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Publications in 2023

ABSTRACT: This paper reports on the deposition of amorphous and crystalline thin films of Ga2O3 by reactive pulsed direct current magnetron sputtering from a liquid gallium target onto fused (f-) quartz and c plane (c-) sapphire substrates, where the temperature of the substrate is varied from room temperature (RT) to 800 °C. The deposition rate (up to 37 nm/min at RT on f-quartz and 5 nm/min at 800 °C on c-sapphire) is two to five times higher than the data given in the literature for radio frequency sputtering. Deposited onto unheated substrates, the films are X-ray amorphous. Well-defined X-ray diffraction peaks of β-Ga2O3 start to appear at a substrate temperature of 500 °C. Films grown on c-sapphire at temperatures above 600 °C are epitaxial. However, the high rocking curve full width at half maximum values of ≈2.4–2.5° are indicative of the presence of defects. A dense and void-free microstructure is observed in electron microscopy images. Composition analysis show stoichiometry close to Ga2O3 and no traces of impurities. The optical properties of low absorptance (<1%) in the visible range and an optical band gap of approximately 5 eV are consistent with the data in the literature for Ga2O3 films produced by other deposition methods.

Vacuum, Volume 209, March 2023, 111789
DOI: 10.1016/j.vacuum.2022.111789
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ABSTRACT: Solid state ionics is one of the key research topics of the Institute of Solid State Physics, University of Latvia since its establishment. The research direction included topics ranging from electrochromic phenomena in transition metal oxides through gas sensors and electronic nose to materials for rechargeable battery electrodes and materials for hydrogen energy. By the late 1980s, the institute had become one of the biggest and most prolific solid state ionic centres in the USSR and Eastern Europe and continues to maintain its position among the regional leaders in the field. Regular regional conferences and workshops were organized and some of the published works can be ranked among the pioneering works in the world of science. This extensive historical review summarizes information on the development of solid state ionics, actual research and achievements from establishment of the institute to the present day. Currently many collaborations are ongoing with partners across Europe and beyond in research ranging from battery materials and smart windows for zero energy buildings to hydrogen production, maintaining and growing its strength as key national, regional, and international centre of research excellence in solid state ionics.

Journal of Solid State Electrochemistry, February 2023
DOI: 10.1007/s10008-023-05419-8
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ABSTRACT: An experimental investigation was conducted to explore spectroscopic and structural characterization of semiconducting yttrium oxide thin film deposited at 623 K (±5K) utilizing reactive pulsed direct current magnetron sputtering. Based on the results obtained from both x-ray diffraction and transmission electron microscope measurements, yttrium monoxide is very likely formed in the transition region between β-Y2O3 and α-Y2O3, and accompanied by the crystalline Y2O3. Resulting from either the low energy separation between 4d and 5s orbitals and/or different spin states of the corresponding orbitals’ sublevels, the stability of monoxide is most presumably self-limited by the size of the crystal in thermodynamic terms. This behavior develops a distortion in the structure of the crystal compared to the metal oxide cubic structure and it also effectuates the arrangement in nanocrystalline/amorphous phase. In addition to this, spectroscopic ellipsometry denotes that the semiconducting yttrium oxide has the dominant, mostly amorphous, formation character over crystalline Y2O3. Our purpose, by means of the current findings, is to advance the understanding of formation kinetics/conditions of yttrium with an unusual valency (2+).

Vacuum, Volume 211, May 2023, 111942
DOI: 10.1016/j.vacuum.2023.111942
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ABSTRACT: In this critical review, we call attention to a widespread problem related to the vast disagreement in elastic moduli values reported by different authors for nanostructures made of the same material. As a particular example, we focus on ZnO nanowires (NWs), which are among the most intensively studied nanomaterials due to their remarkable physical properties and promising applications. Since ZnO NWs possess piezoelectric effects, many applications involve mechanical deformations. Therefore, there are plenty of works dedicated to the mechanical characterization of ZnO NWs using various experimental and computational techniques. Although the most of works consider exactly the same growth direction and wurtzite crystal structure, reported values of Young’s modulus vary drastically from author to author ranging from 20 to 800 GPa. Moreover, both – diameter dependent and independent – Young’s modulus values have been reported. In this work, we give a critical overview and perform a thorough analysis of the available experimental and theoretical works on the mechanical characterization of ZnO NWs in order to find out the most significant sources of errors and to bring out the most trustable results.

