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Following points are addressed in this contribution: Advantages of correlative analysis in electron microscopy; Measurement principle of the different electron microscopy modes used; Presentation of the nanomaterials used for this study; Role of sample preparation; and, with particular description, the Sequence kV-variation with InLens SE & transmission SEM detection of the same field-of-view.
The ACCORDs project, funded through Horizon Europe, is pioneering a novel approach to investigate Graphene Family Materials (GFMs) through image analysis. Our aim is to unveil how these materials might influence health and the environment. To achieve this, we are developing a platform designed for the easy retrieval, access, sharing, and utilisation of GFM data and the coordination between biological and physico-chemical data formats. Integral to this platform is an OMERO-based library for image storage, alongside data collection forms and image analysis tools. Efforts are underway to streamline the process for researchers to upload and disseminate their findings, manage information within a database and navigate the data with ease. Adhering to REMBI guidelines, which set the standard for annotating biological images with metadata, we ensure our data collection is comprehensive and adheres to established best practices. Initially, we are employing thresholding and basic machine learning techniques for image segmentation, laying the groundwork for advanced analysis through deep learning to gain more profound insights. Upon completion, the project will deliver a comprehensive platform facilitating efficient data and image management concerning GFMs. This platform will enable the straightforward discovery and use of protocols and results, all organised in accordance with the FAIR principles – Findable, Accessible, Interoperable, and Reusable.
This initiative is poised to significantly impact materials science, enhancing our comprehension of the safety and environmental implications of 2D materials.
The recently certified reference material (CRM) BAM-N012 as cubical iron oxide FeOx nanoparticles (NPs) of 8 nm area equivalent square edge length (ESL) and the RM candidate BAM-N013 as nearly spherical NPs of 22 nm size were analyzed in detail by electron microscopy (EM).
For the metrological characterization with SEM, STEM in SEM and TEM, the understanding of the imaging contrasts and sensitivities, and the correct interpretation of the (art)effects which are inherent to each detection mode is necessary.
The same sample areas with NPs deposited on a TEM grid were analyzed by two SEM acquisition modes, i. e. SE InLens and STEM in SEM using a dedicated transmission sample holder, and further, correlatively, analyzed with TEM.
With increasing kV, SE InLens shows increasing particle size (unless overcharging at the particle boundaries is filtered), as a known effect. For STEM-in-SEM the particle size decreases significantly and individual particles are identified easier (at 2 kV only a few single particles can be detected automatically).
❑ Documentation of the sample preparation and measurement conditions (including optimization process) is important for reproducibility.
❑ Plasma cleaning, analysis in the transmission mode at SEM is recommended for FeOx NPs.
❑ Selection of the threshold algorithm can significantly alter the reported ECD.
Traceable morphological and chemical characterization of nanomaterials with respect to the various possible sizes, size distributions, shapes, and concentrations of real-world nanoparticles (NPs) is a challenging task. Particularly for the nonspherical, non-monodisperse nanoparticles – as typically for most of the commercial particles, including their strong tendency to agglomerate, there is a lack of standard operation procedures providing accurate nanoparticle characterisation.
In the framework of the pre-standardisation framework of VAMAS (Versailles Project on Advanced Materials and Standards, www.vamas.org) two interlaboratory comparison (ILC) studies are being carried out under the Technical Working Area (TWA) 34 “Nanoparticle Populations”:i) Project #15 addresses the analysis of the size and shape distribution of TiO2 bipyramidal NPs by traceable imaging methods such as TEM, SEM, STEM-in-SEM, AFM as well as with SAXS as an ensemble method. This ILC is thought as the next level development of the case studies exemplified in the published ISO standards ISO 21363 and ISO 19749. It was agreed to complete the first ILC with the NPs already prepared according to the same procedure on a TEM grid, and, at a later stage, to carry out second ILCs with the same NPs distributed to the participants as liquid suspensions together with protocols for the uniform NP deposition on suited substrates - as developed and optimized within the European project nPSize. Once having good deposition protocols available, the door for automated image analysis gets opened. Corresponding image analysis protocols and reporting templates have been distributed to the ILC participants, too.
ii) Project #16: two spherical SiO2 NP samples with bi-modal size distributions in two nominal relative number concentrations were prepared and distributed also as liquid suspensions accompanied by sample preparation, measurement, and image analysis protocols and reporting templates. Here, the NP concentration is the primary parameter to be measured. For the imaging methods it is targeted to
measure the relative nanoparticle concentrations (relative populations of the two modes).
The results of all the participating laboratories, in both ILCs, compiled in comparative representations will be shown and discussed for the first time. The reduction of the measurement uncertainties associated to the size, shape and number-concentration results induced by the significant improvement of the sample preparation on substrates (as single particles with a high-density coverage), combined with well-defined image analysis procedures will be highlighted.
Finally, a very recent 3rd ILC an the determination of lateral size of Graphene Oxide flakes by SEM is presented as project P13 under VAMAS TWA41 Graphene and Related 2D.
The recently certified reference material (CRM) BAM-N012 as cubical iron oxide FeOx nanoparticles (NPs) of 8 nm area equivalent square edge length (ESL) and the RM candidate BAM-N013 as nearly spherical NPs of 22 nm size were analyzed in detail by electron microscopy (EM).
For the metrological characterization with SEM, STEM in SEM and TEM, the understanding of the imaging contrasts and sensitivities, and the correct interpretation of the (art)effects which are inherent to each detection mode is necessary.
The same sample areas with NPs deposited on a TEM grid were analyzed by two SEM acquisition modes, i. e. SE InLens and STEM in SEM using a dedicated transmission sample holder, and further, correlatively, analyzed with TEM.
With increasing kV, SE InLens shows increasing particle size (unless overcharging at the particle boundaries is filtered), as a known effect. For STEM-in-SEM the particle size decreases significantly and individual particles are identified easier (at 2 kV only a few single particles can be detected automatically).
❑ Documentation of the sample preparation and measurement conditions (including optimization process) is important for reproducibility.
❑ Plasma cleaning, analysis in the transmission mode at SEM is recommended for FeOx NPs.
❑ Selection of the threshold algorithm can significantly alter the reported ECD.
Porous films play an important role particularly in energy applications like photovoltaics, electrolysis or batteries. Thin film properties such as thickness, chemical composition, crystallinity of the framework, and porosity define the activity of the porous films. The accurate morpho-chemical characterisation of mesoporous thin films is a challenging analytical task which requires the consideration of new analytical approaches based on the combination of data of different methods able to address the structure and chemical composition at the nanoscale. In this contribution we characterise thin mesoporous iridium-titanium mixed oxide film properties by Electron Probe Microanalysis (EPMA) with Energy-Dispersive X-ray Spectroscopy (EDS) at an SEM applied in a dedicated “thin film analysis” approach (1). Thus, the film mass deposition, film thickness and the film density can be determined. Further, by dividing the measured film density to an assumed (theoretical) metal oxide framework (skeletal) density, the thin film porosity can be extracted, too.
In order to assess the homogeneity of the thin film properties like the chemical composition, Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) and Auger Electron Spectrometry are applied in the depth profiling mode, so that possible in-depth gradients are detected. Lateral inhomogeneities in the chemical composition and structure of the thin mesoporous films are also identified by applying the same methods in the line-scan or mapping mode, which can be further combined with in-depth sputtering for 3D information. The role of the spatial resolution of the analytical methods considered, which can go down well below 100 nm, will be highlighted.
In this lecture, following points are addressed:
– Advantages of correlative analysis in electron microscopy
– Measurement principle of the different electron microscopy modes used
– Presentation of the nanomaterials used for this study
– Role of sample preparation
– Sequence kV variation with InLens & transmission detection of the same field-of-view
– Conclusive remarks including Monte Carlo simulations
AbstractRecently, we have developed an algorithm to quantitatively evaluate the roughness of spherical microparticles using scanning electron microscopy (SEM) images. The algorithm calculates the root-mean-squared profile roughness (RMS-RQ) of a single particle by analyzing the particle’s boundary. The information extracted from a single SEM image yields however only two-dimensional (2D) profile roughness data from the horizontal plane of a particle. The present study offers a practical procedure and the necessary software tools to gain quasi three-dimensional (3D) information from 2D particle contours recorded at different particle inclinations by tilting the sample (stage). This new approach was tested on a set of polystyrene core-iron oxide shell-silica shell particles as few micrometer-sized beads with different (tailored) surface roughness, providing the proof of principle that validates the applicability of the proposed method. SEM images of these particles were analyzed by the latest version of the developed algorithm, which allows to determine the analysis of particles in terms of roughness both within a batch and across the batches as a routine quality control procedure. A separate set of particles has been analyzed by atomic force microscopy (AFM) as a powerful complementary surface analysis technique integrated into SEM, and the roughness results have been compared.
Validated and standardized methods in microplastic analysis are indispensable for robust monitoring and regulation. Alongside also reference materials are urgently needed. An interlaboratory comparison (ILC) offers a powerful tool to address both these challenges. The present study aimed to compare the precision and accuracy of various methods for the detection and quantification of microplastic in a water-soluble matrix. Additionally, it evaluated the suitability of the test materials (containing environmentally relevant plastic polymers) to serve as reference materials for the microplastic analysis.
In this ILC several most used thermo-analytical and spectroscopic methods have been addressed: Pyrolysis-Gas Chromatography Mass Spectrometry (Py-GC/MS), Thermal Extraction-Desorption Gas Chromatography Mass Spectrometry (TED-GC/MS), micro-Fourier Transform Infrared Spectroscopy (µ-FTIR), and micro-Raman Spectroscopy and Laser Direct Infrared Spectroscopy (LDIR). Microplastic powders of polyethylene (PE) and polyethylene terephthalate (PET) were used to assess suitability of the test materials (microplastic tablets) for method validation and use in the ILCs. The participants were guided with a SOP how to dissolve the test samples and, depending on their selected method, either quantify the number of particles (by the spectroscopic methods) or determine the mass fraction of microplastic particles per sample (by the thermo-analytical methods).
ACCORDs is an Horizon Europe project working in the development of an imaging-based characterization framework (ACCORDs framework) for the holistic correlative assessment of Graphene Family Materials (GFMs) as a representative of 2D nanomaterials (NMs) to assess and predict 2D NMs health and environmental risks. The ACCORDs framework will operationalise safe and sustainable by design (SSbD) strategies proposed in past or ongoing H2020 projects or within OECD by correlating low-, medium-, and high-resolution physico-chemical-biological imaging-based methods with non-imaging methods in a tiered approach. ACCORDs will deliver the ACCORDs framework and user guidance, new imaging-based characterisation methods, reference in vitro tests, new reference 2D NMs for different matrices, a new minimum information reporting guideline for FAIR data sharing and reuse of images as well as an atlas with reference images for diagnostics of compromised safety of GFMs/GFM products. The new guidelines and standard proposals will be submitted to standardisation bodies to allow creation of regulatory ready products. The novelty of ACCORDs is in translating the principles of medical imaging-based diagnostics to 2D material hazard diagnostics. ACCORDs will accelerate industrial sectors in the area of aviation, marine construction, drone production, flexible electronics, photovoltaics, photocatalytics and print inks-based sensors. The value ACCORDs proposes to the graphene industry are practical, easy, imaging-based tools for GFM quality monitoring next to the production line with a possibility to be correlated with advanced highresolution imaging characterization methods in case hazard i.e. deviation from controls (benchmark values) are diagnosed. The ACCORDs framework and tools will contribute to the European Green Deal by addressing the topic: “Graphene: Europe in the lead” and to a new European strategy on standardization, released on 2nd February, 2022.
An overview with the basics of size and shape measurement of particles and 2D structures according to established methodologies (and popular imaging processing software packages) with imaging techniques is given. Main descriptors are explained based on practical cases are determined interactively at the flipchart.
