Use Of X-ray Photoelectron Spectroscopy Research Articles

Sustainable and Cost-Efficient Production of Micro-Patterned Reduced Graphene Oxide on Graphene Oxide Films

This study tackles the critical demand for sustainable synthesis methods of reduced graphene oxide (rGO), highlighting the environmental drawbacks of conventional chemical processes. We introduce a novel, green synthesis technique involving the irradiation of a 500 eV argon ion beam, which not only facilitates the creation of micro-patterned rGO on a graphene oxide (GO) film but also enables simultaneous material characterization and patterning. By adjusting the irradiation exposure time between 0 and 80 s, we achieve meticulous control over the attributes and the reduction process of the material. The use of X-ray photoelectron spectroscopy (XPS) allows for real-time monitoring of the reduction from GO to rGO, evidenced by a notable reduction in the intensities of C-O, C=O, and O-C=O bonds, and an increase in C-C bond intensities, indicating a significant reduction level. Our research demonstrates the efficient production of eco-friendly rGO using precise, controlled argon ion beam irradiation, proving its advantages over traditional methods. These results contribute to the development of sustainable material science technologies, with potential applications in electronics, energy storage, and more.

An innovative pretreatment protocol to eliminate silver contamination-induced voltammetric interference on graphite-glass working electrode

In the last decades, a significant amount of research has been focused on the development of miniaturized and portable electrochemical sensors in the form of screen-printed electrodes (SPEs). When performing voltammetric measurements using SPEs, especially in the case of carbon-based electrodes, additional peaks can appear and overlap with analytes’ signals or otherwise interfere with results. Therefore, the development of pretreatment methods that enable the removal of interferences is of great importance for SPEs utilization, e.g. for sensor applications. Moreover, electrode pretreatment can also be used to improve electron transfer kinetics, including reversibility of the studied redox processes. In this work, we present the evaluation of different pretreatment methods using cyclic voltammetry and potentiostatic anodization, applied on an in-house graphite-glass composite working electrodes. With the use of X-ray photoelectron spectroscopy and scanning electron microscopy it was confirmed that the surface of working electrode was contaminated by sub-micrometer sized silver particles, which resulted in two interference peaks. Several strong acids, including H2SO4, HNO3, and HCl, as well as phosphate buffer solution, were evaluated as electrolytes for electrochemical pretreatment. A rapid, simple, and low-cost pretreatment protocol that enables the removal of the interference peaks, as well as improved voltammetric signals for [Fe(CN)6]3−/4− redox probe was developed. We propose the optimal pretreatment method in H2SO4 as a protocol that could be universally applied for carbon, carbon-glass, or similar types of SPEs before performing voltammetric experiments and/or further modifications of SPEs.

Evaluating potential of Cr-doped indium oxide nanoparticles as a DMS material

ABSTRACT Cr-doped In2O3 nanoparticles have been prepared via combustion method. Glycine fuel was used for the synthesis. The prepared compounds were evaluated for their potential as a dilute magnetic semiconductor (DMS) by studying their magnetic properties. X-ray diffraction (XRD) pattern was studied to identify the crystal structure of pristine and doped In2O3 compounds. Morphology and particle size of the compounds have been estimated using transmission electron microscope (TEM). Valence state of the elements was found out by making use of X-ray photoelectron spectroscopy (XPS) technique. Electrical resistivity has been measured which displayed higher resistance value for doped samples. Magnetisation studied with vibrating sample magnetometer (VSM) at room temperature displayed weak ferromagnetism in the doped samples. The measurements at 50 K displayed antiferromagnetic/paramagnetic alignment. The importance of preparative method, nano-size, room-temperature defects and oxygen vacancies in regulating magnetism in DMS has been discussed.

