Category: Articles

Growth of lithium hydride thin films from solutions: Towards solution atomic layer deposition of lithiated films

KUNDRATA, Ivan – FRÖHLICH, Karol – VANČO, Ľubomír – MICUŠÍK, Matej – BACHMANN, Julien

In Beilstein Journal of Nanotechnology. Vol. 10, (2019)

https://doi.org/10.3762/bjnano.10.142

Abstract

Lithiated thin films are necessary for the fabrication of novel solid-state batteries, including the electrodes and solid electrolytes. Physical vapour deposition and chemical vapour deposition can be used to deposit lithiated films. However, the issue of conformality on non-planar substrates with large surface area makes them impractical for nanobatteries the capacity of which scales with surface area. Atomic layer deposition (ALD) avoids these issues and is able to deposit conformal films on 3D substrates. However, ALD is limited in the range of chemical reactions, due to the required volatility of the precursors. Moreover, relatively high temperatures are necessary (above 100 °C), which can be detrimental to electrode layers and substrates, for example to silicon into which the lithium can easily diffuse. In addition, several highly reactive precursors, such as Grignard reagents or n-butyllithium (BuLi) are only usable in solution. In theory, it is possible to use BuLi and water in solution to produce thin films of LiH. This theoretical reaction is self-saturating and, therefore, follows the principles of solution atomic layer deposition (sALD). Therefore, in this work the sALD technique and principles have been employed to experimentally prove the possibility of LiH deposition. The formation of homogeneous air-sensitive thin films, characterized by using ellipsometry, grazing incidence X-ray diffraction (GIXRD), in situ quartz crystal microbalance, and scanning electron microscopy, was observed. Lithium hydride diffraction peaks have been observed in as-deposited films by GIXRD. X-ray photoelectron spectroscopy and Auger spectroscopy analysis show the chemical identity of the decomposing air-sensitive films. Despite the air sensitivity of BuLi and LiH, making many standard measurements difficult, this work establishes the use of sALD to deposit LiH, a material inaccessible to conventional ALD, from precursors and at temperatures not suitable for conventional ALD.

Tailored Langmuir-Schaefer Deposition of Few-Layer MoS2 Nanosheet Films for Electronic Applications

KALOSI, Anna – DEMYDENKO, Maksym – BODÍK, Michal – HAGARA, Jakub – KOTLÁR, Mário – KOSTIUK, Dmytro – HALAHOVETS, Yurily – VÉGSÖ, Karol – ROLDAN, Alicia Marin – MAURYA, Gulab Singh – ANGUŠ, Michal – VEIS, Pavel – JERGEL, Matej – MAJKOVÁ, Eva – ŠIFFALOVIČ, Peter

In Langmuir. Vol. 35, iss. 30 (2019)

https://doi.org/10.1021/acs.langmuir.9b01000

Abstract

Few-layer MoS2 films stay at the forefront of current research of two-dimensional materials. At present, continuous MoS2 films are prepared by chemical vapor deposition (CVD) techniques. Herein, we present a cost-effective fabrication of the large-area spatially uniform films of few-layer MoS2 flakes using a modified Langmuir–Schaefer technique. The compression of the liquid-phase exfoliated MoS2 flakes on the water subphase was used to form a continuous layer, which was subsequently transferred onto a submerged substrate by removing the subphase. After vacuum annealing, the electrical sheet resistance dropped to a level of 10 kΩ/sq, being highly competitive with that of CVD-deposited MoS2 nanosheet films. In addition, a consistent fabrication protocol of the large-area conductive MoS2 films was established. The morphology and electrical properties predetermine these films to advanced detecting, sensing, and catalytic applications. A large number of experimental techniques were used to characterize the exfoliated few-layer MoS2 flakes and to elucidate the formation of the few-layer MoS2 Langmuir film.