Traceable morphological and chemical characterization of nanomaterials with respect to the various possible sizes, size distributions, shapes, and concentrations of real-world nanoparticles (NPs) is a challenging task. Particularly for the nonspherical, non-monodisperse nanoparticles – as typically for most of the commercial particles, including their strong tendency to agglomerate, there is a lack of standard operation procedures providing accurate nanoparticle characterisation.
In the framework of the pre-standardisation framework of VAMAS (Versailles Project on Advanced Materials and Standards, www.vamas.org) two interlaboratory comparison (ILC) studies are being carried out under the Technical Working Area (TWA) 34 “Nanoparticle Populations”:i) Project #15 addresses the analysis of the size and shape distribution of TiO2 bipyramidal NPs by traceable imaging methods such as TEM, SEM, STEM-in-SEM, AFM as well as with SAXS as an ensemble method. This ILC is thought as the next level development of the case studies exemplified in the published ISO standards ISO 21363 and ISO 19749. It was agreed to complete the first ILC with the NPs already prepared according to the same procedure on a TEM grid, and, at a later stage, to carry out second ILCs with the same NPs distributed to the participants as liquid suspensions together with protocols for the uniform NP deposition on suited substrates - as developed and optimized within the European project nPSize. Once having good deposition protocols available, the door for automated image analysis gets opened. Corresponding image analysis protocols and reporting templates have been distributed to the ILC participants, too.
ii) Project #16: two spherical SiO2 NP samples with bi-modal size distributions in two nominal relative number concentrations were prepared and distributed also as liquid suspensions accompanied by sample preparation, measurement, and image analysis protocols and reporting templates. Here, the NP concentration is the primary parameter to be measured. For the imaging methods it is targeted to
measure the relative nanoparticle concentrations (relative populations of the two modes).
The results of all the participating laboratories, in both ILCs, compiled in comparative representations will be shown and discussed for the first time. The reduction of the measurement uncertainties associated to the size, shape and number-concentration results induced by the significant improvement of the sample preparation on substrates (as single particles with a high-density coverage), combined with welldefined image analysis procedures will be highlighted.
Porous films play an important role particularly in energy applications like photovoltaics, electrolysis or batteries. Thin film properties such as thickness, chemical composition, crystallinity of the framework, and porosity define the activity of the porous films. The accurate morpho-chemical characterisation of mesoporous thin films is a challenging analytical task which requires the consideration of new analytical approaches based on the combination of data of different methods able to address the structure and chemical composition at the nanoscale. In this contribution we characterise thin mesoporous iridium-titanium mixed oxide film properties by Electron Probe Microanalysis (EPMA) with Energy-Dispersive X-ray Spectroscopy (EDS) at an SEM applied in a dedicated “thin film analysis” approach. Thus, the film mass deposition, film thickness and the film density can be determined. Further, by dividing the measured film density to an assumed (theoretical) metal oxide framework (skeletal) density, the thin film porosity can be extracted, too.
In order to assess the homogeneity of the thin film properties like the chemical composition, Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) and Auger Electron Spectrometry are applied in the depth profiling mode, so that possible in-depth gradients are detected. Lateral inhomogeneities in the chemical composition and structure of the thin mesoporous films are also identified by applying the same methods in the line-scan or mapping mode, which can be further combined with in-depth sputtering for 3D information. The role of the spatial resolution of the analytical methods considered, which can go down well below 100 nm, will be highlighted.
Recent publications indicate that the order of electrochemical anodization (before or after the laser processing step) plays an important role for the response of bone-forming osteoblasts—an effect that can be utilized for improving permanent dental or removable bone implants. For exploring these different surface functionalities, multimethod morphological, structural, and chemical characterizations are performed in combination with electrochemical pre- and postanodization for two different characteristic microspikes covered by nanometric laser-induced periodic surface structures on Ti–6Al–4V upon irradiation with near-infrared ps-laser pulses (1030 nm wavelength, ≈1 ps pulse duration, 67 and 80 kHz pulse repetition frequency) at two distinct sets of laser fluence and beam scanning parameters. This work involves morphological and topographical investigations by scanning electron microscopy and white light interference microscopy, structural material examinations via X-ray diffraction, and micro-Raman spectroscopy, as well as near-surface chemical analyses by X-ray photoelectron spectroscopy and hard X-ray photoelectron spectroscopy. The results allow to qualify the mean laser ablation depth, assess the spike geometry and surface roughness parameters, and provide new detailed insights into the near-surface oxidation that may affect the different cell growth behavior for pre- or postanodized medical implants.
Morphological and chemical analysis of mesoporous mixed IrOx-TiOy thin films as electrode materials
(2024)
Porous films play an important role particularly in energy applications like photovoltaics, electrolysis or batteries. Thin film properties such as thickness, chemical composition, crystallinity of the framework, and porosity define the activity of the porous films. The accurate morpho-chemical characterisation of mesoporous thin films is a challenging analytical task which requires the consideration of new analytical approaches based on the combination of data of different methods able to address the structure and chemical composition at the nanoscale. In this contribution we characterise thin mesoporous iridium-titanium mixed oxide film properties by Electron Probe Microanalysis (EPMA) with Energy-Dispersive X-ray Spectroscopy (EDS) at an SEM applied in a dedicated “thin film analysis” approach (1). Thus, the film mass deposition, film thickness and the film density can be determined. Further, by dividing the measured film density to an assumed (theoretical) metal oxide framework (skeletal) density, the thin film porosity can be extracted, too.
In order to assess the homogeneity of the thin film properties like the chemical composition, Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) and Auger Electron Spectrometry are applied in the depth profiling mode, so that possible in-depth gradients are detected. Lateral inhomogeneities in the chemical composition and structure of the thin mesoporous films are also identified by applying the same methods in the line-scan or mapping mode, which can be further combined with in-depth sputtering for 3D information. The role of the spatial resolution of the analytical methods considered, which can go down well below 100 nm, will be highlighted.
Traceable morphological and chemical characterization of nanomaterials with respect to the various possible sizes, size distributions, shapes, and concentrations of real-world nanoparticles (NPs) is a challenging task. Particularly for the nonspherical, non-monodisperse nanoparticles – as typically for most of the commercial particles, including their strong tendency to agglomerate, there is a lack of standard operation procedures providing accurate nanoparticle characterisation.
In the framework of the pre-standardisation framework of VAMAS (Versailles Project on Advanced Materials and Standards, www.vamas.org) two interlaboratory comparison (ILC) studies are being carried out under the Technical Working Area (TWA) 34 “Nanoparticle Populations”:i) Project #15 addresses the analysis of the size and shape distribution of TiO2 bipyramidal NPs by traceable imaging methods such as TEM, SEM, STEM-in-SEM, AFM as well as with SAXS as an ensemble method. This ILC is thought as the next level development of the case studies exemplified in the published ISO standards ISO 21363 and ISO 19749. It was agreed to complete the first ILC with the NPs already prepared according to the same procedure on a TEM grid, and, at a later stage, to carry out second ILCs with the same NPs distributed to the participants as liquid suspensions together with protocols for the uniform NP deposition on suited substrates - as developed and optimized within the European project nPSize. Once having good deposition protocols available, the door for automated image analysis gets opened. Corresponding image analysis protocols and reporting templates have been distributed to the ILC participants, too.
ii) Project #16: two spherical SiO2 NP samples with bi-modal size distributions in two nominal relative number concentrations were prepared and distributed also as liquid suspensions accompanied by sample preparation, measurement, and image analysis protocols and reporting templates. Here, the NP concentration is the primary parameter to be measured. For the imaging methods it is targeted to
measure the relative nanoparticle concentrations (relative populations of the two modes).
The results of all the participating laboratories, in both ILCs, compiled in comparative representations will be shown and discussed for the first time. The reduction of the measurement uncertainties associated to the size, shape and number-concentration results induced by the significant improvement of the sample preparation on substrates (as single particles with a high-density coverage), combined with welldefined image analysis procedures will be highlighted.
This contributions shows the first results of the ongoing interlaboratory comparisons under VAMAS/TWA 34 Nanoparticle populations related on the determination of pasrticle size distribution and relative concentration of nanoparticles and an example of an ILC running under VAMAS/TWA 41 Graphene and Related 2D Materials on the determination of the lateral diemsnions of graphene oxide flakes by Scanning Electron Microscopy. The link to related standardisation projects at ISO/TC Nanotechnologies are explained.
Advanced materials, such as nanomaterials, 2D materials, or thin films, play a crucial role in driving economic development and addressing major challenges in the coming years. These challenges include mitigating the impact of climate change, advancing lightweight engineering, enhancing catalysis, and improving medical applications.
To comprehend the performance of these materials and ensure their acceptance across various sectors as safe and sustainable for both humans and the environment, the availability of reference procedures, materials, and data is essential. One versatile tool for establishing such references and evaluating the proficiency of individual laboratories and their competencies is through (international) interlaboratory comparisons (ILC). Notably, initiatives like the Versailles Project on Advanced Materials and Standards (VAMAS) provide a platform for conducting ILCs.
This webinar will showcase various examples of interlaboratory comparisons, illustrating their impact on the development of reference products.
A thousand times thinner than a human hair, nanoparticles (NPs) are finding applications in a range of modern products. However, as some can affect human health or the environment, knowing the types present is essential. Electron microscopy is the ‘gold standard’ for NP analysis, allowing identification based on manual size analysis, but a new method was required to analyse these particles quickly, accurately and in a consistent way.
Nanoparticles (NPs) are tiny – around 1 to 100 billionths of a meter – and can have different chemistries and behaviours than the same material of larger size. This property has led to advances in a wide range of industries, but it can also confer toxicity. Size measurements are the main way NPs are identified but a lack of standardised methods for identifying ones with complex shapes has hindered evaluation of their potential harm.
The main objective was to assess homogeneity of two bimodal gold materials, namely nPsize1 and nPSize2, containing approximately 1:1 and 10:1 particle number-based ratio of ~30nm and ~60nm particles. Particle number-based concentration within the two size fractions was determined with spICP-MS using the particle frequency method of calibration.
Luminescence lifetimes are an attractive analytical method for detection due to its high sensitivity and stability. Iridium probes exhibit luminescence with long excited-state lifetimes, which are sensitive to the local environment. Perfluorooctanoic acid (PFOA) is listed as a chemical of high concern regarding its toxicity and is classified as a “forever chemical”. In addition to strict limits on the presence of PFOA in drinking water, environmental contamination from industrial effluent or chemical spills requires rapid, simple, accurate, and cost-effective analysis in order to aid containment. Herein, we report the fabrication and function of a novel and facile luminescence sensor for PFOA based on iridium modified on gold surfaces. These surfaces were modified with lipophilic iridium complexes bearing alkyl chains, namely, IrC6 and IrC12, and Zonyl-FSA surfactant. Upon addition of PFOA, the modified surfaces IrC6-FSA@Au and IrC12-FSA @Au show the largest change in the red luminescence signal with changes in the luminescence lifetime that allow monitoring of PFOA concentrations in aqueous solutions. The platform was tested for the measurement of PFOA in aqueous samples spiked with known concentrations of PFOA and demonstrated the capacity to determine PFOA at concentrations >100 μg/L (240 nM).