A Review of Development of Chemical Sensors

A comprehensive summary of the most recentre search concentrating on chemical sensors utilizing nano tubes,Nano rods,Nano belts, and nano wiresis given in this article. The experimental principle, sensor device design,sensor mechanism, and multiple significant conclusionsreceivethevastmajorityofourattention.Thefollowingfoursectionsprovide additional information on the creation of chemical sensors based on nanostructured materials: nanotube sensors, Nano rod sensors, Nano belt sensors and Nano wire sensors. Weconcludethisreviewwithpersonalperspectivesonthedirectionstowardswhichfuture research on nanostructured sensors might be directed. At ambient temperature, the nanotube sensors show a far faster response time and a significantly higher sensitivity than the current solid-state sensors. Reversibility of the sensor can be obtained by heating it to a high temperature or by slowly recovering under ambient conditions. Over the past decade, synthesized nanomaterial’s, such as carbon nanotube, nanoparticle, quantum dot, and nanowire, have already made breakthroughs in various fields, including biomedical sensors. Enormous surface area-to-volume ratio of the Nano materials increases sensitivity dramatically compared with macro-sized material. Herein we present a comprehensive review about the working principle and fabrication process of nanowire sensors. Then anotube sensor sex hibit a fast response and asubstantially higher sensitivity than thatofexistingsolid-statesensorsatroomtemperature.Sensorreversibilityisachievedbyslow recovery under ambient conditions or by heating to high temperatures.Synthesized Nano materials, including carbon nanotubes, nanoparticles, quantum dots, and nanowires, have already achieved significant advances in a number of sectors, including biological sensors, during the last ten years. When compared to macro-sized material, the nanoparticles' enormous surface area-to-volume ratio significantly boosts sensitivity. We provide a thorough overview of the fabrication process and operating principle of the nanowire sensor here. Recent advances including self-powering, reusability, sensitivity in high ionic strength solvent,andlong-term stabilityaresurveyedandhighlightedas well.Nanowire isexpectedtolead significant improvement of biomedical sensor in the near future.Advantages and disadvantages of the sensors are provided along with brief descriptions. An electrical device that monitors changes in a quantity, such as voltage, temperature, pressure, or humidity, is called a sensor. As a result, classification is done according to the attribute that a sensor measures. A temperature sensor detects even the smallest variations in its environment or shifts in temperature, such as hot or cold weather. Microelectronic manufacturing techniques have been used to manufacture chemical and electrochemical sensors.Thedevelopment ofchemical sensors has been spurred forward by the recentadvancesinmicromachingtechnology.Chemicalsensorresearchhasadvancedthanksto micro machining methods like sacrificiallayers, plasmaetching, andchemicalanisotropicetching. These methods enable the creation of low mass, low power driven devices as well as controlled working conditions and temperature. Researchersbecameinterestedinthesecarefullychoseninvitronanostructureswhentheywere combined with nanomaterials because the improved properties of these nanostructures led to advances inthe analytical performance of chemical and biosensors. Thisstudycoversthe latest advancements in recognition elements that are integrated in to chemical sensors and bio sensors used in the food, medical, and environmental domains. These elements include both traditional ones like enzymes and antibodies as well as more modern ones like aptomers and phages.Cyclic voltammetry and electron microscopy are frequently used in the characterization of chemically modified sensors and biosensors because they enable the confirmation of electrode mechanisms and surface morphologies. X-ray photoelectron spectroscopy (XPS), among other methods, is a special tool for obtaining information on the sensor surface that is qualitative, quantitative/semi-quantitative, and speciation-related. However, XPS is still not widely applied in this industry. The purpose of this work is to review a few selected studies that demonstrate how wellXPSperformswhencharacterizingthetopsurfacelayersofbiosensorsandchemically Modified sensors. The reader is provided with the necessary background information in a brief introduction to X-ray photoelectron spectroscopy. The use of XPS to characterize sensors appropriate for environmental and food analysis is highlighted.

Surface science insight note: A linear algebraic approach to elucidate native films on Fe3O4 surface

Standard materials are often used to obtain spectra that can be compared to those from unknown samples. Spectra measured from these known substances are also used as a means of computing sensitivity factors to allow quantification by X‐ray photoelectron spectroscopy (XPS) of less well‐defined materials. Spectra from known materials also provide line shapes suitable for inclusion in spectral models which, when fitted to spectra, permit the chemical state for a sample to be assessed. Both types of information depend on isolating photoemission signals from the inelastically scattered signal. In this Insight note, technical issues associated with the use of XPS of as received Fe3O4 powder sample surface are discussed. The Insight note is designed to show how linear algebraic techniques applied to data collected from a sample marketed as pure Fe3O4 powder are used to verify that XPS has been performed on chemistry representative of the sample. The methods described in this Insight note can further be utilized in elucidating complex XPS data obtained from thin films formed or evolved during cyclic/non‐steady use of complex (electro)catalyst surfaces, especially in the presence of contaminants.

