TY - CONF A1 - Resch-Genger, Ute T1 - Suitable geometries for the measurement of photoluminescence quantum yields of luminescent and scattering samples – The DIN TNS project N2 - The characterization of the optical properties of photoluminescent systems, that scatter, like dispersions of nanoparticles with sizes exceeding about 25 nm or solid nanophosphors is of increasing importance for many applications in the life and material sciences. Examples present nanoscale optical reporters and dye-doped microparticles for bioimaging, fluorescence assays or DNA sequencing as well as nanocrystalline emitters like semiconductor quantum dots and rods or lanthanide-based nanophosphors embedded into solid matrices for solid state lighting, display technologies, or barcoding/security applications. The assessment and comparison of material performance as well as the development of rational design strategies for improved systems require spectroscopic tools, which enable the determination of the signal-relevant optical properties like photoluminescence quantum yields and brightness values. This encouraged us to built up an integrating sphere setup enabling absolute measurements of photoluminescence spectra and quantum yields of transparent and scattering photoluminescent dispersions and solid samples in different measurement geometries, i.e., direct and indirect illumination and the combination of both geometries and perform first measurements with selected emitters. Here, the design of this setup is presented and first recommendations concerning suitable measurement geometries are given. T2 - DKE-Sitzung CY - Frankfurt am Main, Germany DA - 31.08.2016 KW - Nanoparticle KW - Integrating sphere KW - Fluorescence KW - Quantum yield KW - Method KW - Standardization KW - Calibration KW - Reference material PY - 2016 AN - OPUS4-38643 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Resch-Genger, Ute ED - Mousavi, M. ED - Thomasson, B. ED - Li, M. ED - Kraft, Marco ED - Würth, Christian ED - Andersson-Engels, S. T1 - Beam-profile-compensated quantum yield measurements of upconverting nanoparticles N2 - The quantum yield is a critically important parameter in the development of lanthanide-based upconverting nanoparticles (UCNPs) for use as novel contrast agents in biological imaging and optical reporters in assays. The present work focuses on the influence of the beam Profile in measuring the quantum yield (f) of nonscattering dispersions of nonlinear upconverting probes, by establishing a relation between f and excitation light power density from a rate equation analysis. A resulting 60% correction in the measured f due to the beam profile utilized for excitation underlines the significance of the beam profile in such measurements, and its impact when comparing results from different Setups and groups across the world. KW - Fluorescence KW - Lanthanide KW - Upconversion KW - Brithtness KW - Quantification KW - Nanoparticle KW - Absolute fluoreometry KW - NIR KW - IR KW - Quantum yield KW - Integrating sphere spectroscopy KW - Method PY - 2017 DO - https://doi.org/10.1039/c7cp03785f SN - 1463-9076 SN - 1463-9084 VL - 19 IS - 33 SP - 22016 EP - 22022 PB - Royal Society of Chemistry AN - OPUS4-42583 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Huang, K. A1 - Liu, H. A1 - Kraft, Marco A1 - Shikha, S. A1 - Zheng, X. A1 - Agren, H. A1 - Würth, Christian A1 - Resch-Genger, Ute A1 - Zhang, Y. T1 - A protected excitation-energy reservoir for efficient upconversion luminescence N2 - Lanthanide-doped upconversion nanoparticles (UCNPs) are of great interest for biomedical applications. Currently, the applicability of UCNP bionanotechnology is hampered by the generally low luminescence intensity of UCNPs and inefficient energy Transfer from UCNPs to surface-bound chromophores used e.g. for photodynamic therapy or analyte sensing. In this work, we address the low-Efficiency issue by developing versatile core-Shell nanostructures, where high-concentration sensitizers and activators are confined in the core and Shell Region of representative hexagonal NaYF2:Yb,Er UCNPs. After Doping concentration optimization, the sensitizer-rich core is able to harvest/accumulate more excitation energy and generate almost one order of Magnitude higher luminescence intesity than conventional homogeneously doped nanostructures. At the same time, the activator Ions located in the Shell enable a ~6 times more efficient resonant energy Transfer from UCNPs to surface-bound acceptor dye molecules due to the short distance between donor-acceptor pairs. Our work provides new insights into the rational design of UCNPs and will greatly encrease the General applicability of upconversion nanotechnologies. KW - Fluorescence KW - Lanthanide KW - Upconversion KW - Brightness KW - Quantification KW - Nanoparticle KW - Absolute fluorometry KW - NIR KW - IR KW - Quantum yield KW - Integrating sphere spectroscopy KW - Method KW - Energy transfer KW - Shell KW - Particle architecture PY - 2017 DO - https://doi.org/10.1039/c7nr06900f SN - 2040-3372 SN - 2040-3364 VL - 10 IS - 1 SP - 250 EP - 259 PB - The Royal Society of Chemistry AN - OPUS4-43893 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Resch-Genger, Ute T1 - Absolute Determination of