TY - JOUR A1 - Homann, Christian A1 - Peeters, Régis A1 - Mirmajidi, Hana A1 - Berg, Jessica A1 - Fay, Michael A1 - Rodrigues, Lucas Carvalho Veloso A1 - Radicchi, Eros A1 - Jain, Akhil A1 - Speghini, Adolfo A1 - Hemmer, Eva T1 - Rapid microwave-assisted synthesis of morphology-controlled luminescent lanthanide-doped Gd2O2S nanostructures N2 - Gadolinium oxysulfide (Gd2O2S) is an attractive material of demonstrated suitability for a variety of imaging applications, leveraging its magnetic, scintillating, and luminescent properties, particularly when doped with optically active lanthanide ions (Ln3+). For many of these applications, control over size and morphology at the nanoscale is crucial. This study demonstrates the rapid microwave-assisted Synthesis of colloidal Ln2O2S (Ln = Gd and dopants Yb, Er, Tb) nanostructures in as little as 20 min. Structural characterization using X-ray diffraction analysis (XRD), Raman spectroscopy, as well as Transmission electron microscopy (TEM), including elemental mapping via energy dispersive X-ray spectroscopy (EDS), unveiled the key role of elemental sulphur (S8) in the reaction mixtures for materials growth. By systematically varying the Ln-to-S ratio from 1 : 0.5 to 1 : 15, controlled morphologies ranging from triangular nanoplatelets to berry- and flower-like shapes were achieved. Doping with Er3+/Yb3+ endowed the nano-triangles with upconverting and near-infrared emitting properties. Tb3+-doped Gd2O2S exhibited the characteristic green Tb3+ emission under UV excitation, while also showing X-ray excited optical luminescence (XEOL), rendering the material interesting as a potential nano-scintillator. KW - Upconversion KW - Microwave-assisted synthesis KW - Synthesis KW - Fluorescence KW - Nano KW - Particle KW - NIR KW - XRD KW - X-ray fluoressence KW - Morphology control KW - Raman PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-647907 DO - https://doi.org/10.1039/D5TC01646K SN - 2050-7526 VL - 13 IS - 35 SP - 18492 EP - 18507 PB - Royal Society of Chemistry (RSC) AN - OPUS4-64790 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Oskoei, Párástu T1 - Effects of upconversion nanoparticles with a thermo-responsive nanovalve loaded with doxorubicin in melanoma cells N2 - Melanoma skin cancer has an increasingly higher incidence , and w hen detected in advanced stages, tumour eradication is often incomplete, contributing to poor prognosis with conventional treatments. Upconversion nanoparticles (UCNPs) have unique properties, such as excitability under near infrared (NIR) excitation light, which confers a relatively high penetration depth in tissue that allow their effective use in several biomedical applications Mesoporous silica nanoparticles (MSN) with nanovalves or derived coatings have widely been used for triggered and targeted drug delivery in the past. Anticancer drugs can be loaded into the pores of MSN, enabling controlled drug release. In this work, UCNPs were coated with a mesoporous silica shell yielding UCNP@MSN core shell nanoparticles which were equipped with thermoresponsive retro Diels Alder nanovalves and then loaded with DOX , a chemotherapeutic agent for melanoma treatmen t (UCNP@MSN DOX) Subsequent DOX release from this drug delivery system was triggered by 980 nm NIR light. Melanoma cells exposed to UCNP@MSN DOX or the NIR laser exhibited no change in ROS production , while the combination of both induced an increase in ROS production. This combination of conditions also induced changes on apoptosis and necrosis levels. These findings underscore the potential use of UCNP @MSN drug delivery systems with thermoresponsive caps as effective drug delivery platforms for melanoma therapy. T2 - VII iBiMED Symposium CY - Aveiro, Portugal DA - 23.05.2025 KW - Nano KW - Particle KW - Lanthanide KW - Upconversion KW - Surface chemistry KW - Mesoporous silica KW - Doxorubicin KW - Nanomedicine KW - Triggered release KW - pH KW - Cellular uptake KW - Toxicity KW - Folate KW - Ligand PY - 2025 AN - OPUS4-64373 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Oskoei, Párástu T1 - Cell mechanisms induced by doxorubicin-loaded UCNP@MSN nanoparticles with a thermosresponsive nanovalve in melanoma cells N2 - Upconversion nanoparticles (UCNPs) exhibit several remarkable optical properties, including excitation by near infrared (NIR) light, which enables deep tissue penetration, multiple distinct emission bands across a wide range of wavelengths, long luminescen ce lifetimes, and high photostability. These features make them particularly attractive for various biomedical applications. Mesoporous silica nanoparticles (MSNs), functionalized with nanovalves or specific coatings, have been explored for controlled and targeted drug delivery, where therapeutic agents are encapsulated within the nanopores, allowing spatiotemporal release 1 3 ]]. Among the promising approaches, photoactivated drug delivery systems have drawn considerable interest due to their versatility and potential. One relevant application is in the treatment of melanoma, an aggressive form of skin cancer with a rising global incidence. In advanced stages, conventional therapies often fail to achieve complete tumour eradication, resulting in poor prognose s 4 In this study, UCNPs were coated with a mesoporous silica shell to form core shell UCNP@MSN nanoparticles, which were further functionalized with thermoresponsive retro Diels Alder nanovalves and loaded with doxorubicin (DOX), a chemotherapeutic drug used in melanoma treatment. Upon exposure to 980 nm NIR light, DOX release was successfully triggered in the culture medium. Exposure to functionalized UCNPs decreased the viability of the tested melanoma cell lines, with further reductions observed when the ex posure to the nanoparticles was combined with irradiation. Subsequently, t he toxicity mechanisms were evaluated and showed that w hile individual treatments with either the functionalized UCNPs or NIR irradiation alone had no effect on reactive oxygen species (ROS) production, their combination significantly increased ROS levels in two of the three tested cell lines. This combined treatment also led to notable increases in apoptotic , necrotic or both type of cells’ percentages on all cell lines. Overall, these findings highlight the potential of these nanoparticles with thermoresponsive gating mechanisms as effective platforms for targeted drug delivery in melanoma therapy. T2 - EUROTOX 2025 CY - Athens, Greece DA - 14.09.2025 KW - Nano KW - Particle KW - Lanthanide KW - Upconversion KW - Surface chemistry KW - Mesoporous silica KW - Doxorubicin KW - Nanomedicine KW - Triggered release KW - pH KW - Cellular uptake KW - Toxicity KW - Folate KW - Ligand PY - 2025 AN - OPUS4-64372 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Oskoei, Parastu T1 - Thermoresponsive UCNP@MSN Nanoparticles for Doxorubicin Delivery in Melanoma Cells N2 - Upconversion nanoparticles (UCNPs) possess unique photophysical characteristics, such as excita bility by near infrared (NIR) light, which facilitates deep tissue penetration, multi color emission , long luminescence lifetimes, and an excellent photostability. These features have made UCNPs promising tools for biomedical applications . M esoporous silica nanoparticles (MSNs) functionalized with stimuli responsive nanovalves or specific coatings enable the encapsulation and controlled release of therapeutic agen ts, thereby offering spatiotemporal precision in drug delivery 1 3 ]]. Among drug delivery strategies, photoresponsive systems have attracted growing attention due to their potential for clinical applications . This is especially relevant for melanoma, an aggressive skin cancer with increasing global incidence, for which conventional therapeutic modalities remain largely insufficient in advanced stage 4 In this work, core shell UCNP@MSN nanoparticles were synthetised by coating UCNPs with a mesoporous silica layer, which was subsequently functionalized with thermoresponsive retro Diels Alder nanovalves [ and loaded with the chemotherapeutic agent doxorubicin (DOX). Controlled drug release was effectively achieved under 980 nm NIR i llumination . Treatment with functionalized nanoparticles significantly reduced the viability of melanoma cell lines, with an enhanced cytotoxicity being observed upon combined nanoparticle exposure and NIR illumination . Mechanistic analyses revealed that neither UCNPs nor NIR i llumination alone could induce the production of reactive oxygen species (ROS); however, their combination induced a marked increase in ROS levels in two of the three tested cell lines. Furthermore, this dual treatment promoted substantial apoptotic and/or necrotic responses across all cell models. These findings underscore the potential of UCNP@MSN nanoplatforms, equipped with thermoresponsive ga tes , as efficient photoactivated drug delivery systems for melanoma therapy. T2 - Conference Jornadas CICECO CY - Aveiro, Portugal DA - 09.10.2025 KW - Nano KW - Particle KW - Lanthanide KW - Upconversion KW - Surface chemistry KW - Mesoporous silica KW - Doxorubicin KW - Nanomedicine KW - Triggered release KW - pH KW - Cellular uptake KW - Toxicity KW - Folate KW - Ligand PY - 2025 AN - OPUS4-64371 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 - Andresen, Elina T1 - Lanthanide based multi element nanoparticles: a versatile platform for surface chemistry analysis and potential reference materials N2 - The use of engineered nanoparticles of different size, shape, and composition is continuously increasing in the life and materials sciences. This calls for methods and reference materials enabling the reliable and accurate determination of nanoparticle size, particle size distribution, shape, number concentration, degree of aggregation and agglomeration in different environments as well as for nanoparticle dispersibility and stability. We are currently building up and exploring a platform of lanthanide-based nanocrystals (LnNCs) with application-specifically tuned size, shape, composition, architecture, optical properties, and surface chemistry for emerging applications in life sciences. As a prerequisite for the broad applicability of these nanomaterials, we assess simple, robust, and easily upscaleable synthesis protocols for LnNCs with defined morphologies and tunable optical properties, and the short-term and long-term stability of LnNCs with selected surface coatings in aqueous environments under different application-relevant conditions. T2 - Anakon 2025 CY - Leipzig, Germany DA - 10.03.2025 KW - Nano KW - Particle KW - Method KW - Lanthanide KW - Synthesis KW - Upconversion KW - Ligand KW - Quality assurance KW - Particle number concentration KW - Reference material KW - Surface chemistry PY - 2025 AN - OPUS4-62768 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Arai, Marylyn Setsuko A1 - Ravaro, Leandro Piaggi A1 - Brambilla, Gabriel A1 - Maia, Lauro June Queiroz A1 - Reza Dousti, Mohammad A1 - de Camargo, Andrea Simone Stucchi T1 - Upconverting Nanoparticles and Cu(I) Complex-Based Platform for Oxygen Sensing, Thermometry, and Emission Color Tuning N2 - Multifunctional nanoplatforms combine different material properties to meet a wide range of applications, allowing highly customizable systems. In this rapidly advancing research field, we introduce a multifunctional nanomaterial based on the synergy between Tm3+-doped upconverting nanoparticles (UCNPs) and a Cu(I) complex (CuCom). This material is designed for oxygen sensing, optical thermometry, and emission color tuning. In various concentrations, the CuCom complex was electrostatically integrated into a mesoporous silica shell surrounding the core UCNPs (UCNP@mSiO2). The optimized system, UCNP@mSiO2@CuCom-10, was evaluated for different applications. Due to the spectral overlap between the CuCom absorption and the nanoparticles emission, excitation at 980 nm allows most of the UV-blue emission output from the UCNPs to be transferred to the CuCom via luminescent resonance energy transfer (LRET), producing red emission from the molecule. The remaining Tm3+ emission enables optical thermometry, while CuCom’s sensitivity to molecular oxygen supports its application in gas sensing. In upconversion mode, the nanoplatform achieved a Stern−Volmer constant for O2 sensing of 1.64 and demonstrated thermometric relative sensitivities of 0.9% and 1% K−1 at room temperature, with a linear response from 193 to 373 K. Additionally, the emission color of UCNP@mSiO2@CuCom-10 can be tuned from blue to white and yellow, by varying the excitation and temperature, adding further functionality to the system. This multifunctional platform suggests promising applications in biology, medicine, and environmental monitoring. KW - M KW - O2 sensing KW - Upconversion KW - Luminescence resonance energy transfer (LRET) KW - Optical thermometry KW - Mesoporous silica shell PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-625869 SN - 2574-0970 DO - https://doi.org/10.1021/acsanm.4c06351 VL - 8 SP - 854 EP - 862 PB - American Chemical Society (ACS) AN - OPUS4-62586 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - McGonigle, Rebecca A1 - Glasgow, Jodie A1 - Houston, Catriona A1 - Cameron, Iain A1 - Homann, Christian A1 - Black, Dominic J. A1 - Pal, Robert A1 - MacKenzie, Lewis E. ED - MacKenzie, Lewis E. T1 - Autoclave reactor synthesis of upconversion nanoparticles, unreported variables, and safety considerations N2 - Autoclave reactors are widely used across chemical and biological sciences, including for the synthesis of upconversion nanoparticles (UCNPs) and other nanomaterials. Yet, the details of how autoclave reactors are used in such synthesis are rarely reported in the literature, leaving several key synthesis variables widely unreported and thereby hampering experimental reproducibility. In this perspective, we discuss the safety considerations of autoclave reactors and note that autoclaves should only be used if they are (a) purchased from reputable suppliers/manufacturers and (b) have been certified compliant with relevant safety standards. Ultimately, using unsuitable autoclave equipment can pose a severe physical hazard and may breach legal safety requirements. In addition, we highlight several parameters in autoclave synthesis that should be reported as standard to maximise the reproducibility of autoclave synthesis experiments across materials and chemistry research. We encourage users of autoclave synthesis vessels to: (1) adopt high-safety autoclaves and (2) report the many experimental variables involved to enhance experimental reproducibility. KW - Reference material KW - Nano KW - Particle KW - Shell KW - Fluorescence KW - Lifetime KW - Decay kinetics KW - Synthesis KW - Quality assurance KW - Method KW - Energy transfer KW - Upconversion KW - Autoclave synthesis KW - Data comparability PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-625672 DO - https://doi.org/10.1038/s42004-025-01415-3 VL - 8 IS - 1 SP - 1 EP - 7 PB - Springer Science and Business Media LLC AN - OPUS4-62567 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Würth, Christian T1 - Time resolved spectroscopy of upconverting lanthanide based upconversion nanocrystals N2 - This presentation gives an overview of time correlated population and depopulation processes of the electronic states of lanthanide doped nanoparticles. The fundamental principles of sensitized photon upconversion are explained. Theoretical principles and the correlation to experimental results are shown. Examples are given for particle growth, dissolution as well as influences of size, doping concentration and microenvironment. T2 - Principles and Applications of Time-resolved Fluorescence Spectroscopy CY - Berlin, Germany DA - 12.11.2024 KW - Upconversion KW - Time domain PY - 2024 AN - OPUS4-61652 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - de Camargo, Andrea Simone Stucchi T1 - Luminescent multifunctional nanostructures for sensing and theranostics applications N2 - The research carried out at the Laboratory of Spectroscopy of Functional Materials at IFSC/USP, in Brazil, is focused on the synthesis and structural-property correlation of luminescent materials including rare-earth (RE) doped glasses, ceramics and hybrid host-guest materials. For the past five years, we have been particularly interested in the development of single- and multifunctional nanosystems based on core-shell upconversion nanoparticles (UCNP) associated with dyes, organometallic complexes and other organic molecules, for biophotonic and sensing applications. In these systems, we take advantage of energy transfer between the UCNPs and the molecules to either supress or enhance luminescent response. Examples include the possibility of bioimaging and photodynamic therapy of bacteria and cancer cells, simultaneous magnetothermia and thermometry, localized O2 sensing, fast detection and quantification of biological markers (e.g. kidney disease) and microorganisms. On what concerns the development of luminescent sensors - a recently started project, our aim is to develop paper-based platforms for point-of-care devices. In this presentation, an overview of our contributions for the past years and our future aims will be presented with several examples. T2 - ICL2023 - 20th International Conference on Luminescence CY - Paris, France DA - 27.08.2023 KW - Upconversion KW - Sensing KW - Theranostics KW - Nanoparticles KW - Photodynamic therapy PY - 2023 AN - OPUS4-60362 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Zhang, Fengchan A1 - Oiticica, Pedro Ramon Almeida A1 - Abad-Arredondo, Jaime A1 - Arai, Marylyn Setsuko A1 - Oliveira, Osvaldo N. A1 - Jaque, Daniel A1 - Fernandez Dominguez, Antonio I. A1 - de Camargo, Andrea Simone Stucchi A1 - Haro-González, Patricia T1 - Brownian Motion Governs the Plasmonic Enhancement of Colloidal Upconverting Nanoparticles N2 - Upconverting nanoparticles are essential in modern photonics due to their ability to convert infrared light to visible light. Despite their significance, they exhibit limited brightness, a key drawback that can be addressed by combining them with plasmonic nanoparticles. Plasmon-enhanced upconversion has been widely demonstrated in dry environments, where upconverting nanoparticles are immobilized, but constitutes a challenge in liquid media where Brownian motion competes against immobilization. This study employs optical tweezers for the three-dimensional manipulation of an individual upconverting nanoparticle, enabling the exploration of plasmon-enhanced upconversion luminescence in water. Contrary to expectation, experiments reveal a long-range (micrometer scale) and moderate (20%) enhancement in upconversion luminescence due to the plasmonic resonances of gold nanostructures. Comparison between experiments and numerical simulations evidences the key role of Brownian motion. It is demonstrated how the three-dimensional Brownian fluctuations of the upconverting nanoparticle lead to an “average effect” that explains the magnitude and spatial extension of luminescence enhancement. KW - Upconversion KW - Plasmon enhancement KW - Optical tweezers KW - Brownian motion KW - Nanoparticles PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-603551 DO - https://doi.org/10.1021/acs.nanolett.4c00379 VL - 24 IS - 12 SP - 3785 EP - 3792 PB - American Chemical Society (ACS) AN - OPUS4-60355 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Kossatz, Philipp T1 - Upconversion Nanoparticles as Luminescent Probes for Cement N2 - Safety is a key parameter for the design and construction of buildings. The most widely used construction material to date is concrete that consists of about 15-20 wt.-% cement, which is responsible for the main concrete properties, i.e., strength and durability. Despite many standards regulating the quality of cement, at present, there exists no viable method to track the cement life cycle “from cradle to grave”. This led to an increasing interest in simple and robust methods for studying the processes and changes occurring during the life cycle of cement. In this context, we explored the applicability of fluorescence measurements which can be performed with relatively inexpensive and miniaturized instrumentation yet require robust optical probes which survive the harsh cement environment. Therefore, we developed a platform of lanthanide-based upconversion nanoparticles (UCNPs), consisting of a NaYF4 matrix doped with Yb3+ and Er3+ with sizes between 20 nm and 55 nm, which show characteristic multi-color emission patterns, composed of narrow bands of varying intensity in the ultraviolet, visible, near-infrared, and short-wave spectral region and examined their potential for cement probing and the non-invasive monitoring of the hydration processes occurring during cement formation. UCNPs of different size and chemical composition were synthesized via a thermal decomposition approach under inert conditions. The tailor-made design of different emission patterns was achieved by tuning particle size and morphology, material composition, and particle surface chemistry in upscaleable syntheses. For cement probing, different types of UCNPs were added to cement and the evolution of the UCNP emission pattern was used to probe in-situ changes of physico-chemical parameters in the cementitious environment during hydration, utilizing a simple and portable custom-designed optical setup. The observed changes in the UCNP emission patterns are characteristic for a given particle size, surface chemistry, and cement composition. In addition to fluorescence measurements, conventional isothermal heat flow calorimetry was used to study the influence of UCNP addition on cement hydration kinetics. Subsequently, both sets of measurements were correlated. Our results underline the potential of our optical approach ad UCNPs for the non-invasive probing of cementitious systems and cement hydration. This can be also exploited for cutting-edge applications of construction materials such as 3D concrete printing. T2 - Summer School Exciting Nanostructures CY - Bad Honnef, Germany DA - 31.07.2023 KW - Cement Hydration KW - Upconversion KW - Fluorescence Spectroscopy PY - 2023 AN - OPUS4-58203 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Meng, M. A1 - Zhang, T. A1 - Wang, J. A1 - Cheng, Z. A1 - Li, Z. A1 - Qiao, X. A1 - Wen, J. A1 - Resch-Genger, Ute A1 - Long, W. A1 - Ou, Jun T1 - Preparation of NaYF4: Yb3+/Tm3+@NaYF4@β-CD upconversion nanoparticles and application of their fluorescence temperature sensing properties N2 - The NaYF4: Yb3+/Tm3+@NaYF4@β-CD upconversion nanoparticles were successfully prepared by the solvothermal method, and the samples were pure hexagonal phase with good crystallinity and homogeneous size, asevidenced by XRD and TEM analysis. The FT-IR analysis shows that β-CD is successfully encapsulated on the surface of NaYF4: Yb3+/Tm3+@NaYF4 nanoparticles. The fluorescence intensity 3and lifetime were significantly increased after coating the inert layer on the surface of core nanoparticles. After further surface modification of β-CD, the fluorescence intensity and fluorescence lifetime were reduced, but the overall fluorescence was stronger. Temperature measurements using the fluorescence intensity ratio technique were found to have relatively low reliability and absolute sensitivity for temperature measurements using thermally coupled energy levels. However, the reliability of temperature measurements using non-thermally coupled energy levels is significantly higher and the absolute sensitivity is much higher than for measurements at thermally coupled levels. Since the maximum absolute sensitivity, maximum relative sensitivity and minimum temperature resolution are determined to be 0.1179 K-1, 2.19 %K􀀀 1 and 0.00019 K, respectively, NaYF4: Yb3+/Tm3+@NaYF4@β-CD upconversion nanoparticles are expected to be widely used in the biomedical field due to their feasibility, reliability, non-toxicity and harmlessness. KW - Upconversion KW - Surface modification KW - Fluorescence intensity ratio KW - Thermally coupled levels KW - Non-thermally coupled levels PY - 2023 DO - https://doi.org/10.1016/j.optmat.2022.113389 SN - 0925-3467 VL - 136 SP - 1 EP - 11 PB - Elsevier B.V. AN - OPUS4-57105 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Meng, M. A1 - Zhang, T. A1 - Wang, J. A1 - Cheng, Z. A1 - Liu, Y. A1 - Qiao, X. A1 - Wen, J. A1 - Resch-Genger, Ute A1 - Long, W. A1 - Ou, J. T1 - NaYF4:Yb3+/Tm3+@NaYF4:Yb3+ Upconversion Nanoparticles for Optical Temperature Monitoring and Self-Heating in Photothermal Therapy N2 - The core−shell NaYF4:Yb3+/Tm3+@NaYF4:Yb3+ upconversion nanoparticles were successfully prepared by a solvothermal method, and a layer of mesoporous silica (mSiO2) was successfully coated on the periphery of the core−shell nanoparticles to transform their surface from lipophilic to hydrophilic, further expanding their applications in biological tissues. The physical phase, morphology, structure, and fluorescence properties were characterized by X-ray diffraction (XRD), field emission transmission electron microscopy (TEM), Fourier infrared spectroscopy (FT-IR), ζ potential analysis, and fluorescence spectroscopy. It was found that the material has a hexagonal structure with good hydrophilicity and emits intense fluorescence under 980 nm pump laser excitation. The non-contact temperature sensing performance of nanoparticles was evaluated by analyzing the upconversion fluorescence of Tm3+ (1G4 → 3F4 and 3F3 → 3H6) in the temperature range of 284−344 K. The absolute and relative sensitivities were found to be 0.0067 K−1 and 1.08 % K−1, respectively, with high-temperature measurement reliability and good temperature cycling performance. More importantly, its temperature measurement in phosphate-buffered saline (PBS) solution is accurate. In addition, the temperature of the cells can be increased by adjusting the laser power density and laser irradiation time. Therefore, an optical temperature sensing platform was built to realize the application of real-time monitoring of cancer cell temperature and the dual function of photothermal therapy. KW - Sensor KW - Temperature KW - Lanthanide KW - Tag KW - Fluorescence KW - Nanoparticles KW - Synthesis KW - Environment KW - Monitoring KW - Sensing KW - Nano KW - Life sciences KW - Upconversion PY - 2023 DO - https://doi.org/10.1021/acsanm.2c05110 VL - 6 IS - 1 SP - 759 EP - 771 PB - ACS Publications AN - OPUS4-57081 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Würth, Christian T1 - Time resolved spectroscopy of upconverting lanthanide based upconversion nanocrystals N2 - The optical properties of these materials strongly depend on the excitation power density, i.e., the number of photons absorbed per time interval. The upconversion quantum efficiencies (ΦUC) of these materials, the excitation power dependent population i.e. the emission characteristics, and the deactivation dynamics are influenced by nanoparticle architecture, doping concentration, and the microenvironment. We will discuss how time resolved measurements can help to understand the fundamental photophysical mechanisms and discuss differences to other nanocrystals like quantum dots. T2 - 19th International Course on “Principles and Applications of Time-resolved Fluorescence Spectroscopy” CY - Berlin, Germany DA - 16.11.2022 KW - Nanoparticle KW - Lanthanide KW - Upconversion KW - Energy transfer PY - 2022 AN - OPUS4-57000 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Meng, M. A1 - Zhang, R. A1 - Zhenlong, F. A1 - Yang, J. A1 - Ansari, A. A1 - Ou, Jun A1 - Würth, Christian A1 - Resch-Genger, Ute T1 - Retracted article: Effect of Ca2+ doping on the upconversion luminescence properties of NaYF4:Yb3+/Tm3+ nanoparticles and study of its temperature measurement performance N2 - A solvothermal method was used to prepare a series of Yb3+/Tm3+/Ca2+ co-doped NaYF4 nanoparticles with different Ca2+ contents. Strong upconversion blue fluorescence could be observed under 980 nm laser excitation of the samples. The effect of different Ca2+ contents on the luminescence intensity was investigated, and it was found that the UV-vis upconversion luminescence increased and then decreased with an increasing Ca2+ concentration during the increase of the Ca2+ content from 0 mol% to 25 mol%, reaching the strongest fluorescence at 15 mol%, which was up to about 28 times stronger than that without Ca2+ doping. Furthermore, the mechanism was investigated, and it was found that the doping of Ca2+ disrupted the symmetry of the crystal field, resulting in a significant enhancement of the overall fluorescence. Applied to fluorescence intensity ratio thermometry, the absolute and relative sensitivities are as high as 0.0418 K−1 and 2.31% K−1, respectively, with a minimum temperature resolution of 0.0129 K. KW - Sensor KW - Temperature KW - Lanthanide KW - Luminescence KW - Nanoparticles KW - Upconversion KW - Advanced materials PY - 2022 DO - https://doi.org/10.1039/D2CE00562J SN - 1466-8033 VL - 24 IS - 27 SP - 4887 EP - 4898 PB - Royal Society of Chemistry CY - London AN - OPUS4-56952 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wang, Cui A1 - Reichenauer, F. A1 - Kitzmann, W.R. A1 - Kerzig, Ch. A1 - Heintze, K. A1 - Resch-Genger, Ute T1 - Efficient Triplet-Triplet Annihilation Upconversion Sensitized by a Chromium(III) Complex via an Underexplored Energy Transfer Mechanism N2 - Sensitized triplet-triplet annihilation upconversion (sTTA-UC) mainly relies on precious metal complexes thanks to their high intersystem crossing (ISC) efficiencies, excited