Analysis of nanoparticles and nanomaterials using X-ray photoelectron spectroscopy

Objectives. The main aim of this review is to summarize the existing knowledge on the use of X-ray photoelectron spectroscopy (XPS) for the characterization of nanoparticles and nanomaterials.Results. XPS or electron spectroscopy for chemical analysis can provide information on the qualitative and quantitative composition, valence states of the elements of the samples under study, the chemical composition of the surface and interfaces that determine the properties of nanoparticles and nanostructured materials. The review describes the role of several different methods for the characterization of nanomaterials, highlights their advantages and limitations, and the possibilities of an effective combination. The main characteristics of XPS are described. Various examples of its use for the analysis of nanoparticles and nanomaterials are given in conjunction with additional methods to obtain complementary information about the object under study.Conclusions. XPS provides depth information comparable to the size of nanoparticles (up to 10 nm depth from the surface) and does not cause significant damage to the samples. Two disadvantages of XPS analysis are sample preparation requiring a dry solid form without contaminations and data interpretation. XPS provides information not only on the chemical identity, but also on the dielectric properties of nanomaterials, recording their charging/discharging behavior. Chemical information from the surface of nanoparticles analyzed by XPS can be used to estimate the thickness of nanoparticle coatings. XPS has a high selectivity, since the resolution of the method makes it possible to distinguish a characteristic set of lines in the photoelectron spectrum at kinetic energies determined by the photon energy and the corresponding binding energies in elements. The intensity of the lines depends on the concentration of the respective element. Obtaining a sufficiently complete picture of the properties of nanomaterials requires the use of a group of complementary instrumental methods of analysis.

X-ray Photoelectron Spectroscopy (XPS) Analysis of Nitrogen Environment in Small Extracellular Vesicle Membranes: A Potential Novel Technique with Application for Cancer Screening.

Small extracellular vesicle (EV) membranes display characteristic protein-lipidic composition features that are related to their cell of origin, providing valuable clues regarding their parental cell composition and real-time state. This could be especially interesting in the case of cancer cell-derived EVs, as their membranes could serve as valuable tools in liquid biopsy applications and to detect changes in the tumor malignancy. X-Ray Photoelectron Spectroscopy (XPS) is a powerful surface analysis technique able to detect every chemical element present, being also sensitive to their chemical environment. Here we explore the use of XPS as a fast technique to characterize EV membrane composition, with possible application in cancer research. Notably, we have focused on the nitrogen environment as an indicator of the relative abundance of pyridine-type bonding, primary, secondary and tertiary amines. Specifically, we have analyzed how tumoral and healthy cells have different nitrogen chemical environments that can indicate the presence or absence of malignancy. In addition, a collection of human serum samples from cancer patients and healthy donors was also analyzed. The differential XPS analysis of EVs collected from patients confirmed that the patterns of amine evolution could be related to markers of cancer disease, opening the possibility of their use as a non-invasive blood biomarker.

Use of X-Ray Photoelectron Spectroscopy as an analytical tool for the study of contamination by Teflon in the synthesis of Mo(VI)Cl2O2Bipy/TiO2 catalysts

The preparation of catalysts can involve various sources of contamination, which can seriously affect the quality of the prepared materials. In the present work, a case of fluorine contamination in a set of catalyst samples was studied, in which using the X-Ray Photoelectron Spectroscopy (XPS) technique, it was evidenced by the F 1s signal that this element was present in the form of Teflon, since its binding energy corresponded mainly to the CF2 species. Furthermore, using the C 1s signal, it was also possible to corroborate the presence of the CF2 group, which is associated with the main component of the Teflon carbon chains. The use of this information made it possible to identify that the solvent dehydration procedure (previous step to obtaining the catalysts) could lead to contamination with Teflon since it involved various accessories with Teflon, organic solvents and high temperature; the Teflon tape and the magnetic stirrer being the possible sources of contamination.