Vacuum, Volume 211, May 2023, 111942
DOI: 10.1515/ntrev-2022-0505
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ABSTRACT: While gallium oxide Ga2O3 has recently shown promise as a new ultra-wide bandgap semiconductor in the form of thin films and nanowires (NWs), its widespread applicability is limited due to lack of native p-type conductivity, thus requiring fabrication of heterojunctions. A potential matching material is spinel zinc gallate ZnGa2O4. In this work we demonstrated and compared two novel approaches of one-dimensional Ga2O3-ZnGa2O4 core-shell NW heterostructure preparation: (a) a direct deposition of a ZnGa2O4 coating using a reactive magnetron co-sputtering; (b) annealing of a sacrificial few-nm-thick ZnO coating, deposited via atomic layer deposition, at high temperature to enable solid state reaction between ZnO and Ga2O3. The as-grown nanostructures were characterized via scanning and transmission electron microscopies, X-ray diffraction and X-ray photoelectron spectroscopy. Room temperature optical features were disclosed using photoluminescence and optical absorption. While both methods are viable for production of the heterostructures, smoother and more uniform ZnGa2O4 coating around Ga2O3 NWs was obtained via sacrificial layer conversion in comparison to the sputter-deposited one. These heterostructures could potentially be used for photocatalysis and nanoscale ultra-wide bandgap electronics.

Journal of Crystal Growth, Available online 12 June 2023, 127319 (In Press, Journal Pre-proof)
DOI: 10.1016/j.jcrysgro.2023.127319
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ABSTRACT: Recently gallium oxide (Ga2O3) has become one of the most actively studied materials due to its competitive electronic properties such as wide bandgap, high breakdown field, simple control of carrier concentration, and high thermal stability. These properties make gallium oxide a promising candidate for potential applications in high-power electronic devices. β-Ga2O3 crystals are commonly grown by the Czochralski method in an iridium (Ir) crucible. For this reason, Ir is often present in Ga2O3 crystals as an unintentional dopant. In this work the impact of Ir incorporation defects on potential p-type conductivity in β-Ga2O3 is studied by means of density functional theory. The metastable α-Ga2O3 phase was investigated as the model object to understand the processes caused by iridium doping in gallium oxide-based systems. Obtained results allow us to understand better the influence of Ir on Ga2O3 electronic structure, as well as provide interpretation for optical transitions reported in recent experiments.

Scientific Reports volume 13, Article number: 8522 (2023)
DOI: 10.1038/s41598-023-35112-9
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ABSTRACT: Many modern applications, including quantum computing and quantum sensing, use substrate-film interfaces. Particularly, thin films of chromium or titanium and their oxides are commonly used to bind various structures, such as resonators, masks, or microwave antennas, to a diamond surface. Due to different thermal expansions of involved materials, such films and structures could produce significant stresses, which need to be measured or predicted. In this paper, we demonstrate imaging of stresses in the top layer of diamond with deposited structures of Cr2O3 at temperatures 19°C and 37°C by using stress-sensitive optically detected magnetic resonances (ODMR) in NV centers. We also calculated stresses in the diamond-film interface by using finite-element analysis and correlated them to measured ODMR frequency shifts. As predicted by the simulation, the measured high-contrast frequency-shift patterns are only due to thermal stresses, whose spin-stress coupling constant along the NV axis is 21±1 MHz/GPa, that is in agreement with constants previously obtained from single NV centers in diamond cantilever. We demonstrate that NV microscopy is a convenient platform for optically detecting and quantifying spatial distributions of stresses in diamond-based photonic devices with micrometer precision and propose thin films as a means for local application of temperature-controlled stresses. Our results also show that thin-film structures produce significant stresses in diamond substrates, which should be accounted for in NV-based applications.

Optics Express Vol. 31, Issue 11, pp. 17950-17963 (2023)
DOI: 10.1364/OE.489901 (Open Access)


ABSTRACT: Tribovoltaic devices are attracting increasing attention as motion-based energy harvesters due to the high local current densities that can be generated. However, while these tribovoltaic devices are being developed, debate remains surrounding their fundamental mechanism. Here, we fabricate thin films from one of the world’s most common oxides, TiO2, and compare the tribovoltaic performance under contact with metals of varying work functions, contact areas, and applied pressure. The resultant current density shows little correlation with the work function of the contact metal and a strong correlation with the contact area. Considering other effects at the metal–semiconductor interface, the thermoelectric coefficients of different metals were calculated, which showed a clear correlation with the tribovoltaic current density. On the microscale, molybdenum showed the highest current density of 192 mA cm-2. This work shows the need to consider a variety of mechanisms to understand the tribovoltaic effect and design future exemplar tribovoltaic devices.

