Nanoscale Chemical Analysis of Thin Film Solar Cell Interfaces Using Tip-Enhanced Raman Spectroscopy.

Interfacial regions play a key role in determining the overall power conversion efficiency of thin film solar cells. However, the nanoscale investigation of thin film interfaces using conventional analytical tools is challenging due to a lack of required sensitivity and spatial resolution. Here, we surmount these obstacles using tip-enhanced Raman spectroscopy (TERS) and apply it to investigate the absorber (Sb2Se3) and buffer (CdS) layers interface in a Sb2Se3-based thin film solar cell. Hyperspectral TERS imaging with 10 nm spatial resolution reveals that the investigated interface between the absorber and buffer layers is far from uniform, as TERS analysis detects an intermixing of chemical compounds instead of a sharp demarcation between the CdS and Sb2Se3 layers. Intriguingly, this interface, comprising both Sb2Se3 and CdS compounds, exhibits an unexpectedly large thickness of 295 ± 70 nm attributable to the roughness of the Sb2Se3 layer. Furthermore, TERS measurements provide compelling evidence of CdS penetration into the Sb2Se3 layer, likely resulting from unwanted reactions on the absorber surface during chemical bath deposition. Notably, the coexistence of ZnO, which serves as the uppermost conducting layer, and CdS within the Sb2Se3-rich region has been experimentally confirmed for the first time. This study underscores TERS as a promising nanoscale technique to investigate thin film inorganic solar cell interfaces, offering novel insights into intricate interface structures and compound intermixing.

Optimization of quasi-hemispherical CdZnTe detectors by means of first principles simulation.

In this paper we present the development of quasi-hemispherical gamma-ray detectors based on CdZnTe. Among the possible single-polarity electrode configurations, such as coplanar, pixelated, or virtual Frisch-grid geometries, quasi-hemispherical detectors are the most cost-effective alternative with comparable raw energy resolution in the high and low energy range. The optimal configuration of the sensor in terms of dimension of the crystals and electrode specifications has been first determined by simulations, and successively validated with experimental measures. Spectra from different sources have been acquired to evaluate the detectors performances. Three types of detectors with different CZT volumes have been fabricated, namely 10 × 10 × 5 mm3, 15 × 15 × 10 mm3 and 20 × 20 × 10 mm3. In the case of 10 × 10 × 5 mm3 crystals, the optimum pixel size determined by our simulation tool was confirmed by experiments: the best spectroscopic resolution of 1.3% at 662 keV has been found for a 750 µm diameter pixel detector. The best energy resolution values obtained for the 15 × 15 × 10 mm3 and 20 × 20 × 10 mm3 detectors were respectively 1.7% and 2.7% at 662 keV.

Exploring Cu-Doping for Performance Improvement in Sb2Se3 Photovoltaic Solar Cells.

Copper-doped antimony selenide (Cu-doped Sb2Se3) thin films were deposited as absorber layers in photovoltaic solar cells using the low-temperature pulsed electron deposition (LT-PED) technique, starting from Sb2Se3 targets where part of the Sb was replaced with Cu. From a crystalline point of view, the best results were achieved for thin films with about Sb1.75Cu0.25Se3 composition. In order to compare the results with those previously obtained on undoped thin films, Cu-doped Sb2Se3 films were deposited both on Mo- and Fluorine-doped Tin Oxide (FTO) substrates, which have different influences on the film crystallization and grain orientation. From the current-voltage analysis it was determined that the introduction of Cu in the Sb2Se3 absorber enhanced the open circuit voltage (VOC) up to remarkable values higher than 500 mV, while the free carrier density became two orders of magnitude higher than in pure Sb2Se3-based solar cells.

Fabrication of Small-Pixel CdZnTe Sensors and Characterization with X-rays.

Over the past few years, sensors made from high-Z compound semiconductors have attracted quite some attention for use in applications which require the direct detection of X-rays in the energy range 30-100 keV. One of the candidate materials with promising properties is cadmium zinc telluride (CdZnTe). In the context of this article, we have developed pixelated sensors from CdZnTe crystals grown by Boron oxide encapsulated vertical Bridgman technique. We demonstrate the successful fabrication of CdZnTe pixel sensors with a fine pitch of 55 m and thickness of 1 mm and 2 mm. The sensors were bonded on Timepix readout chips to evaluate their response to X-rays provided by conventional sources. Despite the issues related to single-chip fabrication procedure, reasonable uniformity was achieved along with low leakage current values at room temperature. In addition, the sensors show stable performance over time at moderate incoming fluxes, below 106 photons mm-2s-1.