Evolving efforts to maintain and improve XPS analysis quality in an era of increasingly diverse uses and users

Based on literature analysis, X‐ray photoelectron spectroscopy (XPS) use continues to increase exponentially. This increased use is accompanied by anecdotal reports and systematic analyses indicating a growing presence of significantly flawed data analyses. Recognition of this problem within the surface analysis community has increased with an understanding that both inexperienced users and increased use of XPS outside the surface analysis community contribute to the problem. The XPS community has initiated several efforts to help address the problem, which is not unique to XPS. This paper describes some of the specific problems identified and some of the community efforts intended to address them. Here, we describe activities focused on three specific issues: (i) requests for detailed guides and protocols and bite‐sized versions of information for non‐experts, (ii) incomplete data and analysis reporting, and (iii) the high rate of peak fitting problems. A 2019 survey identified the need for guides, protocols, and standards to assist XPS users. One set of such guides has been published, and another is being assembled. Providing incremental bites of useful information is the goal of a series of papers on specific challenges to surface analysis with example solutions has been initiated as Notes and Insights papers in Surface and Interface Analysis. Examination of XPS‐containing papers finds that information to establish the credibility and reproducibility of XPS results is often very incomplete. Unfortunately, ISO and ASTM standards require an amount of parameter reporting that seems excessive and unrealistic for many research publications. Initial approaches to develop and distribute a graded approach to parameter reporting are briefly described. Multiple efforts are underway to address the high rate of problems associated with photoelectron peak fitting. These include guides to peak fitting, guides to peak identification and fitting for specific elements, and the development of a peak fitting social network. The fitting social network is designed to facilitate interactions between new and experienced XPS users; analysts trying to fit XPS data (for publication or other reasons) can ask questions and establish dynamic conversations. Encouraging and enabling high‐quality XPS analysis and reporting requires several different types of effort from all members of the surface and interface analysis community.

XPS-Analysis of solvent residues in different polymeric biomaterials

Abstract For the use of polymers as biomaterials in the production of implants, several processing methods are needed. Besides injection molding or Fused Deposition Modeling as temperature based processes, also solvent based processes were performed such as solvent-casting and electrospinning. As fabrication of medical devices makes use of potentially hazardous or toxic solvents, they have to be extracted from the final medical device. For analyses of residual solvents different methods can be used e.g. gas chromatography (GC), coulometric elemental analysis or thermogravimetrical analyses (TGA). Here we present first results for the use of X-ray photoelectron spectroscopy (XPS) to yield elemental as well as spatial information on residual solvents in polymeric materials. Therefore we analysed PLLA as biodegradable electrospun polymer, TPC-ET as biostable polymer and a PLLA-iron composite as example of a polymer metal composite via XPS and etching processes. It was possible to determine residual halogen containing solvents in all tested polymers processed from polymeric solution. As discrimination between polymer and solvent was made possible by specific elements, XPS measurements may be a suitable tool to identify even small amounts of solvent. Thus XPS analyses will help to optimize polymer processing in order to remove residual solvents.

Chemical and Morphological Changes of Graphite Electrodes at Low Cathodic Potentials and Its Relevance to Li-Ion Batteries

Lithium-ion (Li-ion) batteries have become ubiquitous to modern-day electronics and electric vehicles. A detailed understanding regarding the reversible and irreversible nature of Li-ion electrode processes is a prerequisite to rationally delineate the factors affecting device performance and clarify degradation mechanisms. This includes, for instance, the role of electrode cracking and solid solid-electrolyte-interphase (SEI) formation which can contribute toward irreversible capacity loss. In terms of experimental approaches, aside from the high surface area electrodes used in practical systems, one powerful approach is to incorporate the study of well-defined electrodes and surface science techniques.1 Herein, we employ highly oriented pyrolytic graphite (HOPG) as a well-defined model anode in Li-ion batteries and reveal the chemical and morphological changes at low cathodic potentials prior to the potentials of bulk SEI formation.2 To achieve this, we employ the use of X-ray photoelectron spectroscopy (XPS) and ultrahigh vacuum scanning tunneling microscopy (UHV-STM). We utilize a so-called UHV-EC setup to provide a snapshot-like analysis of the electrode surface without the involvement of electrode washing or exposure to air.Upon cathodic polarization at ca. 1.75V (Figure 1), STM imaging shows the onset and occurrence of graphite exfoliation which can originate from the intercalation of solvated Li+ ions. Meanwhile, XPS shows a minimal amount of residual electrolyte along with the observation of LiF indicating the decomposition of the Li salt (LiPF6). The future extensions of our methodology and additional details will be provided at the presentation. Figure 1. (a) Cathodic linear sweep voltammogram in 1.1 M LiPF6 EC/DMC. Following polarization at ca. 1.75 V (b) STM imaging, and (c) XPS F 1s and Li 1s spectra.