ACS Appl. Mater. Interfaces 2023, 15, 27, 33140–33147
DOI: 10.1021/acsami.3c05830
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ABSTRACT: WO3/Cu/WO3 coatings are transparent electrodes, but conductivity and transmittance have been observed to decrease with time. This paper reports the improved stability of WO3/Cu/WO3/Cu/WO3 coatings deposited by magnetron sputtering on glass and polyethylene terephthalate substrates. The stability issues due to Cu oxidation and migration can be addressed by adjusting the deposition parameters. Lowering the sputtering pressure results in denser WO3 films, confirmed by spectroscopic ellipsometry, and thus more stable coatings. The coatings retain their properties in an inert atmosphere, indicating that Cu oxidation is the main reason for the decrease in conductivity, rather than its migration observed by X-ray photoelectron spectroscopy. Optical property modeling is used to optimize the thickness of the three-layer coatings to obtain the highest figure-of-merit for a transparent electrode. A structure of glass/WO3 (70 nm)/Cu (10 nm)/WO3 (45 nm) gives a sheet resistance of 14 Ω/sq. and a light transmittance of 65% at 600 nm. In addition, the antimicrobial properties of these coatings are revealed. A decrease up to 105 of the gram-negative Escherichia coli and gram-positive Staphylococcus aureus bacterial colony formation units is found for several WO3/Cu/WO3-based coatings. In the case of the MS2 (Emesvirus zinderi) bacteriophage, a decrease in infectious particles for up to 104 plaque-forming units is obtained. The results indicate that more stable samples also had higher antimicrobial activity.

Surfaces and Interfaces, Volume 41, October 2023, 103259
DOI: 10.1016/j.surfin.2023.103259 
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ABSTRACT: Nanowires (NWs) are among the most studied nanostructures as they have numerous promising applications thanks to their various unique properties. Furthermore, the properties of NWs can be tailored during synthesis by introducing structural defects such as nano-twins, periodic polytypes, and kinks, i.e., abrupt changes in their axial direction. Here, this work reports for the first time the postsynthesis formation of such defects, achieved by exploiting a peculiar plasticity that may occur in nanosized covalent materials. Specifically, in this work the authors found that single-crystal CuO NWs can form double kinks when subjected to external mechanical loading. Both the microscopy and atomistic modeling suggest that deformation-induced twinning along the (110) plane is the mechanism behind this effect. In a single case the authors are able to unkink a NW back to its initial straight profile, indicating the possibility of reversible plasticity in CuO NWs, which is supported by the atomistic simulations. The phenomenon reported here provides novel insights into the mechanisms of plastic deformation in covalent NWs and offers potential avenues for developing techniques to customize the shape of NWs postsynthesis and introduce new functionalities.

Small 2023, 2304614
DOI: 10.1002/smll.202304614
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ABSTRACT: We characterize the nonlinear optical properties of indium–tin oxide (ITO) quantum dots (QDs) in the IR range using the Z-scan method. We present results of three-photon absorption (3PA), third harmonic generation (3HG), and Kerr-effect-induced nonlinear refraction in ITO QDs. Z-scan measurements were carried out for the QDs solution, while 3HG was demonstrated using QD thin films. The Kerr-induced nonlinear refractive index was analyzed along the 800–950 nm range showing an increase in this parameter from −6.7 × 10−18 to −1.5 × 10−17 m2 W−1. At longer wavelengths (1000–1100 nm), the higher-order effects started to contribute to a nonlinear refractive index. The 3PA coefficient at 950 nm was measured to be 1.42 × 10−32 m3/W2. We discuss the peculiarities in the wavelength-dependent variation of the coefficient of nonlinear absorption responsible for 3PA in the range of 800–1150 nm. Third harmonic generation was analyzed in the 1200–1550 nm spectral range. The absolute value of 3HG conversion efficiency in the 150 nm thick film at the wavelength of laser radiation (1350 nm) was estimated to be ~10−5.