All-Inorganic CsPbBr3 Perovskite Films Prepared by Single Source Thermal Ablation.

Hybrid organo-lead halide perovskites are becoming the benchmark material for next generation photovoltaics and a very important player for other applications such as photodetectors and light emitting diodes. Nevertheless, the most important issue hindering the large-scale application of these materials remains their intrinsic instability due to the organic cation. Although the substitution with inorganic cesium (Cs) enhances stability, in most cases solution deposition methods of fully inorganic perovskites result in high surface roughness and poor surface coverage. This work reports on the evaporation of the CsPbBr3 precursor by Single Source Thermal Ablation, showing that just after deposition films consist of a mixture of CsPbBr3, CsPb2Br5, and Cs4PbBr6 due to a vertical composition gradient. We point out that mild post deposition treatments lead to the conversion of CsPb2Br5 and Cs4PbBr6 into CsPbBr3 due to its higher thermodynamic stability. Conversion results into smooth and pinhole-free CsPbBr3 films with good light absorption and emission properties. We demonstrate the suitability of obtained films for planar devices by preparing perovskite-based pure-green light emitting diodes, thus promoting Single Source Thermal Ablation as a promising alternative deposition technique for all-inorganic perovskite-based devices.

Sub-Micropillar Spacing Modulates the Spatial Arrangement of Mouse MC3T3-E1 Osteoblastic Cells.

Surface topography is one of the main factors controlling cell responses on implanted devices and a proper definition of the characteristics that optimize cell behavior may be crucial to improve the clinical performances of these implants. Substrate geometry is known to affect cell shape, as cells try to optimize their adhesion by adapting to the irregularities beneath, and this in turn profoundly affects their activity. In the present study, we cultured murine calvaria MC3T3-E1 cells on surfaces with pillars arranged as hexagons with two different spacings and observed their morphology during adhesion and growth. Cells on these highly ordered substrates attached and proliferated effectively, showing a marked preference for minimizing the inter-pillar distance, by following specific pathways across adjacent pillars and displaying consistent morphological modules. Moreover, cell behavior appeared to follow tightly controlled patterns of extracellular protein secretion, which preceded and matched cells and, on a sub-cellular level, cytoplasmic orientation. Taken together, these results outline the close integration of surface features, extracellular proteins alignment and cell arrangement, and provide clues on how to control and direct cell spatial order and cell morphology by simply acting on inter-pillar spacing.

Analytical approaches for the characterization and quantification of nanoparticles in food and beverages.

Estimating consumer exposure to nanomaterials (NMs) in food products and predicting their toxicological properties are necessary steps in the assessment of the risks of this technology. To this end, analytical methods have to be available to detect, characterize and quantify NMs in food and materials related to food, e.g. food packaging and biological samples following metabolization of food. The challenge for the analytical sciences is that the characterization of NMs requires chemical as well as physical information. This article offers a comprehensive analysis of methods available for the detection and characterization of NMs in food and related products. Special attention was paid to the crucial role of sample preparation methods since these have been partially neglected in the scientific literature so far. The currently available instrumental methods are grouped as fractionation, counting and ensemble methods, and their advantages and limitations are discussed. We conclude that much progress has been made over the last 5 years but that many challenges still exist. Future perspectives and priority research needs are pointed out. Graphical Abstract Two possible analytical strategies for the sizing and quantification of Nanoparticles: Asymmetric Flow Field-Flow Fractionation with multiple detectors (allows the determination of true size and mass-based particle size distribution); Single Particle Inductively Coupled Plasma Mass Spectrometry (allows the determination of a spherical equivalent diameter of the particle and a number-based particle size distribution).

Nanoscale mapping of plasmon and exciton in ZnO tetrapods coupled with Au nanoparticles.