Reliable measurement of the size of polydisperse, complex-shaped commercial nanopowders is a difficult but necessary task, e.g., for regulatory requirements and toxicity risk assessment. Suitable methods exist for the accurate characterization of the size of non-aggregated, stabilized, spherical and monodisperse nanoparticles. In contrast, industrial nanoscale powders usually require dedicated sample preparation procedures developed for the analysis method of choice. These nano-powders tend to agglomerate and/or aggregate, a behavior which in combination with an innate broad particle size distribution and irregular shape often significantly alters the achievable accuracy of the measured size parameters. The present study systematically tests two commercially available nanoscale powders using different sample preparation methods for correlative analysis by scanning electron microscopy, dynamic light scattering, Brunauer–Emmet–Teller method and differential mobility analysis. One focus was set on the sample preparation by embedding nanoparticles in carbon-based hot-mounting resin. Literature on this topic is scarce and the accuracy of the data extracted from cross sections of these particles is unclearly stated. In this paper systematic simulations on the deviation of the size parameters of well-defined series of nanoparticles with different shapes from the nominal value were carried out and the contributing factors are discussed.
Here, we elucidate nonclassical multistep crystallization pathways of transition metal phosphates from aqueous solutions. We followed precipitation processes of M-struvites, NH4MPO4·6H2O, and M-phosphate octahydrates, M3(PO4)2·8H2O, where M = Ni, Co, or NixCo1–x, by using in situ scattering and spectroscopy-based techniques, supported by elemental mass spectrometry analyses and advanced electron microscopy. Ni and Co phosphates crystallize via intermediate colloidal amorphous nanophases, which change their complex structures while agglomerating, condensing, and densifying throughout the extended reaction times. We reconstructed the three-dimensional morphology of these precursors by employing cryo-electron tomography (cryo-ET). We found that the complex interplay between metastable amorphous colloids and protocrystalline units determines the reaction pathways. Ultimately, the same crystalline structure, such as struvite, is formed. However, the multistep process stages vary in complexity and can last from a few minutes to several hours depending on the selected transition metal(s), their concentration, and the Ni/Co ratio.
Liaison of ISO/TC 202 Microbeam Analysis with VAMAS/TWA 37 Quantitative Microstructural Analysis
(2023)
The progress in activities on Microbeam Analysis under VAMAS/TWA 37 is reviewed. Particularly the liaison with the new projects within the ISO technical committee TC 202 is presented and discussed with respect to the identification and launching corresponding VAMAS projects. The ongoing project "FIB sample processing for TEM" is presented in detail.
Titanium and its alloys are known to allow the straightforward laser-based manufacturing of ordered surface nanostructures, so-called high spatial frequency laser-induced periodic surface structures (HSFL). These structures exhibit sub-100 nm spatial periods – far below the optical diffraction limit. The resulting surface functionalities are usually enabled by both, topographic and chemical alterations of the nanostructured surfaces. For exploring these effects, multi-method characterizations were performed here for HSFL processed on Ti–6Al–4V alloy upon irradiation with near-infrared ps-laser pulses (1030 nm, ≈1 ps pulse duration, 1–400 kHz) under different laser scan processing conditions, i.e., by systematically varying the pulse repetition frequency and the number of laser irradiation passes. The sample characterization involved morphological and topographical investigations by scanning electron microscopy (SEM), atomic force microscopy (AFM), tactile stylus profilometry, as well as near-surface chemical analyses hard X-ray photoelectron spectroscopy (HAXPES) and depth-profiling time-of-flight secondary ion mass spectrometry (ToF-SIMS). This provides a quantification of the laser ablation depth, the geometrical HSFL characteristics and enables new insights into the depth extent and the nature of the non-ablative laser-induced near-surface oxidation accompanying these nanostructures. This allows to answer the questions how the processing of HSFL can be industrially scaled up, and whether the latter is limited by heat-accumulation effects.
Although the use of noble metal catalysts can increase the efficiency of hydrogen evolution reaction, the process is still limited by the characteristics of the metal-hydrogen (M−H) bond, which can be too strong or too weak, depending on the metal employed. Studies revealed that the hydrogen affinity for the metal surface (i.e. H absorption/desorption) is regulated also by the potential at the metal nanoparticles. Through controlled periodic illumination (CPI) of a series of metal/TiO2 suspensions, here we demonstrated that an increase of the HER efficiency is possible for those photodeposited metals which have a Tafel slope below 125 mV. Two possible explanations are here reported, in both of them the M−H interaction and the metal covering level play a prominent role, which also depend on the prevailing HER mechanism (Volmer-Heyrovsky or Volmer-Tafel).
Liaison activities within ISO/TC 202 'Microbeam Analysis' which are relevant to ISO/TC 229 'Nanotechnologies' are reported acoording to the structure defined by ISO/TC229 Nanotechnologies Liaisons Coordination Group (NLCG): new standards/documents, coordination issues, and further detailed specific information, e.g. publications, events, comments.
The progress of the VAMAS interlaboratory comparison Project P13 "Lateral size of graphene oxide flakes by SEM" within the Technical Working Area 41 "Graphene and Related 2D Materials" is presented. The challenges at sample preparation on substrates for accurate measurement and image analysis as well as two different analysis approaches, containing exact guidance how to measure the main descriptors for the lateral size measurement of the imaged graphene oxide flakes with Scanning Electron Microscopy are highlighted. The implementation of the results into the corresponding ISO technical specification AWI/TS 23879 is also discussed and planned, in relation with the AFM part.
Regional standardisation activities and how VAMAS can help in any way to promote activities are reported.
Activities related to organisational updates, government initiatives/priorities (especially related to Materials), details of any strategy documents publicly available, networks within Germany and how we engage are presented.
The VAMAS/TWA 45 Project 2 “Development of standardized methodologies for characterisation of microplastics with microscopy and spectroscopy methods” involving 85 participants around the world is primarily discussed with respect to the results received and a first data evaluation. Status of the Project "Guidelines for defining reference materials for plastic degradation in marine environment" is reported and two new project proposals are presented: "Development of standardized methodologies for characterisation of nanoplastics (starting soon, BAM as leader?) and "Development of analytical protocols for the identification and quantification of microplastics of fibrous shape (still in negotiation)".
Quantitative Microstructural Analysis - VAMAS TWA 37 & Liaison with ISO/TC 202 Microbeam Analysis
(2023)
The progress in activities on Microbeam Analysis under VAMAS/TWA 37 is reviewed. Particularly the liaison with the new projects within the ISO technical committee TC 202 is presented and discussed with respect to the identification and launching corresponding VAMAS projects. The ongoing project "FIB sample processing for TEM" is presented in detail.
Newly developed methodical approaches with an emphasis on correlative imaging analysis of morphology and chemistry of nanomaterials will be presented. Correlative imaging by high-resolution SEM with STEM-in-SEM as well as with EDS, and further with AFM, or with the new technique TKD (Transmission Kikuchi Diffraction) will be explained on various examples of nanostructures, both as starting materials and as embedded/functionalized nanoparticles in products. The unique analytical benefits of the Auger electron probe as a veritable nano-tool for the local surface chemistry will be highlighted. Examples of hybrid analysis of the bulk of nanomaterials by X-ray Spectroscopy and the highest surface-sensitive methods XPS and ToF-SIMS as advanced surface characterization methods available in the Competence Centre nano@BAM will be showed. Particularly for the spatially resolved analysis of the chemistry of nanostructures, such in-depth and lateral gradients of chemistry within mesoporous thin layers, or the completeness of the shells of core-shell nanoparticles, the latter methods are inherent.
Other dedicated developments like approaches for the quantitative determination of the porosity of thin mesoporous layers by electron probe microanalysis (EPMA) with SEM or the quantitative determination of the roughness of particle surface by high-resolution imaging with electron microscopy will be also presented.
The basic principles of generation of electrons and X-rays and the operation of SEM/EDS instruments are presented. Examples, recent successes and challenges in the analysis of nano-structures are given. Multi-method analytical approaches with the focus on imaging the nanoscale are highlighted. Details on the sample preparation and persepective on the automated analysis (sample preparation, measurement, data analyis and storage) are given. Metrological aspects, standardisation, and reference materials are also emphasized by examples.
Accurate characterisation of the morphology (size) and chemistry of graphene-related 2D materials (GR2M) is key in understanding their extraordinary functionalities. Hence, not only the tailoring of these functionalities aiming at applications of increased-performance becomes possible, but also the correlation of the physico-chemical properties with the understanding of the potential toxicity eventually enables a safe and sustainable development of the GR2M for new applications. Whilst AFM and Raman Spectroscopy are recommended to measure the thickness of GO flakes, Scanning Electron Microscopy (SEM) is the most suited method to assess their lateral size, which varies between tens of µm down to below 100 nm. In this paper, procedures for the accurate determination of lateral size of graphene oxide (GO) flakes by SEM are presented. The prerequisite for accurate flake size analysis is the proper sample preparation, i.e. deposition of ideally isolated flakes on a substrate, with the flakes being unfolded, non-overlapped, parallel with the substrate, and having a high coverage density. Examples of optimum image caption conditions and image analysis procedures will be presented. The size descriptors and their measurement are described in the context of the corresponding analysis approach: i) length and width of the flakes with a quick and rough, but robust procedure, and ii) exact contouring of the flakes as part of a highly accurate, but more time-consuming measurement approach. The possibility of application of automated image analysis is discussed as the alternative to the manual flakes analysis.
Since its isolation, graphene has received growing attention from academia and industry due to its unique properties. However, the “what is my material” barrier hinders further commercialization. X-ray photoelectron spectroscopy (XPS) is considered as a method of choice for the determination of the elemental and chemical composition. In this work the influence of the morphology of graphene particles on the XPS results is studied and investigated as a function of X-ray energy, using conventional XPS with Al K𝜶 radiation and hard X-ray photoemission spectroscopy (HAXPES) using Cr K𝜶 radiation. Thereby, the information depth is varied between 10 and 30 nm. For this purpose, two commercial powders containing graphene nanoplatelets with lateral dimensions of either ≈100 nm or in the micrometer range are compared. These larger ones exist as stack of graphene layers which is inspected with scanning electron microscopy. Both kinds of particles are then functionalized with either oxygen or fluorine. The size of the graphene particles is found to influence the degree of functionalization. Only the combination of XPS and HAXPES allows to detect the functionalization at the outermost surface of the particles or even of the stacks and to provide new insights into the functionalization process.
The datasets from (Hard Energy) X-ray photoelectron spectroscopy, X-ray diffraction and Scanning Electron Microsopy are related to the publication
G. Chemello, X. Knigge, D. Ciornii, B.P. Reed, A.J. Pollard, C.A. Clifford, T. Howe, N. Vyas, V.-D. Hodoroaba, J. Radnik
"Influence of the morphology on the functionalization of graphene nanoplatelets analyzed by comparative photoelectron spectroscopy with soft and hard X-rays"
Advanced Materials Interfaces (2023), DOI: 10.1002/admi.202300116.
Elemental composition and thickness determination of thin films by electron probe microanalysis
(2023)
Electron probe microanalysis (EPMA) applies to solid samples of homogenous (bulk) chemical composition and can usually not be applied to structures which are inhomogeneous in the micrometer range such as thin film systems down to a few nm. However, in combination with the established thin film software Stratagem, the thickness as well as the elemental composition of thin films on a substrate can be determined. This has been recently successfully demonstrated for Fe-Ni on Si and Si-Ge on Al2O3 thin film systems. For both systems five samples of different elemental composition and a reference were produced and characterised by inductively coupled plasma mass spectrometry (ICP-MS), Rutherford backscattering (RBS), and transmission electron microscopy (TEM) as reference values. Last year, a new and open-source thin film evaluation programme called BadgerFilm has been released. It can also be used to determine thin film composition and thickness from intensity ratios of the unknown sample and standards (k-ratios). In this contribution, we reevaluated the data acquired for the Fe-Ni and Si-Ge systems using the BadgerFilm software package and compared the obtained elemental compositions and thickness values with the results of the Stratagem software and the reference methods. The conclusion is that the BadgerFilm software shows good agreement with the elemental composition and thickness calculated by Stratagem (mostly <2% for both composition and thickness) and with the reference values for two representative thin film systems (<1%–2% for composition and <10%–20% for thickness).
