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Two-dimensional (2D) transition metal dichalcogenides are potential candidates for ultrathin solid-state lubricants in low-dimensional systems owing to their flatness, high in-plane mechanical strength, and low shear interlayer strength. Yet, the effects of surface topography and surface chemistry on the tribological properties of 2D layers are still unclear. In this work, we performed a comparative investigation of nanoscale tribological properties of ultra-thin highly-ordered PtSe2 layers deposited on the sapphire substrates with the in-plane and out-of-plane crystallographic orientation of the PtSe2 c-axis flakes, and epitaxial PtSe2 layers. PtSe2 c-axis orientation was found to has an impact on the nanotribological, morphological and electrical properties of PtSe2, in particular the change in the alignment of the PtSe2 flakes from vertical (VA) to horizontal (HA) led to the lowering of the coefficient of friction from 0.21 to 0.16. This observation was accompanied by an increase in the root-mean-square surface roughness from 1.0 to 1.7 nm for the HA and VA films, respectively. The epitaxial films showed lower friction caused by lowering adhesion when compared to other investigated films, whereas the friction coefficient was similar to films with HA flakes. The observed trends in nanoscale friction is attributed to a different distribution of PtSe2 structure.

Some of the distinct optical, catalytical, and electronic properties of few-layer MoS2 films arise from a specific orientation of the MoS2 layers. The growth of horizontally or vertically aligned M...

The development of defect analysis for inorganic semiconductors in the past century paved the way for the success story of today’s electronics. By analogy, defect analysis plays a critical role in ...

Recently, few-layer PtSe2 films have attracted significant attention due to their properties and promising applications in high-speed electronics, spintronics and optoelectronics. Until now, the transport properties of this material have not reached the theoretically predicted values, especially with regard to carrier mobility. In addition, it is not yet known which growth parameters (if any) can experimentally affect the carrier mobility value. This work presents the fabrication of horizontally aligned PtSe2 films using one-zone selenization of pre-deposited platinum layers. We have identified the Se : Pt ratio as a parameter controlling the charge carrier mobility in the thin films. The mobility increases more than twice as the ratio changes in a narrow interval around a value of 2. A simultaneous reduction of the carrier concentration suggests that ionized impurity scattering is responsible for the observed mobility behaviour. This significant finding may help to better understand the transport properties of few-layer PtSe2 films.

The crystallographic alignment of an ultra-thin MoS2 film strongly influences its properties and is, therefore, substantial for various applications. Developing the methods for controlled growth is...

Hybrid materials of π-conjugated molecular semiconductors combined with 2D materials exhibit significant potential for novel (opto)electronics. The overall characteristics of molecular growth, such...

Small π-conjugated organic molecules have attracted substantial attention in the past decade as they are considered as candidates for future organic-based (opto-)electronic applications. The molecular arrangement in the organic layer is one of the crucial parameters that determine the efficiency of a given device. The desired orientation of the molecules is achieved by a proper choice of the underlying substrate and growth conditions. Typically, one underlying material supports only one inherent molecular orientation at its interface. Here, we report on two different orientations of diindenoperylene (DIP) molecules on the same underlayer, i.e. on a few-layer MoS2 substrate. We show that DIP molecules adopt a lying-down orientation when deposited on few-layer MoS2 with horizontally oriented layers. In contrast, for vertically aligned MoS2 layers, DIP molecules are arranged in a standing-up manner. Employing in situ and real-time grazing-incidence wide-angle X-ray scattering (GIWAXS), we monitored the stress evolution within the thin DIP layer from the early stages of the growth, revealing different substrate-induced phases for the two molecular orientations. Our study opens up new possibilities for the next-generation of flexible electronics, which might benefit from the combination of MoS2 layers with unique optical and electronic properties and an extensive reservoir of small organic molecules.