Metallic nanoparticles can be used to enhance optical absorption or emission in semiconductors, thanks to a strong interaction of collective excitations of free charges (plasmons) with electromagnetic fields. Herein we present direct imaging at the nanoscale of plasmon-exciton coupling in Au/ZnO nanostructures by combining scanning transmission electron energy loss and cathodoluminescence spectroscopy and mapping. The Au nanoparticles (~30 nm in diameter) are grown in-situ on ZnO nanotetrapods by means of a photochemical process without the need of binding agents or capping molecules, resulting in clean interfaces. Interestingly, the Au plasmon resonance is localized at the Au/vacuum interface, rather than presenting an isotropic distribution around the nanoparticle. On the contrary, a localization of the ZnO signal has been observed inside the Au nanoparticle, as also confirmed by numerical simulations.

Modeling, Fabrication and Testing of a Customizable Micromachined Hotplate for Sensor Applications.

In the sensors field the active sensing material frequently needs a controlled temperature in order to work properly. In microsystems technology, micro-machined hotplates represent a platform consisting of a thin suspended membrane where the sensing material can be deposited, usually integrating electrical stimuli and temperature readout. The micro-hotplate ensures a series of advantages such as miniaturized size, fast response, high sensitivity, low power consumption and selectivity for chemical sensing. This work compares the coplanar and the buried approach for the micro-hotplate heaters design with the aim to optimize the fabrication process and to propose a guideline for the choice of the suitable design with respect to the applications. In particular, robust Finite Element Method (FEM) models are set up in order to predict the electrical and thermal behavior of the micro-hotplates. The multiphysics approach used for the simulation allows to match as close as possible the actual device to the predictive model: geometries, materials, physics have been carefully linked to the fabricated devices to obtain the best possible accuracy. The materials involved in the fabrication process are accurately selected in order to improve the yield of the process and the performance of the devices. The fabricated micro-hotplates are able to warm the active region up to 400 °C (with a corresponding power consumption equal to 250 mW @ 400 °C) with a uniform temperature distribution in the buried micro-hotplate and a controlled temperature gradient in the coplanar one. A response time of about 70 ms was obtained on the virtual model, which perfectly agrees with the one measured on the fabricated device. Besides morphological, electrical and thermal characterizations, this work includes reliability tests in static and dynamic modes.

Microtexturing of the conductive PEDOT:PSS polymer for superhydrophobic organic electrochemical transistors.

Superhydrophobic surfaces are bioinspired, nanotechnology artifacts, which feature a reduced friction coefficient, whereby they can be used for a number of very practical applications including, on the medical side, the manipulation of biological solutions. In this work, we integrated superhydrophobic patterns with the conducting polymer PEDOT:PSS, one of the most used polymers in organic electronics because highly sensitive to ionized species in solution. In doing so, we combined geometry and materials science to obtain an advanced device where, on account of the superhydrophobicity of the system, the solutions of interest can be manipulated and, on account of the conductive PEDOT:PSS polymer, the charged molecules dispersed inside can be quantitatively measured. This original substrate preparation allowed to perform electrochemical measurements on ionized species in solution with decreasing concentration down to 10(-7) molar. Moreover, it was demonstrated the ability of the device of realizing specific, combined time and space resolved analysis of the sample. Collectively, these results demonstrate how a tight, interweaving integration of different disciplines can provide realistic tools for the detection of pathologies. The scheme here introduced offers breakthrough capabilities that are expected to radically improve both the pace and the productivity of biomedical research, creating an access revolution.

Human stress monitoring through an organic cotton-fiber biosensor.

Selective detection of bioanalytes in physiological fluids, such as blood, sweat or saliva, by means of low-cost and non-invasive devices, is of crucial importance to improve diagnosis and prevention in healthcare. To be really useful in everyday life a sensing system needs to be handy, non-invasive, easy to read and possibly wearable. Only a sensor that satisfies these requirements could be eligible for applications in healthcare and physiological condition monitoring. Herein an organic electrochemical transistor has been investigated as a simple, low-cost and e-textile biosensor, fully integrated on a single cotton yarn. The biosensor has been used for real-time detection of adrenaline, selectively compared to the saline content in human physiological fluids. The sensing mechanism is based on the oxidation of adrenaline at the Pt-gate electrode surface, with the formation of adrenaline-quinone and adrenochrome. Two independent organic electrochemical transistors, characterized by different gate-electrode materials, detect saline and adrenaline concentrations, respectively, in real human sweat. Measurements performed in real-time mode show the complete independence of adrenaline detection from NaCl and, hence, guarantee the simultaneous monitoring of both concentrations. The oxidation of adrenaline has been studied by means of absorption spectroscopy in air, with either silver or platinum working electrodes. Our results confirm that the oxidation reaction driven by the Pt-electrode leads to the formation of adrenochrome, while with the Ag-electrode the oxidation is similar to the spontaneous one occurring in air. The cotton-based biosensor shows the possibility of monitoring human performances (hydration and stress) in situ and using a non-invasive approach, opening new unexplored opportunities in healthcare, fitness and work safety.