The obvious benefits derived from the increasing use of engineered nano-, new, and advanced materials and associated products have to be weighed out by a governance process against their possible risks. Differences in risk perception (beliefs about potential harm) among stakeholders, in particular nonscientists, and low transparency of the underlying decision processes can lead to a lack of support and acceptance of nano-, new, and other advanced material enabled products. To integrate scientific outcomes with stakeholders needs, this work develops a new approach comprising a nine-level, stepwise categorization and guidance system entitled “Knowledge, Information, and Data Readiness Levels” (KaRLs), analogous to the NASA Technology Readiness Levels. The KaRL system assesses the type, extent, and usability of the available data, information, and knowledge and integrates the participation of relevant and interested stakeholders in a cocreation/codesign process to improve current risk assessment, communication, and governance. The novelty of the new system is to communicate and share all available and relevant elements on material related risks in a user/stakeholder-friendly, transparent, flexible, and holistic way and so stimulate reflection, awareness, communication, and a deeper understanding that ultimately enables the discursive process that is needed for the sustainable risk governance of new materials.
In the present paper we show an approach of measuring large numbers of nanoparticles in a single scan TKD. TiO2 anatase nanoparticles (NP) of bipyramidal shape were deposited on standard carbon grid used for TEM. The procedure used promoted formation of NP ‘monolayer’ islands with uniform distribution of NPs on the carbon surface which allowed mapping of large number of nanoparticles in the single island.
Collection of whole map covering ~2800 nanoparticles took nearly 20 minutes. Inverse pole figure color coded map indicates that the NPs are either lying on a {101} facet (within 10° range around perfect {101} parallel to the carbon surface orientation) on the carbon film or are lying on a {100} facet (within 10° range around the perfect {100} parallel to the carbon surface orientation). Very unlikely was the NP orientation standing on a {001} face. The NPs size distribution described as equivalent circle diameter (ECD) has been also evaluated and the mean NP ECD was 59 nm with standard deviation of 15 nm, i.e. in good agreement with electron microscopy or AFM results.
This study shows high potential of the technique for crystalline NPs analysis with respect to geometrical orientation of the particles on the substrate. With known orientation, the 3D dimensional characterisation of such non-spherical NPs becomes possible from 2D projection electron micrographs. Moreover, the NP size distribution can be easily extracted. Superior accuracies down to 1-2 nm are achievable. The approach is applicable also on thin lamellae extracted from particulate (or mesoporous) layers.
Following points are presented and discussed: i) nPSize as an EMPIR project on the nanoparticle size and shape distribution of (more) complex particles including sample preparation and machine learning approaches; ii) parallel development of ISO 21363 (PSSD by TEM), ISO 19749 (PSSD by SEM), ISO 22292 (3D TEM), ISO 52408 (NP Prep for AFM and EM), iii) VAMAS and pre-standardisation, TWA 34 „Nanoparticle Populations“ with two nPSize ILC projects P15 & P16 – results to be published and integrated in ISO 21363 (PSSD by TEM); iv) Remaining challenges: platelets, 2D materials (TiO2 and GR2M); v) Reference data sets as part of a complete Characterisation Workflow.
Electron probe microanalysis (EPMA)is a non-destructive technique which assumes a sample of homogenous (bulk) chemical composition and can, therefore, not be used for thin film samples. However, in combination with one of the possible thin film software packages, STRATAGEM, the thickness as well as the composition of such films on a substrate can be determined.
This has been demonstrated for FeNi on Si and SiGe on Al2O3 film systems. For both systems five samples with different elemental composition and a reference were produced and characterised by the Korean research institute KRISS using inductively coupled plasma mass spectrometry (ICP-MS), Rutherford backscattering (RBS), and transmission electron microscopy (TEM).
In 2021, a new and open source thin film evaluation programme called BADGERFILM has been released. It can also be used to determine thin film composition and thickness from intensity ratios of the unknown sample and standards (k-ratios).
In this contribution, we re-evaluated the data acquired for the FeNi and SiGe systems using the BADGERFILM software package and compared the resulting composition and thickness with the results of the established STRATAGEM software and other reference methods. With the current evaluation, the BADGERFILM software shows good agreement with the composition and thickness calculated by STRATAGEM and provided by the KRISS.
These results between two well-known layered material systems analysed with available conventional EMPA approaches (STRATAGEM and direct thickness measurement by TEM) and a new one (BADGERFILM) proves that reliable non-destructive thin film analysis is possible. In this way, we validate the performance of the new software, which is not at all self-explanatory for such
complex quantification algorithms lying behind the final quantified results.
(Pre)Standardisation and Metrology in Microbeam Analysis – Ongoing Activities and Opportunities
(2023)
The presentation addresses the current ongoing projects as well as the gaps and opportunities in microbeam analysis within ISO/TC 202 Microbeam Analysis standardisation body and in-liaison Technical Working Areas (TWAs) at the pre-standardization platform of VAMAS (Versailles Project on Advanced Materials and Standards).
An overview on the VAMAS technical working areas (TWA) and projects where Germany is active has been given. The role of VAMAS as an international pre-standardisation platform, including its intense collaboration with international bodies ISO, CEN, OECD and CCQM and national organizations like DIN has been highlighted.
The progress of the VAMAS Project 16 "Measurement of (relative) number concentration of bimodal silica nanoparticles including deposition from liquid suspension" in TWA 34 Nanoparticle Populations is presented. Follwowing points are discusssed:
- Validate the performance of imaging methods to measure the relative number concentration
• electron microscopy (SEM, TEM) and atomic force microscopy (AFM)
• two modes of bimodal (30 and 60 nm) silica nanoparticles
- Validate the performance of small angle X-ray scattering (SAXS) for the traceable measurement of the number concentration of the two modes.
The progress in the VAMAS Project #15" Measurement of particle size and shape distribution of bipyramidal titania including deposition from liquid suspension" within TWA 34 Nanoparticle Populations is presented with highlight of the following points:
- Determine and compare particle size and shape distribution by means of:
• electron microscopy (SEM, TEM, STEM-in-SEM)
• atomic force microscopy (AFM)
• small angle X-ray scattering (SAXS)
- Determine uncertainty induced by deposition protocol from liquid suspension with comparison to known values from a prior ILC with already deposited nanoparticles on TEM grids.
- Provide comparative validation of protocols for the techniques other than TEM.
Die Bestimmung der Nanopartikelgrößen- und -formverteilung nach OECD TG 125 mit der Transmission and Scanning Electron Microscopy (SEM/TEM) wird punktuell vorgestellt:
- Generelles Messprinzip
- Beispiele
- Korrelative Mikroskopie
- Welchen Durchmesser misst die Methode?
- Welche Partikel kann diese Methode messen?
- Welche Informationen kann diese Methode liefern?
- Wo stößt die Methode an ihre Grenzen?
- Implementierung und Datenauswertung,
- Reporting.
Anschließend wurde eine Q&A-Session für die Imaging-Methoden organisiert.
The study described in this paper was conducted in the framework of the European nPSize project (EMPIR program) with the main objective of proposing new reference certified nanomaterials for the market in order to improve the reliability and traceability of nanoparticle size measurements. For this purpose, bimodal populations as well as complexly shaped nanoparticles (bipyramids, cubes, and rods) were synthesized. An inter-laboratory comparison was organized for comparing the size measurements of the selected nanoparticle samples performed with electron microscopy (TEM, SEM, and TSEM), scanning probe microscopy (AFM), or small-angle X-ray scattering (SAXS). The results demonstrate good consistency of the measured size by the different techniques in cases where special care was taken for sample preparation, instrument calibration, and the clear definition of the measurand. For each characterization method, the calibration process is described and a semi-quantitative table grouping the main error sources is proposed for estimating the uncertainties associated with the measurements. Regarding microscopy-based techniques applied to complexly shaped nanoparticles, data dispersion can be observed when the size measurements are affected by the orientation of the nanoparticles on the substrate. For the most complex materials, hybrid approaches combining several complementary techniques were tested, with the outcome being that the reliability of the size results was improved.
The new recommended definition of a nanomaterial, 2022/C 229/01, adopted by the European Commission in 2022, will have a considerable impact on European Union legislation addressing chemicals, and therefore tools to implement this new definition are urgently needed. The updated NanoDefiner framework and its e-tool implementation presented here are such instruments, which help stakeholders to find out in a straightforward way whether a material is a nanomaterial or not. They are two major outcomes of the NanoDefine project, which is explicitly referred to in the new definition. This work revisits the framework and e-tool, and elaborates necessary adjustments to make these outcomes applicable for the updated recommendation. A broad set of case studies on representative materials confirms the validity of these adjustments. To further foster the sustainability and applicability of the framework and e-tool, measures for the FAIRification of expert knowledge within the e-tool’s knowledge base are elaborated as well. The updated framework and e-tool are now ready to be used in line with the updated recommendation. The presented approach may serve as an example for reviewing existing guidance and tools developed for the previous definition 2011/696/EU, particularly those adopting NanoDefine project outcomes.
We present how mesoporosity can be engineered in transition metal phosphate (TMPs) materials in a template-free manner. The method involves a transformation of a precursor metal phosphate phase, called M-struvite (NH4MPO4·6H2O, M = Mg2+, Ni2+, Co2+, NixCo1-x2+). It relies on the thermal decomposition of crystalline M-struvite precursors to an amorphous and simultaneously mesoporous phase, which forms while degassing of NH3 and H2O. The temporal evolution of mesoporous frameworks and the response of the metal coordination environment were followed with in-situ and ex-situ scattering and diffraction, as well as X -ray spectroscopy. Despite sharing the same precursor struvite structure, different amorphous and mesoporous structures were obtained depending on the involved transition metal. We highlight the systematic differences in absolute surface area, pore shape, pore size, and phase transitions depending on a metal cation present in the analogous M-struvites. The amorphous structures of thermally decomposed Mg-, Ni- and NixCo1-x-struvites exhibit high surface areas and pore volumes (240 m²g-1 and 0.32 cm-3 g-1 for Mg and 90 m²g-1 and 0.13 cm-3 g-1 for Ni). We propose that the low-cost, environmentally friendly M-struvites could be obtained as recycling products from industrial and agricultural wastewaters. These waste products could be then upcycled into mesoporous TMPs through a simple thermal treatment for further applications, for instance, in (electro)catalysis.
Functionalized Ti3C2Tx nanosheets based biosensor for point-of-care detection of SARS-CoV‑2 antigen
(2023)
MXenes are considered a promising class of two-dimensional materials with extraordinary physical and electrochemical properties. Distinguished features like high specific surface area and outstanding electrical conductivity make them suitable for electrochemical biosensing applications. Here, we report the development of a biosensor involving the functionalized MXene−titanium carbide nanosheets (Ti3C2Tx-NS) and monoclonal antibodies against the SARS-CoV-2 nucleocapsid protein (anti-SARS-CoV-2 mAb) to design a point-of-care device for detection of the SARS-CoV-2 nucleocapsid protein (SARS-CoV-2 NP) antigen. Few-layered titanium carbide nanosheets (denoted as FL-Ti3C2Tx-NS) have been synthesized using a single-step etching and delamination method and characterized using optical and electron microscopy techniques revealing the suitability for immunosensing applications. Binding studies revealed the excellent affinity between the biosensor and the SARS-CoV-2 NP. Electrochemical detection of SARS-CoV-2 NP is performed using differential pulse voltammetry and read by a smartphone-based user interface. The proposed FL-Ti3C2Tx-NS based biosensor offers the detection of SARS-CoV-2 NP with a limit of detection of 0.91 nM in a wide detection range in spiked saliva samples. Additionally, there is no cross-reactivity in the presence of potential interferants like SARS-CoV-2 spike glycoprotein and bovine serum albumin. These findings demonstrate the potential of MXenes in developing a rapid and reliable tool for SARS-CoV-2 NP detection. While we report the biosensing of SARS-CoV-2 NP, our system also paves the way for the detection of other SARS-CoV-2 antigens like spike protein or other biomolecules based on antigen−antibody interactions.