Understanding the Performance Increase of Catalysts Supported on N-Functionalized Carbon in PEMFC Catalyst Layers

Applying nitrogen-modified carbon support in PEMFCs has been attracting arising interest due to the resulting performance enhancement. In the present study, we attempt to uncover the origin and gain a deeper understanding of the different N-modification processes, whose influences are responsible for the performance improvement. By utilizing chemically modified Ketjenblack supports comprising altered fraction of N-functionalities, we investigate the underlying mechanism of the drastically reduced voltage losses under fuel cell operation conditions. In all, we demonstrate the key role of support modification induced by ammonia in strengthened support/ionomer interactions and alter physico-chemical properties of the carbon support contributing towards enhanced MEA performance. With the use of X-ray photoelectron spectroscopy (XPS), we show unambiguous evidences that not all N modified surfaces yield the desired performance increase. Rather, the latter depends on a complex interplay between different electrochemical parameter and catalyst properties. We want to emphasize the ionomer/support interaction as one important factor for enhanced ionomer distribution and present a prove of a direct interaction between the ionomers´ sidechains and N-functional groups of the support.

Technical and personal remembrances of David A. Shirley in studies of surface magnetism, photoelectron spectroscopy, EUV lithography, and hydrogen storage

This article describes the influence of Professor David A. Shirley on the research science of one of his Ph.D. students in the diverse areas of surface magnetism, x-ray photoelectron spectroscopy (XPS), spin-resolved XPS (SRXPS), extreme ultraviolet (EUV) lithography, and hydrogen storage materials science. Examples are given from the author's work on Cr(001) surface magnetism, XPS, and SRXPS studies of multiplet-splitting in core-level photoemission from Fe. In addition, Dave's influence in understanding the radiation-induced deposition of carbon on EUV optics is described, along with the use of XPS in deciphering how hydrogen storage materials are modified by repeated hydrogen adsorption/desorption cycling. The current status of these particular topics is briefly summarized. These technical remembrances are combined with some fond personal stories about Dave, in recognition of his passing on March 29, 2021.

A Review of X-ray Photoelectron Spectroscopy Technique to Analyze the Stability and Degradation Mechanism of Solid Oxide Fuel Cell Cathode Materials.

Nondestructive characterization of solid oxide fuel cell (SOFC) materials has drawn attention owing to the advances in instrumentation that enable in situ characterization during high-temperature cell operation. X-ray photoelectron spectroscopy (XPS) is widely used to investigate the surface of SOFC cathode materials because of its excellent chemical specificity and surface sensitivity. The XPS can be used to analyze the elemental composition and oxidation state of cathode layers from the surface to a depth of approximately 5–10 nm. Any change in the chemical state of the SOFC cathode at the surface affects the migration of oxygen ions to the cathode/electrolyte interface via the cathode layer and causes performance degradation. The objective of this article is to provide a comprehensive review of the adoption of XPS for the characterization of SOFC cathode materials to understand its degradation mechanism in absolute terms. The use of XPS to confirm the chemical stability at the interface and the enrichment of cations on the surface is reviewed. Finally, the strategies adopted to improve the structural stability and electrochemical performance of the LSCF cathode are also discussed.

