Cd-substitution effect on photoexcitation properties of ZnO nanodots surrounded by carbon moiety

The geometrical structure and photoexcitation properties of Zn27-nCdnO27C42 complexes are investigated by density functional theory (DFT) and time-dependent DFT calculations at the PBE0/6-31G*/SDD level of theory. The cohesive energy and frequency analysis indicate that the hybrid materials are energetically stable. In presence of Cd substituting atoms, energy gap of the ZnO nanodots surrounded by carbon moiety is shown to decrease, as compared to Cd-free complex. In-depth excited state analysis including charge density difference (CDD) mapping and absorption spectrum decomposition is performed to reveal the nature of the dominant excited states and to comprehend the Cd-to-Zn substitution effect on the photoexcitation properties of Zn27-nCdnO27C42. A principal possibility to enhance intramolecular charge transfer through incorporation of certain number of Cd atoms into the ZnO nanodots is shown. Such Cd-induced modifications in optical properties of semi-spherical Zn27-nCdnO27C42 complexes could potentially enable use of this hybrid material in optoelectronic and photocatalytic applications

Nature of photoexcited states in ZnO-embedded graphene quantum dots

The combination of wide-band gap semiconductors like zinc oxide (ZnO) and graphene quantum dots (GQDs) is a promising strategy to tune optoelectronic properties of GQDs and to develop new functionalities. Here we report on a theoretical design of not-yet-synthesized hybrid materials composed of ZnO clusters surrounded by carbon moieties, hereinafter referred to as ZnO-embedded graphene quantum dots. Their structure and light absorption properties are presented, with an in-depth analysis of the nature of the photoexcited states. The stability of the (ZnO)nC96-2n system with n=1, 3, 4, 7, 12 and 27 is investigated by estimating cohesive energy and performing vibrational mode analysis. A strong dependence of the structural and optoelectronic properties of the hybrid material on the amount of ZnO pairs is revealed and discussed. A strong light absorption and unexpected enhancement of Raman modes related to the vibrations in carbon moiety are observed for highly symmetric (ZnO)27C42 system that makes it an ideal study subject. Complementary excited state analysis, charge density difference (CDD) analysis and interfragment charge transfer analysis enabled reaching deep insights into the nature of the excited states. A dominating contribution of doubly degenerate locally excited states in broadband light absorption by (ZnO)27C42 is identified. The present results are helpful to elucidate the nature of the fundamental internal mechanisms underlying the light absorption in ZnO-embedded graphene quantum dots, thereby providing a scientific background for future experimental study of low-dimensional metal-oxygen-carbon materials family

Anodization study of epitaxial graphene:insights on the oxygen evolution reaction of graphitic materials

The photoemission electron microscopy and x-ray photoemission spectroscopy were utilized for the study of anodized epitaxial graphene (EG) on silicon carbide as a fundamental aspect of the oxygen evolution reaction on graphitic materials. The high-resolution analysis of surface morphology and composition quantified the material transformation during the anodization. We investigated the surface with lateral resolution amp;lt;150 nm, revealing significant transformations on the EG and the role of multilayer edges in increasing the film capacitance.Funding Agencies| [EP/K035746/1]; [EP/M000605/1]</p

Особенности влияния условий роста на структурные и оптические свойства пленок Zn0.9Cd0.1O

The influence of the magnetron power and the gas ratio Ar/O2 on the microstructure and the optical properties of Zn0.9Cd0.1O films is studied. The films were deposited with the use of the dc magnetron sputtering technique at a temperature of 250 ◦C. Atomic force microscopy (AFM) and X-ray diffraction (XRD) researches of a surface morphology demonstrated a strong influence of deposition procedure parameters on the film microstructure. The XRD analysis revealed that all grown films were polycrystalline and single-phase. The increase of the gas ratio Ar/O2 was found to be beneficial for the crystalline structure of Zn0.9Cd0.1O ternary alloys. Peculiarities of the control over the band gap and the surface morphology for Zn0.9Cd0.1O ternary alloys by varying the growth parameters are discussed.Дослiджено вплив потужностi магнетрона i спiввiдношення тискiв робочих газiв Ar/O2 на мiкроструктуру та оптичнi властивостi плiвок Zn0.9Cd0.1O. Плiвки осаджено методом магнетронного розпилювання на постiйному струмi при температурi пiдкладки 250 C. Дослiдження морфологiї поверхнi, здійснені за допомогою атомно-силової мiкроскопiї (АСМ), i рентгено-фазовий аналiз (РФА) виявили сильний вплив технологічних параметрiв осадження на мiкроструктуру плiвок. РФА аналiз показав, що всi вирощенi плiвки є полiкристалiчними i однофазними. Встановлено, що зростання парцiального тиску аргону в газовiй сумiшi Ar/O2 сприятливо впливає на кристалічну структуру твердих розчинiв Zn0.9Cd0.1O. Обговорено особливостi контролю ширини забороненої зони та морфологiї поверхнi твердих розчинiв Zn0.9Cd0.1O шляхом змiни параметрiв вирощування.В работе исследовано влияние мощности магнетрона и соотношения давлений рабочих газов Ar/O2 на микроструктуру и оптические свойства пленок Zn0.9Cd0.1O. Пленки осаждены методом магнетронного распыления на постоянном токе при температуре подложки 250 C. Исследования морфологии поверхности, проведенные с помощью атомно-силовой микроскопии (АСМ), и рентгенофазовый анализ (РФА) выявили сильное влияние технологических параметров роста на микроструктуру пленок. РФА анализ показал, что все выращенные пленки являются поликристаллическими и однофазными. Было установлено, что рост парциального давления аргона в газовой смеси Ar/O2 благоприятно влияет на кристаллическую структуру твердых растворов Zn0;9Cd0;1O. Обсуждены особенности контроля ширины запрещенной зоны и морфологи поверхности твердых растворов Zn0;9Cd0;1O путем изменения параметров осаждени