The liaison report from the ISO Technical Committee ISO/TC 202 'Microbeam Analysis' for the November 2022 ISO/TC 229 Nanotechnologies Plenary Meeting Nanotechnologies Liaison Coordination Group (NLCG) is provided. Essential Information such as newly published standards and projects in develeopment relevant for ISO/TC 229 resulted from the progress within the last year and additional comments on behalf of ISO/TC 202 are included in the report.
Luminescent semiconductor quantum dots (QDs) are frequently used in the life and material sciences as reporter for bioimaging studies and as active components in devices such as displays, light-emitting diodes, solar cells, and sensors. Increasing concerns regarding the use of toxic elements like cadmium and lead, and hazardous organic solvents during QD synthesis have meanwhile triggered the search for heavy-metal free QDs using green chemistry syntheses methods. Interesting candidates are ternary AgInS2 (AIS) QDs that exhibit broad photoluminescence (PL) bands, large effective Stokes shifts, high PL quantum yields (PL QYs), and long PL lifetimes, which are particularly beneficial for applications such as bioimaging, white light-emitting diodes, and solar concentrators. In addition, these nanomaterials can be prepared in high quality with a microwave-assisted (MW) synthesis in aqueous solution. The homogeneous heat diffusion and instant temperature rise of the MW synthesis enables a better control of QD nucleation and growth and thus increases the batch-to-batch reproducibility. In this study, we systematically explored the MW synthesis of AIS/ZnS QDs by varying parameters such as the order of reagent addition, precursor concentration, and type of stabilizing thiol ligand, and assessed their influence on the optical properties of the resulting AIS/ZnS QDs. Under optimized synthesis conditions, water-soluble AIS/ZnS QDs with a PL QY of 65% and excellent colloidal and long-term stability could be reproducible prepared.
Binary photoluminescent semiconductor nanocrystals (quantum dots, QDs) are one of the best studied fluorescent nanomaterials, and their unique optoelectronic properties paved the road to many applications in (bio)nanophotonics, optoelectronics, and photovoltaics. However, concerns related to their toxic constituents like cadmium or lead and the emerging interest in greener chemistry synthesis approaches hamper their future applicability. Interesting alternatives for some applications like biosensing or bioimaging are heavy-metal-free ternary QDs like AgInS2 (AIS), CuInS2 (CIS), and quaternary QDs such as AIS-ZnS (ZAIS). In this context, we explored the effect of ligand denticity on the organic-to-aqueous phase transfer of oleylamine-stabilized ZAIS QDs with the hydrophilic ligands mercaptopropionic acid (MPA), dihydrolipoic acid (DHLA), and 3-mercapto-2,2-bis(mercaptomethyl)propanoic acid (3MPA), bearing mono-, bi-, and trialkyl thiol groups. Spectroscopic studies of the resulting water-dispersible ZAIS QDs revealed a considerable influence of ligand denticity and ligand-to-QD ratio on the spectral position and width (FWHM; full width at half-maximum) of the photoluminescence (PL) bands, the PL quantum yields (PL QY), and the PL decay kinetics. Thiol capping and phase transfer resulted in a loss in PL by at least a factor of 2. The ligand-induced PL quenching observed particularly for ligands bearing two or three thiol groups was attributed to the facilitated formation of surface-bound disulfides. The best colloidal stability under high dilution conditions was observed for 3MPA.
The progress in the activities on Microbeam Analysis under VAMAS/TWA 37 is reviewed. Particularly the liaison with the new projects within the ISO technical committee TC 202 is presented and discussed with respect to the possibility of identifying and launching related VAMAS projects/inter-laboratory comparisons. The recently started project FIB sample processing for TEM is presented. Next projects in the pipeline involving EBSD and TKD are shortly announced. The need of more promotion for the engagement of more experts from industry and academia at national, European and international level is highlighted. Also, the competition with the other technical working areas (on 'nano' or materials-related) is critically discussed.
Experience gained at BAM within the European project ISGScope on the accurate measureemnt of graphene oxide flakes by electron microscopy is presented. Particularly, factors such as the type of solvent, substrate temperature, but also proper, gentle measurement parameters and image analysis conditions towards automation are highlighted. The measurement procedures in develeopment are being prepared to launch an inter-laboratory comparison under VAMAS (TWA41) as preparatory guidance for future standardisation at ISO.
Nanoparticle Populations
(2022)
Two new projects P15 Measurement of particle size and shape distribution of bipyramidal titania including deposition from liquid suspension and P16 Measurement of (relative) number concentration of bimodal silica nanoparticles including deposition from liquid suspension have been started at VAMAS/TWA 34 under the lead of BAM. First results are presented and discussed.
Quantitative Microstructural Analysis - VAMAS TWA 37 & Liaison with ISO/TC 202 Microbeam Analysis
(2022)
The progress in activities on Microbeam Analysis under VAMAS/TWA 37 is reviewed. Particularly the liaison with the new projects within the ISO technical committee TC 202 is presented and discussed with respect to the possibility of identifying and launching related VAMAS projects. The recently started project FIB sample processing for TEM is highlighted. Need of more promotion for the engagement of more participants from industry and academia at national, European and international level is highlighted. Also, the competition with the other technical working areas (on 'nano' or materials-related) is critically discussed. Further, a short overview of the VAMAS areas of activities is given where Germany is involved. Planed regional VAMAS Workshops in Germany in 2023 are announced.
In the present talk the basics of the Raman spectroscopy and particularly of Raman microscopy are explained. Advantages and disadvantages of the method are highlighted through selected case studies. In the second part of the lecture examples of correlative imaging with electron, X-ray, ion and optical microscopies from micro- to the nanoscale are highlighted.
One aim of the EMPIR nPSize project 17NRM04 was to develop and validate three classes of candidate reference (test) materials (RTMs), with i) well-defined non-spherical shape, ii) relatively high polydispersity index, and iii) accurate particle concentrations.
To fulfil the requirements of the project, 11 different types of materials were prepared. Following the initial assessment of the materials suitability, nPSize5_PT_UNITO, nPSize6_AC_UNITO and nPSize7_GN_CEA materials were found unsuitable for the project, due to various reasons. PT material was deemed unsuitable due to its predominantly agglomerated nature. AC material contained relatively high amount of impurities (other particle forms). GN material was found too heterogeneous in both the length and width for the purpose of the project. The remaining 8 candidate RTMs were assessed for their homogeneity and stability and used for successful delivery of the associated activities within the nPSize project.
BAM is currently building up a platform of novel nanoRMs relying on iron oxide nanoparticles of different shape, size and surface chemistry. Iron oxide was chosen as a core material because of its relevance to the material and life sciences.
As a first candidate of this series, we present cubic iron oxide nanoparticles with a nominal edge length of 8 nm. These particles were synthesized by thermal decomposition of iron oleate in high boiling organic solvents adapting well-known literature procedures. After dilution to a concentration suitable for electron microscopy (TEM and SEM) as well as for small-angle X-ray scattering (SAXS) measurements, the candidate nanoRM was bottled and assessed for homogeneity and stability by both methods following the guidelines of ISO 17034 and ISO Guide 35.
The particle sizes obtained by both STEM-in-SEM and TEM are in excellent agreement with a minimum Feret of 8.3 nm ± 0.7 nm. The aspect ratio (AR) of the iron oxide cubes were extracted from the images as the ratio of minimum Feret to Feret resulting in an AR of 1.18 for TEM to 1.25 for SEM. Alternatively, a rectangular bounding box was fitted originating from the minimum Feret and the longest distance through the particle in perpendicular direction. This led to AR values of 1.05 for TEM and 1.12 for SEM, respectively. The results confirm the almost ideal cubic shape.
Water splitting using semiconductor photo-catalysts is considered a sustainable method to produce clean hydrogen fuel. Nevertheless, H2 photo-production efficiency remains still low, although extensive research works to understand better the mechanisms of the Hydrogen Evolution Reaction (HER) and the Oxygen Evolution Reaction (OER) are being carried out. In this respect, TiO2 is a key photoactive material, usually employed with a co-catalyst deposited onto the surface to enhance charge carriers’ separation and catalyze surface charge transfer reactions. The deposition of a co-catalyst on the TiO2 nanoparticle surface represents one successful way to enhance the activity of the photocatalyst through a modification of its surface and redox properties. In this context, high-resolution scanning electron microscopy (SEM) coupled with elemental analysis by energy-dispersive X-ray spectroscopy (EDS) is fundamental for studying and understanding the effect of the nanoparticle morphology on the functional properties of shape-controlled TiO2 crystals (bipyramides, platelets, and elongated particles). Different types of metal-semiconductor combinations, TiO2 shapes and dopant metals (Ag, Pt, Au, Rh, Pd) and metal concentrations are discussed.
Electron Probe Microanalysis (EPMA) provides a non-destructive approach in the dedicated thin film analysis mode with the commercial StrataGem software. Recently, the open-source programme BadgerFilm by Moy and Fournelle became available. Similarly to StrataGem, it is based on the algorithm of Pouchou and Pichoir and needs intensity ratios of the unknown sample and standards (k-values). We have evaluated the k-values measured for the FeNi and SiGe film systems using the BadgerFilm software package and compared the thickness and composition with the results obtained with the established StrataGem software and other reference methods. The thicknesses of the SiGe films obtained by the BadgerFilm software agree within 20% with the StrataGem and TEM results; the elemental compositions BadgerFilm-StrataGEM agree within 2% with one exception (9%).
In order to bridge the gap between lab-scale and industrial-scale production of graphene it is necessary to develop processes, equipment and measurement procedures to control the material features. One of the crucial reasons of graphene’s limited commercialization is the lack of standard procedures to properly characterize and define the material chemical and structural properties down to the nanometer level. This leads to many issues regarding material synthesis repeatability, inappropriateness choice of measurands and measurement reproducibility which heavily affect the consistency of the material performance.
In our study, a comparative analysis is performed on two different series (G5 and G6) of industrial graphene powders, each series produced with four types of functionalization: raw graphene, oxygen-functionalized, nitrogen-functionalized and fluorine-functionalized. All the 8 sample variants were analyzed from a chemical and morphological point of view in the form of powders prepared as slightly pressed in metallic sample holders.
The results of the comparative chemical analyses XPS and EDS show a good agreement in the concentration values for all the elements present in the samples, despite the different analysis volumes addressed by the two techniques. For this reason, the samples can be considered homogeneous in both lateral and vertical direction.
A clear influence of the morphology on the composition is evident. Therefore, such correlative measurements of morphology and composition are necessary for a comprehensive characterization of industrial graphene flakes.
For test laboratories operating under accreditation schemes like ISO/IEC 17025 (ISO/IEC 17025), as the international reference for testing and calibration laboratories wanting to demonstrate their capacity to deliver reliable results, a periodical control of the critical instrumental parameters of an Energy-Dispersive X-ray Spectrometer (EDS) is required.
This periodical check of an EDS is specified with exact procedures and materials in the ISO 15632:2021 ”Microbeam Analysis – Selected instrumental performance parameters for the specification and checking of energy-dispersive X-ray spectrometers for use in electron probe microanalysis” (ISO 15632). The EDS check can be simplified to the acquisition of only one 10 kV spectrum from a dedicated test material, EDS-TM002, which is made available by BAM since 2009 (https://webshop.bam.de/webshop_en/). The optional BAM software “EDX spectrometer check” is destined to automatically evaluate this spectrum and determine the performance of the EDS in terms of energy resolution and calibration, as well as possible alteration of low-energy efficiency due to detector contamination. Nearly 200 laboratories have the EDS-TM and associated software package in use.
