary nanoparticle superlattices were prepared at the liquid-air interface, including several arrangements that were previously unknown. Molecular dynamics simulations revealed the particular role of the liquid in templating the formation of superlattices not achievable through self-assembly in bulk solution. Second, upon stabilization, all of these binary superlattices could be transformed into distinct “nanoallotropes”—nanoporous materials having the same chemical composition but differing in their nanoscale architectures.
Keywords: A1 Journal article; Engineering sciences. Technology; Electron microscopy for materials research (EMAT)
Impact Factor: 37.205
Times cited: 113
DOI: 10.1126/science.aan6046
|
|
|
“Mechanistic Insight into the Photocatalytic Working of Fluorinated Anatase {001} Nanosheets”. Kus M, Altantzis T, Vercauteren S, Caretti I, Leenaerts O, Batenburg KJ, Mertens M, Meynen V, Partoens B, Van Doorslaer S, Bals S, Cool P, The journal of physical chemistry: C : nanomaterials and interfaces 121, 26275 (2017). http://doi.org/10.1021/acs.jpcc.7b05586
Abstract: Anatase nanosheets with exposed {001} facets
have gained increasing interest for photocatalytic applications. To
fully understand the structure-to-activity relation, combined
experimental and computational methods have been exploited.
Anatase nanosheets were prepared under hydrothermal conditions
in the presence of fluorine ions. High resolution scanning
transmission electron microscopy was used to fully characterize
the synthesized material, confirming the TiO2 nanosheet
morphology. Moreover, the surface structure and composition
of a single nanosheet could be determined by annular bright-field
scanning transmission electron microscopy (ABF-STEM) and
STEM electron energy loss spectroscopy (STEM-EELS). The photocatalytic activity was tested for the decomposition of organic
dyes rhodamine 6G and methyl orange and compared to a reference TiO2 anatase sample. The anatase nanosheets with exposed
{001} facets revealed a significantly lower photocatalytic activity compared to the reference. In order to understand the
mechanism for the catalytic performance, and to investigate the role of the presence of F−, light-induced electron paramagnetic
resonance (EPR) experiments were performed. The EPR results are in agreement with TEM, proving the presence of Ti3+
species close to the surface of the sample and allowing the analysis of the photoinduced formation of paramagnetic species.
Further, ab initio calculations of the anisotropic effective mass of electrons and electron holes in anatase show a very high effective
mass of electrons in the [001] direction, having a negative impact on the mobility of electrons toward the {001} surface and thus
the photocatalysis. Finally, motivated by the experimental results that indicate the presence of fluorine atoms at the surface, we
performed ab initio calculations to determine the position of the band edges in anatase slabs with different terminations of the
{001} surface. The presence of fluorine atoms near the surface is shown to strongly shift down the band edges, which indicates
another reason why it can be expected that the prepared samples with a large amount of {001} surface, but with fluorine atoms
near the surface, show only a low photocatalytic activity.
Keywords: A1 Journal article; Engineering sciences. Technology; Electron microscopy for materials research (EMAT); Condensed Matter Theory (CMT); Laboratory of adsorption and catalysis (LADCA)
Impact Factor: 4.536
Times cited: 20
DOI: 10.1021/acs.jpcc.7b05586
|
|
|
“Vapor Phase Fabrication of Nanoheterostructures Based on ZnO for Photoelectrochemical Water Splitting”. Barreca D, Carraro G, Gasparotto A, Maccato C, Altantzis T, Sada C, Kaunisto K, Ruoko T-P, Bals S, Advanced Materials Interfaces 4, 1700161 (2017). http://doi.org/10.1002/admi.201700161
Abstract: Nanoheterostructures based on metal oxide semiconductors have emerged
as promising materials for the conversion of sunlight into chemical energy.