Heterostructures composed of two-dimensional (2D) materials are already opening many new possibilities in such fields of technology as electronics and magnonics, but far more could be achieved if the number and diversity of 2D materials is increased. So far, only a few dozen 2D crystals have been extracted from materials that exhibit a layered phase in ambient conditions, omitting entirely the large number of layered materials that may exist in other temperatures and pressures. Here, we demonstrate how these structures can be stabilized in 2D van der Waals stacks under room temperature via growing them directly in graphene encapsulation by using graphene oxide as the template material. Specifically, we produce an ambient stable 2D structure of copper and iodine, a material that normally only occurs in layered form at elevated temperatures between 645 and 675 K. Our results establish a route to the production of more exotic phases of materials that would otherwise be difficult or impossible to stabilize for experiments in ambient., Comment: 15 pages, 6 figures, separate supplementary material included

The few-layer transition metal dichalcogenides (TMD) are an attractive class of materials due to their unique and tunable electronic, optical, and chemical properties, controlled by the layer number, crystal orientation, grain size, and morphology. One of the most commonly used methods for synthesizing the few-layer TMD materials is the chemical vapor deposition (CVD) technique. Therefore, it is crucial to develop in situ inspection techniques to observe the growth of the few-layer TMD materials directly in the CVD chamber environment. We demonstrate such an in situ observation on the growth of the vertically aligned few-layer MoS2 in a one-zone CVD chamber using a laboratory table-top grazing-incidence wide-angle X-ray scattering (GIWAXS) setup. The advantages of using a microfocus X-ray source with focusing Montel optics and a single-photon counting 2D X-ray detector are discussed. Due to the position-sensitive 2D X-ray detector, the orientation of MoS2 layers can be easily distinguished. The performance of the GIWAXS setup is further improved by suppressing the background scattering using a guarding slit, an appropriately placed beamstop, and He gas in the CVD reactor. The layer growth can be monitored by tracking the width of the MoS2 diffraction peak in real time. The temporal evolution of the crystallization kinetics can be satisfactorily described by the Avrami model, employing the normalized diffraction peak area. In this way, the activation energy of the particular chemical reaction occurring in the CVD chamber can be determined.

The last few decades faced on the fabrication of advanced engineering materials involving also different composites. Here, we report on the fabrication of few-layer molybdenum disulfide on top of thin polycrystalline diamond substrates with a high specific surface area. In the method, pre-deposited molybdenum coatings were sulfurized in a one-zone furnace at ambient pressure. As-prepared MoS2 layers were characterized by several techniques including grazing-incidence wide-angle X-ray scattering, atomic force microscopy, scanning electron microscopy, Raman spectroscopy and X-ray photoelectron spectroscopy. We found out that the initial thickness of Mo films determined the final c-axis crystallographic orientation of MoS2 layer as previously observed on other substrates. Even though it is well-known that Mo diffuses into diamond at elevated temperatures, the competing sulfurization applied effectively suppressed the diffusion and a chemical reaction between molybdenum and diamond. In particular, a Mo2C layer does not form at the interface between the Mo film and diamond substrate. The combination of diamond high specific surface area along with a controllable layer orientation might be attractive for applications, such as water splitting or water disinfection.

Recently, few-layer PtSe

Few-layer PtSe2 films are promising candidates for applications in high-speed electronics, spintronics and photodetectors. Reproducible fabrication of large-area highly crystalline films is, however, still a challenge. Here, we report the fabrication of epitaxially aligned PtSe2 films using one-zone selenization of pre-sputtered platinum layers. We have studied the influence of the growth conditions on the structural and electrical properties of the films prepared from Pt layers with different initial thickness. The best results were obtained for PtSe2 layers grown at elevated temperatures (600 {\deg}C). The films exhibit signatures for a long-range in-plane ordering resembling an epitaxial growth. Charge carrier mobility determined by Hall-effect measurements is up to 24 cm2/V.s in these films.

The principles of Raman scattering and the properties of phonons and electrons in graphene are reviewed. The focus is on Raman spectroscopy of mono- and bilayer graphene, particularly perturbations that have a significant influence on the Raman spectra. The distinct behaviour of Raman modes of different orders is discussed.