Practical examples based on various types of artifacts occurred in the EDS spectra and a long-term (>10 years) meticulous observation of the own spectrometers will be discussed. Different types of EDS spectrometers are considered, e.g. Si(Li) and SDD, of various window types (AP, the recent one Si3N4 or even windowless), and with different front contact layers (Au and Ni) (Hodoroaba and Procop, 2014). Evaluation of other parameters or effects such as the deadtime at different count rates or pileup effects is also explained with examples.
The thickness of thin films can be measured by various methods, e.g., profilometry, ellipsometry, atomic force microscopy (AFM), or X-ray reflectometry. For the additional determination of thin film composition, techniques like X-ray photoelectron spectroscopy (XPS) or mass spectrometry-based techniques can be used. An alternative non-destructive technique is electron probe microanalysis (EPMA). This method assumes a sample of homogenous (bulk) chemical composition, so that it cannot be usually applied to thin film samples. However, in combination with the thin film software StrataGEM, the thickness as well as the composition of such films on a substrate can be determined.
This has been demonstrated for FeNi on Si and SiGe on Al2O3 film systems. For both systems five samples with different elemental composition and a reference were produced and characterised by Korean research institute KRISS using inductively coupled plasma mass spectrometry (ICP-MS), Rutherford backscattering (RBS), and transmission electron microscopy (TEM). These samples were used for an international round robin test.
In 2021, a new and open-source thin film evaluation programme called BadgerFilm has been released. It can also be used to determine thin film composition and thickness from intensity ratios of the unknown sample and standards (k-ratios).
In this contribution, we re-evaluated the data acquired for the FeNi and SiGe systems using the BadgerFilm software package and compared the resulting composition and thickness with the results of the established StrataGEM software and other reference methods. With the current evaluation, the BadgerFilm software shows good agreement with the composition and thickness calculated by StrataGEM and as the reference values provided by the KRISS.
The conversion of solar energy into electricity and solar fuels is of crucial importance for a green and sustainable future. Water splitting using semiconductor photo-catalysts is considered a sustainable method to produce clean hydrogen (H2) fuel. Nevertheless, H2 photo-production efficiency remains still low, although extensive research works to understand better the mechanisms of the Hydrogen Evolution Reaction (HER) and the Oxygen Evolution Reaction (OER) are being carried out. In this respect, TiO2 is a key photoactive material, usually employed with a co-catalyst deposited onto the surface to enhance charge carriers’ separation and catalyze surface charge transfer reactions. The deposition of a co-catalyst on the TiO2 nanoparticle surface represents one successful way to enhance the activity of the photocatalyst through a modification of its surface and redox properties. In this context, high-resolution scanning electron microscopy coupled with elemental analysis by energy-dispersive X-ray spectroscopy (EDS) is fundamental for studying and understanding the effect of the nanoparticle morphology on the functional properties of shape-controlled TiO2 crystals (bipyramides, platelets, and elongated particles). Different types of metal-semiconductor combinations, TiO2 shapes and dopant metals (Ag, Pt, etc) and metal concentrations will be discussed.
CS particles show unique properties by merging individual characteristics of the core and the shell materials. An alteration particularly in their surface roughness affects the final performance of the particles in the targeted application. Quantitative evaluation of the roughness of CS microparticles is, however, a challenging task employing microscopic techniques being scarce and showing large differences in terms of methodology and results.
In our previous work, we have reported a systematic study with a reliable analysis tool, which evaluates profile roughness quantitatively, for individual core-shell microparticles using electron microscopy (EM) images of both types, Scanning Electron Microscopy (SEM) and transmission mode SEM (or TSEM). The SEM images contain two-dimensional (2D) information, therefore, provide profile roughness data only from the projection in the horizontal plane (in other words, from the “belly”) of a spherical particle. The present study offers a practical procedure to give access to more information by tilting the sample holder and hence allowing images of a single particle to be recorded at different orientations under the same view angle. From the analysis of these images, extended information on surface roughness of the particle can be extracted. Thus, instead of obtaining 2D information from a single SEM image, three-dimensional (3D) information is obtained from 2D projections recorded at different particle orientations.
Nanosafety is becoming increasingly important as nanomaterials are widely used in industrial processes and consumer products. For nanotoxicity measurements prior sterilization of the samples is necessary, but as structure activity relationships are made with properties of pristine particles, the question arises, if the sterilization process has an impact on the physico-chemical properties of nanoparticles and thus on the biological behavior.
This question will be addressed in this talk. For this purpose, results from SEM and EDS measurements are combined with those of a novel lab-based HAXPES spectrometer in order to obtain a more complete picture. At the end, an influence of sterilization will be evident, which indicates a restructuring of the nanoparticles owing to sterilization.
Electron microscopy (EM) is the gold standard for the characterisation of the morphology (size and shape) of nanoparticles. Visual observation of objects under examination is always a necessary first step in the characterisation process. Several questions arise when undertaking to identify and count particles to measure their size and shape distribution. In addition to challenges with the dispersion and identification of the particles, more than one protocol for counting particles is in use. This paper focuses on precise rules for the counting of particles in EM micrographs, as this influences the measurement accuracy of the number of particles, thus implicitly affecting the size values of the counted particles. We review and compare four different, commonly used methods for counting, which we then apply in case studies. The impact of the selected counting rule on the obtained final particle size distribution is highlighted. One main aim of this analysis is to support the application of a specific, well-defined counting approach in accordance with regulatory
requirements to contribute to achieving more reliable and reproducible results. It is also useful for the new harmonised measurement procedures for determining the particle size and particle size distribution of nanomaterials.
Catalysts are important components in chemical processes because they lower the activation energy and thus determine the rate, efficiency and selectivity of a chemical reaction. This property plays an important role in many of today’s processes, including the electrochemical splitting of water. Due to the continuous development of catalyst materials, they are becoming more complex, which makes a reliable evaluation of physicochemical properties challenging even for modern analytical measurement techniques and industrial manufacturing.
We present a fast, vacuum-free and non-destructive analytical approach using multi-sample spectroscopic ellipsometry to determine relevant material parameters such as film thickness, porosity and composition of mesoporous IrOx–TiOy films. Mesoporous IrOx–TiOy films were deposited on Si wafers by sol–gel synthesis, varying the composition of the mixed oxide films between 0 and 100 wt%Ir. The ellipsometric modeling is based on an anisotropic Bruggeman effective medium approximation (a-BEMA) to determine the film thickness and volume fraction of the material and pores. The volume fraction of the material was again modeled using a Bruggeman EMA to determine the chemical composition of the materials. The ellipsometric fitting results were compared with complementary methods, such as scanning electron microscopy (SEM), electron probe microanalysis (EPMA) as well as environmental ellipsometric porosimetry (EEP).
Morpho-Chemical Characterisation of Me-TiO2 Nanoparticles for Enhanced Photocatalytical Activity
(2022)
The conversion of solar energy into electricity and solar fuels is of crucial importance for a green and sustainable future. Water splitting using semiconductor photo-catalysts is considered a sustainable method to produce clean hydrogen (H2) fuel. Nevertheless, H2 photo-production efficiency remains still low, although extensive research works to understand better the mechanisms of the Hydrogen Evolution Reaction (HER) and the Oxygen Evolution Reaction (OER) are being carried out. In this respect, TiO2 is a key photoactive material, usually employed with a co-catalyst deposited onto the surface to enhance charge carriers’ separation and catalyze surface charge transfer reactions. The deposition of a co-catalyst on the TiO2 nanoparticle surface represents one successful way to enhance the activity of the photocatalyst through a modification of its surface and redox properties. In this context, high-resolution scanning electron microscopy coupled with elemental analysis by energy-dispersive X-ray spectroscopy (EDS) is fundamental for studying and understanding the effect of the nanoparticle morphology on the functional properties of shape-controlled TiO2 crystals (bipyramides, platelets, and elongated particles). Different types of metal-semiconductor combinations, TiO2 shapes and dopant metals (Ag, Pt, etc) and metal concentrations will be discussed.
microscopy (AFM), or X-ray reflectometry. For the additional determination of thin film composition, techniques like X-ray photoelectron spectroscopy (XPS) or mass spectrometry-based techniques can be used. An alternative non-destructive technique is electron probe microanalysis (EPMA). This method assumes a sample of homogenous (bulk) chemical composition, so that it cannot be usually applied to thin film samples. However, in combination with the thin film software StrataGEM, the thickness as well as the composition of such films on a substrate can be determined.
This has been demonstrated for FeNi on Si and SiGe on Al2O3 film systems. For both systems five samples with different elemental composition and a reference were produced and characterised by Korean research institute KRISS using inductively coupled plasma mass spectrometry (ICP-MS), Rutherford backscattering (RBS), and transmission electron microscopy (TEM). These samples were used for an international round robin test.
In 2021, a new and open-source thin film evaluation programme called BadgerFilm has been released. It can also be used to determine thin film composition and thickness from intensity ratios of the unknown sample and standards (k-ratios).
In this contribution, we re-evaluated the data acquired for the FeNi and SiGe systems using the BadgerFilm software package and compared the resulting composition and thickness with the results of the established StrataGEM software and other reference methods. With the current evaluation, the BadgerFilm software shows good agreement with the composition and thickness calculated by StrataGEM and as the reference values provided by the KRISS.
Both essential aspects of the surface of solid matter, its morphology and chemistry, are studied traditionally at BAM starting in the 60’s with different cyclical research focus areas, mostly related either to applicative research or method development. In the recent years, the focus has shifted almost exclusively to the nano-analytics of advanced materials such as complex nanoparticles, (ultra)thin films/coatings, nanocomposites, 2D materials, energy materials, etc. This is also the reason why BAM has established recently the new Competence Center nano@BAM (www.bam.de/Navigation/DE/Themen/Material/Nanotechnologie/sichere-nanomaterialien.html) with the five sub-fields nanoCharacterisation, nanoMaterial, nanoSafety, nanoData and nanoTechnology. The link to the BAM central guidelines to the safety in technology and chemistry is given by the development of reference products such as reference measurement procedures, reference (nano)materials, and newly reference data sets. Thus, an internationally well-networked group in surface analysis has been established @BAM, with regular contributions to integral analytical characterization with metrological and standardization background.
Examples of newly developed methodical approaches will be given with an emphasis on correlative nano-analysis of morphology and chemistry of nanomaterials. Correlative imaging by STEM-in-SEM with high-resolution SEM and EDX, and further with AFM or the new technique TKD (Transmission Kikuchi Diffraction) will be explained on various examples of nanostructures, both as starting materials and embedded/functionalized nanoparticles in products. The unique analytical benefits of the Auger electron probe as a veritable nano-tool for surface chemistry will be highlighted. The panoply of advanced surface characterization methods @BAM is completed by discussing examples of hybrid analysis of the bulk of nanomaterials by X-ray Spectroscopy with the highest surface-sensitive methods X-ray Photoelectron Spectroscopy (XPS) and Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS). Particularly for the analysis of the surface chemistry of nanostructures, such as the completeness of the shells of core-shell nanoparticles or in-depth and lateral gradients of chemistry within mesoporous thin layers, the latter methods are inherent.
Other special developments like approaches for the quantitative determination of the roughness of particle surface by electron microscopy or for the quantitative determination of the porosity of thin mesoporous layers by electron probe microanalysis (EPMA) with SEM will be presented.
The main outcomes of the EMPIR project nPSize are presented and the suitability of the new capabilities, e.g. reference materials, sample preparation protocols, measurement procedures, and data analysis, to be standardized and implemented in accredited analytical laboratories is discussed. Complementation and/or filling gaps of published and ongoing standardisation projects on size, shape and number concentration measurements under ISO/TC 229/JWG 2 are offered.