In the present study, ZnO-based nanocomposites have been developed by
a hybrid vapor phase route, consisting in the chemical vapor deposition
of ZnO systems on fluorine-doped tin oxide substrates, followed by the
functionalization with Fe2O3 or WO3 via radio frequency-sputtering. The
target systems are subjected to thermal treatment in air both prior and after
sputtering, and their properties, including structure, chemical composition,
morphology, and optical absorption, are investigated by a variety of characterization
methods. The obtained results evidence the formation of highly
porous ZnO nanocrystal arrays, conformally covered by an ultrathin Fe2O3
or WO3 overlayer. Photocurrent density measurements for solar-triggered
water splitting reveal in both cases a performance improvement with respect
to bare zinc oxide, that is mainly traced back to an enhanced separation of
photogenerated charge carriers thanks to the intimate contact between the
two oxides. This achievement can be regarded as a valuable result in view of
future optimization of similar nanoheterostructured photoanodes.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 4.279
Times cited: 30
DOI: 10.1002/admi.201700161
|
|
|
“Disentangling the effect of seed size and crystal habit on gold nanoparticle seeded growth”. González-Rubio G, de Oliveira TM, Altantzis T, La Porta A, Guerrero-Martínez A, Bals S, Scarabelli L, Liz-Marzán LM, Chemical communications 53, 11360 (2017). http://doi.org/10.1039/C7CC06854A
Abstract: Oxidative etching was used to produce gold seeds of different sizes and crystal habits. Following detailed characterization, the seeds were grown under different conditions. Our results bring new insights toward understanding the effect of size and crystallinity on the growth of anisotropic particles, whilst identifying guidelines for the optimisation of new synthetic protocols of predesigned seeds.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 6.319
Times cited: 29
DOI: 10.1039/C7CC06854A
|
|
|
“Advanced electron tomography of nanoparticle assemblies”. Altantzis T, Zanaga D, Bals S, Europhysics letters 119, 38001 (2017). http://doi.org/10.1209/0295-5075/119/38001
Abstract: Nanoparticle assemblies have attracted enormous scientific interest during the last
years, due to their unique properties compared to those of their building blocks. To understand
the origin of these properties and to establish the connection with their structure, a detailed and
quantitative structural characterization is essential. Transmission electron microscopy has been
widely used to investigate nano-assemblies. However, TEM images only correspond to a twodimensional
projection of a three-dimensional object. Therefore, in order to obtain the necessary
3D structural information electron tomography has to be applied. By means of advanced electron
tomography, both qualitative and quantitative information can be obtained, which can be used
for detailed theoretical studies.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 1.957
Times cited: 8
DOI: 10.1209/0295-5075/119/38001
|
|
|
“Composite Supraparticles with Tunable Light Emission”. Montanarella F, Altantzis T, Zanaga D, Rabouw FT, Bals S, Baesjou P, Vanmaekelbergh D, van Blaaderen A, ACS nano 11, 9136 (2017). http://doi.org/10.1021/acsnano.7b03975
Abstract: Robust luminophores emitting light with broadly tunable colors are desirable in many applications such as light-emitting diode (LED)-based lighting, displays, integrated optoelectronics and biology. Nanocrystalline quantum dots with multicolor emission, from core- and shell-localized excitons, as well as solid layers of mixed quantum dots that emit different colors have been proposed. Here, we report on colloidal supraparticles that are composed of three types of Cd(Se,ZnS) core/(Cd,Zn)S shell nanocrystals with emission in the red, green, and blue. The emission of the supraparticles can be varied from pure to composite colors over the entire visible region and finetuned into variable shades of white light by mixing the nanocrystals in controlled proportions. Our approach results in supraparticles with sizes spanning the colloidal domain and beyond that combine versatility and processability with a broad, stable, and tunable emission, promising applications in lighting devices and biological research.
Keywords: A1 Journal article; Engineering sciences. Technology; Electron microscopy for materials research (EMAT)
Impact Factor: 13.942
Times cited: 36
DOI: 10.1021/acsnano.7b03975
|
|
|
“Nanorattles with tailored electric field enhancement”. Schnepf MJ, Mayer M, Kuttner C, Tebbe M, Wolf D, Dulle M, Altantzis T, Formanek P, Förster S, Bals S, König TAF, Fery A, Nanoscale 9, 9376 (2017). http://doi.org/10.1039/C7NR02952G
Abstract: Nanorattles are metallic core–shell particles with core and shell separated by a dielectric spacer. These
nanorattles have been identified as a promising class of nanoparticles, due to their extraordinary high
electric-field enhancement inside the cavity. Limiting factors are reproducibility and loss of axial symmetry
owing to the movable metal core; movement of the core results in fluctuation of the nanocavity dimensions
and commensurate variations in enhancement factor. We present a novel synthetic approach for
the robust fixation of the central gold rod within a well-defined box, which results in an axisymmetric
nanorattle. We determine the structure of the resulting axisymmetric nanorattles by advanced transmission
electron microscopy (TEM) and small-angle X-ray scattering (SAXS). Optical absorption and scattering
cross-sections obtained from UV-vis-NIR spectroscopy quantitatively agree with finite-difference
time-domain (FDTD) simulations based on the structural model derived from SAXS. The predictions of
high and homogenous field enhancement are evidenced by scanning TEM electron energy loss spectroscopy
(STEM-EELS) measurement on single-particle level. Thus, comprehensive understanding of
structural and optical properties is achieved for this class of nanoparticles, paving the way for photonic
applications where a defined and robust unit cell is crucial.