Photoluminescence Quantum Yields of Scattering LED Converter Materials – How to Get it Right N2 - Optical measurements of scattering luminescent materials dispersed in liquid and solid matrices and luminescent powders play an important role in fundamental research and industry. Typical examples are luminescent nano- and microparticles and phosphors of different composition in different matrices or incorporated into ceramics with applications in energy conversion, solid-state lighting, medical diagnostics, and security barcoding. The key parameter for the performance of these materials is the photoluminescence quantum yield QY, i.e., the number of emitted photons per number of absorbed photons. QY of transparent luminophore solutions can be determined relatively to a fluorescence quantum yield standard of known QY. Such standards are meanwhile available as certified reference materials.[1] The determination of QY of scattering liquid and solid samples like dispersions of luminescent nanoparticles, solid phosphors, and optoceramics requires, however, absolute measurements with an integrating sphere setup. Although the importance of reliable absolute QY measurements has been recognized, no interlaboratory comparisons (ILCs) on measurement uncertainties and the identification of typical sources of uncertainty have been yet reported. Also, no scattering reference materials with known QY are available. We present here the results of a first ILC of 3 laboratories from academia and industry performed to identify and quantify sources of uncertainty of absolute QY measurements of scattering samples. Thereby, two types of commercial stand-alone integrating sphere setups with different illumination and detection geometries were utilized for measuring QY of transparent and scattering dye solutions and solid phosphors. As representative and industrially relevant solid and scattering samples, YAG:Ce optoceramics of varying surface roughness were chosen, applied, e.g., as converter materials for blue light emitting diodes. Special emphasis was dedicated to the influence of the measurement geometry, the optical properties of the blank, utilized to determine the number of photons of the incident excitation light absorbed by the sample, and the sample-specific surface roughness. While matching QY values could be obtained for transparent dye solutions and scattering dispersions, here using a blank with scattering properties closely matching those of the sample, QY measurements of optoceramic samples with different blanks revealed substantial differences, with the blank's optical properties accounting for measurement uncertainties of more than 20 %. Based upon the ILC results, we recommend non-absorbing blank materials with a high reflectivity (>95 %) such as a 2 mm-thick PTFE target placed on the sample holder which reveals a near-Lambertian light scattering behavior, yielding a homogeneous light distribution within the integrating sphere. T2 - e-MRS 2024 CY - Strasbourg, France DA - 27.05.2024 KW - Luminescence KW - Quantitative spectroscopy KW - Nano KW - Particle KW - Quantum yield KW - Lifetime KW - Quality assurance KW - Phosphor KW - Converter marterial KW - Fluorescence KW - Interlaboratory KW - Comparison KW - Method KW - Uncertainty KW - Reference material PY - 2024 AN - OPUS4-60490 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kunc, F. A1 - Nirmalananthan-Budau, Nithiya A1 - Rühle, Bastian A1 - Sung, Y. A1 - Johnston, L.J. A1 - Resch-Genger, Ute T1 - Interlaboratory Comparison on the Quantification of Total and Accessible Amine Groups on Silica Nanoparticles with qNMR and Optical Assays N2 - Risk assessment of nanomaterials requires not only standardized toxicity studies but also validated methods for nanomaterial surface characterization with known uncertainties. In this context, a first bilateral interlaboratory comparison on Surface group quantification of nanomaterials is presented that assesses different reporter-free and labeling methods for the quantification of the total and accessible number of amine functionalities on commercially available silica nanoparticles that are widely used in the life sciences. The overall goal of this comparison is the identification of optimum methods as well as achievable measurement uncertainties and the comparability of the results across laboratories. We also examined the robustness and ease of implementation of the applied analytical methods and discussed method-inherent limitations. In summary, this comparison presents a first step toward the eventually required standardization of methods for surface group quantification. KW - Nano KW - Nanomaterial KW - Surface KW - Method KW - QNMR KW - Quantification KW - Comparison KW - Quality assurance KW - Optical probe KW - Sensor KW - Interlabority comparison KW - Standardization KW - Optical assay KW - Functional group analysis KW - Silica KW - Particle KW - Safety KW - Environment PY - 2021 DO - https://doi.org/10.1021/acs.analchem.1c02162 SN - 1520-6882 VL - 93 IS - 46 SP - 15271 EP - 15278 PB - ASC Publications AN - OPUS4-53818 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Andresen, Elina A1 - Resch-Genger, Ute A1 - Michaelis, Matthias A1 - Prinz, Carsten A1 - Würth, Christian T1 - Time-resolved