The two VAMAS inter-laboratory comparisons resulted from the nSPize project and just started under TWA 34 Nanoparticle Populations (Projects #15 and #16) of bipyramidal TiO2 anatase and bimodal SiO2 nanoparticles are presented in detail.
Core-shell (CS) particles have been increasingly used for a wide range of applications due to their unique properties by merging individual characteristics of the core and the shell materials. The functionality of the designed particles is strongly influenced by their surface roughness. Quantitative evaluation of the roughness of CS microparticles is, however, a challenging task for Scanning Electron Microscopy (SEM).
The SEM images contain two-dimensional (2D) information providing contour roughness data only from the projection of the particle in the horizontal plane. This study presents a practical procedure to achieve more information by tilting the sample holder, hence allowing images of different areas of a single particle to be recorded at different orientations under the same view angle. From the analysis of these images, quasi three-dimensional (3D) information is obtained.
Three types of home-made particles were investigated: i) bare polystyrene (PS) particles, ii) PS particles decorated with a first magnetic iron oxide (Fe3O4) nanoparticle shell forming CS microbeads, iii) PS/Fe3O4 particles closed with a second silica (SiO2) shell forming core-shell-shell (CSS) microbeads. A series images of a single particle were taken with stepwise tilted sample holder up to 10° by an SEM with high-resolution and surface sensitive SE-InLens® mode.
A reliable analysis tool has been developed by a script in Python to analyze SEM images automatically and to evaluate profile roughness quantitatively, for individual core-shell microparticles. Image analysis consists of segmentation of the images, identifying contour and the centre of the particle, and extracting the root mean squared roughness value (RMS-RQ) of the contour profile from the particle projection within a few seconds.
The variation in roughness from batch-to-batch was determined with the purpose to set the method as a routine quality check procedure. Flow cytometry measurements provided complementary data. Measurement uncertainties associated to various particle orientations were also estimated.
he main objective of the nPSize project is to improve the measurement capabilities for nanoparticle size based on both measurement methods traceable to SI units and new reference materials. Two basic approaches have been used in order to develop measurement procedures resulting in traceable results of the nanoparticle size distribution: physical modelling for the methods used in the project (TSEM, SEM, AFM and SAXS) and machine learning.
Physical modelling: In this part, the physical models associated with different shape measurements for the techniques TSEM, SEM, AFM and SAXS have been collected and further developed with the aim to simulate the resulting signal as measured by the individual methods. Uncertainties and traceability associated with each model were investigated and evaluated. In the following, the progress on these physical models is reported for each individual method.
Machine Learning modelling: The aim of this part is to use machine learning to enable automatic measurement of nanoparticle shape from expert a-priori information only. No physical model will be used as a-priori information in this task.
The accuracy and traceability of the size results obtained by each technique will be analyzed and compared with the physical modelling. A machine learning database will then be used to create automatic detection algorithms.
International standardisation network VAMAS is calling for participants in two studies on the measurement of (relative) number concentration of bimodal silica nanoparticles including deposition from liquid suspension and the measurement of particle size and shape distribution of bipyramidal titania including deposition from liquid suspension.
Whereas the characterization of nanomaterials using different analytical techniques is often highly automated and standardized, the sample preparation that precedes it causes a bottleneck in nanomaterial analysis as it is performed manually. Usually, this pretreatment depends on the skills and experience of the analysts. Furthermore, adequate reporting of the sample preparation is often missing. In this overview, some solutions for techniques widely used in nano-analytics to overcome this problem are discussed. Two examples of sample preparation optimization by au-tomation are presented, which demonstrate that this approach is leading to increased analytical confidence. Our first example is motivated by the need to exclude human bias and focuses on the development of automation in sample introduction. To this end, a robotic system has been de-veloped, which can prepare stable and homogeneous nanomaterial suspensions amenable to a variety of well-established analytical methods, such as dynamic light scattering (DLS), small-angle X-ray scattering (SAXS), field-flow fractionation (FFF) or single-particle inductively coupled mass spectrometry (sp-ICP-MS). Our second example addresses biological samples, such as cells exposed to nanomaterials, which are still challenging for reliable analysis. An air–liquid interface has been developed for the exposure of biological samples to nanomaterial-containing aerosols. The system exposes transmission electron microscopy (TEM) grids under reproducible conditions, whilst also allowing characterization of aerosol composition with mass spectrometry. Such an approach enables correlative measurements combining biological with physicochemical analysis. These case studies demonstrate that standardization and automation of sample preparation setups, combined with appropriate measurement processes and data reduction are crucial steps towards more reliable and reproducible data.
The Competence Centre nano@BAM is presenting a new X-ray Photoelectron Spectrometer – the HAXPES (XPS at hard energy) – for researching advanced materials at the nanoscale. With HAXPES detailed chemical information can now be gained not only from the first outermost nanometres of the sample surface, but also from deeper regions.
Top international experts will share their knowledge and key findings on how to utilise HAXPES for exploring the surface of various advanced materials. Following the lectures, we will show you a short demo of the new instrument and answer your questions.
The roughness as a property of core–shell (CS) microparticles plays a key role in their functionality. Quantitative evaluation of the roughness of CS microparticles is, however, a challenging task with approaches using electron microscopy images being scarce and showing pronounced differences in terms of methodology and results. This work presents a generalized method for the reliable roughness determination of nonplanar specimens such as CS particles from electron microscopic images, the method being robust and reproducible with a high accuracy. It involves a self-written software package (Python) that analyzes the recorded images, extracts corresponding data, and calculates the roughness based on the deviation of the identified contour. Images of single particles are taken by a dual mode scanning electron microscopy (SEM) setup which permits imaging of the same field-of-view of the sample with high resolution and surface sensitive in SE InLens mode as well as in transmission mode (TSEM). Herein, a new type of polystyrene core–iron oxide shell–silica shell particles is developed to serve as a set of lower micrometer-sized study objects with different surface roughness; the analysis of their images by the semiautomatic workflow is demonstrating that the particles’ profile roughness can be quantitatively obtained.
Both essential aspects of the surface of solid matter, its morphology and chemistry, are studied traditionally at BAM starting in the 60’s with different cyclical research focus areas, mostly related either to applicative research or method development. In the recent years, the focus has shifted almost exclusively to the nano-analytics of advanced materials such as complex nanoparticles, (ultra)thin films/coatings, nanocomposites, 2D materials, energy materials, etc. This is also the reason why BAM has established recently the new Competence Center nano@BAM (www.bam.de/Navigation/DE/Themen/Material/Nanotechnologie/sichere-nanomaterialien.html) with the five sub-fields nanoCharacterisation, nanoMaterial, nanoSafety, nanoData and nanoTechnology. The link to the BAM central guidelines to the safety in technology and chemistry is given by the development of reference products such as reference measurement procedures, reference (nano)materials, and newly reference data sets. Thus, an internationally well-networked group in surface analysis has been established @BAM, with regular contributions to integral analytical characterization with metrological and standardization background.
Examples of newly developed methodical approaches will be given with an emphasis on correlative nano-analysis of morphology and chemistry of nanomaterials. Correlative imaging by STEM-in-SEM with high-resolution SEM and EDX, and further with AFM or the new technique TKD (Transmission Kikuchi Diffraction) will be explained on various examples of nanostructures, both as starting materials and embedded/functionalized nanoparticles in products. The unique analytical benefits of the Auger electron probe as a veritable nano-tool for surface chemistry will be highlighted. The panoply of advanced surface characterization methods @BAM is completed by discussing examples of hybrid analysis of the bulk of nanomaterials by X-ray Spectroscopy with the highest surface-sensitive methods X-ray Photoelectron Spectroscopy (XPS) and Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS). Particularly for the analysis of the surface chemistry of nanostructures, such as the completeness of the shells of core-shell nanoparticles or in-depth and lateral gradients of chemistry within mesoporous thin layers, the latter methods are inherent.
Other special developments like approaches for the quantitative determination of the roughness of particle surface by electron microscopy or for the quantitative determination of the porosity of thin mesoporous layers by electron probe microanalysis (EPMA) with SEM will be presented in conjunction with the corresponding advanced materials studied.
Current research projects, promising ideas, including ongoing (pre-)standardization activities in the field of the challenging nano/surface analysis will be touched systematically, with the open goal of identifying future bilateral cooperation possibilities between EMPA and BAM.
Results from different methods applied to micro- and nanoplastics (MNPs) analysis show that there are large gaps in harmonisation with respect to terminology, size classes, sample preparation protocols and, finally, to the comparability of the measurands and descriptors.
Within the European research cluster to understand the health impacts of micro- and nanoplastics (CUSP) working group WG3-Inter-Laboratory Comparisons an overview of the existing detection methods revealing advantages and disadvantages regarding the analytical tasks is being compiled. There is a clear need to develop high class characterized reference materials for MNPs in the size ranges of 100-10 µm and smaller than 10 µm, so that these can be used to validate methods and to make results comparable. Inter-laboratory comparisons (ILCs) on model samples with complex matrices regarding mass, or water samples for number-based methods, will help us to advance the process of harmonization as well as to train users early in process of developing new methods.
We plan to keep all five CUSP projects well-connected also with the 'outside' MNP projects and ILCs and to extract the optimum of needs, capabilities, and efforts in order to launch new VAMAS ILCs which should expand already available ones.
In this paper, the accurate determination of the size and size distribution of bipyramidal anatase nanoparticles (NPs) after deposition as single particles on a silicon substrate by correlative Scanning Electron Microscopy (SEM) with Atomic Force Microscopy (AFM) analysis is described as a new measurement procedure for metrological purposes. The knowledge of the exact orientation of the NPs is a crucial step in extracting the real 3D dimensions of the particles. Two approaches are proposed to determine the geometrical orientation of individual nano‐bipyramides: (i) AFM profiling along the long bipyramid axis and (ii) stage tilting followed by SEM imaging. Furthermore, a recently developed method, Transmission Kikuchi Diffraction (TKD), which needs preparation of the crystalline NPs on electron‐transparent substrates such as TEM grids, has been tested with respect to its capability of identifying the geometrical orientation of the individual NPs. With the NPs prepared homogeneously on a TEM grid, the transmission mode in a SEM, i.e., STEM‐in‐SEM (or T‐SEM), can be also applied to extract accurate projection dimensions of the nanoparticles from the same sample area as that analysed by SEM, TKD and possibly AFM. Finally, Small Angle X‐ray Scattering (SAXS) can be used as an ensemble technique able to measure the NPs in liquid suspension and, with ab‐initio knowledge of the NP shape from the descriptive imaging techniques, to provide traceable NP size distribution and particle concentration.
Ellipsometry-based approach for the characterization of mesoporous thin films for H2 technologies
(2021)
Porous thin layer materials are gaining importance in different fields of technology and pose a challenge to the accurate determination of materials properties important for their function. In this work, we demonstrate a hybrid measurement technique using ellipsometry together with other independent methods for validation. Ellipsometry provides information about the porosity of different mesoporous films (PtRuNP/OMC = 45%; IrOx = 46%) as well as about the pore size (pore radius of ca. 5 nm for PtRuNP/OMC). In addition, the electronic structure of a material, such as intraband transitions of a mesoporous IrOx film, can be identified, which can be used to better understand the mechanisms of chemical processes. In addition, we show that ellipsometry can be used as a scalable imaging and visualization method for quality assurance in production. These require accurate and traceable measurements, with reference materials playing an important role that include porosity and other related properties. We show that our novel analytical methods are useful for improving analytical work in this entire field.
In order to assess new nanomaterials and nanoparticles for potential risks to health and the environment, they need to be well-characterised. The measurement of constituent nanoparticle size, shape, and size distribution are important factors for the risk evaluation process.