state energies, and lifetimes, while complexes of abundant first-row transition metals were only rarely utilized and with often moderate UC quantum yields. [Cr(bpmp)2]3+ (bpmp = 2,6-bis(2-pyridylmethyl)pyridine) containing earth-abundant chromium possesses an absorption band suitable for green light excitation, a doublet excited state energy matching the triplet energy of 9,10-diphenyl anthracene (DPA), a close to millisecond excited state lifetime, and high photostability. Combined ISC and doublet-triplet energy transfer from excited [Cr(bpmp)2]3+ to DPA gives 3DPA with close-to-unity quantum yield. TTA of 3DPA furnishes greento-blue UC with a quantum yield of 12.0 % (close to the theoretical maximum). Sterically less-hindered anthracenes undergo a [4+4] cycloaddition with [Cr(bpmp)2]3+ and green light. KW - Fluorescence KW - Optical probe KW - Sensor KW - ph KW - Quantum yield KW - Quality assurance KW - Cr(III) KW - Lifetime KW - Ligand KW - Theory KW - TTA-UC KW - Energy transfer KW - Upconversion KW - Mechanism KW - Anthracene KW - Photochemistry KW - DFT KW - Cycloaddition KW - Transient absorbtion spectroscopy PY - 2022 DO - https://doi.org/10.1002/anie.202202238 VL - 61 IS - 24 SP - 1 EP - 8 PB - Wiley online library AN - OPUS4-54604 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Meng, M. A1 - Zhang, R. A1 - Fa, X. A1 - Yang, J. A1 - Cheng, Z. A1 - Ansari, A. A. A1 - Ou, Jun A1 - Würth, Christian A1 - Resch-Genger, Ute T1 - Preparation of core–shell structured NaYF4:Yb3+/ Tm3+@NaYF4:Yb3+/Er3+ nanoparticles with high sensitivity, low resolution and good reliability and application of their fluorescence temperature properties N2 - A series of NaYF4:Yb3+/Tm3+@NaYF4:Yb3+/Er3+ nanoparticles doped with Tm3+ and Er3+ were successfully prepared by the solvothermal method. Under 980 nm laser excitation, intense upconversion emission peaks of Tm3+ and Er3+ were observed for all samples. By doping Tm3+ and Er3+ with core–shell partitioning, not only a significant increase in fluorescence intensity could be achieved, but also simultaneous temperature measurements on multiple thermocouple energy levels could be realised. In addition, the temperature sensing performance of different thermocouple energy levels was also investigated, and it was found that the 3 F3 → 3 H6 and 1 G4 → 3 F4 thermocouple energy level pairs of Tm3+ were the best, with maximum absolute sensitivity and maximum relative sensitivity of up to 0.0250 K−1 and 2.155% K−1 respectively, higher than the sensitivity of other thermocouple energy levels. It has a temperature resolution of less than 0.0139 K, which is lower than that of most materials available today. By using this material as a probe to build a fiber optic temperature sensor platform, it was found to have reliable temperature measurement performance. KW - Flourescence KW - Optical probe KW - Sensor KW - Dye KW - Temperature KW - Nano KW - Particle KW - Upconversion KW - Lanthanide KW - Qantum yield KW - Quality assurance KW - Monitoring KW - Infrastructure PY - 2022 DO - https://doi.org/10.1039/d1ce01729b VL - 24 IS - 9 SP - 1752 EP - 1763 PB - RSC Publishing AN - OPUS4-54416 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Grauel, Bettina A1 - Würth, Christian A1 - Homann, C. A1 - Krukewitt, Lisa A1 - Andresen, Elina A1 - Roik, Janina A1 - Recknagel, Sebastian A1 - Haase, M. A1 - Resch-Genger, Ute T1 - Volume and surface effects on two-photonic and three-photonic processes in dry co-doped upconversion nanocrystals N2 - Despite considerable advances in synthesizing high-quality core/shell upconversion (UC) nanocrystals (NC; UCNC) and UCNC photophysics, the application of near-infrared (NIR)-excitable lanthanide-doped UCNC in the life and material sciences is still hampered by the relatively low upconversion luminescence (UCL) of UCNC of small size or thin protecting shell. To obtain deeper insights into energy transfer and surface quenching processes involving Yb3+ and Er3+ ions, we examined energy loss processes in differently sized solid core NaYF4 nanocrystals doped with either Yb3+ (YbNC; 20% Yb3+) or Er3+ (ErNC; 2% Er3+) and co-doped with Yb3+ and Er3+ (YbErNC; 20% Yb3+ and 2% Er3+) without a surface protection shell and coated with a thin and a thick NaYF4 shell in comparison to single and co-doped bulk materials. Luminescence studies at 375 nm excitation demonstrate backenergy transfer (BET) from the 4G11/2 state of Er3+ to the 2F5/2 state of Yb3+, through which the red Er3+ 4F9/2 state is efficiently populated. Excitation power density (P)-dependent steady state and time-resolved photoluminescence measurements at different excitation and emission wavelengths enable to separate surface-related and volume-related effects for two-photonic and threephotonic processes involved in UCL and indicate a different influence of surface passivation on the green and red Er3+ emission. The intensity and lifetime of the latter respond particularly to an increase in volume of the active UCNC core. We provide a threedimensional random walk model to describe these effects that can be used in the future to predict the UCL behavior of UCNC. KW - Nano KW - Nanomaterial KW - Upconversion KW - Nanoparticle KW - Lanthanide KW - Photoluminescence KW - Quantum yield KW - Pphotophysics KW - Lifetime KW - Sensor KW - Excitation KW - Power density KW - Single particle KW - Brightness KW - NIR KW - Mechanism KW - Modeling KW - Simulation KW - Energy transfer PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-535317 DO - https://doi.org/10.1007/s12274-021-3727-y SN - 1998-0124 VL - 15 IS - 3 SP - 2362 EP - 2373 PB - Springer AN - OPUS4-53531 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Resch-Genger, Ute T1 - Tumore abbilden, Biomarker nachweisen, Messungen standardisieren N2 - Zu den am häufigsten eingesetzten Analysemethoden in den Lebens- und Materialwissenschaften gehören Lumineszenzmethoden. Sie nutzen die Emission von Licht nach Absorption von Energie, um Signale zu erzeugen, und umfassen spektroskopische und mikroskopische Messungen. KW - Quality assurance KW - Sensor KW - Imaging KW - Reference material KW - Nano KW - Particle KW - Nanomaterial KW - Upconversion KW - Nanoparticle KW - Lanthanide KW - Photoluminescence KW - Quantum yield KW - Photophysics KW - Lifetime KW - Excitation KW - Power density KW - Single particle KW - Brightness KW - NIR PY - 2021 SP - 75 EP - 77 PB - GDCH AN - OPUS4-53526 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Resch-Genger, Ute T1 - Measuring the Upconversion Luminescence of Ensemble and Single Particle Lanthanide-Based Upconversion Nanocrystals N2 - Lanthanide-based upconversion nanoparticles (UCNPs) like hexagonal 𝛽-NaYF4 UCNPs doped with Yb3+ and Er3+, which efficiently convert 976 nm light to ultraviolet, visible, and near infrared photons, offer new strategies for luminescence-based sensing, barcoding, and Imaging. Their upconversion (UC) luminescence (UCL) features like UCL intensity, quantum yield, relative spectral distribution / UCL luminescence color, and luminescence decay kinetics are, however, strongly influenced by particle size, dopant ion concentration, particle architecture, surface chemistry including presence and thickness of surface passivation and shielding shells, microenvironment/presence of quenchers with high energy vibrations, and excitation power density (P). We present here a comprehensive study of the influence of excitation power density on the UCL features of different types of UCNPs, focusing on Yb3+ and Er3+ co-doped NaYF4 core-only and core-shell nanostructures with different sizes and doping ion concentration, which underlines the importance of P-dependent optimum dopant concentrations for UCNP performance and the potential of P-tuning of UCL. T2 - Materials Challenges in Alternative & Renewable Energy 2021 (MCARE 2021) CY - Online meeting DA - 19.07.2021 KW - Fluorescence KW - Lifetime KW - Method KW - Stability KW - Coating KW - Surface chemistry KW - Lanthanide KW - Upconversion KW - Nano KW - Particle KW - Single particle spectroscopy KW - Quantum yield KW - Microscopy KW - Photophysics PY - 2021 AN - OPUS4-53111 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 - 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 - JOUR A1 - Resch-Genger, Ute A1 - Wang, Cui A1 - You, Y. A1 - Förster, C. A1 - Schubert, H. A1 - Heinze, K. A1 - Seitz, M. T1 - NIR-NIR-Aufkonvertierung in molekularen Chrom-Ytterbium-Salzen N2 - Photonen-Aufkonvertierung in hetero-oligonuklearen, Metallkomplex-Architekturen mit organischen Liganden ist ein interessantes, aber bisher selten beobachtetes Phänomen, trotz des großen Potentials sowohl aus Sicht der Grundlagenforschung als auch aus der Anwendungsperspektive. Nun wurde ein neues photonisches Material aus molekularen Chrom(III)- und Ytterbium(III)-Komplexionen entwickelt. Dieses zeigt im Festkörper bei Raumtemperatur abhängig von der Anregungsleistungsdichte nach Anregung des 2F7/2! 2F5/2-3berganges des Ytterbiums bei ca. 980 nm eine kooperative Sensibilisierung der Chrom(III)-zentrierten 2E/2T1-Phosphoreszenz bei ca. 775 nm. Der Aufkonvertierungsprozess ist unempfindlich gegenüber Luftsauerstoff und kann in Gegenwart von Wassermolekülen im Kristallgitter beobachtet werden. KW - Crystal KW - Sensor KW - NIR KW - Yb(III) complex KW - Cr(III) KW - Upconversion PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-517217 DO - https://doi.org/10.1002/ange.202007200 VL - 132 IS - 42 SP - 18804 EP - 18808 PB - Angewandte Chemie AN - OPUS4-51721 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Saleh, Maysoon I. A1 - Rühle, Bastian A1 - Wang, Shu A1 - Radnik, Jörg A1 - You, Yi A1 - Resch-Genger, Ute T1 - Assessing the protective effects of different surface coatings on NaYF4:YB3+, Er3+, upconverting nanoparticles in buffer and DMEM N2 - We studied the dissolution behavior of β NaYF4:Yb(20%), Er(2%) UCNP of two different sizes in biologically relevant media i.e., water (neutral pH), phosphate buffered saline (PBS), and Dulbecco’s modified Eagle medium (DMEM) at different temperatures and particle concentrations. Special emphasis was dedicated to assess the influence of different surface functionalizations, particularly the potential of mesoporous and microporous silica shells of different thicknesses for UCNP stabilization and protection. Dissolution was quantified electrochemically using a fluoride ion selective electrode (ISE) and by inductively coupled plasma optical emission spectrometry (ICP OES). In addition, dissolution was monitored fluorometrically. These experiments revealed that a thick microporous silica shell drastically decreased dissolution. Our results also underline the critical influence of the chemical composition of the aqueous environment on UCNP dissolution. In DMEM, we observed the formation of a layer of adsorbed molecules on the UCNP surface that protected the UCNP from dissolution and enhanced their fluorescence. Examination of this layer by X ray photoelectron spectroscopy (XPS) and mass spectrometry (MS) suggested that mainly phenylalanine, lysine, and glucose are adsorbed from DMEM. These findings should be considered in the future for cellular toxicity studies with UCNP and other nanoparticles and the design of new biocompatible surface coatings. 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 - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-515984 DO - https://doi.org/10.1038/s41598-020-76116-z SN - 2045-2322 VL - 10 IS - 1 SP - 19318-1 EP - 19318-11 PB - Springer Nature CY - London AN - OPUS4-51598 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Würth, Christian A1 - Manley, P. A1 - Voigt, R. A1 - Ahiboz, D. A1 - Becker, C. A1 - Resch-Genger, Ute T1 - Metasurface Enhanced Sensitized Photon Upconversion: Toward Highly Efficient Low Power Upconversion Applications and Nanoscale E-Field Sensors N2 - Large-scale nanoimprinted metasurfaces based on silicon photonic crystal slabs were produced and coated with a NaYF4:Yb3+/Er3+ upconversion nanoparticle (UCNP) layer. UCNPs on these metasurfaces yield a more than 500-fold enhanced upconversion emission compared to UCNPs on planar surfaces. It is also demonstrated how the optical response of the UCNPs can be used to estimate the local field energy in the coating layer. Optical simulations using the finite element method validate the experimental results and the calculated spatial three-dimensional field Energy distribution helps us to understand the emission enhancement mechanism of the UCNPs closely attached to the metasurface. In addition, we analyzed the spectral shifts of the resonances for uncoated and coated metasurfaces and metasurfaces submerged in water to enable a prediction of the optimum layer thicknesses for different excitation wavelengths, paving the way to applications such as electromagnetic field sensors or bioassays. KW - Nanoparticles KW - Upconversion KW - Metasurface KW - Field sensor KW - Emission enhancement KW - Photonic crystal PY - 2020 DO - https://doi.org/10.1021/acs.nanolett.0c02548 VL - 20 IS - 9 SP - 6682 EP - 6689 PB - ACS Publications AN - OPUS4-51427 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kalmbach, J. A1 - Wang, Cui A1 - You, Yi A1 - Förster, C. A1 - Schubert, H. A1 - Heinze, K. A1 - Resch-Genger, Ute A1 - Seitz, M. T1 - Near-IR to near-IR upconversion luminescence in molecular chromium ytterbium salts N2 - Upconversion photoluminescence in hetero-oligonuclear metal complex architectures featuring organic ligands is an interesting but still rarely observed phenomenon, despite its great potential from a basic research and application perspective. In this context, a new photonic material consisting of molecular chromium(III) and ytterbium(III) complex Ions was developed that exhibits excitation-power density-dependent cooperative sensitization of the chromium-centered 2E/2T1 phosphorescence at approximately 775 nm after excitation of the ytterbium band 2F7/2!2F5/2 at approximately 980 nm in the solid state at ambient temperature. The upconversion process is insensitive to atmospheric oxygen and can be observed in the presence of water molecules in the crystal lattice. KW - Upconversion KW - Lanthanide KW - Photoluminescence KW - Quantum yield KW - Photophysics KW - Lifetime KW - Sensor KW - NIR KW - Cr(III) KW - Yb(III) complex KW - Crystal KW - Triplet-triplet annihilation KW - Sensitization KW - Light harvesting PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-512619 DO - https://doi.org/10.1002/anie.202007200 SN - 1433-7851 SN - 1521-3773 VL - 59 IS - 42 SP - 18804 EP - 18808 PB - Wiley CY - Weinheim AN - OPUS4-51261 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Saleta Reig, D. A1 - Grauel, Bettina A1 - Konyushkin, V. A. A1 - Nakladov, A. N. A1 - Federov, P. P. A1 - Busko, D. A1 - Howard, I. A. A1 - Richards, B. S. A1 - Resch-Genger, Ute A1 - Kuznetsov, S. V. A1 - Turshatov, A. A1 - Würth, Christian T1 - Upconversion properties of SrF2:Yb3+,Er3+ single N2 - Synthesis of new upconversion (UC) materials that can convert near-infrared excitation light into visible emission light with high efficiency has crucial importance for energy and bio-applications. Herein, SrF2 single crystals with a doping concentration of 2 mol% Er3+ and 2–8 mol% Yb3+ were synthesized and the optical properties were studied. The absorption cross-section of the different doping ions was calculated. To identify the most efficient and brightest material absolute excitation power dependent UC photoluminescence quantum yields (ϕUC) and brightness values were determined. In addition, excitation characteristics and luminescence lifetimes were analysed to understand the changes in population pathways and possible quenching mechanisms. A dominant two-photon population behaviour of the red and green emission bands was observed for all investigated doping concentrations of Yb3+ and Er3+. The ϕUC value of 6.5% measured using 230 W cm−2 of 976 nm excitation for SrF2 crystal co-doped with 2 mol% Er3+ and 3 mol% Yb3+. These findings broaden the scope of efficient UC materials apart from the record UC material β-NaYF4:Yb3+, Er3+ and provide benchmark values for cubic-phase and especially SrF2- nano and micrometer sized materials. KW - Luorescence KW - Upconversion KW - Crystal KW - Lanthanide KW - Quantum yield KW - Absolute KW - Lifetime KW - Er(III) KW - Quality assurance KW - Fluorescence standard KW - SrF2 PY - 2020 DO - https://doi.org/10.1039/c9tc06591a VL - 8 IS - 12 SP - 4093 EP - 4101 PB - Journal of Materials Chemistry C AN - OPUS4-50825 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Frenzel, Florian T1 - Spectroscopic study of plasmon enhanced UPCON luminescence of silica-metal core-shell nanocomposites - status report N2 - The presentation focuses on the current state of the optical spectroscopic studies on plasmon enhanced upconversion luminescent processes of silica-metal core-shell nanocomposites. A general introduction of the upconversion process, the theoretical basis of plasmonic enhancement, the theoretical requirements in regard to NP architecture for plasmon enhanced UC will be outlined. The first proof-of-concept measurements show the difficulty in realization the theoretical measurement parameters in laboratory conditions and underline the need for shifting the experiments to single particle level.“ T2 - Gruppenseminar der Nanooptik an der HU Berlin, Prof. Benson, Institut für Physik, Raum 1‘404 CY - Berlin, Germany DA - 09.05.2017 KW - Upconversion KW - Pplasmon enhancement KW - Core-shell nanoparticles KW - Silca-metal nanoparticles PY - 2017 AN - OPUS4-50698 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kraft, Marco A1 - Würth, Christian A1 - Muhr, V. A1 - Hirsch, T. A1 - Resch-Genger, Ute T1 - Explaining the influence of dopant concentration and excitation power density on the luminescence and brightness of beta-NaYF_4:Yb~(3+),Er~(3+) nanoparticles: Measurements and simulations N2 - A systematic study of the luminescence properties of monodisperse β-NaYF4: 20% Yb3+, 2% Er3+ upconversion nanoparticles (UCNPs) with sizes ranging from 12–43 nm is presented utilizing steady-state and time-resolved fluorometry. Special emphasis was dedicated to the absolute quantification of size- and environment-induced quenching of upconversion luminescence (UCL) by highenergy O–H and C–H vibrations from solvent and ligand molecules at different excitation power densities (P). In this context, the still-debated Population pathways of the 4F9/2 energy level of Er3+ were examined. Our results highlight the potential of particle size and P value for color tuning based on the pronounced near-infrared emission of 12 nm UCNPs, which outweighs the red Er3+ emission under “strongly quenched” conditions and accounts for over 50% of total UCL in water. Because current rate equation models do not include such emissions, the suitability of these models for accurately simulating all (de)population pathways of small UCNPs must be critically assessed. Furthermore, we postulate population pathways for the 4F9/2 energy level of Er3+, which correlate with the size-, environment-, and P-dependent quenching states of the higher Er3+ energy levels. KW - Nanoparticle KW - Nanosensor KW - Fluorescence KW - Upconversion KW - Upconversion nanoparticle KW - NIR KW - Photophysics KW - Lanthanide KW - Size KW - Surface chemistry KW - Quantum yield KW - Mechanism KW - Lifetime KW - Decay kinetics KW - Quenching KW - Diameter KW - Cyclohexane KW - Water PY - 2018 DO - https://doi.org/10.1007/s12274-018-2159-9 VL - 11/12 SP - 6360 EP - 6374 PB - Springer Nature AN - OPUS4-50307 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Grauel, Bettina T1 - Progress report NaYF4:Yb,Er upconversion nanoparticles: determination of energy loss processes for the systematic enhancement of the luminescence efficiency N2 - A report on the progress of the PhD work on upconversion nanoparticles is given, showing lifetimes and quantum yields of single- and co-doped Yb,Er nanocrystals with and without inert shell. T2 - Arbeitsgruppenseminar Prof. Oliver Benson CY - Berlin, Germany DA - 23.10.2019 KW - Upconversion KW - Spectroscopy KW - Nanoparticles KW - Lifetime PY - 2019 AN - OPUS4-49754 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wiesholler, L. M. A1 - Frenzel, Florian A1 - Grauel, Bettina A1 - Würth, Christian A1 - Resch-Genger, Ute A1 - Hirsch, T. ED - Resch-Genger, Ute ED - Hirsch, Thomas T1 - Yb,Nd,Er-doped upconversion nanoparticles: 980 nm versus 808 nm excitation N2 - Yb,Nd,Er-doped upconversion nanoparticles (UCNPs) have attracted considerable interest as luminescent reporters for bioimaging, sensing, energy conversion/shaping, and anticounterfeiting due to their capability to convert multiple near-infrared (NIR) photons into shorter wavelength ultraviolet, visible or NIR luminescence by successive absorption of two or more NIR photons. This enables optical measurements in complex media with very little background and high penetration depths for bioimaging. The use of Nd3+ as substitute for the commonly employed sensitizer Yb3+ or in combination with Yb3+ shifts the excitation wavelength from about 980 nm, where the absorption of water can weaken upconversion luminescence, to about 800 nm, and laser-induced local overheating effects in cells, tissue, and live animal studies can be minimized. To systematically investigate the potential of Nd3+ doping, we assessed the performance of a set of similarly sized Yb3+,Nd3+,Er3+-doped core- and core–shell UCNPs of different particle architecture in water at broadly varied excitation power densities (P) with steady state and time-resolved fluorometry for excitation at 980 nm and 808 nm. As a measure for UCNPs performance, the P-dependent upconversion quantum yield (Φ) and its saturation behavior were used as well as particle brightness (B). Based upon spectroscopic measurements at both excitation wavelengths in water and in a lipid phantom and B-based calculations of signal size at different penetration depths, conditions under which excitation at 808 nm is advantageous are derived and parameters for the further optimization of triple-doped UCNPs are given. KW - Lanthanide KW - Upconversion KW - Nanoparticle KW - Photoluminescence KW - Quantum yield KW - Lifetime KW - Brightness KW - Nd excitation KW - Excitation power density KW - Modelling KW - NIR PY - 2019 DO - https://doi.org/10.1039/C9NR03127H SN - 2040-3372 SN - 2040-3364 VL - 11 IS - 28 SP - 13440 EP - 13449 PB - Royal Society of Chemistry CY - London AN - OPUS4-48608 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Radunz, Sebastian A1 - Schavkan, A. A1 - Wahl, Sebastian A1 - Würth, Christian A1 - Tschiche, H. R. A1 - Krumrey, M. A1 - Resch-Genger, Ute T1 - Evolution of Size and Optical Properties of Upconverting Nanoparticles during High-Temperature Synthesis N2 - We investigated the growth of β-phase NaYF4:Yb3+,Er3+ upconversion nanoparticles synthesized by the thermal decomposition method using a combination of in situ and offline analytical methods for determining the application-relevant optical properties, size, crystal phase, and chemical composition. This included in situ steady state luminescence in combination with offline time-resolved luminescence spectroscopy as well as small-angle X-ray scattering (SAXS) transmission electron microscopy (TEM), X-ray diffraction analysis (XRD), and inductively coupled Plasma optical emission spectrometry (ICP-OES). For assessing the suitability of our optical monitoring approach, the in situ-collected spectroscopic data, which reveal the luminescence evolution during nanocrystal synthesis, were compared to measurements done after cooling of the reaction mixture of the as-synthesized particles. The excellent correlation of the in situ and time-resolved upconversion luminescence with the nanoparticle sizes determined during the course of the reaction provides important insights into the various stages of nanoparticle growth. This study highlights the capability of in situ luminescence monitoring to control the efficiency of UCNP synthesis, particularly the reaction times at elevated temperatures and the particle quality in terms of size, shape, and crystal structure, as well as luminescence lifetime and upconversion quantum yield. KW - Rare earth nanoparticles KW - Upconversion KW - TEM KW - SAXS PY - 2018 UR - https://pubs.acs.org/doi/pdf/10.1021/acs.jpcc.8b09819 DO - https://doi.org/10.1021/acs.jpcc.8b09819 VL - 50 IS - 122 SP - 28958 EP - 28967 PB - American Chemical Society CY - Washington, DC AN - OPUS4-47169 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kraft, Marco A1 - Würth, Christian A1 - Muhr, Verena A1 - Hirsch, Thomas A1 - Resch-Genger, Ute T1 - Particle-size-dependent upconversion luminescence of NaYF4: Yb, Er nanoparticles in organic solvents and water at different excitation power densities N2 - A systematic study of the luminescence properties of monodisperse β-NaYF4: 20% Yb3+, 2% Er3+ upconversion nanoparticles (UCNPs) with sizes ranging from 12–43 nm is presented utilizing steady-state and time-resolved fluorometry. Special emphasis was dedicated to the absolute quantification of size- and environment-induced quenching of upconversion luminescence (UCL) by highenergy O–H and C–H vibrations from solvent and ligand molecules at different excitation power densities (P). In this context, the still-debated Population pathways of the 4F9/2 energy level of Er3+ were examined. Our results Highlight the potential of particle size and P value for color tuning based on the pronounced near-infrared emission of 12 nm UCNPs, which outweighs the red Er3+ emission under “strongly quenched” conditions and accounts for over 50% of total UCL in water. Because current rate equation models do not include such emissions, the suitability of these models for accurately simulating all (de)population pathways of small UCNPs must be critically assessed. Furthermore, we postulate population pathways for the 4F9/2 energy level of Er3+, which correlate with the size-, environment-, and P-dependent quenching states of the higher Er3+ energy levels. KW - Quantum Yield KW - Nanoparticle KW - Quenching KW - Upconversion PY - 2018 DO - https://doi.org/10.1007/s12274-018-2159-9 VL - 11 IS - 12 SP - 6360 EP - 6374 PB - Tsinghua Univ. Press CY - Beijing AN - OPUS4-47172 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Neumann, L. A1 - Jakobs, F. A1 - Spelthann, S. A1 - Zaremba, D. A1 - Radunz, Sebastian A1 - Resch-Genger, Ute A1 - Evert, R. A1 - Kielhorn, J. A1 - Kowalsky, W. A1 - Johannes, H. H. T1 - Integration of beta-NaYF4 Upconversion Nanoparticles into Polymers for Polymer Optical Fiber Applications N2 - Producing active polymer optical fibers (POFs) is a key step towards new applications such as fluorescent fiber solar concentrators (FFSCs), sensors, contactless coupling devices, or fiber integrated light sources and lasers. Therefore, integration of fluorescent nanoparticles into the polymer matrix is necessary and becomes accessible via in situ polymerization. For optical applications, the polymer has to fulfill various requirements such as chemical and physical stability, optical transparency in the application-relevant spectral region as well as a good synthetic accessibility. A common material for these is poly(methyl methacrylate) (PMMA). The beta-phase NaYF4 : Yb3+, Er3+ upconversion nanoparticles (UCNP) were synthesized from the rare earth salts via thermal decomposition method in high-boiling point solvent 1-octadecene and capping agent oleic acid. Current results show hazy samples of the polymer with integrated nanoparticles made from monomer solution of methyl methacrylate. However, further optical tuning such as increasing the transparency of the bulk samples by changing the monomer solution to non-polar n-butyl methacrylate (nButMA) or cyclohexyl methacrylate (CHMA) or further optimization of the UCNP shell could lead to more suitable polymer bulk samples. KW - Active fibers KW - Rare earth nanoparticles KW - Upconversion KW - Polymer PY - 2018 UR - https://journals.ioffe.ru/articles/46830 DO - https://doi.org/10.1134/S0030400X18110206 SN - 0030-400X VL - 125 IS - 5 SP - 711 EP - 715 PB - Pleiades Publishing CY - New York, NY AN - OPUS4-47167 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Resch-Genger, Ute T1 - Biophotonics and analytics - Photoluminescence properties of nanocrystals and surface group analysis N2 - Correlating the photoluminescence (PL) properties of nanomaterials like semiconductor nanocrystals (QDs) and upconversion nanocrystals (UCNPs) assessed in ensemble studies and at the single particle level and studying their surface chemistry is increasingly relevant for applications of these nanomaterials in the life and material sciences. Here we present a comparison of the spectroscopic properties of ensembles and single nanocrystalline emitters and simple methods for the quantification of functional groups and ligands on particle surfaces. The overall goal of this study was to derive particle architectures and surface chemistries well suited for spectroscopic and microscopic applications. T2 - Institutskolloqium Jozef Stefan Institute CY - Ljubljana, Slovenia DA - 07.11.20218 KW - Lanthanide KW - Nanoparticle KW - Nanocrystal KW - Upconversion KW - Absolute fluorometry KW - Integrating sphere spectroscopy KW - NIR KW - IR KW - Fluorescence KW - Surface chemistry KW - Deactivation pathways KW - Modeling KW - Photophysics KW - Size KW - Cleavable probe PY - 2018 AN - OPUS4-46578 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Neumann, L. A1 - Jakobs, F. A1 - Spelthann, S. A1 - Zaremba, D. A1 - Radunz, Sebastian A1 - Resch-Genger, Ute A1 - Evert, R. A1 - Kielhorn, J. A1 - Kowalsky, W. A1 - Johannes, H.