Stoichiometry, structure and mechanical properties of co-sputtered Ti 1-x Ta x B 2±Δ coatings

GRANČIČ, B. – PLEVA, Milan – MIKULA, M. – ČAPLOVIČOVÁ, Mária – SATRAPINSKYY, L – ROCH, Tomáš – TRUCHLÝ, M. – SAHUL, Martin – GREGOR, M. – ŠVEC, Peter, Sr. – ZAHORAN, Miroslav – KÚŠ, Peter

In Surface & Coatings Technology. Vol. 367, June (2019)

https://doi.org/10.1016/j.surfcoat.2019.04.017

Abstract

Magnetron co-sputtering from TiB2 and TaB2 stoichiometric targets is used to prepare AlB2-prototype ternary Ti1-xTaxB2±Δ solid solution, with x in the range from 0 to 1. Using this technique, the boron-to-metal ratio (B/Me) varies with the actual Ti and Ta content. The boron-to‑tantalum ratio can be increased by decreasing the TaB2 target voltage, which has a considerable effect on the coating structure. Coatings with B/Me > 2 reveal highly textured nanocolumnar structure, while the coatings with B/Me < 2 tend to be nanocrystalline (without any preferred crystallite orientation) or amorphous. All the deposited coatings have a hardness higher than 32 GPa. The under-stoichiometric (B/Me < 2) coatings show material pile-up around the cube-corner indent edges, an indication for plastic flow and increased ductility.

An elevated concentration of MoS2 lowers the efficacy of liquid-phase exfoliation and triggers the production of MoOx nanoparticles

In Physical Chemistry Chemical Physics. Vol. 21, iss. 23 (2019)

https://doi.org/10.1039/C9CP01951K

Abstract

It is generally accepted that liquid-phase exfoliation (LPE) enables large-scale production of few-layer MoS2 flakes. In our work, we studied in detail few-layer MoS2 oxidation in the course of standard LPE in a water/ethanol solution. We demonstrate that an increase of the initial MoS2 concentration above a certain threshold triggers a pronounced oxidation and the exfoliation process starts to produce MoOx nanoparticles. A subsequent decrease of the water pH along with an increased content of SO42− suggests an oxidation scenario of few-layer MoS2 oxidation towards MoOx nanoparticles. Moreover, the lowered pH leads to agglomeration and sedimentation of the few-layer MoS2 flakes, which significantly lowers their production yield. We employed a large number of physico-chemical techniques to study the MoS2-to-MoOx transformation and found a threshold value of 10 mg ml−1 of the initial MoS2 concentration to trigger this transformation.

Tailoring the interparticle distance in Langmuir nanoparticle films

BENKOVIČOVÁ, Monika – HOLOS, Ana – NÁDAŽDY, Peter – HALAHOVETS, Yurily – KOTLÁR, Mário – KOLLÁR, Jozef – ŠIFFALOVIČ, Peter – JERGEL, Matej – MAJKOVÁ, Eva – MOSNÁČEK, Jaroslav – IVANČO, Ján

In Physical Chemistry Chemical Physics. Vol. 21, iss. 18 (2019)

Abstract

The ability to control the interparticle distance in self-assembled arrays of nanoparticles plays an important role in a large number of applications, which require tunable electronic and photonic properties. Importantly, practical applications in real devices rely on arrays satisfying more stringent requirements of lateral homogeneity controlled over a large scale. Herein, the interparticle distance in ordered nanoparticle assemblies was controlled by varying the nanoparticle effective size via the molecular chemical nature and chain length of the ligand. Iron oxide nanoparticles (IONPs) were functionalized by three types of ligands, namely (i) a mixture of oleic acid/oleylamine (OA/OAm), (ii) poly(n-butyl acrylate) (PBA) and (iii) polystyrene (PS), while two different molar masses of PBA and PS were used. The polymeric ligands with narrow dispersity and bearing phosphonic chain-end groups were prepared by atom transfer radical polymerization. Functionalization of the IONPs with polymeric ligands was achieved using a ligand exchange method. Both the hydrodynamic diameter and size distribution of the nanoparticles in colloidal solution were determined by dynamic light scattering (DLS). The mean interparticle distances in Langmuir–Schaefer monolayers prepared on solid substrates were assessed by means of the pair correlation function calculated from the atomic force microscopy (AFM) images. Furthermore, the lateral ordering, homogeneity, and interparticle distances averaged over a mesoscopic scale of the ordered monolayers were studied by the grazing-incidence small-angle X-ray scattering (GISAXS) technique. We demonstrate that the (nanoparticle) centre-to-centre distance in the ordered assemblies constituted by the IONPs with the core diameter of about 6 nm can be varied from 7.6 to about 12 nm with the resulting interparticle gap change by a factor of about 4.