luminescence spectroscopy for monitoring the stability and dissolution behaviour of upconverting nanocrystals with different surface coatings† N2 - We demonstrate the potential of time-resolved luminescence spectroscopy for the straightforward assessment and in situ monitoring of the stability of upconversion nanocrystals (UCNPs). Therefore, we prepared hexagonal NaYF4:Yb3+,Er3+ UCNPs with various coatings with a focus on phosphonate ligands of different valency, using different ligand exchange procedures, and studied their dissolution behaviour in phosphate-buffered saline (PBS) dispersions at 20 °C and 37 °C with various analytical methods. The amount of the released UCNPs constituting fluoride ions was quantified by potentiometry using a Fluoride ion-sensitive electrode and particle disintegration was confirmed by transmission electron microscopy studies of the differently aged UCNPs. In parallel, the luminescence features of the UCNPs were measured with special emphasis on the lifetime of the sensitizer emission to demonstrate its suitability as Screening parameter for UCNP stability and changes in particle composition. The excellent correlation between the changes in luminescence lifetime and fluoride concentration highlights the potential of our luminescence lifetime method for UCNP stability screening and thereby indirect monitoring of the release of potentially hazardous fluoride ions during uptake and dissolution in biological systems. Additionally, the developed in situ optical method was used to distinguish the dissolution dynamics of differently sized and differently coated UCNPs. KW - Fluorescence KW - Lifetime KW - Method KW - Quantification KW - Stability KW - Coating KW - Surface chemistry KW - Lanthanide KW - Fluoride KW - Electrochemistry KW - ICP-OES KW - Upconversion KW - Nano KW - Particle KW - Aging KW - Quality assurance KW - TEM PY - 2020 DO - https://doi.org/10.1039/d0nr02931a VL - 12 IS - 23 SP - 12589 EP - 12601 PB - Royal Society od Chemistry AN - OPUS4-52088 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Resch-Genger, Ute T1 - Influence of Surface Chemistry and Size on the Stability of β-NaYF4:Yb,Er Nanocrystals in Various Environments N2 - The use of inorganic lanthanide-doped upconversion nanoparticles (UCNP) in bioimaging and cellular studies requires biocompatible particles. One possible cause of UCNP toxicity is the release of potentially harmful fluoride and lanthanide ions as revealed by dilution studies in aqueous environments, particularly under high dilution conditions. To address this issue, suitable surface coatings preventing such effects in combination with fast screening methods suited for online monitoring and in situ analyses are desired. Here we present systematic studies of differently sized β-NaYF4:Yb,Er UCNP stabilized with different surface coatings and hydrophilic ligands varying in binding strength to the particle surface in various aqueous environments at different temperatures and UCNP concentrations. The concentration of the fluoride and lanthanide ions released upon particle dissolution was quantified electrochemically with a fluoride ion-sensitive electrode and inductively coupled plasma optical emission spectrometry (ICP-OES) and monitored fluorometrically, thereby exploiting the sensitivity of the upconversion luminescence to changes in size and surface chemistry. Moreover, changes in surface chemistry were determined with X-Ray photoelectron spectroscopy (XPS). Based upon our results, we could derive optimum screening parameters for UCNP stability studies and determine conditions and coating procedures and ligands for enhancing UCNP stability in aqueous environments. T2 - UPCON2021 CY - Online meeting DA - 06.04.2021 KW - Fluorescence KW - Lifetime KW - Method KW - Quantification KW - Stability KW - Coating KW - Surface chemistry KW - Lanthanide KW - Fluoride KW - Electrochemistry KW - ICP-OES KW - Upconversion KW - Nano KW - Particle KW - Aging KW - Quality assurance KW - Mass spectrometry KW - XPS PY - 2021 AN - OPUS4-52411 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kossatz, Philipp A1 - Mezhov, Alexander A1 - Andresen, Elina A1 - Prinz, Carsten A1 - Schmidt, Wolfram A1 - Resch-Genger, Ute T1 - Assessing the Applicability of Lanthanide-Based Upconverting Nanoparticles for Optically Monitoring Cement Hydration and Tagging Building Materials N2 - Chemically stable, lanthanide-based photon upconversion micro- and nanoparticles (UCNPs) with their characteristic multicolor emission bands in the ultraviolet (UV), visible (vis), near-infrared (NIR), and short-wave infrared (SWIR) arepromising optical reporters and barcoding tags. To assess the applicability of UCNPs for the monitoring of early stage cement hydration processes and as authentication tags for cementitious materials, we screened the evolution of the luminescence of Selfmade core-only NaYF4:Yb,Er UCNPs and commercial μm-sized Y2O2S:Yb,Er particles during the first stages of cement hydration, which largely determines the future properties of the hardened material. Parameters explored from the UCNP side included particle size, morphology, surface chemistry or coating, luminescence properties, and concentration in different cement mixtures. From the cement side, the