EMPIR project Improved traceability chain of nanoparticle size measurements (17NRM04, nPSize) is working to assess a range of traceable nanoparticle measurement approaches, including Electron Microscopy (SEM, TEM, STEM-in-SEM), Atomic Force Microscopy and Small Angle X-ray Scattering, and deliver improved calibration methods to users. For the techniques under investigation, physical models of their response to a range of nanoparticle types are developed. Validated reference materials are also used for inter-comparisons of measurement systems, with an evaluation of the associated measurement uncertainty. With project contributions to standards development work, manufacturers will be better placed to assess the human and environmental risks posed by nanomaterials across a whole range of products.
An overview is given on the synthesis of TiO2 nanoparticles with well-defined nonspherical shapes (platelet like, bipyramidal, and elongated), with the focus on controlled, reproducible synthesis, as a key requirement for the production of reference materials with homogeneous and stable properties. Particularly with regard to the nanoparticle shapes, there is a high need of certified materials,
solely one material of this type being commercially available since a few months (elongated TiO2). Further, measurement approaches with electron microscopy as the golden method to tackle the nanoparticle shape are developed to determine accurately the size and shape distribution for such nonspherical particles. A prerequisite for accurate and easy (i.e., automated) image analysis is the sample preparation, which ideally must ensure a deposition of the nanoparticles from liquid suspension onto a substrate such that the particles do not overlap, are solvent-free, and have a high deposition density. Challenges in the Synthesis of perfectly monodispersed and solvent-free TiO2 nanoparticles of platelet and acicular shapes are highlighted as well as successful measurement approaches on how to extract from 2D projection electron micrographs the most accurate spatial information, that is, true 3D size, for example, of the bipyramidal nanoparticles with different geometrical orientations on a substrate.
The presentation is structured in the following three parts:
i) Report of the Working Group 4 X-Ray Spectroscopy including the publication of ISO 15632:2021 Microbeam analysis — Selected instrumental performance parameters for the specification and checking of energy-dispersive X-ray spectrometers for use in electron probe microanalysis,
ii) Liaison activities between ISO/TC202 Microbeam Anaylsis and VAMAS/TWA34 Quantitative Microstructural Analysis, and
iii) Liaison activities from ISO/TC202 Microbeam Analysis for ISO/TC229 Nanotechnologies.
Most relevant projects are highlighted for information and further discussions. New initiatives and better promotion of strategic projects are addressed.
It sounds like being a simple analytical task, it is definitely not. The way toward accurate measurement of the size distribution of nanoparticles (NPs) with complex shape, having a broad size polydispersity, with inhomogeneous chemistry, and with a high degree of agglomeration/aggregation is very challenging for all available analytical methods. Particularly for the NPs with complex shape, the access to the smallest dimension (as e.g. required for regulatory purposes) can be enabled only by using imaging techniques with spatial resolution at the nanoscale. Moreover, the full 3D-chacterisation of the NP shape can be provided either by advanced characterization techniques like 3D-TEM tomography or by correlative analysis, i. e. synergetic/complementary measurement of the same field-of-view of the sample with different probes. Examples of the latter type of analysis are: i) electron microscopy for the lateral dimensions and AFM for the height of the NPs, ii) SEM with STEM-in-SEM (also called T-SEM), iii) Electron Microscopy with TKD (Transmission Kikuchi Diffraction) for determination of the geometrical orientation of crystalline NPs, iv) Raman and SEM for e.g. thickness of graphen flakes, or v) Electron Microscopy for descriptive NP shape and SAXS for the NP concentration, the latter as a NP property able to be measured with higher and higher accuracy. For all these types of measurement, reference NPs are necessary for the validation of the measured size. Particularly non-spherical reference NPs are still missing. Examples of such new reference NPs as characterized by the correlative analyses enumerated above will be presented in detail in the contribution.
The progress in activities on Microbeam Analysis under VAMAS/TWA 37 is reviewed. Particularly the liaison with the new projects within the ISO technical committee TC 202 is presented and discussed with respect to the possibility of identifying and launching related VAMAS projects. Need of more promotion for the engagement of more participants from industry and academia at national, European and international level is highlighted. Also, the competition with the other technical working areas (on 'nano' or materials-related) is critically discussed. Further, a short overview of the VAMAS areas of activities is given where Germany is involved.
ACEnano is an EU-funded project which aims at developing, optimising and validating methods for the detection and characterisation of nanomaterials (NMs) in increasingly complex matrices to improve confidence in the results and support their use in regulation. Within this project, several interlaboratory comparisons (ILCs) for the determination of particle size and concentration have been organised to benchmark existing analytical methods. In this paper the results of a number of these ILCs for the characterisation of NMs are presented and discussed. The results of the analyses of pristine well-defined particles such as 60 nm Au NMs in a simple aqueous suspension showed that laboratories are well capable of determining the sizes of these particles. The analysis of particles in complex matrices or formulations such as consumer products resulted in larger variations in particle sizes within technologies and clear differences in capability between techniques. Sunscreen lotion sample analysis by laboratories using spICP-MS and TEM/SEM identified and confirmed the TiO2 particles as being nanoscale and compliant with the EU definition of an NM for regulatory purposes. In a toothpaste sample orthogonal results by PTA, spICP-MS and TEM/SEM agreed and stated the TiO2 particles as not fitting the EU definition of an NM. In general, from the results of these ILCs we conclude that laboratories are well capable of determining particle sizes of NM, even in fairly complex formulations.
A case study on the TEM analysis of the size and shape distribution of TiO2 bipyramidal nanoparticles prepared on TEM grids was included in the recently published ISO standard ISO 21363. It was agreed to organize at a later stage a second inter-lab comparison with the nanoparticles distributed to the participants as a liquid suspension. Protocols for uniform nanoparticle deposition on suited supports developed and optimized within the EMPIR nPSize project are also prepared to be distributed. For this, we have chosen the VAMAS platform (www.vamas.org) which offers an excellent international infrastructure of laboratories with high competence in nanoparticle measurement. The VAMAS technical working area dedicated to nanoparticle measurement is TWA 34 ‘Nanoparticle populations’. For this type of nanoparticles, the size and shape distributions are the primary parameters to be reported. Due to the good deposition protocols developed, an automated image analysis is enabled (in contrast to the manual analysis of irregular TiO2 nanoparticles.
In parallel with the TiO2 nanoparticle exercise, two spherical SiO2 nanoparticle samples with bi-modal size distributions (nominal relative number concentrations of 1:1 and 10:1) are prepared for a second VAMAS inter-lab comparison. Here, the nanoparticle concentration is the primary parameter to be measured. For the imaging methods it is targeted to measure the relative nanoparticle concentrations of the two modes. For the absolute nanoparticle concentration to be measured by imaging methods it is necessary to control the volume of the liquid suspension deposited on the substrate and to obtain such a homogeneous nanoparticle deposition on the substrate which allows to count (or extrapolate) all the deposited particles.
A particle roughness analysis tool, based on electron microscopy images (SEM and TEM). The influence of various parameters on the calculated roughness was also investigated: the setting of the proper threshold, accelerating voltage, etc. The samples were gradually tilted to extend imaging information of more than only one projection. Furthermore, the measurement uncertainty of the profile roughness of particles associated to various orientations was estimated.
A case study on the TEM analysis of the size and shape distribution of TiO2 bipyramidal nanoparticles prepared on TEM grids was included in the recently published ISO standard ISO 21363. It was agreed to organize at a later stage a second inter-lab comparison with the nanoparticles distributed to the participants as a liquid suspension. Protocols for uniform nanoparticle deposition on suited supports developed and optimized within the EMPIR nPSize project are also prepared to be distributed. For this, we have chosen the VAMAS platform (www.vamas.org) which offers an excellent international infrastructure of laboratories with high competence in nanoparticle measurement. The VAMAS technical working area dedicated to nanoparticle measurement is TWA 34 ‘Nanoparticle populations’. For this type of nanoparticles, the size and shape distributions are the primary parameters to be reported. Due to the good deposition protocols developed, an automated image analysis is enabled (in contrast to the manual analysis of irregular TiO2 nanoparticles.
In parallel with the TiO2 nanoparticle exercise, two spherical SiO2 nanoparticle samples with bi-modal size distributions (nominal relative number concentrations of 1:1 and 10:1) are prepared for a second VAMAS inter-lab comparison. Here, the nanoparticle concentration is the primary parameter to be measured. For the imaging methods it is targeted to measure the relative nanoparticle concentrations of the two modes. For the absolute nanoparticle concentration to be measured by imaging methods it is necessary to control the volume of the liquid suspension deposited on the substrate and to obtain such a homogeneous nanoparticle deposition on the substrate which allows to count (or extrapolate) all the deposited particles.
Electrochemical methods offer great promise in meeting the demand for user-friendly on-site devices for Monitoring important parameters. The food industry often runs own lab procedures, for example, for mycotoxin analysis, but it is a major goal to simplify analysis, linking analytical methods with smart technologies. Enzyme-linked immunosorbent assays, with photometric detection of 3,3’,5,5’-tetramethylbenzidine (TMB),form a good basis for sensitive detection. To provide a straightforward approach for the miniaturization of the detectionstep, we have studied the pitfalls of the electrochemical TMB detection. By cyclic voltammetry it was found that the TMB electrochemistry is strongly dependent on the pH and the electrode material. A stable electrode response to TMB could be achieved at pH 1 on gold electrodes. We created a smartphonebased, electrochemical, immunomagnetic assay for the detection of ochratoxin A in real samples, providing a solid basis forsensing of further analytes.
Luminescent solar concentrators (LSC) allow to obtain renewable energy from building integrated photovoltaic systems. As promising efficient and long-term stable LSC fluorophores semiconductor nanocrystals like Quantum dots (QDs) with size and composition tunable optoelectronic properties have recently emerged. The most popular II/VI or IV/VI semiconductor QDs contain, however, potentially hazardous cadmium or lead ions, which is a bottleneck for commercial applications. A simple aqueous based, microwaveassisted synthesis for environmentally friendly and highly emissive AgInS2/ ZnS QDs is developed using 3-mercaptopropionic acid (MPA) and glutathione (GSH) and their incorporation into polylaurylmethacrylate (PLMA) polymer slabs integrable in LSC devices (10.4 × 10.4 × 0.2 cm3, G = 12.98).
With this simple approach, optical power efficiencies (OPE) of 3.8% and 3.6% and optical quantum efficiencies (OQE) of 24.1% and 27.4% are obtained, which are among the highest values yet reported.
The publicly available document encapsulates the first version of the Catalogue of Services of the future EC4Safenano Centre (CoS 2019).
The CoS 2019 is structured in 12 Service Categories and 27 Service Topics, for each of the 12 categories considered. This architecture configures a 12 x 27 matrix that allows ordering the potential EC4Safenano offer in 324 types of services/groups of services.
Each type of service/group of services is described, in a simple and friendly way, by means of a specific service sheet: the EC4Safenano - Service Data Sheet (EC4-SDS). These EC4-SDSs allow structuring and summarizing the information of each service, providing the customer with a concise view of characteristics of the service and also the contact details with the service provider.
The CoS 2019 deploys a map of services consisting of a set of 100 EC4-SDSs, covering 7 of the 12 Service Categories and 17 of the 27 Service Topics.
The harmonization of services is visualized as a future necessary step in EC4Safenano, in order to strengthen the offer and provide added value to customers with a growing offer of harmonized services in future versions of the CoS.
The information contained in this document is structured in 3 main sections, as follows:
• Catalogue structure. This section describes in short the main characteristics of the CoS 2019.
• Catalogue content. This section represents the core part of the document and encapsulates the set of 100 SDSs displaying the offer proposed by the CoS 2019.
• Online Catalogue. This section describes the resources implemented by EC4Safenano to facilitate the on-line consultation of the CoS 2019 by customers and other interested parties.