Low temperature sensing properties of a nano hybrid material based on ZnO nanotetrapods and titanyl phthalocyanine.

ZnO nanotetrapods have recently been exploited for the realization of high-sensitivity gas sensors, but they are affected by the typical drawbacks of metal-oxides, i.e., poor selectivity and a relatively high working temperature. On the other hand, it has been also demonstrated that the combined use of nanostructured metal oxides and organic molecules can improve the gas sensing performance sensitivity or selectivity, even at lower temperatures. A gas sensor device, based on films of interconnected ZnO nanotetrapods properly functionalized by titanyl phthalocyanine (TiOPc), has been realized in order to combine the high surface to volume ratio and structural stability of the crystalline ZnO nanostructures with the enhanced sensitivity of the semiconducting TiOPc molecule, especially at low temperature. The electronic properties of the resulting nanohybrid material are different from those of each single component. The response of the hybrid nanostructure towards different gases has been compared with that of ZnO nanotetrapod without functionalization in order to highlight the peculiar properties of the hybrid interaction(s). The dynamic response in time has been studied for different gases and temperatures; in particular, an increase in the response to NO2 has been observed, even at room temperature. The formation of localized p-n heterojunctions and the possibility of exchanging charge carriers at the hybrid interface is shown to be crucial for the sensing mechanism.

Mesoporous single-crystal ZnO nanobelts: supported preparation and patterning.

We demonstrate that highly porous ZnO nanobelts can be prepared by thermally decomposing ZnS(en)(0.5) hybrid nanobelts (NBs) synthesized through a solvothermal route using Zn layers deposited on alumina substrates as both the Zn substrate and source. Hybrid decomposition by thermal annealing at 400 °C gives porous ZnS NBs that are transformed by further annealing at 600 °C into wurtzite single crystal ZnO nanobelts with an axial direction of [0001]. The evolution of the morphological and structural transformation ZnS(en)(0.5)→ ZnS → ZnO is investigated at the nanoscale by transmission and scanning electron microscopy analyses. Control of the ZnO NB distributions by patterning the Zn metallization on alumina is achieved as a consequence of the parent hybrid NB patterned growth. The presence of NBs on alumina in a ∼100 µm wide region between Zn stripes allows us to fabricate two contact devices where contact pads are electrically connected through a porous ZnO NB entanglement. Such devices are suitable for employment in photodetectors as well as in gas and humidity sensors.

Unpredicted nucleation of extended zinc blende phases in wurtzite ZnO nanotetrapod arms.

Tailoring the structural and electronic properties of 3D nanostructures via bottom-up techniques would pave the way for novel low-cost applications. One of such possibilities is offered by ZnO branched nanostructures like tetrapods, that have recently attracted attention for nanodevice applications from nanoelectronics to drug delivery. The conventional picture is that ZnO arms are thermodynamically stable only in the wurtzite phase. Here, we provide the first experimental evidence of unpredicted extended zinc blend phases (50-60 nm long) embedded in the arms of ZnO wurtzite tetrapods. In particular, decisive evidence is obtained from the one-to-one correlation between high lateral resolution cathodoluminescence spectroscopy, monochromatic contrast maps, and atomic resolution transmission electron microscopy images of ZnO single TPs. This observation is not specific to ZnO and can have a general validity for the understanding of the nucleation mechanisms in semiconducting 3D nanostructures for device applications.

Large-area self-catalysed and selective growth of ZnO nanowires.

A simple procedure to selectively grow zinc oxide nanowires (ZnO NWs) on a large scale without any catalyst is reported. The process is based on the use of a zinc metal layer deposited onto substrates before the NW growth. The zinc layer, which becomes liquid at the synthesis temperature, favours the correct local conditions for a selective growth of pure ZnO NWs in an effective area of several square centimetres (up to 20 cm(2) in our laboratory-scale reactor). The proposed method is suitable for patterned ZnO NW synthesis.