Nanomaterials 2023, 13(16), 2320
DOI: 10.3390/nano13162320 (Open Access)
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ABSTRACT: Spray deposition and inkjet printing of various nanostructures are emerging complementary methods for creating conductive coatings on different substrates. In comparison to established deposition techniques like vacuum metal coating and lithography-based metallization processes, spray deposition and inkjet printing benefit from significantly simplified equipment. However, there are number of challenges related to peculiar properties and behaviour of nanostructures that require additional studies. In present work, we investigate electroconductive properties and sintering behaviour of thin films produced from nanostructures of different metals (Ag, Cu and Cu-Ag) and different shapes (nanowires and spherical nanoparticles), and compare them to the reference Ag and Cu magnetron deposited films. Synthesized nanostructures were studied with transmission electron microscopy. Morphology and crystallinity of produced metal films were studied with scanning electron microscopy and X-ray diffraction. The electrical parameters were measured by the van der Pauw method. All nanowires-based films provided high conductivity and required only modest thermal treatment (200 °C). To achieve sufficient sintering and conductivity of nanoparticles-based films, higher temperatures are required (300 °C for Ag nanoparticles and 350 °C for Cu and Cu-Ag nanoparticles). Additionally, stability of nanowires was studied by annealing the samples in vacuum conditions inside a scanning electron microscope at 500 °C.

Thin Solid Films Volume 784, 1 November 2023, 140087
DOI: 10.1016/j.tsf.2023.140087
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ABSTRACT: The development and testing of antimicrobial coatings continues to be a crucial approach, considering the ongoing emergence of antibiotic-resistant bacteria and the rapid transmission of highly pathogenic viruses. In this study, three types of coatings—pure metallic copper (Cu), zinc oxide (ZnO), and a three-layer zinc oxide and copper mixed coating (ZnO/Cu/ZnO)—were deposited by magnetron sputtering on polyethylene terephthalate substrates to evaluate their antimicrobial potential using various microorganisms, including viruses. Gram-positive Staphylococcus aureus and Gram-negative Escherichia coli bacteria were used for the assessment of antibacterial properties. Antiviral testing was performed using MS2 bacteriophage and replication-deficient Semliki Forest virus, both representing single-stranded RNA-containing viruses. The samples’ ability to cause reactive oxygen species formation was measured, and the effect on bacterial metabolic activity was evaluated. Cu-coated samples showed high inhibitory activity (>95%) against E. coli and S. aureus bacteria, as well as against tested viruses (SFV and MS2). The antibacterial and antiviral properties of ZnO/Cu/ZnO and ZnO coatings were not significant. Although ZnO/Cu/ZnO and ZnO caused inhibition of the metabolic activity of the bacteria, it was insufficient for complete bacteria eradication. Furthermore, significant reactive oxygen species (ROS) production was detected only for single Cu-coated samples, correlating with the strong bacteria-killing ability. We suppose that the ZnO layer exhibited a low release of Zn ions and prevented contact of the Cu layer with bacteria and viruses in the ZnO/Cu/ZnO coating. We conclude that current ZnO and Cu-ZnO-layered coatings do not possess antibacterial and antiviral activity.

Coatings 2024, 14(1), 14
DOI: 10.3390/coatings14010014 (Open Access)
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ABSTRACT: This paper reports on the deposition and photoluminescence of amorphous and crystalline thin films of zinc gallium oxide with Ga:Zn atomic ratio varied between 0.3 and 5.7. The films are prepared by reactive direct current magnetron co-sputtering from liquid/solid gallium/zinc targets onto fused quartz substrates; the temperature of the substrate is varied from room temperature (RT) to 800 °C. The sputtering process is effectively controlled by fixing the sputtering power of one of the targets and controlling the power of the other target by plasma optical emission spectroscopy. The method, in conjunction with oxygen flow adjustment, enables the production of near-stoichiometric films at any temperature used. The composition analysis suggests a few at% oxygen deficiency in the films. The resulting deposition rate is at least an order of magnitude higher compared to the commonly used radio-frequency sputtering from a ceramic ZnO:Ga2O3 target. Deposited onto unheated substrates, the films with Ga:Zn ≈ 2 are X-ray amorphous. Well-defined X-ray diffraction peaks of spinel ZnGa2O4 start to appear at a substrate temperature of 300 °C. The surface of the as-deposited films is dense and exhibits a fine-featured structure observed in electron microscopy images. Increasing the deposition temperature from RT to 800 °C eliminates defects and improves crystallinity, which for the films with Ga:Zn ratio close to 2 results in an increase in the optical band gap from 4.6 eV to 5.1 eV. Room temperature photoluminescence established the main peak at 3.1 eV (400 nm); a similar peak in Ga2O3 is ascribed to oxygen-vacancy related transitions. A prominent feature around 2.9 eV (428 nm) is attributed to self-activation center of the octahedral Ga-O groups in the spinel lattice of ZnGa2O4. It was found that photoluminescence from ZnGa2O4 depends significantly on the stoichiometric ratio between Ga and Zn and the deposition/annealing temperature.