Keywords: A1 Journal article; Engineering sciences. Technology; Electron microscopy for materials research (EMAT)
Impact Factor: 7.367
Times cited: 69
DOI: 10.1039/C7NR02952G
|
|
|
“3D porous nanostructured platinum prepared using atomic layer deposition”. Pulinthanathu Sree S, Dendooven J, Geerts L, Ramachandran RK, Javon E, Ceyssens F, Breynaert E, Kirschhock CEA, Puers R, Altantzis T, Van Tendeloo G, Bals S, Detavernier C, Martens JA, Journal of materials chemistry A : materials for energy and sustainability 5, 19007 (2017). http://doi.org/10.1039/C7TA03257A
Abstract: A robust and easy to handle 3D porous platinum structure was created via replicating the 3D channel system
of an ordered mesoporous silica material using atomic layer deposition (ALD) over micrometer distances.
After ALD of Pt in the silica material, the host template was digested using hydrogen fluoride (HF). A fully
connected ordered Pt nanostructure was obtained with morphology and sizes corresponding to that of
the pores of the host matrix, as revealed with high-resolution scanning transmission electron
microscopy and electron tomography. The Pt nanostructure consisted of hexagonal Pt rods originating
from the straight mesopores (11 nm) of the host structure and linking features resulting from Pt
replication of the interconnecting mesopore segments (2–4 nm) present in the silica host structure.
Electron tomography of partial replicas, made by incomplete infilling of Zeotile-4 material with Pt,
provided insight in the connectivity and formation mechanism of the Pt nanostructure by ALD. The Pt
replica was evaluated for its potential use as electrocatalyst for the hydrogen evolution reaction, one of
the half-reactions of water electrolysis, and as microelectrode for biomedical sensing. The Pt replica
showed high activity for the hydrogen evolution reaction and electrochemical characterization revealed
a large impedance improvement in comparison with reference Pt electrodes.
Keywords: A1 Journal article; Engineering sciences. Technology; Electron microscopy for materials research (EMAT)
Impact Factor: 8.867
Times cited: 9
DOI: 10.1039/C7TA03257A
|
|
|
“Three-dimensional atomic models from a single projection using Z-contrast imaging: verification by electron tomography and opportunities”. De Backer A, Jones L, Lobato I, Altantzis T, Goris B, Nellist PD, Bals S, Van Aert S, Nanoscale 9, 8791 (2017). http://doi.org/10.1039/C7NR02656K
Abstract: In order to fully exploit structure–property relations of nanomaterials, three-dimensional (3D) characterization at the atomic scale is often required. In recent years, the resolution of electron tomography has reached the atomic scale. However, such tomography typically requires several projection images demanding substantial electron dose. A newly developed alternative circumvents this by counting the number of atoms across a single projection. These atom counts can be used to create an initial atomic model with which an energy minimization can be applied to obtain a relaxed 3D reconstruction of the nanoparticle. Here, we compare, at the atomic scale, this single projection reconstruction approach with tomography and find an excellent agreement. This new approach allows for the characterization of beam-sensitive materials or where the acquisition of a tilt series is impossible. As an example, the utility is illustrated by the 3D atomic scale characterization of a nanodumbbell on an in situ heating holder of limited tilt range.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 7.367
Times cited: 33
DOI: 10.1039/C7NR02656K
|
|
|
“Highly Emissive Divalent-Ion-Doped Colloidal CsPb1–xMxBr3Perovskite Nanocrystals through Cation Exchange”. van der Stam W, Geuchies JJ, Altantzis T, van den Bos KHW, Meeldijk JD, Van Aert S, Bals S, Vanmaekelbergh D, de Mello Donega C, Journal of the American Chemical Society 139, 4087 (2017). http://doi.org/10.1021/jacs.6b13079
Abstract: Colloidal CsPbX3 (X = Br, Cl, and I) perovskite nanocrystals (NCs) have emerged as promising phosphors and solar cell materials due to their remarkable optoelectronic properties. These properties can be tailored by not only controlling the size and shape of the NCs but also postsynthetic composition tuning through topotactic
anion exchange. In contrast, property control by cation exchange is still underdeveloped for colloidal CsPbX3 NCs. Here, we present a method that allows partial cation exchange in colloidal CsPbBr3 NCs, whereby Pb2+ is exchanged for several isovalent cations, resulting in doped CsPb1−xMxBr3 NCs (M= Sn2+, Cd2+, and Zn2+; 0 < x ≤ 0.1), with preservation of the original NC shape. The size of the parent NCs is also preserved in the product NCs, apart from a small (few