Small π-conjugated organic molecules have attracted substantial attention in the past decade as they are considered as candidates for future organic-based (opto-)electronic applications. The molecular arrangement in the organic layer is one of the crucial parameters that determine the efficiency of a given device. The desired orientation of the molecules is achieved by a proper choice of the underlying substrate and growth conditions. Typically, one underlying material supports only one inherent molecular orientation at its interface. Here, we report on two different orientations of diindenoperylene (DIP) molecules on the same underlayer, i.e. on a few-layer MoS

Oligothiophenes and their functionalized derivatives have been shown to be a viable option for high-performance organic electronic devices. The functionalization of oligothiophene-based materials allows further tailoring of their properties for specific applications. We have synthesized a new thiophene-based molecule 1-[5′-(2-naphthyl)-2,2′-bithiophen-5-yl]hexan-1-one (NCOH), and we have studied the optical and structural properties of NCOH thin films. NCOH is a highly substituted member of the oligothiophene family, designed to improve its molecular stacking, where the presence of an electron-withdrawing group enhances its electron transport capabilities. Employing in situ and time-resolved grazing-incidence wide-angle X-ray scattering (GIWAXS) measurements, we determined the NCOH thin film crystallographic structure and its evolution starting from the early stages of the film growth. We observed strong optical anisotropy resulting from a highly oriented crystallographic structure. Additionally, we investigated the substrate-induced changes of the molecular orientation utilizing the few-layer MoS2 with different orientations of the atomic layers. This study, with its primary focus on the fundamentally important n-type molecular semiconductor, contributes to the field of organic-based (opto-)electronics.

The frictional properties of two-dimensional (2D) materials are strongly dependent on the crystallographic orientation and number of layers. Although friction anisotropy caused by crystallographic orientations has been reported for various 2D materials, the flexural deformations and different defects complicate the insight into the mechanism of the in-plane friction anisotropy of these materials. Here, the anisotropic friction behavior between an atomic force microscopy tip and monolayer (ML) and few-layer (FL) MoSe2 flakes grown by CVD was performed by nanofriction measurements at different crystallographic directions, applied loads (FA), and tip scanning velocities. Our results reveal that the angular dependence of the friction forces is highly anisotropic for both types of MoSe2 flakes, and the anisotropy decreases with FA. Importantly, the anisotropies demonstrate opposite angular dependence for ML and FL MoSe2 flakes. As confirmed by the friction scanning velocity dependences, this difference seems to originate from different friction mechanisms for ML and FL MoSe2 flakes. The friction of FL flakes was predominantly influenced by atomic stick–slip motion. In contrast, ML MoSe2 is characterized by a coexistence of deformation-induced and atomic stick–slip motion. The experimental results presented here extend the understanding of the tribological properties of dry lubricants operating at the nanoscale.

Few-layer films of transition metal dichalcogenides have emerged as promising candidates for applications in electronics. Within this group of 2D materials, platinum diselenide (PtSe2) was predicted to be a compound with one of the highest charge carrier mobility. Recently, the successful integration of group III–V nitride semiconductors with NbNx-based superconductors was reported with a semiconductor transistor grown directly on a crystalline superconductor. This opens up the possibility of combining the macroscopic quantum effects of superconductors with the electronic, photonic, and piezoelectric properties of the semiconducting material. Here, we report on the fabrication of a few-layer PtSe2 film on top of an NbN substrate layer by selenization of pre-deposited 3 nm thick Pt layers. We found the selenization parameters preserving the chemical and structural integrity of both the PtSe2 and NbN films. The PtSe2 film alignment can be tuned by varying the nitrogen flow rate through the reaction chamber. The superconducting critical temperature of NbN is only slightly reduced in the optimized samples compared to pristine NbN. The carrier mobility in PtSe2 layers determined from Hall measurements is below 1 cm2/V s.