Journal of Alloys and Compounds, Volume 976, 5 March 2024, 173218
DOI: 10.1016/j.jallcom.2023.173218
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ABSTRACT: Hydrogen peroxide is essential for biological processes and normally occurs in low concentrations in living organisms. However, exposure of plants to biotic and abiotic stressors can disrupt their defense mechanisms, resulting in oxidative stress with elevated H2O2 levels. This oxidative stress can damage cell membranes, impair photosynthesis, and hinder crucial plant functions. The primary focus of this article is to investigate the effects of salt and herbicide stress factors on the growth of rye samples. For precise quantification of the released H2O2 concentration caused by these stress factors, a non-enzymatic electrochemical sensor was developed, employing nanostructured CuO and Co3O4 oxides. Nanostructured electrodes exhibit high sensitivity and selectivity towards H2O2, making them suitable for detecting H2O2 in real samples with complex compositions. Rye samples exposed to NaCl- and glyphosate-induced stress demonstrated notable concentrations of released H2O2, displaying an increase of up to 30% compared to the control sample. Moreover, optical absorption measurements revealed a substantial decrease in chlorophyll concentration (up to 35% compared to the control group) in rye samples where elevated H2O2 levels were detected through electrochemical methods. These findings provide further evidence of the harmful effects of elevated H2O2 concentrations on plant vital functions.

Chemosensors 2023, 11(10), 532
DOI: 10.3390/chemosensors11100532 (Open Access)
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ABSTRACT: In this article, the fabrication, characterization, tribological performance, and micromechanical properties of nanostructured smart coatings (NSC) based on the multilayered alternating carbonitride/nitride bilayer {TiMe-CN/TiAlSi-N}n system are discussed. The symbol “Me” denotes refractory metals Hf or Nb, and the index “n” shows the number of superlattice periods. The NSC samples were deposited onto bearing steel (100Cr6) substrates using a reactive high-power physical vapor deposition (PVD) technique that can be scaled up for industrial use. The deposited multilayered NSC contained crystalline nanometer-scale TiMe-CN/TiAlSi-N nanoparticles strengthened by Hf or Nb additives, which increased surface microhardness up to 3000 HV. The measured steady-state friction coefficient (CoF) was within the 0.2–0.4 range, and a specific wear rate lower than 2 × 10−6 mm3/Nm was observed in the dry friction regime. The impact of NSC substrate hardness and NSC coating thickness on microhardness measurement values was investigated. A thicker coating provided a higher integrated (coating + substrate) microhardness value at a lower indentation test force (<0.3 N). As the indentation test force increased, the obtained microhardness values decreased faster for the coatings deposited on a softer substrate. The surface roughness impact on wear properties for specific NSC coatings was observed.

Coatings 2023, 13(3), 552
10.3390/coatings13030552 (Open Access)
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ABSTRACT: This article presents a study of the mechanism of porous space formation on the surface of single-crystal indium phosphide. The dissolution features of crystals of various types of conductivity and crystallographic orientation of the surface are demonstrated. The attention is focused on the formation of pore chain channels on the surface of n-InP (111). The main stages of the pore formation process are highlighted, which are described according to two competing theories—spontaneous seeding and defect–dislocation mechanism.

Applied Nanoscience (2023)
DOI: 10.1007/s13204-023-02973-5


ABSTRACT: We, at the ab initio level, simulated the rearrangement magnitudes of the adjacent neighboring ions, surrounding the (100) surface F-center in ABO3 perovskite matrixes. They are noticeably greater than the respective ionic shift magnitudes of the adjacent neighboring ions surrounding the bulk F-center. In ABO3 perovskites, the electron charge is noticeably better bounded on the inside of the bulk oxygen vacancy, as interior the respective (100) surface vacancy. The oxygen vacancy formation energy, located on the (100) surface of ABO3 perovskites, as a rule, is smaller as in the bulk. This slight energy distinction encourages the oxygen vacancy segregation from the ABO3 perovskite bulk to their (100) surfaces. The ABO3 complex oxide (100) surface F-center generated defect levels are positioned nearer to the (100) surface CB bottom than the bulk F-center generated respective defect levels. In contrary, the BaF2, SrF2 and CaF2, both, surface and bulk F-center charges are well localized inside the fluorine vacancy. The ionic rearrangement magnitudes of the adjacent neighboring ions, surrounding the surface and bulk F-centers in BaF2, SrF2 and CaF2 matrixes, are much smaller regarding the respective situation in ABO3 perovskites.

Modern Physics Letters B, 2023
DOI: 10.1142/S0217984923420046

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Institute of Solid State Physics, University of Latvia, Thin Films Laboratory