%) contraction of the unit cells upon incorporation of the guest cations. The partial Pb2+ for M2+ exchange leads to a blue-shift of the optical spectra, while maintaining the high photoluminescence quantum yields (>50%), sharp absorption features, and narrow emission of the parent CsPbBr3 NCs. The blue-shift in the optical spectra is attributed to the lattice contraction that accompanies the Pb2+ for M2+ cation exchange and is observed to scale linearly with the lattice contraction. This work opens up new possibilities to engineer the properties of halide perovskite NCs, which to date are demonstrated to be the only known
system where cation and anion exchange reactions can be sequentially combined while preserving the original NC shape, resulting in compositionally diverse perovskite NCs.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 13.858
Times cited: 535
DOI: 10.1021/jacs.6b13079
|
|
|
“High-Yield Seeded Growth of Monodisperse Pentatwinned Gold Nanoparticles through Thermally Induced Seed Twinning”. Sánchez-Iglesias A, Winckelmans N, Altantzis T, Bals S, Grzelczak M, Liz-Marzán LM, Journal of the American Chemical Society 139, 107 (2016). http://doi.org/10.1021/jacs.6b12143
Abstract: We show here that thermal treatment of small seeds results in extensive twinning and a subsequent drastic yield improvement (>85%) in the formation of pentatwinned nanoparticles, with pre-selected morphology (nanorods, bipyramids and decahedra) and aspect ratio. The “quality” of the seeds thus defines the yield of the obtained nanoparticles, which in the case of nanorods avoids the need for additives such as Ag+ ions. This modified seeded growth method also improves reproducibility, as the seeds can be stored for extended periods of time without compromising the quality of the final nanoparticles. Additionally, minor modification of the seeds with Pd allows their localization within the final particles, which opens new avenues toward mechanistic studies. All together, these results represent a paradigm shift in anisotropic gold nanoparticle synthesis.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 13.858
Times cited: 267
DOI: 10.1021/jacs.6b12143
|
|
|
“Depth sectioning combined with atom-counting in HAADF STEM to retrieve the 3D atomic structure”. Alania M, Altantzis T, De Backer A, Lobato I, Bals S, Van Aert S, Ultramicroscopy 177, 36 (2016). http://doi.org/10.1016/j.ultramic.2016.11.002
Abstract: Aberration correction in scanning transmission electron microscopy (STEM) has greatly improved the lateral and depth resolution. When using depth sectioning, a technique during which a series of images is recorded at different defocus values, single impurity atoms can be visualised in three dimensions. In this paper, we investigate new possibilities emerging when combining depth sectioning and precise atom-counting in order to reconstruct nanosized particles in three dimensions. Although the depth resolution does not allow one to precisely locate each atom within an atomic column, it will be shown that the depth location of an atomic column as a whole can be measured precisely. In this manner, the morphology of a nanoparticle can be reconstructed in three dimensions. This will be demonstrated using simulations and experimental data of a gold nanorod.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 2.843
Times cited: 13
DOI: 10.1016/j.ultramic.2016.11.002
|
|
|
“Galvanic Replacement Coupled to Seeded Growth as a Route for Shape-Controlled Synthesis of Plasmonic Nanorattles”. Polavarapu L, Zanaga D, Altantzis T, Rodal-Cedeira S, Pastoriza-Santos I, Pérez-Juste J, Bals S, Liz-Marzán LM, Journal of the American Chemical Society 138, 11453 (2016). http://doi.org/10.1021/jacs.6b06706
Abstract: Shape-controlled synthesis of metal nanoparticles (NPs) requires mechanistic understanding toward the development of modern nanoscience and nanotechnology. We demonstrate here an unconventional shape transformation of Au@Ag core−shell NPs (nanorods and nanocubes) into octahedral nanorattles via roomtemperature galvanic replacement coupled with seeded growth. The corresponding morphological and chemical transformations were investigated in three dimensions, using state-of-the-art X-ray energy-dispersive spectroscopy (XEDS) tomography. The addition of a reducing agent (ascorbic acid) plays a key role in this unconventional mechanistic path, in which galvanic replacement is found to dominate initially when the shell is made of Ag, while seeded growth suppresses transmetalation when a composition of Au:Ag (∼60:40) is reached in the shell, as revealed by quantitative XEDS tomography. This work not only opens new avenues toward the shape control of hollow NPs beyond the morphology of sacrificial templates, but also expands our understanding of chemical transformations in nanoscale galvanic replacement reactions. The XEDS electron tomography study presented here can be generally applied to investigate a wide range of nanoscale morphological and chemical transformations.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 13.858