-H. T1 - Integration of β-NaYF4 Upconversion Nanoparticles into Polymers for Polymer Optical Fiber Applications N2 - Producing active polymer optical fibers (POFs) is a key step towards new applications such as fluorescent fiber solar concentrators (FFSCs), sensors, contactless coupling devices, or fiber integrated light sources and lasers. Therefore, integration of fluorescent nanoparticles into the polymer matrix is necessary and becomes accessible via in situ polymerization. For optical applications, the polymer has to fulfill various requirements such as chemical and physical stability, optical transparency in the application-relevant spectral region as well as a good synthetic accessibility. A common material for these is poly(methyl methacrylate) (PMMA). The β-phase NaYF4:Yb3+,Er3+ upconversion nanoparticles (UCNP) were synthesized from the rare earth salts via thermal decomposition method in high-boiling point solvent 1-octadecene and capping agent oleic acid. Current results show hazy samples of the polymer with integrated nanoparticles made from monomer solution of methyl methacrylate. However, further optical tuning such as increasing the transparency of the bulk samples by changing the monomer solution to non-polar n-butyl methacrylate (nButMA) or cyclohexyl methacrylate (CHMA) or further optimization of the UCNP shell could lead to more suitable polymer bulk samples. T2 - PCNSPA 2018 - Photonic Colloidal Nanostructures: Synthesis, Properties, and Applications CY - St. Petersburg, Russia DA - 04.06.2018 KW - Copolymer KW - Active fibers KW - Rare earth nanoparticles KW - Upconversion PY - 2018 SP - 1 EP - 9 AN - OPUS4-45883 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Neumann, L. A1 - Jakobs, F. A1 - Spelthann, S. A1 - Zaremba, D. A1 - Radunz, Sebastian A1 - Resch-Genger, Ute A1 - Evert, R. A1 - Kowalsky, W. A1 - Johannes, H.-H. T1 - Upconverting POF by Incubation of β-NaYF4:Yb3+, Er3+ Nanoparticles via in situ Polymerization for Production of active Polymer Optical Fibers N2 - In the past, integration of fluorescent dyes into polymers for active polymer optical fibers (POFs) is well studied, however, photobleaching of organic chromophores is still a problem for several optical applications. Inorganic luminescent nanoparticles like lanthanide-based systems can present an alternative due to their high chemical stability. Furthermore they do not show photobleaching and photoblinking. Certainly, integration of nanoparticles into a polymer matrix is challenging because of their high affinity to agglomeration which leads to scattering of the polymer samples. T2 - 27th International Conference on Plastic Optical Fibers CY - Seattle, Washington, USA DA - 04.09.2018 KW - Copolymer KW - Active fibers KW - Rare earth nanoparticles KW - Upconversion PY - 2018 SP - 1 EP - 5 CY - Seattle, Washington, USA AN - OPUS4-45882 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Radunz, Sebastian T1 - Investigation of upconverting nanoparticle growth utilizing in-situ luminescence monitoring in combination with offline small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM) N2 - - UCNPs were succesfully synthesized and characterized - Various stages of UCNP growth were tracked using different analytical methods including real time in-situ & time-resolved luminescence spectroscopy, SAXS and TEM measurements - Additional size determination will be performed using inductively coupled plasma - mass spectrometry (ICP-MS) T2 - BAM-PTB-Nanoworkshop CY - PTB, Berlin, Germany DA - 14.05.2018 KW - Rare earth nanoparticles KW - Upconversion KW - TEM KW - SAXS PY - 2018 AN - OPUS4-45884 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Resch-Genger, Ute T1 - Spectroscopic characterization of semiconductor and lanthanide-based nanocrystals with vis and NIR emission N2 - Common approaches to improve the optical properties of semiconductor quantum dots and lanthanide doped nanophosphors present core/shell structures as radiationless deactivation at the particle surface is usually the main energy loss mechanism. This has led to increasingly sophisticated particle architectures using multishell systems with shells of different chemical composition and thickness and initiated an increasing number of quantitative spectroscopic studies focusing on the key performance parameter photoluminescence quantum yield to identify optimum particle structures. This is particularly challenging in the long wavelength region > 1000 nm and for nonlinear emitters like upconversion nanocrystals. Here, we present suitable absolute methods to quantify the photoluminescence of these different emitters in the vis/NIR/IR and as function of excitation power density and underline the impact of such measurements on a profound mechanistic understanding of the nonradiative deactivation pathways in semiconductor and upconversion nanocrystals of different size and particle architecture in different environments. T2 - NANO 2018 CY - Hong Kong, People's Republic of China DA - 24.06.2018 KW - Upconversion KW - Semiconductor KW - Quantum dot KW - Nanoparticle KW - Absolute fluorometry KW - Integrating sphere spectroscopy KW - NIR KW - IR KW - Fluorescence KW - Surface chemistry KW - Deactivation pathways KW - Modeling KW - Size PY - 2018 AN - OPUS4-45797 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Homann, C. A1 - Krukewitt, Lisa A1 - Frenzel, Florian A1 - Grauel, Bettina A1 - Würth, Christian A1 - Resch-Genger, Ute A1 - Haase, M. T1 - NaYF4:Yb,Er/NaYF4 Core/Shell Nanocrystals with High Upconversion Luminescence Quantum Yield N2 - Upconversion core/shell nanocrystals with different mean sizes ranging from 15 to 45 nm were prepared via a modified synthesis procedure based on anhydrous rare‐earth acetates. All particles consist of a core of NaYF4:Yb,Er, doped with 18 % Yb3+ and 2 % Er3+, and an inert shell of NaYF4, with the shell thickness being equal to the radius of the core particle. Absolute measurements of the photoluminescence quantum yield at a series of different excitation power densities show that the quantum yield of 45 nm core/shell particles is already very close to the quantum yield of microcrystalline upconversion phosphor powder. Smaller core/shell particles prepared by the same method show only a moderate decrease in quantum yield. The quantum yield of 15 nm core/shell particles, for instance, is reduced by a factor of three compared to the bulk upconversion phosphor at high power densities (100 W cm−2) and by approximately a factor of 10 at low power densities (1 W cm−2). KW - Core shell structure KW - Upconversion KW - Non lienear processes KW - Nanoparticle KW - Quantum yield PY - 2018 DO - https://doi.org/10.1002/anie.201803083 VL - 57 IS - 28 SP - 8765 EP - 8769 PB - Wiley-VCH AN - OPUS4-45574 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Würth, Christian A1 - Fischer, S. A1 - Grauel, Bettina A1 - Alivisatos, A. P. A1 - Resch-Genger, Ute T1 - Quantum Yields, Surface Quenching, and Passivation Efficiency for Ultrasmall Core/Shell Upconverting Nanoparticles N2 - We synthesized and characterized a set of ultrasmall hexagonal-phase NaGdF4: 20% Yb3+, 2% Er3+ upconversion nanoparticles with core diameters of 3.7 ± 0.5 nm. In order to assess passivation effects and the influence of possible core−shell intermixing and to identify optimum particle structures for combined imaging in the visible and near-infrared (vis−NIR: 410−850 nm) and short-wave infrared (SWIR: 1520 nm), NaYF4 shells of varying thicknesses (monolayer to 10 nm) were introduced and the influence of this parameter on the upconversion and downshifting photoluminescence of these particles was studied at different excitation power densities. This included excitation power-dependent emission spectra, slope factors, quantum yields, and excited state decay kinetics. These measurements revealed enhancement factors of the upconversion quantum yield of >10 000 in the low power region and an excitation power density-independent quantum yield of the downshifted emission at 1520 nm between 0.1 and 14%. The optimized shell thickness for combined vis and SWIR imaging was identified as 5 nm. Moreover, lifetimes and quantum yields can be continuously tuned by shell thickness which can be exploited for lifetime multiplexing and encoding. The fact that we did not observe a saturation of the upconversion quantum yield or the excited state decay kinetics with increasing shell thickness is ascribed to a strong intermixing of the active core with the inert shell during the shelling procedure. This indicates the potential of spectroscopic tools to detect cation intermixing. KW - Nanoparticle KW - Upconversion KW - Quenching PY - 2018 DO - https://doi.org/10.1021/jacs.8b01458 IS - 140 SP - 4922 EP - 4928 PB - American Chemical Society AN - OPUS4-45378 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Würth, Christian T1 - Systematic characterization of Upconversion nanoparticles: Effect of size, microenvironment, Energy transfer, shells N2 - Solid state multi-band emitters like lanthanide doped up-conversion nanoparticles (UCNPs) are promising materials for energy and biotechnologies. These materials are excitable in the near infrared (NIR) and show emission bands from UV to SWIR with excellent photostability, and long luminescence lifetimes in the µs range. The efficiency of these materials, i.e. the multiphoton absorption processes, the excitation power dependent population, and deactivation dynamics are strongly influenced by the particle size, structure, doping concentration, surface chemistry, and microenvironment. For applications UCNPs have to be optimized to meet the application relevant optical properties like the upconversion quantum yield (UC) and downshifting quantum yield (PL), luminescence lifetime and emission spectra. We investigated ß-NaYF4 NPs co-doped with Yb3+ and Er3+ in aqueous and organic media and as powder. For the later, bulk and nanomaterial is compared. For dispersed particles the influence of surface chemistry (ligands), microenvironment (solvent) and size (10 to 43 nm) was studied. Especially for bioapplications the Förster-Resonance-Energy-Transfer (FRET) efficiency from UCNPs to organic dye molecules (rose bengal and sulforhodamine B) was optimized with respect to the UCNP size. T2 - UpCon 2018 CY - Valencia, Spanien DA - 02.04.2018 KW - Nanoparticle KW - Upconversion KW - Quenching PY - 2018 AN - OPUS4-44762 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CHAP A1 - Resch-Genger, Ute ED - Schäferling, Michael T1 - Luminescent nanoparticles for chemical sensing and imaging N2 - The implementation of fluorescent methods is of outstanding importance in the field of optical chemical sensor Technology and biosciences. Their bioanalytical applications are manifold including fluorescence microscopy, fluorescence in situ hybridization, DNA sequencing, fluorescence-activated cell sorting, immunoassays, analysis of DNA and Protein microarrays, and quantitative PCR, just to name a few examples. Particularly, fluorescence microscopy is a valuable method in the versatile field of biomedical imaging methods which nowadays utilizes different fluorescence Parameters like emission wavelength/Color and lifetime for the discrimination between different targets. Sectional Images are available with confocal microscopes. Tissue, cells or single cellular compartments can be stained and visualized with fluorescent dyes and biomolecules can be selectively labeled with fluorescent dyes to Monitor biomolecular interactions inside cells or at Membrane bound receptors. On the other hand , fluorophores can act as indicator (or "molecular probe") to visualize intrinsically colorless and non-fluorescent ionic and neutral analytes such as pH, Oxygen (pO2), metal ions, anions, hydrogen peroxide or bioactive small organic molecules such as Sugars or nucleotides. Thereby, their photoluminescent properties (fluorescence or phoporescence intensity, exitation and/or Emission wavelength, emission lifetime or anisotropy) respond to the presence of these species in their immediate Environment. In general, the use of luminescent probes has the advantage that they can be delivered directly into the sample, and detected in a contactless remote mode. By now, these probes are often encapsulated in different types of nanoparticles (NPs) made from (biodegradable) organic polymers, biopolymers or inorganic materials like silica or bound to their surface. KW - Fluorescence KW - Upconversion KW - NIR KW - Sensor KW - Nanoparticle KW - Surface chemistry KW - Quantum yield KW - Liftetime KW - Nanocrystal KW - Lanthanide KW - Semiconductor KW - Polymer KW - Silica KW - Imaging KW - Application KW - Dye KW - Quantum dot PY - 2017 SN - 978-3-319-48260-6 SN - 978-3-319-48259-0 DO - https://doi.org/10.1007/978-3-319-48260-6_5 SN - 1573-8086 SP - 71 EP - 109 PB - SPRINGER INTERNATIONAL PUBLISHING AG CY - Cham, Schweiz AN - OPUS4-44011 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Resch-Genger, Ute T1 - Effect of particle architecture, dopant concentration, size, and excitation power density on the luminescence efficiency of upconversion nanocrystals N2 - Lanthanide-based upconversion nanoparticles (UCNPs) offer new strategies for luminescence-based sensing and imaging. One of the best studied materials are hexagonal ß-NaYF4 UCNPs doped with 20% Yb3+ and 2% Er3+, which efficiently convert 976 nm light to photons emitted at 540 nm, 655 nm, and 845 nm, respectively, reveal Long luminescence lifetimes (> 100 µs), and are very photostable and chemically inters.[1,2] The properties of their upconversion (UC) luminescence (UCL) are, however, strongly influenced by particle size, concentration and spatial arrangement of dopant Ions, surface chemistry, and microenvironment.