Graphene oxide is a complex material whose synthesis is still incompletely understood. To study the time evolution of structural and chemical properties of oxidized graphite, samples at different temporal stages of oxidation were selected and characterized through a number of techniques: X-ray photoelectron spectroscopy for the content and bonding of oxygen, X-ray diffraction for the level of intercalation, Raman spectroscopy for the detection of structural changes, electrical resistivity measurements for probing charge localization on the macroscopic scale, and scanning transmission electron microscopy for the atomic structure of the graphene oxide flakes. We found a nonlinear behavior of oxygen uptake with time where two concentration plateaus were identified: Uptake reached 20 at % in the first 15 min, and after 1 h a second uptake started, reaching a highest oxygen concentration of >30 at % after 2 h of oxidation. At the same time, the interlayer distance expanded to more than twice the value of graph...

Very thin MoS2 films were prepared on hexagonal GaN/AlGaN/GaN (0001) and Si (100) substrates from a stoichiometric target by a pulsed laser deposition. Combined results from Raman and X-ray reflectivity measurements have shown that the thinnest samples are 2–2.5 nm thick. The thickness increases with the number of laser pulses applied albeit no simple direct proportion between the two quantities has been observed. Concerning the stoichiometry, the distribution of Mo and S elements within as-deposited films is rather complex. The stoichiometric MoS2 is making-up only a part of the film. In spite of this, selected area electron diffraction studies have clearly confirmed that the films deposited on Si (100) are nanocrystalline and oriented perpendicularly to the substrate surface while an epitaxial growth of MoS2 films was observed on GaN/AlGaN/GaN (0001) substrates.

As long as the carbon family materials are pristine, powerful methods for their individual characterization have been established and well understood. However, as soon as these materials contain a mixture of sp2 and sp3 hybridized carbons, the spectroscopic characterization becomes challenging. In this paper we present on some aspects of multiply spectroscopic characterizations of sp2-sp3 carbon heterosystems, which can play an important role for their correct structural assignment. We study a composite of single-wall carbon nanotubes (SWCNT) with diamond nanoparticles and a SWCNT paper coated with nanocrystalline diamond films. The SWCNT paper serves here as a reference. We evaluate the surface free energy measured by contact angle technique, morphology imaged by scanning electron microscopy and the chemical composition determined by X-ray photoelectron spectroscopy, Raman spectroscopy at different excitation wavelengths and by attenuated total reflection (ATR) Fourier Transform Infrared spectroscopy (FTIR) using different ZnSe ATR prisms. We demonstrate that, because of the resonant nature of Raman process in SWCNTs, the particular conditions at Raman measurement (laser excitation wavelength, laser intensity) strongly influence the measured spectra of the sp2-sp3 hybridized heterosystems. We also show how the dimensions of the ATR prism affect the results of the FTIR measurements of the SWCNT papers.

Few-layer MoS

Few-layer MoS2 films are promising candidates for applications in numerous areas, such as photovoltaics, photocatalysis, nanotribology, lithium batteries, hydro-desulfurization catalysis and dry lubricants, especially due to their distinctive electronic, optical, and catalytic properties. In general, two alignments of MoS2 layers are possible – the horizontal and the vertical one, having different physicochemical properties. Layers of both orientations are conventionally fabricated by a sulfurization of pre-deposited Mo films. So far, the Mo thickness was considered as a critical parameter influencing the final orientation of MoS2 layers with horizontally and vertically aligned MoS2 grown from thin (1 nm) and thick (3 nm) Mo films, respectively. Here, we present a fabrication protocol enabling the growth of horizontally or vertically aligned few-layer MoS2 films utilizing the same Mo thickness of 3 nm. We show that the sulfur vapor is another parameter influencing the growth mechanism, where a sulfurization with higher sulfur vapor pressure leads to vertical MoS2 layers and slow sulfur evaporation results in horizontally aligned layers for a thicker Mo starting layer.