Cashew Apple Extract: A Novel, Potential Green Reducing Agent for the Synthesis of Reduced Graphene Oxide

Abstract Reduced graphene oxide (rGO) is one of the promising materials which are used in energy storage devices, field effect resistors and as an additive in polymer composites for functional and structural applications. The reduction of graphene oxide (GO) to rGO is popular and attractive. Chemical reduction of GO is considered as one of the promising methods for the large-scale production of rGO. Herein, we report for the first time a sustainable, eco-friendly and facile approach for synthesizing rGO using cashew apple extract as a reducing agent. Reduction of GO by cashew apple extract was confirmed by the bathochromic shift in the UV-Visible spectrum. The extent of reduction by cashew apple extract at temperatures (80°C, 120°C, and 180°C) was determined by making use of X-ray Photoelectron Spectroscopy (XPS), X-ray Diffraction (XRD), Raman Spectroscopy and Fourier Transform Infrared Spectroscopy (FTIR) and were morphologically confirmed using Transmission Electron Microscopy (TEM). Through this research work, we propose an environment friendly approach for the production of rGO.

(Invited) Modeling and Characterizing Defects in Semiconductors for Photovoltaics

Photovoltaics are minority carrier devices and highly impacted by semiconductor defects. Furthermore the materials often must be synthesized at high rates using inexpensive processing. The result is that many solar cell technologies are produced from highly defective polycrystalline materials. This talk describes the use of a variety of techniques to study and model defects and the stability of the materials in a variety of semiconductors including Si, CdTe, (Ag,Cu)(In,Ga)Se2, and the hybrid perovskites. Examples include the use of x-ray photoelectron spectroscopy to study degradation in a hybrid perovskite, capacitance and scanning probe techniques to study defects in (Ag,Cu)(In,Ga)Se2 and CdTe, and modeling to understand defects in TiO2 in photoelectrochemical cells. The talk will also include a brief review of the state of photovoltaic technology, the energy generation technology currently being installed at the highest net rate in the U.S., how it interfaces with other technologies such as batteries, and the challenges and opportunities related to continued expansion of PV in our energy infrastructure.

Removal of metoprolol by means of photo-oxidation processes

In this study, β-blocker metoprolol was degraded by photocatalysis and photo-Fenton catalyzed by doped TiO2. The effect of two main variables was elucidated, content and type of doping cation (Fe or Cu). The catalysts were synthesized by Evaporation-Induced Self-Assembly (EISA) method and their performance was compared with typical Degussa P25. All synthesized materials were found to be mesoporous with a specific surface in the range of 121–242 m2/g, they all exhibited anatase phase, and crystallites in the range of 6–10 nm. The use of X-ray photoelectron spectroscopy (XPS) allowed to establish not only the presence of the expected Ti4+ but also Ti3+ species. Cu2+ and Fe3+ species were also identified in the doped catalysts. It was found that the addition of Cu and Fe diminished the energy band gap of synthesized TiO2, from 3.20 eV to 2.58 and 2.64, respectively. The content of Cu is directly correlated with this effect. In photocatalysis, the doping of TiO2 did not have an effect of metoprolol degradation rate. This was improved, however, approximately 60% by the synthesized TiO2 compared to Degussa P25. On the other hand, the photo-Fenton-like process catalyzed by Cu-TiO2 exhibited the highest degradation (total removal) and mineralization extent (90%), being faster than the photocatalytic process and the UV-H2O2 system. Another difference between both methods, was the amount and type of intermediates generated. These were identified by LC-MS. Photo-Fenton catalyzed by Cu/TiO2 can be considered as an effective process with high oxidative power in the metoprolol degradation.

Spray Pyrolysis Synthesis of Pure and Mg-Doped Manganese Oxide Thin Films

Pure and Mg-doped manganese oxide thin films were synthesized on heated glass substrates using the spray pyrolysis technique. The surface chemical composition was investigated by the use of X-ray photoelectron spectroscopy (XPS). Structural and morphological properties were studied by using X-ray diffraction (XRD), scanning electron microscope (SEM) and atomic force microscopy (AFM). Optical properties were characterized by UV-visible spectroscopy. XPS spectra showed typical Mn (2p3/2), (2p1/2) and O (1s) peaks of Mn3O4 with a slight shift attributed to the formation of different chemical states of manganese. XRD analysis revealed the tetragonal phase of Mn3O4 with a preferred (211) growth orientation that improved with Mg-doping; likewise, grain size is observed to increase with the Mg doping. SEM images of Mn3O4 films showed rough surfaces composed of uniformly distributed nanograins whose size decreases with the Mg-doping. The manganese oxide films surface observed in AFM show a textured, rough and porous surface. The combination of transmittance and absorption data in the UV-visible range allowed determining the energy values of the Eg band gap (1.5–2.5 eV). The decrease of the band gap with the Mg-doping increase is attributed to the influence of the greater size of the Mg2+ ion in the manganese oxide lattice.