influence of the mineral composition of the cement matrix was representatively examined for ordinary Portland cement (OPC) and its constituents tricalcium aluminate (C3A), tricalcium silicate (C3S), and gypsum at different water to cement ratios. Based on reflection and luminescence measurements, enabling online monitoring, which were complemented by XRD and isothermal heat-flow calorimetric measurements to determine whether the incorporation of these particles could impair cement hydration processes, well suited lanthanide particle reporters could be identified as well as application conditions. In addition, thereby the reporter influence on cement hydration kinetics could be minimized while still preserving a high level of information content. The best performance for the luminescence probing of changes during early stage cement hydration processes was observed for 25 nm-sized oleate (OA)-coated UCNPs added in a concentration of 0.1 wt %. Higher UCNP amounts of 1.0 wt % delayed cement hydration processes size- and surface coatingspecifically in the first 24 h. Subsequent luminescence stability screening studies performed over a period of about one year support the applicability of UCNPs as optical authentication tags for construction materials. KW - Quality assurance KW - Fluorescence KW - Nano KW - Particle KW - Synthesis KW - Quantum yield KW - NIR KW - Mechanism KW - Characterization KW - XRD KW - Calorimetry KW - Advanced material KW - Cement KW - Monitoring KW - Surface KW - Size KW - Lifetime KW - Barcode KW - Lanthanide KW - Upconversion KW - Encoding KW - Method PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-638318 DO - https://doi.org/10.1021/acsomega.5c02236 SN - 2470-1343 VL - 10 IS - 29 SP - 31587 EP - 31599 PB - ACS Publications CY - Washington, DC AN - OPUS4-63831 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Resch-Genger, Ute T1 - The emp project smurfnano – Standardizing the quantification of surface functionalities, ligands, and coatings on nanomaterials N2 - For industrial applications such as medical diagnostics, drug delivery, sensing, catalysis, energy conversion and storage, opto-electronics, and information storage, meanwhile engineered nanoparticles (NPs) with various chemical compositions and surface functionalities are routinely fabricated. NP function, interaction with biological species, and environmental fate are largely determined by surface functionalities. Reliable, reproducible, and standardized surface characterization methods are therefore vital for quality control of NPs, and mandatory to meet increasing concerns regarding their safety. Also, industry, international standardization organizations, regulatory agencies, and policymakers need validated and standardized measurement methods and reference materials. These needs are addressed by the recently started European metrology project SMURFnano involving 12 partners from different National Metrology Institutes, designated institutes, and research institutes, two university groups as well as one large company and one SME producing NPs. This project as well as first results derived from the development of test and reference materials with a well characterized surface chemistry and ongoing interlaboratory comparisons will be presented. T2 - LNE Workshop CY - Paris, France DA - 04.11.2025 KW - Quality assurance KW - Fluorescence KW - Nano KW - Particle KW - Synthesis KW - Characterization KW - Advanced material KW - Surface KW - Standardization KW - Reference material KW - Functional group KW - Quantification KW - Coating KW - Automation KW - Potentiometry KW - Method KW - Validation KW - Optical assay KW - Fluram KW - qNMR KW - Comparison KW - ILC PY - 2025 AN - OPUS4-64725 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Resch-Genger, Ute T1 - Characterization and quantification of functional groups and coatings on nanoobjects an overview N2 - Characterization of Nanoparticles – Questions to Ask, Functional Nanoparticles (NPs) – Organic, Inorganic, and Hybrid Nanoparticles Nanomaterial Characterization Standardization – Addressing Remaining Gaps Surface FGs Particle Surface Chemistry - Why is it Important? Particle Surface Chemistry - A Key Driver for Performance, Applications, and Safety Aspects Method Development for Quantifying FGs and Ligands on Particle Surfaces FG Quantification – Method Choice & Criteria Relevant for Data Interpretation Quantifying the Amount of Total and Accessible FGs on Aminated Silica Nanoparticles (SiO2-NH2) Comparing the Total and Accessible –NH2 Content on Aminated Silica NPs of Different Size Characterization of Nanoparticles Standardization Standardized Measurements of Surface FGs on Nanoparticles EMP Project SMURFnano EMP Project SMURFnano Work Packages & Goals Certified Reference Materials from BAM T2 - e-MRS 2024 (Spring Meeting of the European Materials Research Society, Altech Symposium) CY - Strasbourg, France DA - 27.05.2024 KW - Luminescence KW - Nano KW - Particle KW - Quantum yield KW - Quality assurance KW - Interlaboratory comparison KW - Method KW - Uncertainty KW - Reference material KW - Surface analysis KW - Optical assay KW - NMR KW - Silica KW - Ligand PY - 2024 AN - OPUS4-60495 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -