Megaelectronvolt-Secondary Ion Mass Spectrometry (MeV-SIMS) is an emerging Ion Beam Analysis technique for molecular speciation and submicron imaging. Various setups have been constructed in the ...recent years. Still a systematic investigation on the dependence of MeV-SIMS yields on different ion beam parameters is missing. A reliable measurement method of the beam current down to the attoampere range is needed for this investigation. Therefore, a new detector has been added to the MeV-SIMS setup at the Ruđer Bošković Institute (RBI), which measures the current directly using a Si PIN-diode. In this work, we present the constructed system, its characteristics, and results of the first yield measurements. These measurements have already identified important factors that have to be considered while constructing a MeV SIMS setup.
Full text
Available for:
GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK, ZRSKP
Graphene is an ideal material for biosensors due to the large surface area for multiple bonding sites, the high electrical conductivity allowing for high sensitivity, and the high tensile strength ...providing durability in fabricated sensor devices. For graphene to be successful as a biosensing platform, selectivity must be achieved through functionalization with specific chemical groups. However, the device performance and sensor sensitivity must still be maintained after functionalization, which can be challenging. We compare phenyl amine and 1,5-diaminonaphthalene functionalization methods for chemical vapor deposition grown graphene, both used to obtain graphene modified with amine groups-which is required for surface attachment of highly selective antibody bio-receptors. Through atomic force microscopy (AFM), Raman spectroscopy, and time-of-flight secondary ion mass spectrometry imaging of co-located areas, the chemistry, thickness, and coverage of the functional groups bound to the graphene surface have been comprehensively analyzed. We demonstrate the modification of functionalized graphene using AFM, which unexpectedly suggests the removal of covalently bonded functional groups, resulting in a "recovered" graphene structure with reduced disorder, confirmed with Raman spectroscopy. This removal explains the decrease in the I
/I
ratio observed in Raman spectra from other studies on functionalized graphene after mechanical strain or a chemical reaction and reveals the possibility of reverting to the non-functionalized graphene structure. Through this study, preferred functionalization processes are recommended to maintain the performance properties of graphene as a biosensor.
Organic‐inorganic hybrid semiconductors are an emerging class of materials for direct conversion X‐ray detection due to attractive characteristics such as high sensitivity and the potential to form ...conformal detectors. However, existing hybrid semiconductor X‐ray detectors display dark currents that are 1000–10 000× higher than industrially relevant values of 1–10 pA mm−2. Herein, ultra‐low dark currents of <10 pA mm−2, under electric fields as high as ≈4 V µm−1, for hybrid X‐ray detectors consisting of bismuth oxide nanoparticles (for enhanced X‐ray attenuation) incorporated into an organic bulk heterojunction consisting of p‐type Poly(3‐hexylthiophene‐2,5‐diyl) (P3HT) and n‐type 6,6‐Phenyl C71 butyric acid methyl ester (PC70BM) are reported. Such ultra‐low dark currents are realized through the enrichment of the hole selective p‐type organic semiconductor near the anode contact. The resulting detectors demonstrate broadband X‐ray response including an exceptionally high sensitivity of ≈1.5 mC Gy−1 cm−2 and <6% variation in angular dependence response under 6 MV hard X‐rays. The above characteristics in combination with excellent dose linearity, dose rate linearity, and reproducibility over a broad energy range enable these detectors to be developed for medical and industrial applications.
Organic‐Inorganic hybrid systems are a promising class of materials for X‐ray detection. However, their performance is restricted by high dark currents. This work introduces a methodology to achieve hybrid X‐ray detectors with ultra‐low dark currents through enrichment of the p‐type semiconductor at the absorber/anode interface.
Full text
Available for:
BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
We have observed that sperm quality parameters indicative of spermatozoa hyperactivation such are lower "linearity" and "straightness", and as showed by this research "elongation", were more ...pronounced in patients with normal spermiogram compared to the group of men with reduced sperm motility who were undergoing routine in vitro fertilisation. The research encompassed 97 men diagnosed with normozoospermia (n = 20), asthenozoospermia (n = 54) and oligoasthenozoospermia (n = 23). The findings indicate that sperm quality of patients with normal spermiogram diagnosed according to WHO criteria, may be compromised by showing premature spontaneous hyperactivation which can decrease the chances of natural conception. We assessed synergistic effects of multiple chemical elements in ejaculated semen to find if premature spontaneous hyperactivation of spermatozoa can be a sign of imbalanced semen composition especially of elements K, Ca, Cu and Zn. Human semen samples showing low or high baseline status of chemical elements concentrations were found in samples from all three diagnostic groups. However, correlation of K/Ca and Cu/Zn ratios, taking into account samples from all three groups of men, were negative at statistical significance level p = 0.01. We tested if the negative correlation between K/Ca and Cu/Zn ratio works for greater number of semen samples. We found the negative correlation to be valid for 175 semen samples at statistical significance of p = 0.00002. The ratio of K/Ca and Cu/Zn, i.e. increased concentrations of K and Zn in comparison to concentrations of Ca and Cu, were associated with a decrease of "straightness" in the group of men with normal spermiogram and pronounced spontaneous hyperactivation of spermatozoa, implying that these elements act in synergy and that the balance of elements and not their absolute concentrations plays the major role in premature spermatozoa hyperactivation in ejaculated semen.
Full text
Available for:
DOBA, IZUM, KILJ, NUK, PILJ, PNG, SAZU, SIK, UILJ, UKNU, UL, UM, UPUK
Understanding the degradation mechanism of organic light-emitting diodes (OLED) is essential to improve device performance and stability. OLED failure, if not process-related, arises mostly from ...chemical instability. However, the challenges of sampling from nanoscale organic layers and interfaces with enough analytical information has hampered identification of degradation products and mechanisms. Here, we present a high-resolution diagnostic method of OLED degradation using an Orbitrap mass spectrometer equipped with a gas cluster ion beam to gently desorb nanometre levels of materials, providing unambiguous molecular information with 7-nm depth resolution. We chemically depth profile and analyse blue phosphorescent and thermally-activated delayed fluorescent (TADF) OLED devices at different degradation levels. For OLED devices with short operational lifetimes, dominant chemical degradation mainly relate to oxygen loss of molecules that occur at the interface between emission and electron transport layers (EML/ETL) where exciton distribution is maximised, confirmed by emission zone measurements. We also show approximately one order of magnitude increase in lifetime of devices with slightly modified host materials, which present minimal EML/ETL interfacial degradation and show the method can provide insight for future material and device architecture development.
Organic semiconductors are a promising material candidate for X‐ray detection. However, the low atomic number (Z) of organic semiconductors leads to poor X‐ray absorption thus restricting their ...performance. Herein, the authors propose a new strategy for achieving high‐sensitivity performance for X‐ray detectors based on organic semiconductors modified with high –Z heteroatoms. X‐ray detectors are fabricated with p‐type organic semiconductors containing selenium heteroatoms (poly(3‐hexyl)selenophene (P3HSe)) in blends with an n‐type fullerene derivative (6,6‐Phenyl C71 butyric acid methyl ester (PC70BM). When characterized under 70, 100, 150, and 220 kVp X‐ray radiation, these heteroatom‐containing detectors displayed a superior performance in terms of sensitivity up to 600 ± 11 nC Gy−1 cm−2 with respect to the bismuth oxide (Bi2O3) nanoparticle (NP) sensitized organic detectors. Despite the lower Z of selenium compared to the NPs typically used, the authors identify a more efficient generation of electron‐hole pairs, better charge transfer, and charge transport characteristics in heteroatom‐incorporated detectors that result in this breakthrough detector performance. The authors also demonstrate flexible X‐ray detectors that can be curved to a radius as low as 2 mm with low deviation in X‐ray response under 100 repeated bending cycles while maintaining an industry‐standard ultra‐low dark current of 0.03 ± 0.01 pA mm−2.
Organic semiconductors are a promising class of materials for X‐ray detection. However, their performance has been restricted by poor X‐ray attenuation. This work introduces a methodology to achieve organic X‐ray detectors with high sensitivity via high Z heteroatom inclusion that leads to additional benefit of tissue equivalence and conformable functionality.
Full text
Available for:
FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Ambient Pressure MeV SIMS (AP MeV SIMS) is a special application of MeV SIMS technique for molecular detection and imaging under ambient conditions. There are several advantages of using ambient over ...non-ambient techniques such as minimising or completely avoiding sample preparation that can contribute to the reducing of costs and shortening of analysis. Moreover, by performing analysis in ambient conditions negative vacuum influence on samples will be avoided. The emergence of ambient mass spectrometry techniques over the past decade has been enormous with a broad range of applications such as food quality, environmental analysis and life sciences 1,2. On the other hand, the disadvantage of ambient pressure mass spectrometry techniques is the influence of the ambient background which can suppress the signal from the target. In AP MeV SIMS, molecular species present in ambient surrounding of the sampling site will also be ionised by ion beams hence secondary ions originating from the sample have to be transported in the most efficient manner from the site of interaction of ion beams and target into the mass spectrometer capillary and, finally, into the mass spectrometer 3. In this work, we present the optimisation of the mass spectrometer capillary temperature, distances of mass spectrometer and sheath gas, in our case helium, with respect to the beam axis and angle of the helium flow capillary with respect to the sample.
Full text
Available for:
GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
Lithium-ion batteries are the most ubiquitous energy storage devices in our everyday lives. However, their energy storage capacity fades over time due to chemical and structural changes in their ...components, via different degradation mechanisms. Understanding and mitigating these degradation mechanisms is key to reducing capacity fade, thereby enabling improvement in the performance and lifetime of Li-ion batteries, supporting the energy transition to renewables and electrification. In this endeavor, surface analysis techniques are commonly employed to characterize the chemistry and structure at reactive interfaces, where most changes are observed as batteries age. However, battery electrodes are complex systems containing unstable compounds, with large heterogeneities in material properties. Moreover, different degradation mechanisms can affect multiple material properties and occur simultaneously, meaning that a range of complementary techniques must be utilized to obtain a complete picture of electrode degradation. The combination of these issues and the lack of standard measurement protocols and guidelines for data interpretation can lead to a lack of trust in data. Herein, we discuss measurement challenges that affect several key surface analysis techniques being used for Li-ion battery degradation studies: focused ion beam scanning electron microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, and time-of-flight secondary ion mass spectrometry. We provide recommendations for each technique to improve reproducibility and reduce uncertainty in the analysis of NMC/graphite Li-ion battery electrodes. We also highlight some key measurement issues that should be addressed in future investigations.
Full text
Available for:
IJS, KILJ, NUK, PNG, UL, UM
In 2017, we introduced the OrbiSIMS instrument that features a dual analyser configuration with a time‐of‐flight (ToF) mass spectrometer (MS) and an Orbitrap MS, which confer advantages of speed and ...high‐performance mass spectrometry, respectively. The ability to combine the MS performance usually found in a state‐of‐the‐art proteomics and metabolomics MS with 3D imaging at the microscale and from nanolayers of <10 nm of material has proved popular in a broad field of application from organic electronics to drug discovery. There are now several instruments in operation around the world, and metrology is needed to help ensure repeatability and reproducibility of the intensity scale. We conduct a systematic study of two key parameters, the target potential, VT, and the collision cell pressure, P, in the transfer optics on the transmitted secondary ion intensities. We measure VT–P maps of the ions across the mass range for Ag as a representative of inorganic materials and two different organic materials, Irganox 1010 and NPB (N,N′‐Di1‐naphthyl‐N,N′‐diphenyl‐4,4′‐biphenyldiamine). The manufacturer's defaults for these values ensure very good transmission for a broad range of analyte classes. However, the maps reveal a sometimes complex behaviour and indicate the possibility for additional separation of ions based on their shape, labile nature and kinetics of formation. Guidance is provided on how to optimise these parameters for sensitivity for different material classes and also the need for optimisation to improve spectral repeatability and reproducibility.
Full text
Available for:
BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
10.
Featured Cover Matjacic, Lidija; Seah, Martin P.; Trindade, Gustavo F. ...
Surface and interface analysis,
April 2022, 2022-04-00, 20220401, Volume:
54, Issue:
4
Journal Article
Peer reviewed
The cover image is based on the Article Martin P Seah MBE – Shining a Light on Surface Chemical Analysis by Ian Gilmore et al., https://doi.org/sia.7058.
Full text
Available for:
BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
PDF