Covalent Diamond-Graphite Bonding: Mechanism of Catalytic Transformation

Covalent Diamond-Graphite Bonding: Mechanism of Catalytic Transformation

Semir Tulić, Thomas Waitz, Mária Čaplovičová, Gerlinde Habler, Marián Varga, Mário Kotlár, Viliam Vretenár, Oleksandr Romanyuk, Alexander Kromka, Bohuslav Rezek, Viera Skákalová

In ACS Nano. Vol. 13, iss. 4 (2019)

https://doi.org/10.1021/acsnano.9b00692

Abstract

Aberration-corrected transmission electron microscopy of the atomic structure of diamond–graphite interface after Ni-induced catalytic transformation reveals graphitic planes bound covalently to the diamond in the upright orientation. The covalent attachment, together with a significant volume expansion of graphite transformed from diamond, gives rise to uniaxial stress that is released through plastic deformation. We propose a comprehensive model explaining the Ni-mediated transformation of diamond to graphite and covalent bonding at the interface as well as the mechanism of relaxation of uniaxial stress. We also explain the mechanism of electrical transport through the graphitized surface of diamond. The result may thus provide a foundation for the catalytically driven formation of graphene–diamond nanodevices.

Effect of temperature and carrier gas on the properties of thick InxAl1-xN layer

Prerna Chauhan, Stanislav Hasenöhrl, Edmund Dobročka, Ľubomír Vančo, Roman Stoklas, Jaroslav Kováč, Peter Šiffalovič, Ján Kuzmík

In Applied Surface Science. Vol.470, (2019)

https://doi.org/10.1016/j.apsusc.2018.10.231

Abstract

Thick (>150nm) InxAl1-xN layers were grown on GaN/sapphire (0001) by organometallic vapor phase epitaxy. Growth temperature of InxAl1-xN layers was reduced from 790 to 730°C, to examine the effects of growth temperature in InxAl1-xN layers grown under H2 carrier gas. Indium incorporation, surface morphology, electrical, and optical properties of InxAl1-xN layers were examined as a function of growth temperature. Increase in In-molar fraction, as determined by high resolution X-ray diffraction, was observed with decreasing growth temperature of InxAl1-xN layers at the expense of surface roughness. Unstrained InxAl1-xN layer was achieved at 730°C under H2 carrier gas with x=0.18. However, InxAl1-xN layer grown under N2 carrier gas at 730°C to study the effects of carrier gas, was observed with two times higher In-molar fraction (x=0.37) and one order lower carrier concentration. This work shows the essential requirement of a multi-characterization approach to establish a connection between structural, electrical, and optical properties to improve our understanding towards InxAl1-xN. Edge threading dislocations density is found to be the most important parameter in deciding the characteristics of an InxAl1-xN layer.

Effect of temperature and carrier gas on the properties of thick InxAl1-xN layer

Effect of temperature and carrier gas on the properties of thick InxAl1-xN layer

Prerna Chauhan, Stanislav Hasenöhrl, Edmund Dobročka, Ľubomír Vančo, Roman Stoklas, Jaroslav Kováč, Peter Šiffalovič, Ján Kuzmík

In Applied Surface Science. Vol.470, (2019

doi.org/10.1016/j.apsusc.2018.10.231

Abstract

Thick (>150nm) InxAl1-xN layers were grown on GaN/sapphire (0001) by organometallic vapor phase epitaxy. Growth temperature of InxAl1-xN layers was reduced from 790 to 730°C, to examine the effects of growth temperature in InxAl1-xN layers grown under H2 carrier gas. Indium incorporation, surface morphology, electrical, and optical properties of InxAl1-xN layers were examined as a function of growth temperature. Increase in In-molar fraction, as determined by high resolution X-ray diffraction, was observed with decreasing growth temperature of InxAl1-xN layers at the expense of surface roughness. Unstrained InxAl1-xN layer was achieved at 730°C under H2 carrier gas with x=0.18. However, InxAl1-xN layer grown under N2 carrier gas at 730°C to study the effects of carrier gas, was observed with two times higher In-molar fraction (x=0.37) and one order lower carrier concentration. This work shows the essential requirement of a multi-characterization approach to establish a connection between structural, electrical, and optical properties to improve our understanding towards InxAl1-xN. Edge threading dislocations density is found to be the most important parameter in deciding the characteristics of an InxAl1-xN layer.

Biomass waste-carbon/reduced graphene oxide composite electrodes for enhanced supercapacitors

GUARDIA, Laura – SUÁREZ, Loreto – QUEREJETA, Nausika – VRETENÁR, Viliam – KOTRUSZ, Peter – SKÁKALOVÁ, Viera – CENTENO, Teresa A.

In Electrochimica Acta. Vol. 298, iss. 3 (2019)

Abstract

We present a simple and effective alternative which optimizes electrodes based on low-cost carbons for high-performance supercapacitors. The combination with reduced graphene oxide (rGO) greatly improves the operation of microporous carbons easily produced by one-pot activation of grape seeds. The use of composite electrodes with rGO lowers the supercapacitor resistance and enables a much higher rate capability.

The mixture of rGO flakes and particles of a highly porous carbon obtained by KOH activation allows retaining the high capacitance of 260 F g−1 of the standard electrodes at 1 mA cm−2 in aqueous H2SO4 whereas the value at 200 mA cm−2 is increased by around 2.4 times. Consequently, at high current density, the capacitor assembled with these composites stores eight times more energy and the power density is multiplied by four.

The synergy between rGO and an ultramicroporous carbon produced by CO2-activation results extremely profitable, the cell assembled with composite electrodes reaching three times more energy and power at 200 mA cm−2 than the best performance of the standard counterpart.

More importantly, the higher density of the composite electrodes leads to a capacitance of around 200 F cm−3 which translates into a remarkable improvement in the supercapacitor operation normalized to volume.

Evidence of relationship between strain and In-incorporation: Growth of N-polar In-rich InAlN buffer layer by OMCVD

CHAUHAN, Prerna – HASENÖHRL, Stanislav – DOBROČKA, Edmund – CHAUVAT, Marie-Pierre – MINJ, A. – GUCMANN, Filip – VANČO, Ľubomír – KOVÁČ, Jaroslav jr. – KRET, S. – RUTERANA, Pierre – KUBALL, Martin – ŠIFFALOVIČ, Peter – KUZMÍK, Ján

In Journal of Applied Physics. 125, iss. 10 (2019)

https://doi.org/10.1063/1.5079756

Abstract

Two In𝑥Al1−𝑥NInAl1−N layers were grown simultaneously on different substrates [sapphire (0001) and the Ga-polar GaN template], but under the same reactor conditions, they were employed to investigate the mechanism of strain-driven compositional evolution. The resulting layers on different substrates exhibit different polarities and the layer grown on sapphire is N-polar. Moreover, for the two substrates, the difference in the degree of relaxation of the grown layers was almost 100%, leading to a large In-molar fraction difference of 0.32. Incorporation of In in In𝑥Al1−𝑥NInAl1−N layers was found to be significantly influenced by the strain imposed by the under-layers. With the evolutionary process of In-incorporation during subsequent layer growth along [0001], the direction of growth was investigated in detail by Auger electron spectroscopy. It is discovered that the In0.60Al0.40NIn0.60Al0.40N layer grown directly on sapphire consists of two different regions with different molar fractions: the transition region and the uniform region. According to the detailed cross-sectional transmission electron microscopy, the transition region is formed near the hetero-interface due to the partial strain release caused by the generation of misfit-dislocations. The magnitude of residual strain in the uniform region decides the In-molar fraction. In𝑥Al1−𝑥NInAl1−N layers were analyzed by structural and optical characterization techniques. Our present work also shows that a multi-characterization approach to study In𝑥Al1−𝑥NInAl1−N is a prerequisite for their applications as a buffer layer.