Ubiquitous carbon nanomaterials have great potential for emerging technologies, but they also pose a threat to human health at the end of their lifecycle, especially when they are introduced into waste or ground waters. Graphene field-effect transistors (GFET) and real time in situ confocal Raman microscopy (CRM) were employed to detect a submonolayer of carbon quantum dots (CQDs) in water. An effective GFET channel was formed on exfoliated and chemical vapor deposited (CVD) graphene. The adsorption of CQDs was monitored by measuring conductance changes in GFETs. The graphene channel was functionalized with (3-aminopropyl) triethoxysilane (APTES), which allowed for easy observation of a shift in the charge neutrality point (CNP) when the graphene channel was exposed to CQDs. The affinity of the CQD's carboxyl terminal groups to the aminofunctionalized channel enabled a highly sensitive CQD detection based on changes in the GFET conductivity. The adsorption of the CQDs induced a positive shift of the CNP with a limit of detection at concentrations of 239 ppm and 62 ppm for the exfoliated and CVD graphene, respectively. A supporting study of graphene functionalization and CQD adsorption was performed by real time in situ CRM, ellipsometry, and ex situ X-ray photoelectron spectroscopy. © 2019 Author(s).

Tribological properties of a surface are controlled by its topography and chemical structure as suggested by theoretical studies. However, the effect of crystallographic orientation on the tribological properties is still controversial. By tuning the heating rate during sulfurization of CVD Mo films, we prepared the few-layer MoS2 films with similar surface topography but different crystallographic c-axis orientation. This resulted in distinctly different tribological behavior both on the nanoscale and macroscale that can be attributed to different surface chemistry and surface electronic and phonon structures. In particular, horizontally aligned MoS2 sheets with c-axis oriented along the surface normal favor the weak van der Waals forces which resulted in a twice lower coefficient of friction comparing to the vertically aligned MoS2 sheets. These results demonstrate the possibility to optimize tribological properties by crystallographic orientation as required for the thin solid-state lubricating layers for extreme conditions.

In recent years, molybdenum disulfide (MoS2) has been investigated due to its unique electronic, optical, and mechanical properties with a variety of applications. Sulfurization of pre-deposited MoO3 layers is one of the methods of the preparation of large-area MoS2 thin films. The MoO3 layers have been grown on c-sapphire substrates, using two different techniques (rf sputtering, pulsed laser deposition). The films were subsequently annealed in vapors of sulfur at high temperatures what converted them to MoS2 films. The quality of MoS2 is strongly influenced by the properties of the precursor MoO3 layers. The pre-deposited MoO3, as well as the sulfurized MoS2, have been characterized by several techniques including Raman, Rutherford backscattering spectroscopy, atomic force microscopy, scanning electron microscopy, and X-ray diffraction. Here we compare two types of MoS2 films prepared from different MoO3 layers to determine the most suitable MoO3 layer properties providing good quality MoS2 films for future applications.

Correction for ‘Tuning the charge carrier mobility in few-layer PtSe2 films by Se : Pt ratio’ by Jana Hrdá et al., RSC Adv., 2021, 11, 27292–27297, DOI: 10.1039/D1RA04507E.

Metal-induced crystallisation with layer exchange is applied on Ni/C bilayer stacks deposited by three PVD techniques on SiO2. The layer stacks were deposited at room temperature by either ion beam sputtering, direct current magnetron sputtering or high-power impulse magnetron sputtering. The influence of the Ni morphology on the layer exchange degree αLE and the resulting graphitic ordering is studied by atomic force microscopy, Rutherford backscattering spectrometry and Raman spectroscopy. The initial RMS roughness of the Ni top layer varied with the deposition technique by a factor of 20, from 0.3 to 6.1 nm. After annealing in UHV at up to 700 °C, layer exchange was observed for all samples. Still, the layer exchange degree was affected by the roughness of the initial bilayer stack. The highest value of 96% was achieved for magnetron-sputtered samples, what is by ∼35% higher than for the initially roughest Ni surfaces. Raman spectroscopy showed the formation of graphitic carbon, characterised by a strong 2D line, for all three bilayer stacks. The degree of graphitic ordering increased with decreasing Ni surface roughness.