[3,4] In addition, the multiphotonic absorption processes responsible for UCL render UCL dependent on excitation power density (P). The rational design of brighter UCNPs particle architectures encouraged us to assess systematically the influence of these parameters on UCL for differently doped UCNPs relying on the commonly used ß-NaYf4 matrix using steady state and time resolved fluorometry as well as integrating sphere spectroscopy for P varied over almost three orders of magnitude. This includes comprehensive studies of the influence of size and shell, Yb3+ and Er3+ dopand concentrations, and energy Transfer processes from UCNPs to surface-bound organic dyes or vice versa [5]. Our results underline the need for really quantitative luminescence studies for mechanistic insights, the potential of high p to compensate for UCL surface quenching, and the matrix- and P-dependence of the optimum dopand concentration. T2 - BIOSPIE 2018 CY - San Francisco, USA DA - 27.01.2018 KW - Upconversion KW - Nanoparticle KW - Absolute fluorometry KW - Integrating sphere spectroscopy KW - NIR KW - IR KW - Fluorescence KW - Surface chemistry KW - Deactivation pathways KW - Modeling KW - Size PY - 2018 AN - OPUS4-43939 LA - deu 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 - JOUR A1 - Resch-Genger, Ute A1 - Pilch, A. A1 - Würth, Christian A1 - Kaiser, Martin A1 - Wawrzynczyk, D. A1 - Kurnatowska, M. A1 - Arabasz, S. A1 - Prorok, K. A1 - Samoc, M. A1 - Strek, W. A1 - Bednarkiewicz, A. T1 - Shaping luminescent properties of Yb3+ and Ho3+ co-doped upconverting core-shell ß-NaYF4 nanoparticles by dopant distribution and spacing N2 - At the core of luminescence color and lifetime Tuning of rare earth doped upconverting nanoparticles (UCNPs), is the understanding of the Impact of the particle architecture for commonly used sensitizer (S) and activator (A) Ions. In this respect, a series of core@Shell NaYF4 UCNPs doped with Yb3+ and Ho3+ ions are presented here, where the same dopant concentrations are distributed in different particle architectures following the scheme: YbHo core and YbHo@..., ...@YbHo, Yb@Ho, Ho@Yb, YbHo@Yb, and Yb@YbHo core-Shell NPs. As refealed by quantitative steady-state and time-resolved luminescence studies, the relative spatial Distribution of the A and S ions in the UCNPs and their protection from surface quenching has a critical Impact on ther luminescence characteristics. Although the increased amount of Yb3+ Ions boosts UCNP Performance by amplifying the Absorption, the Yb3+ ions can also efficiently dissipate the energy stored in the material through energy Migration to the surface, thereby reducing the Overall energy Transfer Efficiency to the activator ions. The results provide yet another proof that UC Phosphor chemistry combined with materials Engineering through intentional core@shell structures may help to fine-tune the luminescence Features of UCNPs for their specific future applications in biosensing, bioimaging, photovoltaics, and Display technologies. KW - Fluorescence KW - Upconversion KW - NIR KW - Nonlinear KW - Nanoparticle KW - Surface chemistry KW - Quantum yield KW - Liftetime KW - Nanocrystal KW - Lanthanide KW - Ho(III) KW - Yb(III) KW - Mechanism KW - Absolute flourescence KW - Excitation power density dependence PY - 2017 DO - https://doi.org/10.1002/smll.201701635 SN - 1613-6810 VL - 13 IS - 47 SP - 1701635, 1 EP - 13 PB - WILEY-VCH Verlag GmbH & co. KGaA CY - Weinheim AN - OPUS4-43629 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Resch-Genger, Ute T1 - Absolute Fluorescence Measurements > 800 nm - Setup Design, Challenges, and Characterization of Semiconductor and Lanthanide-based Nanocrystals N2 - There is an increasing interest in optical reporters like semiconductor and lanthanide-based nanocrystals with emission > 800 nm and recently also > 1000 nm for bioanalysis, medical diagnostics, and safety barcodes. Mandatory for the comparison of different emitter classes and the rational design of the next generation of reporters for the short wavelength infrared (SWIR) region are reliable and quantitative photoluminescence measurements in this challenging wavelength region. This is of special relevance for nanocrystalline emitters like semiconductor quantum dots and rods as well as for upconversion and downconversion nanocrystals, where surface states and the accessibility of emissive states by quenchers largely control accomplishable quantum yields and hence, signal sizes and detection sensitivities from the reporter side. Such measurements are currently hampered by the lack of suitable methods and standards for instrument calibration and validation as well as by the lack of quantum yield standards with emission > 800 nm and especially > 1000 nm. In this respect, we present the design of integrating sphere setups for absolute and excitation power densitydependent measurements of emission spectra and quantum yields in the wavelength region of 650 to 1650 nm including calibration strategies and first candidates for potential fluorescence standards. Subsequently, the photoluminescence properties of different types of nanocrystals are presented and discussed including absolute photoluminescence measurements of upconversion and down conversion emission in different solvents. T2 - MRS 2017 CY - Boston, MA, USA DA - 26.11.2017 KW - Upconversion KW - Nanoparticle KW - Absolute fluorometry KW - Integrating sphere spectroscopy KW - NIR KW - IR KW - Fluorescence KW - Surface chemistry KW - Deactivation pathways KW - Semiconductor quantum dot KW - SWIR KW - Quantum yield KW - Energy transfer KW - Size PY - 2017 AN - OPUS4-43202 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Resch-Genger, Ute T1 - Challenges and examples for quantitative fluorescence measurements > 800 nm with semiconductor and lanthanide-doped nanocrystals N2 - There is an increasing interest in molecular and nanoscale with emission > 800 nm and recently also > 1000 nm for bioanalysis, medical diagnostics, bioimaging, and safety barcodes. Mandatory for the comparison of different emitter classes and the rational design of the next generation of reporters for the short wavelength infrared (SWIR) Region are reliable and quantitative photoluminescence measurements in this challenging wavelength region. This is of special relevance for nanocrystalline emitters like semiconductor quantum dots and rods as well as lanthanide-based upconversion and downconversion nanocrystals, where surface states and the accessibility of emissive states by quenchers largely control accomplishable photoluminescence quantum yields and hence, signal sizes and detection sensitivities from the reporter side. Such measurements are currently hampered by the lack of suitable methods and standards for instrument calibration and validation and quantum yield standards with emission > 800 nm and especially > 1000 nm. In this respect, we present the design of integrating sphere setups for absolute and excitation power density-dependent measurements of emission spectra and photoluminescence quantum yields in the wavelength Region of 650 to 1650 nm including calibration strategies and first candidates for potential fluorescence standards. Subsequently, the photoluminescence properties of different types of nanocrystals are presented including the upconversion and downconversion emission of differently sized and surface functionalized lanthanide-doped nanoparticles and photoluminescence quenching effects are quantified. T2 - SHIFT 2017 CY - Teneriffa, Spain DA - 13.11.2017 KW - Upconversion KW - Nanoparticle KW - Absolute fluorometry KW - Integrating sphere spectroscopy KW - NIR KW - IR KW - Fluorescence KW - Surface chemistry KW - Deactivation pathways KW - Semiconductor quantum dot KW - SWIR KW - Quantum yield PY - 2017 AN - OPUS4-43203 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Resch-Genger, Ute T1 - Effect of Particle Size and Excitation Power Density on the Luminescence Efficiency of Upconversion Nanocrystals in Different Dispersion Media N2 - Upconversion nanoparticles (UCNPs) offer new strategies for luminescence-based sensing and imaging. One of the best studied materials are ..-NaYF4 UCNPs doped with 20 % Yb3+ and 2 % Er3+, which efficiently convert 976 nm light to photons emitted at 540 nm, 655 nm, and 845 nm, respectively, reveal long luminescence lifetimes (> 100 µs), are photostable and chemically inert. Their upconversion (UC) luminescence (UCL) properties are, however, strongly influenced by particle size, surface chemistry, and microenvironment. In addition, the multiphotonic absorption processes responsible for UCL render UCL excitation power density (..) dependent. This makes quantitative UCL measurements as well as the determination of UC quantum yields (.UC) very challenging. The rational design of brighter UCNPs particle architectures and the interest in identifying optimum particle architectures for FRET-based sensing and imaging schemes, which often rely on core-only UCNPs to minimize donor-acceptor distances, encouraged us to assess the influence of particle size and P on UCL. Here, we present the photophysical properties of a series of hexagonal NaYF4 UCNPs with sizes from 10 to 43 nm with different surface ligands dispersed in organic solvents and water studied by steady state and time-resolved fluorometry as well as quantitatively by integrating sphere spectrometry with P varied over about three orders of magnitude. Our results underline the need for really quantitative luminescence studies for mechanistic insights and the potential of high P to compensate for UCL quenching due to high energy phonons and surface effects. T2 - 15th Conference on Methods and Applications in Fluorescence CY - Bruges, Belgium DA - 10.09.2017 KW - Upconversion KW - Nanoparticle KW - Absolute fluorometry KW - Integrating sphere spectroscopy KW - NIR KW - IR KW - Fluorescence KW - Surface chemistry KW - Deactivation pathways KW - Photophysics KW - Quantum yield PY - 2017 AN - OPUS4-43181 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Monks, Melissa-Jane T1 - Rare earth strontium fluoride nanocrystals prepared via sol gel synthesis - Spectroscopic study of upconversion luminescence properties N2 - Obtaining high quality upconverting nanocrystals with only little crystal defects and hence, a high luminescence, affords a reliable synthesis route. Only this guarantees the reproducibility of the material and its spectroscopic properties required for future application. The fluorolytic sol-gel synthesis appears to be a convenient attempt, as this is a method with only few steps influencing the material properties, which can be well controlled. Also creating bright upconverting nanocrystals requires a profound understanding of the interplay of photophysical processes like multiphoton absorption, radiative and non-radiative pathways, and energy transfer in the material. Based on steady-state and time resolved luminescence measurements at different excitation power densities, the influence of the lanthanide doping ratio and synthesis parameters such as the annealing process on SrF2-nanocrystals obtained via the fluorolytic sol-gel synthesis was systematically studied. T2 - GDCh Wissenschaftsforum Chemie CY - Berlin, Germany DA - 10.09.2017 KW - Upconversion KW - Strontiumfluoride KW - Annealing study KW - Doping study KW - Luminescence PY - 2017 AN - OPUS4-42944 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 - Gorris, H.H. A1 - Resch-Genger, Ute T1 - Perspectives and challenges of photon-upconversion nanoparticles - Part II: Bioanalytical applications N2 - In Part II of this Review series on lanthanide-doped photon-upconversion nanoparticles (UCNPs), we present and critically discuss the Performance and suitability of UCNPs as background-free luminescent Reporters in bioimaging and bioanalytical applications. The preparation of a biocompatible nanoparticle surface is an integral step for all life - science-related applications. UCNPs have found their way into a large number of diagnostic platforms, homogeneous and heterogeneous assay formats, and sensor applications. Many bioanalytical detection schemes involve Förster resonance energy transfert (FRET), which is still debated for UCNPs and Needs to be much improved. The Need for dedicated and standardized instruments as well as recent studies on the Dissolution and potential toxicity of UCNPs are addressed. Finally we outline future Trends and challenges in the field of upconversion. KW - Fluorescence KW - Lanthanide KW - Upconversion KW - Brightness KW - Quantification KW - Nanoparticle KW - Absolute fluorometry KW - NIR KW - IR KW - Quantum yield KW - Assay KW - Bioconjugation KW - Imaging KW - FRET KW - Sensor PY - 2017 DO - https://doi.org/10.1007/s00216-017-0482-8 SN - 1618-2650 SN - 1618-2642 VL - 409 IS - 25 SP - 5875 EP - 5890 PB - Springer AN - OPUS4-41706 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Resch-Genger, Ute A1 - Gorris, H.H. T1 - Perspectives and challenges of photon-upconversion nanoparticles - Part I: routes to brighter particles and quantitative spectroscopic studies N2 - Lanthanide-doped photon-upconversion nanoparticles (UCNPs) have been the Focus of many Research activities in materials and life sciences in the last 15 years because of their potential to convert light between different spectral regions and their unique photophysical properties. To fully exploit the application potential of These facinating nanomaterials, a number of challenges have to be overcome, such as the low brightness, particularly of small UCNPs, and the reliable quantification of the excitation-power-density-dependent upconversion luminescence. In this series of critical Reviews, recent developments in the design, Synthesis, optical-spectroscopic characterization, and application of UCNPs are presented with Special Focus on bioanalysis and the life sciences. Here we guide the reader from the Synthesis of UCNPs to different concepts to enhance their luminescence, including the required optical-spectroscopic assessment to quantify material Performance; surface modification strategies and bioanalytical applications as well as selected examples of the use of UCNPs as reporters in different Assay formats are addressed in part II. Future Trends and challenges in the field of upconversion are discussed with Special emphasis on UCNP Synthesis and material characterization, particularly quantitative luminescence studies. KW - Fluorescence KW - Lanthanide KW - Upconversion KW - Brightness KW - Quantification KW - Nanoparticle KW - Absolute fluorometry KW - NIR KW - IR KW - Quantum yield PY - 2017 DO - https://doi.org/10.1007/s00216-017-0499-z SN - 1618-2650 SN - 1618-2642 VL - 409 IS - 25 SP - 5855 EP - 5874 PB - Springer AN - OPUS4-41665 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kaiser, M. A1 - Würth, Christian A1 - Kraft, Marco A1 - Hyppänen, I. A1 - Soukka, T. A1 - Resch-Genger, Ute T1 - Power-dependent upconversion quantum yield of NaYF4:Yb3+,Er3+ nano- and micrometer-sized particles – measurements and simulations N2 - Photophysical studies of nonlinear lanthanide-doped photon upconverting nanoparticles (UCNPs) increasingly used in biophotonics and photovoltaics require absolute measurements of the excitation power density (P)-dependent upconversion luminescence (UCL) and luminescence quantum yields (ΦUC) for quantifying the material performance, UCL deactivation pathways, and possible enhancement factors. We present here the P-dependence of the UCL spectra, ΦUC, and slope factors of the different emission bands of representative 25 nm-sized oleate-capped β-NaYF4:17% Yb3+, 3% Er3+ UCNPs dispersed in toluene and as powder as well as ΦUC of 3 μm-sized upconversion particles (UCμP), all measured with a newly