Times cited: 75
DOI: 10.1021/jacs.6b06706
|
|
|
“Shape Control of Colloidal Cu2-x S Polyhedral Nanocrystals by Tuning the Nucleation Rates”. van der Stam W, Gradmann S, Altantzis T, Ke X, Baldus M, Bals S, de Mello Donega C, Chemistry of materials 28, 6705 (2016). http://doi.org/10.1021/acs.chemmater.6b03098
Abstract: Synthesis protocols for colloidal nanocrystals (NCs) with narrow size and shape distributions are of particular interest for the successful implementation of these nanocrystals into devices. Moreover, the preparation of NCs with well-defined crystal phases is of key importance. In this work, we show that Sn(IV)-thiolate complexes formed in situ strongly influence the nucleation and growth rates of colloidal Cu2-x S polyhedral NCs, thereby dictating their final size, shape, and crystal structure. This allowed us to successfully synthesize hexagonal bifrustums and hexagonal bipyramid NCs with low-chalcocite crystal structure, and hexagonal nanoplatelets with various thicknesses and aspect ratios with the djurleite crystal structure, by solely varying the concentration of Sn(IV)-additives (namely, SnBr4) in the reaction medium. Solution and solid-state 119Sn NMR measurements show that SnBr4 is converted in situ to Sn(IV)-thiolate complexes, which increase the Cu2-x S nucleation barrier without affecting the precursor conversion rates. This influences both the nucleation and growth rates in a concentration-dependent fashion and leads to a better separation between nucleation and growth. Our approach of tuning the nucleation and growth rates with in situ-generated Sn-thiolate complexes might have a more general impact due to the availability of various metal-thiolate complexes, possibly resulting in polyhedral NCs of a wide variety of metal-sulfide compositions.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 9.466
Times cited: 27
DOI: 10.1021/acs.chemmater.6b03098
|
|
|
“Direct Observation of Luminescent Silver Clusters Confined in Faujasite Zeolites”. Altantzis T, Coutino-Gonzalez E, Baekelant W, Martinez GT, Abakumov AM, Van Tendeloo G, Roeffaers MBJ, Bals S, Hofkens J, ACS nano 10, 7604 (2016). http://doi.org/10.1021/acsnano.6b02834
Abstract: One of the ultimate goals in the study of metal clusters is the correlation between the atomic-scale organization and their physicochemical properties. However, direct observation of the atomic organization of such minuscule metal clusters is heavily hindered by radiation damage imposed by the different characterization techniques. We present direct evidence of the structural arrangement, at an atomic level, of luminescent silver species stabilized in faujasite (FAU) zeolites using aberration-corrected scanning transmission electron microscopy. Two different silver clusters were identified in Ag-FAU zeolites, a trinuclear silver species associated with green emission and a tetranuclear silver species related to yellow emission. By combining direct imaging with complementary information obtained from X-ray powder diffraction and Rietveld analysis, we were able to elucidate the main differences at an atomic scale between luminescent (heat-treated) and nonluminescent (cation-exchanged) Ag-FAU zeolites. It is expected that such insights will trigger the directed synthesis of functional metal nanocluster-zeolite composites with tailored luminescent properties.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 13.942
Times cited: 57
DOI: 10.1021/acsnano.6b02834
|
|
|
“Hydrophilic Pt nanoflowers: synthesis, crystallographic analysis and catalytic performance”. Mourdikoudis S, Altantzis T, Liz-Marzan LM, Bals S, Pastoriza-Santos I, Perez-Juste J, CrystEngComm 18, 3422 (2016). http://doi.org/10.1039/C6CE00039H
Abstract: Water-soluble Pt nanoflowers (NFs) were prepared by a diethylene glycol-mediated reduction of Pt acetylacetonate
(Pt(acac)2) in the presence of polyethyleneimine. Advanced electron microscopy analysis showed that NFs consist of
multiple branches with truncated cubic morphology and different crystallographic orientations. We demonstrate that the
nature of the solvent strongly influences the resulting morphology. The catalytic performance of Pt NFs in 4–nitrophenol
reduction was found to be superior to that of other nanoparticle-based catalysts. Additionally, Pt NFs display good
catalytic reusability with no loss of activity after five consecutive cycles.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 3.474
Times cited: 30
DOI: 10.1039/C6CE00039H
|
|
|
“An alternative approach for ζ-factor measurement using pure element nanoparticles”. Zanaga D, Altantzis T, Sanctorum J, Freitag B, Bals S, Ultramicroscopy 164, 11 (2016). http://doi.org/10.1016/j.ultramic.2016.03.002