X-Ray Photoelectron Spectroscopy on Microbial Cell Surfaces: A Forgotten Method for the Characterization of Microorganisms Encapsulated With Surface-Engineered Shells.

Encapsulation of single microbial cells by surface-engineered shells has great potential for the protection of yeasts and bacteria against harsh environmental conditions, such as elevated temperatures, UV light, extreme pH values, and antimicrobials. Encapsulation with functionalized shells can also alter the surface characteristics of cells in a way that can make them more suitable to perform their function in complex environments, including bio-reactors, bio-fuel production, biosensors, and the human body. Surface-engineered shells bear as an advantage above genetically-engineered microorganisms that the protection and functionalization added are temporary and disappear upon microbial growth, ultimately breaking a shell. Therewith, the danger of creating a “super-bug,” resistant to all known antimicrobial measures does not exist for surface-engineered shells. Encapsulating shells around single microorganisms are predominantly characterized by electron microscopy, energy-dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy, particulate micro-electrophoresis, nitrogen adsorption-desorption isotherms, and X-ray diffraction. It is amazing that X-ray Photoelectron Spectroscopy (XPS) is forgotten as a method to characterize encapsulated yeasts and bacteria. XPS was introduced several decades ago to characterize the elemental composition of microbial cell surfaces. Microbial sample preparation requires freeze-drying which leaves microorganisms intact. Freeze-dried microorganisms form a powder that can be easily pressed in small cups, suitable for insertion in the high vacuum of an XPS machine and obtaining high resolution spectra. Typically, XPS measures carbon, nitrogen, oxygen and phosphorus as the most common elements in microbial cell surfaces. Models exist to transform these compositions into well-known, biochemical cell surface components, including proteins, polysaccharides, chitin, glucan, teichoic acid, peptidoglycan, and hydrocarbon like components. Moreover, elemental surface compositions of many different microbial strains and species in freeze-dried conditions, related with zeta potentials of microbial cells, measured in a hydrated state. Relationships between elemental surface compositions measured using XPS in vacuum with characteristics measured in a hydrated state have been taken as a validation of microbial cell surface XPS. Despite the merits of microbial cell surface XPS, XPS has seldom been applied to characterize the many different types of surface-engineered shells around yeasts and bacteria currently described in the literature. In this review, we aim to advocate the use of XPS as a forgotten method for microbial cell surface characterization, for use on surface-engineered shells encapsulating microorganisms.

Compositional, Structural, Morphological, and Optical Properties of ZnO Thin Films Prepared by PECVD Technique

ZnO thin films were synthesized on silicon and glass substrates using the plasma-enhanced chemical vapor deposition (PECVD) technique. Three samples were prepared at substrates temperatures of 200, 300, and 400 °C. The surface chemical composition was analyzed by the use of X-Ray Photoelectron spectroscopy (XPS). Structural and morphological properties were studied by using X-ray diffraction (XRD) and scanning electron microscopy (SEM). Optical properties were carried out by UV-visible spectroscopy. XPS spectra showed typical peaks of Zn(2p3/2), Zn(2p1/2), and O(1s) of ZnO with a slight shift attributed to the substrate temperature. XRD analysis revealed hexagonal wurtzite phases with a preferred (002) growth orientation that improved with temperature. Calculation of grain size and dislocation density revealed the crystallization improvement of ZnO when the substrate temperature varied from 200 to 400 °C. SEM images of ZnO films showed textured surfaces composed of grains of spherical shape uniformly distributed. The transmittance yields are reaching 80%, and the values of the band-gap energy indicate that the ZnO films prepared by PECVD present transparent and semiconducting properties.