Graphene Decorated with Iron Oxide Nanoparticles for Highly Sensitive Interaction with Volatile Organic Compounds

Gases, such as nitrogen dioxide, formaldehyde and benzene, are toxic even at very low concentrations. However, so far there are no low-cost sensors available with sufficiently low detection limits and desired response times, which are able to detect them in the ranges relevant for air quality control. In this work, we address both, detection of small gas amounts and fast response times, using epitaxially grown graphene decorated with iron oxide nanoparticles. This hybrid surface is used as a sensing layer to detect formaldehyde and benzene at concentrations of relevance (low parts per billion). The performance enhancement was additionally validated using density functional theory calculations to see the effect of decoration on binding energies between the gas molecules and the sensor surface. Moreover, the time constants can be drastically reduced using a derivative sensor signal readout, allowing the sensor to work at detection limits and sampling rates desired for air quality monitoring applications

Clustering and Morphology Evolution of Gold on Nanostructured Surfaces of Silicon Carbide: Implications for Catalysis and Sensing

A fundamental understanding of the behavior of gold (Au) nanostructures deposited on functional surfaces is imperative to discover and leverage interface-related phenomena that can boost the efficiency of existing electronic devices in sensorics, catalysis, and spintronics. In the present work, Au layers with nominal thickness of 2 nm were sputter-deposited on graphenized SiC substrates represented by buffer layer (BuL)/4H-SiC and monolayer epitaxial graphene (MLG)/4H-SiC. Morphometric analysis by means of scanning electron microscopy shows that Au on BuL self-assembles in nearly round-shaped plasmonically active islands, while on MLG, a fractal growth of considerably larger and ramified islands is observed. To correlate the experimentally established differences in surface morphology on the two types of graphenized substrates with energetics and kinetics of Au nanostructure growth, the deposit-substrate interaction strength was studied using density functional theory (DFT) calculations, molecular dynamics simulations, and optical measurements. The theoretical considerations involve participation of Au clusters with different sizes and energetics at the initial stages of the metal nanostructure formation. The results indicate that gold exhibits a considerably stronger interaction with BuL than with MLG, which can be considered as a key aspect for explaining the experimentally observed morphological differences. From the statistical analysis of Raman spectra, indications of Au intercalation of MLG are discussed. The current research shows that, due to its unique surface chemistry, buffer layer has peculiar affinity to gold when compared to other atomically flat surfaces, which is beneficial for boosting high-performance catalytic and sensing technologies based on low-dimensional materials

Міністерство фінансів України як головний орган управління державними фінансами

The discovery of graphene and its unique properties has inspired researchers to try to invent other two-dimensional (2D) materials. After considerable research effort, a distinct "beyond graphene" domain has been established, comprising the library of non-graphene 2D materials. It is significant that some 2D non-graphene materials possess solid advantages over their predecessor, such as having a direct band gap, and therefore are highly promising for a number of applications. These applications are not limited to nano- and opto-electronics, but have a strong potential in biosensing technologies, as one example. However, since most of the 2D non-graphene materials have been newly discovered, most of the research efforts are concentrated on material synthesis and the investigation of the properties of the material. Applications of 2D non-graphene materials are still at the embryonic stage, and the integration of 2D non-graphene materials into devices is scarcely reported. However, in recent years, numerous reports have blossomed about 2D material-based biosensors, evidencing the growing potential of 2D non-graphene materials for biosensing applications. This review highlights the recent progress in research on the potential of using 2D non-graphene materials and similar oxide nanostructures for different types of biosensors (optical and electrochemical). A wide range of biological targets, such as glucose, dopamine, cortisol, DNA, IgG, bisphenol, ascorbic acid, cytochrome and estradiol, has been reported to be successfully detected by biosensors with transducers made of 2D non-graphene materials.Funding Agencies|EC FP-7 International Research Staff Exchange Scheme (IRSES) Grant [318520]; Linkoping Linnaeus Initiative for Novel Functional Materials (LiLi-NFM); European Union [604391]; Swedish Research Council (VR) Marie Sklodowska Curie International Career Grant [2015-00679]</p

A DFT Study of Phosphate Ion Adsorption on Graphene Nanodots: Implications for Sensing

The optical properties of graphene nanodots (GND) and their interaction with phosphate ions have been investigated to explore their potential for optical sensing applications. The absorption spectra of pristine GND and modified GND systems were analyzed using time-dependent density functional theory (TD-DFT) calculation investigations. The results revealed that the size of adsorbed phosphate ions on GND surfaces correlated with the energy gap of the GND systems, leading to significant modifications in their absorption spectra. The introduction of vacancies and metal dopants in GND systems resulted in variations in the absorption bands and shifts in their wavelengths. Moreover, the absorption spectra of GND systems were further altered upon the adsorption of phosphate ions. These findings provide valuable insights into the optical behavior of GND and highlight their potential for the development of sensitive and selective optical sensors for phosphate detection