Abstract: It is very challenging to measure the chemical composition of hetero nanostructures in a reliable and quantitative manner. Here, we propose a novel and straightforward approach that can be used to quantify energy dispersive X-ray spectra acquired in a transmission electron microscope. Our method is based on a combination of electron tomography and the so-called ζ-factor technique. We will demonstrate the reliability of our approach as well as its applicability by investigating Au-Ag and Au-Pt hetero nanostructures. Given its simplicity, we expect that the method could become a new standard in the field of chemical characterization using electron microscopy.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 2.843
Times cited: 19
DOI: 10.1016/j.ultramic.2016.03.002
|
|
|
“An alternative approach for \zeta-factor measurement using pure element nanoparticles”. Zanaga D, Altantzis T, Sanctorum J, Freitag B, Bals S, Ultramicroscopy 164, 11 (2016). http://doi.org/10.1016/J.ULTRAMIC.2016.03.002
Abstract: It is very challenging to measure the chemical composition of hetero nanostructures in a reliable and quantitative manner. Here, we propose a novel and straightforward approach that can be used to quantify energy dispersive X-ray spectra acquired in a transmission electron microscope. Our method is based on a combination of electron tomography and the so-called zeta-factor technique. We will demonstrate the reliability of our approach as well as its applicability by investigating Au-Ag and Au-Pt hetero nanostructures. Given its simplicity, we expect that the method could become a new standard in the field of chemical characterization using electron microscopy. (C) 2016 Elsevier B.V. All rights reserved.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 2.843
Times cited: 19
DOI: 10.1016/J.ULTRAMIC.2016.03.002
|
|
|
“Homogeneous Protein Analysis by Magnetic Core-Shell Nanorod Probes”. Schrittwieser S, Pelaz B, Parak WJ, Lentijo-Mozo S, Soulantica K, Dieckhoff J, Ludwig F, Altantzis T, Bals S, Schotter J, ACS applied materials and interfaces 8, 8893 (2016). http://doi.org/10.1021/acsami.5b11925
Abstract: Studying protein interactions is of vital importance both to fundamental biology research and to medical applications. Here, we report on the experimental proof of a universally applicable label-free homogeneous platform for rapid protein analysis. It is based on optically detecting changes in the rotational dynamics of magnetically agitated core-shell nanorods upon their specific interaction with proteins. By adjusting the excitation frequency, we are able to optimize the measurement signal for each analyte protein size. In addition, due to the locking of the optical signal to the magnetic excitation frequency, background signals are suppressed, thus allowing exclusive studies of processes at the nanoprobe surface only. We study target proteins (soluble domain of the human epidermal growth factor receptor 2 – sHER2) specifically binding to antibodies (trastuzumab) immobilized on the surface of our nanoprobes and demonstrate direct deduction of their respective sizes. Additionally, we examine the dependence of our measurement signal on the concentration of the analyte protein, and deduce a minimally detectable sHER2 concentration of 440 pM. For our homogeneous measurement platform, good dispersion stability of the applied nanoprobes under physiological conditions is of vital importance. To that end, we support our measurement data by theoretical modeling of the total particle-particle interaction energies. The successful implementation of our platform offers scope for applications in biomarker-based diagnostics as well as for answering basic biology questions.
Keywords: A1 Journal article; Engineering sciences. Technology; Electron microscopy for materials research (EMAT)
Impact Factor: 7.504
Times cited: 16
DOI: 10.1021/acsami.5b11925
|
|
|
“A New Method for Quantitative XEDS Tomography of Complex Heteronanostructures”. Zanaga D, Altantzis T, Polavarapu L, Liz-Marzán LM, Freitag B, Bals S, Particle and particle systems characterization 33, 396 (2016). http://doi.org/10.1002/ppsc.201600021
Abstract: Reliable quantification of 3D results obtained by X-ray Energy Dispersive Spectroscopy (XEDS) tomography is currently hampered by the presence of shadowing effects and poor spatial resolution. Here, we present a method that overcomes these problems by synergistically combining quantified XEDS data and High Angle Annular Dark Field – Scanning Transmission Electron Microscopy (HAADF-STEM) tomography. As a proof of principle, the approach is applied to characterize a complex Au/Ag nanorattle obtained through a galvanic replacement reaction. However, the technique we propose here is widely applicable to a broad range of nanostructures.
Keywords: A1 Journal article; Engineering sciences. Technology; Electron microscopy for materials research (EMAT)
Impact Factor: 4.474
Times cited: 29
DOI: 10.1002/ppsc.201600021
|
|
|
“Supracrystalline Colloidal Eggs: Epitaxial Growth and Freestanding Three-Dimensional Supracrystals in Nanoscaled Colloidosomes”. Yang Z, Altantzis T, Zanaga D, Bals S, Van Tendeloo G, Pileni M-P, Journal of the American Chemical Society 138, 3493 (2016). http://doi.org/10.1021/jacs.5b13235
Abstract: The concept of template-confined chemical reactions allows the synthesis of complex molecules that would hardly be producible through conventional method. This idea was developed to produce high quality nanocrystals more than 20 years ago. However, template-mediated assembly of colloidal nanocrystals is still at an elementary level, not only because of the limited templates suitable for colloidal assemblies, but also because of the poor control over the assembly of nanocrystals within a confined space. Here, we report the design of a new system called “supracrystalline colloidal eggs” formed by controlled assembly of nanocrystals into complex colloidal supracrystals through superlattice-matched epitaxial overgrowth along the existing colloidosomes. Then, with this concept, we extend the supracrystalline growth to lattice-mismatched binary nanocrystal superlattices, in order to reach anisotropic superlattice growths, yielding freestanding binary nanocrystal supracrystals that could not be produced previously.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 13.858
Times cited: 57
DOI: 10.1021/jacs.5b13235
|
|
|
“Preparation and study of 2-D semiconductors with Dirac type bands due to the honeycomb nanogeometry”. Kalesaki E, Boneschanscher MP, Geuchies JJ, Delerue C, Morais Smith C, Evers WH, Allan G, Altantzis T, Bals S, Vanmaekelbergh D, Proceedings of the Society of Photo-optical Instrumentation Engineers
T2 –, Proceedings of SPIE 8981, 898107 (2014). http://doi.org/10.1117/12.2042882
Abstract: The interest in 2-dimensional systems with a honeycomb lattice and related Dirac-type electronic bands has exceeded the prototype graphene1. Currently, 2-dimensional atomic2,3 and nanoscale4-8 systems are extensively investigated in the search for materials with novel electronic properties that can be tailored by geometry. The immediate question that arises is how to fabricate 2-D semiconductors that have a honeycomb nanogeometry, and as a consequence of that, display a Dirac-type band structure? Here, we show that atomically coherent honeycomb superlattices of rocksalt (PbSe, PbTe) and zincblende (CdSe, CdTe) semiconductors can be obtained by nanocrystal self-assembly and facet-to-facet atomic bonding, and subsequent cation exchange. We present a extended structural analysis of atomically coherent 2-D honeycomb structures that were recently obtained with self-assembly and facet-to-facet bonding9. We show that this process may in principle lead to three different types of honeycomb structures, one with a graphene type-, and two others with a silicene-type structure. Using TEM, electron diffraction, STM and GISAXS it is convincingly shown that the structures are from the silicene-type. In the second part of this work, we describe the electronic structure of graphene-type and silicene type honeycomb semiconductors. We present the results of advanced electronic structure calculations using the sp3d5s* atomistic tight-binding method10. For simplicity, we focus on semiconductors with a simple and single conduction band for the native bulk semiconductor. When the 3-D geometry is changed into 2-D honeycomb, a conduction band structure transformation to two types of Dirac cones, one for S- and one for P-orbitals, is observed. The width of the bands depends on the honeycomb period and the coupling between the nanocrystals. Furthermore, there is a dispersionless P-orbital band, which also forms a landmark of the honeycomb structure. The effects of considerable intrinsic spin-orbit coupling are briefly considered. For heavy-element compounds such as CdTe, strong intrinsic spin-‐orbit coupling opens a non-trivial gap at the P-orbital Dirac point, leading to a quantum Spin Hall effect10-12. Our work shows that well known semiconductor crystals, known for centuries, can lead to systems with entirely new electronic properties, by the simple action of nanogeometry. It can be foreseen that such structures will play a key role in future opto-electronic applications, provided that they can be fabricated in a straightforward way.
Keywords: P1 Proceeding; Engineering sciences. Technology; Electron microscopy for materials research (EMAT)
Times cited: 2
DOI: 10.1117/12.2042882
|
|
|
“Thermal Stability of CoAu13Binary Nanoparticle Superlattices under the Electron Beam”. Altantzis T, Yang Z, Bals S, Van Tendeloo G, Pileni M-P, Chemistry of materials 28, 716 (2016). http://doi.org/10.1021/acs.chemmater.5b04898
Abstract: One primary goal of self-assembly in nanoscale regime is to implement multifunctional binary nanoparticle superlattices into practical use. In the last decade, considerable effort has been put into the fabrication of binary nanoparticle superlattices with controllable structure and stoichiometry. However, limited effort has been made in order to improve the stability of these binary nanoparticle superlattices, which is a prerequisite for their potential application. In this work, we demonstrate that the carbon deposition from specimen contamination can play an auxiliary role during the heat treatment of binary nanoparticle superlattices. With the in-situ carbon matrix formation, the thermal stability of CoAu 13 binary nanoparticle superlattices is unambiguously enhanced.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 9.466
Times cited: 10
DOI: 10.1021/acs.chemmater.5b04898
|
|
|
“Quantitative 3D analysis of huge nanoparticle assemblies”. Zanaga D, Bleichrodt F, Altantzis T, Winckelmans N, Palenstijn WJ, Sijbers J, de Nijs B, van Huis MA, Sanchez-Iglesias A, Liz-Marzan LM, van Blaaderen A, Joost Batenburg K, Bals S, Van Tendeloo G, Nanoscale 8, 292 (2016). http://doi.org/10.1039/c5nr06962a
Abstract: Nanoparticle assemblies can be investigated in 3 dimensions using electron tomography. However, it is not straightforward to obtain quantitative information such as the number of particles or their relative position. This becomes particularly difficult when the number of particles increases. We propose a novel approach in which prior information on the shape of the individual particles is exploited. It improves the quality of the reconstruction of these complex assemblies significantly. Moreover, this quantitative Sparse Sphere Reconstruction approach yields directly the number of particles and their position as an output of the reconstruction technique, enabling a detailed 3D analysis of assemblies with as many as 10 000 particles. The approach can also be used to reconstruct objects based on a very limited number of projections, which opens up possibilities to investigate beam sensitive assemblies where previous reconstructions with the available electron tomography techniques failed.
Keywords: A1 Journal article; Engineering sciences. Technology; Electron microscopy for materials research (EMAT); Vision lab
Impact Factor: 7.367
Times cited: 34
DOI: 10.1039/c5nr06962a
|
|
|
“Controlled Living Nanowire Growth: Precise Control over the Morphology and Optical Properties of AgAuAg Bimetallic Nanowires”. Mayer M, Scarabelli L, March K, Altantzis T, Tebbe M, Kociak M, Bals S, Garcia de Abajo FJ, Fery A, Liz-Marzan LM, Nano letters 15, 5427 (2015). http://doi.org/10.1021/acs.nanolett.5b01833
Abstract: Inspired by the concept of living polymerization reaction, we are able to produce silver-gold-silver nanowires with a precise control over their total length and plasmonic properties by establishing a constant silver deposition rate on the tips of penta-twinned gold nanorods used as seed cores. Consequently, the length of the wires increases linearly in time. Starting with approximately 210 nm x 32 nm gold cores, we produce nanowire lengths up to several microns in a highly controlled manner, with a small self-limited increase in thickness of approximately 4 nm, corresponding to aspect ratios above 100, whereas the low polydispersity of the product allows us to detect up to nine distinguishable plasmonic resonances in a single colloidal solution. We analyze the spatial distribution and the nature of the plasmons by electron energy loss spectroscopy and obtain excellent agreement between measurements and electromagnetic simulations, clearly demonstrating that the presence of the gold core plays a marginal role, except for relatively short wires or high-energy modes.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 12.712
Times cited: 117
DOI: 10.1021/acs.nanolett.5b01833
|
|
|
“Femtosecond Laser-Controlled Tip-to-Tip Assembly and Welding of Gold Nanorods”. Gonzalez-Rubio G, Gonzalez-Izquierdo J, Banares L, Tardajos G, Rivera A, Altantzis T, Bals S, Pena-Rodriguez O, Guerrero-Martinez A, Liz-Marzan LM, Nano letters 15, 8282 (2015). http://doi.org/10.1021/acs.nanolett.5b03844
Abstract: Directed assembly of gold nanorods through the use of dithiolated molecular linkers is one of the most efficient methodologies for the morphologically controlled tip-to-tip assembly of this type of anisotropic nanocrystals. However, in a direct analogy to molecular polymerization synthesis, this process is characterized by difficulties in chain-growth control over nanoparticle oligomers. In particular, it is nearly impossible to favor the formation of one type of oligomer, making the methodology hard to use for actual applications in nanoplasmonics. We propose here a light-controlled synthetic procedure that allows obtaining selected plasmonic oligomers in high yield and with reaction times in the scale of minutes by irradiation with low fluence near-infrared (NIR) femtosecond laser pulses. Selective inhibition of the formation of gold nanorod n-mers (trimers) with a longitudinal localized surface plasmon in resonance with a 800 nm Ti:sapphire laser, allowed efficient trapping of the (n – 1)-mers (dimers) by hot spot mediated photothermal decomposition of the interparticle molecular linkers. Laser irradiation at higher energies produced near-field enhancement at the interparticle gaps, which is large enough to melt gold nanorod tips, offering a new pathway toward tip-to-tip welding of gold nanorod oligomers with a plasmonic response at the NIR. Thorough optical and electron microscopy characterization indicates that plasmonic oligomers can be selectively trapped and welded, which has been analyzed in terms of a model that predicts with reasonable accuracy the relative concentrations of the main plasmonic species.
Keywords: A1 Journal article; Engineering sciences. Technology; Electron microscopy for materials research (EMAT)
Impact Factor: 12.712
Times cited: 101
DOI: 10.1021/acs.nanolett.5b03844
|
|