designed integrating sphere setup, enabling controlled variation of P over four orders of magnitude. This includes quantifying the influence of the beam shape on the measured ΦUC and comparison of experimental ΦUC with simulations utilizing the balancing power density model of the Andersson-Engels group and the simulated ΦUC of UCμP from the Berry group, underpinned by closely matching decay kinetics of our UC material. We obtained a maximum ΦUC of 10.5% for UCμP and a ΦUC of 0.6% and 2.1% for solid and dispersed UCNPs, respectively. Our results suggest an overestimation of the contribution of the purple and an underestimation of that of the red emission of β-NaYF4:Yb3+,Er3+: microparticles by the simulations of the Berry group. Moreover, our measurements can be used as a guideline to the absolute determination of UCL and ΦUC KW - Upconversion KW - Photophysics KW - Nanoparticles PY - 2017 DO - https://doi.org/10.1039/c7nr02449e VL - 9 IS - 28 SP - 10051 EP - 10058 PB - The Royal Society of Chemistry AN - OPUS4-41550 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Resch-Genger, Ute T1 - Quantitative Characterization of Functional Nanomaterials with vis/NIR Emission N2 - The rational design of functional nanomaterials for optical applications in the material and life sciences requires optical-spectroscopic methods for the quantitative characterization of their signal-relevant optical properties. Additionally, methods for the simple and quantitative analysis of the surface chemistry are desired as the chemical nature and number of the surface groups and ligands can affect the optical features and controls the interaction of these nanomaterials with their environment. Here, we present quantitative photoluminescenvce studies of different types of vis/NIR-emissive nanomaterials like semiconductor quantum dots and upconversion nanocrystals will be presented and their relevance for the mechanistic understanding of nonradiative decay channels and the rational design of new nanomaterials will be underpinned. In this respect, also validation concepts for such measurements and absolute fluorometry will be introduced. In addition, the potential of optical spectroscopy for surface group and ligand analysis surface chemistry will be demonstrated exemplarily for semiconductor quantum dots T2 - AK Prof. Voss CY - Uni Brunswick, Germany DA - 03.08.2017 KW - Semiconductor KW - Upconversion KW - Nanoparticle KW - Fluorescence KW - Surface group analysis KW - NIR KW - Absolute fluoreometry KW - Integrating sphare spectroscopy KW - Optical probe KW - Assay KW - Thiol ligand PY - 2017 N1 - Geburtsname von Nirmalananthan-Budau, Nithiya: Nirmalananthan, N. - Birth name of Nirmalananthan-Budau, Nithiya: Nirmalananthan, N. AN - OPUS4-41366 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Resch-Genger, Ute T1 - The European Upconversion Network: From the Design of Photon-upconverting Nanomaterials to (Biomedical) Applications (CM1403) WG1 Materials Research & Photophysical Characterization N2 - Lanthanide-doped photon-upconversion nanoparticles (UCNPs) have been in the focus of many research activities in the material and life sciences over the last 15 years because of their potential to convert light between different spectral regions and their unique photophysical properties. In order to fully exploit the application potential of these fascinating nanomaterials, a number of challenges has to be overcome such as the low brightness particularly of small UCNPs and the reliable quantification of the excitation power density (P)-dependent upconversion luminescence (UCL). Here, the need and requirements on the characterization of the optical properties of UCNPs are discussed with special focus on the reliabiliy and comparability of relative and quantitative luminescence measurements and prerequisites for their standardization. T2 - COST Treffen CY - Aveiro, Portugal DA - 26.06.2017 KW - Upconversion KW - Nanoparticle KW - Fluorescence KW - NIR KW - Absolute fluorometry KW - Integrating sphere spectroscopy KW - Reference maerial KW - Standardization KW - Quantum yield PY - 2017 AN - OPUS4-41367 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Frenzel, Florian T1 - Power dependent optical properties of hexagonal β-NaYF4: x % Er3+, 20 % Yb3+ core/ core-shell upconversion nanoparticles in cyclohexane and water N2 - Lanthanide doped photon upconverting nanophosphors (UCNPs) have the unique capability to produce narrow band, multi-color emission in the UV/vis/NIR upon multiphotonic absorption of infrared light, which makes them promising reporters for diagnostic, bioanalytical, and biological applications. This minimizes background signals, which normally occur due to autofluorescence from auxochromes, in biological matrices and enables deep penetration depths in biological applications. Moreover, UCNPs show long luminescence lifetimes in the μs range favorable for time gated emission in conjunction with a high photostability and chemical inertness and they do not blink. One of the most efficient upconversion (UC) phosphors for conversion of 976 nm to 655 nm and 545 nm light presents the hexagonal NaYF4-host crystal doped with 20 % Yb3+ used as sensitizer to absorb infrared light and 2 % Er3+ acting as activator mainly responsible for light emission. The high transparency in the relevant spectral windows of this host together with its low phonon frequencies ensure relatively high luminescence efficiencies. Although UCNPs are ideal candidates for many chemical and biological sensing and imaging applications, compared to other well-known chromophores like organic dyes or QDs, they suffer from a comparatively low brightness due to the low absorption cross sections of the parity forbidden f-f-transitions and low photoluminescence quantum yields (QYUC) particularly in the case of small nanoparticles with sizes of < 50 nm. The rational design of more efficient UCNPs requires an improved understanding of the nonradiative decay pathways in these materials that are influenced by particle architecture including dopant ion concentration and homogeneity of dopant distribution within UCNPs, size/surface-to-volume ratio, surface chemistry, and microenvironment. A promising approach to overcome the low efficiency of UCNPs is to use plasmonic interactions between a noble metal (Ag or Au) structure in the proximity of UCNPs and the incident light. This interaction leads to a modification of the spectroscopic properties due to local field enhancements and can involve an increase of the photoluminescence. In this respect, we study the interactions of UCNPs with metal structures (clusters and shells) by varying shape and size. Here, first results derived from integrating sphere spectroscopy and time-resolved fluorescence measurements are presented. T2 - Summer School "EXCITING NANOSTRUCTURES" CY - Bad Honnef, Germany DA - 17.07.2017 KW - Upconversion KW - Nanoparticle KW - Flourescence KW - Core-shell architecture KW - NIR KW - Absolute flourometry KW - Integrating sphere spectroscopy KW - Er(III) KW - Yb(III) KW - Single particle spectroscopy PY - 2017 AN - OPUS4-41172 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Resch-Genger, Ute T1 - Quantitation of luminescent properties of Yb and Ho co-doped NaYF4 colloidal nanoparticles - novel active-core-active-shell materials and novel characterization methods N2 - At the core of luminescence color and lifetime tuning of rare earth doped upconverting nanoparticles (UCNPs) is the understanding of the impact of the particle architecture for commonly used sensitizer (S) and activator (A) ions. In this respect, we present here a series of core@shell NaYF4 UCNPs doped with Yb3+ and Ho3+ ions, where the same dopant concentrations were distributed in different particle architectures following the scheme: YbHo core and YbHo@..., …@YbHo, Yb@Ho, Ho@Yb, YbHo@Yb, and Yb@YbHo core-shell NPs. As revealed by quantitative steady state and time-resolved luminescence studies, the relative spatial distribution of the A and S ions in the UCNPs and their protection from surface quenching has critical impact on their luminescent characteristics. Interestingly, although the increased amount of Yb3+ ions boosts UCNP performance by increasing the absorption, the Yb3+ ions can also dissipate the energy stored in the material through energy migration to surface, thereby reducing the overall energy transfer efficiency to the activator ions. T2 - COST Workshop CY - Aveiro, Portugal DA - 30.06.2017 KW - Upconversion KW - Nanoparticle KW - Flourescence KW - Core-shell architecture KW - NIR KW - Absolute flourometry KW - Integrating sphere spectroscopy KW - Ho(III) KW - Yb(III) PY - 2017 AN - OPUS4-41161 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Resch-Genger, Ute T1 - Functional Nanomaterials with VIS/NIR Emission-Spectroscopic Properties And Surface Group Analysis N2 - Optical-spectroscopic methods for the quantitative characterization of the optical properties of different types of vis/NIR-emissive nanomaterials like semiconductor quantum dots and upconversion nanocrystals will be presented and their relevance for the mechanistic understanding of nonradiative decay channels and the rational design of new nanomaterials will be underpinned. In this respect, also validation concepts for such measurements and absolute fluorometry will be introduced. In addition, the potential of optical spectroscopy for surface group and ligand analysis surface chemistry will be demonstrated exemplarily for semiconductor quantum dots. T2 - Universität Mainz, AK Professor K. Heinze CY - Mainz, Germany DA - 24.07.2017 KW - Upconversion KW - Nanoparticle KW - Flourescence KW - Surface group analysis KW - NIR KW - Absolute flourometry KW - Integrating sphere spectroscopy KW - Optical probe KW - Assay KW - Thiol ligand PY - 2017 N1 - Geburtsname von Nirmalananthan-Budau, Nithiya: Nirmalananthan, N. - Birth name of Nirmalananthan-Budau, Nithiya: Nirmalananthan, N. AN - OPUS4-41115 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Muhr, V. T1 - Effect of nanoparticle size on time-resolved upconversion resonance energy transfer N2 - Upconversion nanoparticles (UCNPs) offer new strategies for luminescence-based sensing. The potential of UCNPs to serve as donors in Förster resonance energy transfer (FRET) applications is intensely discussed, owing to their anti-Stokes shifted narrow emission bands, chemical inertness, photostability, and long luminescence lifetimes (> 100 μs). Since FRET is distance dependent, the diameter of the particles is expected to affect the FRET efficiency. In order to identify the ideal particle architecture for FRET-based applications, we performed a systematic spectroscopic study of the influence of the UCNP size on the energy transfer using the organic dyes rose bengal and sulforhodamine B acting as model FRET acceptors for the green upconversion emission. High-quality Yb,Er-doped UCNPs with precisely controlled diameters between 10 and 43 nm were prepared using a high temperature synthesis. The monodisperse, oleate-capped particles were directly modified with the organic dyes by a two-step ligand exchange procedure, resulting in the shortest possible donor-acceptor distance. Successful FRET was demonstrated through the simultaneous drastic reduction of the luminescence intensity and the lifetime of the respective upconversion emission. In contrast to intensity measurements, time-resolved studies on both donor and acceptor luminescence allowed for the elimination of dependencies on excitation power density and particle concentration and for the discrimination between inner filter effects and FRET. The maximum FRET efficiency was observed at a particle diameter around 21 nm, which was attributed to an increasing fraction of the total amount of Er3+ donors inside the UCNPs being within Förster distance. Smaller UCNP diameters did not further improve the FRET efficiency, demonstrating the growing contribution of opposing effects, like the competition of non-radiative surface deactivation, at larger surface-to-volume ratios. This comprehensive understanding of energy transfer processes at the surface of UCNPs is essential for the rational design of upconversion FRET platforms for applications in sensing, imaging, and theranostics with improved sensitivity, reliability and comparability. The energy transfer can also be utilized to shift the luminescence emission by the choice of the organic dye in order to explore applications that require specific emission wavelengths due to interfering substances, while still making use of the advantages of near-infrared excitation. T2 - Material Research Society - Spring Meeting CY - Phoenix, Arizona, USA DA - 17.04.2017 KW - Upconversion KW - FRET KW - Organic dyes PY - 2017 AN - OPUS4-40096 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Kraft, Marco T1 - Particle size dependent optical properties of hexagonal β-NaYF4: 2 % Er3+, 20 % Yb3+ upconversion nanoparticles in cyclohexane and water N2 - Hexagonal NaYF4 doped with 20 % Yb3+ and 2 % Er3+ is an efficient upconversion (UC) phosphor for the conversion of 976 nm excitation light to emission at 845 nm, 800 nm, 655 nm, 540 nm and 410 nm light. The emission behavior of nanoparticles made from this material is strongly influenced by particle size, surface chemistry, and microenvironment. Furthermore their UC emission originates from multiphotonic absorption processes, rendering the resulting luminescence spectra and intensities excitation power density (P) dependent. Therefore the rational design of efficient nm-sized UC particles e.g., for applications in the material and life sciences requires reliable spectroscopic tools for the characterization of the optical properties of these materials like the excitation power density (P)-dependent UC quantum yield (QYUC) in dispersion, which presents a measure for the efficiency of the conversion of absorbed into emitted photons. Up to date the P-dependent absolute measurement of QYUC in aqueous media with an excitation wavelength of 976 nm presents a considerable challenge due to the low absorption coefficients of the UC materials and the absorption of water at this wavelength. T2 - International Conference on Advanced Materials and Nanotechnology CY - Queenstown, New Zealand DA - 12.02.2017 KW - Upconversion KW - Quantum yield KW - Lifetime KW - Water KW - Cyclohexane PY - 2017 AN - OPUS4-40093 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Muhr, V. A1 - Würth, Christian A1 - Kraft, Marco A1 - Buchner, M. A1 - Baeumner, A. J. A1 - Resch-Genger, Ute A1 - Hirsch, T. T1 - Particle-size-dependent Förster resonance energy transfer from upconversion nanoparticles to organic dyes N2 - Upconversion nanoparticles (UCNPs) are attractive candidates for energy transfer-based analytical applications. In contrast to classical donor−acceptor pairs, these particles contain many emitting lanthanide ions together with numerous acceptor dye molecules at different distances to each other, strongly depending on the particle diameter. UCNPs with precisely controlled sizes between 10 and 43 nm were prepared and functionalized with rose bengal and sulforhodamine B by a ligand-exchange procedure. Timeresolved studies of the upconversion luminescence of the UCNP donor revealed a considerable shortening of the donor lifetime as a clear hint for Förster resonance energy transfer (FRET). FRET was most pronounced for 21 nm-sized UCNPs, yielding a FRET efficiency of 60%. At larger surface-to-volume ratios, the FRET efficiency decreased by an increasing competition of nonradiative surface deactivation. Such dye-UCNP architectures can also provide an elegant way to shift the UCNP emission color, since the fluorescence intensity of the organic dyes excited by FRET was comparable to that of the upconversion emission of smaller particles. KW - Upconversion KW - FRET KW - Organic dyes PY - 2017 DO - https://doi.org/10.1021/acs.analchem.6b04662 SN - 0003-2700 SN - 1520-6882 VL - 89 IS - 9 SP - 4868 EP - 4874 PB - ACS AN - OPUS4-40092 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Wiesholler, L. M. T1 - Core-shell- Nd3+ - doped upconversion nanoparticles with enhanced luminescence properties for bioanalytical applications N2 - Upconversion nanoparticles are characterized by their ability to convert low energy near-infrared excitation in high energy emissions in the visible range. This is enabled by sequential absorption of two or more photons via energy transfer from the sensitizer lanthanide ion Yb3+ to an activator lanthanide ion, e.g. Er3+. Yb3+ sensitation has the advantage of 980 nm excitation achieved by commercial available low power cw laser modules. Nevertheless, for some applications, especially in aqueous media, which is predominantely in bioanalytical applications, there is the drawback of a local Absorption maximum of water at this wavelength. Sample heating can occur, and excitation power density is strongly distance dependent. To overcome this issue, the idea is to shift the excitation wavelength to 808 nm. This can be achieved by a tandem-excitation using Nd3+ and Yb3+ ions. Nd3+ gets excited by 808 nm irradiation and transfers the energy to Yb3+, which triggers the upconversion emission of the Er3+ ions. Therefore, it is mandatory to separate Nd3+ and Er3+ by core-shell architecture for reducing the energy backtransfer from Er3+ to Nd3+. To further enhance the upconversion luminescence an additional inert shell formed by the host material NaYF4 reduces the quenching effects caused by surface defects and dangling bonds. T2 - MRS Spring Meeting CY - Phoenix, Arizona, USA DA - 17-21. April KW - Core-shell KW - Upconversion KW - Nd3+ PY - 2017 AN - OPUS4-40035 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Würth, Christian T1 - Absolute quantum yield measurements of spectral conversion materials - Instrumentation and applications N2 - The direct measure for the conversion efficiency of absorbed photons into emitted light by an emissive species or chromophore is the photoluminescence quantum yield (pl).1 pl is the fluorometric key quantity that controls the suitability of a molecule or material e.g. for application as a label, probe or sensor molecule or as a converter material. A straightforward approach to pl values presents their absolute determination using an integrating sphere set up. This procedure circumvents the use of standards thereby avoiding additional measurements and uncertainties related to their often debated pl values. In this respect, we discuss the experimental requirements on absolute measurements of down and upconversion quantum yields (UC), the later presents currently one of the most challenging spectroscopic measurements due to its multiphotonic character. We explore the challenges for determination of excitation power density (P) dependent pl(P), present the design and characterization of a unique integrating sphere setup for such measurements in the vis to IR spectral region including its calibration, and the influence of the excitation beam profile to perform pl measurements of liquid and solid materials. As an example for downshifting materials we present doped core-shell CdSe/ZnS semiconductor quantum dots (d-dots) which show a nearly host material and crystal size independent emission with large Stokes shifts and minimum reabsorption.2 Systematic variation of the reaction components, parameters and thickness of the ZnS shell yielded doped nanocrystals with a very high pl, high reproducibility and large quantities. Application of these NCs in the light conversion layers of commercial monocrystalline silicon (mono-Si) solar cells led to a significant enhancement of the external quantum efficiency (EQE) of this devices in the ultraviolet spectral region between 300 and 400 nm. On the other hand, lanthanide-doped up-converting nanoparticles (UCNPs), are promising light converters from the near infrared to the visible region. These NPs show multiple narrow emission bands in the visible (vis) and NIR, excellent photostability, and long luminescence lifetimes. The rational design of brighter UCNP requires an improved understanding of the radiationless deactivation pathways, that are affected by size, surface chemistry, and microenvironment.3 We give an insight into the influences of these parameters on the photophysical key characteristics of the upconversion process such as UC(P), the luminescence decay behavior, the power dependent red-to-green intensity ratio, and intensities of the individual emission bands. T2 - MCare-Materials Challenges in Alternative and Renewable Energy CY - Jeju, Korea DA - 20.02.2017 KW - Energy conversion KW - Quantum yield KW - Doped quantum dots KW - Upconversion PY - 2017 AN - OPUS4-40009 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Würth, Christian T1 - Theory of quantum yields - Excitation power dependent measurements N2 - Introduction to power dependent QY-measurements and upconversion T2 - Cost-action Training school CY - Turku, Finland DA - 03.04.2017 KW - Quantum yield KW - Upconversion PY - 2017 AN - OPUS4-40011 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Näreoja, T A1 - Deguchi, T A1 - Christ, S. A1 - Peltomaa, R A1 - Prabhakar, N A1 - Fazeli, E A1 - Perälä, N A1 - Rosenholm, J A1 - Arppe, Riika A1 - Soukka, T A1 - Schäferling, Michael T1 - Ratiometric Sensing and Imaging of Intracellular pH Using Polyethylenimine-Coated Photon Upconversion Nanoprobes N2 - Measurement of changes of pH at various intracellular compartments has potential to solve questions concerning the processing of endocytosed material, regulation of the acidification process, and also acidification of vesicles destined for exocytosis. To monitor these events, the nanosized optical pH probes need to provide ratiometric signals in the optically transparent biological window, target to all relevant intracellular compartments, and to facilitate imaging at subcellular resolution without interference from the biological matrix. To meet these criteria we sensitize the surface conjugated pH sensitive indicator via an upconversion process utilizing an energy transfer from the nanoparticle to the indicator. Live cells were imaged with a scanning confocal microscope equipped with a low-energy 980 nm laser excitation, which facilitated high resolution and penetration depth into the specimen, and low phototoxicity needed for long-term imaging. Our upconversion nanoparticle resonance energy transfer based sensor with polyethylenimine-coating provides high colloidal stability, enhanced cellular uptake, and distribution across cellular compartments. This distribution was modulated with membrane integrity perturbing treatment that resulted into total loss of lysosomal compartments and a dramatic pH shift of endosomal compartments. These nanoprobes are well suited for detection of pH changes in in vitro models with high biological background fluorescence and in in vivo applications, e.g., for the bioimaging of small animal models. KW - PH sensing KW - Upconversion KW - Nanoparticles KW - Fluorescecne imaging PY - 2017 UR - http://pubs.acs.org/doi/abs/10.1021/acs.analchem.6b03223 DO - https://doi.org/10.1021/acs.analchem.6b03223 SN - 0003-2700 SN - 1520-6882 VL - 89 IS - 3 SP - 1501 EP - 1508 PB - American Chemical Society CY - Washington AN - OPUS4-39083 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Würth, Christian T1 - Setup for the power-dependent absolute quantum yield measurements of luminescent reporters in the VIS and IR spectral region: example of upconversion nanoparticles N2 - The design of bright of upconversion nanoparticles requires an improved understanding of the radiationless deactivation pathways in UCNP, that are affected by their size1,2, surface chemistry,2 and microenvironment 3,4. In this respect, we discuss experimental requirements of an integrating sphere setup for absolute measurements of the excitation power density dependent quantum yield5,6 (UC(P)) in the VIS to IR spectral region. We report systematic studies of the influence of the UCNP size, surface ligands, and solvent on the UC(P), the up- and downconversion luminescence decay behavior, the power dependent intensities of the individual emission bands, and their slope factors. T2 - SPIE Photonics West CY - San Francisco, USA DA - 11.02.2016 KW - Upconversion KW - Quantum Yield PY - 2016 AN - OPUS4-38406 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Würth, Christian T1 - Setup for the power-dependent absolute quantum yield measurements: example of upconversion nanoparticles N2 - Lanthanide-doped up-converting nanoparticles (UCNPs), are promising reporters for bioanalysis and theranostics, which are excitable in the near infrared (NIR) by multiphoton absorption processes, and show multiple narrow emission bands in the visible (vis) and NIR, excellent photostability, and long luminescence lifetimes in the µs range. The rational design of brighter UCNP requires an improved understanding of the radiationless deactivation pathways in UCNP, that are affected by size, surface chemistry, and microenvironment. In this respect, we discuss the experimental requirements on absolute measurements of the upconversion quantum yield and its excitation radiant power density dependence and present the design and characterization of unique integrating sphere setup for such measurements in the vis to IR spectral region including its calibration, the influence of the excitation beam profile and solutions to perform such measurements in aqueous media. T2 - Upcon2016 CY - Breslau, Poland DA - 23.05.2016 KW - Upconversion KW - Quantum yield KW - Nanoparticle PY - 2016 AN - OPUS4-38409 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Kraft, Marco T1 - Particle Size Dependent Absolute Photoluminescence Quantum Yields and Lifetimes of Hexagonal beta-NaYF4: 2 % Er3+, 20 % Yb3+ Upconversion Nanoparticles in Cyclohexane and Water N2 - Hexagonal beta-NaYF₄ doped with 20 % Yb and 2 % Er is an efficient upconversion (UC) phosphor for the conversion of 976 nm to 845 nm, 655 nm and 540 nm light. The emission behavior of this material is strongly influenced by the particle size, surface chemistry, and microenvironment. Especially the design of nm-sized UC particles for bioanalytical applications requires reliable spectroscopic tools for the characterization of the optical properties of these materials like the UC quantum yield (QYUC) in aqueous media. The UC emission originates from multiphotonic absorption processes, rendering the QYUC excitation power density (P) dependent. The P-dependent absolute measurement of QYUC in aqueous media with an excitation wavelength of 976 nm presents a considerable challenge due to the low absorption coefficients of the UC materials and the absorption of water at this wavelength. Here, we present the P-dependent QYUC of 21 nm, 26 nm and 31 nm-sized NaYF₄ UC particles dispersed in cyclohexane and aqueous solutions, in view of bioanalytical applications. To gain a better insight of the photonic nature of the upconversion mechanism and the quenching processes involved, the luminescence decay behavior as well as the P-dependent red-to-green luminescence intensity ratios and slope factors of the different emission bands are studied in both solvents. These results present an important step to the rational design of brighter upconversion nanoparticles. T2 - UPCON conference 2016 CY - Wroclaw, Poland DA - 23.05.2016 KW - Water KW - Upconversion KW - Quantum Yield KW - Lifetime KW - Cyclohexane PY - 2016 AN - OPUS4-38131 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Frenzel, Florian T1 - Spectroscopic study of plasmon enhanced upconversion nanoparticles N2 - The presentation gave an overview of the topic, the aims and the task allocation of the M-ERA.NET founded project named “Nanohype”. In this project four research teams working hand in hand on computational modeling, synthesis and experimental validation to design novel metal-shelled Upconversion-NP combining plasmonic interactions. As Ph.D. student at the BAM I am responsible for the optical characterization (measurements of lifetimes, Quantum Yields and PL emissions ) of these promising novel systems. T2 - SpringSchool, UpCon2016 CY - Wrocław (Breslau), Polen DA - 25.05.2016 KW - Field Enhancement KW - Upconversion KW - Core-Shell KW - FRET KW - Plasmonic PY - 2016 AN - OPUS4-37225 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Zhang, X.-X. A1 - Würth, Christian A1 - Zhao, L. A1 - Resch-Genger, Ute A1 - Ernsting, N.P. T1 - Femtosecond broadband fluorescence upconversion spectroscopy: improved setup and photometric correction N2 - A setup for fluorescence upconversion spectroscopy (FLUPS) is described which has 80 fs temporal response (fwhm) for emission in the spectral range 425–750 nm. Broadband phase matching is achieved with tilted gate pulses at 1340 nm. Background from harmonics of the gate pulse is removed and sensitivity increased compared to previous designs. Photometric calibration of the upconversion process is performed with a set of fluorescent dyes. For Coumarin 153 in methanol the peak position, bandwidth, and asymmetry depending on delay time are reported. KW - Calibration KW - Fluorescence spectroscopy KW - Fluorescence KW - Upconversion KW - Standard KW - Spectral responsivity KW - Time-resolved fluorescence KW - Quality assurance KW - Coumarin 153 KW - Solvation dynamics PY - 2011 DO - https://doi.org/10.1063/1.3597674 SN - 0034-6748 SN - 1089-7623 VL - 82 SP - 063108-1 EP - 063108-8 PB - American Institute of Physics CY - Melville, NY AN - OPUS4-23886 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -